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Copyright © 2007, New Age International (P) Ltd., Publishers Published by New Age International (P) Ltd., Publishers All rights reserved. No part of this ebook may be reproduced in any form, by photostat, microfilm, xerography, or any other means, or incorporated into any information retrieval system, electronic or mechanical, without the written permission of the publisher. All inquiries should be emailed to rights@newagepublishers.com

ISBN (13) : 978-81-224-2872-8

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Preface
The object of the present book is to serve the students with a very elementary knowledge of chemistry. The syllabi of chemistry taught in the name of engineering chemistry in different engineering and technology degree colleges is of very diverse in nature. It is rather quite impossible to give a complete coverage of all the topics in a limited space, but the authors have dealt with modern views of the topics of the syllabi and attempted to give a major coverage of the recent syllabi taught in various institutions. As teachers of some experience, the authors are well aware of the great value for attaching the short questions and answers as well as solutions of the numerical problems. They gave due weightage regarding the matter in writing the book. In an effort to make the book as comprehensive as possible, a large number of topics have been dealt with and the authors hope that this will serve the purpose of making the book useful as a text book of chemistry for engineering degree colleges all over India. The authors wish to express deep sense of gratitude to their beloved student Sri Rajib Das who assisted throughout in writing the book. R Mukhopadhyay Sriparna Datta

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Contents
1 Atoms and Molecules .................................................................................... 1–11
Wave Mechanical Concept of Atom .................................................................................... 1 Application of Schrödinger Equation ................................................................................. 6 Probability Distribution ...................................................................................................... 7 Exercises ............................................................................................................................. 11

2

Valency and Chemical Bonding .............................................................. 12–42
Electronegativity ............................................................................................................... 14 Hydrogen Bond .................................................................................................................. 15 Dipole Moment .................................................................................................................. 16 Chemical Bonding (Wave-Mechanical Concept) .............................................................. 18 VSEPR Theory and Molecular Model .............................................................................. 25 Aromatic Character ........................................................................................................... 33 Short Questions and Answers .......................................................................................... 35 Exercises ............................................................................................................................. 41

3

Nuclear Chemistry ...................................................................................... 43–67
Radioactivity ...................................................................................................................... 43 Nuclear Fission .................................................................................................................. 47 Nuclear Reactors ............................................................................................................... 50 Uses of Radioisotopes ........................................................................................................ 53 Short Questions and Answers .......................................................................................... 62 Exercises ............................................................................................................................. 65

4

Thermodynamics ....................................................................................... 68–103
The First Law of Thermodynamics .................................................................................. 70 Thermochemistry .............................................................................................................. 80 Bond Energy ...................................................................................................................... 83 Second Law of Thermodynamics ...................................................................................... 84 Third Law of Thermodynamics ........................................................................................ 87 Short Questions and Answers .......................................................................................... 98 Exercises ........................................................................................................................... 100

5

Reaction Dynamics/Chemical Kinetics ............................................. 104–136
Introduction ..................................................................................................................... 104
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Mathematical Formulation of First Order Reaction ..................................................... 106 Mathematical Formulation of a Second Order Reaction .............................................. 108 Third Order Reaction ...................................................................................................... 111 Disturbing Factors in the Determination of an Order .................................................. 116 Collision Theory ............................................................................................................... 120 Solved Examples .............................................................................................................. 121 Short Questions ............................................................................................................... 131 Short Questions and Answers ........................................................................................ 131 Exercises ........................................................................................................................... 135

6

Catalyst ......................................................................................................137–149
Catalyst ............................................................................................................................ 137 Definition ......................................................................................................................... 137 Types of Catalyst ............................................................................................................. 138 Short Questions and Answers ........................................................................................ 143 Catalytic Applications of Organometallic Complexes ................................................... 145 Exercises ........................................................................................................................... 148

7

Mechanism of Organic Reactions ....................................................... 150–183
Reaction Types ................................................................................................................. 150 Energy Changes During the Progress of a Reaction ..................................................... 153 Resonance ........................................................................................................................ 157 Steric Hindrance .............................................................................................................. 158 Isomerism......................................................................................................................... 160 R-S System of Nomenclature .......................................................................................... 166 E and Z Nomenclature .................................................................................................... 170 Short Questions and Answers ........................................................................................ 171 Exercises ........................................................................................................................... 182

8

Ionic Equilibrium .................................................................................... 184–203
Law of Mass Action and Ionisation ................................................................................ 184 Acids and Bases ............................................................................................................... 185 pH Scale ........................................................................................................................... 187 Buffer Solutions ............................................................................................................... 189 Solubility Product ............................................................................................................ 192 Solved Examples .............................................................................................................. 195 Short Questions and Answers ........................................................................................ 197 Exercises ........................................................................................................................... 202

9

Electrochemistry ..................................................................................... 204–229
Introduction ..................................................................................................................... 204 Electrolysis ....................................................................................................................... 204 Faraday’s Law of Electrolysis ......................................................................................... 205 Relative Speeds of Ions During Electrolysis (Transport Number) ............................... 208 Determination of Transport Number (Hittorf’s Method) .............................................. 210 Specific Conductance ....................................................................................................... 211 Conductometric Titration ............................................................................................... 217

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Solved Examples .............................................................................................................. 219 Short Questions and Answers ........................................................................................ 223 Exercises ........................................................................................................................... 228

10

Electrochemical Cells ............................................................................. 230–265
Electrode Potential .......................................................................................................... 230 Interpretation of the Electrochemical Series ................................................................ 234 Latimer Diagram ............................................................................................................. 235 Frost Diagram .................................................................................................................. 237 Concentration Cell ........................................................................................................... 239 Indicator Electrodes ........................................................................................................ 242 Battery ............................................................................................................................. 248 Solved Examples .............................................................................................................. 252 Short Questions and Answers ........................................................................................ 256 Exercises ........................................................................................................................... 263

11

Phase Rule ................................................................................................. 266–277
Introduction ..................................................................................................................... 266 The Phase Rule ................................................................................................................ 267 The Water System ........................................................................................................... 268 Sulphur System ............................................................................................................... 269 Eutectic Systems ............................................................................................................. 271 Tin-Magnesium System .................................................................................................. 273 Iron-Carbon Alloy System............................................................................................... 273 Solved Problem ................................................................................................................ 275 Short Questions and Answers ........................................................................................ 275 Exercises ........................................................................................................................... 277

12

Colloids ....................................................................................................... 278–291
Introduction ..................................................................................................................... 278 Classification of Colloids ................................................................................................. 278 Preparation of Colloidal Solutions ................................................................................. 280 Purification of Colloidal Solutions .................................................................................. 282 Properties of Colloidal Solutions .................................................................................... 283 Coagulation of Colloids ................................................................................................... 285 Protection of Colloid ........................................................................................................ 286 Application of Colloids..................................................................................................... 288 Short Questions and Answers ........................................................................................ 289 Exercises ........................................................................................................................... 290

13

Transition Metal Chemistry ................................................................. 292–307
Transition Metals ............................................................................................................ 292 Crystal Field Theory (CFT)............................................................................................. 303 Short Questions and Answers ........................................................................................ 306 Exercises ........................................................................................................................... 307

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14

Metallurgy ................................................................................................. 308–328
Introduction to the Study of Metals ............................................................................... 308 Common Minerals ........................................................................................................... 309 Ores .................................................................................................................................. 311 Fluxes ............................................................................................................................... 313 Furnaces ........................................................................................................................... 314 Powder Metallurgy .......................................................................................................... 320 Some Specific Examples of Extraction of Metals .......................................................... 322 Exercises ........................................................................................................................... 326

15

Adhesives ................................................................................................... 329–337
Adhesives ......................................................................................................................... 329 Adhesive Strength Development .................................................................................... 330 Technique of Bonding ...................................................................................................... 331 Classification of Adhesives ............................................................................................. 333 Short Questions and Answers ........................................................................................ 336 Exercises ........................................................................................................................... 336

16

Explosives and Propellants ..................................................................338–349
Explosives ........................................................................................................................ 338 Classification of Explosives ............................................................................................. 339 Manufacture of Important Explosives ........................................................................... 343 Propellants ....................................................................................................................... 345 Short Questions and Answers ........................................................................................ 348 Exercises ........................................................................................................................... 348

17

Water Treatment ..................................................................................... 350–378
Sources of Water .............................................................................................................. 350 Hardness of Water ........................................................................................................... 351 Sludge and Scale Formation in Boilers .......................................................................... 352 Softening of Water ........................................................................................................... 356 Cold lime-Soda Process ................................................................................................... 357 Hot lime-Soda Process ..................................................................................................... 358 Permutit or Zeolite Process............................................................................................. 359 Ion Exchange or Demineralization ................................................................................. 360 Treatment of Water for Domestic Use ........................................................................... 362 Chemical Analysis of Water ............................................................................................ 366 Short Questions and Answers ........................................................................................ 372 Exercises ........................................................................................................................... 375 Problems ........................................................................................................................... 377

18

Fuels and Combustion ........................................................................... 379–414
Introduction ..................................................................................................................... 379 Calorific Value ................................................................................................................. 379 Solid Fuels ........................................................................................................................ 383 Liquid Fuels ..................................................................................................................... 390

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Gaseous Fuels .................................................................................................................. 399 Solved Examples .............................................................................................................. 404 Short Questions and Answers ........................................................................................ 407 Exercises ........................................................................................................................... 412

19

Silicate Technology ................................................................................. 415–438
Introduction ..................................................................................................................... 415 Cement ............................................................................................................................. 418 Glass ................................................................................................................................. 422 Pottery and Porcelain ...................................................................................................... 427 Refractories ...................................................................................................................... 430 Short Questions and Answers ........................................................................................ 435 Exercises ........................................................................................................................... 437

20

Polymers .................................................................................................... 439–470
Polymerization ................................................................................................................. 439 Plastics (Resins) ............................................................................................................... 445 Important Thermoplastics .............................................................................................. 449 Important Thermosetting Resins ................................................................................... 453 Rubber .............................................................................................................................. 460 Miscellaneous Polymers .................................................................................................. 464 Short Questions and Answers ........................................................................................ 465 Exercises ........................................................................................................................... 468

21

Paints .......................................................................................................... 471–480
Paints ............................................................................................................................... 471 Varnishes ......................................................................................................................... 475 Lacquers ........................................................................................................................... 477 Enamels and Japans ....................................................................................................... 477 Short Questions and Answers ........................................................................................ 478 Exercises ........................................................................................................................... 480

22

Solid State Chemistry ............................................................................ 481–503
Crystal .............................................................................................................................. 481 Fundamental Law of Crystallography ........................................................................... 482 Crystal Lattice ................................................................................................................. 485 Cubic Crystals ................................................................................................................. 487 Transistors (Semiconductor Triodes) ............................................................................. 492 Elements of Band Theory ............................................................................................... 493 Conductors, Semiconductors and Insulators ................................................................. 496 Problems........................................................................................................................... 501 Exercises ........................................................................................................................... 503

23

Chromatography ..................................................................................... 504–511
Introduction ..................................................................................................................... 504 Types of Chromatography ............................................................................................... 504 Exercises ........................................................................................................................... 511

................................................. 529 Mass Spectrometry ................................................... 565 Electron Transport and Oxidative Phosphorylation ... 564 Cobalt .................................................................................................................................................................. 550 Types of Photophysical Pathways ............................................................................................................................ 561–570 Iron ........ 585 Thermal Pollution............................................................................................. 571–589 Air Pollution ..................................................................................................................................... 552 Photochemical Processes for Excited Molecules ............................................................................................................................................................................................................................................................................................ 537 Short Questions and Answers ............................................................................................. 522 Some IR Spectra ................................................................. 513 Beer-Lambert’s Law . 564 Calcium and Magnesium .................................................................................................................................................................................................................................................................................................... 547 25 Photochemistry .................................................................................. 567 Short Questions and Answers ..................................... 540 Exercises ........................................................................................................................................................................................................... 587 Exercises ........................................................................................................ 571 Water Pollution.................................. Deshielding and Chemical Shift ................................................................................. 570 27 Pollution Prevention and Waste Minimisation ........................... 562 Copper .............................. 549 Photolysis ................................................................................................................................................................................... 512–547 Introduction ..............................................................(xii) 24 Instrumental Methods of Analysis .............................. 563 Manganese .............................................................................................................. 525 Shielding................................................................................................... 584 Noise Pollution.................................................................................................................................................................. 560 26 Role of Metals in Biology ................................................................ 556 Exercises .... 569 Exercises ................................................................................................................................................................................................................................................................................................................................... 549 Properties of the Excited States .... 579 Soil Pollution ...... 554 Photosynthesis ..................................................................................................................................................................................548–560 Singlet and Triplet States ......................... 583 Radioactive Pollution .... 589 ................................................................................................................................................................................. 563 Zinc ................................ 564 Nickel ............................................................................. 565 Electron Transfer .............................. 519 Infrared Spectroscopy .................................................. 586 Short Questions and Answers .................................................................................................................................................................................................................................................................................................................................................................... 512 Some Terms Concerning UV ..........

a particle occupies a definite position in space. de-Broglie pointed out in 1924 that radiation including visible light. • A particle is specified by its (i) mass (m). The above equation is known as de-Broglie’s wave equation. (iii) momentum (p). These experiments conclusively proved the wave nature of these radiations. small particles like electron which are considered as minute particles should also act as waves for sometimes. The wavelength of the matter wave is given by h h λ= = p mv where ‘m’ is the mass of the material particle. However.1). (iii) phase. protons. (ii) velocity (v). (iv) amplitude. an electron behaves as a standing wave which goes round the nucleus in a circular orbit.Atoms and Molecules WAVE MECHANICAL CONCEPT OF ATOM Wave Nature of the Electron 1 We have seen upto Bohr’s concept of atom that the electron is treated as a particle. Of course radiation cannot exhibit its particle and wave properties simultaneously. neutrons. radiation behaves as a particle in interaction experiments which include black body radiation. ‘v’ is the velocity and ‘p’ is the momentum. The only necessary condition for the establishment of such a stationary wave is that the length of the orbit should be a whole number multiple of the wavelength of the electron as shown in the following Fig. infrared. (ii) wavelength (λ). (1. (iv) energy (E). According to his hypothesis. it is rather difficult to accept two conflicting ideas. all matter particles like electrons. which sometimes behaves as a wave and sometimes as a particle. that radiation is a wave which is spread out over space and also a particle which is localised at a point in space. 1 . atoms or molecules have an associated wave with them which is called matter wave or pilot wave or de-Broglie’s wave. In view of the above facts. • A wave is specified by its (i) frequency. According to the wave mechanical model of the atom. (v) intensity. ultraviolet and X-rays behave as waves in propagation experiments based on interference and diffraction. The concept of wave nature of matter came from the dual character of radiation. de-Broglie’s Equation (de-Broglie’s matter waves) His suggestion was based on: as radiation like light can act sometimes as a wave and sometimes like a particle. Moreover. photoelectric effect and Compton effect. Here radiation interacts with matter in the form of photons or quanta.

M. The New Atomic Picture In Bohr’s atomic model.e.1 particle. the concept of an electron as a standing wave rather than a particle revolving in an orbit also removes the difficulty met in Bohr’s theory regarding non-radiation of energy by the revolving electron. Moreover. ∴ 2πr = nλ. 1. replaced by de-Broglie’s electron wave.2 If r is the radius of the circular orbit. 1. it is still customary to talk of orbits and shells for the simple reason that even according to the new picture of the atom. 2. etc. Hence.. . 1. the whole of electron mass and charge is spread out uniformly throughout the space immediately surrounding the nucleus of the atom (Fig. 3.. This model has been replaced by wave mechanical model. 1. Charge Density Distance K L M N O Fig.e.2 Old and new models of an atom. electrons are found to distribute their charges in such a way that something analogous to shells is formed. we see that wave mechanical picture leads naturally to Bohr’s postulate that the angular momentum is an integral multiple of h/2π. However. i. then Now. At nodes where the motion is practically zero. Old Bohr’s model is represented by orbits of an atom (Z = 37) (Fig.2).2) and the new wave model is represented by a graph of spherically symmetrical electronic charge with several maxima corresponding to the discrete K. instead of being localised at a point. L. New wave model accepts the electron distribution to be three dimensional. Since ‘mvr’ is the angular momentum of the electron as a Fig. there is assumed to be a little or no charge while at the antinodes the amount of charge is maximum. These waves form stationary waves with their nodes and antinodes. the angular momentum is quantised. N shells. nh mv mvr = nh/2π ENGINEERING CHEMISTRY 2πr = r or where n = 1. i. nucleus of an atom is surrounded by particles known as electrons. λ = h/mv. which revolve in defined shells or orbits. Other quantum conditions can also be derived similarly.

it becomes y = a sin 2π ft − FG H IJ K . At each point along the wave in space. it is impossible to determine its position and momentum simultaneously. ∆ x. The best way is to predict the probability of finding an electron with probable velocity with definite energy in a given region of space in given time. f = frequency of vibration. When differentiated twice with respect to x. y varies periodically with frequency f..(2) y=0 dx 2 λ2 d2 y or . λ = wavelength. The above expression is known as uncertainty relation where ∆ x = change in position.. As we know. It is for this reason the classical concept of Bohr’s model of atom has been replaced by probability approach.∆p ≥ h/2π. Its solution is y = a sin 2π x/λ which defines a standing wave....(1) . But according to uncertainty principle since an electron possesses wave nature..ATOMS AND MOLECULES 3 Heisenberg’s Uncertainty Principle The dual nature of the electron implies that any precise measurement of its position would create uncertainty in measurement of its momentum and position. Thus the uncertainty principle which gives the wave nature of the electron only provides probability of finding an electron in a given space. Schrödinger Wave Equation It is a differential equation capable of describing the motion of an electron.(3) + k2 y = 0 dx 2 The above equation involves only distance as the independent variable. Uncertainty Principle and Bohr’s Theory—Concept of Probability Bohr had postulated that electrons revolve in well defined orbits with fixed velocities (energy). The Heisenberg uncertainty principle states that l It is impossible to determine simultaneously both the position and the momentum of a particle with accuracy. The relation implies that a simultaneous and precise measurement of both position and momentum (velocity) of a dynamic particle like electron is impossible and the extent of inherent uncertainty in any such measurement is of the order of h (Planck’s constant). . the total energy E of an electron is partly kinetic and partly potential. ∆p = change in momentum and h = Planck’s constant. In an ordinary material wave the displacement of whatever is vibrating about its mean position is given by x λ where. On the basis of this principle therefore Bohr’s model of atom no longer stands. d2y + 4π 2 E= ∴ mv = 1 mv2 + V 2 2m(E − V) . y = displacement at time t and at distance x from origin. Let us now see how this equation can be applied to specify an electron in motion. a = maximum displacement from mean position.

4 Now. For three-dimensional motion of an electron.. As.(5) This Schrödinger equation is a basic equation of wave mechanics. i.. So. But in three dimension system |ψ2|dV represents the probability of an electron within the volume range of V to (V + dV).e..dy.(4) The equation (4) is known as the time-independent Schrödinger equation in one dimension. we can write. This mathematical expression displays how the probability of finding an electron varies in space. Generally its solutions are only attained for certain energy values called characteristic or eigen values. It is seen from equations (3) and (4) that × (E − V) . The total probability of finding an electron in space extending to infinity is expressed as follows: +∞ −∞ where dV = dx. Because of the spherical symmetry of an atom the wave functions are most satisfactorily expressed in terms of z ψ2d V = 1 .. The potential energy V of an electron is specified in terms of space co-ordinate not on time. Schrödinger wave equation is time independent. Like other differential equation. the Schrödinger wave equation is also governed by boundary conditions. Schrödinger equation can be employed for determining the total energy of an electron. d 2 ψ d 2 ψ d 2 ψ 8π 2 m (E − V)ψ = 0 + + + dx 2 dy 2 dz 2 h2 or ∇2ψ + 8π 2m h2 (E − V)ψ = 0 . p = mf is a starting point of classical mechanics.ψ* = (a – ib) (a + ib) = a2 + b2. this equation becomes. Substituting this value in equation (1) and replacing y by ψ as is customary.dz.. ψ. The corresponding wave function ψ which is generally complex is called characteristic or eigen function. ψ = a + ib and its conjugate ψ* = a – ib and their product. This is known as the condition of normalisation and the corresponding wave function ψ is said to be normalised. it is impossible to locate an electron in an atom with precision but the nature of the wave function ψ is such that |ψ|2 expresses the probability of finding an electron in a definite volume of space around the nucleus. Significance of ψ and ψ2 l ψ denotes the amplitude of a three dimensional stationary electron wave. which is real. we get d 2ψ dx 2 + 8 π 2m h2 (E − V) ψ = 0 . |ψ2|dx represents the probability of finding an electron within a range of x and x + dx.. de-Broglie wavelength is given by ENGINEERING CHEMISTRY λ= h = mv h 2m(E − V) .. l According to the Heisenberg’s uncertainty principle. k2 = 8 π 2m For a one dimension system.(6) h2 So.

changing from the Cartesian co-ordinates to polar co-ordinates. 1.3 where. This is also same for d-orbital.3 (a) and (b)]. θ. 3s. The angular wave function is a joint function θ and φ which determines the variation of ψ in different directions at a fixed radial distance r.. wave function ψ(r. 2s. Φ(φ) is a function of ϕ which depends on magnetic quantum number (ml). it represents the variation of ψ in the same direction.. which gives the total probability of finding an electron is called the atomic orbital. (i) radial wave function and (ii) angular wave function. θ. the Schrödinger wave equation is It can be shown mathematically that each permitted solution of the wave equation (A) i. φ). ϕ) = R(r) . The total wave function ψ(r. θ.e.e.). which depends on the quantum number n. The radial wave function R(r) shows the variation of wave function with r keeping θ and ψ constants i. (contd. q m e N E f r E N j q r m e (a) (b) Fig. 1..) . θ and ϕ are the polar co-ordinates of the electron with respect to the nucleus (N) as origin [see Fig. For any s orbital (1s.. sin θ.. The wave function ψ(r. etc. The function Θ(θ) is function of θ depending on azimuthal quantum number (l) and magnetic quantum number (ml). The angular dependence of p-orbital is also not influenced by the principal quantum number. the Schrödinger wave equation assumes the following form. Θ(θ) .(A) where r. φ) is denoted as a product of two functions. R(r) is a function that depends on the distance from nucleus. Φ(φ) ∂ 2 ψ ∂ 2 ψ ∂ 2 ψ 8π 2 m (E − V)ψ = 0 + 2 + 2 + ∂x 2 ∂y ∂z h2 where m = mass of the electron. the angular part of the wave function is always the same whatever be the principal quantum number n. respectively).. + 8π 2 µ(E − V) = 0 2 2 2 ∂r ∂θ r ∂r r sin θ ∂ϕ r sin θ ∂θ FG H IJ K FG H IJ K . φ) can be expressed as ψ (r. l (the principal and azimuthal quantum numbers. Highlight: For a small particle like an electron moving in three dimension in the field of nucleus.ATOMS AND MOLECULES 5 spherical polar co-ordinate system with nucleus at the origin. ∂2 ψ ∂ ∂ψ 1 ∂ 2 ∂ψ 1 1 r + 2 + 2 . θ.

Hence. Similarly. The solution of the above second order differential equation furnishes the values of E. since the particle is not allowed over the walls of the box. Application of Schrödinger Equation Particle in a box illustrating energy quantization (Like electrons in metals) Let us consider a particle of mass m which is free to move in a one dimensional box of length l as shown in Fig. the quantised or allowed or permitted energies of electrons and ψ is the wave function. Let the potential energy be infinite for x < 0 and x > l. it is found that the equation can be solved when E assumes certain values which are related by integers. A general solution of Schrödinger equation is: ψ(x) = a sin kx + b cos kx For boundary conditions. ¥ ¥ y¢[x] V V n=1 |y| 2 n=3 n=2 n=1 0 L 0 L V=0 x=0 (a) x=L n=3 (b) n=2 (c) Fig. So. ψ(x) = 0 at x = 0 or ψ(0) = 0 Also 0 = a sin 0 + b cos 0 ψ(x) = 0 at x = l or b = 0 . Alternatively. ENGINEERING CHEMISTRY ψ = wave function or the eigen function of the electron representing the amplitude of the wave associated with the electron. the solution of the above equation produces the electron distribution in space as well as the allowed energy state of the electron. may be taken as zero. we have. it can be stated that the particle is confined to the box and cannot exist outside. h = Planck’s constant. When this equation is applied to hydrogen atom. Hence. ψ function must be zero for all values x > l. z = co-ordinates of the electron.6 V = potential energy of the electron. 1. inside the box V = 0.4. the concept of quantised energy levels and quantum numbers are the consequences of the wave theory. y. E = total energy of the electron.4 The potential energy V of the electron at the bottom of the box is constant. Alternatively. 1. ψ function has to be zero at x = 0 and for all negative values of x. x.

3 . So we can write.e. 2.. rather it possesses discrete set of energy values i. (E. 2. its energy is quantised. p= h 2l 1 ( mv ) 2 p2 mv2 = = 2 2m 2m h2 8ml 2 . 4 and also putting V = 0... A few energy levels are given below: E1 = E2 = E3 = h2 8ml 2 4h 2 8ml 2 9h 2 8ml 2 n=2 n=1 x=0 E2 E1 0 x=L n=3 E3 Energy ∴ En = The reason why a particle in a box i. kl = nπ or k= Substituting this value in eqn. 8ml 2 The above equation means that the particle in a box does not possess any arbitrary amount of energy. 1.ATOMS AND MOLECULES 7 ∴ a sin kl + b cos kl = 0 It can only be possible when.e.5 Highlight: Calculation of minimum energy of a particle in a box from Heisenberg’s uncertainty principle. n2π2 l2 = 8π 2 m E h n 2h 2 So. ∞. . nπ l where x is called quantum number and is equal to 1. we get. 3 . PROBABILITY DISTRIBUTION The directional properties of an election in an orbital of the hydrogen atom cannot be represented in one diagram. ∴ E= E= or.. ∆ x × ∆p = l .. and the particle bounces back in the box. Two separate diagrams are required to meet the demand. ∞. bound particle possesses a quantised energy whereas a free particle does not.. Fig. (2p) = h Now.E. of the electron. So. the total energy of the electron) = K. ∆p = 2p because the momentum changes from + p to – p continuously. where n = 1. Here ∆ x = l. can easily be deduced from the above equation.

e.6 In this diagram..e. A p-level has an accommodation for six electrons distributed over three p-orbitals to each value of the principal quantum number. y-z plane in this case is nodal plane with zero electron density. These three orbitals are at right angles to each other and the three angular probability distributions are shaped like dumb-bells along the three co-ordinate axes and are named as px.e. This is graphically shown in Fig. 1. The different shapes are shown in Fig. (i) Angular probability distributions of orbitals i. y z + y z y z + x x – – + x – px (a) py (b) pz (c) Fig. 1. py and pz orbitals.e. 1. An s-electron has no preferred direction in space i.. how r. there is an equal chance of finding it in any direction around the nucleus..7 It is most likely that in the px orbital the electron will be found in the direction of x-axis and there is no chance of it to be found in any of the directions perpendicular to x-axis i. Similarly..8 ENGINEERING CHEMISTRY These are namely (i) an angular probability distribution i. 1. shapes or boundary surfaces of orbitals gives the probability of finding an electron in a particular direction. y z + x Fig. the nucleus of the atom is at the origin and the surface of the sphere represents the probability of finding the s-electron which is therefore same in all directions.e.7 below.. . how the angular position θ varies from nucleus with respect to a fixed axis and (ii) a radial probability distribution i. In the presence of external magnetic field these vary in their energy content depending on the magnetic quantum number. in the case of py and pz orbitals the electron will be found along y and z axes.6 below. In the absence of magnetic field these orbitals are equivalent in energy content and are said to be triply degenerate. the distance from the nucleus does vary.

9.g. dz2 . e. dxz.8 All the d-orbitals are equivalent in energy in the absence of magnetic field and are said to be five fold degenerate. The lobes of dx 2 − y2 orbital lie along the x and y axes while those of dz2 orbital lie along z-axis. This set is referred to as t2g set. 2s. . The set of the three orbitals namely dxy. 3s. dzx have their lobes lying symmetrically in between the co-ordinated axes indicated by the subscripts to d. the lobes of dxy orbital are pointing or lying in between the x and y axes. 1. 1.8 below. These five orbitals are named as dxy. 1. dx 2 − y2 and dz 2 orbitals form eg set having their lobes along the axes. the probability of finding an electron at a distance r from the nucleus is plotted against r (distance from the nucleus) to get 1s. y z z + – x – + + – + – x – + + – x y y z dxy (a) y z Negative dough nut in x-y plane + x-y plane + x dyz (b) y z – + – + dxz (c) x dz2 (d) px2–y2 (e) Fig. The set of two orbitals i.g. dyz. dx2 − y 2 . 3p and 3d orbitals of hydrogen atom. dyz..e. In these diagrams. e. 2p. These are shown in Fig. The probable distances of an electron are given by radial probability distribution diagram which are given in Fig.ATOMS AND MOLECULES 9 The angular probability distribution of five d-orbitals that can accommodate ten electrons is quite complicated. (ii) The Radial Probability distribution—The angular probability graphs indicate the most probable directions of the electrons but they do not give any indication of the probable distance of the electron from the nucleus.

2p. 3p and 3d orbitals. The larger the value of the principal quantum number the farther is the electron from the nucleus as the angular probability distribution remains uneffected by the value of principal quantum number. The value of r which is the maximum probability in the graph of 1s distribution agrees with the value of r of Bohr’s orbit of hydrogen atom (0. This means the electron can never be at nucleus. . 2s.528Å). Probability 1s Probability 2s r0 1 Distance r (a) 2 Å 0 r1 2 r2 4 Distance r (b) 6 8 Å Probability Probability 3s 2p 0 2 4 6 Distance r (c) 8 Å 0 2 4 8 10 6 Distance r (d) 12 Å Probability 3p Probability 3d Distance r (e) Distance r (f) Fig. 1.10 Highlights: l ENGINEERING CHEMISTRY The probability of finding an electron at the origin is zero which is the nucleus. l l All these facts are based on the proper interpretation of Schrödinger wave equation. The distributions vary according to the principal quantum number.9 Radial probability distribution of 1s. 3s.

Write how the uncertainty principle leads to probability approach. 3. What do you mean by wave nature of an electron? Give the de-Broglie’s wave equation? Correlate Bohr’s postulate of angular momentum with the wave mechanical model. Mention the significance of ψ and ψ2. 7. 8. 2. 11.ATOMS AND MOLECULES 11 EXERCISES 1. 14. 3p. 9. Apply Schrödinger wave equation for particle in one dimensional box illustrating energy quantisation. 6. Write the Schrödinger wave equation using polar co-ordinates. 10. Write Schrödinger wave equation for one dimension. 5. What are eigen values and eigen functions? Give the probability expression for finding an electron in the volume range of V and V + dV. 13. . 4. 3d orbitals. Give the new picture of an atom. Draw angular and radial probability distributions of 2s. 12. Write Schrödinger wave equation for three dimension. Write Heisenberg’s uncertainty principle.

The electrons of the outermost shell of an atom take part in a chemical combination and are called valence electrons. Ar. The inert elements. 12 . + Na Cl Na + Cl – Fig. The other elements have less than eight electrons in their outermost shells and they want to complete their outermost shells with eight electrons (octet theory) to gain the electronic structure of the inert gases. have eight electrons in their outermost shells except He. 1 and Cl atom has got electronic structure ⇒ 2. The electrons remain in the K. 8. L. Kr. These ions remain combined due to electrostatic force of attraction between the so-formed ions. 8. Other electrovalent compounds have been represented as follows by dot-cross method. He. This sort of transfer of electron from one atom to the other results in the formation of Na+ and Cl– ions. The atoms containing eight electrons in the outermost shell cannot participate in the chemical combination and are known as inert elements. This is a very common nature of the atoms and for this sake. Electrovalency: Na atom has got electronic structure ⇒ 2. Na atom can attain inert gas structure by losing one electron and Cl atom can attain inert gas structure by gaining that electron.1. Rn and Xe. The phenomenon can be represented pictorially as in Fig. 2. atoms either lose or gain electrons or share and this idea of electronic arrangement is the basis for electronic theory of valency.Valency and Chemical Bonding 2 Atoms of elements combine to form molecules of compounds.1 This type of combination of two atoms by complete transfer of electrons from the outermost shell of one atom to the other is known as electrovalency. viz. There are three types of valencies — (i) Electrovalency or Ionicvalency (ii) Covalency (iii) Co-ordinate covalency. 7. During chemical combination. Ne. 2. the electrons of the atoms rearrange to form the molecule of the compound. M and N shells in the atoms.

m. 2) Ca + 2(2. They are conductors of electricity in solution or in their molten state. Co-ordinate Covalency In covalency the bonding atoms contribute equal number of electrons to form a bond. 8 . 2) Mg + 2F = µg ++ 2F − (MgF2) 2(2. 7) 2Br = Ca + + . combine to form molecules of a compound they share the electrons to fill up their octets in their outermost shells. 8) Highlight: Electrovalency is seen in the case of atoms with a marked difference in electronegativity values when they combine. × × × × Cl × × × × × × × × × × × × × × × × × Cl × × × Cl × + × × Cl × × × Cl × Cl × Chlorine molecule × × × × × × × × Br × × × × . The other atom contributes no electron towards the bond.p. They can show isomerism. Br × × × × × × × (CaBr2) × Br × . 6 ) S = 2K + 2 ( 2.VALENCY AND CHEMICAL BONDING 13 Some examples of electrovalent compounds : × × × × × × × × (2. are high. 18. 2Br − (2. 8) 2(2. of same or more or less same electronegativity values. They cannot exhibit isomerism. (vi) They are polar in nature.p. 8. In some cases during chemical combinations. 8) ( 2. . 8. 1) 2K + ( 2. Covalency When atoms. This sort of bond formation is known as co-ordiate covalency. 18. + × Cl × × × × Cl × . 8) Similarly 2( 2. 8. 7) ( 2. 8. CCl4). and b. and b. a pair of electrons is being contributed by a single atom. (v) They are soluble in polar solvents (H2O) and insoluble in non-polar solvents (C 6H6. This sort of combining of atoms is known as covalency. 8. generally insoluble in water. . Examples of covalent compounds : × × × × × × × × × × × × × × × × × × × × × × × × × + × × × Comparison of electrovalent and covalent compounds: Electrovalent Compounds (i) (ii) (iii) (iv) They are Non-directional. The atom which donates a pair of electrons is known as ‘donor’ atom and the atom which × × × × × Cl + × + . . m.× Cl . 8. 8. C × Cl × . (v) They are soluble in organic solvents. 8 ) S − − (K2S) ( 2. (i) (ii) (iii) (iv) Covalent Compounds They are directional in nature. are low. After combination the bond acts as a purely covalent bond.p. 8. × × × Cl × Carbon tetrachloride molecule (vi) They are non-polar in nature. They are nonconductors of electricity in solution or in molten state. Ca : + Ca ++ × × Br × × . 8 . 8.p. 8) 2(2.C.

. . × + × º (NH4) + . . H . The power of attracting electrons of one of the atoms in a covalent bond is known as its electronegativity.1 is given in Table 2. .0 Br 2. .8 Pb 1.1 As 2.9 Ra 0. . F or O has got a greater tendency of attracting electron pairs of the bond towards them when they form a covalent bond with any other atom. Pauling Scale) Group → Period↓ 1 2 3 4 5 6 7 I (1) H 2.9 N 3.8 Sn 1.5 Mg 1. H atom has less tendency of this sort.0 F 4. Some examples of coordinate bond formation: H .0 Cl 3. In comparison.1 Po 2. ..– . As for example.9 K 0. .0 Sr 1.8 Ge 1.F B × – × º (BF4) – × . Table 2. F .0 Ba 0.8 Rb 0.2 II (2) III (13) IV (14) V (15) VI (16) VII (17) × . N × × × H H Ammonium ion × H + H . H .5 Ga 1. H .8 Cs 0.1: Electronegativity values (L. . .. The donor atom should have a lone pair of electrons.7 Ti 1.+. × × H H Hydronium ion F .H N.0 Na 0. .0 Al 1. F .5 Si 1.7 Be 1.1 Li 1..4 Te 2.5 Se 2.H O.. The phenomena can be represented as follows: A.2 Ca 1.0 O 3.5 At 2. × + º (H3O) + × F F Electronegativity The attraction and repulsion powers of atoms of different elements are not same. . . Comparative values of electronegativities of different elements taking the electronegativity value of H as 2.6 In 1.1 below.9 Bi 2. H . O..0 P 2..B ⇒ A : B or A – B (Covalency) A:+B ⇒ A : B or A → B (Co-ordinate covalency) The co-ordinate covalency is indicated by the sign ‘→’.8 C 2.14 ENGINEERING CHEMISTRY accepts the pair of electrons is known as ‘acceptor’ atom.. F .8 I 2.9 B 2.7 Fr 0.0 Sb 1. B × × H + . F .5 S 2.

H – F ... viz F... (ii) H¾O Covalent bond H¾O H H H¾O Hydrogen bond H¾O H H .. The relation is represented by the equation — % ionic character = 100 1 − exp 1 − Calculation of partial ionic character of HF molecule: % ionic character in HF molecule = 16(4.. Hydrogen Bondings There are two types of hydrogen bonding: (a) Intermolecular (b) Intramolecular. = 16(xA – xB) + 3. H–F .0 – 2. like O. they are attracted by the hydrogen (H+δ) remaining in the previous molecule and a ‘so-called’ valency is formed as if hydrogen acts a bridge between two electronegative elements.5(4. xA = xB. This type of bond is not very strong. due to its greater electron attraction power. In this condition..... (ii) The atomic radius of the electronegative elements should be small. i.... HCl.. F. (a) Examples of intermolecular hydrogen bonding : (i) .. H–F. Greater the difference (xA – xB).5 (xA – xB)2 LM N R S T 1 ( xA − xB ) 2 4 UOP VQ W Hydrogen Bond Hydrogen atom has got only one electron. the bond gains partial ionic character and the molecule AB becomes polar. it can combine with one atom of a monovalent atom.0 – 2..... When xA ≠ xB. greater is the ionic character of the bond. viz. Example of hydrogen bonding in HF molecules: H – F . • Hydrogen bond is seen when hydrogen is attached to electronegative elements.e. i.1)2 = 43%..VALENCY AND CHEMICAL BONDING 15 This sort of attractions give the covalent bond between two atoms a partial ionic character.. the hydrogen will gain the positive charge partially but the electron will not be detached totally from the hydrogen atom.. when atomic radii are small). As a result. then electron pair of the bond is shifted towards the other atom. the bond A – B is 100% covalent.. H–F .. H hydrogen bond +d –d +d –d +d –d +d –F –d Highlights: • Conditions of hydrogen bond — (i) Hydrogen should be attached to an electronegative element of a covalent bond..e...1) + 3. If the second atom is electronegative. if the charged hydrogen atom comes in contact with strongly electronegative element of the other molecules (hydrogen of HF)... H–F . So.. Partial ionic character of a covalent bond is calculated as follows: When electronegativity values (x) of the two atoms A and B are same. This sort of bond is known as ‘hydrogen bond’. H – F .... The bond energy is less than that of covalent bonds.. N and F (i.e.

These two points in a molecule may fall at the same point or at different places in the molecule. 1 × 10–18 esu-cm is known as 1 Debye.2 Generally. they develop a moment. then. When they fall in different places i.16 ENGINEERING CHEMISTRY + – + – H¾O (iii) O N ¾O H¾O O N ¾O O N ¾O + – H—O O N ¾O + – H—O (b) Examples of Intramolecular hydrogen bonding: H C O H O O N + O H O Salicylaldehyde o-Nitrophenol Properties gained by the molecules due to hydrogen bonding: (i) Due to molecular association arising out of the intermolecular hydrogen bonding.s. The molecules containing the dipole moment are called polar molecules. i.e. two charges (+ve and –ve) are separated by a distance. So within a molecule two or more positive nuclei are surrounded by electrons at different places.u-cm’. 2.’ unit and the distance in ‘cm’ unit. the boiling points of the molecules become high. the charge is expressed in ‘e.. dipole moment. . (ii) Solubility of the molecules in water arises out of hydrogen bonding with water molecule.e. If the magnitude of the charge at the centre of action is e and distance between them is d.u.s. H¾O R H¾O H Dipole Moment Every atom has got nucleus and requisite number of electrons. And this Debye unit is used to express the dipole moment. µ = e × d d e + e– Fig. known as dipole moment.. So within a molecule there is a centre of action of positive charges as well as centre of action of negative charges. volatility becomes less. So the unit of dipole moment is ‘e.

e. CO2. • The dipole moment of a molecule can be calculated from the formula: 2 2 R = µ 1 + µ 2 + 2µ 1µ 2 cos α where. When energy is supplied it is represented by ‘+ve’ sign and called second electron affinity (E2).2 kcal NaCl(s) Crystal Determination of electron affinity of Na atom.8 × 10–18 esu-cm. Neutral gaseous atom A ( g) + e − ( g) → A − ( g) + Anion (Electron affinity of atom A. and in those molecules centre of positive charge action and centre of negative charge action are at the same place. R = Resultant moment of the molecule.7 kcal/g atom of Cl Negative sign indicates that energy is released in the formation. the molecule becomes non-polar and if R has got a positive value the molecule becomes polar.VALENCY AND CHEMICAL BONDING 17 Highlights: • The dipole moment of H2O molecule is 1. H2.0 kcal (– e) Na (a) + – 1 D = +28.4 ∴ E = – 90.2 = + 26 + 28. CH4. ∴ µ ⇒ 0.9 kcal 2 Cl(g) E = ? (+e) Cl (g) U0 = –180.4 kcal 1 D + I + E + U0 2 – 98.e. NH3. Cl(g) → Cl–(g) Q=S+ . CH3OH are polar molecules i. • Cl2.0 kcal Na(g) I = +118.. d ⇒ 0. U0 Þ Lattice energy of NaCl crystal. C6H6.e. i.. i. • HCl. H2O. their centre of action of positive charges and centre of action of negative charges are not same and the molecule is not symmetrical.8 D. its dipole moment is 1. Born-Haber cycle is represented diagrammatically with the formation of NaCl (s) from 1 Na (s) and Cl2 (g) by direct combination to determine electron affinity of ‘Cl’ atom: 2 Na(s) + 1 Cl (g) 2 2 Q = –98. µ1 and µ2 = dipole moments of the different bonds of the molecule.9 + 118 + E – 180. etc. S = +26. The molecules are symmetrical. If R is zero. α = Angle between the covalent bonds Born-Haber Cycle (Determination of Electron Affinity): The electron affinity of an element is the quantity of energy released when an electron is gained or lost by an atom in the gaseous state to form an anion. are non-polar molecules.. E A ) Energy released Electron affinity is represented by the ‘–ve’ sign as energy is liberated in this case.

• The cycle is an application of Hess’s Law (see Chapter 4). Both the theories admit that — (i) A covalent bond is formed as a result of overlapping of the atomic orbitals. Molecular orbital theory. (v) The overlapping orbitals must be valence orbitals and must contain an odd electron. (iii) Maximum overlapping gives a strong bond known as sigma (σ) bond. Schematic representation of the formation of some simple molecules on the basis of valence bond theory: (i) s-s overlapping ⇒ H2 molecule (ii) s-p overlapping ⇒ the formation of HF. two main approaches are — 1.3 Formation of H2 molecule by the overlapping of two 1s atomic orbitals of two H atoms. H2O molecules (i) HF molecule H + F H F Fig. In this connection. Valence-bond theory 2. The application of wave mechanics gives a satisfactory explanation of some of these problems.4 (a) Formation of HFmolecule. The lattice energy for AgCl is greater than that of ionic bondings in NaCl and KCl indicating that there is a contribution of covalent bonding in AgCl. 2. 2. Chemical Bonding (Wave-Mechanical Concept) The classical concept of covalency doesn’t give any idea of the directional characteristic of a bond and also of the bond energy. • The lattice energy for NaCl is –780 kJ mol–1. (iv) Each covalent bond requires overlapping of a pair of orbitals.18 Highlights: ENGINEERING CHEMISTRY • Born-Haber cycle is a thermochemical cycle that can be used to calculate the lattice energy for a compound of a metal with a nonmetal. . that for KCl is –711 kJ mol–1 and that for AgCl is –905 kJ mol–1 calculated as per Born-Haber cycle. H H H : H Fig. • We have utilised Born-Haber cycle in determining the electron affinity of ‘Cl’ atom. • A Born-Haber cycle can also help to determine whether the bonding in a compound is truly ionic. (ii) When the overlapping takes place along the axes of the atomic orbitals maximum overlapping of atomic orbitals can occur. NH3. Molecular orbital theory is gaining much importance.

(iv) Fluorine molecule : p-p overlapping to form a σ-bond. + + NH3 molecule H2O molecule px + px F atom F atom F2 molecule Fig. Fig.5 Formation of H2O molecule.6 px-px overlapping along the axis to form F2 molecule. That concept is the concept of hybridization. 2. But the actual bond angle in water molecule is 104° 27′. But actually bond angle in NH3 is 106° 45′. py pz py pz + + + + 1s z – – – z Fig. (iii) Water molecule x 1s + y + + z – – – – + + + + 1s z + y x In this case also the bond angle appears to be 90°. 2. . If it were the case.VALENCY AND CHEMICAL BONDING 19 (ii) NH3 molecule z 1s H y + + + 1s + + + N 2pz 2py 2px Here the overlapping takes place between the three (2p) orbitals of nitrogen atom with 1s orbital of each hydrogen atom. This fact also leads to the idea of hybridization of orbitals. 2. then bond angle in NH3 should be 90°. So some other concept becomes essential to explain the formation of NH3 molecule.4 (b) Formation of NH3 molecule.

If we consider that C forms four hybrid orbitals of equal energies out of 2s and 2p orbitals and then these hybrid orbitals overlap with s-orbitals of H-atoms along the axes. This can be explained only by the Concept of hybridization.7 σ and π bonds in N2 molecule. .8 sp3 hybridised C atom. but in CH4. C atoms form four identical bonds with H-atom with equal energy. (b) Lateral overlapping of two py and pz orbitals leads to the formation of two π bonds.8). 2. + + px py + Þ pz sp 3 + sp3 sp3 hybrid orbitals + sp3 + sp3 s 109° 28¢ sp 3 C sp 3 sp 3 Fig. (a) Overlapping of two px orbitals along the axes leads to the formation of a sigma bond. Hybridization: Carbon has electronic configuration: 1s2 2s2 2p2. 2.20 (v) N2 molecule: p-p overlapping to form σ and π bonds py pz px py pz py py pz ENGINEERING CHEMISTRY pz p-bond s-bond Fig. Now these four sp3 hybrid orbitals overlap along the axis with s-orbitals of four H-atoms to form a CH4 molecule forming four covalent bonds of same energies. the axes of hybrid orbitals are directed towards the vertices of a regular tetrahedron (Fig. 2. then bond angle and bond energies in CH4 molecule can satisfactorily be explained as follows: 1s C-atom C-atom (ground state) (excited state) ⇒ ⇒ 2s 2p Now this one s-orbital and three p-orbitals of a carbon atom mix to give four hybrid orbitals of equal energies.

Residual 2p orbitals of each sp2 hybridised C-atom overlap laterally to form a π-bond (Fig. . sp2-hybridization Electronic configuration of : 1s C in the ground state Þ C in the excited state Þ Four unpaired electrons 2s 2p sp One 2s and two 2p electrons hybridize to give Þ 2 hybridization 2p 2s and two of 2p orbitals hybridize instead of three 2p orbitals to form three sp2 hybrid orbitals because the three hybrid orbitals are much more directed.9 CH4 molecule.VALENCY AND CHEMICAL BONDING 21 H C H H H Fig. Three sp2 hybrid orbitals of each C-atom form three sigma bonds in ethylene molecule. 2. bond angle in this case is 120°. Highlights: • Ethylene molecule contains five sigma bonds.10). H C H C s-bond H H p-bond p-bond Fig. Lateral overlapping of the two 2p orbitals of two C-atoms leads to the formation of a weak bond known as π-bond (See Fig. • Four sigma bonds are formed due to overlapping of sp2-s orbitals and one out of sp2-sp2 overlapping.10). 2. 2.10 Ethylene molecule. The hybrid orbitals lie in a plane and the axes are directed towards vertices of an equilateral triangle and so. 2.

p p H s p p H H¾C C¾H Fig. During combination with H-atom. 2. In BeF2 molecule the central atom Be has electronic configuration ⇒ 1s2 .12 Structure of acetylene. Since. F sp2–p (s–bond) B sp2–p (s-bond) F sp2–p (s-bond) F Fig. two sp-hybrid orbitals overlap along the axis to give a σ-bond. Then two C-atoms possess total four unchanged p-orbitals.11 Formation of triangular planar BF3 molecule. They overlap laterally to give two π-bonds.22 ENGINEERING CHEMISTRY In boron trifluoride the sp2 hybrid orbitals of B atom overlap with p orbitals of three F atoms along the axes to form three sigma bonds (Fig. (Another example of sp2 hybridization). 2. Boron atom has electronic configuration. 2s2 in its ground state. 2.11). 1s2 2s2 2p1. there is no unpaired electron. sp-hybridization Electronic configuration of: 1s C in the ground state Þ 2s 2p px py pz C in the excited state Þ Four unpaired electrons sp hybridization Electronic configuration of sp hybridized C-atom Þ 2p In the structure of acetylene sp-hybridization takes place. the Be atom cannot form any covalent bond. . So triple bond of acelylene molecule contains one σ-bond and two π-bonds. 2s and 2p hybridise electrons to produce three sp2 hybrid orbitals directed towards the vertices of an equilateral triangle. In the excited state of C-atom there are two hybrid orbitals (sp) and two unchanged p-orbitals.

charge cloud exists symmetrically. Then these 2s and 2px orbitals mix to give two sp-hybridised orbitals. These two hybrid orbitals next overlap with p orbitals of two F-atoms along the axes making BeF2 a linear molecule (Fig. Now. • In double bonds and triple bonds.2: Displaying bond lengths and bond energies Bond Bond length (Å) Bond energy (Kcal) C—C 1. 2p sp hybridized Be atom Þ sp hybridized orbitals 180° F F Be F Be F Fig. there are lateral overlapping and due to this lateral overlapping the π-bonds are formed. Highlights: • When orbitals overlap along the axes.10 225 dsp2-hybridization In this type of hybridisation one s-orbital. 2. • When the number of bonds between the atoms increase the bond energy increases and bond length decreases. the Be atom has the configuration ⇒ 1s2 2s1. Table 2. two p-orbitals (px and py) and one d-orbital ( dx 2 − y2 ) mix to give four equivalent hybrid orbitals. there is σ-bonding. the π-bonds open easily and take part in the chemical reactions. • π-bonds are comparatively weaker than σ-bonds. 2.54 83 C=C 1.34 144 C≡C 1. 2px1 2py0 2pz0.21 196 N—N 1. as they form by lateral overlapping. In this type of bonding. Electronic configuration of: 2s Be in ground state Be in excited state Þ Þ 2p Two unpaired electrons sp hybridization with two unpaired electrons.13). In this type of bonding.VALENCY AND CHEMICAL BONDING 23 In the excited state one of the 2s2 electrons jumps to 2p-orbital before forming any bond. the overlapped charged cloud is parallel to internuclear axis.52 38 N≡N 1. Hence. axes of which are directed towards the .13 Structure of BeF2 (example of sp hybridisation).

So. 2. 2.15).15). The shape of the molecule is trigonal bipyramidal (Fig. 2.14). The hybrid orbitals consist of one group of two equivalent oppositely directed orbitals and the second group of three equivalent orbitals. 2. .3). But in this case. The shape of the molecule will be trigonal bipyramidal (Fig. the hybrid orbitals are not equivalent. 2. px s py pz dz 2 3 dsp Fig. the shape of the molecule becomes square planar and the bond angle is 90° (see Table 2.24 ENGINEERING CHEMISTRY corners of a square.15 Trigonal bipyramidal structure of PCl5. dsp 3 or sp3d hybridization In this type of hybridization dz 2 orbital and one s-orbital and three p-orbitals mix to give five orbitals (Fig. Example of sp3d hybridization: Electronic configuration of: 3s P-atom in ground state Þ P-atom in the excited state Þ 3p 3d Five unpaired electrons sp3 d hybridization 3d Þ These sp3d hybrid orbitals of one P-atom overlap with five p orbitals of five Cl atoms to form PCl5.14 sp3d hybridization. Cl Cl Cl P Cl Cl Fig.

of electron pairs in outer shell of the atom 2 3 4 4 Hybrid orbital sp sp2 sp3 dsp2 Linear Trigonal planar Tetrahedral 90° Shape of the molecule Bond angles Example 180° 120° 109° 28′ 90° 90° BF3.VALENCY AND CHEMICAL BONDING 25 d2sp3 or sp3d2 hybridization Electronic configuration of: 3s S-atom in ground state Þ S-atom in excited state Þ 3p 3d Six unpaired electrons sp d hybridization Þ These sp3d2 hybrid orbitals of one S-atom overlap with p-orbitals of six F-atoms to form SF6. (NH3)2 Cl22– PCl5. C2H4 CH4. SiF4 BeF2. Co(NH 3)6 Fe(CO)5 VSEPR Theory and Molecular Model It is interesting to note that if the central atom in a molecule is surrounded only by overlapped bonding orbital or orbitals containing shared pairs of electrons (Bond pairs. 2.16 Octahedral structure of SF6 molecule. When the central atom contains one or more lone pairs (lp) of electrons in the valence shell with bond pairs (bp) the . the molecule then acquires a regular geometry. F F S F F F F 3 2 Fig.3 No. bp) in the valence shell. 5 ` 6 dsp3 or sp3d d2sp3 or sp3d2 Trigonal bipyramidal Octahedral 120° and 90° 90° SF 6. C2H2 Square planar 90° 90° [Ni (CN)4]2–. Table 2.

It is again greater than the bond pair-bond pair repulsion i.20).18 sp3 hybridized ‘O’ atom. H2O molecule: Fig. and one hybrid orbital contains lone pair of electrons. Molecule containing lone pair and bond pair: Example ammonia molecule: The geometry of the molecule is distorted tetrahedron. Here there are four bond pairs and the shape of the molecule is tetrahedral. Fig. repulsion. Case I. The central atom surrounded by three bond pairs: They remain as apart as possible and the bond angle is 120°. 107° H H H Here O-atom is sp 3 hybridized and only two H-atoms occupy the two corners of a tetrahedron. l.p. The bond angle becomes more reduced (Fig.p l. the orbitals containing lone pairs as well as the bond pairs are so arranged that there is maximum repulsion between them. Case II. 2. Central atom surrounded by four bond pairs: Example methane. N But the bond angle here is 107°. 2. The bond angle is 180°.. 2. 2. The other two corners of the tetrahedron is occupied by the two sp3 hybrid orbitals containing unshared pairs of electrons. Here the bond angle is 105°. the shape of the molecule becomes pyramidal (Fig.96 b. 2. the existence of the two pairs of unshared electrons repel each other strongly and the bond pairs come close to each other than that in the NH3 molecule.e.26 ENGINEERING CHEMISTRY shape of the molecule becomes distorted for minimum energy and for maximum stability.. if the distribution of the orbitals about the central atom of the molecule can be predicted.p. In NH3. H Å 105 O ° O b. In all the above cases there were only bond pairs in the molecules and the molecules have a regular geometry. Central atom surrounded by two bonding pairs: The two bonding pairs remain as apart as possible.19 V-shaped water molecule. we can write lp-lp repulsion > lp-bp repulsion > bp-bp. Now. Example: BeF2. there is sp3 hybridization . The orbital containing lone pair of electrons in the valence shell occupies more space and the lone pair-lone pair repulsion is greater than the lone pair-bond pair repulsion. .19).p. Case III.17). the shape of the molecule and bond angle may be predicted. H H H Fig. Here lp-bp repulsion is greater than the bp-bp repulsion. Case IV. 2. So the bond angle is reduced (107°) and if we overlook the fourth corner of tetrahedron occupying an orbital containing an unshared pair of electrons. Overlooking those two corners of the tetrahedron the H2O molecule becomes ‘V’ shaped (Fig. This is the basis of Valence Shell Electron Pair Repulsion (VSEPR) theory.17 0.

+ – – displaying dipole-dipole interaction (in HCl molecule) + As a result of dipole-dipole interaction. both attractive and repulsive van der Waals forces are important for our understanding of molecular structure. van der Waals forces are weak intermolecular forces which are responsible for weakest attractions between nonpolar molecules. 2.O. Intermolecular forces: In a crystalline solid. These van der Waals forces have very short range.VALENCY AND CHEMICAL BONDING 27 bp – bp repulsion .20 Showing repulsions.) will be one bonding (φB) and the other antibonding (φA): . we can say. There are two kinds of intermolecular forces: (a) dipole-dipole interaction. Since. This is called van der Waals radius. This difference in strength of intermolecular forces is reflected in their physical properties. In non-ionic compound (covalent compound) where the atoms are held by covalent bonds. Molecular orbital theory [linear combination of atomic orbitals.. . So melting of such solids occurs when the highly ordered arrangement of particle in the crystalline lattice changes to the more random arrangements (characteristic of a liquid). ions of molecules are arranged in a symmetrical way.O lp – bp repulsion lp – lp repulsion H H Highlight: NH3 and H2O molecules are examples of distorted molecules due to the presence of lone pairs in the hybrid orbitals and lp-bp. Every atom has an effective ‘size’. When two non-bonded atoms come closer. the attraction between them steadily increases and reaches a maximum when they are just “touching”.e. if the atoms are forced to come still closer then van der Waals attraction will be replaced by van der Waals repulsion.O. (b) van der Waals forces. the intermolecular forces are very weak. when the distance between the nuclei is equal to the sum of the van der Waals radii. two H-atoms designated by HA and HB containing two 1s-atomic orbitals overlap to form M. . Such attraction is known as van der Waals force of attraction. Thus. polar molecules are held to each other more strongly than non-polar molecules (purely covalent molecules). Then expression for two molecular orbitals (M. the particles act as structural units. So energy requirement for melting is less compared to ionic compounds. Fig. They act only between the portions of different molecules that are in close contact. There must be some forces between the molecules of a non-polar compound. LCAO] Homonuclear diatomic molecule: Let. lp-lp repulsions. non-bonded atoms strongly resist crowding. Thus. they can solidify.. i.

diagram. HB Atomic orbitals . (ii) Molecular orbitals from p atomic orbitals: (a) End-end overlap + – – + s*2p (Antibonding) E – + + + – – + (Bonding) – s2p Fig. + s* is (Antibonding. 2.22 Representation of M.21) + ENGINEERING CHEMISTRY . fA) + .28 φB = ψA(1s) + ψB(1s) φA = ψA(1s) – ψB(1s) (i) The two conditions can be represented pictorially (Fig. . 2. E HA + + . Molecular orbital Antibonding s1s Energy Atomic orbital 1s 1s Atomic orbital s1s Bonding Fig.23 Linear combination of two 2px orbitals to form σ2p (bonding) and σ*2p (antibonding) molecular orbitals (σ-symmetry). 2. . Energy level diagram (Fig. 2. s is (Bonding fB) Fig. + . 2.22) illustrating the formation and relative energies of ∗ σ1s (bonding) and σ1s (antibonding) molecular orbitals resulting from the combination of two 1s-atomic orbitals on two H-atoms in H2 molecule. Linear combination of 1s-atomic orbitals (σ-symmetry) of two H-atoms to give bonding and antibonding molecular orbitals (σ-symmetry).O.21 Bonding and antibonding orbitals.

24): + – + E – + – + p2 2p Bonding – + – + p2* 2p fA(Antibonding) Fig. N. B. of electrons in bonding molecular orbitals.O. .O. p*z2p 2p z y z z y x 2p p*y2p.B.).25 Order of energy of molecular orbitals (M. 2. the order of energy for molecular orbital is: π 2 p π y ∗2 p σ1s < σ1s* < σ2s < σ2s* < σ2p < y < < σ∗2p π z 2 p π z∗2 p Bond-Order (B. s*2p p*y2p.O.VALENCY AND CHEMICAL BONDING 29 (b) Side-by-side overlap (Fig. ⇒ no. ⇒ 2 N.) of a molecule is calculated as follows: N.24 π-Bonding.A. A.): Bond-order (B. py2p s2p Energy 2s s*2s 2s s2s Fig. (Energy level diagram of molecular orbitals for a homonuclear diatomic molecule) So. 2. − N. of electrons in antibonding molecular orbitals. ⇒ no.B.O. 2. Linear combination of two 2pz orbitals to form πz2p (bonding) and πz2p* (antibonding) molecular orbitals (π-symmetry).

4 B. 2. greater is the stability of the molecule. 2. Thus πy2p and πz2p bonding molecular orbitals which are degenerate are first singly filled and pairing takes place only when more electrons are to be accommodated. In N2 molecule there will be all total 14 electrons of which 4 will be in the K shells which is denoted by KK. Thus molecular orbital posses3ing the lowest energy will be filled first and that possessing the highest energy will be filled up in the last. unstable and does not exist. • Energy level diagram for N2 molecule: . degenerate molecular orbitals). s*2px s*(sp) p* p* 2pz 2py 2px p s2px s*2s 2s 2s 2s 2s 2px 2pz 2py 2pz 2py 2px s(sp) p s*(sp) 2 2 2pz 2py 2px 1 s2s s(sp) 2 Fig.e. • Rules for filling up of molecular orbitals with electrons: (i) The molecular orbitals are filled in the increasing order of their energies. In a similar fashion πy*2p and πz*2p antibonding degenerate molecular orbitals are filled just like degenerate bonding orbitals.26 Molecular orbital diagram from 2s and 2p atomic orbitals. 0 –ve +ve Significance molecule is unstable and does not exist. ENGINEERING CHEMISTRY *Greater the value of B.30 Table 2. (ii) The maximum number of electrons that can fill a molecular orbital is two. *stable and exists. the electrons will first fill them singly and when both of them have been filled singly.27 Molecular orbital diagram allowing s-p interaction. pairing of electrons will occur. if there are two molecular orbitals having the same energy (i. (iii) According to Hund’s rule of maximum multiplicity. The electronic configuration of N-atom is 1s2 2s2 2p3..O.O. Fig.

= 8 – 2 = 3 2 N2 molecule has triple bond (N º N) pz2p py*2p pz*2p A. diagram for N2.O. 2pz 2py 2px 2s 2s s2s Fig. O.VALENCY AND CHEMICAL BONDING 31 So.29 Molecular orbital diagram of B2 (without s-p interaction). • Energy level diagrams of other molecules: s*2px p*2py p*2pz ­ 2px 2py 2pz p2py p2pz ­¯ s2px ­¯ s*2s ­¯ 2s ­¯ s2s B B2 B B ­¯ 2s ­¯ 2s ­¯ s(sp)1 B2 B ­ 2pz 2py 2px ­ 2px 2py 2pz s(sp)2 ­ ­ 2py 2pz ­¯ s*(sp)1 ­¯ 2s s(sp)2 p*2py p*2pz ­ 2py 2px 2pz Fig. s*2p A.O.O. 2.30 Molecular orbital diagram of B2 (with s-p interaction). . 2.O. 2px 2py 2pz py2p s2p E s*2s B.28 M. Fig. the electronic configuration of N2 molecule will be KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) [KK denotes (σ1s2) (σ*1s2)] M. 2.

32 Molecular orbital diagram of O2 (with s-p interaction).31 Molecular orbital diagram of O2 (without s-p interaction).34 Molecular orbital diagram of NO (with s-p interaction). Fig. 2. 2. • Electronic configuration of O2 molecule: s*2px ­ ­ p*2py p*2pz ­ ­ ­¯ 2pz 2py 2px ­¯ ­¯ p2py p2pz ­¯ s2px ­¯ s*2s ­¯ 2s ­¯ N s2s NO O ­¯ 2s ­ ­ ­¯ 2pz 2py 2px KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) (π*2p1) (πz*2p1) y s*sp)2 ­ ­ p*2py p*2pz ­ ­ ­¯ 2pz 2py 2px ­¯ s(sp)2 ­ ­ p2py p2pz ­¯ s*(sp)1 ­¯ 2s ­¯ N s(sp)1 NO O ­¯ 2s ­ 2pz ­ ­¯ 2py 2px Fig. 2. Fig.32 • Electronic configuration of B2 molecule: KK(σ2s2) (σ*2s2) (σ2p2) s*2px ­ ­ p*2py p*2pz ­ ­ ­¯ 2pz 2py 2px ­¯ ­¯ p2py p2pz ­¯ s2px ­¯ s*2s ­¯ 2s ­¯ O s2s O2 O O ­¯ 2s ­¯ 2s ­¯ ­ ­ ­¯ 2pz 2py 2px ­ ­ ­¯ 2pz 2py 2px ­¯ ENGINEERING CHEMISTRY s*sp)2 ­ ­ p*2py p*2pz ­ 2pz s(sp)2 ­ ­ p2py p2pz ­¯ s*(sp)1 ­¯ 2s ­ ­¯ 2py 2px s(sp)1 O2 O Fig. 2.33 Molecular orbital diagram of NO (without s-p interaction). .

(ii) Heat of hydrogenation of benzene is lower than that expected.5: Electron Distribution in Molecular Orbitals of some Simple Molecules shown in above M.VALENCY AND CHEMICAL BONDING 33 [Energy level diagram for heteronuclear diatomic molecule] Table 2. Kekule established the structure of benzene as follows: or According to the Kekule’s structure there should be four isomeric di-substituted benzenes. Aliphatic compounds are mainly open chain compounds. The idea of resonance could explain all the three above anomalies and established the structure of benzene as put forward by Kekule. diagrams Molecule B2 C2 N2 O2 CO NO σ(sp)1 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ σ*(sp)1 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ π(2p) ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ σ(sp)2 π*(2p) σ*(sp)2 unpaired electrons 2 0 0 2 0 1 Aromatic Character Organic compounds have been classified into two broad subdivisions: (i) aliphatic and (ii) aromatic. They may be cyclic also but they resemble the open chain compounds in their properties. . The word aliphatic came from ‘fatty’ and the word aromatic came from ‘fragrant’. Br Br Br Br Kekule’s structure fails to explain certain characteristics of benzene viz: (i) Benzene undergoes substitution reaction rather than addition. too: Br Br Br Br . Br Br Br Br . (iii) The C—C bond lengths in benzene are equal and intermediate between a single and a double bond. Aromatic compounds a2e benzene or the compounds that resemble benzene in chemical behaviour. have no longer their significance.O.

And this delocalisation gives extra stability to the molecule resulting in formation of stronger bonds and this stability is accounted by the term delocalisation energy. Orbital Picture of Benzene sp2-hybridized Benzene is a flat molecule. The delocalisation in benzene molecule gives π-clouds above and below of the plane of the ring as shown in the Fig. And there still remains six electrons in the six p-orbitals with two equal lobes. i. This delocalisation energy is frequently used instead of resonance energy. which has 36 Kcal mole–1 extra stability. benzene follow an entirely different path. H C H C 120° H s C C C H (ii) The six p-orbitals are shown with overlapping.e. When overlapping is not restricted between two nuclei and it occurs between more than two nuclei. one lying above the plane and the other lying below the plane of paper. which is substitution in which the benzene ring system is retained.36 Delocalised π clouds in benzene. known as aromatic properties.39Å) between a single and a double bond.34 Highlights: ENGINEERING CHEMISTRY • The idea of resonance explains six identical bonds in benzene. as its six carbon atoms are sp2 hybridised. which is a new type of bond. The 36 Kcal of resonance energy is responsible for a new set of properties. . So. benzene possesses chemical properties that are not intermediate between compounds containing single or double bond.6 Kcal mole–1 to be converted into cyclohexadiene. If we fit the six carbon atoms. it is an intermediate in length. Fig. H s H 120° C 120° (i) Only s-bonds are shown. hydrogenation of benzene requires 5.36). Because the resonating Kekule’s structures have a resonance hybrid structure. As for example. the phenomenon is known as delocalisation. 2. (1.. we get a regular hexagon with a bond angle 120°.35 Each p-orbital of one C-atom can overlap equally well with the p-orbitals of the other two carbon atoms on both the sides. a hybrid bond or benzene bond. • As a result of this resonance stabilisation. p-clouds Benzene ring p-clouds Fig. 2. • Benzene is more stable than expected. • We see that addition will lead to a less stable product by destroying the resonance stabilized benzene ring system. (2.

Q.VALENCY AND CHEMICAL BONDING 35 So. What is the special feature of an electrovalent bond or ionic bond? Ans. Here Hückle number corresponds to n = 1. Such electron transfer occurs from metals to nonmetals. Benzene has six π-electrons (known as aromatic sextet). tropylium ion. Ans. etc. 1. Q. Such a bond is formed by complete transfer of electrons from one atom to the other. Thus ions are formed. 4. 3. . It refers to the bonding force that holds together the constituent atoms in a molecule. Ionic bonding is the result of electrostatic forces of attraction between the positive metal ions and negative non-metal ions. In that sense benzene is an ideal aromatic compound and forms the foundation stone of aromatic chemistry. Benzene molecule is flat. necessary and sufficient conditions for aromaticity are: (i) The molecule should be cyclic and flat. What is a chemical bond? Ans. possessing properties entirely different from constituent atoms is known as a molecule. (ii) Covalent and (iii) Co-ordinate bonds. phenanthrene (n = 3) • Heterocyclic compounds: pyrrole (n = 2). This requirement is called (4n + 2) π rule or Hückle rule. What is a molecule? Ans. anthracene (n = 3). Mention the types of bonds. 2. (ii) The molecule should contain delocalised π-cloud. Benzenoid aromatic compounds: naphthalene 10 p electrons antenacene (Anthracene) 14 p electrons phenanthrene 14 p electrons Non-benzenoid aromatic compounds: N H pyrrole 6 p electrons : (+) N pyridine 6 p electrons (–) cyclopentadienyl anion 6 p electrons : tropylium ion 6 p electrons SHORT QUESTIONS AND ANSWERS Q. pyridine (n = 2) etc. 3. Q. Most important types are: (i) Electrovalent. (iii) The π-cloud must contain a total of (4n + 2) π electrons where n = 0. 2. When a group of atoms of same and different elements stay together with a definite combination (of atoms). 1. Highlights: • Benzenoid aromatic compounds: naphthalene (n = 2). • Non-benzenoid aromatic compounds: cyclopentadienyl anion.

7) two fluoride ions (2. 5. H C ::C× H H H Þ H—C = C—H Þ NºN Triple bond + + Shared electrons . 8.C . Attraction Proton in nucleus Fig. (b) 2. 7. Covalent bond is formed when two atoms participating in bond formation share equally their electrons to produce a molecule of an element or a compound. (a) N. 8) + (2. (i) Single covalent bond. .36 ENGINEERING CHEMISTRY Q.37 (a) Forces of attraction during H2 molecule formation. Cl ×– × × Chloride ion (2. 8. Give dot and cross diagrams for NaCl and CaF2 molecule formation. 6. Ca : Calcium atom (2. + 4H × Þ H H . . 8) .. Ans. + 2H × Þ H×C:: C×H .Cl : : : : : : : Þ : Cl : Cl : Þ Cl—Cl Single bond .× . Sodium atom (2. (b) . 8. 1) + × Chloride atom (2. .C. 8) ×× Ans. 7) ×× Cl × × ×× ×× Þ Na+ Sodium ion (2. × ×F× ×× × – Q. . . ××× F× ×× × ×– .N : : Þ : : N::N . 2) + × × ×× F× × ×× ×× F × × Þ Ca++ Calcium ion (2. . 2. × . 8.. 8) + ×× . . + 4H × H . : : + . H H Þ H—C—H H (ii) Double covalent bond. Give examples of single. double and triple covalent bonds by dot and cross diagrams. Q. The atoms held together by the attraction between the positive charges of the nuclei of the atoms participating in the bond formation and the negative charges of the shared electrons by the atoms. Þ H ×C × H ×. 8. ×. 8. Q. How are the atoms held together in a covalent bond? Ans. Þ H—C º C—H (b) 2. 8.C .× . . What is a covalent bond? Ans. : : + . Na. (a) :Cl . : : : : (a) O: + :O Þ : : : : O ::O Þ O=O Double bond (iii) Triple covalent bond.

(a) Covalent bond holds together the atoms of nonmetals in a molecule and giant structures.e. Covalent radius Þ 0.037 nm H2 Covalent radius Þ 0. The coordinate bond is indicated by an arrow to express this unequal sharing. A polar bond is formed when sharing takes place between the atoms of different electronegativities i... When two atoms of the element (same or different) are joined by a single covalent bond. the length of single covalent bonds between atoms of different elements can be determined fairly accurately by adding the covalent radii of the two atoms. O = O. (b) Molecules have a definite shape because covalent bonds have a definite length and direction. What is the special feature of a coordinate bond? Ans. Fig. What is covalent radius? Ans. 11. 2. What is the special feature of a covalent bond? Ans. between dissimilar atoms during bond formation viz. . Ans.VALENCY AND CHEMICAL BONDING 37 Q. (iii) Hydrogen bond.190 nm. What are polar and non-polar covalent bonds? Ans. Covalent radius of an atom is half of the distance between the nuclei of two like atoms bonded together by a single covalent bond.141 nm sum of covalent radii HCl Fig.114 nm van der Waals radius » 0. Covalent radius = 0. A nonpolar bond is formed when sharing takes place between the atoms of same electronegativity i. van der Waals radii determine the effective size of a molecule. (i) Metallic bond. 13.. van der Waals radius is the effective radius of an atom when held in contact with another atom by weak intermolecular forces. This type of bond is formed by unequal sharing of electron pair. etc. 9. Q. one of the participating atoms in the bond formation donates both the electrons for bond formation. Cl—Cl. 12. e. Br—Br. (ii) van der Waals bond. Q.37 (c) Covalent and van der Waals radii for bromine.g. Q.104 nm Cl2 Bond length Þ 0. The covalent radius of an element is half the bond length.. 2. H+δ → Cl–δ Q. Mention special types of bonds. between similar atoms during bond formation.37 (b) Forces of attraction during H2 molecule formation. H—H. 10.e.

the energy needed to break the second O—H bond is 428 kJ mol –1. so enthalpy change is always positive. are the two bond dissociation energies same? Ans. Bond dissociation energy is the energy (or enthalpy) for breaking one mole of a covalent bond in a gaseous molecule. Q. 17. 20. What is a π-bond? Ans. Q. sp2-s. sp2-p etc. Q. the energy needed to break the first O—H bond is 498 kJ mol–1. double and triple bonds? Ans. e = magnitude of charge separated in esu. Bond breaking is endothermic. Ans. Q.38 ENGINEERING CHEMISTRY H H   H  N : + H+ ⇒ H  N → H   H H Q. π-bond is formed by sideway overlapping of mainly p-orbitals of different atoms. What do you mean by bond energy? Ans. In water molecule. This type of bond is formed by axial overlapping of s-s. What is a sigma bond? LM MM MM N OP PP PP Q + Ans. CH4 → CH3 + H° CH3 → CH2 + H° CH2 → CH + H° CH → C + H° D ⇒ 102 Kcal mol–1 D ⇒ 105 Kcal mol–1 D ⇒ 108 Kcal mol–1 D ⇒ 83 Kcal mol–1 Total D ⇒ 398 Kcal mol–1 . sp-s. Mathematically dipole moment is expressed as: µ=e×d where. Q. Q. of different atoms whereby maximum overlapping of orbitals is possible. Energy is needed to break covalent bonds. What do you mean by dipole moment? Ans. A double bond contains one σ and one π bond and a triple bond contains one σ and two π bonds. Bond energy (or enthalpy) is the mean value of bond dissociation energies (or enthalpies) (D) used for approximate calculation estimating the enthalpy changes for the reaction. A single bond is always a σ-bond. Calculate the C–H bond energy in CH4 molecule. In H—O—H (g) molecule. sp3-p. d = distance in cm. µ = dipole moment. 18. What are special features of single. HCl (g) ⇒ H(g) + Cl(g) ∆H ⇒ + 432 kJ mol–1. as the centre of action of positive charge due to nuclei and centre of action of negative charge due to electrons do not coincide. So the bond dissociation energies of two or more bonds between similar atoms are not the same. 14. 16. The dipole moment in a molecule develops due to the separation of positive and negative charges by a distance. p-p or sp orbitals and also sp3-s. 15. 19.

= where. What do you mean by electronegativity? Ans.O. Molecular orbitals are the solutions to the Schrödinger wave equation like atomic orbitals.23). the more polar the bond.O. The bigger the difference in the electronegativity of the elements forming a bond. M.. 0. B. 4 Q. Bonding M. Give the conception of a bonding molecular orbital. φA results from subtraction of the two atomic orbitals (φA = ψA – ψB) i. Give the concept for antibonding molecular orbitals.120nm B Q.) are obtained by the overlapping of atomic orbitals of the atoms linked by a covalent bond. CaF2 etc. Higher the bond order. H ¾Cl ¯ +d –d polar bond.e. 25. are shorter than single bonds. The stronger the pulling power of an atom. Q.) is given by the expression. Q. (φB) is obtained when ++ regions of both the atomic orbitals (A. What do you mean by bond length? Ans. stabler is the molecule. The bonding molecular orbital is a region in space where the probability of finding the bonding electrons is maximum. In a simplified form.21 and 2. 398 = 99..VALENCY AND CHEMICAL BONDING 39 C—H bond energy in CH4 is mean value of D values i. by the overlapping of + – regions of the atomic orbitals (see Figs. Ans.e. is produced by addition of two atomic orbitals (φB = ψA + ψB). in turn. 24. Q.) overlap along the internuclear axis (see Figs. 2.134nm B C≡C .e. Q. The bonding in a compound becomes ionic if the difference in electronegativity of the two bonded atoms becomes so large that the more electronegative atom can remove completely the electron from the other atom. MgO.O. Bond order (B. Nb . 23.. Interpret the idea of bond order. Bond length is the distance between the nuclei of atoms bonded by one or more covalent bonds. Antibonding orbitals (φA) are also solutions to the Schrödinger wave equation like the bonding molecular orbitals. Na ⇒ number of antibonding electrons.O. it may be stated that molecular orbitals (M. Nb − N a 2 ⇒ number of bonding electrons. 2. When does a bonding in a covalent compound become fully ionic? Ans.157nm B C=C 0. the higher its electronegativity. Bond order zero and negative indicates that molecule does not form or exist.23) i.21 and 2.5 Kcal mole–1. Ans. E(C—H) ⇒ C–C 0. The pulling power of an atom of the bonding electrons towards itself when linked by a covalent bond with another atom is known as electronegativity.O.O. 26. Ans. 21. This happens in compounds like NaCl. For the same two atoms triple bonds are shorter than double bonds which. But in this case. 22.

.O. 29..40 Q. The molecule does not exist. = Nb − N a 8−4 ⇒ =2 2 2 So. That is why. (i) sp3. (v) sp3d. (i) B. = 2−1 1 = 2 2 He2+ also has transient existence. 30. The intermixing the atomic orbitals of slightly different energies so as to redistribute their energies and to give a new set of orbitals (known as hybrid orbitals) of equivalent energies and shape is known as hybridisation. (ii) B. 31. (iii) B. (iii) sp. (ii) sp2. O2 molecule is paramagnetic. Here the number of bonding electrons exceeds the number of electrons in antibonding orbital. (ii) H2+. 1− 0 1 = 2 2 H2+ has a transient existence. H− F −δ . (iv) dsp2. H− F − δ . = b = =1 2 2 H-atoms are held together by one covalent bond. Ans. Q.. According to Hund’s rule two unpaired electrons fill the degenerate (orbitals of same energy) πy*2p and πz*2p orbitals (see Figs. Ans. = 2−2 =0 2 Here the number of electrons in σ-orbital = the number of electrons in σ*-orbital. H− F −δ Due to hydrogen bonding. (iii) He2+. Q. HCl is gas and HF is less acidic than HCl. one is σ and the other is π-bond. What is hybridisation of atomic orbitals? ENGINEERING CHEMISTRY Ans. 28. (iv) He2 and interpret the result.. Hydrogen bond in HF inhibits release of H+ partially in aqueous solution...O. (vi) d2sp3. Here. O2 molecule is paramagnetic. O2 molecule contains double bond (O = O). +δ +δ +δ +δ .O. What do you mean by hybrid orbitals? Ans. 2. Q. Explain.32). N − Na 2−0 Ans. 27. there is molecular association in HF and effective molecular weight of HF is high and that is why its volatility is less and it is liquid whereas in HCl molecule there is no hydrogen bonding because Cl is less electronegative than F and atomic radius of Cl is greater than that of F. so it is less acidic. ⇒ Ans. Q. Q. Mention the types of hybridisation. Hybrid orbitals are formed from the mixing of atomic orbitals of different types and are oriented in space in a characteristic manner determined by the type of hybridisation. The electronic configuration of: O-atom ⇒ 1s2 2s2 2p4 The electronic configuration of: O2-molecule ⇒ KK(σ2s2)(σ*2s2)(σ2p2)(πy2p2)(πz2p2)(πy*2p1)(πz*2p1) (iv) B. B. So He is monoatomic.O. Explain why HF is liquid.31 and 2.O. the number of electrons in s-orbital is greater than the number of electrons in s*-orbital. 32. H− F −δ . Calculate the bond orders of: (i) H2O.

H O H O H O H Hydrogen bond H H O H Fig. a molecule of water is surrounded by four water molecules and every molecule of water form hydrogen bonds giving a tetrahedral structure. 6. (b) Give a concise account of delocalisation of benzene.38 H-bonding in ice. (vi) H2O. These electrons can form hydrogen bonds.VALENCY AND CHEMICAL BONDING 41 Q. When ice melts. Q. 5. Write a note on co-ordinate bond. 2. bond angle and shape of the following molecules: (i) BeF2. Due to loss of this void space. (v) NH3. Ans. 33. (ii) BF3. So a crystal of ice is not a single molecule but an associated molecule. Explain H2O is a liquid and H2S is a gas. Give the state of hybridisation. (a) Explain the structure of benzene. C2H6O. this tetrahedral structure is destroyed. . The density of water is greater than that of ice. 3. In H2O molecule. And each oxygen H atom contains two lone pairs. Explain the bond order of N2 molecule. By X-ray crystallography. 7. So. H Ans. EXERCISES 1. it has been established that in a crystal of ice. Q. every oxygen atom is connected to two hydrogen atoms as covalent bonds. 4. And the water molecules are hydrogen bonded in a chain. H H——O– – –H——O– – –H——O C 2H 5 C 2H 5 C 2H 5 H-bonding in ethyl alcohol. 35. What is hybridisation? Give different types of hybridisations with examples. (iii) CH2 = CH2. H——O– – –H——O– – –H——O– – –H——O H H H H The reason is same as in Q no. Explain. (iv) CH ≡ CH. Explain sp. But there is no H-bonding in dimethyl ether molecule as H here is not attached to O-atom. there is some void space in ice. so it is more volatile than ethyl alcohol. 2. O Covalent bond Ans. when ice melts its volume reduces and density increases. there is no molecular association due to H-bonding in dimethyl ether. formula. H—C—O—C—H Dimethyl ether H H There is H-bonding in ethyl alcohol and due to molecular association H is attached to O-atom in every molecule of ethyl alcohol. Discuss hydrogen bonding and explain why density of ice is less than that of water. 8. Write a short note on ionic bonding. Due to tetrahedral structure. H H Explain. sp2 and sp3 hybridisations with examples. 31 above. 34. ethyl alcohol is less volatile than dimethyl ether though both have the same mol.

15. Two elements having the atomic numbers 11 and 17. combine to form a compound. 10. (f) Aromaticity. 11. 16. (b) Give the characteristics of covalent bond. Give its name also. (d) Hund’s rule. Give the molecular orbital diagrams of H2 and O2 molecules. 12. What is VSEPR theory of molecular model? Explain with suitable examples. State the nature and formula of the compound so formed. What is dipole moment? How is dipole moment of a molecule calculated? 13. Explain inter and intramolecular hydrogen bonding with examples. 14.42 ENGINEERING CHEMISTRY 9. (b) Molecular orbital theory. Discuss Born Haber cycle with an example. (c) Explain sp3hybridisation. respectively. . Write short notes on: (a) Intermolecular forces. (a) Explain hydrogen bonding. (c) Resonance. (e) Delocalization.

and γ Rays Property (i) Nature α-Rays (i) Streams of positively charged particles which are merely nuclei of He atoms. The rays emitted are 4 classified as alpha [ 2 He++]. (ii) γ (ii) Representation (ii) –1e° or –1 β° or β. such as—radium. It is quite obvious that the conventional energy sources. As compounds of those elements exhibit radioactivity. These rays can affect photographic plate.Nuclear Chemistry Nuclear Chemistry is the branch of chemistry that deals with the changes in the nuclei. polonium etc. They have very small wavelengths of the order of 10–10 to 10–13 m. 3 RADIOACTIVITY Becquerel in 1896 observed that uranium or its compounds emit a kind of rays spontaneously. such as coal.) 43 . in brief. each consisting of 2 protons and 2 neutrons. γ-Rays (i) It is similar to Xrays and neutral in nature. β. and gamma (neutral). So we are to discuss. So scientists are searching for non-conventional energy sources such as–solar energy. thorium. the idea of radioactivity before going to discuss the source of nuclear energy which is the main feature of nuclear chemistry. The idea of exploiting nuclear energy came after the discovery of radioactivity. The atoms of some of the elements were found to exhibit radioactivity. beta (uninegative charge). (Contd. Radioactive elements emit the radiation and create new elements. A comparative study of the rays emitted during radioactive disintegration is displayed in the following table.1: Comparison among α. (ii) [2He4]+2 or α β-Rays (i) Streams of fast moving negatively charged particles which have the same e/m value as the cathode rays. petroleum will be exhausted in near future. nuclear energy etc. so it can be said that radioactivity is a nuclear phenomenon. He named this phenomenon of emission of spontaneous radiation by uranium as radioactivity. Radioactivity is an irreversible process and emits more heat than that of any of the chemical processes (109 cal mol–1). Table 3.

83 × 108 m/sec. β.u. or γ-rays to give daughter elements.6 × 10–19 coulomb.2 × 10–19 coulomb. (v) 2.36 × 108 to 2.u. Nuclei with 84 or more protons are radioactive.s.000 to 30. (vi) Medium (iv) No charge (0) (v) Velocity (v) Nearly same as light 3 × 108 m/sec. Nuclei with even numbers of protons and neutrons are more stable than that with odd numbers.8 × 10–10 e.000 km per sec.u. These numbers are magic numbers. 240 200 160 Mass number. 2.1 . or 3. or 1. 8.m. ENGINEERING CHEMISTRY (iii) 1 of hydrogen 1836 atoms or 0.u. These nuclei are unstable and emit spontaneously α.5 show radioactivity. 3. (iii) No mass (0) (iv) Charge (iv) Possess positive charge of 2 units = 9. Z 70 90 Fig.000548 a. (vi) Low (iv) Possess negative charge of 1 unit = 4. 82 and 126 protons or neutrons are more stable than other nuclei containing different number of protons and neutrons.s.m. 20.6 × 10–10 e. A 120 80 40 0 10 30 50 Atomic number. Nuclei containing 2. (vi) Maximum (vi) Penetrating power It has been observed that heavier elements in which neutron-proton ratio (N/p) exceed 1. 3.44 (iii) Mass (iii) 4 a. (v) Nearly 1/10 the speed of light or 20. Nuclear Stability 1. 50.

Integrating we have. 3. At any instant of time....e.2). then the ratio A/Z for a nucleus is 2 i. the decay curve is exponential in nature (Fig.NUCLEAR CHEMISTRY 45 The graph (Fig. When the value of Z is less. Fraction present t=T t = 2T t = 3T Time t Fig. light elements possess equal number of protons and neutrons and the nucleus is stable. Radioactive Decay The radioactive decay follows an exponential law. i. − So. i.e. The graph is more or less linear. 3.1) is a plot of proton number (Z) vs mass number (A). So it can be said that radioactivity is a phenomenon to stabilize the nucleus by decreasing the ratio A/Z of the nucleus. .2 Decay curve of radioactive substances. the rate of disintegration is proportional to the number of atoms (N) present. when t = 0 N = N0. dN dN dN/ dt − ∝N or = λN or λ= − dt dt N where λ = disintegration constant may be defined as the ratio of the amount of the substance which disintegrates in a unit time to the amount of substance present. when the proton number of the nucleus exceeds 20 the nucleus shows the tendency to be unstable and when the proton number (Z) exceeds 83 the nucleus becomes more or less unstable. The ‘negative sign’ indicates that with passage of time ‘t’ the number of atoms decreases. then ∴ or ∴ dN = − λdt N loge N = – λt + C loge N0 = C loge N = – λt + loge N0 loge N = – λt N0 [C = integration constant] If ‘N0’ be the number of atoms present initially.e.e–λt When M0 = original mass and M = mass at time t. As the difference of Z and A increases the nucleus becomes totally unstable. the equation is M = M0. 3.e–λt Hence.

The term 4n means mass number is divisible by 4. When a β-particle is emitted the daughter element formed shifts to one column forward (right side) in the periodic table i. 82 Pb 207 82 Pb. Units of Radioactivity The unit of radioactivity is ‘curie’. The series are 4n or Thorium series.. N 1 = = e −λ T N0 2 and through a chain of successive Starting element of (4n + 2) series is and end product is 206 . The curie is defined as that quantity of any radioactive substance which gives 3. atomic number of daughter element is increased by one unit. respectively. 4n + 2 or Uranium series and 4n + 3 or Actinium series. . Naturally occurring radioactive disintegration series are shown below. 238 92 U 232 90 Th If T is the half-life of the radioactive element. The curie is a very large unit.693 = . Half-Life ∴ T= Half-life of a radioactive element is the time required for half of the atoms to decay away. It starts and ends at α 234 90Th 200 82 Bi . λ λ The above equation is a relation between half life (T) of a radioactive element and its disintegration constant (λ).46 ENGINEERING CHEMISTRY log e 2 0. atomic number of the daughter element decreases by two units.7 × 1010 disintegrations per second. In the 4n series starting element is disintegration it produces ultimately 208 82 Pb .. in the periodic table i.e. Radioactive Disintegration Series Number of naturally occurring radio isotopes is about forty. Hence for all practical purposes millicurie [1 mCi = 10–3 Ci] and the microcurie [1 µCi = 10–6 Ci] are used. then we can write. Details of disintegration chart of (4n + 2) series is given below: 238 92 U  →  α  →  α β 234 91 Pa  →  α β 234 92 U  →  β α 230 90Th  →   →  β α 226 88 Ra 214 84 Po  →   →  α 222 86 Rn 210 82 Pb  →   →  β 218 84 P o 210 83 Bi  →  β 214 82 Pb  →  α 214 83 Bi  →  210 84 Po  →  206 82 Pb (Stable Lead) Group displacement (Radioactive displacement) law: When an α-particle is emitted the new element formed is shifted two columns back (left side) of the original element. whereas 4n + 2 and 4n + 3 means mass number when divided by 4 gives a remainder of 2 and 3. For (4n + 3) series starting element is with 237 93 Np 235 92 U and end product is An artificially made disintegration series is Neptunium series (4n +1). Half-lives for radioactive isotopes can be as short as a fraction of a second or as long as millions of years.e.

1 a.6 × 10–6 ergs and 1 a.m. Highlight: E = mc2 = 1 × (3 × 1010)2 g cm2 sec–2 = 9 × 1020 g cm2 sec–2 = 9 × 1020 ergs = 9 × 1013 joules.u.g. we get radioactive 13 phosphorus which is ultimately converted to silicon.m.m. German scientists Hahn and Strasman bombarded uranium atom with neutrons and obtained two elements with atomic numbers 56 and 36.66 × 10 −24 g. Mass-Energy conversion factor We know that.023 × 10 23 = 1. 1 MeV = 1. So. = 1. ∴ 1 a.u. So. .u.u. 1 eV = 1.u. c = velocity of light. 1 This phenomenon is known as Artificial Radioactivity. 27 13 Al + 4 He → 2 30 15 P 30 15 P 30 19 Si 1 + 0n → + 0e .023 × 1023 1 a.6 × 10–12 ergs. The famous equation in this regard is E = mc2 where E = energy .66 × 10–24 g.6 × 10 −6 ≈ 931 MeV. = 6 12 1 12 1 g= g × So.NUCLEAR CHEMISTRY 47 Artificial Radioactivity If an atom of a non-radioactive element is bombarded by a powerful particle.m. Einstein established from theoretical standpoint that mass and energy are mutually convertible. Mass–Energy Equivalence In 1905. 1 × 12 C 1 a. if we bombard 27 Al with an alpha (α) particle. = 1 6.m. it is converted to a radioactive atom. The year 2005 has been declared as year of physics to observe the centenary of this famous equation.u.m. = 1.). e. Nuclear Fission In 1939. Atomic Mass Unit Masses of atoms are usually expressed in atomic mass units (a. = N 12 N where N (Avogadro number) = 6.6 × 9 × 10 20 1. 1 g of matter is equivalent to 9 × 1013 J of energy.

u.m.m.u. The generated neutrons again can bombard another 335U atoms and another fissions can occur and this phenomenon will occur in chain within 10–8 sec.8973 a.m. 141 56 Ba 92 36 Kr 1 30 n Final masses ⇒ 140.m. and this amount of energy will be generated within 10–6 second. ⇒ 1. 3. This process of repeated fission is known as chain reaction (Fig.u. the generation of huge amount of energy leads to an explosion with a temperature of one crore degree.m. This nuclear fission reaction is the principle of an atom bomb.0261 a.0526 a. A small fraction of mass is lost and is converted to energy according to the equation: E = mc2. For the reaction. 1 g of U-235 will generate 2 × 107 kcal. 235 92 U 1 0n Initial masses ⇒ 235. 1 0n (Secondary neutrons) Neutrons Fission Fragments 235 92U Fig. ⇒ ⇒ 91. 92 56 36 This phenomenon of splitting a nucleus into two approximately equal fragments is called nuclear fission or simply fission.u.9139 a.u. 3. 3. 236.m. So.8373 a.48 235 92 U ENGINEERING CHEMISTRY 1 1 + 0 n → 266 U → 141 Ba + 92 Kr + 3 0 n.m.u. Energy Released in a Fission Reaction It has been estimated that the mass generated after fission is not equal to the total weight of uranium fissioned and bombarding neutrons. 235.3) and as a result it can generate a huge amount of energy.3 Chain reaction as a result of bombardment of 92U235 with one neutron and perfission three secondary neutrons are released.0439 a. . 235 1 141 92 1 92 U + 0 n → 56 Ba + 36 Kr + 3 0 n.u.0087 a.

To utilise the energy released during the fission.m. we are to control the chain reaction to get the heat energy according to necessity.00893 = 7.2 × 1013 J.. And during this fusion reaction some mass is destroyed.m.u. Atomic Fusion At a very high temperature. Highlight: It can be shown that when 1 kg of uranium is completely fissioned. the motion of neutrons are retarded by graphite or heavy water to control the chain reaction.2153 × 931 ≈ 200 MeV..0005486 + 3 × 1. which is equivalent to an energy of 0.0601058 a. Now-a-days.0419258 a. 1 1 2 Mass Defect and Binding Energy After the discovery of isotopes. the energy released would be 8.m. the atomic weights are calculated from number of protons.00758 + 4 × 1.m.00389 ∴ ∆m = 0.e. The transformations for fusion reactions are: 2 1H (i) 3 H + 2 H → 4 He + 1 n + 17 MeV 1 1 2 0 (ii) 3 H + 1H → 4 He + 20 MeV etc. 16O scale) .0162 → 4.02863 × 931 MeV = 26.u. i. (Energy released due to above fusion) The difficulty is to attain the high temperature for such fusion process. which is equivalent to 0. Aston examined the atomic weights of various elements and concluded that the atomic weights of all the elements would be a whole number. The calculated mass (M) and actual weight (A) is determined considering the contribution for the presence of isotopes. the atomic weight will be 3 3 × 0. electrons and neutrons. the atomic weights of the different elements depend upon another factor: in a. the atomic weights become fractions.NUCLEAR CHEMISTRY 49 So. The difference of these two quantities is called mass defect (∆) or ∆m ∴ ∆ = M – A. For a 7 Li atom.u. that means such a fusion process would also lead to liberation of huge amount of energy which causes explosion.6545 MeV. two nuclei combine to give a new atom.2153 a.m. Besides that. (in 3 So. the mass lost is 0. + 2 H → 4 He + Energy 1 2 2 × 2.u.0601058 – 7. which is sufficient to supply energy at the rate of 2. This phenomenon is known as atomic fusion. But it is believed that such condition is attained for preparing thermonuclear bombs such as hydrogen bomb. fission reaction is retarded and thereby controlled and the heat generated is being absorbed by molten Na–K alloy and this heat is utilised in generating steam for thermal power. But due to the presence of isotopes in unequal amounts. mass defect (∆) = 7.01818 a.01818 = 0.u. So.2 megawatt continuously for one year.02863 a.m. But actual atomic weight of 7 Li is 7. in an atomic reactor.u. two nuclei combine to give a comparatively heavy nucleus.

. Nuclear reactors may be looked upon as a nuclear furnace where fuel is 235U. they are rapidly slowed down and brought to rest due to collison with other atom of the metal. so it has been expressed by multiplying 104.4 The graph is a plot of binding energy/nucleon vs. the nuclear binding energy will be 0. a fraction is obtained which is known as packing fraction (f) 0. composition and the purpose for which they are used. A small value of packing fraction indicates greater stability of the nucleus. and this is the reason for mass defect.” In other words it is a device where controlled nuclear fission of 235U. 10 Binding energy/Nucleon (MeV) 9 8 7 6 5 4 3 2 1 0 20 40 60 80 100 120 140 160 180 200 220 240 Mass number (A) Fig. 233U or 239Pu and also chain reaction takes place and produces.03 MeV. So. NUCLEAR REACTORS “A nuclear reactor is an apparatus in which nuclear fission is produced in the form of a controlled self sustaining chain reaction. • Neutron energies: (a) High energy—as in fast reactors (b) Intermediate energy (c) Low energy—as in thermal reactors. packing fraction is average mass defect for any particle. The mechanism for heat generation: In the nuclear reactors due to the fission fragments which move at high speed because they take bath in a dense mass of metal.81 Therefore. construction. neutrons and radio-isotopes. mass number (A). 3. 233U etc.0419258 m−A × 10 4 = × 10 4 f= A 4 = 104. Nuclear reactors are of various types depending on their neutron spectrum.50 ENGINEERING CHEMISTRY When protons and neutrons unite a small fraction of mass is converted to nuclear binding energy.4). 3. When mass defect is divided by mass number. heat. In doing so energy is converted to heat.0419258 × 931 = 39. The value of packing fraction is very small. The reactors are differentiated by the following features. a higher value indicates looseness of packing of protons and neutrons in the nucleus and as such lower stability of the atom (Fig.

• Types of Coolants: (b) Water or organic liquids (a) Gaseous (air. heterogeneous. natural uranium. graphite moderated. the nuclear reactors are: (i) Thermal. Heterogeneous. 0. A nuclear reactor is constructed of the following components: 1. research reactor. power breeder reactor. 3. Depending on the above factors. The reactor core consists of an assembly of fuel elements. the fission chain reaction takes place and the energy is liberated in the form of heat. Reactor Core: Reactor cores are generally a right circular cylinder with dia. The cylinder is enclosed in a pressure vessel.5). 3. In the reactor core.28%. coolant and moderator. (b) Heterogeneous–where moderator remains separated from the fuel. Reactor Control rods Steam to turbine Moderator Coolant Water Core Pressure uranium fuel vessel Shielding Fig. air cooled. liquid metal cooled. enriched uranium.714%) (b) Enriched uranium (Higher % of 235U) (c) Uranium 233 (obtained from 232Th) (d) 234Pu (obtained from 238U) • Types of fuel moderator assembly: (a) Homogeneous–in which fuel is dissolved in the moderator.NUCLEAR CHEMISTRY 51 • Types of fuel: (a) Natural uranium (238U = 99. They are usually clad in a thin sheath of Zr or Al stainless steel. 235U = 0. The cylinder with the pressure vessel is considered as reactor core. (ii) Fast. CO2) (c) Liquid metals. controlled rods.5 Nuclear reactor. The fuel elements are either in the form of plates or rods of uranium metals.5 m to 15 m. . For the passage of the coolants. • Purposes: (a) For research (b) For production of 239Pu (c) For power generation. This provides retention of radioactivity and corrosion resistance. enough space is provided between the individual rods (Fig. • Moderators: (a) Heavy water (D2O) (b) Ordinary water (H2O) (c) Graphite (d) Beryllium (e) Beryllium oxide.

• Molten metallic Na or K are excellent coolants. To shut down a reactor the control rods are inserted to a considerable depth so that the chain reaction ceases. The only disadvantage is they are inferior to H2O or liquid metals as coolants. They can act also as the moderator. D2O Liquid metals (Na. Na is highly reactive to O2 and H2 and becomes radioactive by capturing the neutron. They need pressurisation. (ii) necessitating the use of pressure (iii) It is very expensive but its advantage outweighs its high cost. It is used to reflect back some of the leaking neutrons from the reactor core. (ii) they do not become radioactive by neutron capturing. K) Organic liquids (polyphenyles) Gases (CO2) Highlights: • D2O. Water is corrosive at high temperature. Beryllium (Be) can withstand high temperature. Coolants: Function of the coolants is to remove the heat produced in the reactors. . The following are the drawbacks of D2O: (i) Low boiling point. However. The control system also plays an important role to control the chain reaction. 5. H2O are good coolants. so that violent and damaging consequences may be avoided. (iii) To shut down the reactor normally or under emergency condition. Their boiling points are low. The control system works on the simple principle of absorbing excess neutrons generated due to fission with the help of control rods made of either boron strips or cadmium strips.52 ENGINEERING CHEMISTRY 2. Categories H2O. The excellent moderator is D2O because it slows down the neutrons efficiently and it can be used as coolants as well. (ii) To keep power production steady. Reflector: A reflector is usually made of the same material as the moderator (not shown in the figure). Movement of control rods can be made mannual or automatic. being very expensive it is used in special cases. (iii) they are not corrosive and (iv) stable at high temperature. (b) a low cross-section is used for better neutron absorption. Control mechanism: This part is an essential part of the reactor and serves the following purposes: (i) To bring the reactor to its normal operating level. 3. Reactor grade graphite is not good as a moderator but it is cheaper than Be. they do not become radioactive due to neutron capture. Moderator: Function of moderator is to slow down the fast moving fission neutrons. 4. • Use of polyphenyls are advantageous for—(i) they do not require pressurisation. Three rods are sufficient for any amount of excess neutrons. To start up the reactor it is necessary to carefully withdraw the control rods and adjust them. • Air cooling is suitable for low power reactors. The advantage is. So it needs shielding. A moderator should have the following characteristics: (a) low mass number elements to have a high flowing capacity.

(iv) 60Co (γ-radiations) is used in cancer therapy. In the breeder reactor. physics.9. (ii) 59Fe is used to diagnose the blood disorder. it is a thick steel or iron covering. It is used to absorb γ-rays and the neutrons leaking through the inner thermal shield.5 neutrons is used up as follows: (i) 238U captures 0. they can take up CO2 and water. 2. The application of isotopes depends on the fact that the chemical properties of the isotope of a given element are essentially identical.5 neutrons escape out of the reactor. (iii) 131I is used to diagnose malfunctioning of liver. 235U is fissioned by the slow moving neutrons. Uses of Radioisotopes Radioisotopes provide a powerful tool for the solutions of enormous problem in chemistry. coolant absorbs 0. biology and physiology. (a) Thermal Shield: It is kept very close to the reactor core. two shields are used. In this case. The detection of a radioisotope is made on the basis of its radioactivity and a stable isotope by means of a mass spectrometer. At the same time. .NUCLEAR CHEMISTRY 53 6.5 neutrons remain in the reactor and 0. In general type of reactors the conversion factor is 0. that 239Pu 235 U produces 239Pu by capturing those 0. etc.9 neutrons and it is noteworthy to mention is a manmade nuclear fuel. plant absorbs elemental P both from the soil and from the added fertilizer. particularly brain tumours. it was found that O2 came only from water. The radioactivity or mass of an isotope can act as a ‘tag’ or ‘label’ which permits the fate of the element or of a compound containing this element to be traced through a series of chemical and physical changes. Shielding: It is an important consideration for a reactor installation. How much of the P is consumed from the fertilizer by the plant can only be determined by tracer technique. kidney. A few example of the use of radioactive tracers are given below: (a) Photosynthesis in plants: When plants come in contact with sunlight. Breeder Reactor The conversion factor is defined as “The ratio of the number of secondary fuel atoms produced to the number of primary fuel atoms consumed”.9 neutrons (ii) Moderator. (c) Medicine and diagnosis: (i) Radioisotopes are used to locate the presence of tumours. (b) Biological Shield: It is a layer of concrete of few decimeter thick surrounding the thermal shield. O2 is liberated.6 neutrons. which are then converted into sugar and starches. industry. By performing experiments with labelled oxygen in CO2 or H2O. 6CO2* + 10H2O → C6H12O6* + 6H2O* + 6O2 6CO2 + 12H2O* → C6H12O6 + 6H2O + 6O2* (b) Agriculture: During growth. per nuclear fission. Among which one neutron is used to maintain the steady chain reaction. The O2 produced may come from CO2 or H2O molecules or from both. The residual 1. A reactor with the conversion factor above unity is known as breeder reactor. The element which is ‘labelled’ or ‘tagged’ is called a ‘tracer element’. Its purpose is to weaken the γ-rays and neutrons coming out of the reactors so that they cannot do any harm to the persons in immediate vicinity. In high power reactors.

The appearance of radioactivity in engine oil or in lubricants shows that the process of wear and tear of the pistons has started. we can write. A similar relation holds good for U235. we have. still left. U238 = amount of U238 in the rock Pb206 = amount of Pb206 in the rock λ = decay constant t = age of the rock. U238 t = lapse of time (age of rock). . the acyl oxygen cleavage or alkyl oxygen cleavage can be determined as follows: O   CH3¾C¾O—C2H5 + H2O* → CH3— C —OH + C2H5*OH (alkyl oxygen cleavage) O O   CH3¾C¾OC2H5 + H2O* → CH3— C —*OH + C2H5OH (acyl oxygen cleavage) O (f ) Biological research: Isotopic tracers have been widely used in cellular biology. N0 = amount of N = amount of U238 N = N0e–λt in the rock when it was formed. In ester hydrolysis. From the above two equations. (ii)The wear and tear of engines can be determined by making the metal of the piston rings radioactive. so we have U235 = (U235 + Pb207) e − λ ′ t where λ′ = decay constant for U235. (e) Research: Reaction mechanism can be ascertained with radioactive tracer technique. Pb 206 U 238 (e λt − 1) = 235 λ ′ t Pb 207 U (e − 1) The present ratio of U238 to U235 is 139. The disappearance of radioactivity indicates that all the P have been removed. behaviour of cells has been studied with the help of labelled DNA molecules. In mitosis. λ and λ′ can be determined from the half-lives of two isotopes of U. amount of Pb206 present in the mineral = N0 – N So.54 ENGINEERING CHEMISTRY (d) Industry: (i) In steel industry to test whether P is removed completely from cast iron radiophosphorus is used. The radioactive decay equation is. Since all U238 has been decayed to Pb206. U238 = (U238 + Pb206)e–λt where. where. (g) Isotopic dating in Geology: The age of a rock or mineral containing uranium can be determined by its radioactive decay.

U238.303 log a− x t a = amount of U238 originally present in the rock at the time it was formed. the age of a rock can be determined as follows.NUCLEAR CHEMISTRY 55 Hence. a = (a – x) = C 14 C 12 C 14 C 12 2.303 U 238 + Pb 206 log t U 238 where.303 t1/2 Pb 206 log 1 + 238 0. present in the rock at time t is: a = U238 + Pb206 and (a – x) = U238 represent their respective masses. as the plant assimilates CO2 with C14O2 during photosynthesis. JK U238 Since. age of the rock (t) can be calculated. (a – x) = amount of U238 still left after the lapse of time (t).303 Pb 206 log 1 + 238 t U F GH I. values of Pb206 and U238 can be determined experimentally. Alternatively.693 t1/ 2 Thus. provided the ratio Pb206 to Pb207 is determined with the help of a mass spectrometer. by measuring C14 to C12 ratio and t1/2 of C14 (5. λ= a 2. t= Here.303 t1/ 2 a log . JK (h) Radio-carbon dating technique: The age of a piece of wood or animal fossil can be determined by radio-carbon dating technique. the decay constant of is known from the relation λ= 0. λ= 2.693 U F GH I. 0. The radioactive decay follows the first order rate law. After the death of the plant. t= 2.730 yrs) age of the wood (t) can be calculated. U238 λ = decay constant of U238. no more CO2 is assimilated so ratio C14 to C12 in the plant changes. . λ= 2. C14 is formed in the atmosphere as follows : This is present in atmosphere as C14O2 with C12O2. 14 7N + 0n1 (from cosmic rays) → 6C14 + 1H1 In radio-carbon dating ratio C14 to C12 is assumed constant in the plant. Pb206 So. the age of the rock can be calculated.693 a− x ratio in the fresh plant ratio in dead plant.

= 4. Total time = (8378 – 1898) = 6480 yrs. 2.m. .00387 a.D. Mass of one α-particle = 4. when t = Example 3. then the above equation will take the form.8672 × 10 −15 = 1.368 N0 ≈ 0. Example 1.66 × 10–24 g = 6. Sol. Prove that N ≈ 0.37 N0..5 mg. = λ 14. λ N = N0 e − λ.478 × 106 years.718 Highlight: • The radioactive constant (λ) may also be defined as the reciprocal of time during which the number of a radioactive element falls to 37% of its original mass.693 sec. This source is estimated to emit 2300 α-particles/sec. No. We have.8672 × 10–21 g As So Half-life (t1/2) of Pu239 F 1I Mass of radium left = M G J H 2K F 1I = 200 G J H 2K 0 6480 =4 1620 n 4 = 12.646 × 10–24 g Mass of 2300 α-particles = 2300 × 6.37 N0. 1 λ = N0e–1 = N0 e N0 = 0.D.56 ENGINEERING CHEMISTRY So.8672 × 10–15 sec–1. age of the wood (t) can be calculated. by measuring the ratio C14 to C12 in the fresh and dead plants. of half-lives (t1/2) = Example 2. A radioactive source contains one microgram (µg) of Pu239.693 0. Sol. (t1/2 of radium is 1620 years). Assuming that it were to remain undisturbed since 1898 A.u. in all directions. Estimate half-life of Pu239 from this data.867 × 10 −21 / 1 = 14.00387 × 1. = M 1 × 10 −6 0. calculate how much of Madam Curie’s 200 mg of radium would be left in the year 8378 A.464 × 10–24 g = 14. N = N0e–λt 1 . Sol. − dM = λM dt λ= = − d M/ dt − 14.

48 × 105 yrs.88 × 10–14 × 62000 × 365 × 24 × 3600 ∴ or.NUCLEAR CHEMISTRY 57 Example 4. as follows: λt = 8. The half-life period of radium is 1620 years.69 × 105 disintegrations/sec.28 × 10–4 year–1.28 × 10–4 × t × 0.189 M M= M0 1. Now. A radioactive sample initially contains 4. λ = 8.693 = 4. N0 1 = = 100 N 0. and 0. M0 = Initial mass of 92U234 M = Mass at the end of 62. (a) How much of it will remain unchanged after 62.693 × 62000 ×t= = 0.88 × 10–14 × = 7.88 × 10–14 s–1). or. (a) We know. 1.173 t1/2 2. The mass of radium would be left behind at the end of time t = 1 – 0.000 years ? (b) What will be its activity at the end of that time? (t1/2 = 2.189 3. In how many years will one gram of pure element (a) lose one centigram (b) be reduced to one centigram? Sol.01 = 0. e0. Example 5. ∴ (b) Here log10 log10 N = N0e–λt N0 = eλt N N0 = λt × 0..364 × 10 −3 × 6. Sol.4343 N 100 = 4. = t1/2 1620 Let.99 g.0 mg of 92U234.68 years. λ= 0.023 × 10 23 234 (b) Activity of 92U 234 A = λN = 8.693 0.4343 99 t = 23.693 0. or. M = M0e–λt λt = We have.364 mg. time during which one centigram of radium is lost due to disintegration be = t.000 yrs. ∴ Mass of 92U 234 M0 = M .189 = 0.173 M = M0e0.173 left unchanged = is: 4 = 3. (a) Let.48 × 10 5 λt may also be calculated.173 = 1. or.01 . or.

023 × 10 23 214 Highlights: • For one curie. ∴ ∴ Highlights: • A new absolute unit of radioactivity is rutherford (rd).760 years. For 1 rd activity. Example 7. 238 92 U m × 6.023 × 10 23 238 Example 8. the mass of t1/2 = 4.s–1. The unit for measuring radioactivity is curie (Ci).7 × 1010 disintegrations/sec.02 × 10 23 214 dN = 10 6 dis.28 × 10–4t × 0. estimate its age. (t1/2 for U is 4.5.9 × 10–18 × ∴ m = 3. U238 = (U238 + Pb206) e–λt .5 × 109 years) Sol.9 × 10–18 × ∴ m = 80. ENGINEERING CHEMISTRY Example 6. Sol. One rutherford is defined as that quantity of a radioactive substance which gives 106 dis. Assuming that the rock originally contained no lead.7 × 1010 = 4. m × 6.5 × 109 years) is: (λ = 0.02 × 10 23 214 3. The ratio of mass of Pb206 to the mass of U238 in a certain rock specimen is found to be 0.7 × 1010 = 4. m × 6.98. s −1 dt 106 = 4. the mass of is 106 = 4. The number of atoms of RaB contained in mass (m) = Now.31 × 10–4 × m = 3. ∴ ∴ − dN = λN dt m × 6.3 × 10–13 g.58 ∴ ∴ log10 100 = 4. We know that. Calculate the mass for RaB for 1 rd activity.693/4. Sol.4343 t = 10.1 × 10–8 g. 92U 238 • For one rutherford. Calculate the mass of RaB in gram which gives 3.023 × 10 23 238 3.5 × 109 × 365 × 24 × 3600 and m × 6.7 × 1010 dis/s. • Smaller units like millirad (mrd) and microrad (µrd) are also used. One Ci is defined as that quantity of a radioactive material which gives 3.2 × 106 g.31 × 10–4 × m = 8.

Half-life period of C14 is 5760 years.303 × 5577 log 6 0.693 2.5 × 10 9 log 2 = 4.5) e–λt = 1.5 = 2.9 = 0.303 × 5577 × 0.3 g of Pb206.693 .6021 = 11. 0.303 × 5760 × 0.303 t1/2 Pb 206 log 1 + 238 0. The amount of 6C14 isotope in a piece of fresh wood is found to be 1/6th of the total carbon.63 × 109 years.303 t1/2 1 log 0.303 × 5760 1 log 0. 0.3 × 0. ∴ or. Calculate the age of the ore. Sol.3 = 0.303 × 4.1761 t = 0.05 log 1 + = 0.05 206 2.05 238 10.7782 = = 20.525 yrs.693 U F GH 2.693 1/ 4 2.1761 t = 2. Calculate the age of wood.170 yrs. or. (t1/2 = 4.693 0.693 1/ 6 2.5 × 109 years.303 × 4. We have. ∴ ∴ 0. We have.5 × 10 9 0.693 Example 11.693 Example 10.5 × 109 years) Sol.5 λt = 2. 0.05 = FG H I JK IJ K 2. What is the age of the old piece of wood? Sol. Example 9. t= = 2.23 × 0.5 × 10 9 1 = 1+ F GH Pb 206 U 238 I JK e –λt 1 = (1 + 0. A sample of U238 is found to contain 11.303 × log10 1. (t1/2 of C = 5577 yrs).NUCLEAR CHEMISTRY 59 or. t= 11. An old piece of wood in a museum has a disintegration rate which is 25% of the disintegration rate of an equal weight of a new piece of wood.5 e–λt eλt = 1.9 g of U238 and 10.693 4. t= = 2. Mole of U238 = Mole of Pb206 = We have.

u.303 × 6.00387 14.u.m.15 MeV 2He 4 [Q 1 a.00753 Total = 18. so the reaction is endoergic.m.u.60 ENGINEERING CHEMISTRY Example 12. On the other hand. The half-life of Ac222 is 6.693 1/ x 2. Calculate the fraction of the sample of this substance present at the end of 10 hrs.01140 Product particles 17 8O 1 1H Mass (a.00814 Total = 18.) 17. Sol.01140 = 0. t= or or ∴ 10 = 2.948 x≈3 ∴ the fraction of the Sample = 1 . (a) What is Q-value for a nuclear reaction? (b) Calculate the Q-value for the following nuclear reaction: 14 7N + 2 He4 → 8O17 + 1H1. such a reaction is exothermic or exoergic. there is decrease in mass in the reaction. This energy which is generally abbreviated by Q is also known as energy balance of the reaction as per Einstein’s theory or more commonly as Q-value. there is gain of mass in the reaction. 3 Example 13.m.u. and such reaction are called endothermic or endoergic. there is increase in mass and absorption of energy. = 931MeV] + 7N14 = 8O17 + 1H1 + Q ∴ Q-value of the reaction is = – 0. the reaction is = 18. the reaction is accompanied by liberation of energy.303 × 6. (b) Interacting particles 2He 7N 4 Mass (a.01264 14 Increase in mass ∴ Q-value So. If Q-value is positive.4696 2.0045 1. Sol.4696 = 2.00124 a.00124 × 931 MeV = 1.13 hrs.13 log x 0.693 = 0. = – 1.00124 a.303 t1/2 1 log 0.m. if Q-value is negative. = 0.m.693 10 × 0.) 4. .01264 – 18.13 log x = x = Antilog 0.u.15 MeV The Q-value for the reaction is negative. there is absorption of energy. (a) The overall energy liberated or absorbed in a nuclear reaction is called nuclear reaction energy.

= 0. The reaction is 92U235 + 0n1 = 36Kr95 + 57Ba139 + 2 0n1 + Q 235 92 U or Q = (235. 3 Li6 = 6.u. = 0. Show the following reaction is exoergic 3 Li 7 + 1H1 = 2 He4 + 2 He4.3 MeV.m. .00387 4. and the mass of neutron is 1. the reaction is accompanied by liberation of energy (decrease in mass).u. The mass of proton is 1. Calculate the energy released in the following fission reaction: + 0n1 → 36 Kr95 + 57 Ba139 + 2 0n1.01822 1.258 MeV.) 4.216 MeV. Example 16.01702) – (2 × 4. So the reaction is exothermic of exoergic.u.m.00387 a. Here.0086 a. + 1D2 = 2 He4 + 2 He4 + Q where isotopic masses are.353 a.00774 ∴ ∴ 3Li 7 + 1H1 = 2He4 + 2He4 + Q Q = Decrease in mass = (8.m. Calculate the limiting energy per nucleon 20Ca40. = 0. Sol.67 MeV.353 × 931 MeV.02636 Product particles 2He 4 4 2He Sol.02636 – 8.01474 2 He = 4.0086) – 39. Sol. 6 4 = 2. Mass (a.) 7.m.03402 × 931 = 31.954 + 2 × 1.u.0078 + 20 × 1.m.124 + 1.u.m.2151 × 931 MeV = 200.00814 Total = 8. Example 18.00774) = 0. Interacting particles 7 3Li 1 1H Mass (a.975 a.03402 a. Q = (2.m.01702 a. Q value is positive. ∴ Binding energy per nucleon = 40 = 8. Calculate the energy released from the fusion of 3 Li6 and 1D2 by the reaction.u.01862 a. Sol.2151 a.00387 Total = 8.u.975 a.945 + 138.0099) – (94.u.m. (energy released/fission of U 235 MeV = 200 MeV). which has atomic mass of 39.m.u. Calculate (i) the fission rate of U 235 for producing power of 1 watt and (ii) the energy released in the complete fission of 1 kg of U 235.u. 3 Li 2 1D Example 15. = 0.m.01862 × 931 = + 17.01474 + 6. ∴ Energy released Example 17.0099) = 0.0078 a.m.u. Mass defect ∆m for Ca-atom = (20 × 1. 0. From the above equation.NUCLEAR CHEMISTRY 61 Example 14.u.03387) = 0.m.

53 kg. Sol.6 × 10–13 J = 32 × 10–12 J. Energy consumed in the city in a day = 100 × 106 × 24 × 3600 = 864 × 1010 J Since efficiency of the reactor is 20%.023 × 1026 atoms or nuclides. Energy required to be produced in a day 864 × 10 10 = 432 × 10 11 J 0.. A city requires 100 MW of electrical power on an average. disintegration. (Q 1 MeV = 1.2 × 10 −11 (ii) 1 kg atom of U235 = 235 kg = 6. . ∴ No. SHORT QUESTIONS AND ANSWERS Q. What do you mean by nuclear chemistry? Ans. of U235 atoms to be fissioned = = 432 × 10 11 = 13. 3.025 × 10 26 = 530 × 10–3 kg = 0. its stability. Nuclear chemistry is concerned with changes of the nuclei i.6 × 10–13 J = 3.2 × 10–11 J or W. using U 235 as the nuclear fuel. energy released per 1 kg of U235 = 200 × 6.5 × 10 23 kg = 6.62 Sol. calculate the amount of fuel required for one day’s operation.e.5 × 1023 32 × 10 −12 6. If this is to be supplied by a nuclear reactor of efficiency 20%. Given that energy released per fission of U 235 is 200 MeV.6 × 10–13 J) Example 19. Hence.s. So. fission rate for generation of 1 watt 1 = = 3.023 × 10 26 MeV.5 × 1023 atoms of U235 are present in 235 × 13. 1.023 × 1026 atoms of U235 are present in 235 kg ∴ 13.2 Energy released/nuclide = 200 × 1. (i) Energy released per fission of U235 nuclide ENGINEERING CHEMISTRY = 200 MeV = 200 × 1. etc.2 × 1013 J. 235 = 8.1 × 1010 fissions sec–1.

Q. How does a nuclear reaction differ from a chemical reaction? Ans. β-particle is generated in the nucleus as follows: 1 0n → –1e0 + 1H1 So. Q. What is γ-decay? Ans.  Q. (i) The nuclei of radioactive elements are unstable. 7. 3. 5.and β-particles are emitted from the nucleus. Nuclear reaction involves the changes of the nucleus whereas ordinary chemical reaction involves the changes in extranuclear electrons of the atoms. A γ-decay has been depicted in the following figure. What is β-emission? Ans. (iv) γ-rays are the secondary effects of the nuclear disintegration. What is the theory behind radioactivity emission? Ans. (ii) The nuclei of radioactive elements disintegrate forming atoms of new elements called ‘daughter elements’. The emission of an α-particle from a radioactive nucleus is designated as α-emission. 4. γ-rays have been proved to arise from the transition of a nucleon from one energy state to the other. The emission of a β-particle from a radioactive element is known as β-emission. Rutherford and Soddaz postulated that. What is radioactivity? Ans. Q. Thus. A β-particle is a single negatively charged particle and positive nucleus does not contain any electron. What is α-emmision? Ans. The phenomenon of spontaneous emission of radiations from the nuclei of heavy elements is called radioactivity. 6. nuclei of the atoms remain unaffected in a chemical reaction. 2. RaD 210 82Pb E = 65 KeV b-ray 83Bi 210 E = 47 KeV g-ray RaE 210 83Bi E=0 . nucleus gains a proton at the cost of a neutron. Q. the atomic number of the daughter element increases by one unit. (iii) α. on emission of a β-particle. The transformation of UI to UXI by α-emission may be represented as follows: 92UI 238 −α → 2He4 + 90UXI234. So it appears strange.NUCLEAR CHEMISTRY 63 Q.

11. Q. (iii) Radioactive change is always exothermic.64 ENGINEERING CHEMISTRY Q. What do you mean by radioactive decay constant? Ans. 12. (ii) Chemical change is mostly reversible. (ii) Radioactive change is irreversible. etc. Chemical change (i) Chemical change depends upon external conditions like pressure. 9. As for example: 56Ba 92U 235 140 + 36Kr + 38Sr 93 + 3 0n + 2 0n 1 + 0n ¾¾® 1 92U 236 54Xe 55Cs 144 90 1 144 + 37Rb 90 + 2 0n 1 A huge amount of energy is released during nuclear fission according to famous Einstein’s equation E = mc2. Q. temperature. The division of a nucleus into two approximately equal parts is termed ‘nuclear fission’. − or dN = λN dt λ= − d N/ dt N So. This chain of successive disintegrations is termed ‘radioactive series’. What do you mean by radioactive series? Ans. Compare radioactive change and chemical change. the daughter element is also radioactive then it decays further and the process continues till a stable isotope is reached. The radioactive decay equation is. during radioactive disintegration. which disintegrates in a unit time to the amount of the substance present. 10. it may be defined as the rate of disintegration when the number of radioactive nucleus present is one. (iii) Chemical change may be exothermic or endothermic. Whereas modern techniques of artificial transmutation of elements have made it possible to produce radioactivity in many other lighter elements. Such type of radioactivity is known as “artificial or induced radioactivity”. Radioactive change (i) Radioactive change does not depend upon external conditions like temperature. Q. etc. 8. If. the radioactive decay constant (λ) may be defined as the ratio of the amount of the substance. Q. (iv) Radioactive change is a nuclear phenomenon. . Natural radioactivity is exhibited by heavier elements found in nature. pressure. Ans. (iv) Chemical change involves only outermost electrons of the atoms. What do you mean by natural radioactivity and artificial radioactivity? Ans. What do you mean by nuclear fission? Ans. Alternatively. No change takes place of the nucleus of the atom. and this reaction is the principle for atom bomb.

3. + 0n1 → 92U239 β → 93Np239 β → 94Pu239   Nuclear reactions are used to give birth to radioactive isotopes to be used as tracers. 2He 4 + 1H3 → 2He4 + energy. Ans. combining of two lighter nuclei into a heavy nucleus with release of large amount of energy.NUCLEAR CHEMISTRY 65 Q. Ans. What is radioactivity? Give an account of the discovery of radioactivity? How will you show that radioactivity is nothing but a nuclear property? If you are given a piece of mineral. Q. they fuse to produce elements with even proton numbers. (ii) Fission takes place at ordinary temperature. 15. Compare fission and fusion reactions. nuclear reactions can be used to make elements that do not occur in nature. 16. Si. (iv) Fission gives rise to chain reaction. Q. with higher proton numbers than uranium. (v) Fusion does not give rise to chain reaction. What do you mean by nuclear fusion? Ans. Nuclear reactions are the changes affecting the nuclei of atoms. Nuclear reactions are brought about by bombarding nuclei with high energy particles in particle accelerators or with beams of neutrons from nuclear reactors. Fission (i) Fission involves breaking up of a heavy nucleus into lighter ones with release of large amount of energy. How are nuclear reactions carried out? Mention the uses of nuclear reactions. In the sun. EXERCISES 1. 14. 238 92 U Q. since 2He4 has even number of nucleons. The pressure and temperature at the centre of very large stars is high enough for nuclei to fuse to form heavier elements such as C. the phenomenon is known as ‘nuclear fusion’. 2. (iii) During fusion. It is also the process that accounts for the origin of all the elements. positrons are emitted. Apart from atom bombs and alternative energy sources. When two light nuclei combine with release of a huge amount of energy.13. at a temperature of ten million degrees. how can you determine by simple experiments if the mineral is radioactive? . (ii) Fusion takes place at very high temperature (106 K). Fusion (i) Fusion involves. Fe. 4 1H1 → 2He4 + 2 positrons + 109 kJ. Why the elements with even proton numbers are more abundant than other elements? Ans. neutrons are emitted. 2 1H 1 1H + 1H2 → 2He4 + energy Nuclear fusion is the source of energy of the sun and the other stars. (iii) During fission. the following fusion takes place.

[Ans. 1 4 7 3 Li 26.. Give a relation between half-life and the decay constant of a radioactive substance. Give a brief account of the nuclear reactors.76 MeV] 28. + 7 Be. What are the units of radioactivity? 7. 92 0 24. + 1H 2 1 + 1H → ..] .1 g? [Ans. 9. What informations are available from these curves? 18.. The half-life of radium is 1590 years.m. [Ans. + . Mass of neutron = 1. 5. What are radio-isotopes? How are they prepared? Mention their uses.66 4. What are the causes of nuclear instability? Explain with suitable examples.u. Write notes on: (i) Radioactive equilibrium (ii) Atomic weight of lead in radioactive minerals (iii) Tracer technique..4 × 1010 yrs. Calculate the binding energy in MeV per nucleon of 12 . State and explain the law of radioactive disintegration. What is radioactive displacement law? 12. 22.. 17. What is nuclear fission? Show how nuclear fission is a chain reaction. 10. 21. Derive a relation between mass defect and nuclear binding energy. 13. Write a short note on nuclear fusion. Explain the terms: (i) Disintegration constant (ii) Half-life period 6.93 × 10–5 yrs.m.. 8. Calculate the time required for 10% disintegration of a sample of thorium.. Why is natural radioactivity mostly limited among heavier elements? 14..u. 2385 yrs. → → 24 12 Mg 239 90Th 10 5B + 4 He → .4 MeV.00866 a. range and velocity. Where is the radioactive displacement law invalid? 23.04 1 amu = 931. 6. What is a nuclear reaction? Discuss some uses of nuclear reactions. Calculate the amount of energy released during the bombardment of 1 n on 235 U .and γ-rays? Compare their ionising power.] 27. Complete the following nuclear reactions: 9 4 Be + 4 He → 2 24 11 Na 238 92 U 12 6C + . 25. Explain artificial radioactivity with suitable examples. + . β. ENGINEERING CHEMISTRY What are α-. 11. Give a comparative account of the nuclear binding energy curve and packing fraction curve. 15. What do you mean by the half-life period of a radioactive element? Show that the half-life is independent of the amount of the substance. Actual mass of C-atom = 12. What is nuclear binding energy? 16.. 19. 20.. 54. Write a short note on radio-carbon dating. Write a short note on nuclear transmutation. 6C Given: Mass of H-atom = 1. Given the t1/2 of thorium = 1. How long will it take for 1 g of the element to lose 0.00782 a.

u.01605 a.003 a.m. 0 min–1 g–1.u. .m. 2 Mass of 1 n = 1.01286 a. A neutron breaks into a proton and an electron. 16.0 counts min–1 g–1.m. Given t1/2 = 5760 years. Given the t1/2 of cobalt = 5. [Ans. Calculate the decay constant of 60Co. Mass of 2H = 2.73 MeV] 35.016 a.5 × 109 yrs.m. Calculate the age of the wooden article. 1 a.5 × 10–6] 32.00812 a. of 206Pb.u.13 yr–1] 36.u. 2970 years] 30.009 a.m. [Ans. [Ans. [Ans.7 times that in a living plant. Calculate the weight of 1 curie of 222Rn. Distinguish between nuclear fuel and a chemical fuel. 16. [Ans. Given: t1/2 for 14 6C = 5. Write short note on components of a nuclear power reactor and their functions. Calculate the approximate life period when the plant died.33. Calculate the energy released in the nuclear fusion reaction: 2 1H 1 + 3 H → 4 He + 0 n 1 2 Given: Mass of 2 H = 2.76 MeV] A fresh sample of wood shows 15.u.6747 × 10–24 g.5 × 109 years] 31. [Ans.82 days.862 years] 38.m. Calculate the energy released in MeV from the reaction: 10 5B + 2 H → 1 11 5B + 1H 1 Given: Mass of 10B = 10. A radioactive element disintegrates to 1/16th of its original mass in 160 days.NUCLEAR CHEMISTRY 67 29. [Ans. 0.760 yrs. 40 days] 33.u. Calculate the age of the rock.u.m. 0. Mass of electron = 9 × 10–28 g. [Ans. A sample of uranium ore is found to contain 11. Mass of 1H = 1.6725 × 10–24 g.u.114 MeV] 34. 1 Mass of 3 H = 3. Given: Mass of neutron = 1.m. What is its halflife period? [Ans.9 g of 238U and 10. 39. A piece of wood was found to have 14C/12C ratio 0.2 counts 37. 1 Mass of 4 He = 4. Calculate the energy produced in MeV.3 years.01472 a. 9. 4. = 931 MeV.u.m. 6. Mass of proton = 1. Given t1/2 of uranium = 4. Half life of 222Rn in 3. Mass of 11B = 11. An old wooden article shows 2.014 a.

A system is defined as any matter or its part. 2. etc. are dependent upon the mass of the system and are called extensive property. Thus. composition. Intensive property. Properties of a system. surface tension.. Extensive property.. Einstein comments: “It (thermodynamics) is the only physical theory of universal content concerning which I am convinced that. • Before beginning with the laws of thermodynamics following terms are needed to be defined. viscosity. Composition. chosen for study and separated from the rest of the universe by a real or imaginary boundary. the system is said to have undergone a change of state. are independent of the mass of the system and are called intensive properties. example is a sealed flask containing matter in a closed system. A system is said to be an isolated system when it is capable of exchanging either energy or matter with the rest of the universe. etc. Properties like volume. the energy and matter remain constant for the system.. temperature. The rest of the universe is called the surroundings. volume. refractive index. 3. energy. An open system is a system. Properties like temperature. volume. it will never be overthrown”. example is a plant or any living being. pressure and temperature are the fundamentally important properties. within the framework of applicability of its basic concepts. 68 4 . which can exchange both mass and energy across the boundary. The set of thermodynamic variables such as pressure. There is no such perfectly isolated system other than our universe itself. When one or more of these variables undergo change. which is capable of exchanging only energy with the surroundings but no mass transfer across the boundary is permitted. which describe a system is called the “state of the system”. Refractive index. 1.Thermodynamics Thermodynamics is concerned with the flow of heat and therefore deals with the quantitative relationship between heat and work. The physical characteristics which are experimentally measurable and which enable us to define a system are called thermodynamic parameters or properties of the system. Hence. State of a system. Thermodynamic deductions are not made on the basis of any hypothesis about the molecular structure of matter but the three simple laws of thermodynamics are based on human experience and these relations were tested experimentally for centuries starting from heat engines to cellular enzymatic processes and are considered inviolable. The science of thermodynamics actually covers a much wider field covering energy-changes in all physical and chemical processes as well as mutual transformations of all the different forms of energy. Thermodynamic systems. A closed system is one. pressure. etc. dielectric constant are also other properties. surface area. viscosity. density. specific heat.

pressure and composition. rotational. expansion of gases from high pressure to low pressure. internal energy is found to return to its original value. Equilibrium state. If a change takes place in which the volume of the system remains constant the process is called an isochoric process. a system in equilibrium state has definite temperature. Internal energy.. its thermodynamic parameters also return to their original values. vibrational movements of the molecules of the system. the change in the internal energy ∆E = E2 – E1 is independent of the path of transformation but depends on the initial and final conditions of the system. (cyclic integration of E is 0). z dE = 0 . example. net change in internal energy is zero i. free energy change (∆G) and entropy change (∆S) are such functions. Internal energy change (∆E). which is accompanied by volume changes. All the natural processes are irreversible. the system returns to its initial state. which depends only on the state of the system but not on the paths followed for the change. the process is called an adiabatic process and the temperature of the system may increase or decrease. chemical composition. 4. A process can be made reversible by performing the change very slowly with no friction and no finite temperature differences. temperature is uniform and also same with the surroundings and there is no unbalanced force the system and also between the system and the surroundings. The magnitude of internal energy of a system is determined by the kinetic. A system is said to be in equilibrium when its composition is fixed. If a change takes place at a constant temperature maintained throughout. enthalpy change (∆H). it is called an isothermal process. The absolute value of the internal energy of a system cannot be ascertained. This energy is a function of the temperature.e. it can be stated that when a system changes from initial state (1) to a final state (2) and comes back to (1) (Fig. State function is a thermodynamic property.1). if a cyclic process is completed. An irreversible process is such that the system and the surrounding after undergoing changes cannot get back to their initial state and tend to proceed to a definite direction but cannot proceed to the reverse direction. etc. It is an extensive property.. Every system within itself has a quantity of energy which is called the internal or intrinsic energy. Otherwise.e.e. Hence.THERMODYNAMICS 69 If. as a result of a series of changes. If a process is carried out at constant pressure. ∑∆E = 0. such a process is called a cyclic process. heat flowing from a hotter to a colder body. so dE is path independent and E is a state function. If a change takes place in a thermally insulated system which does not permit heat exchange with the surrounding. A process is said to be reversible if the energy change in each step of the process can be reversed in direction by an infinitesimal change in any of the variables acting on the system. pressure and volume of the system. the process is called an isobaric process. Irreversible processes are all spontaneous processes. If a system undergoes a series of changes and returns to its initial state i. When a system changes from a thermodynamic state 1 to a thermodynamic state 2.. Five moles of a substance in a specified state has five times the internal energy possessed by a single molecule in a similar state. hence the sum of the changes of internal energy for a cyclic process i. So internal energy (E) is a state function.

When the volume (V) is constant. heat supplied to a system is q. according to the first law Heat absorbed = Increase of internal energy + Work done by the system i. ∴ W = – ∆E. If the system is under a pressure P and volume increases by dV. dq and dw represent small quantities of heat absorbed and external work done by the system.e. and it may be stated as “the energy of an isolated system remains constant and whenever a quantity of some form of energy disappears. Hence. is of pressure × volume type. the work done becomes P dV and hence the mathematical expression of first law becomes. hence dE = dq – P × 0 [Q dv = 0] ∴ dE = dq or ∆E = qV Cyclic process: We have already found that if a system undergoes change through path (1) and returns to its original state via path (2). it completes a cyclic path and the overall change of energy (E) i. q = 0. an exactly equivalent quantity of some other form of energy must make its appearance”. Thus. The law was first stated by Mayer in 1842 and Fouli’s classical research on equivalence between heat and work established the fact in 1845 and finally generalised by Helmholtz in 1847. work done by the system = decrease in internal energy of the system. Hence.. we arrive at a very important relation that for a cyclic process.e.70 ENGINEERING CHEMISTRY Cyclic process Fig. Since heat energy cannot be lost. from first law. So in an adiabatic process. dE = dq – P. Here the work. . respectively. exclusively. Joule-Thomson effect Joule-Thomson effect states: “When a gas under high pressure is permitted to expand into a region of low pressure. it suffers a fall in temperature”. Mathematical formulation of the first law Let us suppose. ∆E = q – W = 0 ∴ q = W.1 THE FIRST LAW OF THERMODYNAMICS The first law of thermodynamics is simply the law of conservation of energy. q = ∆E + W or ∆E = q – W If the above change is infinitesimally small. For an adiabatic change. dV for very very small changes. 4. we can write dE = dq – dw where dE is the increase in internal energy. it may be used up by the system as partly increasing the internal energy of the system and partly in doing mechanical work. the algebraic sum of all the heat terms is equal to the algebraic sum of all the work terms.. dV = 0. ∆E = 0.

q = 0. Heat content or Enthalpy of a system The pressure (P) and volume (V) of a system are thermodynamic variables and their product PV is expressed as energy. For an ideal gas.e. when heat does not flow out of the system nor does it come into system from the surrounding. So. 4. ∆E = –ve. a system at constant pressure is undergoing a change from states 1 to 2. Thus. Since E is a characteristic of the system (state function).2 Joule-Thomson expansion. P2V2 – P1V1 = W. Constancy of Enthalpy (isoenthalpic) in Joule-Thomson expansion Joule-Thomson experiment is carried out adiabatically. from first law of thermodynamics.. for an ideal gas.2) and the work done is P2V2 – P1V1. Hence.e. Change in enthalpy = change in internal energy. from the first law of thermodynamics q = (E2 – E1) + W = (E2 – E1) + (P2V2 – P1V1) = (E2 + P2V2) – (E1 + P1V1) = H2 – H1 = ∆H. ∆H = (E2 + P2V2) – (E1 + P1V1) = (E2 – E1) + (P2V2 – P1V1) ∴ At constant pressure. The volume increase is from V1 to V2. 4. work done by the gas is. Heat absorbed by the system is q. according to the first law. ∆V = 0. there should be no change in temperature. thus the gas while expanding does some work and hence the temperature falls. i. But Joule-Thomson observed that most gases cooled down by such a pressure drop.THERMODYNAMICS 71 Joule and Thomson performed an experiment where a gas was allowed to expand adiabatically through a porous plug against a constant pressure.e.e. the energy of the gas falls i. The gas expands is passing through porous plug (Fig. Suppose. Porous plug V1 P1 P2 V2 Fig. Hence.. Hence. ∆E = q – W = q – 0 = q. Since the expansion is carried out adiabatically i. The work done is at the expense of the kinetic energy of the molecule while they are separated from each other. ∴ ∆H = ∆E + 0 = ∆E. The quantity (E + PV) is universally represented as H and called the heat content or enthalpy of a system. not on the path followed during the change. . if the process is carried out at constant volume change in enthalpy and change in internal energy are equal. Suppose V1 volume of gas at pressure P1 is forced through the porous plug and expands to a volume V2 at a lower pressure P2. Hence. H is a similar state function. P1V1 = P2V2 ∴ W = 0. i. Hence. when q = 0.. the gas was allowed to do no work and there was no interchange of heat with the surroundings. ∆H = ∆E + PV = ∆E + W = q (heat absorbed) and at constant volume.. ∆H will depend only on the initial and final states of the system.

we can define Joule-Thomson coefficient (µ) by the relation.e.e. The gas is to be expanded from volume V1 to volume V2. if the temperature is high.. Inversion temperature If the gas in above expansion suffers a fall in temperature by dT. P1 V1 .e. from first law. thermostat at T K. a × ∆l is the volume swept by the piston. 4. The gas has a volume V1 and the piston is at point A. H2 warms up on expansion.. The work of expansion (W) will be given by the product of opposing force and the displacement. This temperature is called the “inversion temperature. E2 – E1 = – P2V2 + P1V1 ∴ E2 + P2V2 = E1 + P1V1 or H2 = H1.. then instead of cooling the gases are heated.. For gases having positive µ value cools on expansion but for H2 gas µ is negative i. W= FG δT IJ H δP K H V2 W = nRT ln V 1 z V2 V1 PdV = z V2 V1 nRT dV V [Q PV = nRT] P V2 = 2 in an isothermal expansion of a perfect gas. For every gas there is a temperature where µ = 0. W = force × displacement = force × area × distance A = P × a × l.3).3 Then.72 Hence. 2a µ= –b RT The significance of µ is fall in temperature in degrees by a gas in free expansion for a pressure drop of 1 atm. Ti” of the gas. The cylinder is kept in a constant temperature bath i.. W = P × a × ∆l. i.e.. change in enthalpy is equal to heat absorbed at constant pressure. it is dV Fig. 4. µ= µ is zero for an ideal gas (PV = nRT). ∆H = ∆E + P∆V = ∆E + P(V2 – V1) = ∆E + w = qP (heat absorbed at constant pressure) i. under adiabatic conditions. i. µ becomes negative. when neither heating nor cooling of the gases occurs on expansion after pasing through orifices. for a lowering of pressure dP.e.e. The cooling effect is seen when the temperature is low. ENGINEERING CHEMISTRY ∆E = q – W = 0 – (P2V2 – P1V1) i. But. At every step a minute distance (∆l) of the piston may be T V1 made so that work done (W) is. Work done in a reversible isothermal expansion: Suppose n moles of a gas is enclosed in a cylinder by a frictionless piston (Fig. For van der Waals gas. isothermal condition is maintained. ∴ Since.

PV = nRT. which is molar heat capacity measured at constant volume condition. Cv = ∴ ∆H > ∆E. thereby volume changes from V1 to V2 at constant temperature T and pressure P. ∆n is negative Heat capacity Heat capacity (C) of a substance is the amount of heat needed to raise the temperature of 1 gm of the substance by 1°C. ∆H = ∆E + ∆n. dq dT FG ∂E IJ H ∂T K V . P(V2 – V1) = (n2 – n1) RT. Similarly. ∴ or ∴ ∆n is positive. When the reaction involves gaseous contraction. Molar heat capacity at constant volume is Cv. molar heat capacity of the substance is the amount of heat required to raise the temperature of 1 mole of the substance by 1°C. ∴ ∆H < ∆E. ∆H = ∆E. for 1 mole of an ideal gas. We know. For n moles of an ideal gas.THERMODYNAMICS 73 W = nRT ln Then. or or Relation between Cp and Cv: ∆H = ∆E + ∆(PV) ∆H ∆E ∆ (PV) = + ∆T ∆T ∆T Cp = Cv + ∆ (PV) ∆T . Molar heat capacity at constant pressure is measured by keeping the pressure constant ∴ Cp = ∂H dq = ∂T dT FG IJ H K P . When there is no volume change. When the reaction involves gaseous expansion. From first law of thermodynamics. C= At constant volume condition. RT. W = RT ln V2 . V1 Enthalpy of a gaseous reaction n1 moles of reactant gases react to produce n2 moles of gaseous products. P∆V = ∆n . V2 P1 = nRT ln V1 P2 So.RT. ∆H = ∆E + P∆V. If dq heat is required for dT increase in temperature then for 1 mole of substance. work done (W) during reversible isothermal expansion is.

.

• It is convenient to calculate total entropy change in two parts. the entropy of the system decreases. Thus. For example. k = Boltzmann constant. • From experience we can say. V. the entropy of the universe is ever increasing. ∆Stotal = ∆Ssystem + ∆Ssurroundings. The energy unavailable as work is proportional to the increase of entropy. the odour of the gas spreads all over the room randomly and equilibrium is reached when the entropy also becomes maximum. entropy signifies unavailable form of energy of the system during transformation of heat into work. w = thermodynamic probability.e. T and path independent.3. • Gases generally have higher entropies than liquids. Dividing both the sides of the equation (III) by T. So. Hence. w increases when S increases. Thus. when an order to a system is brought. the container is fitted with a frictionless movable piston at constant pressure P. entropy increases and vice-versa.THERMODYNAMICS 75 the disorder and irreversibility and when equilibrium is reached. . Conversely. disordered form is more probable than ordered form. • Any irreversible process is accompanied by increase in entropy. it has the maximum disorder. Boltzmann expressed this idea by the relation. only a part of the total energy is made available for useful work. • If system absorbs heat. The volume of the gas changes from V1 to V2. For example. where S = entropy. the pressure on the gas is approximately equal to the external pressure P. The higher the entropy. Since the process is reversible. As w is always greater than one. 4.e. • Entropy is a state function dependent on P. As all spontaneous processes are irreversible. T V . from 1st law of thermodynamics. the entropy of the system goes on increasing and reaches a maximum value at equilibrium. dq = dE + dW = dE + P dV. the less the availability of work. dT dV +R . Entropy of an ideal gas In the case of a reversible expansion of an ideal gas in a container as in Fig. • Entropy is a measurement of randomness of a system... solidification of a liquid brings about orderly state and thereby entropy decreases.(III) dq dE PdV = + T T T ∴ dS = Cv . wasted. Highlights: • Prediction of direction of changes is possible with a thermodynamical quantity known as entropy (S). • A spontaneous change occurs in the direction leading to a total increase of entropy. some energy is always dissipated i. (i) the entropy change of the system and the entropy change of the surroundings i. increase of randomness enhances thermodynamic probability.. if a gas with strong odour is let loose at the corner of a room. S = k ln w. In any system..

T1 V1 P V2 = 1 P2 V1 z V2 V1 dV V Since. let a heat reservoir at T1 (state 1) is brought in contact with a second reservoir at T2 (state 2) where T1 > T2. ∴ ∆S = Cv ln P1 T2 + R ln . for a change from states 1 to 2 we have. At constant volume V. ∆S = S2 – S1 = z 2 1 q T1 q The decrease in entropy of state 2 = T2 T − T2 q q − = q. the change of entropy (∆S) is given by: dqr . which is evacuated (Fig. The vessel is connected to a vessel of volume V2 by a tube containing stop cock. hence. P2 T1 At constant temperature i. P2 V1 At constant pressure P. and small quantity of heat q flows from T1 to T2. P1 V ∆ST = R ln 2 = R ln . for an ideal gas at constant temperature. From the first law of thermodynamics.e. for isothermal expansion. The decrease in entropy of state 1 = Irreversible isothermal expansion of an ideal gas Let n moles of an ideal gas is enclosed in a vessel of volume V1.4).76 Thus. The change of entropy of a given system from state 1 to state 2 is always the same and is path independent if the path is reversible. T2 ∆Sp = Cp ln T 1 ∆Sv = Cv ln T2 . we have.. T When the flow of heat is irreversible. the irreversible heat flow leads to increase in entropy. 4. 1 ∴ Net change of entropy = T2 T1 T1T2 The difference is a positive quantity. ENGINEERING CHEMISTRY z S2 S1 dS = Cv z T2 T1 dT +R T or. So. q = ∆E + W . T1 Entropy change in irreversible process Entropy is a state function. The vessels are kept in a thermostat of the temperature T. ∆S = Cv ln T2 V + R ln 2 .

But the changes in entropy can be determined. Thus. we have. ∆Sirr. if this expansion is carried out irreversibly at T K from volume V1 to a volume (V1 + V2) after opening the stop cock (Fig. (system) would be same. 4. ds is a perfect differential. ∆Suniverse = ∆Ssystem + ∆Ssurrounding = R ln = R ln V1 + V2 +0 V1 V1 + V2 A positive quantity. dq = dE + PdV Dividing both the sides of the above equation by T. dq dE PdV dT dV = + +R = Cv (for 1 mol of gas) T T T T V dS = Cvd (ln T) + Rd (ln V) S = Cv ln T + R ln V + S0 We know. Cp – Cv = R for an ideal gas. So we have. As there is no thermal change. 4. ∆Ssurrounding = 0 Hence. Fig. of the gas. or. S1 = Cv ln T1 + R ln V1 + S0 S2 = Cv ln T2+ R ln V2 + S0 ∴ ∆S = S2 – S1 = Cv ln V2 T2 + R ln V1 T1 For an isothermal change. S = (Cp – R) ln T + R ln RT + S0 P or. V1 P2 . where S0 is a constant. S = Cp ln T – R ln P + S0′ We cannot determine the absolute value of the entropy of an ideal gas. for the irreversible expansion of gas.THERMODYNAMICS 77 Now. qrev = ∆E + RT ln = 0 + RT ln V1 + V2 V1 V1 V2 T V1 + V2 V1 . V1 Entropy change of a mixture of gases From first law of themodynamics. we have.4 Since S is a state function. if the temperature of an ideal gas changes from T1 to T2 and the volume from V1 to V2 for 1 mol.4). or. So. we have ∆S = R ln V2 P1 = R ln .

Work function (A) Let us define. fraction of gas i. ∆Smix = (S A mix + S Bmix ) – (SA + SB) = S A mix + S Bmix – SA – SB or. . change of entropy due to mixing. for mixing any number of gases. The entropies of the two gases in the mixture are SA(mix) = nA[C PA ln T − R ln pA + S A 0 ] SB(mix) = nB[C PB ln T − R ln pB + S B 0 ] So. ∆Smix = – n R where xi = mol. Such a spontaneous irreversible process leads to an entropy increase. ∆Smix = – n R ∑xi ln xi = – n R[xA ln xA + xB ln xB] LM n Nn A ln xA + nB ln xB n OP Q A = E – TS ∆AT = ∆E – T∆S = ∆E – q = – Wmax (Q ∆T = 0) For an isothermal process. In general. or.78 ENGINEERING CHEMISTRY When two gases come in contact. Let. hence. they diffuse and mix-up irreversibly. xB = n n The total moles of mixture = n = nA + nB mol. work function is such a thermodynamic property of the system that decreases in work function A i. Moles of gas A is nA Moles of gas B is nB Temperature is T Pressure is P Then. pA pB = xA and = xB (As mol. fraction = pressure fraction) P P ∆S = – nA R ln xA – nB R ln xB. SA = nA [C PA ln T − R ln P + S A 0 ] SB = nB [C P ln T − R ln P + S B 0 ] B After mixing. So.e. (– ∆A) gives the maximum amount of work available during isothermal process. fraction of A. maximum work is involved.. the total pressure (P) P = pA + pB. – ∆AT = Wmax where Wmax is reversible. ∆S = – nA R ln pA p – nB R ln B P P nA nB . ∴ or. xA = Now.

G = H – TS. ∴ Free energy and useful work Suppose a reversible change takes place at constant temperature T and at constant pressure P.. So. This relation correlates free energy change to cell potential) (ii) ∆G = ∆H – T∆S (at constant T) ∆G° = ∑G°(products) – ∑G°(reactants) ∆G = ∆H – T∆S. Gibb’s free energy is related to enthalpy and entropy as. T. T∆S = ∆H + Wuseful ∆H – T∆S = – Wuseful = (∆G)P. – (∆G)P. Standard free energy change G is a state function. (at constant temperature). Therefore. The standard state is defined at constant pressure of 1 atmosphere and constant temperature i. = – nFE (n = number of electrons. and for an isothermal process FG δA IJ H δV K T = – P. for isochoric process Free energy (G) F δA I G δT J H K v = – S. q = ∆E + P∆V + Wuseful = ∆H + Wuseful Now. which are very useful for physicochemical studies are: • Gibb’s free energy (G) and • Helmholtz free energy or work function (A). Hence.e. . we have. from the first law of thermodynamics. standard free energy change (∆G°) is defined as the free energy change for a process taking place at standard state for the reactants and the products obtained are also in their standard states. Two thermodynamic functions. it is necessary to assign a standard value for the free energy of a system at a specified state. decrease in Gibb’s free energy is a measure of the ‘useful work’ obtainable from the process. Therefore. T = Wuseful. The work of expansion of volume is expressed by P∆V and suppose the system does an additional amount of work which is denoted by useful work. 25°C or 298 K. since ∴ or. F = Faraday and E = emf of a cell. ∴ Relations of ∆G (i) ∆G = Wuseful (at constant T and P). To assign numerical values to free energy change of a system.THERMODYNAMICS 79 A = E – TS or dA = dE – TdS – SdT = dE – dq – SdT = – PdV – SdT. q = T∆S.

the net heat-content change or energy content THERMOCHEMISTRY . where R = gas constant. • Mathematical expression of first law: dE = dq – dW • Kirchoff’s equation: ∆H 2 − ∆H 1 (T2 − T1 ) = ∆Cp. entropy change and temperature by Gibb’s-Helmholtz equation as ∆G = ∆H – T∆S. the initial and the final states would be at equilibrium with each other and finally if ∆G is positive. heat content (H) or energy content (E) of the initial reactants again returns to the same magnitude. K is the equilibrium constant of a reaction. (iv) ∆G = 0 (at equilibrium. but the sum total of energy of the universe remains constant. This law states that the heat change accompanying a chemical process in one direction is equal in magnitude but opposite in sign to that accompanying the same process taking place in the opposite direction. If ∆G is negative. The energy from chemical reactions comes from the breaking or formation of bonds. A. The thermal changes in chemical processes are governed by two general principles. ∆S. • Entropy is a measure of randomness or disorder of a system. Highlights: • First law of thermodynamics states—the energy may change from one form to another. At constant temperature and pressure always system tends to attain a position of minimum free energy which is the position of equilibrium. the process will not take place spontaneously. ∆G must be negative. for a spontaneous process. If ∆G is zero. both of which are corollaries of the first law. etc. As such. at constant T and P). ∆S = All types of chemical reactions are accompanied by heat changes. “unavailable energy”. The reactions in which heat is evolved are termed exothermic and in which heat is absorbed are endothermic.303 RT log K. It is also defined as qrev . Thus. Entropy change. 1 1 H (g) + Cl2(g) → HCl(g) ∆H = – 92 kJ 2 2 2 1 1 HCl(g) → H2(g) + Cl2 (g) ∆H = + 92 kJ 2 2 According to the first law. any change shall spontaneously occur. ∆G..80 ENGINEERING CHEMISTRY (iii) ∆G° = – RT ln K = – 2. T • State function is one which depends only on the initial and final states of the system but independent of the path followed e.g. T = temperature in kelvin. Law of Lavoisier and Laplace. but it may reverse. • Free energy change is a state function and is related to enthalpy change.

This law states that for a chemical process the amount of heat evolved or absorbed is the same whether the process takes place in one or several steps. In the case of organic compounds. 4. Hess’s Law of Constant Heat Summation.THERMODYNAMICS 81 change is zero i.. 2 2 Summing up we get. Example: (a) H2 + Cl2 = 2 HCl +43.e. • Enthalpy changes of reaction from enthalpy changes of formation. when molar quantities react and indicated by a balanced equation. B..600 cal which is exothermic whereas for the formation of 2 moles of HI. Let us take the example of formation of CO2 in one step and two steps (a) and (b): C + O2 = CO2 ∆H = – 94. etc. (i) Heat of reaction. complete combustion means when these compounds are converted finally to CO2 and H2O.05 Kcal 1 (a) C + O2 = CO ∆H1 = – 26. multiplication of the quantities i..42 – 69. so heat of combustion is always negative. From first law we find that ∆HP and ∆EV will be independent of the path. ∆H terms algebraically.42 Kcal 2 1 (b) CO + O = CO2 ∆H2 = – 67. which are difficult Highlights: Hess’s law is used to calculate: • Enthalpy changes (∆H) of formation from enthalpy changes of combustion.5 Bomb calorimeter.05 Kcal.680 cals (endothermic) Thus. • Lattice energies is the Born-Haber cycle.5). The principal advantage of this law is that thermochemical equations can be treated as simple algebraic equations and the heat of formation. heat of transition. Heat of reaction (∆H) is the difference between the heat contents of the products and the reactants. Example: C2H5OH + 3O2 = 2CO2 + 3H2O ∆H = – 325 Kcal . to measure experimentally can be easily found out by addition. 12. subtraction. “bomb calorimeter” which is a pressure vessel internally enamelled with platinum (Fig. 4.63) Kcal which illustrates the law = – 94.63 Kcal.e. ∆H1 + ∆H2 = (– 26. heat changes in the two directions must be equal in magnitude but opposite in sign. Heat change for the complete combustion of a gm-mole of the substance at a given temperature under normal pressure is called its heat of combustion. (ii) Heat of combustion. The experimentally determined values of heat of combustion are useful.680 cal of heat is absorbed and the reaction is endothermic. The heat of combustion is experimentally determined in a Fig.608 cals (exothermic) (b) H2 + I2 = 2 HI –12. Combustion reactions are always exothermic. the heat of reaction for the formation of 2 moles of HCl is 43.

. when the enthalpy of formation of a compound is negative. the heat change becomes constant. it is needed to assume some arbitrary value for substances at a given state. Thus. (v) Heat of solution and heat of dilution. i. The value of heat of solution obtained graphically by extrapolating ∆H to infinite dilution is the integral heat of solution at infinite dilution. At high dilution. the enthalpy of any element at 1 atm and 298 K is assumed to be ‘zero’. Example: ∆Hf of HI is + 26. the stability of a compound is inversely proportional to the enthalpy of formation of a compound. The heat of solution changes with concentration.9 kJ and ∆Hf of HF is – 161.8 kJ. (iv) Heat of formation. The standard enthalpy of formation (∆Hfo) is just the negative of the heat of formation. Example: KCl(s) + 50 H2O = KCl (50 H2O) – 4276 Cal.82 ENGINEERING CHEMISTRY (iii) Heat of neutralisation of an acid or a base is defined as the amount of heat liberated (exothermic) when 1 gm equivalent of an acid is neutralized by one gm equivalent of base in large excess of water. (vi) Heat of fusion. The enthalpy of formation is related to the stability of compound. Example: HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O ∆H = – 13. The heat change taking place when 1 gm mole of the solute is completely dissolved in a solvent is called the heat of solution. the energy content of the corresponding compound is lower than its constituent elements and hence the compound is stable. they can be assumed to be completely dissociated. . In order to measure the change in enthalpy.e.7 Kcal HCl(aq) + KOH(aq) → KCl(aq) + H2O ∆H = – 13.e.7 kJ indicates the HF is much more stable than HI. Therefore. Whereas. all in their respective standard states and at a reference temperature. It is the amount of heat liberated or absorbed when one mole of the compound is formed from its constituent elements. If the acid and base are both strong. Conventionally. the heat of neutralisation is really the heat of formation of 1 gm mole of water from 1 gm ion of hydrogen and hydroxyl ion. the more stable is the compound. KCl(s) + 100 H2O = KCl (100 H2O) – 4391 Cal. The lower the enthalpy of formation of a compound.7 Kcal. Heat of fusion is always positive. the heat of neutralisation deviates considerably from 13. it means the energy content of the compound is greater than the energy content of its constituent elements and hence the compound is unstable.. and this is always the equivalent of 13.e. But when a weak acid or a weak base is neutralized.7 Kcal of heat. If the enthalpy of formation of a compound is positive. one gm mole of KCl dissolved in 50 moles of water and in 200 moles of water will cause different heat changes.. Example: H2O(s) → H2O(l) ∆H = 6 kJ. i.7 Kcal. H+ + A– + B+ + OH– = B+ + A– + H2O i. H+ + OH– = H2O. C(graphite) + 2 H2 (g) → CH4(g) ∆Hf = – 74. Heat change taking place when 1 mole of a substance changes from solid to its liquid phase at its melting point is known as the heat of fusion of the substance.

for CH4 (methane) molecule. we can find the bond energy for C—H bonds by taking in average one-fourth of the total heat of formation of methane. Example: H2O(l) → H2O(g) ∆H = 42 kJ.p. Highlights: • Enthalpy change is the exchange of energy between a reaction mixture (system) and its surroundings when the reaction takes place at constant pressure. • It is impossible to measure ∆H°298 directly. the reaction is exothermic i.4 kJ. This difference in bond energy is related to the more reactive nature of OH radicals than oxygen.THERMODYNAMICS 83 (vii) Heat of vaporization. 396 = 99 Kcal/mol. or b. For water the energy of separating a H-atom is 118 Kcal.e. Example: I2(s) → I2(g) ∆H = 62. This energy is dependent on the nature of the atoms present as well as the environment.p. i. the system gains energy from its surroundings. • Values measured under nonstandard conditions are corrected to give the value under standard conditions. the system loses energy to surroundings. It is also positive. • Enthalpy change for melting. towards H atoms to form stable molecules. the reaction is endothermic i. It is the heat change involved in converting 1 mole of substance from liquid to the gaseous state at its boiling point. whereas this energy of separating the second H-atom from the residual OH group is 102 Kcal. we can also take the average of the four different dissociation energies of C—H bond of methane.e. the standard enthalpy change is represented by ∆H°298. Taking average of the two bond energies we have 118 + 102 = 110 Kcal for O—H bonds.. • If ∆H is negative. It is the heat change involved in converting 1 mole of solid directly to its vapour at a temperature below the melting point of the substance. 4 Alternatively.. • The standard conditions for change of enthalpy (∆H) are 298 K and 1 bar (100 kPa). Bond Energy Bond energy is defined as the average energy required to break the bonds present in a molecule of gaseous compound. to atoms or radicals in gaseous form. • The present unit of ∆H is kJ mol–1. Example.. Many values are determined indirectly using Hess’s law. . • If ∆H is positive.e. vaporisation are measured at m. (viii) Heat of sublimation. 2 Similarly. sublimation. • The enthalpy change (∆H) is calculated when starting temperature of the reactants and final temperature of the products are the same. Bond energy is also called the heat of formation of the bond.

The engine must take up heat at higher temperature. Application of bond energies (i) The heat of reaction can be calculated from the bond energies since in a reaction certain bonds are formed and certain bonds are broken. Second law of thermodynamics guides the conditions under which heat and work are interconvertible. = 670.5) Kcal. Example: Heat of formation of ethane is. From the above experience.5 and 43. (b) It is impossible for a self-acting machine unaided by any external agency. (iii) Bond energy varies with the total environment of the molecule. Bond energy decreases as H—F > H—H > C—C > N—N > F—F. but the entropy approaches a maximum. Without the help of a “thermodynamic engine” the conversion of heat into work is impossible and the engine must work in a reversible cyclic process. convert a portion of it into work and give up the rest of heat to a body at lower temperature. For the conversion of heat into work two conditions must be fulfilled. i. second law of thermodynamics can be stated in some different important forms. 2C(g) + 6H(g) → H H   H— C — C —H(g)   H H ∆Hf for ethane is = 1 × (bond energy for C—C) + 6 × (bond energy for C—H) = (1 × 79. SECOND LAW OF THERMODYNAMICS Heat is readily available and man is interested to convert this heat energy to useful work.3 + 6 × 98. Effect of temperature on free energy-(Gibbs-Helmholtz equation) We know. (ii) Bond energy varies with the difference between the electronegativity of the two atoms. Example: bond energy for H—F and H—Cl are 56. (d) The energy of the universe is constant. H = E + PV and G = H – TS = E + PV – TS . without producing some other effects in the system. 1. the total enthalpy change involved in these bond breaking and making gives the heat of reaction. to convey heat from a body at a low to one at a high temperature.1 kJ/mol. 2.84 Variation of bond energy ENGINEERING CHEMISTRY (i) Bond energy varies with the size of the atoms. So.e. (c) All spontaneous processes tend to equilibrium.3 Kcal mol–1. (a) It is impossible to convert heat completely into an equivalent amount of work.. ∆H reaction = Σ ∆H (bonds broken) + Σ ∆H (bonds formed) = Σ Bond energy (reactants) – Σ Bond energy (products) (ii) Heat of formation can also be calculated from the average bond energy summation. respectively.

Application of thermodynamics to phase transition i. ∆G has negative value and the reaction becomes spontaneous. (c) If both ∆H and ∆S are positive and T∆S > ∆H.. the process will be spontaneous only when ∆H is greater than T∆S.e. (b) In endothermic process. the criteria for spontaneous processes are: (a) If ∆H is negative and ∆S is positive – ∆G becomes negative. (ClapeyronClausius equation) Change of phase taking place during freezing. etc. can be studied thermodynamically. vaporization. Imagine a very small change of a small amount of liquid vaporizing at . the reaction occurs if T∆S is positive and greater than ∆H. (a) When a reaction is exothermic i.THERMODYNAMICS 85 dG = dE + PdV + VdP – TdS – SdT dq = dE + PdV dG = dq + VdP – TdS – SdT Differentiating. ∆H is positive.. which relates free energy and ethalpy changes at constant pressure. Hence. when the free energy of the reactants and the products are equal. Let G1 and G2 be the free energies of a liquid and its vapour. change of phase. (b) If both ∆H and ∆S are negative and ∆H > T∆S. which are in equilibrium at a temperature T.e. ∴ Again for reversible mechanical process dS = ∴ ∴ ∴ For an isobaric process ∴ We know ∴ ∴ dq = TdS dq T dG = VdP – SdT dG = – SdT = – ∆S. ∆H is neagtive.. We know that if ∆G is negative the reaction takes place spontaneously and when ∆G = 0 i. we get We know. (c) When ∆H is negative and ∆S is also negative. and ∆S is positive.e. Significance of Gibbs-Helmholtz equation Gibbs-Helmholtz equation is a very useful equation in thermodynamics as it encompasses both the essence of first and second laws of thermodynamics and almost any relation of thermodynamics can be deduced from this equation. p ∴ F ∂∆G IJ G ∂T K H FG ∂G IJ H ∂T K P =–S G = H – TS ∆G = ∆H – T∆S ∆G = ∆H – T FG ∂∆G IJ H ∂T K p This is Gibbs-Helmholtz equation. the reaction attains equilibrium.

RT 2 P Assuming.303R T1 T2 LM N OP Q . as net or. 2.. With the help of the integrated Clapeyron-Clausius equation we can determine the boiling point of a liquid at a different pressure when the boiling point of it is known at one pressure along with the latent heat of vaporization. log OP Q P2 L 1 1 = − P1 2.303R T1T2 1 Thus. P2 T2 − T1 L log P = . the volume V1 of the liquid can be neglected as it is very small compared to the volume of vapor V2. The drop in free energy of the liquid is –∆G1 and corresponding gain in free energy of the vapour is +∆G2. T(V2 − V1 ) dT where q is molar heat of transition from one phase to another. S − S1 ∆S ∆P = 2 = V2 − V1 V2 − V1 ∆T ∆S = q T ∆S q dP = = T(V2 − V1 ) V2 − V1 dT q dP = . from the vapour pressures P1 and P2 at different temperatures T1 and T2 we can determine the molar heat of vaporization with the integrated Clapeyron-Clausius equation. Determination of latent heat. 2. Application of Clapeyron-Clausius equation 1. This equation is the famous Clapeyron-Clausius equation. for ideal gas ∴ or. P2 L 1 1 ln P = R T − T 1 1 2 LM N or. latent heat is constant and on integrating. or. L q dP = = T V2 T V2 dT (q = L = latent heat of vaporization) PV = RT. i.86 ENGINEERING CHEMISTRY equilibrium. T(V2 − V1 ) dT When two phases of liquid (Vol. ∴ Now. V1) and vapor (Vol. V = LP dP = RT 2 dT RT P dT dP =L. LM N OP Q or. Thus. Effect of pressure on boiling point. Since the system is in equilibrium. Since. V2) are in equilibrium. ∴ ∆G = 0 ∴ ∆G1 = ∆G2 V1∆P – S1∆T = V2∆P – S2∆T. We know q dP = .e.

So. ∴ (I) z T Cp T 0 dT S0 = 0.303 C p d log T (II) Cp Cp T 1 log T 2 O 10 T 20 30 Fig. Example. Hence. THIRD LAW OF THERMODYNAMICS In 1912. we have ST – S0 = From 3rd law. Many reactions occur in nature which have ∆G = positive only when they are coupled with another reaction whose ∆G is much larger negative. • Entropy and the third law—Third law can be used to determine the entropy of a substance. Absolute value of entropy can be measured by determining the heat capacities (Cp) of a substance at different temperature. These Cp values are plotted against T and can be extrapolated to T = 0. The area of the curve between T = 0 and the required temperature gives the value of absolute entropy of the substance at the required temperature. Mathematically. At absolute zero temperature. Coupling of non-spontaneous reactions Those chemical/biological reactions only take place spontaneously for which ∆G = negative. there is no disorder and hence the entropy of all pure substances at absolute zero is zero. kinetic energy of a substance is zero and it is present in a perfectly arranged crystalline state. Effect of temperature on vapour pressure of a liquid: Again from the similar expression we can calculate the vapour pressure of a liquid at a different temperature if the vapour of it is known at a particular temperature alongwith its latent heat.6 Graphical determination of entropy.THERMODYNAMICS 87 3. 4. Biochemical reaction in our body like oxidation of glucose releases large amount of energy and a part of this energy is utilised by our system to convert ADP (Adenosine diphosphates) to ATP (Adenosine triphosphate). ATP is a high energy molecule. Planck enunciated the third law of thermodynamics as “the entropy of a solid or a liquid is zero at the absolute zero of temperature”. ∴ ST = ST = z T z T Cp 1 0 dT = z T 0 C p d ln T 0 2. so when in the . the energy required for the first reaction to occur is supplied by the second reaction which is coupled to it.

• Second law of thermodynamic states: It is impossible to convert heat completely into work. the changes in entropy of both the system and the surrounding are to be considered when a system is in equilibrium. Highlights: • Intensive property is independent of the amount of substance present in the system e. • ∆G is negative for a spontaneous reaction. Thus. dS + dS′ = 0 For a spontaneous process. if ∆G is positive the process is non-spontaneous. • Clapeyron-Clausius equation is: q dP = . • ∆G is positive for non-spontaneous reaction. temperature. • For a spontaneous process at a definite T and P. • ∆S for a spontaneous process is ∆S > 0. the amount of heat evolved or absorbed is the same whether the process takes place in one step or in several steps. refractive index. free energy is released which can again be coupled to another biochemical reaction of our system that is non-spontaneous or requires energy. dS + dS′ > 0 where dS and dS′ are the changes of entropy of the system and the surroundings respectively. pressure. viscosity. . if the ∆G is negative the change is spontaneous. surface tension. dStotal > 0 When a reversible process is at equilibrium. • Third law of thermodynamics states: The entropy of a solid or a liquid is zero at the absolute zero of temperature. • ∆G is zero for reaction at equilibrium. • A spontaneous process always has a net increase in entropy for the computation of the change of entropy. the energy of glucose oxidation can be utilised to carry out other non-spontaneous reaction via ATP. density. dStotal = 0 For any spontaneous irreversible process. reactions with increasing enthalpy may also occur spontaneously. etc.g.. specific heat. T(V2 − V1 ) dT Spontaneity of changes of a system • Many of the spontaneous processes are accompanied with a decrease in enthalpy but this statement is not always true. • The entropy of the universe is increasing.88 ENGINEERING CHEMISTRY cyclic process ATP is hydrolysed to ADP. • Hess’s law states: For a chemical process. if ∆G is zero the initial and final states of the system will be at equilibrium. we can calculate ∆G of the system.

Just like temperature.THERMODYNAMICS 89 Chemical Potential (µ) Free energy per mole at a given temperature T and pressure (P) is called the chemical potential µ or G . dH = TdS + VdP 3. T) ∴ ∆G = G2 – G1 = z 2 1 Vd P . It can be proved easily. µ = µi = FG ∂G IJ H ∂n K T. G ∂V J G ∂S J H K H K F ∂P I F ∂S I . Maxwell’s Relations 1. dG = µ(II) dn – µ(I) dn dG = 0. n For a species i which is component of a mixture we can express its chemical potential µi as follows. pressure or electric potential it tends to equalise within all parts of a system. chemical potential of water in ice must be same in both the phases. We have. chemical potential. Chemical potential of an ideal gas at temperature. dG = – Sdt + VdP = O + VdP (at constant. dE = TdS – PdV 2. which have extensive applications in both physical and chemical phenomena. These four derivatives are very well known relations. Therefore. Chemical potential also has such a tendency. T. that is why the study of chemical potential has become important. n j where nj represents the constant composition of a mixture. H ∂P K H ∂S K F ∂V IJ = – FG ∂S IJ (iv) G H ∂T K H ∂P K S P P T . ∴ µ(I) = µ(II) F ∂T I = – F ∂P I . P . Thus. But for equilibrium. dG = VdP – SdT. we have (ii) FG ∂T IJ = FG ∂V IJ . G (for a pure substance). It is to be noted that free energy is an extensive property but chemical potential is an intensive property. Ice (I) Water (II) If dn moles are transferred from phase I to phase II. (iii) G J = G H ∂T K H ∂V J K (i) S V V T Applying the cross-derivative rule. For the equilibrium. dA = – PdV – SdT 4.

n1 . ni∆x. n1. we have. if we express partial molal free energies in terms of µ. T.. dn2 + . n1 . T and all other moles are constant except n2. . n3 dn2 . T and V.. ni T. T . n 2 3 dn1 + F ∂G I GH dn JK 2 The term F ∂G I G dn J H K 2 P. µ2 – µ1 = RT ln P2 P1 P2 . 1 P. We get. T .. G2 – G1 = RT ln or. Gibbs-Duhem Relations The free energy G of a system is a state function.. n3 . T .. Let us have a system containing n1 moles of A1. the free energy then will depend upon the quantities of the components. the changed amounts of A1 are n1∆ x.. n2 .. T) if we take an open system in which the quantities of the components may vary.. G = f (P.(a) Now at constant temperature and pressure. G depends upon P. ni P. it is a function of T.. that is. etc.. ni 1 P. F ∂G I GH dn JK i P. dGP. T. then the free energy (G) of the system is given by. n1 .. G ∂P J H K H ∂T K F ∂G IJ dG = VdP – SdT + G H dn K dP + P. T. µ = µφ0 + RT ln P or. P1 ENGINEERING CHEMISTRY Since G2 and G1 are molar free energies µ2 and µ1 respectively. F ∂G IJ dT + FG ∂G IJ G ∂T K H H ∂n K F ∂G I = V FG ∂G IJ = – S. under this convention the chemical potential µi for the ith component of the mixture is given by.. of A2.. we increase the constituents by the same proportions ∆x.e. n 2 3 dn1 + FG ∂G IJ H ∂n K 2 P. As they are interrelated we can write for a fixed composition of a system. n3 . we get. pressure 1 atmosphere. T. ni We know. n2 moles of A2.. G = G0 + RT ln P where µ0 is the standard chemical potential but not a constant. µ1 becomes µφ0 if we apply the standard conditions i. this term is called the partial molal free energy of the component A2. n . n2∆ x and Ai.) If all the variables vary. n . means that P.90 Applying this to one mole of an ideal gas (PV = RT). n3 . G = f (P.T = µ1 dn1 + µ2 dn2 + µ3 dn3 + . P.. = ∑µi dni . dG = F ∂G I G ∂P J H K T. the complete differential will be given by. n j At constant temperature and pressure..

Free energy change for one mole of any gas at a constant temperature is given by: dG = V. G is an extensive property. dG = G∆x dG = µ1n1∆x + µ2n2∆x + . Deduction of Van’t Hoff’s reaction isotherm (Application of thermodynamics to homogeneous equilibrium or thermodynamics of chemical equilibrium): Let us consider a general reaction We. So. GB. free energy change for the reaction (i) is given by ∆G = Gproducts – Greactants = (cGC + dGD) – (aGA + bGB) .) . = ∑µn (ii) dG = µ1dn1 + µ2dn2 + µ3dn3 + .dT At constant temperature.... (i) G = µ1n1 + µ2n2 + µ3n3 + . = 0 We have thus three useful relations for chemical potentials with the composition of the system. where G G0 = G when P = 1 atm. ∫ dG = RT dP P LMQ N PV = RT or V = RT P O P Q dP P So. or.... we have... respectively... G = µ1n1 + µ2n2 + ..dP – S.. + µini + .. = ∑µdn (iii) 0 = n1dµ1 + n2dµ2 + n3dµ3 + . = ∑ndµ These relations are commonly known as Gibbs-Duhem relations.dP.. (dG)T = V. + µini∆x + . dG = (µ1dn1 + µ2dn2 + µ3dn3 + ... So. PC and PD are GA. dn1 = n1 ∆x. Again. therefore it will increase by the amount G∆x hence. GC and GD... aA + bB → cC + dD G = H – TS = E + PV – TS dG = dE + PdV + VdP – TdS – S dT.. dq = dE + PdV and dS = dq/T .. C and D at their respective pressures PA. Let the energy/mole of A.(i) [Q H = E + PV] ∴ dG = V. dn2 = n2 ∆x...(ii) 0 = integration constant known as standard free energy i...T Integrating both sides. + µini∆x + ..e.. G∆x = µ1n1∆x + µ2n2∆x + .(b) Subtracting equation (a) from (b) n1dµ1 + n2dµ2 + n3dµ3 + .. = ∑µini Now..dP = R.. complete differentiation of this equation gives us. dni = ni ∆x Since. Then.. G = G0 + RT ln P . Hence. B. know.) + (n1dµ1 + n2dµ2 + n3dµ3 + .(iii) z ...THERMODYNAMICS 91 Therefore. PB.

(iv) Now. = – RT ln Keq ∴ ∆G0 = – RT ln Keq (PC ) c (PD ) d LM (P ) (P ) OP NM (P ) (P ) QP C A c a D d B b eq ∆G° is a constant as G is a state function LMwhere K MN eq = (PC ) c (PD ) d (PA ) (PB ) a b O P P Q . • The above relation shows that equilibrium constant (Keq) can be calculated from a table of standard free energy values. ∆G = 0 So. • The above expression gives free energy change for a reaction.. ∆G = + RT ln (PA ) a (PB ) b (PC ) c (PD ) d . at equilibrium. GB.. It is of great importance as it gives a quantitative relation for free energy change accompanying a chemical reaction.e. – ∆G is called the Affinity of the reaction. P = 1). According to first law of thermodynamics q = ∆E – w Here or. Calculate the increase in internal energy per mol of water assuming water vapour to behave as an ideal gas. One gm of water requires 536 calories of heat for conversion to steam at 100°C.(vi) This expression (vi) is called Van’t Hoff reaction isotherm.. q = 536 × 18 cal mol–1 ∆E = q – w = 9648 – 746 = 8902 cal mol–1 = 8. w = PV = RT = 2 × 373 cals = 746 cals. Highlights: • ∆G° = – RT ln Keq when pressures of reactants and products are one (i. Example 1. we have ∆G = – RT ln Keq + RT ln or.(v) Combining (iv) and (v)..92 ENGINEERING CHEMISTRY Substituting the values of GA. Sol. ... – ∆G = RT ln Keq – RT ln (PA ) a (PB ) b (PA ) a (PB ) b (PC ) c (PD ) d . GC and GD from (ii) and (iii).902 Kcal mol–1. ∆G0 = – RT ln ∆G° is the difference in free energy between the products and the reactants. we have ∆G = (cGC0 + cRT ln PC + dGD0 + dRT ln PD) – (aGA0 + aRT ln PA + bGB0 + bRT ln PB) = (cGC0 ∆G0 + dGD – 0 aGA0 – bGB0) + RT ln (PA ) a (PB ) b (PC ) c (PD ) d So.

Sol. after absorbing 990 cals.4942 kJ. Calculate the heat of reaction of C2H4(g) + H2(g) → C2H4(g) at that temperature. qp = qv (As n2 = n1) Example 5. mols of gaseous reactant. Calculate the value of ∆E for the reaction at 500 K.13 w = 8. Here ∆E = q – w q = 990 cals = 990 × 4. and ethane are 337. Zn + H2SO4 → ZnSO4 + H2↑ w = P(V2 – V1) = PV2 = nRT = RT = 8. ∴ ∆H = ∆E + ∆nRT. Calculate the heat of combustion at constant pressure of carbon.314 × 300 kJ. T = 500 K R = 2 cal deg–1 mol–1 = 2 × 10–3 Kcal deg–1 mol–1 ∆E = ∆H – ∆nRT = – 109 – (– 1) × 2 × 10–3 × 500 = – 108 Kcal.836 kJ 10 7 × 10 3 ∆E = 4. Sol. .2 10 3 kJ = 4. Here. [Q V1 = 0] [Q n = 1] Example 3. Heats of combustion of ethylene. 1000 Example 4.158 – 0.836 = 3.36 × 10 9 kJ = 0. Calculate the internal energy change of the system. 1 mol.332 kJ. 8. 68. We have. qp = qv + ∆nRT. The amount of work of a system is 8. 372. n2 = 1 ∴ We have. (Given qv at 200°C is 97000 cals). = – 97000 + 0 × RT = – 97000 cals. n1 = 1 mols of gaseous product. ∆n = n2 – n1 = 0. We know. hydrogen.3.2.36 × 109 ergs. Mg(s) + 2HCl(g) → MgCl2(s) + H2 (g) (Given ∆H = – 109 Kcal). of heat.8 Kcal mol–1 at a definite temperature.314 × (273 + 27) = = 2. Here C(s) + O2(g) = CO2(g) qv = – 97000 cal. So. ∆n = 1 – 2 = – 1.THERMODYNAMICS 93 Example 2. Example 6.36 × 109 ergs = ∴ 8. Sol. Here. Calculate the work done by the following reaction at 27°C. Sol.

8 Kcal. (ii) H2 + ∆H = – 337. O2(g) → 2O(g). 2 2 Sol.8 Kcal ∆H = + 372.7 Kcal. Example 8. H2O(g) → H2(g) + (i) + (ii) – (iii) gives = H2(g) + i.. From equation (ii) H2(g) + 1 O (g) → O(g).. (iv) 2CO2 + 3H2O → C2H6 + Adding the equations (i). 2 2 7 O.3 Kcal. ∆H = 68.(ii) . ENGINEERING CHEMISTRY 1 O → H2O. ∆H = 60 Kcal. ∆H = – 372. C . 1 O (g) → H2O(g).(i) . for dissociation of one O—H bond energy requirement is 222 ÷ 2 = 111 Kcal. 1 1 O2(g) + H2O(g) → 2H(g) + O(g) + H2(g) + O2(g) 2 2 ∆H = 222 Kcal. 2 2 (iii) C2H6 + or. H2O(g) → 2H(g) + O(g)... C2H4 + 3O2 + H2 + ∴ 1 7 O + 2CO2 + 3H2O → 2CO2 + 2H2O + H2O + C2H6 + O2 2 2 2 (∆H = – 32. 2 2 From equation (iii). (ii) and (iv) we have. Calculate O—H bond energy from the following heats of reactions.94 Sol.. We know that. H2(g) → 2H(g).(iii) C2H4 + H2 → C2H6. and for breaking of these two bonds energy requirement is 222 Kcal.7 Kcal) ∆H = – 32.. So. 2 2 7 O → 2CO2 + 3H2O.. there are two O—H bonds in a molecule of water.2 Kcal.e. ∴ O—H bond energy is 111 Kcal. ∆H = 104 Kcal ∆H = 120 Kcal ∆H = – 58 Kcal . Given the standard enthalpies of combustion: ∆H° (C3H8) = – 2220 kJ mol–1 C ∆H ° (C) = – 393 kJ mol–1 C ∆H° (H2) = – 286 kJ mol–1. Calculate the enthalpy of formation of propane (C3H8 ) at 298 K. (i) C2H4 + 3O2 → 2CO2 + 2H2O. 1 O (g) 2 2 ∆H = 58 Kcal. Given. Example 7.

Sol. 18 13 DH 86 ca ls . ∆H150° – ∆H100° = – 0. Thermochemical cycle: Yellow P 23 DH 2 DHT (DH1) 3 Red P ca ls H3PO4 According to Hess’s law – ∆HT = ∆H2 – ∆H3 = 2386 – 2113 cals = 273 cals. Calculate the enthalpy change of transition from yellow P to Red P from the given thermochemical cycle. calculate the latent heat of water at 150°C.THERMODYNAMICS 95 Sol.45 – 1 = – 0. respectively for the interval. Example 10. Cp for steam = T2 – T1 = 423 – 373 = 50 K. The latent heat of evaporation of water at 100°C at constant pressure is 538 cal g–1. Basis = 1 g. ∆H ° (C3H8) = (– 2323) – (– 2220) kJ mol–1 f = – 103 kJ mol–1. Sol. ∆H2 – ∆H1 = ∆Cp(T2 – T1) ∆Cp = 0.55(50) 21 8. C C = 3 × (– 393) + 4 × (– 286) kJ mol–1 = – 2323 kJ mol–1 ∆H3 = ∆H ° = – 2220 kJ mol–1 C Hence. Example 9.1 . If average Cp for water and steam are 1 cal g–1 and 8. A thermodynamic cycle is drawn: 3C(s) + 4H2(g) + 5O2(g) 2 DH DH1 C3H8(g) + 5O2(g) DH 3 3CO2(g) + 4H2O(l ) According to Hess’s law – ∆H1 = ∆H2 – ∆H3 ∆H1 = ∆H °f (C3H8) ∆H2 = 3 ∆H ° (C) + 4 × ∆H ° (H2). We have.1 cal mol–1.55. ∆H150° =?. ∆H100° = 538 Cp for water = 1.

∆E = 0 q = W = RT ln dS = V2 V1 [Positive quantity] V2 qrev = R ln V1 T Example 15. Sol. Hv = 545. R = 1. Sol. We know that Therefore.303 RT ln P 2 = 2. Here.5 × 18 cal mol–1 = 9819 cal mol–1.96 ∆H150° = ∆H100° – 0.55 × 50 = 510.987 cal K–1 mol–1. 2 1 Example 12.19 × 32 = = 4.31 × 298 log = 1.1 Example 14.33 J mol–1. Given latent heat – 19. At what temperature will water boil when the atmospheric pressure is 528 mm Hg? Given latent heat of vapourisation of water is 545.19 × 32 12.5 cal g –1.5 cal g–1 = 545. P2 = 1 atm = 760 mm of Hg. Calculate the change of molar entropy during melting of ice. dS = = qrev T 12. dS = = qrev T 19.66 kJ.303R T1 T2 1 LM N OP Q . Calculate change of entropy in isothermal reversible expansion of one mole of an ideal gas. 273 Example 13.9°C). Calculate the maximum work done for the isothermal reversible expansion of one mole of an ideal gas at 25°C from 2 atm to 1 atm. P1 = 528 mm of Hg.14 × 18 = 1. Given L = 12. Calculate the change of molar entropy during the conversion of liquid oxygen to oxygen gas at its b. Sol. we have P2 ∆H v 1 1 − log P = 2. (– 182.26 J mol–1. Sol. T2 = 100°C = 373 K. (273 − 182. Maximum work P1 = 2.14 J g–1.5 cal g–1. Example 11. Sol. From the integrated form of Clausius-Clapeyron equation.9) 90. T1 = ?.p.303 × 8.19 J g–1.66 × 103 J = 1.55 × 50 ENGINEERING CHEMISTRY = 538 – 0.

The value of Kp (equilibrium constant) of the reaction regarding ammonia synthesis at 27°C is 3. 1 3 N (g) + H2(g) NH3(g) + 11. From the 1st law of thermodynamics.987 528 T1 = 363 K. heat energy. (i) Since operation is isothermal and the gas is ideal so. Calculate the entropy change for the process.2 Kcal. So. For one mole of an ideal gas the entropy change in a reversible process is ∆S = Cp ln T2 P + R ln 1 T1 P2 Here.7 J = 1012. Sol. 300 7 Example 19. Example 18.25) cal [Q 1 lit. log 9819 760 = 0. Cp = Cv + R = (5 + 2) cal = 7 cal. 2 2 2 Consider the reaction to be independent of heat and temperature.49 × 10–2 atm–1. P1 = 1 atm. (ii) Now. 363 1 + 2 × ln = – 2.303 × 1. H 0. ∆H = ∆E + P∆V = 0 + 1012. Sol.314 J IJ = 1012. But. The initial temperature and pressure for one mole of an ideal gas is (Cv = 5 cal) 27°C and 1 atm. ∆E = 0.25 cal] = 485 cal. from 1st law. Example 17. W = P(V2 – V1) = 1 atm (20 – 10) dm3 = 10 atm dm3 = 10 atm L = 10 L atm × (iii) (iv) FG 8. Find the change in internal energy. Pressure is increased reversibly upto 7 atm and temperature is incremented to 90°C. work done by system. ∆E = 0 or q = W. internal energy will decrease by an amount of 185 cal. = (20 × 24. T2 = 90°C = 363 K.1582 = 2. ∆E and ∆H for isothermal reversible expansion of an ideal gas at 27°C from a volume of 10 dm3 to 20 dm3 against a constant external pressure of one atmosphere? Sol.7 J. q = ∆E + W or. T1 = 27°C = 300 K.THERMODYNAMICS 97 ∴ or. for a reversible process.7 J.5577 cal deg–1. atm = 24. A gas during expansion from 10 litre to 20 litre under 2 atmospheric pressure absorbs 300 cal. Thus find the value of Kp for the following reaction at 37°C. ∆E = q – W = (300 – 485) cal = – 185 cal. W.7 J. ∴ ∆S = 7 ln .atm. Work done in an irreversible process is given by W = P(V2 – V1) = 2(20 – 10) = 20 lit. P2 = 7 atm. LM 1 − 1 OP N T 373 Q 1 Example 16.0821 L atm K q = W = 1012. Calculate q.

See text page 85. State First law with mathematical expressions. Q. State intensive property of a system.987 cal deg–1 mol–1.. they occur at atmospheric pressure. R = 1. Derive Clapeyron-Clausius equation and mention its applications. What is enthalpy? Ans. The molar heat of sublimation of a solid is always greater than the molar heat of vaporization of the corresponding liquid.987 300 × 310 LM N OP Q OP Q K P2 = 1. 3. See text page 68. Why? Ans. Q.49 × 10–2 atm–1. From Van’t Hoff equation. Ans. 2. Alternatively. so enthalpy is more useful than internal energy. The entropy of a substance becomes zero when the substance is perfectly crystalline i. Ans. T1 = 27°C = 300 K. ∴ K P2 T2 − T1 ∆H log K = 2. K P2 = ? ∆H = – 11. ordered state and at the temperature of 0 K.303 × 1.9038 × 10–2 atm–1. Internal energy and ethalpy of a system are measured by keeping the volume and the pressure constant. See text page 84. When does the entropy of a substance become zero? Ans. 3.2 Kcal = – 11200 cal. 6. T2 = 37°C = 310 K. See text page 71. Since the molar heat of sublimation is the summation of heat of melting and heat of vaporization so it is always greater than the heat of vaporization of the corresponding liquid. Q. . 8. in most of the reactions.98 Sol. Ans. Ans. Why is enthalpy more useful than internal energy? Ans. Q. we have K P2 ∆H T2 − T1 ln K = R T1T2 P1 ENGINEERING CHEMISTRY LM N OP Q Here. Since.49 × 10 −2 K P2 = 310 − 300 − 11200 2. 5. K P1 = 3.e. Q. SHORT QUESTIONS AND ANSWERS Q. See text page 66.303R T1T2 P1 LM N log or. 4. Q. Derive Gibbs-Helmholtz equation and mention its significance. 1. it can be stated as the net energy of the universe remains constant. respectively. 7. Q.

So.e. (b) Internal energy of the system changes.THERMODYNAMICS 99 Q. Define reversible and irreversible processes. See page 69.. Entropy is the measurement of randomness i.e. Ans. ∆E = q – W or 0=q–W [Q ∆E = 0] or W = q. Ans. 15. 9. 11. What do you mean by entropy? Ans. W = – ∆E So. i. Apply the first law of thermodynamics for the following cases (a) adiabatic change. 1 2 Q.e.. Write the expression for work obtained in an isothermal irreversible reversible process. Isothermal change (a) Temperature of the system remains constant. (b) Change in internal energy does not take place. Write down the expression for maximum work done in an isothermal reversible process. Wirr = P2(V2 – V1). disorder of the system. dS is defined as dS = reversible . Q. 14. Distinguish between adiabatic and isothermal changes. 13. then to what extent or in which direction would the transformation take place. (a) For adiabatic change So. (c) PV = Constant for such process. Adiabatic change (a) Heat exchange between the system and the surrounding does not occur. (b) cyclic process. (ii) If it so occurs. V2 P1 Ans. the work done by the system is equal to the decrease in internal energy. The first law does not indicate: (i) Whether the transformation of intrinsic energy of a substance would occur at all. Q. 12. (c) PVγ = constant for such process. W = nRT ln V = nRT ln P . Q. Its change q i. from first law. 10. Ans. q=0 ∆E = q – W or ∆E = 0 – W [Q q = 0] So. in cyclic process the work done by the system is equal to the amount of heat absorbed by the system. T Q. For cyclic process the internal energy does not change at all. in adiabatic process. So. . from first law. What are the limitations of first law of thermodynamics? Ans. ∆E = 0. Ans. Q..

Q. Ans. See page 72. 17. Ans. See page 70. 24. 21. Q. Q. Define work function and free energy. Short Questions: (i) Derive an expression for the variation of heat of reaction with the temperature with the help of first law of thermodynamics. Define Cp and Cv. It is based on which law? Explain. Explain that Joule-Thomson experiment is isoenthalpic. 23. (iii) Define the concepts of Helmholtz free energy and Gibb’s free energy. Q. State with example the significance of Hess’s law. Ans. Q. Q. State Maxwell’s relations. See page 89.65 Kcal 2 2 1 mole of O2 both at unit pressures at constant 2 temperature (25°C). 16. EXERCISES 1. See page 81. Describe a relation between the two. 82. How can you measure a spontaneous system with the help of free energy? Ans. What is inversion temperature? Ans. 22. It means that if a mole of H2 and 1 O = H2O is – 54. Define (a) heat of formation. 18. Q. See page 84. 19. Q. ENGINEERING CHEMISTRY Q. 20. 25. See page 73. (iv) What is the significance of entropy? What is the criteria for spontaneity? (v) Derive Kirchoff’s equation. Ans. State the law of Laplace and Lavoisier. (ii) Derive Clapeyron-Clausius equation and state its applications. What do you mean by a cyclic process? Ans. . State relation between them. Ans. Q. Ans. See page 80. (b) heat of combustion.65 Kcal. State the second law of thermodynamics. See page 71. See page 81. See pages 78 and 79.100 Q. What do you mean by ∆G° for the reaction H2 + at 25°C? Ans. Ans. 26. (c) heat of neutralisation. the decrease in free energy is 54. See text page 79. Alternatively it can be stated as the net entropy of the universe tends to a maximum. Ans. Q. 27.

(c) Give the mathematical expression for first law of thermodynamics. (iii) Which is an intensive property? (a) Pressure (b) Time (c) Volume. (a) Show that for a gaseous expansion. (ix) Entropy of a system changes during melting. (b) Only H+ and OH– ions react in each case.THERMODYNAMICS 101 (vi) What is Joule-Thomson effect? (vii) What is bond energy? How can you calculate the bond energy of C—C bond in ethane? (viii) Write notes on (a) Heat of formation. (xi) State function. 7. 3. (iii) Extensive properties. (c) What do you mean by inversion temperature? 5. 9. (x) Isobaric process. Derive Kirchoff ’s equation. (b) Define molar heat capacities. Derive an expression for the work done during reversible isothermal expansion of an ideal gas. ∆H > ∆E. (x) Why is entropy a state function? 2. Show that entropy change in an irreversible process is positive. (ix) State Hess’s law and explain how it can be used to calculate the heats of formation. (x) On increasing pressure. Objective Type Questions: (i) Which is a state function? (a) q (b) W (c) q – W (d) q/W. (ii) Which is an extensive property? (a) Temperature (b) Viscosity (c) Volume. (iv) Intensive properties. (v) Heat of neutralization of a strong acid with a strong base is constant since (a) Salts are formed. (c) Give characteristics of entropy. 4. (vi) Irreversible process. (viii) All living systems are (a) adiabatic systems (b) Closed systems (c) Open system. (a) What do you mean by entropy? (b) Give physical significance of entropy. (viii) Adiabatic process. (ii) Heat of combustion. During melting it (a) decreases (b) increases (c) remains unchanged. . (iv) When is a system in equilibrium? (a) ∆G is zero (b) ∆S is minimum (c) ∆G is maximum. (vii) All naturally occurring processes proceed spontaneously to (a) increase in free energy (b) decrease in free energy (c) decrease in entropy. boiling point of water (a) remains unchanged (b) increases (c) decreases. 8. Derive an expression for entropy for an ideal gas. (a) What is Joule-Thomson effect? (b) Prove the constancy in Joule-Thomson expansion. (v) Reversible process. (d) Explain the relation: S = k ln w. (vii) Isothermal process. 10. 6. (c) Strong acid and strong base react completely. (a) What do you mean by thermodynamics? (b) Explain the terms— (i) Isolated system. (ix) Isochoric process. (c) Prove that Cp – Cv = R. (ii) Closed system. (vi) The expression of first law of thermodynamics is (a) q = ∆H – W (b) ∆H + P∆V = ∆E (c) ∆E = q – W.

6 Kcal] 5. (vii) Heat of vaporisation. How can you determine the bond energy and lattice energy with the help of Hess’s law? 16. Calculate ∆E. (iv) Heat of formation. where xi = mole fraction of gas. 4. 790 cals] The volume of a 45 g nitrogen gas is expanded from 5 litre to 10 litre at 25°C isothermally and reversibly. (a) What do you mean by work function (A)? (b) What do you mean by free energy (G)? (c) What is the relationship between free energy and useful work? (d) What do you mean by standard free energy change? 14. – 4.788 × 107 ergs] During isothermal reversible expression of 4 g of helium gas at 27°C the pressure reduces from 10 atm to 1 atm. (c) Explain the terms (i) Heat of reaction.102 ENGINEERING CHEMISTRY 11. Calculate ∆E and ∆H if 10 litres of helium at N. (b) Mention the applications of Hess’s law.8 cals] The heats of formation of CO2 from diamond and graphite are – 94500 and – 94050 cal. ∆H.36 × 109 ergs work after absorbing 990 cals. 19. What is the enthalpy change in the transformation of diamond to graphite? [Ans. Consider the gas to behave like an ideal. 133. When ice melts at 0°C. What do you mean by Van’t Hoff reaction isotherm? Derive an expression for the reaction isotherm lL + mM + . (viii) Heat of sublimation. g–1.1 cals. The density of ice is 0. (b) Give the significance of Gibbs-Helmholtz equation.1 cals] A system performs 8. q and w per mole. [Ans. heat from the surrounding.82 and of water of unity.05 and – 68. Derive Maxwell’s relation and state its usefulness. Entropy change for the mixture of gases can be represented by – ∆Smix = – nR Σ xi ln xi 13.. 223. of the general reaction aA + bB + . 12.. 17. – 450 cal] Calculate the heat of oxidation of ethyl alcohol to carbon dioxide.P. [Ans. are heated inside a gas cylinder to 100°C assuming it to behave ideally and having Cv = 3.T.32 Kcal. respectively. Derive Clausius-Clapeyron equation. 15.8. (v) Heat of solution. (ii) Heat of combustion. 1440. (1440. cals. 2. Show that entropy change for an irreversible isothermal expansion of an ideal gas is positive. 21. Derive an expression for chemical potential at a temperature T in terms of P. . 22. [Ans. Calculate the work done in calories. when the heats of formation of carbon dioxide and liquid water are given as – 94. [Ans. Derive Gibbs-Duhem relations. Long Questions 1. 3 R. 18. 20. (a) How can you determine spontaneity of changes of a system? (b) What do you mean by chemical potential (µ)? (c) Show that chemical potential does not change during phase transfer of a compound.. (a) Derive Gibbs-Helmholtz equation. 7. 326. The heat of formation of ethyl alcohol is – 66. (vi) Heat of fusion. Considering the gas to be an ideal find out the work obtained in this case. the latent heat of fusion is 80 cals. 6. 1381.4 Kcal.. Find the internal energy change of the system.01 × 106 ergs) 2. 1440 cals. . 2 [Ans. (a) State Hess’s law. (iii) Heat of neutralisation.

∆G and ∆H for a particular reaction at 127°C are – 12 Kcal and 17.300.4 Kcal] 15.5 Kcal. [Ans. ∆A and ∆G for vaporisation of 2 moles of benzene (b. 94380 cals and 68380 cals. 1.03 20000 × 2000 = 5677 × 107 ergs. Calculate the free energy change of g mole of SO2 at 25°C and 10 atm pressure. The van der Waal’s constant for CO2. 153080 cals] 9. carbon and hydrogen are 754300 cals.043 litre mol–1. Find out ∆S. ∆U. 760 mm Hg] . Calculate ∆Q.31 × 107 × 300 log 20 − 0. Calculate the vapour pressure at 100°C. Calculate the work done if a = 1.42 × 1012 dynes cm 4 mol–1 and b = 30 c. H2 + Br2 → 2 HBr. Given. – 17120 cals] 10. ∆G°298 = – 71. – 13.5 Kcal. Calculate the entropy change in vaporisation of ether.c mol–1. heat of benzene is 0. 13. 70 g of nitrogen gas was initially at 50 atm and 25°C. Given. Find the change in entropy when 1 kg of benzene at 10°C is mixed with 4. [Ans. l) = – 68320 cal. W = RT ln V2 − b 1 1 . Find heat of formation of caustic soda from the following data: Na + H2O = NaOH (aq) + H2 + 1 H + 98. Br—Br bond energy = 192.9879 eV] 17.86 kJ] 368. The vapour pressure of water at 90°C is 530 mm Hg. Evaluate the heat of formation of methyl alcohol.5 kJ mol–1. What is the inversion temperature of the gas? [Ans. +a − V1 − b V2 V1 LM N O P Q W = 2. From the following bond enthalpies calculate ∆H for the reaction.380 2 2 NaOH + water = NaOH (aq) + 13. [Ans.303 × 8. 2 L M N O P Q ∆H f (CO2 . ∆H(H O.000 2 2 1 O = H2O + 68. The sp.03 2000 − 20000 ergs + 1. Calculate the heat of formation of benzene given that the heats of combustion of benzene.75 eV] 20. [Ans. Given. The average latent heat of vaporisation of water is 546 cal g –1 within the temperature range 90°C – 100°C. [Ans. 0] 12. [Ans. boiling point = 35°C. – 57040 cal] 14.2 K and G = 101 cal g–1) [Ans. (Ans. = 353. Bond energy H—H = 435. Isothermally at 27°C one mole of a van der Waal’s gas expands reversibly from 2 litres to 20 litres.THERMODYNAMICS 103 8. – 70. ∆W. 0.8 Kcal mol–1.5 Kcal.1 eV] 18.0 kg of benzene at 30°C. ∆G = 0. The heat of combustion of methyl alcohol is – 173.p. [Ans.59 litre2 atm/mol–2 and b = 0.24 kJ mol–1.39. 0. 1. H—Br bond energy = [Ans. [Hint.65 Kcal. ∆A = – 1. respectively.] 11. ∆S = 44. g) = – 94050 cal. [Ans.5 cal/°K. ∆H. Calculate ∆S. It was allowed to expand isothermally against a constant external pressure of one atmosphere. – 108. a = 3.3 kJ mol–1. 21.43 Kcal/mol–1] 19. 2036 K] 16.42 × 1012 2 − 0. L = 6500 cal mol–1.

we know that the rate of reaction is dependent on the active masses of reacting substances. [B]b where [A] and [B] are the concentrations of the reactants at that instant. Every chemical reaction has a definite velocity at a definite temperature. k is a constant known as rate constant or specific reaction rate. (r) → r = k . Though thermodynamics has got an enormous influence in chemical equilibrium yet has no valid application in studying the rate of reaction. The passage towards equilibrium takes some time which may be almost instantaneous or very long. Highlights: • Higher the value of k higher the reaction rate. The velocity of a reaction is not same even at constant temperature. the rate constant is called specific reaction rate. But can say nothing about how fast the equilibrium will attain. x = concentration of the product. • Reaction rate is determined by the decreasing concentration of the reactants in unit time. Actually active mass means ‘molar concentration’. As for example: CH3COOC2H5 + H2O → CH3COOH + C2H5OH 2H2O2 → 2H2O + O2 5 Velocity of Reaction From law of mass action. dx dc • Mathematically r = – = dt dt where c = concentration of the reactant. i. [A]a . the rate constant will express the rate of the reaction.. For a reaction → aA + bB cC + dD rate of reaction. Modern techniques have been developed to study the reaction rate which gets completed in milliseconds or even in microseconds. we can predict how far the reaction would go. But there are several other reactions where the rate can be easily measured. k = r. When [A] = [B] = 1 then. • The rate of a reaction can also be determined by the increasing concentration of the products in unit time. In this case.e. 104 .Reaction Dynamics/Chemical Kinetics INTRODUCTION From the study of chemical equilibrium involving law of mass action.

• The order of a reaction will be determined by the power terms of the concentrations of the rate equation. As for example.REACTION DYNAMICS/CHEMICAL KINETICS 105 To consider the rate of a reaction. we should take into account the ‘order’ and the ‘molecularity’ of a reaction. [H2O2] Here we see rate is proportional to the first power of the concentration of H2O2. the powers of the concentration terms are added to get the order of a reaction. the order of the reaction will be = (a + b). atoms or ions taking part in a chemical reaction is known as molecularity of the reaction. Molecularity of a Reaction The minimum number of molecules. So. the rate equation will involve the concentration of the reactants. Therefore. minimum two molecules of HI will be required. the molecularity is ‘two’. [H2][I2] r = k[CH3COOC2H5] [NaOH] Order 2 2 2 Highlights: • The number of molecules of the equation for the chemical change has got no relation with the order of a reaction. • The order of a reaction may be zero or fraction. . for decomposition of H2O2. for a reaction: aA + bB → Products rate of the reaction (r) = k . [B]b. As for example 2HI = H2 + I2 For this reaction. Order of a Reaction The rate of reaction will definitely depend on the concentration of the reactants. So it is a first order reaction. [A]a . [HI]2 r = k . So. Table 5. In the experimentally determined rate equation. The experimentally determined rate equation for the decomposition of H2O2 is: r = k .1 Reactions (i) 2HI = H2 + I2 (ii) H2 + I2 = 2HI (iii) CH3COOC2H5 + NaOH = CH3COONa + C2H5OH Experimentally determined rate r = k . Again for the reaction: 2H2O2 = 2H2O + O2 But the reaction can be written as H2O2 = H2O + O So. one molecule is needed and hence the molecularity is one.

5 So. dt.5 and the molecularity is 2. • For the reaction BrO3– + 5Br– + 6H+ = 3Br2 + 3H2O The observed rate = k . So. a− x Integrating we have. dt dx = k . If c be the concentration. the order of the reaction is four but the molecularity is twelve. [NO]2 [O2] 2N2O5 = 4NO2 + O2. Then. the order of the reaction is 2. (a – x) x At time ‘t’. or x=0 – ln a = z – ln (a – x) = kt – ln a ln a = kt a– x . x = concentration of the product at time t. [N2O5] So. – ln (a – x) = kt + z where z = integration constant when t = 0. • For the reaction CO + Cl2 = COCl2 Rate = k . [BrO3–] [Br–] [H+]2 So. the order of the reaction is one and the molecularity is two. both the order and the molecularity of the reaction are three. a = initial concentration of A. (a – x) dt or dx = k . [CO] [Cl2]1. Mathematical Formulation of First Order Reaction The reactions. then the rate of the reaction = – where k = rate constant.106 Highlights: • For the reaction The observed rate = k . the rate equation will be dc = kc. Therefore. • 2NO + O2 = 2NO2 Rate = k . where the experimentally determined rate of the reaction is dependent on the first power of the concentration of the reactant. ENGINEERING CHEMISTRY So. are called first order reactions. Let the reaction be A → Products.

t1/2 = LM N OP Q c • If we put a – x = c i. kt = ln 0 c ∴ c = c0 .693 .e. (iv) From the equation. a first order reaction is never completed. dc dc / C fraction of reactants = C=– (iii) k=– dt time dt So.303 0. 2. 1 a (ii) k = . the value of k will be same.. So.303 . t a– x • The rate equation can be written as (a – x) ln = – kt a a– x = e–kt a (a – x) = a . it is purely a dimensionless number. • The above equation expresses a number of characteristics of a first order reaction— k= a is a common ratio. ln 2 k 2. ln t a− x 2. 1 t = . log10 2 = = . ln a/(a – x) k The half-life of a first order reaction can be calculated (i) a 1 a x= . log = . then the equation x = a(1 – e–kt) will be a = a(1 – e–kt) ∴ t = infinity. e–kt x = a(1 – e–kt). for any unit of a– x concentration.303t −k ∴ log c is plotted against ‘t’ we get a straight line with a negative slope = .REACTION DYNAMICS/CHEMICAL KINETICS 107 or or or or a 1 . k k (v) For complete reaction x = a. we have. ln .303 a . unit of k will be time–1. So. t a– x So. concentration at any time ‘t’ and a = c0. log c = + log c0 2. e–kt –k Therefore. k is change of fraction of reactants in unit time. ln a 2 k a– 2 1 = .

take part and the rate of the reaction is proportional to the concentration of each of them. are called second order reaction. Let.108 Examples of a First Order Reaction (i) Decomposition (gas phase) (a) 2N2O5 → 4NO2 + O2 (b) N2O4 → 2NO2 (c) CH3CH2Cl → C2H4 + Cl2 CH 2  CH 2   (d) → 2C2H4 CH 2  CH 2 ethylene cyclobutane ENGINEERING CHEMISTRY (ii) Isomerisation (gas phase) (a) CH2¾CH2 ¾¾® CH3CH = CH2 cyclopropane propylene CH2 (b) CH  CH 2 → CH2 = CH—CHe = CH2 1.    CH  CH 2 Cyclobutene (iii) Decomposition (solution phase) (a) H2O2 → H2O + COOH O2N NO2 ¾¾® NO2 NO2 O2N NO2 1 O2 2 (b) (iv) Hydrolysis C12H22O11 + H2O → C6H12O6 + C6H12O6 Cane Sugar Glucose Fructose (v) Solvolysis (CH3CO)2O + 2C2H5OH → 2 CH3COOC2H5 + H2O (vi) Radioactive disintegration: Ra → Rn + α Mathematical Formulation of a Second Order Reaction Reactions in which two molecules. 3-butadien. A + B → C + D Initial concentration of A = a Initial concentration of B = b . the reaction be represented by. identical or different.

. x = 0 ∴ ln ln b–x b = k(b – a)t + ln a– x a (b – x) b(a – x) b = ln – ln (a – x) a(b – x) a b(a – x) a(b – x) = ln a(b – x) b (a – x) – k(b – a)t = ln k(b – a)t = – ln k= = 1 a(b – x) ln (b – a)t b(a – x) 2. dx = k(a – x)2 or dt . concentration of both the reactants are equal i. initially.303 a(b – x) log (b – a)t b(a – x) dx = k(b – x)2 dt If. a = b.e. then we can write.REACTION DYNAMICS/CHEMICAL KINETICS 109 Decrease in concentration of A and B at time t = x Concentration of A at time t = a – x Concentration of B at time t = b – x Concentration C and D at time t = x Rate of the reaction = k[A] [B] or or ∴ or or or dx = k(a – x) (b – x) dt k dt = FG IJ k dt H K FG 1 – 1 IJ dx = k dt 1 b – a H a – x b – xK 1 L 1 1 M a – x dx – b – x dxOPQ = k dt b– aN 1 1 1 – dx = b– a a– x b– x z dx 1 1 1 – dx = (a – x)(b – x) b– a a– x b– x z z z LM N OP Q z z z 1 [– ln (a – x) + ln (b – x)] b−a = kt + z (integration constant) or At ∴ ∴ or ∴ ln b–x = k(b – a)t + z a– x b =z a t = 0.

time–1 = l . mol–1 sec–1 [l = litre] dt c time conc 2 (iii) Physical significance ∴ k= k= dx = When c = 1 dt i. half decomposition time of a second order reaction is inversely proportional to the first 1 power of initial concentration and is equal to when a = 1 k (ii) Unit of rate constant k t1/2 = dx = k(a – x)2 = kc2 when (a – x) = c dt dx 1 conc 1 . if we put a – x = c t a(a − x) 1 1 = kt + . = = k a(a – x) k a(a – a / 2) ak i.. z= dx ( a – x) 2 = k dt 1 = kt + z (integration constant) a– x 1 a kt = kt = 1 1 – a–x a 1 1 – c a ∴ or k = x 1 .e. x = 0. ∴ then.110 Taking ENGINEERING CHEMISTRY dx = k(a – x)2 dt or or when t = 0.. k is the rate of decomposition at unit concentration of the reactants. c a Characteristic of a Second Order Reaction (i) Time of half reaction x a/ 2 1 1 1 .e. Examples of a Second Order Reaction (i) Decomposition (gas phase): (a) (b) (c) (a) (b) 2HI → H2 + I2 2NO2 → 2NO + O2 2NOCl → 2NO + Cl2 H + D2 → HD + D Cl + H2 → HCl + H (ii) Displacement reaction (gas phase): . 2 = × = conc–1 .

sec–1 Dependent on concentration. a=b=c the rate equation becomes. t1/ 2 Third Order Reaction The rate equation for a third order reaction is A + B + C → Products where. c l mol–1 . Independent of initial concentration.REACTION DYNAMICS/CHEMICAL KINETICS 111 (iii) Dimerisation (gas phase): CH 2 = CH  CH = CH 2 → CH 2  CH = CH  CH 2 butadiene   CH 2  CH = CH  CH 2 dimer (iv) Addition (gas phase): H2 + I2 → 2HI (b) OH– + CH3I → CH3OH + I– (vi) Hydrolysis of an ester: CH3COOC2H5 + OH– → CH3COO– + C2H5OH (vii) Esterification: CH3COOH + C2H5OH → CH3COOC2H5 + H2O Comparison Points Rate equation Linearity Unit of k k k= First order reaction Second order reaction k= (v) Substitution reaction (Solution phase): (a) I– + CH3Br → CH3I + Br– 1 a ln t a–x 1 x t a( a – x) log c decreases linearly with time sec–1 Independent of concentration. Inversely proportional to initial concentration. dx = k(a – x)3 dt . Initial concentration of A = a Initial concentration of B = b Initial concentration of C = c dx = k(a – x)(b – x)(c – x) dt no. 1 increases linearly with time. When. of moles of each reactant decomposed at time t = x.

L M N 1 L k= M 1 2t N ( a – x) 1 1 1 – 2 2 2 (a – x) a 2 OP Q 1 O 1 x (2a – x) – P = t 2 a ( a – x) a Q 2 2 2 . (iii) Unit of k is mole–1 sec–1.e. . x = 0 1 1 . =Z ∴ 2 a2 1 1 1 – = kt 2 ( a – x) 2 2a 2 Z= 1 2a2 or ∴ ∴ kt = Characteristics of a Third Order Reaction 1 (i) Where x = a. .112 = kc3 = Again or Integrating. (ii) k is dependent on the unit of concentration. 2a – a a 2 – a2 a 1 2 1 1 4 2 4 = = k= .. in other words. FG H FG IJ H K IJ K Examples of Third Order Reaction (i) 2NO + O2 → 2NO2 (ii) 2NO + Cl2 → 2 NOCl (iii) SnCl2 + 2FeCl3 → SnCl4 + 2FeCl2 Zero Order Reactions There are certain reactions where rate of reaction does not diminish with time i. 2 1 1 1 3 2 a . rate of the reaction is proportional to the zero power of the concentration of the reactant i. the time required for the completion of the same fraction of the change is inversely proportional to the square of the initial concentration.. a 2 2 2 13 1 3 1 1 3 1 . . 2 = t 2 a2 2k a2 k 2 a 1 ∴ t∝ 2 a So. the rate of the reaction is not dependent on the concentration of the reactant or. = kt + z 2 (a – x) 2 When t = 0. = or t = .e. kc2(c – x) ENGINEERING CHEMISTRY [when a – x = c] [when a = b ≠ c and (a – x) = c] dx = k(a – x)3 dt dx = k dt ( a – x) 3 (Integration constant) 1 1 . 2 1 4 t t t 1 a4 1 a 2a 2 .

ortho-H2 → para-H2. many fractional order reactions are known. because dc is constant. c0 – c t i..e.. i. dt Examples of Zero Order Reactions These reactions are controlled by catalyst.e.REACTION DYNAMICS/CHEMICAL KINETICS 113 [Q [A]0 = 1] dc = k[ A ]0 = k dt where concentration of the reactant A = c – or or – – [c – c0] = k[t – 0] or c0 – c = kt z z c c0 dc = t 0 k dt = k z t 0 dt Characteristic of a Zero Order Reaction (i) We have. the reaction velocity is constant and is independent of concentration. – 2SbH3 → 2Sb + 3H2. – dc = Kc1/n dt where concentration of the reactant = c.. . the rate of reaction is proportional to fractional power of concentration of the reactant. CH3COCH3 + Br2 → CH3COCH2Br + HBr HI + → prs W 1 1 H2 + I2 2 2 Fractional Order Reactions Not all reactions are of integral or zero order. Sb dc = Kc 3 / 2 dt – dc = Kc3/5 dt – dc = Kc3/2 dt Usually such order involves a mechanism where atoms or free radicals are intermediates of the reaction. In those reactions. the amount decomposing in unit time is constant. k= (ii) In zero order reactions when c plotted against t would give a straight line of slope k . i. independent of concentration or time. The bromination of acetone in acid solution is of zero order with respect to Br2. since the reaction velocity is not influenced by a change in concentration of bromine.e. which is equal to k (Zero order rate constant). Examples of Fractional Order Reaction (i) (ii) (iii) CH3CHO → CH4 + CO.

After complete hydrolysis of sugar. Due to presence of excess water. The rate equation comes to – dc = k′[C12H22O11] dt dx = k′(a – x) dt k′ = or or 1 a . i. By putting the value ‘a’ and (a – x) the value of ‘k’ is determined. The method is laborious and too complicated to give a satisfactory constant value. the rate equation of the reaction is – dc = k[C12H22O11] [H2O] dt In solution the amount of water is excessively high compared to sugar.. (a – x) is determined. the change of concentration of sugar is very negligible. Such solvolytic first order reactions are called Pseudo unimolecular reactions. So. ln t a– x So.e. the incident so happens. characteristics of first order reaction is seen actually in second order reaction. LM N OP Q . The order of the reaction is determined by that equation which gives the satisfactorily constant value of ‘k’.114 ENGINEERING CHEMISTRY Pseudo Unimolecular Reactions Let us take the reaction C12H22O11 + H2O → C6H12O6 + C6H12O6 Sucrose Glucose Fructose If we determine the rate of the reaction. Other pseudo unimolecular reactions are: (i) COS + H2O → CO2 + H2S (ii) CH3COOCH3 + H2O → CH3COOH + CH3OH (iii) (CH3CO)2O + 2C2H5OH (excess) → 2CH3COOC2H5 + H2O Methods for the Determination of the Order of a Reaction (i) Substitution methods (with the help of rate equations) The following are the expressions of rate constants for different reactions: First order reaction Second order reaction Third order reaction ⇒ ⇒ ⇒ k= k= k= a 1 ln t a– x x 1 . But is still employed for simpler reactions. So [H2O] is constant. the reaction is dependent on the concentration of both the reactants. So. we see that the reaction is of the second order. t a(a – x) 1 1 1 – 2 2 2t ( a – x ) a To determine the rate of a reaction a definite amount (a) of the reactant is taken and with the passage of time ‘t’ the change in concentration (x) is determined mechanically or by chemical analysis.

By plotting log c vs t if a straight line is obtained the reaction is of first order. So. the rate equations for the two experiments will be dc R1 = – 1 = kc1n. we can get the order of a reaction. 5. If t1/2 remains constant the reaction is of the first order. the first experiment the initial concentration = c1. i. (iv) Graphical method If we plot ‘time’ vs ‘a function of concentration’. For. if t1/2 varies inversely as the initial concentration the reaction is of the second order. For the second experiment the initial concentration = c2.693/k (fixed) Second order = 1/(ak) Third order = 1/(a2k′) In separate sets of experiments if different concentrations are taken and t1/2 are measured the order can easily be determined. 1/a will give a straight line. (iii) Van’t Hoff’s differential method Let. the reaction is of third order. 5. If the plot t1/2 vs.e. dt dc2 R2 = – = kc2n. 1/a2 gives a straight line. the order of a reaction be = n. plot of t1/2 vs.1 .REACTION DYNAMICS/CHEMICAL KINETICS 115 (ii) Half-life method The half-lives (t1/2) for reactions of different orders are as follows: First order = 0. If a plot of 1/c vs ‘t’ gives a straight line the reaction is of second order and if the plot of 1/c2 vs ‘t’ gives a straight line the reaction is of third order (Fig.1 (a) and (b)). dt Taking ‘log’ on both the sides log R1 = log k + n log c1 log R2 = log k + n log c2 n= log R 1 − log R 2 log c1 − log c2 If the rates of reaction determined initially R1 and R2 are known. or A Amount decomposed (x) dx C q B Slop = tan q = dx dt Rate of reaction (dx/dt) Time (t) (a) (a – x) (b) Fig. so the order can be determined..

yield 10% (side reaction) Example: CH2 = CH2 CH3. There are certain disturbing factors which influence the reaction and constant values for k are not obtained. so the interpretation of the order of a reaction from their velocity data becomes difficult. But many of the reactions are not so simple. The other reactions occur simultaneously. Each reaction gives a set of products. the experimentally determined rate for this reaction is a net result for the two opposing reactions. Simultaneous reactions Side reactions Opposing reactions Consecutive reactions (a) Side reaction: Sometimes the reactants undergo two or more independent reactions simultaneously. Some of these factors are given below: Simultaneous Reactions In a simple reaction.CH2OH dx = k1c dt C2H4 + H2O C2H5OH dy CH3CHO + H2 = k 2c dt [k1 and k2 are not same] (b) Opposing reaction: The reversible reactions also interfere to give the constant value of ‘k’.CH2.116 ENGINEERING CHEMISTRY Disturbing Factors in the Determination of an Order The reaction which takes a single path has no interfering influence in the main reaction. But many reactions are complicated. These reactions are called simultaneous reactions. These reactions interfere to give a constant value of k. Example: CH3COOH + C2H5OH k1 k2 CH3COOC2H5 + H2O .Cl CH3. B + C. The reaction which gives the major product is called main reaction and the other is called side reaction. the reactants react to give products. There are three types of simultaneous reactions. The rate constant values are not obtained constants for a number of reactions. yield 90% (main reaction) A P + Q. A+B C+D So.

COOC2 H5 CH 2 COONa Ethyl Succinate k2 + C2 H 5 OH Ethyl Sodium Succinate CH 2 COOC 2 H 5 CH 2COONa k2  + NaOH →  + C 2 H 5OH CH 2 COONa CH 2 COONa Sodium Succinate (iv) H2O2 + 2HI → 2H2O + I2 H2O2 + I– → H2O + IO– IO– + 2H+ + I– → H2O + I2 Of these reactions. These types of reactions are known as consecutive reactions. As for example—period of induction is noted during the reaction of H2 and Cl2 in the presence . CH2 . k2 k1 Period of induction Sometimes it is seen that even though the proper conditions for the reaction are maintained the reaction does not start. (c) Consecutive reaction: In many reactions. A → B → C Examples: (i) (CH3)2O → CH34 + HCHO → CO + H2 k1 k1 k2 k1 k2 (ii) 2NO + H2 → N2 + H2O2 H2O2 + H2 → 2H2O (iii) CH 2 . CH2 .REACTION DYNAMICS/CHEMICAL KINETICS 117 O¾CO CH2 CH2¾CH2 (Lactone) CH2OH . the products obtained change to a third product. This period of static state of reaction is known as period of induction. which can be measured and that determines the order of the reaction. dt where k1 = rate constant for the forward reaction k2 = rate constant for the backward reaction Here the reverse reaction interferes the determination of the rate constant of the main reaction. the first proceeds very slow. COOH (Hydroxy butaric acid) k1 k2 + H2O Rate equation for the first reaction is: dx = k1(a – x)(b – x) – k2 x2. COOC2 H5 CH 2 COOC2 H 5 k1  + NaOH →  CH 2 . After some time the reaction starts and proceeds as usual with normal speed.

The relation can be expressed mathematically as follows: ln k = A – where A and E are constants. Generally. Then. value of k will increase. negative catalysts are responsible for this inactivity in the period of induction or sometimes slow production of an active intermediate. we can write. 5. Rate of a reaction gets doubled when temperature increases by 10°. Let. induction period is observed in photochemical and polymerisation reactions.118 ENGINEERING CHEMISTRY of light..e. ln k1 E 1 1 =− – k2 R T1 T2 LM N OP Q . Generally. rate of a reaction will increase i. ln k1 = A – E RT or E d ln k = RT 2 dT E RT1 and ln k2 = A – E RT2 Subtracting the above two equations we have. 5. Their values are different for different reactions.2 Plot of ln k against 1/T for a reaction. He established that when loge k or ln k is plotted against (Fig. Keeping concentration constant if we increase the temperature. Arrhenius first related temperature T of a reaction with k.2). 4 2 0 –2 ln k 1 a straight line is obtained T Gradient = –Ea R –4 –6 –8 –10 7 8 9 10 4 1 × 10 T 11 12 Fig. Effect of Temperature on Reaction Rate (Arrhenius Equation) Temperature has a great influence on reaction rate: Arrhenius studied the fact and concluded that rate of every reaction increases with increase of temperature. rate constant of a reaction at temperature T1 = k1 and rate constant of that reaction at temperature T2 = k2.

which take part in a chemical reaction should get activated by gaining a minimum definite amount of energy. • The exponential form of the above equation is known as Arrhenius equation E /RT . 5. Highlights: • Temperature coefficient of a chemical reaction is defined as the ratio of two rate constants of the reaction at two temperatures differing by 10°. if we can determine the two rate constants k1 and k2 we can find out the value of E from the above equation. For every reaction. otherwise the reaction will not be Potential energy Ea A+B DH C+D C+D A+B Progress of reaction Fig. Arrhenius equation describes how the rate constant for a reaction varies with temperature and makes it possible to determine the activation energy for the reaction. the molecules should be raised to a state of sufficient energy. we can determine the value of k2 when k1 is known.REACTION DYNAMICS/CHEMICAL KINETICS 119 or log k1 E 1 1 – =– k2 2.3 . k = Rate constant Ea = Energy of activation R = Gas constant T = Absolute temperature A = Another constant known as frequency factor. − Energy of Activation (Ea) of a Reaction: its Significance The molecules of reactants. k25° (usually) k35° LM MN OP PQ 1 gives a straight line so the equation of the straight line is: T ln k = a – b T where k is the specific reaction rate and T is the absolute temperature. If E for a reaction is known.303R T1 T2 So. which is known as energy of activation (Ea). k = Ae a where. Temperature co-efficient = • Plot of ln k vs.

E or ln k = ln z – E/RT = A – RT This supports the experimentally derived equation. So. After the reaction. e–E/RT. the reaction becomes endothermic and when the liberated energy is greater than Ea the reaction becomes exothermic (See Fig. the ratio of total number of collisions and the number of collisions giving E to the molecules is e–E/RT. These activated molecules take part in the reaction. e–E/RT. which lead to the reaction. This energy state is different for different reactions. which a molecule should possess to get activated to take part in a reaction. When the liberated energy is less than Ea.3). • The collisions. but orientation of collision is also important. According to Maxwell.e. 5. Number of collisions per second (z) in any given volume can be obtained from kinetic theory. the reaction becomes possible when molecules of A and B collide. the theory of collision can be accepted. others cannot take part in the reaction unless activated. It is observed that the number of molecules reacted is always less than the number of molecules collided i. ∴ k = z . • There is always an equilibrium between ordinary molecules and excited or activated molecules with an energy difference Ea. Effective collisions are sufficiently energetic. Let the total number of collisions be z. • Theoretically. this excess energy is liberated in the form of heat. When two gases A and B react. The minimum amount of energy over the average energy of a molecule required to get activated for participation in a reaction is called energy of activation. Arrhenius proposed that only the molecules attaining energy of activation Ea due to collision can take part in the reaction. Some molecules are more energised than the others. every collision does not give rise to reaction. the molecules of the reactants collide to take part in a reaction. Ea is minimum energy which a molecule must have as a prerequisite to take part in a chemical reaction. Highlights: • A simple collision between the reacting molecules does not necessarily cause reaction. . These number of molecules will react. At any state. Collision Theory According to this theory. at a temperature T.120 ENGINEERING CHEMISTRY possible. are called effective collisions. the molecules possess an average energy. Again the number of molecules reacted in one second can be obtained from rate constant k (experimentally determined).. ∴ Number of collisions of molecules possessing E = z . • Not only effective collisions are responsible for a reaction. Highlights: • Energy of activation (Ea) is the critical value of energy.

6 46. For a Ist order reaction k= Here. it is added colloidal gold and at interval of 5 minutes an aliquot (5 ml) is taken and cooled in ice cold water and titrated against standard KMnO4 solution.0 a 1 . 5.1 = 0. k = 50 t = 10. of properly oriented molecules per unit volume per unit time] × fraction of molecules equal to or greater than threshold energy.0427 min–1 19. ln t a– x a = 46.0434 min–1 5 37.1 ln = 0.0 ln .1 . putting 5 37. Decomposition of H2O2 Time 0 Time value (KMnO4 in cc) 46.6 30 12. In an experiment. k = 46.REACTION DYNAMICS/CHEMICAL KINETICS 121 + H2 I2 Collision Reaction + Product HI + HI Collision Collision Transition state (effective collision) molecules react when they collide in a preferential direction Ineffective Ineffective Fig.8 20 19.e. x. k = 30 1 t = 50.1 Sol.8 46. 5. 250 cc of H2O2 solution of strength 2 (N) is taken..3 46.044 min–1. ln = 0.1 10 29.1 t=5 k= 1 46.0436 min–1 29.044 min–1 12. So.3 50 5.1 ln = 0. SOLVED EXAMPLES Example 1.1 ln = 0.4 Rate of a reaction = [No.1 at at at at 1 10 1 t = 20. The titre values will give the change in concentration of H2O2 i. Determine from the following data the value of k and establish that the decomposition is of the Ist order. Now. k = 20 1 t = 30.

79 Time Vα – Vt k 2. rotation after time ‘t’ and rotation after infinite time where the reaction is assumed to be completed. Sol.09 + 10.05 25.18 18 27. Here. 2 ml of aliquot (reaction mixture) was withdrawn at different intervals and titrated against a standard alkali.71 .303 22..79 log 183 12.71 k= = 0.60 29. Vt and Vα are the volumes of alkali initially.32 42. rt and rα are initial rotation.83 log 27.43 k= = 0.00321 min–1 119 15.79 log 119 15.43 2.24 = 22.03 – 19.4 + 17.83 log 18 28.20 26. Sol.83 log = 0.18 rt – rα.74 Show that the reaction is of the Ist order. after a time t and after an infinite time.00519 min–1 18 28.14 1 34. 27. k = 32.14 k= = 0.18 32.00485 min–1. 1 cc methyl acetate was added to a flask containing 20 ml 0.7 + 15 – 10.09 + 21. Here a = Vα – Vo a – x = Vα – Vt where Vo. 50 cc of this solution and 50 cc of (N) HCl is mixed at constant temperature. of alkali used: 19.83 k= log = 0. The optical rotation of this solution is measured at regular intervals and the final reading is taken after 24 hrs.14 k= r – rα 1 ln 0 t rt – rα 1 34. The data are as follows: Time ( in minutes): 0 75 119 183 α Vol.03 From the above data show that the hydrolysis is of the Ist order.303 22.79 Since.00486 min–1 7. A 20% sugar solution is taken.. Vα – Vo = 42.00316 min–1 183 12.24 24.05 25. The data is given below: The optical rotation of sucrose in 1(N) HCl at various times is given in the following table: Time (in minute) 0 7. the k-values are fairly constant by putting the data in the Ist order rate equation i. r0 – rα = 24.79 = 34.5(N) HCl kept at a temperature of 25°C. The mixture is poured in a polarimeter tube.e. respectively.122 ENGINEERING CHEMISTRY Since the ‘k’ values are fairly constant by putting the data in the Ist order-rate equation the reaction i.14 1 34.e.79 75 17. Example 2.05 α Rotation (degrees) + 24.00395 min–1 75 17. a = r0 – rα (a – x) = rt – rα where r0.303 22. decomposition of H2O2 is of the Ist order.83 2. the hydrolysis of methyl acetate is of the Ist order.83 Time 7.74 k= = 0. Example 3.

0407 min–1 17 a = 100% a – x = (100 – 75)% = 25% k= k= 2. the hydrolysis of methylacetate is of the Ist order.000433 20 . ∴ Sol. t1/2 to be determined for Ist order reaction t1/2 is and Here. Sol.693 k k= ∴ t1/2 = 0. Determine the time of 50% completion of the reaction.303 100 log = 0. 0.693 k 0. t1/2 = t1/2 0. Example 4. i.303 100 log 4 = 34 minutes .e..e. Radioactive disintegration is of the Ist order ∴ ∴ ∴ Here 0. log ∴ t= = 0. Calculate the time for 80% disintegration.REACTION DYNAMICS/CHEMICAL KINETICS 123 Since the ‘k’ values are fairly constant by putting the data in the Ist order rate equation i..9 minutes.303 100 log t 25 2. We know Here.17 yrs. 0. Sol.693 1600 = k 0.693 min–1 = 0.303 log k= t a–x a = 100 % (a – x) = 100 – 80 = 20 t1/2 = t= 2. Time of 50% reaction. 0. ∴ Here. Half-life for a first order reaction is 17 mins.693 = 72.000433 year–1 1600 a 2. The half-life for radium is 1600 years.693 k = 17 mins. A Ist order reaction is 25% completed in 30 mins.0407 k 25 Example 6.0095 min–1 30 75 0.303 100 log = 37.303 2.0095 Example 5.303 .693 k= year–1 = 0. log t a– x t = 30 min a = 100% a = (100 – 25)% = 75% 2. k= a 2. Calculate the rate constant and time for 75% completion of the reaction.

32 3.76 9.24 1 9. [A]n dt Let a be the initial concentration and x be the concentration which has reacted in the time ‘t’.0067 conc–1 sec–1 16 × 15 6. ∴ ∴ – d[ A ] – d(a – x) dx = = = k(a – x)n dt dt dt dx Q z L M N ( a – x) n x = k dt =k dx (a – x) n 0 t=0.87 × = 0.0069 conc–1 sec–1 16 × 25 4.59 k= k= k= k= k a = 16 c.. Let the reaction be nA → Products. Example 8. The rate equation is – d[ A ] = k .41 Since the k values are fairly constant by putting in the 2nd order rate equation i.13 25 4.c. the hydrolysis of ethylacetate by NaOH is of the 2nd order.41 1 5. of acid (a – x) 0 16 5 10.24 6. So the concentration of A at time t is (a – x).76 × = 0. Deduce the rate constant and t1/ 2 for nth order reaction.13 4.13 1 11.124 ENGINEERING CHEMISTRY Example 7.0066 conc–1 sec–1 16 × 35 3.32 35 3. An aliquot (25 cm) of the reaction mixture was titrated against a standard acid at regular time intervals. The 2nd order rate equation is k= Here T 5 15 25 35 x 1 at (a – x) x 5.32 1 12.24 15 6.87 11. Sol.68 × = 0.59 × = 0. Sol. The following is the data for the hydrolysis of ethyl acetate by NaOH solution. t n–1 (n – 1) ( a – x) a OP Q . Time (in minute) Vol.007 conc–1 sec–1 16 × 5 10. a–x 10.41 Show that the reaction is of the 2nd order.x=0 z t 0 dt 1 1 1 − n− 1 = k .e.68 12.

5 mol l–1 50 1 = 0. the time of half completion for a reaction is found to change from 50 sec.REACTION DYNAMICS/CHEMICAL KINETICS 125 ∴ k= For t1/2. t1/2’s are related to initial concentrations as a T1 = 2 a1 T2 a2 = 1 mol l–1 ∴ or ∴ or FG IJ H K n–1 Here. In a 2nd order reaction. to 25 sec. When the initial concentration is changed from 0. Sol. a1 = 0.2 × 10–3 mol–1 litre min–1 5. x = a/2 ∴ LM N LM 1 1 t= k(n – 1) N ( a – x) LM N LM 2 1 = k(n – 1) N a 1 1 1 – n–1 n–1 t (n – 1) ( a – x) a n–1 – 1 a n–1 OP Q OP Q OP Q t1/2 = t1/2 1 1 1 – n– 1 k(n – 1) ( a / 2) (a) n– 1 n− 1 ∴ −1 n− 1 unit of k is (conc)–(n–1) (time)–1.2 mol litre–1. where the initial concentration of the reactants is the same half of the reactants are consumed in 10 mins. what is the initial concentration of the reactants? Sol. a / 2 60a 1 = 3. T1 = 50 sec.5 25 2 = 2n–1 n–1=1 n=2 FG IJ H K n– 1 .5 to 1 mol l–1.2 × 10–3 = a= ∴ a/2 1 = 60 . x at(a – x) t = 60 mins.2 × 10–3 mol–1 litre min–1. T2 = 25 sec. If the specific reaction rate is 5. x = a/2 k = 5. 60 × 5. Calculate the time taken for the concentration to be reduced to 20% of the initial value.2 × 10 –3 Example 10. For a 2nd order reaction k= Here. OP Q Example 9. a .

If one percent decomposes in the first minute in a unimolecular reaction. Sol. In a 2nd order reaction.075 mol l–1. ak(a – x′ ) 0.2 a = 0. The reaction is found to be 20% complete in 40 minutes.1 mol l–1 x = 0. t = ? (a – x′) = 0. Calculate the rate constant.1 × 0.025 mol l–1 ∴ t′ = x′ 0.303 100 log 1 99 = 2.126 So.04 l mol–1 sec–1 at1/2 0. Sol.01 min–1 when t = 1 hr = 60 mins or 2.303 × 0.01 = 60 a–x k= . time required to complete 75% of the reaction.2 Example 11.5 × 50 25 k 0.303 160 log 60 a– x 2. half-life period. k = 0.75a = 0. calculate how much would remain undecomposed at the completion of the first hour.303 a log 1 a–x a – x = (100 – 1) = 99 a = 100 k= 2.1 mol l–1.0625 × 0.1 – 0. ak 0.303 100 log 0. a = 0. ∴ 2.0625 l mol–1 min–1 k= ∴ t1/2 = 1 1 = = 160 mins.1 × 40 × 0.0625 x′ = 0.1 × 0. ak(a – x) 0. a – x = (0.08 1 at1/2 = 0.2)mol l–1 = 0.2 × 0.8 × 25 = = 200 sec.5 × 0.1 = 0. the initial concentration of reactants is 0. ∴ k= t= ENGINEERING CHEMISTRY 1 1 1 = = l mol–1 sec–1 = .0044 min–1 = 0.625 Example 12.075 = = 480 mins.08 mol l–1 For the second order reaction. Here. k= x 0.0625 mol–1.02 = at(a – x) 0. For a unimolecular reaction k= Here. the reaction is of the 2nd order.02 mol l–1 t = 40 min.

204 ∴ a – x′ 2. A certain substance A is mixed with equal moles of a substance B.3865 × 2 = = 1.89. what will be the above relation if the concentration unit is mol m–1? Sol.01 = log = log 100 – log (a – x) a– x 2.303 a log 2 a – x′ [where x′ = amount reacted] a 1. k2 = mole–1 lt–1 k2 = mole–1 103 ml t–1 or 10–3 k2 = mole–1 ml t–1 For third order reaction.2605 = 2 – 0. For nth order reaction.75a (i) When first order in when time t′ = 2 hrs.25a = 2.204 = 16 a − x′ (a – x′) = . and unit of k = mole1–n ln–1t–1 when c = mol l–1 mole1–n ln–1 t–1 = mole1–n 103(n–1) mln–1 t–1 when c = mol ml–1 For first order reaction. Example 13. How much A and B will be left increased at the end of two hours if the reaction is: (i) first order in A and independent of B.303 log (a – x) = log 100 – 0.7395 (a – x) = Antilog 1. k1 = 10–3 k2 = 10–6 k3. Example 14. If k1 = k2 = k3 for three reactions being respectively of first. k1 = t–1 (k1 will remain same) For second order reaction.3865 = ∴ ∴ log A=K= 2.7395 = 54. 1.303 log 1 a – 0.303 log 4 = 1. At the end of one hour A is 75% reacted. (ii) first order in A and first order in B? Sol.75a 0.303 a a log = 2.5% 16 16 a = Antilog 1. second and third orders when concentration is expressed in mole l–1. Let.REACTION DYNAMICS/CHEMICAL KINETICS 127 or or ∴ ∴ 100 60 × 0.2605 = 1.303 a 100 = = 12. x = 0. 2.89 % undecomposed = 54.3865 hr–1. the reaction will be. k3 = mole–2 l2 t–1 = mole–2 106 ml2 t–1 or 10–6 k3 = mole–2 ml2 t–1 So. initial concentration = [A] = [B] = a t = 1 hrs.

8203 = LM N OP Q Ea 30 × 2. 100 – FG H 6 a 7 IJ K 6 .987 273 × 303 2.987 Cal K–1 . 968 cal mole–1. Calculate the activation energy of this reaction. ∴ At k= ENGINEERING CHEMISTRY x 0. Calculate the temperature at which its half-life is 10 mins. k = Ac − Ea / RT where A is called the Arrhenius factor and Ea is the energy of activation.303 × 1. k2 Ea T2 – T1 = k1 2. the over all order of the reaction is 2.75a = = 3a–1 hr–1 at(a – x) a × 1 × 0. .t. Rate constants at two temperatures are given by Arrhenius equation.. 0.25a (when t = 1 hr) t′ = 2 hrs. The values of Arrhenius factor and activation energy are 4 × 1013 s–1 and 98.45 × 10 1. respectively for a first order reaction. Sol.987 273 × 303 ∴ Ea = 22.5% % of B left unreacted = 100% (Q order = 0 w. k = Here.6 kJ mol–1. The exponential form of Arrhenius equation is.3. k= 3a–1 = x′ when x′ = amount of reactants A and B reacted at(a – x′ ) x′ a × 2 × (a – x′ ) 6a 7 or 6 = x′ a – x′ ∴ x′ = So.693 t1/ 2 t1/2 = 10 mins = 600 sec. 7 Example 15. % of A and B left unreacted = a – i. Example 16.128 So.303R T1T2 T1 = 273 K LM N OP Q T2 = 303 K k1 = 2.303 × 1.e.r. As the reaction is first order. 100 ≈ 14. The specific reaction rates of a chemical reaction at 273 K and 303 K are respectively 2.45 × 10–5 and 162 × 10–5. Sol. B) (ii) In the second case.45 × 10–5 R = 1. mole–1 k2 = 162 × 10–5 ∴ log Ea 162 × 10 –5 303 – 273 = –5 2. log Here. % of A left unreacted = 12.

mol–1. T1 = (800 + 273) = 1073 R = 8. K2 E (T – T1 ) = a 1 K 1 2.0 × 10–3 l mol–1 s–1 has an activation energy of 45 kJ mol–1.1431 = 1.600 J. R = 8.REACTION DYNAMICS/CHEMICAL KINETICS 129 0. = log Here.155 × 10–3 sec–1 From Arrhenius equation we have.314 J mol–1 K–1 log ∴ ∴ ∴ K2 4.5 × 104 J mol–1 T2 = (875 – 273) = 1148 K. let us state we have a population inversion with n2 > n1.39 K1 K2 = 1.303 × 8. A second order reaction. Let.555 = 98600 = 373 K. 2.303 × 8. A = 4 × 1013 sec–1 k = 1.1431 = K 1 2. the populations be n 2 and n1 and energies of the two states be E 2 and E 1. The use of lasers has initiated new types of spectroscopic experiments and has improved the precision of spectroscopic experiments. then photons of frequency 1→2= E 2 – E1 are spontaneously emitted as molecules drop from the state 2 to the state 1.115 × 10 JK 3 –3 98600 K 98600 K 2.115 × 10–3 sec–1. h . T= ∴ T= F 4 × 10 I 2.303 log 10 (k/A) = – Ea/RT ∴ k= or Ea 2.0 × 10–3 l mol–1 s–1.316 × 16. Example 17.303R log( A /K) Here. To achieve a laser action a Population inversion should be generated in the system. What is the value of the rate constant at 875°C? Sol.316 J mol–1 K–1.303 RT1T2 K1 = 5 × 10–3 l mol–1 s–1.303 × 8. When E2 > E1.314 × 1073 × 1148 K2 = Antilog 0.693 600 = 1.Ea = 98.39 × 5 × 10–3 l mol–1 s–1 = 7. Ea = 4. Lasers in Chemistry Laser means “light amplification by stimulated emission of radiation”. whose rate constant at 800°C was found to be 5.5 × 10 4 (1148 – 1073) = 0.316 × G H 1. We have.

• • • • • Laser Technique A laser can be used to excite a major fraction of a reactant species to a specific vibration level in a molecular beam. Those photons emitted along the Fig. States involved in laser action. Those photons emitted at the cylindrical axes pass out of the system and 1 have no role in the laser action. Thousands of different lasers exist. For example. Thus. This sort of idea can be utilised to a selective excitement of a particular normal vibrational mode that involves mainly vibration of a particular bond and to break preferentially that bond. laser axis travel forward and backward between the end mirrors and stimulate emission for further photons. will resonate in the cavity. Dye laser. The HF chemical laser can be used as an antimissile. Photons of frequency 1 → 2 will also induce absorption from state 1 to state 2 but as the system contains n2 > n1 stimulated emission will predominate over absorption and we will get a net amplification of radiation of frequency ν1→2.5. These properties make laser useful in spectroscopy and kinetics. Semiconductor laser or diode laser. a liquid or a gas. where n is an integer. Gas laser. we can take the following two reactions: (i) H + HOD → OD + H2 (ii) H + HOD → HO + HD. An example of chemical laser: One can use the reaction: H + F2 → HF + F. such that nλ = l . 3 2 The laser system is contained in a cylindrical cavity whose ends have parallel mirrors. This makes the laser nearly 2 monochromatic.5).130 ENGINEERING CHEMISTRY These photons will stimulate other molecules in the state 2 to emit photons of frequency 1 → 2 and drop to state 1 (Fig. . Let l be the distance between the mirrors and light only with wavelength = λ. Chemical laser. the material in which the laser action can be employed may be a solid. which is an elementary step of the mechanism of reaction: H2 + F2 → 2HF (chain reaction) A laser in which the population inversion can be produced by a chemical reaction is called a chemical laser. A few photons are spontaneously emitted when the molecules go from the state 2 to state 1. laser light can be employed to control the outcome of the reaction. 5. visible or UV region. Then we can study the dependence of the reaction probability on the vibrational quantum states of these reactants. Kinds of lasers Solid-state metal ion laser. the laser output is highly monochromatic and highly directional. The frequency emitted lies in the IR. 5. The presence of end mirrors makes the laser a standing wave pattern.

2. ∆A ∆B Rate of reaction = – or + ∆t ∆t Unit = Concentration time inverse. 6. similarly. This technique is called Femtosecond Transition State Spectroscopy (FTS) or laser femto chemistry. Differentiate average rate from instantaneous rate.1.REACTION DYNAMICS/CHEMICAL KINETICS 131 By using laser. The rate of a reaction is defined as the decrease in concentration of the reactants or increase in concentration of the products at unit time. 1. 5. 4. Chemical kinetics is that branch of chemistry which deals with the rate of a chemical reaction. Q. Give one major application of laser. (1) Temperature. Average rate = ∆A Change in concentration = ∆T Total time (involved for the change) . (2) Order of a reaction. What do you mean by rate of a reaction? Ans. Whether control of chemical reactions by lasers will ever have commercial applications is not clear. What is a laser? Q. Q. 3. Mention various kinds of lasers. The breaking of a chemical bond in a molecule occurs within a fraction of a second (10–13 to second). Q. 7. the reaction be A → B. one can preferentially break the O – H bond in HOD. It is the rate of the reaction when the concentration of the reactants are unity. Q. 4. Give an example of chemical laser. What do you mean by FTS? Q. 5. What are the factors that can change the value of k? Ans. Can you break a bond preferentially by the application of laser? Q. Unimolecular reactions are best studied by FTS. Ans. Let. SHORT QUESTIONS AND ANSWERS Q. Explain why the laser radiation is monochromatic. 3. Q. By using laser light. The experiments are done using either molecular beams or gaseous molecules in a chamber. What is specific reaction rate or rate constant (k)? Ans. 10 –12 SHORT QUESTIONS Lasers in Chemistry: Q. excitation of O-D stretching vibration in HOD leads to break the O–D bond preferentially. the bond breaking process can be observed spectroscopically. 2. What do you mean by chemical kinetics? Ans. Q. Q. The rate of reaction is increased if the concentration of the reactants increases.

Compare order and molecularity of a reaction. What is the molecularity of a reaction? Ans. . C12H22O11 + H2O → C6H12O6 + C6H12O6 A + B → Products the rate will be Rate = K . In modern definition it is related to the mechanism of the reactions.132 ENGINEERING CHEMISTRY Instantaneous rate is the rate of the reaction determined at the particular moment of time. (iv) Order may be a whole number. Highlight: For elementary reaction order is necessarily equal to molecularity. It is equal to the total number of reacting species atoms. So molecularity is a theoretical approach and its value is always a whole number. temperature. Q. Order (i) Order is a purely experimental fact related to the rate equation of the reactions. Its classical definition is connected with the overall chemical equation. Aα . (ii) If a reaction is Molecularity (i) Molecularity is a theoretical concept. What do you mean by the order of a reaction? Ans. If the reaction is: The molecularity of the above reaction is two. 9. Molecularity of a reaction in equal to the sum of the coefficients of various reactants appearing in a balanced chemical equation i. For complex reactions it may or may not be equal. zero or a fraction. The average rate approaches the instantaneous rate when ∆t becomes smaller.e. Q. [A]α [B]β experimentally observed fact. 8. What are unimolecular and bimolecular reactions? Ans. Q. 7. Cγ where k = rate constant and the order of the reaction α + β + γ.. 6. Q. (iii) Molecularity does not depend on such factors. It is not connected with the chemical equation of the reaction. B β . (iv) Molecularity is always a whole number. Modern definition is—it is the number of molecules taking part in the rate determining step of the mechanism. When the molecularity is one it is unimolecular reaction and when it is two then the reaction is bimolecular. (iii) Order changes with physical conditions like → pressure. If we take a reaction: αA + βB + γC → Products the rate = k . ions of molecules the concentration of which changes actually during the course of a chemical reaction. (ii) It is the sum of the stoichiometric coefficients of a chemical equation. Ans. etc. it is the sum of the stoichiometric coefficients in the simplest chemical equation.

Give examples of first order reaction. 11. A second order reaction is a reaction. Q. dt Q. Q. One hour. Hence. 1. For a second order reaction one hour is needed for a change of concentration a to a/2. What is a second order reaction? Ans. half-life in this case is inversely proportional to the initial concentration. ∴ Rate = – dA = k . Q. concentration will be zero at infinite time. For a reaction: A + B → Products Rate = k . time will be asymptotic plot. Rate of growth of bacterial culture. 16. Ans. What is the time for the change from c/2 to c/4? Ans. If the rate of a chemical reaction varies to the first power of concentration of the single reactant. it is a constant quantity. 2. Is a first order or a second order reaction completed? Ans. 10. the rate of which is directly proportional to the square of the concentration of a single reactant or equal to concentration of two different reactants. a second order reaction is also an incomplete reaction. t = ∞ So. So. So the reaction is not completed. Q. [A] = rate equation for a first order reaction. Comment on half-life of a first order and a second order reaction. 12. For a first order reaction one hour is needed for a change of concentration c to c/2. x 1 t a(a – x) x = a. [A]2 = Rate equation for second order reaction. For a second order reaction the integrated form of the rate equation is: k= when. t1/2 for a first order reaction = t1/ 2 for a second order reaction = 0. 13. What is a first order reaction? Ans. ak So. [A] [B] or Rate = k . Q. Radioactive disintegration process.REACTION DYNAMICS/CHEMICAL KINETICS 133 Q. 15. 14. it is known as first order reaction. What will be the time for the change from a/2 to a/4? . A → Products. Integrated form for a first order rate equation is: c = c0e–kt The plot of concentration vs. Ans.693 . k 1 .

What is the special characteristic of a zero order reaction? Ans. t = H¾H + I¾I Initial state H¾H Transition state Final state 2HI I¾I Activated state I Ea Energy Final state DH > 0 Initial state DH < 0 II Final state Reaction co-ordinate Fig. where c0 = initial concentration t c = concentration at time t. So.1 = 2 hrs. It is the minimum amount of energy from zero level of the reactant molecule which must possess in order to react. Activation energy of a reaction is defined as the extra energy over and above the average potential energy of the reactants. t1/2 = 2. Chemical reactions occur through an intermediate stage known as transition state or activated complex (Fig. It is denoted by ET. 19. 21. 18. ak 1 a/ 2 . the reaction will be completed and for a zero order reaction. 17. 5. 5. c = 0.134 Ans. What is transition state theory? Ans. Q. k or t 1/2 = 2 . c0 ka which is a finite quantity. EA = ET – ER Q.6 . ′ Q.6). when. What is threshold energy? Ans. t1/2 = When concentration changes from a/2 to a/4. How are the activation and threshold energies related? Ans. Q. Q. the rate is not at all dependent on the concentration of the reactants. It is denoted by EA. 20. What is activation energy? Ans. which must be supplied to the reactants to enable them to cross-over the energy barrier between the reactants and products. When concentration changes from a to a/2. t1/2 = ∴ t1/ 2 ′ 1 = ′ t1/ 2 ak 1 1 = ak / 2 2 ENGINEERING CHEMISTRY 1 . The integrated form of zero order reaction is K= c0 – c .

∆H > 0 endothermic reaction (Curve I) ∆H < 0 exothermic reaction (Curve II) Q. of the reaction mixture was titrated at regular intervals against standard acid. 5. State the molecularity and order of the above reaction. 8.13 25 4. Derive the rate constant for a 1st order reaction and show that it is an incomplete reaction. the reactants A and B are at equal concentrations. Discuss any two methods of determination of order. show that the reaction is of the 2nd order. 25 c. Discuss the various factors affecting the rate of a reaction. ‘order of a reaction’ and ‘molecularity of a reaction’. Derive an expression for rate constant of zero order reaction and discuss about its (i) half-life. 4. Calculate the rate constant and the time taken to complete 80% of the reaction. Half-time change for a 1st order reaction is 40 mins. The hydrolysis of ethyl nitrobenzoate by aqueous NaOH was followed at 25 °C. Briefly develop the concept of activation energy and temperature. 6. From the given data. What is the utility of the study of chemical kinetics? Ans. . 9. they attain impact. The study of chemical kinetics helps to determine the mechanism of a chemical reaction. Describe an accurate method for determining order of a reaction with three reactants. What is the rate constant of the reaction at the same temperature? [ 0. 17.REACTION DYNAMICS/CHEMICAL KINETICS 135 Particles in collision react only if. of acid (c. 10. 7. EXERCISES 1. 2. [34. Explain the terms ‘rate constant’. During the hydrolysis of ethyl acetate by NaOH using equivalent concentration. 3.c.c. Explain the meaning of pseudo unimolecular reaction. 5 Br– + BrO3– + 6H+ → 3Br2 + 3H 2O k Rate = Constant × [Br–] [BrO–3] [H+]2. Distinguish between rate and specific reaction rate of a chemical reaction. The volumes of acid used by unchanged NaOH are given below: Time (minute) Vol.) 0 16 5 10. 12.85 mins] 16.24 15 6. Classify the statement: “decomposition of H2O2 is of the 1st order”. by titration of the hydroxide against standard acid at different stages in reaction. The half-life period of a 1st order reaction is 15 mins. Indicate how the specific reaction rate of a first order reaction can be evaluated. 22. How does rate of a reaction vary with temperature? What is Arrhenius equation? 11.32 35 3. they attain the energy of the transition state. upon impact.41 Show that the reaction is of the 2nd order.0173 min–1] 15. What is meant by order of a reaction? Derive an expression for the velocity coefficient of a second order reaction. 13. 14. Derive the rate constant expression of a 2nd order reaction: A + B → c. For. (ii) completion time.

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18. The half-life periods for the decomposition of ammonia (catalytically) are as follows : Pressure in mm 50 100 200 Half-life period in hrs. 3.52 1.92 1 Find the reaction is of which order. 19. The decomposition of Cl2O7 at 400 K in the gas-phase to Cl2 and O2 is a 1st order reaction. (i) After 55 seconds at 400 K the pressure of Cl2O7 falls from 0.062 to 0.044 atm. Calculate the rate constant. (ii) Calculate the pressure of Cl2O7 after 100 sec. of decomposition at this temperature. [Ans. 6.236 × 10–3 sec–1; 0.0332 atm] 20. A 2nd order reaction, where a = b, is 20%, is completed in 500 seconds. How long will it take to go to 60% completion? [Ans. 3000 seconds] 21. The following data were obtained in the hydrolysis of ethyl acetate, using equal concentration of ester and NaOH: Time (minutes): 0 5 15 25 35 Vol. of HCl (c.c.) 16.0 10.24 6.13 4.32 3.41 Show that reaction is of 2nd order. 22. A 1st order reaction has rate constant equal to 1.25 × 10–4 sec–1 at 298 K and 8.5 × 10–4 sec–1 at 318 K. Calculate the activation energy of the reaction. [Ans. 18, 050 Cal mol–1] 23. Two reactions: (i) A → Products, (ii) B → Products, follow first order kinetics. The rate of the reaction (i) is denoted when the temperature is raised from 300 K to 310 K. The half-life for this reaction at 310 K is 30 minutes. At the same temperature B decomposes twice as fast as A. If the energy of activation for the reaction (ii) is half that of reaction (i), calculate the rate of the reaction (ii) at 300 K. [Ans. 0.0327 min–1] 24. The activation energy for the reaction 2HI (g) mol–1 H2 (g) + I2 (g) is 209.5 kJ at 581 K. Calculate the fraction of molecules of reactants having energy equal to or greater than activation energy. [Ans. 1.462 × 10–19] 25. When log K (velocity constant for a reaction) was plotted against 1/t, the slope of the line was found to be – 5400 K. Calculate the energy of activation for this reaction (R = 8.314 JK–1 mol–1) [Ans. 103.4 kJ mol–1]

Catalyst
CATALYST
The Swedish chemist Berzelius in 1835 noticed that velocity of a number of reactions increased by the mere presence of a very small quantity of a foreign substance, which was not at all related to the reactants. Berzelius named the phenomenon of acceleration of the reaction as catalysis and the substance influencing the reaction, a catalyst. Since all reactions tend to attain equilibrium, it can be said that catalysts smoothen the passage towards equilibrium.

6

DEFINITION

A catalyst is a substance, not related to the reactants, influences the velocity of the reaction by not involving itself in the reaction. The phenomenon of influencing a reaction by a foreign substance is known as catalysis or ‘a catalyst is a substance which enhances the rate of reaction approaching equilibrium but without involving itself in the process’. A catalyst may also retard a chemical reaction. So the proper definition of a catalyst will be—a catalyst is a substance which alters the rate of a chemical reaction without involving itself in the reaction. (i) Positive catalysis or catalysis. A catalyst which increases the rate of a reaction is called a positive catalyst or a catalyst and the phenomenon is catalysis. (ii) Negative catalysis. The catalyst which retards the rate of a reaction is called a negative catalyst and the phenomenon is negative catalysis.

Examples of Catalysis
Positive Catalysis Reaction (i) (ii) (iii) (iv) 2KClO3 → 2KCl + 3O2 2H2O2 → 2H2O + O2 Catalyst MnO2 Pt Pt or V2O5 Fe H+ ion

(v) C12H22O11 + H2O → C6H12O6 + C6H12O6 Negative Catalysis Reaction (i) 2H2O2 → 2H2O + O2 (ii) 2H2 + O2 → 2H2O 137

2SO2 + O2 → 2SO3 N2 + 3H2 → 2NH3

Catalyst H2SO4 CO

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Characteristics of a Catalyst
(i) (ii) (iii) (iv) (v) A small amount is effective. Catalyst remains unaltered at the end of the reaction. Catalyst hastens the attainment of equilibrium. Catalyst has no influence on the point of equilibrium. Catalytic action is universal.

Highlights: • Catalyst undergoes no chemical change in a reaction. So it has no influence on the standard free energy change ∆G° i.e., on K, the equilibrium constant of the reaction as the two are related by – ∆G° = RT ln K. • So, the point of equilibrium is independent of the catalyst. • Catalyst only helps to attain the equilibrium rapidly. • Catalyst merely lowers the energy barrier (Ea) of a reaction. • So “a catalyst is a substance that makes a chemical reaction that could happen, but does not happen, happen”.

k1 , so if a catalyst changes k1, it will also change k2 in the same k2 proportion so that their ratio K remains unchanged. • This means if a catalyst accelerates the forward reaction, it also accelerates the backward reaction, it never increases the equilibrium yield.
• Since K =

Types of Catalysis
Catalysis

Homogeneous

Heterogeneous

There is a third type of catalysis in mainly biological systems. Those catalysts are termed Enzymes or Low catalysts.

Homogeneous Catalysis
In this type of catalytic reactions, the catalyst remains in the same phase with the reactants and is evenly distributed throughout the reaction phase. This type of catalytic reactions occur in gas or solution phase i.e., in one single phase. Examples of homogeneous catalysis in gas phase (a) NO in HNO3 vapour in the oxidation of SO2 (Chamber process) 2SO2(g) + O2(g) + [NO(g)] → 2SO3(g) + [NO(g)] (b) H2(g) + Cl2(g) + [moisture] → 2HCl(g) + [moisture] (c) NH3(g) + HCl(g) + [moisture] → NH4Cl(g) + [moisture] Examples of homogeneous catalysis in solution phase (a) Inversion of cane sugar C12H22O11 + H2O → C6H12O6 + C6H12O6 + [H+] (b) Decomposition of H2O2 in the presence of I
I− H+

–

2H2O2 → 2H2O + O2

CATALYST

139

Heterogeneous Catalysis
In this type of catalytic reactions, the catalyst forms a separate phase, usually a finely divided solid either as such or supported on an inert solid such as asbestos or gas (fluidised bed). This is usually termed contact catalysis. This type of catalysis has a great technical importance. Examples of Heterogeneous Catalysis: (a) (b) 2SO2(g) + O2(g) → 2SO3(g) N2(g) + 3H2(g) → 2NH3(g)
Fe( s) Pt( s)

(Pt-Catalyst) (Fe-Catalyst)

Activation energy and Catalysis reaction

According to collision theory: the molecules of reactants collide to give products. Schematically it is represented as follows:
+

Reactant molecules

Transition state

Product molecules
Uncatalysed reaction

Potential energy

Ea Ea ¢ Reactants

Catalysed reaction

Products Progress of reaction

Fig. 6.1 Progress of reaction.

The minimum amount of energy required to attain transition state is called energy of activation, Ea. Catalyst lowers the energy of activation (Ea) of a reaction.

Important Applications of Catalysts
Reactions (i) Dehydration (ii) Hydrolysis (iii) Oxidation Examples C2H5OH → C2H4 + H2O Vegetable oil + H2O → Fatty acid   + glycerol 2SO2 + O2 → 2SO3 C6H6 + O2 → Maleic anhydride C10H8 + O2 → Phthalic anhydride Oil + H2 → Vanaspati N2 + 3H2 → 2NH3 (Haber’s process) Alkene + H2 → Akane Catalyst used Alumina, Zirconia Twitchel’s reagent V2O5 Raney Ni Fe Ni, Pt, Pd (Contd.)

(iv) Hydrogenation

140
(v) Dehydrogenation C6H5C2H5 → C6H5CH = CH2 + H2 (Styrene) Friedel– Craft’s reaction C6H6 + RX → C6H5R + HX Normal paraffin → isoparaffin Long chain paraffin → branched chain alkanes Benzene + Cl2 → Chlorobenzene Ethene → Polythene Styrene → Polystyrene Vinyl chloride → PVC

ENGINEERING CHEMISTRY

Cr2O3/MoO3 Anhydrous AlCl3, BF3, HF Anhydrous AlCl3 Bauxite, MoO3 Fe or anhydrous FeCl3 Zeigler catalyst or Peroxides or Persalts

(vi) Alkylation (vii) Isomerisation (viii) Cracking (ix) Halogenation (x) Polymerisation

Phase Transfer Catalyst
This type of catalytic reaction may be considered as a combination of homogeneous and heterogeneous catalyses. If we take water and a non-aqueous solvent like benzene and if the reactants remain in the benzene phase and the catalyst in the water phase the reaction is accomplished at the interface provided a little surface active agent (detergent) is added to the system. This type of catalytic reaction is now widely used. Highlights: Two other types of catalytic reactions are to be noted. (i) Autocatalysis—Examples of such autocatalytic reaction are: (a) Hydrolysis of ester—water formed in the reaction catalyses the reaction. (b) Decolourisation of KMnO4 by oxalic acid. Mn+2 ion formed initially catalyses the reaction. (ii) Induced catalysis—Sodium arsenite solution is not generally oxidised by O2 but sodium sulphite is oxidised. If air is passed through a solution containing the two salts, both of them undergo simultaneous oxidation. This type of catalytic reaction is known as induced catalytic reaction.

Catalyst Poison
Certain foreign substances, when present in very trace amount, may damage the efficiency of the contact catalyst and may even destroy the catalytic activity. These substances are called catalyst poisons or anti-catalysts. As2O3 acts as a catalyst poison in the contact process for the manufacture of H2SO4. The poison acts very likely by blocking the active sites of the catalyst.

Catalyst Promoters
Promoters are the substances which promote the catalytic activity or enhance the activity of a catalyst by its presence. An important catalyst promoter is Al2O3 and alkali metal oxide, when used with iron in the Haber’s process, the catalytic action increases. Highlights: Characteristics of catalytic reactions: (i) Catalyst remains unchanged in mass and chemical composition at the end of the reaction. (ii) Always a small quantity of catalyst is required. (iii) A catalyst is more effective in a finely divided state.
(Contd.)

CATALYST

141

(iv) A catalyst is specific in its action. (v) A catalyst cannot initiate a reaction. (vi) A catalyst does not change the position of equilibrium but can only shorten the time required to attain the equilibrium.
A+B Reaction: A + B C+D

Catalytic reaction

Rate of reaction

Equilibrium

Without use of a catalyst C+D Time

Fig. 6.2 Effect of catalyst on time to attain equilibrium.

(vii) Change of temperature can alter the rate of a catalytic reaction as for a noncatalytic reaction.

Mechanism of Catalytic Reactions
The following two theories have been widely accepted: (i) Intermediate compound formation theory (ii) Adsorption theory. (i) Intermediate compound formation theory This theory explains the catalytic reaction due to the formation of an unstable intermediate compound which is more reactive compared to the reactants. The following examples can be given in support of the above theory: (a) NO2 acts as an oxygen carrier in Lead Chamber process. 2NO + O2 = 2NO2 ... fast SO2 + NO2 = SO3 + NO the net reaction being 2SO2 + O2 = 2SO3 (slow if uncatalysed) (b) The intermediate formation of ethyl hydrogen sulphate in the dehydration of alcohol by conc. H2SO4 to ether. (c) In Friedel–Craft reaction, anhydrous AlCl3 forms an intermediate compound with RCl and finally generates R+ for the reaction. RCl + AlCl3 → R ... AlCl 4
δ+ δ−

R+ + AlCl4– .

(ii) Adsorption theory (Heterogeneous catalysis) This theory mainly explains the mechanism of a catalytic reaction between two gases catalysed by a solid. Here, the catalyst works by adsorption of the gas molecule on its surface. The adsorption theory is compared to the intermediate compound formation theory. Here, the

142

ENGINEERING CHEMISTRY

intermediate compound is an activated complex formed on the catalyst surface. The adsorption theory can be explained by the following Fig. 6.3.
H H
H H

Ni

Ni

Ni

Ni

Ni

Ni

Ni

Ni

(a) Adsorption of H2 molecule
H C H H Ni C H Ni H H

(b) H–H bond weakened and broken by chemisorption
H H H Ni Ni C C H H H Ni Ni

+

Ni

Ni

(c) Formation of activated complex with ethene.

(d) The product ethane released from catalyst surface.

Fig. 6.3 (a), (b), (c) and (d).

Biochemical Catalysts (Enzymes)
Numerous organic reactions occur in the body of living beings, either plants or animals, to maintain the life processes. These reactions are catalysed by certain organic compounds which are known as biocatalysts or enzymes. Enzymes are invariably protein molecules. But not all protein molecules are enzymes. This statement can be explained by the fact that those protein molecules containing an active site are enzymes. The protein molecules, which do not contain those active sites cannot function as enzymes. It is assumed that enzymes act on a substrate to give products. The following figure explains the enzymatic activity: Enzymatic activity can be explained as: Enzyme + Substrate Enzyme – Substrate → Products + Enzyme The reaction is abbreviated as: E+S E – S → P + E. where E = enzyme, S = substrate (reactant), ES = activated complex, P = products. The reaction may be represented pictorially as follows (Fig. 6.4).
[activated complex]

S + ES [activated complex] E Active sites Products E +

Fig. 6.4 Illustration of the lock-and-key model of enzyme catalysis.

CATALYST

143

Examples of enzymatic reactions (i) Inversion of cane sugar C12H22O11 + H2O → C 6 H 12 O 6 + C6 H 12O 6
glucose Invertase

fructose

(ii) Fermentation C6H12O6 → 2 C2H5OH + 2CO2 (iii) (iv) Highlights: • Enzymatic reactions generally take place at 35°-45°C. • Enzymes lose their activity at higher temperatures. • Enzymes do not act in cold conditions. • Enzymatic activity is pH dependent. • For its full activity, enzyme needs help of another factor (compound) known as co-factor or co-enzyme. • Enzymatic reactions are generally dependent on the concentrations of enzymes. • Enzymatic reactions not at all depend on the concentration of the reactant i.e., substrate i.e., enzymatic reactions are zero order reactions. Amylose → Maltose
Amylase Zymase

1 Peroxidase H2O2 → H2O + O. 2 2

SHORT QUESTIONS AND ANSWERS
Q. 1. What is a catalyst? Ans. A catalyst is a substance that speeds up chemical reactions without changing itself. Q. 2. What is the effect of a catalyst on free energy change of a reaction? Ans. A catalyst cannot change the free energy change of a reaction. Q. 3. What is the effect of a catalyst on the equilibrium constant of a reaction? Ans. A catalyst does not alter the equilibrium constant of a reaction, it only shortens the time of attaining the equilibrium. Q. 4. Mention the effect of a catalyst on activation energy (Ea) of a reaction. Ans. A catalyst lowers the activation energy of a reaction. Q. 5. Draw a distribution curve showing how the proportion of molecules able to react increases when a catalyst lowers the activation energy.

144

ENGINEERING CHEMISTRY

Number of molecules with kinetic energy (E)

Activation energy with a catalyst Activation energy without a catalyst

Kinetic energy (E)

Fig. 6.5

Give experimental evidence that different catalyst has no influence on the yield of a reaction. Ans. It has been observed that at the same temperature the yield of SO3 is the same, whether the catalyst used be Pt, Fe2O3 or V2O5 . Q. 6. Give important uses of negative catalysts of technical importance. Ans. An important type of negative catalyst is termed anti-oxidants. Aromatic amines, thiourea, etc., are used as antioxidants for prolonging the life of rubber. Widest technical use of negative catalyst is TEL as ‘antiknock’ compound in motor fuel. n-propyl gallate, lentoxy anisole are added to retard the rancidity of oil. Q. 7. What is autocatalysis? Ans. When one of the products of a reaction itself acts as a catalyst for that reaction the phenomenon is called autocatalysis. Q. 8. Draw a graph for an autocatalytic reaction.

Completion of reaction

Rate of reaction

Sigmoid curve

Time

Fig. 6.6

Ans. In autocatalysis reaction as the catalytic product is gradually formed, the rate of reaction increases. The rate is maximum when the reaction is complete (Fig. 6.6). Q. 9. Why is the hydrolysis of ethyl acetate autocatalytic? Ans. As traces of moisture initiate the reaction, CH3COOH is formed acts as catalyst. CH3COOC2H5 + H2O → CH 3COOH + C2H5OH
catalyst

CATALYST

145

Q. 10. What are homogeneous and heterogeneous catalysts? Give examples. Ans. If the catalyst is in the same phase as the reactants, it is a homogeneous catalyst. If the catalyst is in a different phase, it is a heterogeneous catalyst. Example: (i) Homogeneous catalyst = Hydrolysis of ester, both acid and base catalysed. (ii) Heterogeneous catalyst (contact catalyst) = In Haber’s process for manufacture of ammonia (Fe + Al2O3 + K2O). Q. 11. What are enzymes? Ans. Enzymes are proteins in nature and are the catalysts for biochemical reactions. Q. 12. Do you know any use of enzymes in detergent? Ans. Some washing powders contain proteases—enzymes that remove blood stains on dirty clothes. Q. 13. Mention the main characteristics of an enzyme. Ans. Enzymes are highly specific. Each enzyme catalyses a particular reaction. Every enzyme has an ‘active site’, that is, just right shape and size for the substrate molecules. Each enzyme works best at a particular temperature and pH.

CATALYTIC APPLICATIONS OF ORGANOMETALLIC COMPLEXES
Effective Atomic Number (E.A.N.)
To explain the formation of a complex of a metal with a ligand, it was suggested by Sidgwick that metal ions will tend to accept the electron pairs from donors, i.e., ligand until they have obtained a sufficient number of electrons, so that a metal ion in the resulting complex has an effective atomic number of the nearest inert gas. This rule will help to understand the formation of a complex which in turn will lead to get a better explanation of complex compounds acting as catalysts in various reactions. So, the effective atomic number (E.A.N.) of a metal is obtained by deducting the number of electrons lost in the metal ion formation, then adding the number of electrons gained by coordination i.e., two electrons from each ligand having one co-ordination centre. The rule can be exemplified by the following table:
E.A.N. Determination Metal ion Fe2+ Co3+ Cu+ Ni2+ Atomic no. of metal 26 27 29 28 Co-ordination number 6 6 4 4 Electrons lost in ion formation 2 3 1 2 Electrons added by co-ordination 12 12 8 8 E.A.N. 36 (Kr) 36 (Kr) 36 (Kr) 34 (Se)

The 18-electron Rule
This is another way of expressing noble gas electron number rule i.e., effective atomic number rule regarding complex formation. The statement of 18-electron rule is that the valence shell of metal atom will attain 18 electrons by saturation of (n – 1) d, ns and np orbitals of metals by the ligands. Thus, the saturation will occur as follows: 10 (for (n – 1) d subshell) + 2 (for ns subshell) + 6 (for np subshell) = 18 electrons.

146 To illustrate, let us cite the following examples:
Compounds Central metal atom with oxidation number Ni(0) Electronic configuration of the central metal of (n–1) d subshell 3d10

ENGINEERING CHEMISTRY

No. of electrons donated by ligands 2 × 4 (four CO groups) = 8

Total no. of electrons in (n – 1) d, ns and np levels 10 + 8 = 18 electron valence shell configuration 8 + 10 = 18 electron valence shell configuration

(i) Ni (CO)4

(ii) Fe(CO)5

Fe(0)

3d8

2 × 5 (five CO groups) = 10

The attainment of 18 electrons in the valence shell of the metal atom or satisfying 18electron rule is one of the useful criteria of elucidating the structure of metal carbonyls. Structure and bonding in organometallic complexes, the 16-and 18-electrons rule: The role of metals in catalytic cycles during some chemical reactions: • Hydrogenation using (Ph3P)3RhCl The hydrogenation of unsaturated organic compounds i.e., mostly alkenes is an important industrial reaction. Almost all large scale hydrogenation processes are carried out using Raney Ni as catalyst, which acts heterogeneously. Homogeneous systems are used for pharmaceutical industries. Organometallic chemists made the process very popular. The hydrogenations of alkenes and alkynes have been studied extensively. (Ph3P)3 RhCl, which is generally known as Willkinson’s catalyst, acts as a homogeneous catalyst for the hydrogenation of alkenes and alkynes. The catalyst is not able to reduce other organic functional groups, though it is a very reactive compound. It is dissociated (only 5%) into 14 electron species in pure solvents, thus: (Ph3P)3 RhCl (Ph3P)2RhCl + PPh3 The species (Ph3P)2 RhCl is of low coordinating power. The action of the Willkinson’s catalyst is represented by the following cycle. In the cycle there are four co-ordination compounds (II – V). The 14-electron species (II) is formed by dissociation of phosphene ligand from (I). The structure (II) is seen to possess a vacant coordination site shown by a square. This is because stable Rh(I) complexes are generally four coordinated (16-electron species). The 14-electron species (II) which takes two hydrogen atoms to give (III) by oxidative addition (III) is still unsaturated and has a vacant site, so it can readily accept π electrons from the alkene to give (IV). The stage IV is very very significant in the overall hydrogenation process as in this stage, the substrates alkene, hydrogen are now bonded to the same metal atom. Next step is the rearrangement of the coordination site to give V. (V) undergoes reductive elimination to release the alkane and regenerate the 14-electron species.

CATALYST

147
L3RhCl (I) L+ L Rh Cl C—C H H 14e (II) –L L H2 addition of H2

L

H Rh

H

Cl L H Rh Cl 16e (V) Cl C C 18e (IV) L L H Rh L PH3P = L Vacant site = H C—CH 16e (III)

L

C—C

Fig. 6.7 Catalytic applications of organometallics.

Highlights: • Oxidative addition refers to the increase in coordination site of the central metal. • Reductive elimination refers to the decrease in coordination site of the central metal. • Hydroformylation The reaction of an alkene with synthesis gas i.e., mixture of carbon monoxide and hydrogen (CO + H2) to produce an aldehyde, is known as hydroformylation. The reaction, which takes place in presence of a catalyst is as follows: R.CH=CH2 + CO + H2 → RCH2CH2CHO + R CH— CH 3 | CHO Several transition metal compounds are used as catalyst in hydroformylation. But among them, catalysis by cobalt or rhodium compounds is of interest. Industrially cobalt carbonyl is used as catalyst at 130° – 170°C and under 200 – 300 atm pressure. As this needs high pressure reactor the initial installation cost of the plant is high for an industrial process.
Catalyst

Define with illustrations: (i) catalysis. Write notes on: (i) Adsorption theory of catalysis. (iii) negative catalysis. How does a catalyst accelerate the speed of a reaction? Explain with proper energy profile diagram.8 EXERCISES 1. (ii) Enzyme catalysis. 9. 3. 2. 4. 5. 6.”—explain. What will be a more effective catalyst—platinum as a lump or finely divided platinum? Give reason. although it shortens the time required to establish the equilibrium. (ii) positive catalysis. What do you mean by (i) homogeneous and (ii) heterogeneous catalytic reactions? What are catalyst poisons and promoters? Discuss a few important catalytic processes. 8. “A catalyst doesn’t affect the final state of equilibrium. 1 Co2(CO)8 2 – 1 H2 + 1 H2 2 2 HCo(CO)4 RCH2CH2CHO + CO – CO RCH = CH2 Insertion of alkene into Co—H HCo(CO)3 Hydrogenolysis of Co-acyl RCH2CH2Co(CO)3 CO RCH2CH2CCo(CO)3 O RCH2CH2Co(CO)4 O Insertion of —C into Co-alkyl Fig. 6.148 ENGINEERING CHEMISTRY The mechanism of hydroformylation using cobalt carbonyl as catalyst is shown in the scheme. 7. Give a brief account of the various theories of the mechanism of catalysis. .

mentioning the specific catalyst used. Discuss with suitable mechanisms—the processes of hydrogenation and hydroformylation. 12. 17.CATALYST 149 10. 13. 16. . Write an account of the kinetics of heterogeneous catalytic reaction. (iii) Phase transfer catalysis. (ii) Specificity of catalytic action. 11. Write briefly on acid-base catalysis. 15. What are the chief criteria of catalysis? Describe four applications of catalysis. Write notes on: (i) Hydrogenation catalysts and oxidation catalysts and their application in India. Write short notes on: (i) Effective atomic number (ii) 18-electron rule. 14. Give one example of an industrially important catalytic reaction. (ii) Catalyst and energy of activation. Write notes on: (i) Catalyst and equilibrium point.

If the bond is between two atoms of unequal electronegativities. This inductive effect has a great influence on the character of organic compounds as well as on organic reactions. If the bond is between two same atoms. As for example. i. the bond between carbon and chlorine is polarised and the bonding electron is displaced towards chlorine atom as follows: – Inductive Effect As a result of the displacement of the bonding electrons between C—Cl. For example. 150 . +++δ. which has been indicated by +δ.55 × 10–3) molecule becomes much easier than that of acetic acid (Ka = 1.85 × 10–5).. Rearrangement In organic compounds.Mechanism of Organic Reactions REACTION TYPES Types of organic reactions may be depicted as follows: Organic reactions 7 1. ++δ. The inductive effect is seen to exist upto third carbon atom from the electronegative atom in the chain +++d ++d 3 2 C®C®C®Cl 1 +d –d But the charge on the carbon atoms gradually decreases.e. This phenomenon is explained as follows: Due to inductive effect of chlorine atom the release of proton from chloroacetic acid (Ka = 1. And in this condition the bond is said to be polarised. in methyl chloride. Elimination 4. It will depend on the elctronegativity values of the two atoms. chloroacetic acid is more acidic than acetic acid. etc. One covalent bond is made of a pair of electrons. of the same electronegativities. Addition 3. And this effect is permanent. This sort of bond polarisation due to the presence of electronegative element like chlorine is known as inductive effect. the carbon atom is attached to other atoms by covalency. then the influence of the atoms on the bond is not the same. Substitution 2. then the influence of the atoms on the bond is same. and acquires ionic character. carbon atom acquires a small positive charge and the chlorine atom acquires a small negative charge. The displacement of the bonding electrons will be towards the atom of greater electronegativity.

Due to (+I) effect of CH3 group. H (c) heterolytic bond breaking (b) heterolytic bond breaking This type of bond breakings give rise to free radicals as well as carbocations (C+) and carbanions (C–). It is an example of (+I) effect.. Sometimes non-polar covalent molecules like bromine get polarised under the influence of double bond. Free radicals are generated due to homolytic fission and carbocations and carbanions are generated due to heterolytic fission of the bond. If an organic molecule contains a double bond. O   CH3→ C →O→H O   H— C ←O←H Another phenomenon is worthwhile to mention. then the π electrons are transferred completely to one of the bonded atoms under the influence of attacking reagents. electron displacement by repulsion is known as (+I) effect. This sort of polarisation effect is the cause of many organic reactions. The bond break-up may be homolytic or heterolytic. This effect is temporary and is known as electromeric effect.MECHANISM OF ORGANIC REACTIONS 151 H O    Cl  C  C  O – + H +  H O H    Cl ← C ← C ← O ← H  H An example of (–I) effect The electronegativity scale is represented as follows: NO2 > F > COOH > Cl > Br > I > OH > OCH3 The electron displacement due to electronegative atom is known as (–I) effect. a) the mechanism of the : : HA H . CH3COOH is weaker acid than HCOOH. Homolytic and Heterolytic Fissions of a Bond During the occurrence of an organic reaction there is always a bond breaking and a bond making process. on the contrary. When the reaction takes place through free radical formation (Fig. HA + + – C :: C C ¾C + – A C ¾C The effect is generally represented by a bend arrow. So organic reactions can take place through free radical formation or through the formation of carbocations and carbanions. . Electron repulsion of the bonding electrons by the CH3 group in acetic acid molecule makes H+ release comparatively difficult. C .H (a) homolytic bond breaking C H C .

. substitution of methane takes place through free radical mechanism. i. . (iii) Termination: R C C n C . Br–. i. nucleophiles mean nucleus seeking. . (RCO2)2 → 2R CO2 → 2 R + 2CO2     . Nucleophiles may be negatively charged or a neutral molecule having an atom with a lone pair of electrons. Nucleophiles Electrophiles (a) OH–. CH 3 + Cl 2 → CH 3Cl + Cl . Electrophiles or electrophilic reagents 2.e. CH 3 + CH 3 → CH 3 7 Propagation step 8 9 7 Termination step 8 – CH 9 3 Initiation step Polymerisation reactions also take place through free radical mechanism. That means electrophiles are positively charged species. C + nC C R C C n C C . b and c above) the mechanism is known as ionic mechanism. Cl–. When the reaction takes place through the formation of an ion (Figs. (b) Halogen and halogen acids. . Classification of Reagents The reagents which take part in ionic reactions are categorised as: 1. C C + (RCO2)2 Catalyst Monomer R C C n C C. (i) Initiation: . . CN–. I– (b) Double and triple bonds of alkenes and alkynes. On the contrary. these reagents attack at the point of highest electron density of a molecule. they attack at the positive centre of a polarised molecule. . (a) H+ and other positive ions. C +R R C C n C C R There are other ways of termination of a polymerisation reaction. . So it is a free radical substitution reaction.152 ENGINEERING CHEMISTRY reaction is called free radical mechanism. Free Radical Mechanism The chlorination of methane. R + C = C → R  C  C• (free radical)     (ii) Propagation: R C ..e. Nucleophiles or nucleophilic reagents Electrophiles mean electron seeking. Cl + CH 4 → HCl + CH 3 . It is represented as follows: Cl2 → 2Cl• heat or hν . Cl + Cl → Cl 2 .e. i..

7. R3N:.MECHANISM OF ORGANIC REACTIONS 153 (c) Compounds containing an atom with (c) H2SO4. (d) R2O:. Nucleophilic reactions Again electrophilic reactions may be of the two types viz. Reaction: CH4 + Cl ¾® CH3 + HCl Progress of reaction (one-step process) . AlCl3. If we take chlorination of methane for example. etc. electron pair acceptors and nucleophiles are Lewis bases i. electron pair donors. Electrophilic reactions 2. :NH3 . HNO3. Conventionally. BF3. And so is the case with nucleophilic reactions. HNO2. Fig. etc. the reaction is called electrophilic reaction and when the attacking reagent is a nucleophile. the reaction is called nucleophilic reaction.e. And the reactions of electrophiles and nucleophiles may be considered as neutralisation reactions. The methane molecules must collide with chlorine molecules. a lone pair. DH = 1 Kcal .1 Potential energy changes during progress of reaction: (One-step process) an exothermic reaction. The minimum amount of energy that must be provided by a collision for reaction to occur is called the energy of activation (Eact). Some common ionic organic reactions are: • Electrophilic addition • Electrophilic substitution • Nucleophilic addition • Nucleophilic substitution and • Elimination reaction Energy Changes during the Progress of a Reaction Energy is needed to break a bond and energy is released while making a bond. Classification of Reactions Broadly.1). Another type of reaction is very common in organic chemistry which is known as elimination reaction. (d) NO2.e. That means electrophiles are Lewis acids i. etc. . Eact = 4 Kcal Potential energy CH4 + Cl . the reactions may be classified as follows: 1. The potential energy at any stage of the reaction is indicated by the height of the curve (see Fig. addition and substitution. if the attacking reagent be an electrophile... The source of Eact is the kinetic energy of moving molecules. nucleophiles donate an electron pair and the electrophiles accept it and makes a bond. CH3 + HCl . 7.

S1 T. Electrophilic addition. Step 1. .154 Examples: ENGINEERING CHEMISTRY 1.H + NO2 Ar .) (I) Potential energy diagram for nitration T. Electrophilic substitution takes place in three steps.S. NO2 + H Progress of reaction (Two-step process) + + T.S. Bromine molecule gets polarised when comes in close contact with a π bond. Formation of a transition state: (+) (+) NO2 H NO2 Transition state (T. Electrophilic substitution. that carbocation gets attached to the Br– generated. Nitration of benzene is an example of electrophilic substitution. The positive bromine ion then gets attached to a carbon atom attached to a double bond making other carbon atom of the double bond a carbocation. Thus addition of a bromine molecule takes place to a double bond: CH 2 Br CH 2 Br δ +   +  →   + CH 2 Br CH 2 Br δ – H H C C d+ H H d– H H C + C Br H H + Br (–) H H Br C C Br H H Br ¾ Br The addition of HBr to ethylene is also an example of electrophilic addition: CH 2 CH 2   + H  Br →   + H δ +  Br δ– CH 2 CH 2 H H C C d+ H H d– H H C + C H H H + Br – H H Br C C H H H H ¾ Br 2.S2 Potential energy + H NO2 Ar. Generation of an electrophile: HNO3 + 2H2SO4 2HSO4– + H2O+ + +NO2 Step 2.

the transition state readily goes to the stable aromatic form by releasing a proton and the release of the proton is helped by generated HSO4–. So hydrolysis of alkyl halide is an example of nucleophilic substitution. CH3 CH3 CH3 C Cl Slow H 3C H3C H3C C + Cl + – Tertiary butyl carbocation Tertiary butyl carbocation is stable due to the (+I) effect of the methyl groups. Nucleophilic attack on the carbon atom of C—X bond in a haloalkane or alkyl halide. Here the rate equation is rate = K [alkyl halide] . That is why. Here the attack of nucleophile (CN–) occurs on a carbonyl carbon leading to an addition reaction. The carbonyl group of the ketone polarises HCN and the addition takes place as follows: (a) (b) Here after the attack of the electrophile the stable aromatic system is disturbed. H3C H 3C H3C C + OH + – Fast H3C H 3C H3C C OH Step 2. leads to substitution. Br or I. Back to aromaticity from the transition state (I). Then the nucleophile OH– attacks and forms a new bond. Nucleophilic addition. Ionisation of the alkyl halides i. Nucleophilic substitution. R R R R C C d+ O O d– R R C d+ O d– R d+ CN H 4. The rate equation is: rate = K[C(CH3)3Cl] Step 1. Addition of HCN to a ketone is an example of nucleophilic addition. (b) SN2 reaction: This is a one-step process.. Study of the rate equations of the reactions suggests that there are two different mechanisms: d– R C O (–) CN +H + R R C OH CN (a) Nucleophilic substitution unimolecular (SN1) (b) Nucleophilic substitution bimolecular (SN2).e. RX. the base during reaction. (a) SN1 reaction.e. formation of a carbocation intermediate by breaking of C—Cl bond..MECHANISM OF ORGANIC REACTIONS 155 Setp 3. This is a two-step process. this step is slow. (+) NO2 H – + HSO4 NO2 + H2SO4 3. [OH–] . where X = Cl. This step is rate determining step of the substitution i.

C Å C H :B Fast C C + H:B (b) E2 reaction. X HO C+X – Here the mechanism shows that C—X bond breaks as the nucleophile OH– forms a new bond with carbon simultaneously. C C H Slow X – + C + C H A carbocation Step 2. Br Example 1. H H OH H     Conc. (a) E1 reaction. Elimination reaction.156 ENGINEERING CHEMISTRY The mechanism of the substitution can be represented as follows: – OH + C X HO C T. The elimination reaction is of two types and they are base catalysed elimination reactions: (a) Unimolecular reaction (E1) (b) Bimolecular reaction (E2).S. C C + KOH (alcoholic) C C + KBr + H2O H Elimination of a hydrogen halide from an alkyl halide produces alkene. This is a reaction that splits off a simple compound from a molecule to form a double bond. H 2SO 4 H  C  C  C  H → H  C — C  C  H Heat (– H 2O)       H H H H H H . This reaction occurs in one step process X C C H :B X + – C C + H:B Another example of elimination reaction is the removal of water from an alcohol to form an alkene. This reaction occurs in two steps: X Step 1.

The primary conditions for drawing the resonating structures are: (a) Position of atoms in the molecule cannot be changed and the molecule should be planar. The difference in energy of any of the contributing structures and the hybrid structure is called the resonance energy (Fig. The resonance hybrid structure is more stable than any of the contributing structures. 1.39 Å instead of 1. 7. (b) Position of σ-bonds cannot be changed.2). Whenever a molecule can be represented by two or more structures that differ only in the arrangement of electrons the different structures arrived at have the same arrangement of atomic nuclei. The Kekule structure is still the accepted structure for benzene. 3. Despite having three double bonds benzene undergoes substitution reactions more easily than addition reactions. Each of these drawn structures contributes to the resonance hybrid (Fig. (c) Only π electrons and non-bonded electrons can be shifted. That theory is the concept of resonance.54 Å for a single bond and 1. All the C—C bond lengths in benzene is 1.34 Å for a C==C bond. So the idea needs to be discussed here: According to Kekule the benzene molecule has following two structures (I) and (II).2). This acceptance is not for the discovery of new facts about benzene but is a result of modification of the structural theory. there is resonance. Benzene is more stable than expected. Then all the structures so drawn are the structures of the molecule concerned and none of these structures can staisfactorily explain all the properties of the molecule but a hybrid of all these structures which cannot be represented by any one of them is the actual structure of the molecule.MECHANISM OF ORGANIC REACTIONS 157 This is an example of acid catalysed elimination reaction. 7. . (I) (II) The structures (I) and (II) cannot satisfactorily explain all the properties of benzene. 2. Thus H H C H OH H C H C H H ¾¾¾® H+ H H C H + H OH H C C H H ¾¾¾® – H2 O H H C H C + H C H H H H H ¾¾¾® H C H C H C H H Resonance The idea of resonance has a major role in understanding the mechanisms of reactions.

Hyperconjugation (No bond resonance) The stabilities of tertiary. Kekule structures. 4.2 Kcal (calc) (obs) Cyclohexane Cyclohexene + H2 28.e.. the odd electron and the bond pair of the C—H bond.158 ENGINEERING CHEMISTRY Graphical representation of the idea of resonance from the heats of hydrogenation values.e. For this overlapping.e. (ii) The resonance hybrid structure of benzene contains no single or double bond but a special type of bond that is why all C—C bonds in benzene are equal in length..e.2 Stability of benzene (Resonance energy).8 Kcal/mol but actually it is 49. benzene to be 85. the three electrones i. Sign of resonance Resonance energy 36 Kcal Cyclohexatriene + 3H2 (Resonating structures) Benzene + 3H2 (Resonance hybrid structure) Cyclohexadiene + 2H2 Potential energy 49. But it is apparent that the C—H bond is something less than a single bond and the odd electron is partly accommodated by the H atoms. o–groups in 2. the hyperconjugation may be represented as follows: .6 (obs) Fig.4 Kcal 57.8 Kcal (calc) 55.8 Kcal/mole. H H H H H H H H Each of the above no-bond resonance structures appears strange. That is. In terms of resonance. benzene is more stable by 36 Kcal/mole than expected which is resonance energy of benzene. ←→ H • C — C ←→ H  C — C ←→ H  C — C         . help to bind together the three nuclei i. 4..8 Kcal (obs) 85. This type of delocalisation involving σ-orbital is known as hyperconjugation.. 7. . 6-tribromoaniline does not. this additional stability possessed by benzene is responsible for substitution reactions of benzene and for a new set of properties called aromatic properties or aromaticity. Steric Hindrance Aniline reacts to form anil with benzaldehyde but 2. secondary and primary alkyl radicals is due to delocalisation of odd electrons through overlapping of the p orbital occupied by the odd electron and the σ-orbital of the alkyl group.e. Explanation (i) We should expect from the graph that the heat of hydrogenation of cyclohexatriene i. two carbons and one hydrogen.. Victor Meyer attempted to explain these abnormalities by steric hindrance i. (iii) As a resonance hybrid benzene is more stable than either of the contributing resonating structures i. H H H H H H H H        H  C  C.

The effect of steric hindrance requires a knowledge of reaction mechanism. the geometry of both the initial molecule and the transition state. consequently..) 1.S. 2-shift A carbonium ion (Carbocation) is formed during a reaction and and rearranges to form a stable carbonium ion (Carbocation) as for example CH3 Å CH3 .. tending to shield the molecule from the attacking reagent benzaldehyde. H C . it does so via transition state. CH2 . R (A hydride shift) C Å C C C Å (An alkyl shift) R (1. SN1 reactions will not be affected by the influence of steric hindrance whereas SN2 reactions are very much affected by steric hindrance. 2-shift.From the foregoing discussion we can say. state of hybridisation at the attacked C-atom changes sometimes and the effect of steric hindrance becomes pronounced in T. When a chemical reaction occurs. In an SN2 reaction: Nu .. These are the rearrangements in which the migrating group moves from one atom to the neighbouring next atom. C X Nu C X Nu C+X – The transition state accommodates more atoms than the initial state. 2-shifts) . + C .MECHANISM OF ORGANIC REACTIONS 159 6-tribromoaniline mechanically interfere the attack by the reagent i.... This shift is very much important in understanding organic reactions. Also. Crowded transition state (T. R C Å C H C + C Å C . The term spatial factor is used to denote steric hindrance.S.e. H C . CH3 Tertiary (3°) carbocation Å (Rearrangement) H Primary (1°) carbocation This type rearrangement takes place by migration of a hydrogen atom with a pair of electrons known as a hydride shift or an alkyl group with a pair of electrons known as alkyl shift or 1. C¾CH2 CH3 CH3 . C . NH2 + OCH NH = CH Anil Br Br Br NH2 + OCH NO reaction The term steric hindrance originally considers the geometry of the molecule. CH2 .

CH2 .) . Structural isomerism may be classified as: (a) Chain isomerism (b) Functional group isomerism (c) Position isomerism (d) Metamerism. CH 2 . Cl 1-chloropropane (Contd.160 ENGINEERING CHEMISTRY Isomerism Different organic compounds having the same molecular formula are known as isomers.CH 2 . The phenomenon is known as isomerism.CHO Propanaldehyde (ii) CH3COCH 3 (ii) CH3— CH —CH3  OH isopropylalcohol (ii) CH3— CH —CH3  Cl 2-chloropropane (c) Position isomerism (i) C3H8O (i) CH3CH2CH2OH n-propylalcohol (ii) C 3H7Cl (i) CH 3 . Examples are displayed in the following table. The isomerism is of two types: (i) Structural isomerism (ii) Stereoisomerism. Types of isomerism (a) Chain isomerism Molecular formula (i) Butane [C4H10] Different structures (Compounds) (i) CH3 — CH 2 —CH 2  CH 3 (ii) CH 3  CH  CH 3 n-butane  CH 3 Isobutane (ii) Pentane [C5H12] (i) CH 3—CH2—CH2—CH3 n-pentane CH3  (ii) CH3— CH —CH2—CH3 Isopentane CH3  (iii) CH3  C  CH3  CH3 Neopentane (b) Functional group isomerism (i) C2H6O (ii) C3H6O (i) CH 3CH 2OH ethyl alcohol (ii) CH3—O—CH3 dimethyl ether acetone (i) CH3.

4(b). CH3 C H H C CH3 H CH3 C H H C CH3 CH3 H CH3 Fig.3 The groups at the end of a single C—C bond can rotate freely relative to each other giving rise to different conformations of molecules. 7. The two conformers of ethane are given in Fig. 7.4 (a) Newman projection formula for ethane. The topic has been treated later on. The rotation about C2—C3 bond of n-butane gives different conformers as depicted in Fig. 7. CH3¾CH2CH2CH3 4 3 2 1 (n-butane) . The lack of rotation about double bonds gives rise to geometric isomerism. 7. They are known as ‘skew’ or ‘Gauche’ forms.OH (ii) OH para- (d) Metamerism (isomerism in the same class of organic compounds) (i) C4H10O (i) C2H5—O—C2H5 diethyl ether (ii) CH 3—O—C3H7 methyl n-propyl ether (iii) CH 3 O CH CH3 CH3 Methyl isopropyl ether Bond rotation (Fig. 7. Conformational Isomerism The different spatial arrangements arising out of the rotation of a C—C single bond are known as conformations. Eclipsed form (I) Anti form or staggered form (II) Fig.MECHANISM OF ORGANIC REACTIONS 161 OH OH OH OH (iii) C6H9(OH)2 (i) ortho- (ii) meta. There are many other conformers between these two extremes.4(a).3) is possible about single covalent bonds but is prevented under normal conditions by double bonds or triple bonds. The different structures obtained due to the rotation of this C—C single bond are known as conformers.

1 Kcal 3.. 7. • Any pair of tetrahedral carbon attached to each other tend to have their bonds staggered (i. In two Gauche conformations.4 (c) Conformers of cyclohexane.. ethane-like). Conformations of Cyclohexane Factors influencing the stability of conformations: To go deep into the chemistry i.5 Kcal Potential energy 0. . And the result can be either destabilisation or stabilisation of the conformation. the —CH3-groups are 60° apart and they are less stable than the anti-form and more stable than the eclipsed form. we must take help of conformational analysis. the stability of the cyclic compound and its reactivity. 7..e. 7.4(c)].4 (b) Potential energy changes during rotation about C2—C3 bond of n-butane. • Any deviations from the normal. In the case of cyclohexane the following conformations are common [Fig. the eclipsed conformation is least stable due to severe crowding.e. i. 180°). we see that the anti-conformation of n-butane is more stable (CH3-groups are as apart as possible. sp3 hybridised carbon (bond angle 109. Any deviation from the staggered conformation is accompanied by torsional strain.9 Kcal CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 Anti CH3 Gauche Angle of rotation Eclipsed Gauche Fig.e.5°) are accompanied by angle strain.162 ENGINEERING CHEMISTRY 4. This nonbonded interaction can either be repulsive or attractive. HA HB HA HB HA HB Chair Conformer Twist Conformer Boat Conformer Fig. • Any two atoms or groups that are not bonded to each other can interact. From the potential energy diagram.4–6.

5). 7.4 (e) The boat conformation is less stable than the chair conformation at an energy maximum. The half chair form is a most unstable form which lies at energy maximum (see Fig. it is thus not a conformer but a transition state between two conformers.4(e).4(d)]: Fig. Here the three pairs of tetrahedral carbon of cyclohexane remain in staggered forms. Between the chair form and twist form there are half chair forms with angle strain and torsional strain. For boat cyclohexane the Newman projection formula is as Fig. 7.4 (d ) Cyclohexane (chair form) staggered form of ethane. So the chair cyclohexane is more stable conformer of the cyclohexanes. 7.5 Potential energy diagram (conformations of cyclohexane). 1. The twist form or skew boat form is a conformer lying at energy minimum.MECHANISM OF ORGANIC REACTIONS 163 Newman projection formula of chair conformer [Fig. Here the three pairs of tetrahedral carbon of cyclohexane remain in eclipsed forms.6 Kcal Chair form Half chair Twist form Boat form Twist form Fig. . 7.3 Kcal Potential energy 11 Kcal 5. 7. 7. Cyclohexane (boat form) Eclipsed ethane Fig.

This part of the science. which deals with structures in three dimensions is called stereochemistry. Polarized light is a light beam in which all the waves are vibrating in the same plane. Asymmetric molecules are chiral and can exist in distinct mirror image forms. (i) Optical isomerism. giving rise to optical isomerism. CH3 Two optical isomers of lactic acid (Fig. Light is plane-polarized after passing through a sheet of Polaroid.7 Two configurations of lactic acid. Optical isomers rotate the plane of polarized light (Fig. 7. 7. Generally.7). The two general types of stereoisomerism are: (i) Optical isomerism and (ii) Geometrical isomerism.6). 7. axes or planes of symmetry.Optical isomers rotate the plane of polarised light. Since conformational isomers differ from each other only in this way. Ordinary light Polarizer Planepolarized light Fig. Optical isomerism is shown by the compound containing at least one chiral carbon atom (asymmetric). Simple test of determining chirality of a three dimensional molecule is non-superimpossibility of its mirror images (Fig. Any carbon atom with four different groups or atoms attached to it is asymmetric.7) are molecules with no centers. a chiral carbon atom is one that is attached to four different atoms or groups. Mirror COOH COOH H OH HO H CH3 Fig.6 Arrangement for producing plane polarized light.164 ENGINEERING CHEMISTRY Stereoisomerism Isomers that differ with respect to the arrangements of atoms or groups in space are known as stereoisomers and the phenomenon is known as stereoisomerism. 7. that their atoms are oriented is space. 7. they also belong to the stereoisomers. .

where n = number of chiral carbon atoms in the molecule. The two configurations of lactic acid rotate plane of polarised light in the same degrees but in the opposite directions. . the stereoisomers (I) and (II).8 (a) The mirror image forms of lactic acid. CH3 H Cl C2H5 (I) Cl H Cl H C2H5 (II) CH3 H Cl H H C2H5 (III) CH3 Cl Cl Cl Cl C2H5 (IV) CH3 H H Fig. 3-Dichloropentane.6) either right or left.8 (c) Stereoisomers of 2. 7.MECHANISM OF ORGANIC REACTIONS 165 H C H C HO2C OH CH3 H3C HO CO2H Mirror Fig.8 (b) Then the test of chirality is very simple. 7. Asymmetric Molecules If we translate the three-dimensional molecule to a two-dimensional figure. COOH COOH H OH HO H CH3 D(–)-Lactic acid mirror CH3 L(+)-Lactic acid Fig. we get Fischer projection formula of the molecule. If we rotate Fischer projection formula of one molecule on the plane of the paper by 180° none of the configurations arrived at which is superimpossible on the other. These types of molecules rotate plane of polarised light (see Fig. (I) and (III). (III) and (IV) are pairs of enantiomers. These two forms of stereoisomers (configurations) are known as enantiomers. 7. (II) and (IV) are diastereomers. For compound containing two different chiral carbon atoms. Highlights: • Number of possible stereoisomers = 2n. The prefix (±) is used to designate the racemic mixture. They can be separated by various physical and chemical methods. • A mixture of equal parts of enantiomers is called racemic modification. 7.

. Lower part of the molecule is mirror image of the upper part of the molecule and the molecule becomes optically inactive due to internal compensation. 7. There are certain methods of assigning R-S notations to any chiral centre of a molecule. based on ‘sequence rule’. • Then the molecule is viewed from the position far from the lowest priority group and a hypothetical path is drawn moving from 1 → 2 → 3 or a → b → c. the configuration is known as trans isomers (E-isomers). 7. d. such that 1 → 2 → 3 → 4 or a → b → c → d. When similar groups are attached to the same side of the molecule.8 (e) R-S System of Nomenclature R-S system of nomenclature was developed by Cahn. etc. 2.166 ENGINEERING CHEMISTRY Stereoisomers which are not pairs of enantiomers are known as diastereomers. 4 or a.8(e)]. The geometrical isomerism is also a case of diastereoisomerism [Fig. then the stereocentre is designated to have ‘R’ configuration. If the path describes a counter clockwise or anticlockwise path.8(d)]. CH3 H H CH3 Cl Cl Fig. c. 7. Another interesting phenomenon arises among the compounds containing similar chiral carbon atoms [Fig. H3C C H cis-2-butene (Z-2-butene) CH3 C H H C CH3 C CH3 H Trans-2-butene (E-2-butene) Fig. Geometrical Isomerism This type of isomerism arises out of restricted rotation about C = C bond. The system is often termed as “absolute configuration” assignment as this type of specifying configuration is independent of any reference compound. This type of isomer is known as mesoform. If the path provides a clockwise motion. These are as follows: • The number of stereocentres in the molecule are identified. b. then the stereocentre is said to have ‘S’ configuration [Fig.9]. • The four different groups (ligands) attached to each of the stereocentres are found out and given priority 1. When similar groups are attached or the opposite side of the C = C bond. 3. 7. the configuration is known as cis-isomers (Z-isomers). The (R) or (S) designation is written in italics within the parentheses followed by a hyphen before the name of the compound.8 (d) Optically inactive isomer (meso form). Ingold and Prelog to designate the configurations of stereoisomers having chiral centres. 7.

in the case of —CH2NH2 and —CH2CH3 . H. latter. in 1-bromo-1-chloroethane (CH3CHClBr). • When the preferences cannot be determined on the basis of the atomic number of the atoms directly attached to the chiral carbon. Br. C H H but in the case of H C H H .e.. So. the four ligands attached to the central chiral centre are CH3.MECHANISM OF ORGANIC REACTIONS 167 1 4 C 2 1 4 C 2 3 3 C 3 4 C 3 1 1 2 4 2 1 ® 2 ® 3 anticlockwise (S)–Configuration 1 ® 2 ® 3 clockwise (R)–Configuration Fig. H. Among these. The priorities are then determined at the first point of difference. the chiral centre is attached to CH3. the atomic numbers of next sets of atoms in the unassigned groups are taken into consideration. CH3 —CH2CH3 the two atoms are hydrogen and the third one is carbon i.. The atomic numbers of atoms directly attached to the chiral centre show the priority order to be Br > Cl > CH3 > H.e. in this case. C2H5. other three atoms are hydrogen i. Similarly.9 Assigning R and S notations. —CH2CH3 gets priority over —CH3. The two groups are viewed as follows: In the case of —CH3. Sequence rules for determining the priority of groups or ligands • The four different groups attached to a chiral centre get their priorities according to the atomic number of the atom of each group attached directly to the chiral centre. with 2-chlorobutane (CH3CHClC2H5). 7. the former will get priority over the . Cl. Cl is of highest and H is of lowest priority. For example. Cl. As for example. For deciding the preference between —CH3 and CH2CH3 decision cannot be made on the basis of first C–atom of each group attached directly to the chiral centre.

168 ENGINEERING CHEMISTRY • A double or triple-bonded atom X to C is considered to be equivalent to two or three X′s. . let us consider the following examples: Glyceraldehyde CHO  H  C  OH  CH 2 OH —CHO is considered as Here O.  A For example : H H    C CH   C C C C   CC   C C H   C O  O H   C O  O —CH = CH2 means —C ≡ C— means —CH = O means To illustrate the above phenomenon. For example  C = X means  C X  X C X X X and —C ≡ X equals   But one thing to be kept in memory is that a real  C  A has priority over — C ==A. H. O. The complete priority sequence is then —OH → —CHO → —CH2OH → H. The priority sequence of 1-amino-2-methyl- HC C CH 1-phenyl-propane is —NH2 → C6H5 → C3H7 → H. The —C6H5 group is considered as C . H of —CHO attains the priority over the O. H of —CH2OH group.

by convention it is D-configuration. In L-alanine the priority sequence is same but the rotation is clockwise with hydrogen in the horizontal line. rotation is anticlockwise with hydrogen on the horizontal axis. Then the groups are placed across the horizontal lines and the last carbon is at the bottom of the vertical line.e. Fischer projection of 3-chloro-1-pentene is: (b) Cl H3C5¾C4H2¾CH¾H2C 3-Chloro-1-pentene * CH = CH2 (a) (d) CH2 H Cl Fischer projection formula (c) CH2CH3 Priority sequence is: Cl→ —CH = CH2 → CH2CH3 Rotation is anticlockwise and hydrogen is on the horizontal line. clockwise and hydrogen falls on the vertical line then the configuration of the asymmetric carbon atom is assigned to be ‘R’ carbon atom (with asterisk is asymmetric carbon atom).  Fischer projection formula is: (b) (d) COOH (a) (b) (a) COOH H H NH2 H2N (c) (c) CH3 Mirror CH3 D-alanine (I) L-alanine (II) In configuration (I) hydrogen falls on the left hand side of horizontal line.. So configuration is ‘R’. enantiomer will inevitably be L-configuration.e. The configuration of the asymmetric carbon is ‘S’. . In D-alanine the priority sequence is NH2 → COOH → CH3 . • To determine ‘R’ or ‘S’ enantiomer of the compound we are to draw the Fischer projection formula.e. i.MECHANISM OF ORGANIC REACTIONS 169 Example: (i) 3-chloro-1-pentene. the number ‘1’ carbon should be on the top of the vertical line. * (ii) Alanine —C3H3C2 H(NH2) COOH . • Then the asymmetric carbon atoms are to be determined. So the configuration of carbon number ‘3’ is ‘R’.. hydrogen will fall on the right hand side of the horizontal line. Its optical isomer i. • If the sequence is the same i. Then the sequence rule is applied to get the priority sequence. For Fischer projection formula. then the configuration of the asymmetric carbon atom is assigned to be ‘S’.. • Then configuration is specified if priority sequence is a → b → c → d is clockwise and hydrogen (d) remains in the horizontal line.

3R). the configuration is ‘S’. (IV) (2R.3S)-2. The symbol (E) is used when the groups of higher priority are on the opposite sides of the double bond. double bond.e..170 ENGINEERING CHEMISTRY (iii) For 2.3-Dichlorobutane. (III) and (IV) are known as mesoforms.is applied for trans-isomer and Z. i. In the case of (I) the priority sequence for carbon number (2) is Cl → CH(Cl)CH3 → CH3. (II) (2S. the terms cis and trans are adequate but if three or four of the substituents are different then the nomenclature of these geometrical isomers or diastereomers leads to ambiguity and sometimes to confusion. Generally E.is for cis-somer when the groups of higher priority are on the same side of the reference plane. 3S). So the IUPAC nomenclature of the compound (I) is: (2S. E and Z Nomenclature For the compounds of the type Cab = Cab or Cab = Cac. CO2H > H) H H3C H which is represented as H COOH (E)-2-Butenoic acid Similarly: H H COOH H H H COOH CH3 H CH3 (Z)-Butene dioic acid (Haleic acid) (CO2H > H .C2 *H(Cl). For example: 2-Butenoic acid. So the configuration is ‘S’. 3R). So. 4-Hexadiene . Here also the sequence rule is applied. then the symobol (Z) is used to specify the configuration. 3-dichloro butane [C4H3C3 *H(Cl). They are optically inactive due to internal compensation. 4E)-2.C1H3] the Fischer projection is CH3 H Cl Cl H Cl H CH3 H Cl H H CH3 Cl Cl Cl Cl CH3 H H 2 3 2 3 2 3 2 3 CH3 (I) CH3 (II) CH3 (III) CH3 (IV) (I) and (II) are enantiomers. The priority sequence for carbon number ‘3’ is Cl → CH(Cl)CH3 → CH3. the others are: (II) (2R. (I) and (III) or (II) and (III) are diastereoisomers. COOH > H) (2E. Similarly. CH3 C C H COOH (CH3 > H.

Q.. Nucleophilic reagents may be negatively charged viz. 3. R = K[C4H9Br] [OH–] The suggested mechanism is: CH3 H C H Br HO H CH3 : : C H In SN2 reaction two molecules are involved in the rate determining step. i. Hydrolysis of primary halogenoalkane viz. NH3 with unshared pair of electrons. 4. bromobutane is a second order reaction. and substitution of X– takes place by OH–. Ans. Q. 2-bromo 2-methylpropane is first order. How can you ascertain that X– is a weakly basic group and OH– is a strongly basic group? Ans. Rate equations suggest that there are two different mechanisms for nucleophilic substitution—explain. 1. OH–. Rate equation for the reaction is: Rate = K[C4HgBr] The suggested mechanism is: CH3 C CH3 CH3 Br Slow CH3 [Rate determining step] C + CH3 + Br – CH3 fast OH– CH3 C CH3 CH3 OH : : H:O: ! + : Br : – . Q. substitution of weakly basic group takes place by a strongly basic group.MECHANISM OF ORGANIC REACTIONS 171 SHORT QUESTIONS AND ANSWERS Q. Since the attacking reagent (OH–) is a nucleophilic reagent. and neutral molecules like H2O. What are nucleophilic reagents? Ans. Nucleophilic reagents can supply an electron pair. CN– etc. X– is a weak base as its conjugate acid HX is a strong acid.e. Obviously a nucleophilic reagent attacks a molecule at the point of low electron density. Hydrolysis of tertiary halogenoalkanes viz. Why is the RX + KOH → ROH + KX called nucleophilic substitution? Ans. and OH– is a strong base as its conjugate acid H2O is very weak. The rate equation is. 2.

. So. H2SO4? Ans. H H H C C + CH2 = CH2 + H + H H This reaction is an example of dehydration of an alcohol. 5. Q.. why does 2-bromo-2-methylpropane follow SN1 path? Ans.+ CH3CH2—OH + H+ → CH3CH2 O : H . This carbocation eliminates an H+ to give an alkene. More the number of methyl groups. more is the stability of carbocation. CH3 < CH3 CH2 < (CH3 )2 CH < (CH3 )3 C 1° Primary + + + + + 2° Secondary 3° Tertiary and see that CH3 is the least stable and (CH3)3C+ is the most stable carbocation. . This is an example of acyl nucleophilic substitution.. Ans. Q. When a methyl group is attached to a carbocation (C+). SN2 is a one step process and SN1 is a two step process. 6. So we can write the following stability sequence. then a water molecule is eliminated to give a carbocation H + + . more is the dispersal of charge and more the dispersal of charge. At first ethanol is protonated. this is an example of nucleophilic substitution. That is why the ionisation in the first case is possible and SN1 path is followed. so. Of the two isomeric C4H9 Br.172 ENGINEERING CHEMISTRY The mechanism shows that C—Br bond breaks first to form a carbocation intermediate. . CH3 CH2— O : H → CH3 C H2 + H2O. What do you expect if ethanol is heated with conc. H . In SN1 mechanism one molecule is involved in rate determining step. Q. Then the nucleophile forms a bond with the carbocation formed. Is the following reaction a nucleophilic substitution? O   CH3— C —X + NH3 → CH3CONH2 + HX. 7. the charge is dispersed by its (+I) effect. O NH3 CH3 C X CH3 + O C – X –H + O CH3 C – O X CH3 C+ X NH2 – : NH3 NH2 Here substitution of X– takes place by nucleophilic NH3. 2-bromo-2methylpropane ionises to give most stable 3° carbocation whereas 1-bromomethane gives 1° carbocation. .

the negatively charged oxygen acts as a base and accepts an H+ from HCN. Benzophenone does not form bisulphite compound. OH  C6H5 COC6H5 + NaHSO3 → C6H5  C  SO3 Na  C6H 5 . CH 3 CH 3   H+ Ans. First step of nucleophilic addition HCN to ethanal: H CN – H O NC C O: : : – + C CH3 CH3 To complete the reaction. Give an example of nucleophilic addition. Explain. CH3 CH2 CH  CH 2OH + H+ → CH3CH2 CH  CH 2 O H CH 3  + → CH3CH2 CH C H 2 –H2O The formed carbocation is 2°. 2-Methylbutanol on dehydration gives 2-methyl but-2-ene—explain. 10. H CH3 C H CH3 C CH3 CH3 CH CH3 C 2-methyl but-2-ene CH3 Q.2 hydride shift. 9. This rearranges to the most stable 3° carbocation by 1. Second step of nucleophilic addition of HCN to ethanal: H NC C O: + HCN H – : : NC C CH3 OH + CN – CH3 Q. Ans. 8. CH3 CH3 CH2 C H CH2 + CH3 CH3CH2 C + 3° carbocation CH3 This species then eliminates a proton to give 2-methyl but-2-ene.MECHANISM OF ORGANIC REACTIONS 173 Q.

C N : : N – – : : C (Resonance) So the products of the reaction are: C2H5 Br + Ag CN → C2H5 NC + C2H5CN + Ag Br major minor Q. 14. N O2. So. 15. CH2 + + CH2 + Q. Indentify the products of the following reaction: Ans. CH3 I. : : : O–N=O – : : O=N=O R—X + KNO2 → RONO + RNO2 + KX Q. Arrange the reactivity of the following towards nucleophilic reagent: CH3F. Ans. CCl4. so ionisation of benzyl chloride takes place and path is followed. Q.. 17. R—X + KNO2 → A + B + C : : : : O – N = O is an ambident nucleophile. C6H5 CH 2 is resonance stabilised. 13. So. Ans. 12. as it has lone pairs C ≡ N . 16.. Due to resonance C—Cl bond attains a partial double bond character and C—Cl bond energy increases and no carbocation is formed. Q.174 ENGINEERING CHEMISTRY Ans. C H 3 . Allyl Bromide undergoes nucleophilic substitution readily—explain. CN– . CH3Cl : : : – : : : : – : : minor (B) (C) : : : CH2 – CH = CH2 + CH2 + CH2 . CH3Br. it can attack from both the sides of the species. Give the products of the reaction of ethyl bromide and AgCN. Vinyl chloride does not undergo nucleophilic substitution—explain. 11. SN1 Ans. The bulky group (C6 H5) surrounding carbonyl group prevents the attack of nucleophilic (SO3–2) due to steric hindrance and hence the nucleophilic addition to form the bisulphite compound does not take place. Q. CN– is an ambident nucleophile i. Allyl carbocation is resonance stabilised major (A) ! : : : CH2 = CH – CH2 + and behaves as if the chlorine atom is ionic. Find out the nucleophile from the following: + . CH2 = CH – CH 2 + OH– → CH2 = CH–CH2OH (SN1) + + Q. CN–.e. Benzyl chloride undergoes SN1 reaction—explain. Ans. vinyl chloride does not undergo nucleophilic substitution. + CH2 = CH – Cl CH2 – CH = Cl: Ans.

R R C R¢ R² (+)– Br Slow HO OH – C R² R R¢ 50% C R¢ + Fast R R¢ R² C OH 50% (±) Br + R² – ... Why do haloalkanes give cyanides with KCN– and isocyanides with AgCN? Ans. 20. halide ions (X–). 22. slow fast OC 2H 5 Q. NH2– are harder bases and are the worst as a leaving group. The stronger or harder as a base. CN– being ambident nucleophile. R – X + Ag+ [CN–] → Ag X↓ + R+ + [CN–] → R – N+ ≡ C! In the absence of such promotion by Ag+ e. with Na+ [CN–] the SN2 reaction is found N ≡ C– + R – X → [N ≡ C---R---X] → N ≡ C ≡ R + X– T. Ans. What is the characteristic of a better leaving group? Ans. C ≡ N ←→ C = N – . Both the reagents act as nucleophilic and release CN–. worse as a leaving group.MECHANISM OF ORGANIC REACTIONS 175 Ans.. The best leaving groups are anions of strong acids e. Ans. RX + KOH → ROH + KX whereas in alcoholic medium C2H5OH + KOH C2H5O–K+ + H2O.S. – RCH2CH2X → RCH = CH2 Q.g. 21. .. What do you mean by leaving group? Ans. Ag+ promotes R+ formation from RX by precipitating AgX and reaction takes SN1 path. The –OC2H5 is strongly basic and preferentially help elimination. Q. 18. CH3I > CH3Cl > CH3Br > CH3F as bond dissociation energies (D) is of the order C—F > C—Cl > C—Br > C—I. OR–. Aqueous KOH with RX gives alcohol whereas alcoholic KOH alkene— explain. 19.g. SN takes place. Thus C—I bond is readily broken and the reactivity of CH3I is greatest. Q. . In aqueous medium. –OH. Discuss the stereochemistry of SN1 and SN2 reactions.. there are two active sites in the CN– – . The charged species (group) that is replaced during a substitution reaction is a leaving group. In SN1 reaction racemisation takes place that means (+)– and (–)– isomers form in equal amounts if we take an optically active RX. Q.

5 × 104 fold faster than the reaction CH3 I with N– if we change the 3 solvent from CH3OH to HCON(CH3)2 (DMF). The order of reactivity of halogen acids towards an alcohol is— HI > HBr > HCl. SN1 reaction becomes faster if the solvent polarity increases. 25. Q. Because in CH3OH due to hydrogen bonding N– is 3 solvated and its nucleophilic activity is reduced. 24. the order or reactivity of the alcohols follows the order 3° > 2° > 1°—explain. Nucleophilicity of X– decreases in order: I– > Br– > Cl–. For a given HX. Discuss the effect of solvent on SN1 and SN2 reactions. That is. In SN2 reaction: R HO – R C Br HO R¢ T. Developing ion pair gets solvated easily and helps the process ionisation. Increase in solvent polarity has little effect in SN2 reaction. Change of solvent may have marked effect on SN2 reaction. Q. Transfer from protic polar solvent to polar nonprotic solvent may change the reaction pathway from SN1 → SN2 by increasing the effectiveness of the nucleophilic. 23. there is attack by X– to give RX. always racemisation takes place during SN1 reaction. The reaction rate becomes 4. . it is quite likely that attack by OH– would take place with equal readiness from either side of planar carbocation leading to 50/50 mixture of the (+)– and (–)–forms. The change of solvent (I) affects the rate of the reaction (II) which may change the mechanistic pathway.. The alcohol is first protonated. Whereas in DMF the hydrogen loading is absent and N3– remains unsolvated and powerful nucleophile can attack..176 ENGINEERING CHEMISTRY As the planar carbocation is formed in rate determining step and the process of formation is slow. So. –d R Br R² –d + R¢ C HO C R² R¢ R² The back side attack by the nucleophile always leads to inversion of configuration in SN2 reaction. Q.S. The solvolysis of (CH3)3 Br becomes 3 × 104 times faster in 50 % ethanol than in ethanol alone.-O + H2 ] → RX + H2O. Explain. only a slight decrease in reaction rate is observed. Hence the order of reactivity of HX is ROH → R – OH+ → [ X − δ . Ans. the reaction is nucleophilic substitution and the leaving group is H2O. Increase in solvent polarity and ion solvating ability may change reaction pathway from SN2 → SN1.-R. 2 HX X– HI > HBr > HCl. Ans.

and anion formed has ) got resonance stability. Q..MECHANISM OF ORGANIC REACTIONS 177 Ans. Since the stability of carbocation follow the order: 3° > 2° > 1°. (ii) the electronegativity of A. By far. (iii) factors stabilising A–. (i) The strength of H—A bond. H— C←O←H Due to electron pull. . 27. This reaction is known as dehydrohalogenation. Q. that is determined by two empirical rules. O   Ans. Rate = K[RCH2CH2Br][B] H H C H C H ¾¾¾® (i) B ! : R C H R C H CH CH3 + Br – Br H Hb Hb CH3CH2CH = CH2 (A) 2 5 ¾¾¾® – (ii) CH3 C H CH Y a CH2 OC H CH3CH = CHCH3 (B) In substrates which have alternative β-hydrogen available. Hence. HCOOH is an acid—explain. The alkene which has least alkyl substituents on the double bond carbons. 28. Elimination of a molecule of hydrogen halide from a haloalkane produces an alkene. H2O from a molecule of organic compound to form a double bond. Elimination reaction is a reaction that splits off a simple molecule of a compound e. (iv) the nature of the solvent. 26. What do you mean by an elimination reaction? Ans. the reactivity of alcohols follow the order: 3° > 2° > 1° for a given HX. What is the origin of acidity in organic compounds? Ans. N+(CH3)3 –OEt – 95% 5% Hofmann Q. Table Substrate CH3CH2 CH CH3  Y Y Br Base –OEt – Alkenes A 19% B 81% Name of the Rule Saytzev Rule The alkene will predominate which has most alkyl substituents on the double bond carbons. more than one alkenes can be obtained. H+ release is possible.g. the most common elimination mechanism is the one step E2 pathway.

Q. CH3 → C → O → H Acidity in CH3COOH is somewhat reduced due to (+I)-effect of the CH3 group and that effect is more pronounced in (CH3)2CHCOOH and still more pronounced in (CH3)3CCOOH. F ← CH2COOH > Cl ← CH2COOH > Br – CH2COOH > I-CH2COOH: pKa values are in accordance with the above acidity order. So pKa value gradually increases i. Ans.. : O H ! O H O H : + O + H ! : ! : + : O H ¬ : ¬ : : : : . acidity order will be.16 Ans. 31. 32.86 2. Justify the pKa values Acid CH3COOH FCH2COOH ClCH2COOH BrCH2COOH ICH2COOH pKa 4.76 4.178 O HCOOH + H2O H C O H C O O – ENGINEERING CHEMISTRY + H3O + So.90 3. The electronegativity order of halogens is: F > Cl > Br > I So. 30.e.66 2. Q. Explain. Q.86 5.29) > Cl ← CH2COOH(pKa = 286) Cl ¬ CHCOOH (pKa = 0. Phenol is (i) acidic. Acidity order with pKa values of the following acids is: Cl¬ Cl¬ CH COOH(pKa = 1.65) > Cl Cl Justify. p-orienting. Justify the pKa values Acid CH3COOH (CH3)2CHCOOH (CH3)3CCOOH pK a 4. acidity decreases. HCOOH is an acid as the anion has resonance stability. pKa value decreases. (ii) o. Q. 29. The electron withdrawing substituents with (–I) effect has got marked influence on the acidity of simple aliphatic acids.05 O   Ans. As the number of electron withdrawing groups increases acidity increases.76 2.

Q. But we see that pKa of aniline is 4.62 respectively. pK a values for NH 3 . . 34. the basicity is increased.. . it is less basic than NH3..positions. The electrophiles can attack at those positions leading to electrophilic substitution. 10..64 CH3 ¬ pKa = 10. CH3NH2 is more basic. (CH 3 ) 2 NH are 9. NH3 is basic. : NH2 ! : : : : . NH3 CH3 NH2 ¬ CH3 : : pKa = 9. the anion formed on the release of H+ by phenol molecule is resonance stabilised. *This property common to other groups.positions of the benzene ring of phenol molecule become electron rich. . So. like NH2 .62 i.25.77 respectively.and p. pKa values of NH3. NH 3 is a Lewis base. CH3NH2 and PhNH2 are 9. When benzene ring is attached to a group containing a ‘key atom’ (here ‘O’ has lone pair of electrons) the resonance effect gives rise to increased electron densities in the o.77 Q. Justify.64 and 4. So aniline (pKa = 4. the electron density over ‘N’ atom becomes less than that over NH3.25 pKa = 10. CH 3 NH 2 . . the electron withdrawing effect of –NO2 group in p-nitroaniline makes electron density of ‘N’ atom less than that in aniline and that is why p-nitroaniline becomes less basic.25.e. So phenol is o-. p-orienting. phenol can behave as an acid.. When this donation capacity is increased by any effect.MECHANISM OF ORGANIC REACTIONS 179 (i) The electronegative atom ‘O’ of phenol gets positively charged due to resonance. Benzene having a delocalised π-cloud is susceptible to electrophilic substitution. This increased electron density activates the benzene ring towards electrophilic substitution SE2. The resonating structures of aniline is: NH2 + + + : NH : NH2 ! NH2 NH2 ! Example of resonance Due to resonance. o. The pKa values are in accordance with the above fact. Ans. Do you expect that p-nitroaniline is less basic than aniline? Ans.62) becomes less basic than NH3. Ans. Q. Justify. p-orienting*. helps electrophilic substitution and are o-. it can donate a pair of electrons. The (+I)-effect of CH3 groups increases the electron density of N atom in CH3NH2 and this effect is more pronounced in (CH3)2 NH due to two CH3 groups performing as stronger bases than NH3. due to the (+I) effect of the –CH3 group. 33. 35. Yes.and p. : OR . So bonding electrons of O—H bond will be pulled strongly towards O-atom making release of H+ easier. (ii) Due to resonance. 10.64 and 10. Moreover..

positions due to resonance. 4.. nitration of nitrobenzene molecule becomes difficult. OH O2N OH NO2 pKa = 0. For electrophilic attack.98 – N O Å O – Q. 4. Q. Ans. —NO2 group is m-orienting. 39. Nitration is an electrophilic substitution and takes place easily in the case of phenol. Ans. Ans. Nitration of phenol is easier than that of nitrobenzene—explain.and p. 2. 37.and p. The three —NO2 groups in 2. —NO2 group in nitrobenzene deactivates the benzene ring by withdrawing electrons from the benzene ring and making o. On the contrary. The resonating structures of nitrobenzene are: O¾N O O ¾ N¾O O ¾ N¾O O ¾ N¾O O¾N O Å Å Å Due to resonance. further electrophilic attack at nitrobenzene molecule becomes difficult. that is why electrophile attacks there and msubstitution takes place. So. it is known as picric acid. Introduction of an —NO2 group in the phenol molecule increases its acidity due to (–I) effect of the —NO2 group.e. The eletrophile SO3 is generated as follows: 2H2SO4 – SO3 + H3O+ + HSO4 : : – + – + – – + – – + – – + : : .and p. So. Ans. 36. electron-rich centre is necessary. That is why.positions of benzene ring of nitrobenzene become electron deficient. 6-trinitrophenol exercise pronounced (–I) effect making the phenol molecule total acidic.positions positively charged. Show that sulphonation of benzene is an elctrophilic substitution. In phenol —OH group activates the benzene ring towards further electrophilic substitution by enriching the electron density at o.02 Q. 38.62 O O pKa = 0.9 NO2 pKa = 1. Q. H2SO4. o.180 Ph NH2 NH2 + ENGINEERING CHEMISTRY : : NH2 N pKa = 4. —NO2 group is m-orienting—explain. SO3 dissolved in conc. So. 6-Trinitrophenol (picric acid) is a very strong acid—explain. The sulphonating agent is Oleum i. The m-position of the benzene ring is comparatively electron-rich.

chlorination. in Friedel–Craft’s reaction. the reagents are anhydrous FeCl3 and Cl2. (i) For halogenation viz. So. R Q. Cl2 + FeCl3 FeCl4– + Cl+ + acts as an electrophile during chlorination of benzene. sulphonation of benzene is an electrophilic substitution.. : O: : : : : O: S : S + O: O S OH O : : O: T.e. 2-alkyl shift) CH3 CH3 CH3 C OH C OH Pinacol – H2O : O: : H : CH3 C : ! CH3 C CH3 :OH CH3 –H + ­ CH3 H + CH3 CH3 CH3 C OH C + CH3 OH2 CH3 CH3 CH3 CH3 C OH C Å CH3 CH3 C + C CH3 :OH CH3 CH3 CH3 C O C CH3 Pinacolone CH3 . RCl + AlCl3 AlCl4– + R+ + acts as an electrophile during alkylation i. Cl (ii) For alkylation the reagents are anhydrous AlCl3 and RCl.S O– : So. What are the electrophiles for (i) halogenation and (ii) alkylation reactions of benzene? Ans. Q.MECHANISM OF ORGANIC REACTIONS 181 Second step is attack by electrophile SO3 and the formation of a transition state. 40. So. Pinacol-pinacolone rearrangement (example of 1. Ans. Mention an organic reaction where rearrangement takes place. 41. Electrophile is thus generated. Electrophile is thus generated.

—N(Me)2 group goes out of plane of the benzene ring by free rotation about the single bond. 6-Dimethyl –N. Classify the different organic reactions. What do you mean by electrophiles and nucleophiles? . What is polymerisation reaction? Give an example of such type of reaction with plausible mechanism. Yes. 2. here the electrophile is NO+ HONO + HCl NOCl + H2O + : N (II) – CH3 CH3 CH3 NO + Cl + OH + OH OH + NO NO H +H + NO EXERCISES 1. H3 C H3 C : N CH3 (I) Q. 3. But in (II) lone pair over —N(Me)2 comes into resonance with benzene ring and not so much available for an H+. N-dimethylaniline (II). What do you mean by polarisation? What is the reason behind it? What do you mean by inductive effect? How does it play an important role in organic reactions? Compare the acidity among CH3COOH. So primary condition of resonance. When Phenol is treated with NaNO2 and HCl at 0–5°C. p-nitrosophenol is obtained.182 ENGINEERING CHEMISTRY Q. Is this reaction an electrophilic substitution? Ans.COOH. 43. So lone pair over —N(Me)2 group in (I) is available to be accepted by a proton (H+). 6. 7. 8. CH. the planarity. What is electromeric effect? Is it permanent? State the origin of a carbocation. N-dimethyl aniline (I) is more basic than N.Cl2COOH. is affected and resonance is inhibited. Due to crowding in (I). 4. CH2Cl. 42. State the products obtained during the chlorination of CH4 in diffused sunlight. carbonium ion and free radical. 2. This is an example of steric inhibition of resonance. Mention the mechanism. What do you mean by steric inhibition of resonance? Ans. 5. CCl 3COOH. 9.

8 kcal/mole—explain.and L-glycine (NH2CH 2COOH). 3-dibromopentane. 17. What do you mean by 1. 19. NMe2 Me 22. What do you mean by SN1 and SN2 reactions. Name them as per R—S nomenclature. What do you mean by dehydrohalogenation? Explain with proper mechanism and example. 25. . S-nomenclature. . Heat of hydrogenation value of 1. Draw Fischer projection formula of D.B → AB 12. 3. Explain with proper mechanism involved with examples. Compare the basicity among the following: NH2 NMe2 Me . 16. 11. What is resonance? State the important features of it. 23. 5-cyclohexatriene is 85. Name them as per R. 20. Write a short note on hyperconjugation. What are the significances of the terms: (i) Resonance hybrid and (ii) Resonance energy. Electrophiles are in general Lewis acids–explain.MECHANISM OF ORGANIC REACTIONS 183 10. 21. Draw the energy profile of the following reaction: A + B → A --. 15. 13. 18. 26. What is elimination reaction? Describe different types of elimination reactions. 24. Write a short note on nucleophilic addition reaction. Draw all the Fischer projection formulae of: (i) glyceraldehyde (ii) lactic acid (iii) tartaric acid (iv) 2. Draw the resonance structures of: (i) phenate ion (ii) acetate ion (iii) chlorobenzene (iv) butadiene.8 kcal/mole while that of benzene is 49. 2-shift. 14. What does the term ‘isomerism’ refer to? Give different classifications of isomerism. Write notes on electrophilic addition and electrophilic substitution.

C(1 – α) When C = concentration of HA Ka = ∴ α= H+ + A– Cα Cα Ka = Ionisation constant of an acid (Acid dissociation constant) [H + ] [A − ] C α . 184 . If for a weak acid ‘the degree of dissociation’ is α. the degree of dissociation of a normal solution of a weak electrolyte is approximately equal to the square root of its ionisation constant. when the electrolyte is weak. then C = α2 α α ... of HA. C α = ≈ α2 C [HA] C (1 − α) Ka C [as α is negligible] . 2 Ka = V V = V 1− α 1− α V V 1 V and Then Ka comes to : Ka = ∴ α= α2 (1 − α) V K a V = K′ V ...(2) The expression which relates the variation of degree of dissociation (α) of a weak electrolyte with dilution is known as Ostwald’s dilution law.(1) If V litre of solution contains one gm. Putting C = 1 we get α = Ka i. Ka = Kb = [H + ] [OA c − ] [AcOH] 8 [NH + ] [OH − ] 4 [NH 4 OH] Kb = Ionisation constant of a base. AcOH NH4OH H+ + OAc .. In a solution a weak electrolyte dissociates reversibly. The equation implies that a weak electrolyte will dissociate completely at infinite dilution.e. NH4+ + OH–. mol.Ionic Equilibrium Law of Mass Action and Ionisation Law of mass action is applicable to electrolytic dissociation. then HA At equilibrium.

acids react with alkalies to form salts and water. [H+ ] will decrease i.(3) Now. behaviours of NH2– and OH– ions are same and OH– is derived from a base. The definition of acids and base needs to be extended. So concentration term [ OAc ] increases in the equation (3). It is well known that in neutralisation reactions. The strengths of the acids or bases may be determined by their tendencies to donate or accept a proton in a definite solvent. undissociated [AcOH] will increase. NaOAc being a salt dissociates completely in solution. so we can say NaNH2 is a base i. we can say.e. Some Acid/Base conjugate pairs are shown in the following table. a substance can behave as an acid or a base by not producing H+ or OH– ions. 2NaOH + MgSO4 = Mg(OH)2↓ + Na2SO4 (in water) . As for example. As for example. In the Arrhenius concept neutralisation may be explained as follows: (H+ + Cl–) + (Na+ + OH–) → NaCl + H2O (2H+ + SO4=) + ZnO → ZnSO4 + H2O The indication of neutralisation is: H+ + OH– → H2O i. Let us see its effect on ionisation of AcOH. the formation of water. This phenomenon is known as Common ion effect. NaNH2 dissolves in liquid ammonia and behaves as NaOH in water as is implied from the following equations. In general.IONIC EQUILIBRIUM 185 Common Ion Effect If we add NaOAc to a solution of AcOH. These species may be neutral or charged. Bronsted and Lowry defined: Acid as a species which can donate a proton and base as a species which can accept a proton. there is a base known as conjugate base and for every base there is an acid known as conjugate acid. Whether the species will behave as an acid or a base will depend upon the nature of the solvent. ACIDS AND BASES Arrhenius Theory of Acids and Bases According to this theory an acid is a substance which when dissolved in water gives H+ ions and a base is a substance which when dissolved in water gives OH– ions.e.... AcOH Ka = H+ + OAc . specially in non-aqueous solvents.. the dissociation of AcOH will be suppressed. 2NaNH2 + MgSO4 = Mg(NH2)2↓ + Na2SO4 (in liq. NH3) So. NaOAc → Na+ + OAc [H + ] [OAc − ] [AcOH] .e. the ion ( OAc ) becomes common. Bronsted and Lowry Concept Arrhenius theory is suitable in explaining the reactions of acids and bases in aqueous solutions but it fails to explain the following reactions. For every acid. that common ion effect suppresses the dissociation of a weak electrolyte in solution.. As a result. Cl– is a conjugate base of the acid HCl and HCl is the conjugate acid of the base Cl–. to maintain the value k a constant.

the solution will get enriched with OH– ions and will behave alkaline.186 Acid HClO H2 O HSO4– HCO3– NH4+ [Cr(H2O)6]+3 H+ H+ + + H+ + H+ + H+ + H+ + ENGINEERING CHEMISTRY Conjugate base ClO– OH– SO4= CO3= NH3 [Cr(H2O)5OH]+2 Role of Solvent Solvent makes to act the substances to behave as an acid or a base. Therefore. HCl and HNO3 are of same strengths in water. And water will remain undissociated being a weak electrolyte. Solvent behaves as a base towards acid and vice versa. H2SO4. CH3COO is weak. EtOH C6H6. but in glacial acetic acid their strengths are as follows: HClO4 > HBr > H2SO4 > HCl > HNO3 This phenomenon in water is known as levelling effect of water. HBr. CH3COOH. H2O H+ + OH– – is a strong base as its conjugate acid. As a result. Classification of Solvents Solvent (i) Protophilic (Proton seeking) (ii) Protogenic (Proton generating) (iii) Amphiprotic (Both proton seeking and generating) (iv) Aprotic (Independent of proton seeking and generating) Example H2O. NH3 H2O. . CH3COO– ions will readily accept protons from water molecules setting OH– ions free. • Neutralisation reaction can be explained with the help of the equation: AcidI + BaseII AcidII + BaseI CH3COOH + OH– H2O + CH3COO– • Hydrolysis reaction is explained as follows according to Bronsted Lowry concept: Aqueous solution CH3COONa is alkaline because CH3COONa ionises completely in solution as it is a salt and water being weak electrolyte ionises incompletely. Highlights: • HClO4. CH3COONa → CH3COO– + Na+. acetic acid According to Bronsted. AcidI CH3COOH HCl CH3COOH HF H2 O + + + + + + BaseII H2 O CH3COOH NH3 CH3COOH H2 O (Autoprotolysis of water) AcidII H3O+ CH3COOH2+ NH4+ CH3COOH2+ H3O+ + + + + + + BaseI CH3COO– Cl– CH3COO– F– OH– AcidI and BaseI are conjugate pair and AcidII and BaseII are conjugate pair. CCl4. HF H2O.

It ionises as follows: H2O H+ + OH– or more correctly. So dissociation constant (K) of water is. It is worthwhile to mention that an aqueous solution always contains H+ and OH– ions. K[H2O] = [H+][OH–] (Q [H2O] = constant) Highlights: • We arrive at an important conclusion that in any aqueous solution. we need to know hydrogen ion concentration of a solution. though negligibly small. Therefore. 2H2O H3O+ + OH–. • Dissociation constant of water and ionic product of water are not same. K= [H + ] [OH − ] [H 2 O] or [H 3 O + ] [OH − ] [H 2O] 2 or Kw = [H+][OH–] Kw is known as ionic product of water. N + AlCl3 Acid Base CO O: + B Cl Salt CO Cl N ¾® AlCl3 : CO Base Cl Cl Acid : O ¾® B CO Salt Cl Cl • A substance can behave as an acid even though it does not donate a proton. its value is 10–14 at 25°C. its value at 25°C is 1 × 10–14. Again an alkaline solution contains . Ionic Product of Water Water is very much inferior as an electrolyte. this phenomenon can only be explained by the Lewis concept.IONIC EQUILIBRIUM 187 Lewis Concept An acid is a substance which can accept a pair of electrons and a base is a substance which can donate a pair of electrons. pH Scale For various experiments. the product [H+] [OH–] is constant. Acid + Base Neutralisation effect F3B + :NH3 F3B ← NH3 H+ + :NH3 NH4+ Cu++ + 4NH3 [Cu(NH3)4]++ Highlights: • Neutralisation of AlCl3 (Lewis acid) with pyridine (Lewis base) in C6H5Cl solvent or neutralisation of BCl3 with phthalic anhydride can only be explained in the light of Lewis concept of acids and bases. Even strong acid solution contains OH– ions. [H2O] is constant because of very feeble ionisation of water.

Again 0.188 ENGINEERING CHEMISTRY H+ ions though in small concentration. hydrogen ion concentration of the solution will be 10–12 g. Sorensen (1909) simply applied negative logarithm of hydrogen ion concentration to remove this sort of difficulty for expressing such concentrations. 10–2 g. + (– log10[OH–]) = – log10Kw pH + pOH = pKw = 14 where – log10Kw = pKw.ion l–1. Therefore.ion l–1 which is completely dissociated in aqueous solution.ion l–1. Highlight: Following such conventions we express Ka and Kb as follows: pKa = – log10 Ka. all acidic solutions will have pH less than 7. ∴ pKa = 3. and all alkaline solutions will have pH greater than 7. so its hydrogen ion concentration Let us consider an acid solution of concentration 6000 –4 g.P. where [H+] = 10–7 ∴ – log10[H+] = – log10(10–7) ∴ pH = 7 Again in pure water. in any aqueous solution pH + pOH = 7 + 7 = 14 Highlight: or. the solution becomes alkaline. 1 (N) solution of a strong acid contains an [H+] of 10–1 g.ion l –1. Because [H+] × [OH–] is constant in aqueous medium and its value is 10–14. [OH–] = 10–7 – log10[OH–] = – log10(10–7) ∴ pOH = 7. So. S. So in an aqueous solution when [H+] exceeds that of [OH–]. And in the solution where the [H+] becomes less than that of [OH–]. and pKb = – log10 Kb As for example: Ka for salicylic acid = 10–3.ion l–1. the solution becomes acidic. A simple operation like this made an easy expression for hydrogen ion concentration of the solution. In pure water [H+] = [OH–] = 10–7.L.66 × 10 solution in such a manner. As strong acid dissociates completely in aqueous solution. . Therefore. It is somewhat inconvenient to express the concentration of the will be 1. [H+] = [OH–] = 10–7. so [OH–] of the solution will be 10–13 g. N . pH scale pH [H3O+(aq)]/mol dm–3 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 10 0 10–1 10 –2 10 –3 10–4 10 –5 10 –6 10–7 10 –8 10 –9 10 –10 10–11 10 –12 10 –13 10–14 increasingly acidic ← neutral → increasingly alkaline Now applying this idea in the case of pure water. He defined pH as negative logarithm of hydrogen ion concentration: pH = – log10 [H+] A more convenient scale for expressing concentration of H+ ion in aqueous solutions is thus developed. Pure water is neutral because in pure water.01 (N) strong alkali solution contains [OH–]. ∴ – log10 [H+] [H+] × [OH–] = Kw.

the dissociation is complete.013. One such method is by comparing dissociation constants of the acids.31 (b) [OH–] = 1. [H+] = 10 −14 = 7.7 = 12 – 0.3 × 10 −3 pH = – log10 (7. Sol. Such solutions are known as buffer solutions. Example 2.6 × 10–3 g-ion l–1 – log10 [OH–] = – log10 (1.37 = 4.1 = 1.7959 or 2.9 × 10–4) ∴ pH = 4 – log10 4. Sol. Example 3. Calculate [H+] of a solution of pH 3.7 × 10–12) = 12 – log 7. .2041 = 2.63 – log10 [H+] = 3.7 × 10–12 g-ion litre–1.63.9 × 10–4 (N) acid.63 log10 [H+] = – 3.24. As the acid and base are strong.69 = 3. [OH–] and pH of a weak base [0.37 [H+] = antilog 4. Buffer Solutions Some solutions do not change their pH on addition of little acid or alkali. (b) 0. [OH–] = 0.63 = – 3 – 0.013 × 0. The arrest of pH changes of these solutions is known as buffer action.3 × 10–3 g-ion litre–1.9 = 4 – 0. So. degree of dissociation of acid A1 = α1 Degree of dissociation of acid A2 = α2 The concentrations of the acids were same (C). 1.34 × 10–4 g-ion litre–1. Relative Strengths of Acids and Bases Tendency of donating protons in any aqueous solution is a measure of acidity of the solution. S2 S1 = α2C α 1C = α2 α1 = K 1C K 2C K2 K1 So. So.34 × 10–4 ∴ [H+] = 2.1(N)]. their strengths S1 and S2 are represented by. Sol.9 × 10–4 g-ion l–1 – log10[H+] = – log10(4.0016 (N) base. (a) [H+] = 4.8865 = 11.76 = 11. Calculate [H+]. There are several other processes for comparing strengths of acids.IONIC EQUILIBRIUM 189 Example 1. pH = 3.1135. Both acid and base are strong. If concentrations of two acids A and B are CA and CB respectively. ratio of strengths should be CA: CB. Given: α = 0. Let.76 ∴ pH = 14 – pOH = 14 – 2.63 = 4 – 0.37 = 2. the ratio of dissociation constants of two acids compare their strengths.6 = 3 – 0. Calculate pH of the following solutions: (a) 4.6 × 10–3) ∴ pOH = 3 – log10 1.

external H+ will be removed by BOH H+ (external) + BOH → B+ + H2O.190 ENGINEERING CHEMISTRY Mechanism of buffer action: A buffer solution is generally a mixture of solutions of a weak acid HA and its salt BA. As in this case. here the common ion is A– HA H+ + A– (weak acid) ∴ [H + ] [A − ] [HA] log10 Ka = log [H+] + log10 [A–] – log10 [HA] Ka = log10 Ka = log10 [H+] + log10 or. we can write [A–] = [Salt] as all the A– in the solution are due to ionisation of BA. . the acid be HA and its salt be BA. BA → B+ + A– (Completely dissociated in aqueous solution as it is a salt) HA H+ + A– (Incomplete dissociation in aqueous solution as the acid is weak) – is a strong base as its conjugate acid HA is weak. Again. BA → B+ + A– (complete dissociation) + + OH– BOH B (incomplete dissociation) On addition of acid to such solution. B So the pH of the solution will not change on the addition of a little acid or alkali. Again on addition of alkali to such solution OH– ions are removed as follows: OH– + B+ → BOH + is an acid. a weak base BOH and its salt will give a buffer solution. again whose dissociation is almost prevented due to common ion effect of A–. pH of such solution will not change on addition of little acid or alkali and that is the buffer action of the solution. as OH– is a strong base: OH– (external) + HA → H2O + A– . or. pH of a Buffer Solution (i) Buffer solution (prepared from weak acid and its salt) Let. So. the dissociation of acid HA is very poor. – log10 [H+] = – log10 Ka + log10 pH = pKa + log10 [A − ] [HA] [A − ] [HA] [A − ] [HA] Due to common ion effect. H+ (external) + A– → HA The undissociated molecules of HA will be generated more and more. according to Bronsted concept. ∴ pH = pKa + log10 [Salt] [Acid] This is the famous Henderson equation. So we have. So A– will readily accept H + from A solution which comes from the added acid to the solution. So. If we add a little base to such a buffer solution the external KH– will be removed by the acid HA. So the change of pH will be arrested.

7 2.76 = 0.0-3. when concentration of salt becomes 10 times the concentration of acid and vice versa.2-3. (ii) Buffer solution (prepared from a weak base and its salt) In this case: BOH Kb = B+ + OH– (weak) Kw [B + ] [OH − ] [B + ] = × [BOH] [BOH] [H + ] K [B + ] [H+] = w . • The buffer capacity of a solution is defined by db/dpH. the addition of acid decreases the pH and is equivalent to a negative amount of base.6 5..7-5.8-9. pH depends upon the ratios of the concentration of salt and acid.00 – 4.. pH = pKa + log [Salt] [Acid] [Salt] = 4. K b [BOH] LMQ N [OH − ] = [H + ] Kw O P Q ∴ As entire B+ ions in the solution is due to complete ionisation of BA and BOH is weak ∴ pH = pKw – pKb – log [B + ] [Salt] = pKw – pKb – log [BOH] [Base] where [Salt] = [Base]. then pH = pKw – pKb.e. Highlights: • Buffer solution almost invariably consists of a mixture of a weak acid HA and its salt BA or a mixture of weak base BOH and its salt BA.38 3. The buffer action is favourable in pH ranges pKa ± 1 i. [Given pKaCH3COOH at 25° is 4. where dpH is the increase of pH resulting from the addition of db of base.76 = 5. Prepare a buffer solution of pH 5.738 [Acid] . [Acid] [Salt] = antilog (0.24. i. Sol.2 10 11-12 Example 1.76].8-8 6.24) = 1. Different Buffer Solutions Component conjugate acid–base pair (i) Glycine/Glycine hydrochloride (ii) Phthalic acid/Potassium hydrogen phthalate (iii) Acetic acid/Sodium acetate (iv) NaH2PO4/ Na2HPO4 (v) Boric acid/Borax (vi) NH4OH/NH4Cl (vii) Na2HPO4/Na3PO4 pH ranges 1.IONIC EQUILIBRIUM 191 The acidity or alkalinity of mixed solution.76 + log [Acid] ∴ ∴ log [Salt] = pH – 4.e.

The above equation signifies that the product of concentrations of B+ and A– of a salt is constant independent of the individual concentrations of B+ and A– ions when temperature is constant. BA(s) BA (solution) B+ + A– Applying law of mass action. Solubility Product The law of mass action cannot be successfully applied to the process of electrolytic dissociation except to the cases of weak electrolytes. Calculate Ksp of CaF2 .mol l–1 and [A–] = S g. Ksp = [B+] [A–] = S2 For a salt like BxAy: BxAy(s) BxAy (Solution) xB+ + yA– –1 then [B+] = xS.. then [B+] = S g. K= Highlights: • When the solubility of Mg3(PO4)2 is C mol.3 × 10–8. So [BA (s)] = 1. because a heterogeneous equilibrium is set up as follows. Example 1. ions of each type formed by dissociation of one molecular formula weight of the salt. The solubility of CaF2 is 0. of CaCO3 = 100) Solubility S = 0.Sx+y It is a universally applicable equation. The solubility of chalk is 0.e. CaF2 Ca+2 + 2F– . Therefore. Example 2. [B+] [A–] = constant = Ksp. [B + ] [A − ] [BA( s)] or K[BA(s)] = [B+][A–] The concentration of solid salt [BA (s)] is constant.192 ENGINEERING CHEMISTRY Therefore.ion l–1.0305 gl–1.0305 gl–1 = 3. formula weight per litre and not in g. [A–] = yS If the solubility is S mol l ∴ Ksp = [B+]x [A–]y = (xS)x (yS)y = xxyy. wt. per litre. l–1 Mg3(PO4)2(s) Mg3(PO4)2 (Solution) [Mg+2]3 [PO4–3]2 (3C)3 (2C)2 C5. But it can be successfully applied to the saturated solutions of sparingly soluble salts. By convention it is unity. If S is the solubility of BA. • It is customary to express the concentrations of the ions in g.0002 mol l–1.05 × 10–4)2 = 9. Calculate its solubility product.mol. The solubility product of a salt may be defined as the greatest possible product of concentrations of its constituent ions in its saturated solution expressed in g.738 g-moles of CH3COONa is mixed with 1 g-mole of CH3COOH and the volume of the solution is made upto one litre.l–1. when 1. the desired buffer solution of pH 5 is obtained. The constant Ksp is called the solubility product of the salt BA. ion l–1 i. each concentration term being raised to a power representing the number of gm. equiv.05 × 10–4 mol l–1 Ksp = S2 = (3. (mol. 3Mg+2 + 2PO4–3 its Ksp is = × = 108 • The solubility product of a sparingly soluble binary electrolyte is simply the square of its solubility in pure water expressed in mol l–1.

0002 × (0. ∴ Ksp = S′ × (S′ + 0. we are to suppress the dissociation of NH4OH by adding common ion NH4+. • The presence of a neutral salt without a common ion often results in an increase of solubility of a sparingly soluble salt. (a) At 25° the solubility of BaSO4 is 0. We know that Ksp = [Mg+2] [OH–]2 = 1.01 mole NH4OH and 0. [NH + ] [OH − ] 4 = 1. B+ and A– will combine to give the solid BA(s) and the solubility of BA will decrease. A litre of a solution contains 0.2 = 0. Example 4.IONIC EQUILIBRIUM 193 [Ca+2] = 0. Therefore. 4 2 Sol.2 × 10–11.12 × 10–11.ion l–1 to arrest the precipitation of Mg(OH)2. Example. (a) ∴ (b) [Ba++] = [SO4=] = 13.001 g. [Ba = 137] Sol.12 × 10–11 ∴ [OH–] So. What will be concentration of NH4+ ion from NH4Cl? Given K b NH OH = 1.12 × 10 OP =M N 0.001 Q −11 1/2 = 1.1 × 10–4 g. As a result.ion l–1. To arrest the precipitation of Mg(OH)2. Ksp = [B+] [A–] If we add to the solution a substance.ion Mg+2. Highlights: • It is almost invariably true that addition of a common ion at first diminishes the solubility of a sparingly soluble salt but when relatively large amounts are added the solubility starts to increase. Kb = L 1. For doing so. So. 3. Effect of Common Ion on Solubility We know that.1 g. [F–] = 2 × 0. for a saturated solution of a sparingly soluble salt BA. the changed solubility of BaSO4 = S′. [OH–] should not exceed 1. [NH 4 OH] .0002 g ion l–1 .8 × 10–5.2 gl– at 25°C.1 × 10–4 g.00233 = 10–5 g.00233 gl–.1 (M) 132 ∴ [SO4=] = 0.0002 g ion l–1.8 × 10–5 and K sp Mg(OH) = 1. which has an ion common to the above salt then concentration of that ion will increase.ion l–1 137 + 96 Ksp = [Ba++] . the concentration of other ion will decrease otherwise the constant Ksp will change. [(NH4)2SO4] = ∴ S′ = 10 −10 0. [S′ is negligible compared to 0. ∴ S′ = 2.33 gl–1.ion l–1.1] 10 −1 = 10–9 mol.1) = 10–10. [SO4=] = 10–5 × 10–5 = 10–10.0004)2 = 3. Let. Ksp = [Ca+2] [F–]2 = 0. Calculate the solubility product of the salt. l–1. taking complete dissociation. (b) Calculate the solubility of BaSO4 in a solution of (NH4)2SO4 containing 13.

e. are soluble in salt solutions due to this salt effect. so CS= should be high for them. Q activity (a) = Concentration (c) × activity coefficient (γ) ∴ a = cγ. so their precipitation is arrested here. Ag+) are insoluble.01 ∴ [NH4+] = 1. So in more or less concentrated acid medium they (Gr II) are precipitated and filtered and then filtrate is diluted with water and passed H2S to precipitate CdS and PbS. the ionic products (CM+2 × CS–2) of metal ions exceed the solubility products because of low value of solubility products. Ni+2. Therefore. get precipitated here i. So concentration of sulphide ion CS= remains low. on addition of dil. the value of solubility product of the salt should always be higher than its ionic product. If we add KNO3 to a saturated solution of AgCl the γ-term of the expression of Ksp decreases. Sn+2). which are sparingly soluble in water. [Cl–] increases in order to keep the true Ksp value constant. solubility of a sparingly soluble salt increases on addition of any salt without a common ion.6 × 10–3 g. aCl − So. Application of Common Ion Effect and Solubility Product in Qualitative Inorganic Analysis General Group Separation of Basic Radicals: Precipitation of a salt takes place when its ionic product exceeds its solubility product. whose solubility product of sulphides are low. Sb+3. Group I. Pb+2. despite low S= ion concentration. As a result Fe+3. This effect is known as salt effect. Pb+2. to reduce acidity of the medium water is added to dilute the medium. Group II. So. To increase the ionisation of H 2S. That is why. Highlights: • Many proteins. A salt may not get precipitated even when its ionic product exceeds its solubility product. ionic product (CM+ × CCl–) easily exceeds the solubility products and the cations are precipitated..ion l–1.. The metallic ions (Hg+2. true expression is Ksp = γ Ag + . Again diluted acid medium precipitates colloidal As2S3 and SnS which creates difficulty in filtration. The common ion H+ suppresses the ionisation of H2S.194 or = ENGINEERING CHEMISTRY Effect of a Salt without a Common Ion on Solubility For the correct expression for solubility product we should use activity (a) in place of concentration: i. Al+3. [NH + ] × 1. It is also precipitated in Group II. The reagent is H2S in presence of dil. Ksp = aAg + . Mn+2. The precipitation of .8 × 10–5 0. For a very dilute solution γ = 1 then a = c. It may remain in saturated solution for sometime. for precipitation in chemical analysis. Bi+3.1 × 10 −4 4 = 1. Cu+2. The chlorides of Group I metals (Hg2+2. Zn+2) sulphides have higher values of solubility products. Group III A. γ Cl− [Cl − ] where γ = activity coefficient. As+3. [ Ag + ] . Only PbCl2 has higher solubility product and for that reason it is not completely precipitated here. • The effect of common ion on solubility is utilised in qualitative inorganic analysis to separate the ions present in a solution. [Ag+] . low acidity or higher pH is necessary. CdS and PbS have comparatively higher values of solubility products. The common NH 4+ suppresses the dissociation of weak base NH4OH thereby COH– remains low. IIIB metallic ion (Co+2. Here reagent is NH4Cl/NH 4OH.e. HCl. Cr+3 get precipitated as hydroxides because their solubility products are exceeded. HCl.

Calculate the pH of 0. (b) 1 × 10–8 (M) NaOH solution.1 M HCl to 1 litre. +2.5 × 10–8 pH = – log10[H+] = – log10 (10. pH = 14 – 2 = 12. 1000 ∴ pH = – log10 [H+] = – log10 [2 × 10 –3] = 3 – log 2 = 3 – 0.ion l–1. and (NH 4)2CO 3. 1 . Ca+2. Ba SOLVED EXAMPLES Example 1.1 = 0.5 × 10–8) ∴ = 8 – log10 10. 20 × 0. Calculate [H+]. Example 2.0 × 10 – 8 (M) HCl solution. l–1.98. 10 −14 2×1 –8 (M) = 9.0 × 10–8 + x) = (1.5 × 10 +] = (1. (b) Here let the contribution of OH– ions from water be x.0 × 10–8 + 9. NH4OH. ∴ ∴ pOH = 2.005M Ca(OH)2 solution assuming complete dissociation. [OH–] and pH of a solution prepared by diluting 20 ml of 0.5 × 10–8) [H x= = 10. Sol. the contribution of H+ ions is to be counted during calculation of pH.01 × 10–12 g..IONIC EQUILIBRIUM 195 Zn+2. [OH–] = 2 × 0. the [H+] of the solution = (1 × 10–8 + x) and [OH–] = x ∴ Kw = [H+] [OH–] = (1 × 10–8 + x) × x = 10–14. Sr+2 are precipitated as carbonates.3 = 5. Example 3. Let the contribution of [H+] from water = x.3 – log10 [OH] = 11.3010 = 2. Sol.005 = 10–2 mol. But when it exceeds 10–6.e. ∴ total [OH–] = (1 × 10–8 + x) [H+][OH–] = Kw = 10–14 (1 × 10–8 + x) × x = 10–14 . Group IV metals i. Calculate the pH of (a) 1.6990 ~ 2. ∴ So.7 ∴ pOH = 14 – 2. So.3 [OH] = 10–11. or x2 + 10–8x – 10–14 = 0 Sol.5 = 6. Group IV. Mg+2 and Mn+2 as hydroxides are arrested as their solubility product values for hydroxides are comparatively higher. [H+] = ∴ − 10 −8 ± (10 −8 ) 2 + 4 .7 = 11. (a) When the [H+] is 10–6 or greater the ionisation of water is negligible due to common ion effect.002 = 2 × 10–3 mole l–1. Here reagents are NH4Cl.

8 × 10–5 .8 × 10 −5 = 4.1 = 4.8 × 10 −5 × 0.02) 0. – Sol.74). ENGINEERING CHEMISTRY Example 4. ion l–1 pOH = 8 – log 9.98 × 10–8 g. The solubility product of CaF2 in water at 18°C is 3.5 × 10–8 (M) [OH–] = 9. Sol.5 × 10 −7 4. 0.0 × 10–8x – 10–14 = 0 x = 9.004 = 0.1 – Example 6. A buffer solution contains 0.2C 0.01 Example 5. (a) Calculate the molar concentration of an CH3COOH solution.1 mole of CH3COONa per litre.ion l–1 Example 7. Ksp = [Ca+2] [F–]2 = [S] × [2S]2 where. S = solubility.98 = 7.5 = 6.02.98 molar 0.4 = 3. Sol.196 ∴ ∴ ∴ ∴ ∴ x2 × 1. (Given Ka = 1.1 mole CH3COOH and 0. = 4S3 [H 2CO 3 ] − [HCO3 ] = [H + ] Ka = 4.044 molar.02C × 0.74. Calculate the solubility of CaF2 in water.4 ∴ – log10 [H+] = 7.0004 × C = C(1 − 0. H2CO3 H+ + HCO3 . pH of blood is 7.4 ∴ [H+] = 10–7.45 × 10–11. at equilibrium: ∴ CH3COOH C(1 – α) Ka = = ∴ c= H+ + CH3COO– Cα Cα [H + ] [CH 3 COO − ] [CH 3 COOH] 0.24 × 10–2.74 + log [salt ] [acid] 0.5 × 10 – 7.4.01 (M) AcOH. C 0. Given Ka of H2CO3 = 4. Calculate the ratio of HCO3 and H2CO3 .98 1. Calculate the pH of buffer solution. α = 0. Ka = 1.98 × 10 −8 11 .5 × 10 −7 = _ ~ [H + ] 3. (pKa = 4.5 × 10–8 g. Sol. ∴ ∴ Ka = − [H + ] [HCO 3 ] [H 2 CO 3 ] pH = 7.98 pH = 14 – 6. According to Henderson equation pH of a buffer solution (b) α= pH = pKa + log = 4.02) (b) Calculate the degree of dissociation of 0.

1M NaF solution. K = ionisation constant. SrF2 S= S mole 2S mole Initially = in 0. ∴ Ksp = 8 × 10–10 = [Sr+2] × [F–]2 = S × (0. HSO4 is a conjugate base of H2SO4. 2. Ksp of SrF2 = 8 × 10–12. So.1 M NaF Solution = S mole (2S + 0.01 SHORT QUESTIONS AND ANSWERS Q. For weak electrolytes. Ans. 1.05 × 10–4 mole l–1.IONIC EQUILIBRIUM 197 4S3 = 3. Thus. Sr+2 + 2F– Sol. Cl– is a conjugate base of – acid HCl. What is the Lowry and Bronsted concept of acid and base? Ans. C = concentration of the weak electrolyte. This sort of pairs are known as conjugate acid-base pairs. K= α 2 C2 C(1 − α) where. Every acid has a conjugate base and every base has a conjugate acid. – . Calculate the solubility SrF2 in 0.1)2 = 0. A base is a substance which in aqueous solution gives OH– ions. Give an expression for the ionisation constant. Again HCl is the conjugate acid of Cl– and H2SO4 is the conjugate acid of the base HSO4. α is negligibly small. – Thus HCl and HSO4 are acids as both of them can donate a proton and Cl– and SO4= – are bases as they can accept a proton. 4.1) mol. ∴ 1–α≈1 K = α2C ∴ α = K . and HSO4 Q. HCl is an acid and NaOH is a base. What is the Arrhenius concept of acids and bases? Ans. What are conjugate acid-base pairs? Ans. mol l–1. C Q. differing by a proton. Q. Example 8.45 × 10–11 3 ∴ 3. α = degree of dissociation of a weak electrolyte.45 × 10 −11 mole l–1 4 = 2. Given. 3. An acid is a species (neutral or charged) which can donate a proton and a base is a substance or species (neutral or charged) which can accept a proton.01S ∴ S= 8 × 10 −10 = 8 × 10–8 mol l–1. An acid is a substance which in aqueous solution gives H+ ions. 0.

AcidI + BaseII AcidII + BaseI Q.. 18 Kw = K [H2O] = [H+] [OH–] = 1. H2O/OH–. H2O + H2O or H2O H+ + OH– K= [H2O] = [H3 O + ] [OH − ] [H 2 O] or [H + ] [OH − ] [H 2 O] 1000 = 55. 5. Ans. [H+] = [OH–] [H+] = [OH–] = 10–7 g. H3O+ + OH– Ans.5555 = 100 × 10–16 = 1.. H + acid ..8 × 10–16. ∴ [H+] [OH–] = 10–14 and in pure water. given K for water = 1.. conjugate acids and bases are formed during the reaction. .ion l–1. HNO3/NO3–. Ans.00 × 10–14. acid H base H Cl   Cl  B ← : N  H   H Cl acid base Q. In pure water.5555 moles l–1. 6. Q. Give Lewis concept of acids and bases. Q. NH4+/NH3 and so on.8 × 10–16 × 55. what will be the [H+] or [OH–]? Ans. An acid is a species which can accept a pair of electrons and a base is a species which can donate a pair of electrons.198 Some conjugate acid-base pairs are: ENGINEERING CHEMISTRY If the acid is strong. As.. every acid–base reaction proceeds according to the equation i. its conjugate base will be weak and vice-versa. base H .e. 7. Show that ionic product of water (Kw) is 1 × 10–14. ← : O • • H – . According to Lowry Bronsted concept acid–base reaction always follows the equation: + BaseII AcidII + BaseI AcidI CH3COOH + HF H2 O + H2O H2O H3O+ H3O+ + CH3COO– F– OH– + + CH3COOH CH3COOH2+ + HSO4–/SO4=. Show that solvent acts as a base or an acid according to Lowry Bronsted concept. 8. So. H : N : → H + . H3O+/H2O.

) Weak acid–strong base pH 7 Fig. ion l–1.c. 9. pH = – log10 [H+] or [H+] = 10–pH The acidity or alkalinity of a solution is generally expressed by pH. 10.3 or [H+] = 10–2.1 Neutralisation Curves.3 = 5 × 10–3 mol dm–3.3 or log10 [H+] = – 2. . What is the hydrogen concentration of coca cola with pH 2..02 mol dm–3 HCl? Ans. Explain the pH changes during acid–base titration. Addition of an alkali from a burette to 25 ml of an acid in a conical flask and plotting a graph give a shape determined by the nature of the acid and the base. In alkaline solutions.c. Explain the pH scale. Q. [H+] range = 10–8 – 10–14 g . pH = 2.3 or – log10 [H+] = 2. The pH scale is a logarithmic scale for measuring the concentration of hydrogen ions in aqueous solutions. Phenolphthalein pH 7 Methyl orange 0 0 25 Alkali(c. Ans. = 100 – 10–6 g . 12.e. 13. What is the pH of 0.IONIC EQUILIBRIUM 199 Q.) Strong acid–strong base 0 0 25 Alkali(c. [H+] range In neutral solutions. [H+] = [OH–] = 10–7 g . 8.37? Ans. It is negative logarithm of hydrogen ion concentration. Q. Q. i.7. Ans. pH = – log10 [H+] pH = [H+] = 0 10 0 1 10 –1 2 10 –2 3 10 –3 4 10 –4 5 10 –5 6 10 –6 7 10 –7 8 10–8 9 10 –9 10 11 12 13 14 10–10 10 –11 10 –12 10–13 10 –14 acidic ← neutral → alkaline Q. ion l–1.3010 = 1. pH = – log10 [H+] = – log10 [2 × 10–2] (as the acid is strong) = – log10 2 + 2 log10 10 = 2 – 0. ion l–1 In acidic solutions. What is pH? Ans.699 ≈ 1. 11.

1). 17. (ii) pH of a weak acid = pH = c = concentration of undissociated acid. H3O+ + OH– → 2H2O (l) Enthalpy change of neutralisation is same for all acid-base partners. How can you use pK values for pH calculations? Ans.200 ENGINEERING CHEMISTRY The graphs show the pH range for the colour change of an acid/base indicator for detecting the end point of the titration.7 pH = 14 – pOH = 14 – 1. . Q. (iii) pH of a weak base = 14 – Kb = dissociation constant of weak base. useful for pH calculations. Q. What is pK? Ans. It is to be noted that. 8. We know that. The ‘strong parent’ in the partnership wins. pK is the logarithmic form of an equilibrium constant. Neutralisation reactions do not always produce neutral solutions—explain. it hydrolyses to give a solution that is not neutral. Q. The indicator chosen to detect the end point must change colour completely in the pH range of the near vertical part of the curve (Fig. when exactly equal amounts of acid and alkali have been added. At the equivalence point. the pH is not always neutral. What is the pH of a 0.02 mol. 14. – log10 Ka = pKa. Neutralisation is essentially a reaction between H+ and OH– ions in aqueous solution—explain.02 mole dm–3 pOH = – log 0. 18. hydrolysis of salts does not take place and the solutions remain neutral at the equivalence point (pH = 7). strong or weak. Q.02 = 1. – log10 Kb = pKb. 16. 1 1 p K b + log c 2 2 where c = concentration of undissociated base. 15. Q.7 = 12. Weak acid/strong base end point is alkaline (pH > 7) Strong acid/weak base end point is acidic (pH < 7). Ans.3. a salt is formed. (i) ∴ pKw = pH + pOH = 14 pH = 14 – pOH 1 1 pK a − log c 2 2 when Ka = ionisation constant of weak acid. When a salt formed at the equivalence point has either a ‘parent acid’ or a ‘parent base’ weak. – log10 Kw = pKw Taking logarithms produces a convenient small scale of values. NaOH is a strong base [OH–] = 0. This experimental evidence supports the above view. dm–3 solution of NaOH? Ans. at the equivalence point. Ans. if acid and base both are strong.

H3PO4 has three Ka values–explain. 23. 19. The change in equilibrium position due to addition of an ionic compound that contains one of the ions involved in the equilibrium is known as common ion effect. Q. Q. Kb and Kw. a 1 2 3 Q. Ans. (i) H3PO4 (ii) H2PO4– (iii) HPO4–2 H+ + H2PO4–. (iii) pH value helps to determine the condition of reactions in laboratory and in industry. (ii) A small variation of pH of human blood (6. (iii) The common ion effect alters the solubility of a sparingly soluble salt. Ka × Kb = [HA] [OH − ] [A − ] [H 3 O + ] [A − ] [HA] [OH − ] × = [H3O+] [OH–] [HA] [A − ] = Kw = 10–14. 21. (i) HA + H2O acid H3O + A – Conjugate pair base Ka = (ii) A + H2O – [H 3 O + ] [A − ] [HA] – HA + OH Conjugate pair Kb = Now. K a = 1 − [H + ] [H 2 PO 4 ] [H 3 PO 4 ] − [H + ] [H 2 PO42 ] − [H 3 PO4 ] H+ + HPO4–2. Mention the importance of pH. . K a = 2 − [H + ] [PO 43 ] H+ + PO4–3. (i) The pH value of soil helps to decide the type of fertiliser to be used in agriculture. There are three dissociations for H3PO4 and accordingly ka values. which help to keep pH of a solution more or less constant. Ans. Buffer solutions are mixtures of a weak acid and its salt or a weak base and its salt. K a = −2 3 [HPO 4 ] Ka > K > Ka . 20.7) causes bodyache. Relate Ka. Q. Ans. What is a buffer solution? Ans. ∴ or ∴ Ka × Kb = Kw – log Ka – log Kb = – log Kw pKa + pKb = pKw = 14. (ii) The common ion effect influences the behaviour of buffer solution. What is common ion effect? Ans.IONIC EQUILIBRIUM 201 Q. (i) The common ion effect can change the ionisation of weak acids and weak bases. 22.

0. 13.01) [S −2 ] = [H 2 S] 0. What is the pH of a buffer solution containing 0.4 × 10–15 So. 10. The reaction HCl (aq) + KOH (aq) → KCl (aq) + H2O is neutralisation according to: (a) Bronsted-Lowry concept. ∴ [Mn+2] [S–2] = 0. 14. 7. Deduce Ostwald’s dilution law and state its limitations.4 = 4. Show that it is different from dissociation constant of water.8. K = [H + ] [S −2 ] = 1. 5. 6. What do you mean by solubility product? What is true solubility product? Give an expression for the solubility product of the salt Ax By. Will Ans. 24. 8. Explain the following–Aqueous solution of NaCl conducts electricity while chlorine water does not conduct electricity. BCl3. (MnS) = 1.2.40 = 3. (b) BeCl2. Ans.1 × 10–22 [H 2S] [Q S H 2S = 0. ppt. Which are the strongest Lewis acids in the series? (a) BF3.202 ENGINEERING CHEMISTRY Q.0 mol dm–3 sodium methanoate? pKa(HCOOH) = 3. BI3. Give the Bronsted-Lowry concept of acids and bases. 9. Deduce the relation between solubility and solubility product of CaF2 at room temperature. 20.4 mol dm–3 methanoic acid and 1. will not be obtained. 2. EXERCISES 1.1 × 10–22 = 2H+ + S–2. Elucidate. +2 containing FG N IJ H H 100 K + be precipitated by passing H2S? H2S 1. 3. BCl3. Tricovalent phosphorus compounds can serve as Lewis bases and also as Lewis acids–comment. 12. (b) Lewis theory and (c) Solvent system concept. Derive an expression for pH of the buffer solutions: (a) Weak acid and its salt. 11. Discuss the effect of common ion on solubility product. in the light of Bronsted theory. (b) hydrolysis. Deduce the Hendersen equation and state its utility. ∴ ∴ FG N IJ Mn H 10 K 100 . 19.1M] (0. What is pH? Give its importance and usefulness.1 [S–2] = 10–19. 18.01) 2 × [S −2 ] (0. 4. What is a buffer solution? Explain buffer action. 16. 25.1 × 10–19 = 10–20 Ksp . pH = pKa + log Q.8 + 0. What is the basic equation for acid-base reaction of Bronsted theory? Explain (a) neutralisation. Explain the terms: (i) Buffer solution (ii) Buffer capacity and (iii) Buffer action. 17. (b) Weak base and its salt. 15. . What do you mean by common-ion effect? How is it utilized in qualitative chemical analysis? What do you mean by autoprotolysis of water? Derive an expression for ionic product of water.

6 × 10–8] [Ans.95. 13] [Ans. Given Ksp of AgCl = 1. What will be the pH of a solution obtained by mixing 800 ml of 0. Solubility of Ag2CrO9 29.54 (b) 3. Solubility of PbSO4 is 0. 26. pH of a solution is 10. 1. 5.1M. Given Kb = 2 × 10–5. l–1. Calculate the concentration of H2S required to arrest the precipitation of PbS from a solution of [Ans.78] 25.6 (M)] 0. 23. 28. 2. making a volume equal to 500 ml? [Ans. Calculate the [H+]. 4. of CH3COONa. What will be the pH of a solution obtained by mixing 5g.00345 (N) acid (c) 0. Ksp(PbS) = 3.05 (N) NaOH and 200 ml of 1N HCl? [Ans. 27.014] 24.1N HCl. (a) 2. 2.4 × 10–12} (b) 0.69 × 10–11 moles l–1] in a solution is 4 × g-in Calculate the minimum concentration of Cl– to precipitate –10. Calculate the pH and pOH of: (a) 0. Find α for NH4OH in a solution of .4 × 10–28.3] 22. 10–3 [Ans. [Ag+] g-l–1.89 (c) 11. . 10. 12. [Ans. Calculate the pH and pOH of .038 g-l–1. 1. 11. 5 × 10–8 g-in l–1] AgCl. .000775 (N) acid [Ans.57. of CH3COOH and 7. Given Ka(H2S) = 1.5 g.46. Calculate its solubility product.IONIC EQUILIBRIUM 203 21.001 (M) Pb(NO3)2. Calculate its solubility product.1 × 10–23.00886 (N) base assuming complete dissociation. 1.11.05] [Ans.8 × 10 30. [Ans.

• It involves no chemical change during conduction of current.e. wood. Substances which conduct electricity are conductors. acids. Table 9. Non-metallic conductors (electrolytes) • Flow of ions takes place during the passage of electricity through them. new products are obtained during conduction of current.. Salts. 9. metals. as for example. Again conductors can be divided into two subdivisions: (i) electrolytes and (ii) nonelectrolytes. But some physical changes may occur. 9 Electrolysis Dissociation of a compound by passing electric current through a compound in solution or in fused state is known as electrolysis. asbestos etc.e. bases etc. Substances which conduct electricity and get dissociated in solution or in the fused states were termed electrolytes by Faraday. whereas when non-electrolytes conduct electricity there is no such chemical change. and which do not conduct electricity are nonconductors as for example. Electrolytes dissociate when they conduct electricity i.Electrochemistry INTRODUCTION Substances behave differently towards electric current. An arrangement for electrolysis is shown in Fig. a chemical change occurs then. 204 .. The current is always passed into and out of the electrolyte by means of metal foils or plates Battery + – Anode + Cathode – Voltameter Electrolyte Fig.1 Set-up for electrolysis.1: Comparison Metallic conductors • Flow of electrons takes place during the passage of electricity through them.1. acids. 9. • Chemical change takes place i. alkalies are examples of such electrolytes. Some conduct it and some do not.

C. They are electrodes (cathode and anode). Second law: When the same quantity of electricity is passed through different electrolytes. If W = the mass of ion liberated in gms.. Z is mass of ion liberated by unit quantity of electricity. W = Z i.2 Different voltameters containing different electrolytes. NaCl Na+ + Cl–. that is why the theory is known as Arrhenius ionic theory. positive and negative. NaOH Na+ + OH– etc. Such a dissociation of an electrolyte is called ionic or electrolytic dissociation. This theory of electrolytic dissociation was first put forward by Arrhenius. When an electrolyte (electrically neutral) is dissolved in water (or in fused state). it breaks up into two or more ions of two different kinds. Z is called electrochemical equivalent (E.e.E. The ions produced exist in equilibrium with the undissociated electrolyte molecules. 9. An ion is an atom or a group of atoms carrying positive or negative charge of electricity. + – + – + – + – 1 2 3 H2O + Acid CuSO4 solution AgNO3 solution Fig. the amount of positive charge being exactly equal to the amount of negative charge. then according to first law: W ∝ Q but ∴ W ∝ ct Q=c×t ∴ W = Zct where Z is a constant. the relative masses of ions liberated are proportional to their chemical equivalents.. The anions migrate towards the anode and cations migrate towards the cathode. The liberation of the ions at the electrodes depends upon their discharge potentials.). . Faraday’s Laws of Electrolysis First law: The mass of an ion liberated during electrolysis is directly proportional to the quantity of electricity which has passed through the electrolyte. It is the ions. c = the current strength in amperes. t = the time in secs.e. c = 1 and t = 1.ELECTROCHEMISTRY 205 kept immersed in it. When Q = 1 i. Q = the quantity of electricity in coulombs. which conduct electricity. This dissociation is complete at infinite dilution. not the undissociated molecule.

the quantity of electricity = Q coulomb the quantity of Cu deposited = W1 g the quantity of Ag deposited = W2 g Then. when 1 g of H2 is liberated in cell (1).C. 63. of hydrogen = ZH. E.C. 9. Q = ∴ ∴ or or F=Q= 1 K (for 1 gm. equiv.E.C.E. of any element = Z Z= E × ZH E × ZH ≈ 1.E. W ∝ E (where Q is constant) ∴ or When W = KQE (where E and Q vary) Q= W (K = Constant) KE 1 K Therefore. E Z = EH Z H or Z = E × ZH EH Chemical equivalent of hydrogen = EH. according to Faraday’s second law: W1 E 1 Z 1Q = = W2 E2 Z 2 Q ∴ (from the first law) or E ∝ Z E1 Z 1 = E2 Z 2 or E1 E2 = Z1 Z2 So chemical equivalent of an element is proportional to its electrochemical equivalent.206 ENGINEERING CHEMISTRY That is to say. W ∝ Q (where E is constant) From second law. of any element = Chemical equivalent of the element × E.008 1 So.) W = KQE = QE F From first law. If one of the elements is H. W = ZQ E = ZQ (for 1 gm.C. to liberate 1 gm equiv. This quantity of electricity is called one faraday (F). the quantity of electricity is fixed.E. Let. chemical equivalent of any element = E E.5/2 g Cu will be liberated in cell (2) and 108 g Ag will be liberated in cell (3) (Fig. W = E. equiv. then. of hydrogen.2).) = ZF F= E Z . of any element during electrolysis. E. ∴ Combination of First and Second Laws of Faraday From first law.

t+ ∝ u and t– ∝ v and (t+ + t–) ∝ (u + v) But t+ + t– = 1 v u ∴ t+ = and t– = u+ v u+ v where u and v are the speeds of cations and anions respectively. the total quantity of the current passed will remain same as above i. If 100 cations cross the barrier from left to right. Usually both cations and anions cross the barrier (ab) but in unequal numbers owing to their unequal speeds. It is to be noted that deposition at the electrodes in the above two cases will be same (Fig. cations and anions present in the solution conduct current.. So.78 8.0001118 0. a A N O D E b C A T H O D E Fig. So we can define transport number as the fraction of the current carried by an ion. = n = F Z 1 Z2 Zn Therefore.0 Z 0.ELECTROCHEMISTRY 207 for one gm equivalent of different elements E E 1 E2 = = ...0000104 0. so their transport numbers are unequal. Transport number is proportional to speeds of the ions. in that case.88 31. 9. For example. We can say that the cation transport number is hundred per cent and the anion transport number is zero per cent.. Ions of an electrolyte i.3 Concept of transport number. The case may be totally reversed. .2: Displaying the constancy of E/Z for different elements Element H Ag Cu O E 1. transport number (t) = ni Z i Σ ni Z i where. we can accept that.0003294 0.. 1 F = 96500 coulomb.. 9. ni = number of the ions and Zi = valency of the ions which cross the barrier. then current is wholly carried by cation. if 80 cations cross the barrier (ab) towards cathode compartment and 20 anions cross the barrier (ab) towards anode compartment. Table 9.008 107.0000829 F = E/Z (Coulomb) 96496 96495 96494 96495 ≈ 96500 The concept of transport number.3). the transport number of anions is hundred per cent and that of cations is zero per cent. So. 100 units but the current carried by cations is 80 per cent and the current carried by anions is 20 per cent..e.e.

are kept inside an electrolyte and their potential difference is E. ∴ t+ = t– = t+ = I+ I = n+ z+ eu + n+ z+ ev n+ z+ eu = n+ z+ e(u + v) n+ z+ eu = u u+v n− z− ev n+ z+ ev I− v = = = n+ z+ eu + n+ z+ ev n+ z+ e(u + v) u + v I u u+ v and t– = v u+ v It is obvious that.4 Voltameter. If unit of the charge is ‘e’ (Fig.5).208 ENGINEERING CHEMISTRY Transport number or transference number of an ion is dependent on the speed of the ions. this phenomenon creates an idea that perhaps the ions move at the same rate during electrolysis. the solution contains n(±) number of ions per millilitre + A – B – – v + + + u Fig. The current I is flowing. and the valency of ions is z(±). The following model will make the idea clear (Fig. 9. ions are always discharged in equivalent amounts but their speeds are different. therefore. Let the two electrodes. but it is not so. Similarly. . As every part of the electrolyte is electrically neutral. 9. The number of ions liberated at the positive and negative electrodes per unit area are given by n+ u and n– v. n+z+ = n–z– So. The total current carried by the positive and negative ions = I = I+ + I– = (n+u)z+e + (n–v)z–e. t+ + t– = 1 or t+ = 1 – t– Relative Speeds of Ions During Electrolysis (Transport Number) It has been noted that the ions are liberated in equivalent amounts at the two electrodes.4) Current carried by the positive ions = I+ = (n+u)z+e Current carried by the negative ions = I– = (n–v)z–e. A and B. 9.

(iv) When the ions move at the different speeds. The cations did not move at all. In this case also.e. we get the picture (III). Fall round anode Speed of cation u = = Fall round cathode Speed of anion v = Number of equivalence of electrolyte lost from anode compartment Number of equivalence of electrolyte lost from cathode compartment . 9. (i) 4 molecules each in the anode and cathode compartments and 6 molecules in the middle compartment. We get the picture (IV). but the concentration of both the compartments has fallen to the same extent i. The ‘+’ sign represents a cation and ‘–’ sign represents an anion. by two molecules due to deposition of ions at the respective electrodes.ELECTROCHEMISTRY 209 + I Anode compartment Middle compartment Cathode compartment – ++++ –––– ++++ –– –––– ++ –––– –– ++ ––– –– a ++++++ –––––– ++++++ –––––– ++++++ –––––– ++++++ –––––– o ++++ –––– ++++ –– ++++++ –– ++++++ ––– II III IV Fig. Let there be total 14 molecules in the electrolyte.. Let two cations and two anions have crossed the diaphragms towards cathode and anode. It is evident from the above discussion that the fall of concentration around an electrode is proportional to the speed of the ions moving away from it.e.5 Scheme showing the equivalence of discharge for any relative rate of motion of the two ions. one anion passes towards anode. Let when two cations have crossed the diaphragm towards the cathode. (iii) When the anions and cations move at the same rate. the number of anions and cations discharged is the same i. four. Although concentration in the cathode compartment has fallen by one molecule and that of anode compartment has fallen by two molecules. we get the picture (II).. Let two anions have crossed diaphragm towards the anode. (ii) When only the anions move. The total number of cations and anions discharged is again the same three. The concentration in the anode compartment has not altered while the concentration of the cathode compartment has fallen by two molecules due to deposition of ions at the respective electrode.

AgNO3 AgNO3 present in (x – y) g of water before electrolysis = z g. of AgNO3 lost from anode compartment due to migration No. Y X M A – B + R e w × 170 = Wg.6. The solution collected from anode (anolyte) = x g The amount of AgNO3 in x g anolyte The amount of water containing y g . of silver deposited in the coulometer W – ( y – Z) × 108 170 × w ∴ tNO 3 – = 1 – tAg + . Weight of silver deposited on cathode in the coulometer = w g. Let. 9.210 ENGINEERING CHEMISTRY The total gm. The tubes are fitted with silver plates which act as anode and cathode which are introduced into A and B. A dilute AgNO3 solution (N/20) is taken for electrolysis. tAg + = tAg + = = (W + Z) – y = {W – (y – Z)}g. t+ = t– = The number of electrolytes lost from anode compartment Total number of equivalence of the electrolyte liberated on the electrode The number of electrolytes lost from cathode compartment . loss due to migration. Total number of equivalence of the electrolyte liberated on the electrode Determination of Transport Number (Hittorf’s Method) Two broad vertical glass tubes A. No. B are connected in the middle by a ‘U’ tube ‘e’. the current is stopped. is passed for a period of 2–3 hours through the AgNO 3 solution. 108 If no migration would have taken place. So. the total weight of AgNO3 should have been present (x – y) g of water in the anode compartment = (W + z) g. The three tubes are fitted with stopcocks. The solution from the anode compartment is taken for analysis (Fig. of equiv.6). of equiv. A current 0. 9. After a definite time. A milliammeter M.01 to .02 amp. Actual weight of AgNO3 present = y g so. equivalence liberated from both the compartments is proportional to (u + v). The increase in weight of AgNO3 in anode compartment due to dissolution of silver from the anode = = (x – y) g =yg Fig. coulometer X are connected in series. Transference number determination by Hittorf’s method.

Increase in wt.442 0. But actual increase = 0.153 g.12) g = 0. of Cu+2 in the liquid per unit vol.e. Cd above complex ion formation.05 0.153 g and masses of Cu per unit volume of the anode liquid before and after electrolysis were 0.785. would have been 0.50 0.20 0.79 and 0..153 g.479.91 – 0. due to dissolution of Cu anode during electrolysis = (0.79 g.916 n = tNO 3 – = tAg + = 1 – tNO – = 1 – n = (1 – 0.02 0.79) g = 0.003 formation of complex ions. Increase in wt.153 – 0.91 g. Example 2.033 g.215) = 0. Calculate the transport number of Ag+ and NO3– ions when the speed ratio of the two ions is 0.127 0. Example 1. of Cu-cathode in the coulometer = 0. surrounding anode = 0.10 0. This is true for other complex compounds too.33 = 0.ELECTROCHEMISTRY 211 Highlight: • Abnormal transport number: the transport number of Cd+ ion is normal in CdI2 solution but it decreases abnormally with increase in concentration of CdI2. of Cu+2 in the liquid per unit vol. Calculate the transport number – of the Cu++ and SO4 – ions. Let.916 − v Speed of NO 3 r= 1 u 1– n = (n = tNO 3 – ) or n = 1+ r v n 1 = 0. Fall in concentration due to migration of Cu+2 ions = (0. .215 0.396 0.916 during electrolysis of a silver nitrate solution.153 – and Transport number of SO4 – = (1 – tCu + + ) = (1 – 0.01 0. If no Cu++ had migrated from the anode.521) = 0. u Speed of Ag + = = ratio (r) = 0.12 g. CdI2 ionises as follows in a concentrated solution: Cd+2 + [CdI4]–2 2CdI2 +2 ion is moving towards both cathode and anode and towards anode due to i. In an electrolysis of CuSO4 between copper electrodes the total mass of copper deposited at cathode was 0. Before electrolysis the amt.296 0. This abnormal transport number does indicate the formation of complex ion.12 g.521 1 + 0.444 0. 3 Specific Conductance The resistance (R) of a conductor is proportional to its length ‘l’ and is inversely proportional to its area of cross-section ‘a’. It can only be explained by the 0. ∴ Transport number of Cu++ ( tCu + + ) = It is obvious that Cd+2 is moving towards anode in larger amounts than the cathode and that is the cause of decrease of tCd+ 2 .91 g respectively. After electrolysis the amt. surrounding anode = 0. Concentration (N) tCd + 2 0. increase of wt.

equivalent LM3 N Kv = l 1 .212 ∴ R=ρ. λv = K v × We know that. ENGINEERING CHEMISTRY l a or ρ = Ra l where ρ = constant. i.. Molar Conductivity (λm) It is defined as the conductance of all the ions present in one mole of the electrolyte in a solution. it is the conductivity of 1 cm3 of the solution. λv = KvV. its value is dependent on material of the conductor and is known as specific resistance. the specific conductivity of the solution is known as Kv. as the number of current carrying ions per ml of the solution should gradually decrease. λv = KvV. then 1000 K M –1 cm2 mole–1 . . equivalent–1. If M is the concentration in moles l–1. = = ohm–1 cm–1 = mho cm–1 ρ a R cm 2 × ohm If a solution acts as an electrolyte. The reciprocal of specific resistance is termed specific conductance or specific conductivity (K.V a R cm × 1 × cm 3 cm 2 × ohm × g . If C is the concentration of the solution in g-equivalent l–1. R = ρ Therefore. But the value of λv or λm actually increases with dilution as it is the product Kv × V and on . the conductivity of all the ions of the electrolyte present in the solution is known as equivalent conductance and is abbreviated as λv i. Kappa).. The unit of λm is ohm λm = Effect of Dilution on Conductance The value of specific conductance (K) is expected to fall with dilution of an electrolyte solution.e. the specific conductance of an electrolyte is the resistance in ohm which is offered by a cm3 of the conductor during the passage of electricity.e. then. K= cm × 1 1 l 1 = . l = 1 and a = 1. When. the volume of the solution containing 1 g-equivalent will be 1000/C. = = 1000 C l 1 . Equivalent Conductance If one g-equivalent of an electrolyte is dissolved in V ml of the solution. a R OP Q = ohm–1 cm2 g .

0000752 0.5 127.0000129 CH3COONa 0.5 0.2 75.0001 Specific conductivity (Κ) KCl 0. 9. (ii) Weak electrolytes: Weak acid like acetic acid has a low value of λv at higher concentration and there is rapid increase of λv with dilution. Such electrolytes are called strong electrolytes.0412 0.2 49.000041 0.00132 0.9 122.01 0.82 2.0 0. 9.001225 0.3 Normality 1.1 0.2 76. is necessary to avoid this difficulty. no increase of λv or λm with dilution.1 70.4 61.7 Change of equivalent conductivity with dilution. strong alkali NaOH have high conductances even at low dilutions and there is no sharp increase in their equivalent conductances on dilution.5 Equivalent conductivity (λv) CO3COONa 41. The products of electrolysis will accumulate on the electrodes which will change the effective resistance.6 129.. Such electrolytes whose λv values increase with dilution are known as weak electrolytes (see Fig.000702 0.0001276 0.30 14.00024 0.3 111.8).C. Experimental Determination of Specific Conductance (K) The arrangement of apparatus adopted for the determination is modified Wheatstone’s meterbridge arrangement (see Fig. The use of A.001005 0. The modification is necessary as the passage of current will electrolyse the electrolyte.05115 0. The maximum value of equivalent conductance λv or molar conductivity λm is known as equivalent conductance at infinite dilution or molar conductivity at infinite dilution and abbreviated as λ∞ or µ∞. After a certain dilution there remains no more electrolyte molecule to ionise and then there is no change i.00000768 CH3COOH 0.01 2.e.0247 0.7).ELECTROCHEMISTRY 213 dilution more and more of the electrolyte ionises.00611 0.001 0. m¥ Molar conductivity Strong electrolyte Weak electrolyte Concentration Fig.3 41. .0 Classification of Electrolytes (i) Strong electrolytes: Strong acid HCl.2 102.0982 0. Table 9.000143 0.8 CO3COOH 1.01119 0.0000107 KCl 98.0 107. 9.

The solution whose conductance is to be measured is put into the conductivity cell (see Fig.002768 ohm–1 . =x× FG N IJ KCl solution. cm–1 at 25°C. the area of cross-section of the electrode.214 ENGINEERING CHEMISTRY C R T A a X R S b B Platinum electrodes A. the cell should be placed in a thermostat. Conductivity water (double distilled water) should be used throughout.8 Determination of conductivity of solutions. 9.9). specific resistance ρ is given by the following equation: ρ a = R b Since the conductivity of a solution rapidly increases with temperature.C.C. 9. But the procedure is to calculate a factor for each cell known as cell constant (x). (b) the use of telephone detector or magic eye indicator. The modifications are: (a) the use of A. the resistance R of liquid enclosed between the electrodes is: R=ρ× where l/s = x is cell constant. Specific conductance K = x × Observed conductance.. Specific conductance = Observed conductance × Cell constant When l is the distance between the electrodes and s. 9. the common form is shown in Fig. Source Fig. 9. if the area of the electrodes and the distance between them are accurately known.9. C is a compensating condenser (adjustable). Connections are made by Pt wires. The H 50 K 1 b 1 =x× × ρ a R .9 Conductivity cell.9). Fig. Different cells are in use. Calculation of Specific Conductance (K) If necessary ρ is calculated from the observed resistance. 9. l =ρ×x s The cell constant is known by determining the conductance of K value of the solution has been accurately determined by Kohlrausch to be 0. When the sound in the telephone is minimum or zero reading on the appropriate meter. (c) the electrolyte is taken in a cell containing platinised Pt electrodes (Fig.

00046 0.3 Mobility.5 53.00076 0.5 40.9 59.00064 0.00052 NO 3– HCO 3– CH 3COO– 71.5 73.1 50.e. i. Cation H+ K+ NH 4+ Ag+ λc 349.4 61.00083 0. V cm2/sec volt 0. λ∞ = λc + λa where.9 0.00079 1 SO4– 2 Cl – 1 Ca++ 2 1 Mg++ 2 Na+ It is evident from the table that each ion contributes a certain definite quantity towards λ∞ of the solution. λc = Ionic conductance of cation. volt 0.00362 0.00042 Anion OH– λa 197. The l where l is the distance between the s electrodes and s is the mean area of the electrodes.8 73. Highlights: • It should be noted that cell constant (x) = FG N IJ KCl be l H 50 K 1 the cell constant (x) = ρ1 × 0.8 76.002768.00074 0. .00062 0..00076 0. This regularity was first observed by Kohlrausch and was put in the form of a law which is known as Kohlrausch’s law.ELECTROCHEMISTRY 215 If the observed resistance with cell constant being known it is easy to obtain the specific conductance of any solution by using the above relation. Kohlrausch’s law (Law of independent migration of ions) At 25° the equivalent conductance at infinite dilution (λ∞) values for some electrolytes are given in the table below: Table 9.6 79.00055 0.1 Mobility. U cm2/sec. λ∞ = Ionic conductance of anion.4 44. The law may be stated as follows: The equivalent conductance at infinite dilution (λ∞) of an electrolyte is equal to the sum of ionic conductances of its constituent ions.4 Ionic Conductance and Ionic Mobilities of some Ions at Infinite Dilution at 25°C.00205 0. • According to equation: K = x × observed conductance. the higher is the observed conductance and so for weak electrolytes a conductivity cell having a small cell constant should be used. The lower the cell constant.

And λ∞ = λc + λa = ku + kv = k(u + v) λc u kv ∴ = = = t+ u+ v λ ∞ k(u + v) kv v = = t– = (1 – t+) λ ∞ k(u + v) u + v So. λ∞ + –  ∞  where r+ and r– are numbers of cations and anions and λ + and λ ∞ are molar – ∞ ∞ conductances of cations and anions respectively. ( λ + + λ + λ H + + λ Cl − ) – ( λ Na + + λ Cl – ) = (x + y – z) = (λ CH 3COO − + λ H + ) Na CH 3COO – λ∞(CH3COOH) (iii) Ionic mobility (Absolute velocity of ions) We have.11 ohm–1 + = 53. when the dissociation of an electrolyte is considered complete. Example: The λ∞ values for CH3COONa.22 ohm –1 K Cl– = 76. (ii) Determination of λ∞ of weak electrolytes: λ∞ for weak electrolytes cannot be determined experimentally.4 ohm–1 Na+ = 50. respectively. HCl and NaCl are x. Ah = t+ F C (ii) λ H + + λ Cl − = y 3 . Examples are: λm (KCl) = λK ∞ ∞ ∞ ∞ + λ Cl – and λm (K3PO4) = 3λ K + + λ ′ PO 4 −3 Ionic Conductance of Some ions at 25°C Br– = 78. λm = r+ . because they do not ionise to a sufficient extent in solution. λc ∝ u or λc = ku λa ∝ v or λa = kv where k is a constant. λ∞ + r– . But λ∞ for weak electrolytes can be calculated from Kohlrausch’s law. We have (i) λ Na + + λ CH COO − = x And λa = (iii) λ Na + + λ Cl – = z.34 ohm–1 NH4+ = 73. So. Calculate λ∞ for CH3COOH. y and z. the ionic conductances of cations and anions can be determined from their experimentally determined transport numbers from the above relations.216 ENGINEERING CHEMISTRY Highlight: Kohlrausch’s law can be stated in another way: At infinite dilution.44 ohm–1 Applications of Kohlrausch’s law (i) Determination of ionic conductances.40 ohm–1 NO3– = 71. It 1000 . Ionic conductance possesses a constant value at a definite temperature. Its unit is ohm–1 cm–2 and is directly proportional to the speeds of the ions. each ion makes a definite contribution towards the molar conductance of the electrolyte irrespective of its ∞ association with other ions. except at a infinite dilution. Thus.

Conductometric Titration During a titration. when.ELECTROCHEMISTRY 217 where. A = 1. C = Concentration (equiv. Potential gradient = 1 V cm–1 Specific conductance K = 1 1 = =I ρ V /I [3 V = 1 V cm–1] Let. . • The speeds of most ions (except H+ and OH–) lie in the range 4 × 10–4 to 8 × 10–4 cm sec–1 under 1 volt cm–1. 9. Ionic mobilities can easily be calculated. Ionic conductance = Ionic mobility × F or Ionic mobility = Ionic conductance F Therefore. And the use of this conductivity change is made to determine the equivalent point of reactions involving neutralisation reactions or precipitations. U = Mobility of cation in cm sec–1 under unit potential gradient of 1 V/cm So. • The H+ ions are about five times and OH– ions are three times faster. λa . Ideally two straight lines are obtained which intersect at the equivalence point [Fig. Highlights: • The ions move very slowly. U= FG H IJ K d i = λc × Similarly. And the end point is determined. where V = mobility of anion in cm sec–1 under potential gradient F So. h = The distance through which cation moves. the conductivity of the solution changes depending on the relative mobility of the ions added from the burette or removed from the solution due to reaction. V = 1 V cm–1.10(a)]. U= distance h = time t h K × 1000 1 1 = t+ × = tλ ∞ t C F F 1 λ = c F F [3 t+ λ∞ = λc] For very dilute solutions. dm–3) It = amp × sec = Q = quantity of current (coulomb) F = Faraday. The conductance of the solution is measured after each addition of titrant and the results are expressed graphically (conductance vs volume of titrant). A = Cross-section of the tube through which current passes.

(b) Precipitation Reactions Conductometric titrations of this type may be performed if the reaction product is sparingly soluble salt. Highlight: The stronger the solution used for the titration. end point of the reaction can be determined easily. 9. . (a) Neutralisation Reactions In the titration of a strong acid with a strong base. For this reason.10(b)]. so they conduct electricity very well. In the titration of NaOH with HCl. Conductivity falls as OH– (aq) ions are neutralized Conductivity Conductivity of Na+Cl– (aq) End point Volume of HCl (aq) added Conductance Conductivity rises due to excess H+ (aq) ions added Volume of alkali Fig. 9. 9. The nature of the titration curve is as in Fig. the decrease in conductance is due to the replacement of OH– ions (molar ionic conductivity = 199) by Cl– ions (molar ionic conductivity = 76).10(a)]. So. • Measurements of conductance in the region of equivalence point are of little value due to hydrolysis.10). 9. In the titration of HCl with NaOH. 9. the graph shows a curvature rather than a clear intersection of the two straight lines [Fig. dissociation or solubility of the reaction products. Beyond the equivalence point. the sharper is the end point (Fig. 9. Fig. The point of intersection of the two curves is sharp.10 (b) Changes in conductivity during titration of a weak acid (CH3COOH) (aq) with a strong base (NaOH) (aq). The titration of KCl solution vs AgNO3 solution satisfies the above conditions. The precipitate should be formed fairly rapidly and should not have strong adsorbent properties. The conductance then rises beyond the equivalence point.10 (a) Changes in conductivity during titration of NaOH(aq) with HCl(aq). the initial fall in conductance is due to the replacement of H+ ions (350) with Na+ ions (50) and the rise beyond equivalence point is due to excess OH– ions (199) [Fig. the increase in conductivity is due to excess of H+ ions with very high ionic molar conductivity (350). In water H+(aq) and OH–(aq) ions are very mobile. there is always an initial decrease in conductance.10 (c).218 ENGINEERING CHEMISTRY Highlights: • The change in volume throughout the course of titration must be kept small by using a titrant which is at least 100 times more concentrated than the solution being titrated.

4 cm–1 a 1.25 cm2. due to hydrolysis the titration curve shows a marked curvature (Fig. . The conductance increases as the concentration of the salt increases. 1996 = Cell constant × observed conductivity.2 × 10–3 ohm–1 cm–1.0002765 cm–1 a = 0. The equivalence point is located by extrapolating the straight lines. SOLVED EXAMPLES Example 1.4 × 1996 1996 = 4. In the region of the equivalence point. 50 If the resistance of cell containing this solution is 500 ohms. Titration of a very weak acid with strong base or a very weak base with strong acids results in a small initial conductance. They are 10.10(b)). what is the cell constant? Example 2.10 (c) Titration curve of KCl solution by AgNO3 solution. calculate the cell constant and specific conductivity. Cell constant = l 10.138 cm–1.4 × N KCl solution at 25°C is 0.ELECTROCHEMISTRY 219 Conductance Volume of AgNO3 Fig. If the cell is filled with an electrolyte and offers a resistance of 1996 ohm. apart. 9.0002765 mhos cm–1.25 Observed conductivity = Specific conductivity 1 ohm–1.5 cm. 9.5 = = 8. Sol. or ∴ Cell constant = l a and R=ρ l a 1 R l = =R× =R×K ρ ρ a l = 500 × 0. = 8. Specific conductivity of an Sol. 1 1 = 8. A conductivity cell contains two electrodes of area of cross-section 1.

1 . C 0.4 ρ K = 0.02109 ohm–1 cm–1 72. Example 4. Sol.2 (N) KCl is 2. cm.075 cm–1 a ρ= 3050 R = ohm. Sol. Calculate the equivalent conductance (λv ) of the solution.2 = 105. If the cell is filled with another solution the observed resistance is 3050 ohm.02109 = M 0. Calculate the cell constant.010416 = = 104. cm. × = = R a 32 5. A conductivity cell containing 0. Sol.58 ohm.02 N KCl solution offers a resistance of 550 ohm at a definite temperature. If the cell is now filled with 0.010416 ohm–1 cm–2 λv = 1000 K 1000 × 0.45 ohm–1 cm2 λm(molar conductivity) 1000 K 1000 × 0. Cell constant = R × K = 550 × 0.767 × 10–3 ohm–1 cm–1.075 l/ a = 252.2 N ZnSO4 . 12. The resistance of a decinormal solution of a salt occupying a volume between two Pt electrodes 1. Specific conductivity of a conductivity cell containing 0. the observed resistance of the cell is 72.4 cm2 in area was found to be 32 ohms.18 1000 C λv(equivalent conductivity) = Kv × = 0.9 ohm = Example 5.166 ohm–1 cm–2.5224 × 1 = 0.80 cm apart and 5.02109 × 1000 0.02 N solution at that temperature is 0.1 –1 cm2. Calculate the equivalent and molar conductivities of the ZnSO4 solution.220 ENGINEERING CHEMISTRY Example 3.5224 cm–1 Again. R=ρ l a or 1 1 l 1 18 .002768 ohm–1 cm–1. The specific conductivity of 0. or ∴ Cell constant = l l R=ρ a a R 1 l = =R× =R×K a ρ ρ l = R × K = 4364 × 2. Calculate specific resistance of the solution.18 ohm. K = cell constant × observed conductivity = 1. the observed resistance of the cell is 4364 ohm.002768 = 1.767 × 10–3 cm–1 = 12. = 210.

0388 Example 9. Sol.6 Ohm–1 cm2. λ∞HCl + λ∞AcONa – λ∝NaCl = (λ H + + λ Cl – ) + (λ Na + + λ OAc – ) − (λ Na + + λ Cl – ) = λ H+ + λ OAc – = λ∝AcOH ∴ 426.05α [CH3 COO – ] [H + ] (0. The equivalent conductances at infinite dilution of various electrolytes are λ∞HCl = 426. Equivalent conductance of acetic acid at 25°C is 0.0λ∞ NaCl = 126.6 given: Example 7.05α 0. (Ka = 1. 390.05α . α= ∞ λv λv = 48.15 ohm–1 eq–1 at 298 K. Calculate λ∞(AcOH).05 = .01898.8 × 10 −5 = 0.24 × 10–6 mho –1 . .1233. If ionic conductance of H+ ions and CH3COO– ions at infinite dilution are 0.0348 + 0. Calculate the degree of dissociation of acetic acid.15 = 0. The mobilities of Ag+ and Cl– ions are 53. wt.9 × 10–3 0.8 and 65.5 = λ∞ AcOH = 390.004 ohm–1 m2 eq–1 = 0. Calculate the solubility cm of AgCl in gl–1 (At.0 – 126. l–1 = 0.05 [α being negligible. λ∞(CH3COOH) = λ∞H+ + λ∞CH3COO– = 0. what will be the concentration of acetate ion. Sol. If 3g of acetic acid is added to enough water to make one litre solution.05 18 × 10 –6 = 18. 1 – α ≈ 1] = 0.046. cm–2 Sol.5.028 × 10–3 (N) acetic acid is 48.05α2 ∴ α= Ka = 0. Calculate the percentage ionisation of acetic acid.0388 ∴ Degree of dissolution = λ∞ λv = 0. The equivalent conductance of 1.1 λ∞AcONa = 91.8 × 10–5). Strength of CH3COOH solution = Initially Degree of ionisation At equilibrium CH3COOH = 0. respectively. Its equivalent conductance at infinite dilution is 390.5). Sol. Example 8.1 + 91.05(1 – α) Ka = 3 g equiv.3 mho eq–1 cm2.05α × 0.6 ohm–1 cm–2 eq–1.05 = = . 0. The specific conductivity of saturated solution of AgCl is 1.05(N) 60 CH3COO– + H+ 0 0 α .05) 2 α 2 = = 0.05 (1 – α) [CH 3COOH] 0.0018 = 0.05 1. Calculate the degree of dissolution of acetic acid.004 ohm–1 m2eq–1.0018 ohm–1m2 eq–1. Cl = 35.ELECTROCHEMISTRY 221 Example 6.0348 ohm–1 m2 eq–1 and 0. Example 10. Ag = 108.

of Ag 0.8 = 0.1351 x = 63. wt.24 × 10 –6 = 9.e.88). was found to be 0.000 tAg + = tNO 3 – u 0.478 = 0.5) g l–1 = 0.6350 g.1351 g.1 mhos eq–1 cm2 λv = KvV V= 119.1351 × 31.0398 tCu +2 = ∞ tSO4 = 1 – tCu +2 = 1 – 0. and 0.6236 g.6350 – 0.6236) g = 0. A dilute solution of CuSO4 was electrolysed.1351 g.88 Loss at anode 0. Calculate the transport number of Cu+2 and SO4–2 ions.286 = 0.1495 g l–1.6 107. = = wt. wts.00104 eq l–1 9. The amount of Cu in the anodic solution was found to be 0.6 × 102 l eq–1 ∴ ∴ Solubility = 1 eq l–1 = 0. respectively. Wt.714. placed in series. of Cu from anodic solution (anolyte) [At.3 + 65. = 0.3 = 119.0398 g 107.916 = 1 – tAg + = 1 – 0.522.916 = = = 0. of Cu Eq. of Ag = Eq.1 λ ∞v = = 9. Example 11. λα = λ+ + λ– λα(AgCl) = λ(Ag+) + λ(Cu–) ENGINEERING CHEMISTRY = 58.916.478 u + v 0. Sol.6236 g before and after electrolysis. using Pt-electrodes.916 = v 1.88 2 ∴ ∴ ∴ x= 0. Find the transport number of Ag+ and NO3– ions. Cu(63. ∴ Amt. ∴ Hence.6 × 10 2 = (0.0114 g Wt. The speed ratio of Ag+ and NO3– ions in a solution of AgNO3 electrolysed between Ag-electrodes is 0.916 0. of Ag deposited in voltameter = 0. of Cu in anodic solution before electrolysis ∴ Loss in wt.114 = = 0. = Ag(107. .1351 g of Ag. = (0.916 + 1 1.0104 × 143. wt.222 Sol.. of Cu in anodic solution after electrolysis is Wt. Speed of Ag + Speed of NO 3 – = u 0. According to Kohlrausch’s law. The weight of Ag deposited in a silver coulometer.6 × 105 cm3 eq–1 Kv 1.6350 g.6)] = 0. of Cu deposited equivalent to 0.286 Total loss 0. Example 12. Sol. of Cu( x) wt. i.

What is electrolysis? Ans. 2. Q. Al etc. Mention some important uses of electrolysis process. which is only possible in molten state or in solution. If the anode is graphite or platinum. Q. 8. What is electrochemistry? Ans. the product at the cathode is hydrogen. (ii) Electrochemical cell reactions: Electrochemical cell reactions are mainly redox reactions. What are electrochemical reactions? Ans. Q. 6. 4. Q. the deposition at the cathode depends on the type of metal ion in the salt. 5.e. What are the products of electrolysis of molten salts? Ans. (i) Extraction of Na. from hydrogen ions produced by the ionisation of water 2H+ (aq) + 2e H2(g) During the electrolysis of a salt solution. involved in the cell where electrical energy is produced due to a chemical change. Br . Br. Why are the molten compounds or solutions used as electrolytes? Ans.f. (i) Electrolysis: Electrolysis requires electrical energy from some external source to bring about a chemical change i. it gets deposited at the cathode viz. Cu+2 Cu+2(aq) + 2e Cu°(s) But if the metal is in higher position in electrochemical series. I) . Electrolysis is a process where electric current is used to decompose a molten ionic compound or a solution of ions into elements. During electrolysis of a solution of a salt in water. Electrochemical reactions are the reactions which involve the flow of current. Mention the types of electrochemical reactions. electrical energy is consumed. Ions can only conduct electricity when they are free to move. (ii) Electrolysis of brine to produce NaOH and Cl2 (iii) Electroplating (iv) Copper refining. Metals are deposited at the cathode and the nonmetals are liberated at the anode. the products are halogens from metallic – – –  halides (Cl . Q. What are the products of electrolysis of an aqueous solution of a salt? Ans. I ) 2X– (aq) → X2(g) + 2e (X = Cl.ELECTROCHEMISTRY 223 SHORT QUESTIONS AND ANSWERS Q. in this type of reaction. This statement applies for both generation of e. Q. 7. Ans. If the metal is in lower position of electrochemical series. Ans.m. the liberation at the anode depends on the type of electrode.. Q. 3. Electrochemistry is the study of interrelations of electrical energy and chemical energy and interconversions of the two energies. 1. of a cell as well as electrolysis.

11. 9. hydrogen is liberated at the cathode and bubbles off. 9. Quantity of electricity in an hour = 30000 C/S × 3600 s.000 mol 96. Q.224 ENGINEERING CHEMISTRY Otherwise oxygen is liberated from water.000.000. 10.480 = 25.75 kg. (a) Draw a neat sketch of an electrolytic cell.000 C. Brine is a solution of NaCl in water. What is the effect of concentration of a salt solution during electrolysis? Ans.000. Q. In electrolysis of a dilute solution of NaCl increasing amounts of oxygen are liberated. Electrolysis of brine is the basis of the alkali and chlorine industry—a well known electrochemical industry. Cu(s) → Cu2+ (aq) + 2e. Mass of Na formed per hr.11.480 108. What mass of Na is formed in an hour at the steel cathode? Ans. Amount of Na formed per hr. (a) – + Cathode +ve ions Anode Positive ions gain electrons at the cathode (reduction) and turn into atoms –ve ions Negative ions lose electrons at the anode (oxidation) Electrolyte Fig. (b) Sodium is extracted by the electrolysis of a mixture of a molten NaCl and CaCl2. = 108. atoms of electrode turn into ions.000 A. = = 108. (b) The equation for liberation at the cathode is – Na+ + e → Na Time of electrolysis = 3600 sec. Electrolytic cell. Q. Chlorine is liberated at the anode during electrolysis of a concentrated solution of NaCl. .750 g 96. If the anode is a metal (Cu. Electrolysis of brine is used to manufacture chlorine. What is the utility of electrolysis of brine? Ans. In a commercial cell the current is 30.000 × 23 = 25. or Ag). hydrogen and sodium hydroxide. while the solution turns to NaOH. During electrolysis chlorine is liberated at the anode. The concentration of a salt solution has an effect on the product of electrolysis at the anode.

. l = 1 cm. it allows positive ions to pass but not the negative ions. 14. A membrane cell is shown in Fig. The conductance (C) is the reciprocal of R 1 C= R Unit of conductance = ohm–1 or mho ρ= It is a measure of ease with which current flows through a conductor. R=ρ R. unit of ρ = ohm-cm. a l ρ = R. a . ρ = proportionality constant and is known as specific resistance or resistivity. 9. What is conductance? Ans. unit of R = ohms. l Q. The membrane permits the solution to pass and prevents mixing of NaOH and Cl2. From. Thus it is resistance offered by a conductor of 1 cm3. What do you mean by resistance? Ans. 12. a = area of cross-section of the conductor a l a where. Specific resistance or resistivity is the resistance offered by the conductor of 1 cm length and 1 cm2 area of cross-section. 9.ELECTROCHEMISTRY 225 The cell to be used for electrolysis should be carefully designed so that chlorine can be kept apart from NaOH. Q. Q. 13. R. Two types of cell are in use: (a) mercury cell (b) membrane cell. where a = 1 cm2. otherwise they will react.12 Membrane cell. What do you mean by specific resistance or resistivity? ∴ ρ= Ans. The membrane has ion-exchange properties. where l = length.12. R∝ or l . Cl2(g) H2(g) Brine NaOH(aq) Porous membrane + Ti-electrode – Ni-electrode Fig. Resistance (R) of any conductor is the obstruction offered to the flow of current.

(iii) Conductometric titration. The degree of dissociation (α) is the fraction of the electrolyte that dissociates into ions. What do you mean by equivalent conductivity of an electrolytic solution? Ans. Q. λ m∞ Q. Ans. 18. 16. What is transport number? Ans. 19. . K= 1 1 l = ρ R a It is defined as the conductance of 1 cm3 of a conductor unit of K = ohm–1 cm–1 Q. Q.226 ENGINEERING CHEMISTRY Q. Give the relationship of molar conductivity with concentration. It is the fraction of total quantity of electricity.e. is equal to the sum of ionic conductances of cations and anions. What do you mean by molar conductivity of an electrolyte? Ans. M = molarity of the solution K = specific conductance. 21. What is specific conductance? Ans. (i) Measurement of degree of dissociation. 15. What is the effect of dilution on molar conductivity? Ans. Q. i. 23. b = constant c = concentration λm∞ = molar conductivity at infinite dilution λm = molar conductivity at a given dilution As c → 0 λm = λm∞. The specific conductance (K) is the reciprocal of specific resistance (ρ). FG IJ H K 1000 K C C = normality of the solution. Molar conductivity increases with dilution. Q. For weak electrolytes it is related to λm and λm∞ as follows: λ α= m . Q. Unit of λeq = ohm–1 cm2 equiv–1. What do you mean by degree of dissociation of an electrolyte? Ans. (ii) Determination of solubility and solubility product. The molar conductance. It is the conductivity of all the ions produced in a solution containing one gm mole 1000 K of the electrolyte. 17. at infinite dilution of an electrolyte. The relation is Equivalent conductivity λeq = λm = λm∞ – b c where. Ans. Q. 20. 22. carried by cations or anions. Define Kohlrausch’s law. molar conductivity λm = M where. What are the applications of conductance measurement? Ans. It is the conducting power of all the ions present in a solution of an electrolyte containing 1 g equiv..

Conductance varies linearly with the volume of titre. That is why equivalent conductivity of weak electrolyte increases with dilution.—explain.ELECTROCHEMISTRY 227 Q. Q. degree of dissociation increases. That is why resistance cannot be plotted against volume of titre. λ∞ can be determined by extrapolation of the curve λ vs. will help electrolysis of the electrolytic solution bringing about a change in concentration of the electrolyte which in turn will affect the conductance of the solution. so plot of resistance vs. Why equivalent conductivity at infinite dilution cannot be directly determined experimentally? Ans. and c are related by the equation. 9. Ans. Q. 26.C. All conductance measurements are done with the help of A. In all conductometric titrations. λ = λ∞ – K c So. . However λ are not so related in case for weak electrolytes. 9. volume of titre and not resistance vs volume of titre—explain. Equivalent conductivity-L-ohm –1 cm 0 eq–1 150 Sodium chloride 100 Sodium acetate 50 Acetic acid 0 –4 –8 ÖC – (C in equivalent/liter) Fig. but resistance R = FG H 1 does C IJ K not vary linearly with the volume of titre. 25. Q.13) for strong electrolytes to zero concentration. 24. so is the number of ions. i. Ans. we plot conductance vs. D. Kohlrausch pointed out that at high dilution the equivalent conductivity (λ) is plotted against the square root of concentration (c) gives a straight line which meets the zero axis of concentration at λ∞. c (Fig.C.. volume will not give straight line. at high dilution λ∞.e. So λ∞ for weak electrolytes cannot be experimentally determined by the above equation. Equivalent conductivity of a weak electrolyte depends on the number of ions of the electrolyte present in solution with dilution of a weak electrolyte. the equivalent conductance at infinite dilution. Equivalent conductivity of a weak electrolyte increases with dilution— explain. Ans.13 Extrapolation of λ versus ?. 27.

With the aid of a plot. Mention its units. 28. EXERCISES 1. 9. (b) State Kohlrausch’s experimental equation. What is meant by equivalent conductivity of an electrolyte? Describe the method you would adopt to measure equivalent conductivity as also its value at infinite dilution for KCl and acetic acid. (b) Define specific conductance. specific conductance decreases with dilution. n = F. (a) Define the terms (i) specific conductance and (ii) equivalent conductance. When an electrolyte is diluted. 3. the number of ions per millilitre decreases. 7. conductivity and conductance. Zn Z1 Z2 (ii) Equivalent conductance. (a) Define the terms: (i) Specific conductance (b) Discuss the effect of change in concentration of the solution on specific conductance and equivalent conductance. and E. (e) Give the applications of the theory of electrolytic dissociation. Specific conductances decreases with dilution while the equivalent conductance increases—explain. How will you determine transport number? (b) Specific conductance of an electrolyte decreases. (d) Define Faraday’s second law. explain the variation of equivalent conductance of KCl and CH3COOH on dilution. Ans.E. But it outweighs the minor increase in conductance due to increase in degree of dissociation. E1 E2 E = = . 6. (b) Prove that 4. 11.E. 2. But equivalent conductance increases because the total number of ions per gram equivalent increases with dilution for the increased value of degree of dissociation.E. What do you mean by electrolysis? (a) Explain the terms : (i) Faraday (ii) E. i.2. (c) Write the shortcomings of the theory of electrolytic dissociation. degree of dissociation increases and also the total volume increases. (c) State Kohlrausch’s law..228 ENGINEERING CHEMISTRY Q. 10.. How would you account for the result? (a) Define the specific resistance of a solution. What is an electrolyte? Give examples. (c) Define the absolute ionic mobility.C. (a) State the relationship between the cell constant. (b) Relate C. 8. (a) Define transport number. 5. (b) State and explain Kohlrausch’s law of independent mobilities of ions. while equivalent conductance increases on dilution—explain.e. (a) Write Kohlrausch’s empirical equation. What is meant by the transport number of an ion? How is it determined? A molar solution of CdI2 showed an anion transport number 1. (a) State the Faraday’s laws of electrolysis. . Discuss its significance and applications. As a result..C. (b) State and explain Kohlrausch’s law. Explain a few applications of this law.

A 2.420.0 ohm–1 cm 2] The resistances of 0. Write short notes on : (i) Cell constant (ii) Absolute velocity of an ion (iii) Conductometric titration (iv) Kohlrausch’s extrapolation method of determining λv.02 M KCl solution at this temperature was 0.00277 ohm–1 cm–1. Calculate the equivalent conductance (λv) of the solution (cell constant = 0.0 ohm–1 cm 2.46] 2 mins. what is the cell constant? [Ans.88 cm–1). The specific conductance of 0. tSO = = 0. 144. 4.0128 ohm –1 cm –1. What is the percentage dissociation of acetic acid at this concentration? [Ans. if the cell constant is 0. and its resistance was found to be 37. In a voltameter connected in series. 166. [Ans.1 (N) solution of NaCl is 210 ohm at 18°C.30 ohm of H+ and CH3COO– ions at infinite dilution are 349 and 40 ohm –1 cm2 eq–1. 1. tCu +2 = 0. wt.138 cm –1] The resistance of 0.5 ohms. [Ans. Calculate the equivalent conductance of the given solution.ELECTROCHEMISTRY 229 12.84% CuSO4 solution was electrolysed using Pt cathode and Cu-anode. 19. . If the resistance of 50 cell containing this solution is 500 ohms.18 ohm–1 cm –1] The resistance of a conductivity cell filled with 0. 41.9 ohm–1 cm2] The resistance of a cell filled with 0. Discuss all types of conductometric titrations.215] 24. Why does the equivalent conductivity of a NaCl solution increase with dilution? How can the electrolytic conductance be measured? 16.000275 mhos cm–1. 0.19%] During the electrolysis of CuSO4 solution. [Ans.6). After electrolysis 51. 18. After electrolysis. Calculate the equivalent conductance of AgCl at infinite dilution.74 × 10–4. A 0.785] 4 25. 13.000 ohms respectively at 298 K. 83. Calculate the equivalent conductance (λv) of the solution at the same temperature.519 g of AgNO3. 23. The specific conductance of 0.409 g Cu in 54. Specific conductivity of an 17.0 g of the anode solution (anolyte) was found to contain 0. The ionic conductances The equivalent conductance of 0. The cell was then washed out and filled with 0. NH4NO3 and AgNO3 are 149.4 ohms at 298 K. respectively. [Ans. Also explain the nature of the graph between conductance and volume of titrant used.1 M of CuSO4 . Calculate the equivalent and molar conductances of CuSO4 solution. current was passed for [Ans. [Ans.1 N KCl solution and 0. 99. 20.36 × 10–4 Sm2 eq–1 respectively. [Ans. A one amp.878 cm–1.1 N KCl solution is 0. 1.215.2 ohm–1 cm2] The equivalent conductance at infinite dilution of NH4Cl. Calculate the transport number of Cu+2 and SO 4 – ions [At. 22. N KCl solution at 25°C is 0.058 g of Cu was deposited. Find the transport no. 21. the cathode solution contained 0. = Cu(63.7 g solution.02 N of an electrolytic solution in a conductivity cell were found to be 310 ohms and 2. of Cu+2 ion.02 (N) KCl solution at 25°C is 225 ohms.01 N acetic acid is 16. loss of Cu in the anode compartment was 0. tCu +2 = 0.382 × 10–2 S m 2 eq–1] –1 cm2 eq–1 . S(32) and O(16)]. 14.804 g. 42. The increase in the weight of cathode – was 0.84 × 10–4 and 133. [Ans. Define Kohlrausch’s law and discuss its applications. 15.80% AgNO3 solution was electrolysed using Ag-electrodes. tAg + = 0. of Ag+ in AgNO3.098 (N) KCl was found to be 214. What is the transport no.

atom of Fe+2. atom of Fe to 1 g. Avogadro’s number of electrons are gained to get reduced For 1 g. a cell is constructed of two electrodes and the e. And we get deflection in milliammeter.Electrochemical Cells ELECTRODE POTENTIAL 10 Oxidation is a process where electrons are lost by a substance and reduction is a process where electrons are gained by a substance.m. If we make an arrangement as shown in Fig. Nernst called this tendency as “solution pressure”. As for example in the reaction: 2FeCl3 + SnCl2 2FeCl2 + SnCl4 +3 + Sn+2 i. We take oxidation as a half cell reaction and reduction as another half cell reaction and the total reaction is redox reaction and becomes the source of e. mA NaCl salt bridge HCl Pt FeCl3 A Pt SnCl2 B HCl Fig. By 230 . And for every g. 10. 10. twice the Avogadro’s number of electrons is lost.. Nernst Solution Pressure Theory for Electrode Potential If a metal rod (M) is dipped into a solution containing its ions (M+n) the metal shows a tendency to send ions into solution.m. Reaction in vessel A : Reaction in vessel B : 2Fe+3 + 2e Sn+2 – 2e Fe+2 [reduction] Sn+4 [oxidation] 2Fe+3 + Sn+2 Fe+2 + Sn+4 [cell reaction] So.e. of the cell is obtained from the algebraic sum of the two electrode potentials.1 Construction of a cell.f. of the cell. atom of Sn+2. 55. There is a clear sign of flow of electrons through the metallic wire connected and this arrangement is considered as a cell which generates electric current at the cost of oxidation and reduction reactions occurring simultaneously.1 after sometime.85 g. Fe Fe+2 + Sn+4 +3.f. we get Sn+4 in the vessel B and Fe+2 in vessel A.

Here also a electrical double layer is set up and electrode potential is established. As for example. The electrode potential is also established in the case of every electrode where electrical double layer is set up by exchange of electrons. the solution has a tendency to send M+n ions to the metal rod due to “osmotic pressure”. the system (Pt) Fe+2 (Pt) Fe+3 + e sets up an electrical double layer where an inert metal platinum is dipped into a mixture containing Fe+2 and Fe+3 and an electrode potential is established. in the case of Zn/Zn+2. And each electrode has a potential which is known as single electrode potential (∈). And so is the case with Cu/Cu+2. metal rod becomes negatively charged. On the contrary. Fig.2 Electrode potential. Zn rod sends Zn+2 ions into + – – + the solution and gets negatively charged and attracts – + + – + – – + – + + – positive charges towards the rod and.303 × 8. For example. the metal rod accumulates electrons and as a result. the solution pressure Zn Cu exceeds osmotic pressure. but in this case. To consider the electrodes separately. as a result.341 × 298 log10 aM + n n × 96500 0. This established potential is called electrode potential. R ⇒ Gas constant RT ln aM + n where ∈° is a constant dependent upon the nF n ⇒ Valency of metal T ⇒ Absolute temperature F ⇒ Faraday constant a ⇒ Activity of M+n.ELECTROCHEMICAL CELLS 231 sending the ions.F. of the cell is algebraic sum of the ∈ two electrode potentials. an electric cell is composed of two electrodes. E. At 25°C the equation comes to : ∈ = ∈° + = ∈° + 2. we call each of them as single electrode. osmotic pressure exceeds solution pressure and Cu rod gets positively charged. So.059 log10 aM + n n . an + – – + – + + – + – – + electrical double layer is set up and a potential is CuSO4 ZnSO4 established between the metal rod (Zn) and its ions (Zn+2). But when one exceeds the other the metals get either positively or negatively charged. 10. E = ∈1 + ∈2 Single Electrode Potential (∈) ∈ The electrode potential for an electrode reaction: M+n + ne M (metal) is given by Nernst equation ∈ = ∈° + metal. When “solution pressure” equalises “osmotic pressure” there is no net effect.M.

e.m. Zn is ionised to Zn+2 i.e. • A complete cell consists of two half cells. For example.232 For general purpose.. We are to assign a definite value of electrode potential for a definite electrode. a solution of acid with ([H+] = 1) and to which hydrogen gas is bubbled at one atmosphere and platinum foil is dipped. Total cell reaction is: Zn + Cu+2 Highlights: According to IUPAC convention. to determine the electrode potential.e.059 log10 C + n M n [A form of Nernst equation] For this cell Zn/Zn+2 is anode and Cu/Cu+2 is cathode and at anode. So reduction takes at the right hand electrode and oxidation takes place in the left hand electrode. (See page 227) Zn|ZnSO 4 (solution) H 2SO 4 (solution)|H 2 (Pt) (aZn+2 = 1) (aH + = 1) . • E. then the expression is : ∈ = ∈° + When a = 1.f. We have a zero potential for this electrode. of the cell E = ∈right – ∈left (when both are reduction potentials) E = ∈red + ∈ox. Determination of Standard Potential ∈° of a Metal Electrode The electrode potentials cannot be determined straight. • The double vertical lines denote the junction of the two solutions and this liquid junction potential is eliminated or minimised by the use of a salt bridge. • Oxidation potential may be taken as reduction potential with a minus sign.. • The single vertical lines denote electrical contact. aM + n = C M + n So. Zn+2 + Cu. then ∈ = ∈° ∈° is known as Standard electrode potential of metal M. reduction takes place at the cathode. oxidation takes place at anode and at the cathode Cu+2 is neutralised i. we take the ∈° value for hydrogen electrode to be ‘zero’ i. Ecell = 1. If we construct the following cell: Zn(–)| Zn+2 || Cu+2 |(+) Cu. Now if we want to determine standard electrode potential of zinc (∈°Zn) we are to construct the following cell.. The right hand half cell is regarded as the positive electrode and the left hand half cell is regarded as negative electrode. • Electrons flow through the external wire from the negative electrode to the positive electrode.015 V ENGINEERING CHEMISTRY 0.

Cu++ Calomel electrode (Pt) H2.106.m. Calculate the e.959 Pt.f. H+ Pb. Na+ Li. This list with ∈° values are known as electrochemical series. Fe+++. H+ Cl– Cl2 Au+++ Hg2++ Ag+ Fe+++ Cu++ 1 2 O2 + 2H+ + 2e = H2O Au. 10.e. Mg++ Na. E° of the above constructed cell which is ∈°Zn. Zn++ Mg. of a cell CuSO4 (sol n ) Cu + (aCu = 1) = Standard reduction potential of Cu + std.06 0.m.762 = 1.136 0.799 0. Ag+ Pt. 762 1. of the cell Zn ZnSO4 (solution) (aZn +2 = 1) Sol.f. Liquid junction potential Daniel cell: Cell reaction is: Zn | ZnSO4(C1) || CuSO4(C2) | Cu Zn + Cu+2 E = ∈right – ∈left ° ∈right = ∈Cu + Zn+2 + Cu [when both are reduction potentials] RT [Cu +2 ] ln 2F [Cu] .m.344 0. Pt.866 2.1: Standard Electrode Potentials (Reduction). Au+++ Hg. the electrode potential of other metals are determined similarly and listed in table.. F – Oxidants i. O2.m.1) Example 1.798 0.344 + 0.e. Li+ Pb++ Hg2Cl2 + e = Hg + Cl– + e= + + + + + + H2 2e = Pb 2e = Sn 2e = Zn 2e = Mg e = Na e = Li Reductants i. Typical calculation of e.771 0. of the cell will be E° = ∈°H + ∈°Zn = ∈°Zn [Q ∈°Η = 0] The e. Hg2++ Ag. Fe++ Cu. oxidation potential of Zn. 25°C Electrode F2..23 1. Sn.000 – – – – – – 0. = 0.80 1. and we get standard e.f.f.360 1. Sn++ Zn. Cl2(g).268 0. electropositive H+ Pb++ Sn++ Zn++ Mg++ Na+ Li+ The e. Likewise.ELECTROCHEMICAL CELLS 233 Table. (Table 10.715 2.m. electronegative 1 2 1 2 Electrode reaction (Reduction) F2 + e = F– + e = Cl– + + + + + 3e = Au 2e = 2Hg e = Ag e = Fe++ 2e = Cu 1 2 E°(Volts) 2.f of a cell is measured by potentiometer.122 0.

If a cell is constructed with the two elements as the electrodes then the e.e.m. of the cell.785 volt.059 [Ox] ln Ox = ∈° log 10 (for general purpose) Red–ox + nF aRed [Red] n Here also ∈° values are determined against standard hydrogen electrode. For example – Zn(∈°Zn = – .f. of the cell is obtained from the oxidation potential of anode and reduction potential of cathode.1) 1. These electrodes are known as redox electrodes.m. E = Reduction potential of Cu + Oxidation potential of Fe.234 or Likewise.344) Likewise. 2F [Zn +2 ] 7 4 8 5 9 6 7 8 9 ∴ ° ° Ecell = (∈Cu − ∈Zn ) + Interpretation of the Electrochemical Series (Table 10. higher is the electronegativity of that element. The higher the standard electrode potential (reduction) of an element. possessing lower standard electrode potential (reduction) will displace the metal from the solution of its ions with a higher standard electrode potential (reduction) value. 3.344 + 0. . ln [Zn +2 ] 2F 2F RT [Cu +2 ] ln . Electrode potential (∈) is given by: Oxidant + ne Ox + ne ∈ = ∈°Red–ox + Reductant Red. 2. the non-metals with the higher electronegativity displace the elements possessing lower electronegativity.762) will displace Cu from its solution (∈°Cu = .441 = 0. then e. ∈left = ∈°Zn + = ∈°Cu + ENGINEERING CHEMISTRY RT − ln [Cu +2 ] 2F RT ln [Zn +2 ] 2F [Q [solid] = 1] [Q [solid] = 1] ° Ecell = ∈Cu + 4 5 6 RT RT . Any oxidised or reduced form of an element behaves so. Let Fe and Cu are used as electrodes. a RT 0. Lower position in the table of an element indicates its higher tendency of ionisation. = 0.. The higher electropositive metal i. For example: 2KI + Cl2 → 2KCl + I2↑ Redox-electrodes A mixture of Fe+2/Fe+3 salt in a solution or Ce+3/Ce+4 salt in a solution can act as an electrode if a platinum wire is dipped into either of the solutions.f. ln [Cu +2 ] − ∈°Zn + .

∈° = . the different oxidation states are represented by the corresponding ∈° values as follows: Mn2+ + 2e + Mn.23 V 2 .36 + 7H 2O Mn+2 + 4H2O 1 2 (Pt) Fe+2/Fe+2 Br2/Br– 1 (Pt) IO2–/ 2 I2 Br2 + e (Pt) MnO2/Mn+2 Tl+3/Tl+2 1 2 IO3– + 6H+ + 5e MnO2 + 4H+ 2e Tl+3 + 2e Tl+1 Cr2O72– + 14 H+ + MnO4– + 8H+ + 5e BrO3– + 6H+ + 5e Ce+4 1 2 Cl2/Cl– 2–/2Cr+3 Cl2 + e Cl– 6e 2Cr+3 Cr2O7 MnO4–/Mn+2 1 BrO2–/ 2 Br2 + 1.16 0.065 + 3H2O + 1. ∈° = – 1.20 + 1. A Latimer diagram in a compact form explains a great deal of information and shows the relationships between the various species in a simple and lucid form.36 0.56 V MnO4 + e + + 2e 2+ + 2H O.69 1.41 – 0. MnO2 + 4H Mn ∈° = 1.25 0. Latimer Diagram The redox potential of different oxidation states for a particular element can be summarised with the help of EMF diagram and the simplest type of such diagram is the Latimer diagram.65 The pair which occupies lower position in the table can oxidise the pair which occupies a higher position in the table.2: Normal potentials (∈°) of some redox system (Hydrogen scale) Electrode (Pt) Cr+2/Cr+2 (Pt) V + 2/V+2 (Pt) (Pt) (Pt) (Pt) (Pt) (Pt) 1 (Pt) H+/ 2 H2 Electrode reaction Cr2+ + e V+3 + e H+ + e Sn+4 + 2e Cu+2 + e Fe(CN)63– + e MnO4– + e Fe+3 + e 1 2 1 I 2 2 Electrode potential ∈°(volts) 0.21 – 0. Mn Mn ∈° = 1.15 0.00 + + + + 0. We know that Mn exists in different oxidation states and in acidic medium preferably at zero pH.01 MnO4–/MnO2 Co+2/Co S2O42–/2SO42– 1 2 Ce+4/Ce+3 +e MnO4– + 4H+ + 3e MnO2 + 2H 2O CO+2 + e CO+2 S2O42– + 2e 2SO42– 1 2 Ce+2 Br2 + 3H2O F2/F– F2 + e F– + 2.61 1. ∈° = 2.26 V MnO42– . ∈° = + .52 V MnO2 + 4H+ + e Mn3+ + 2H2O.77 + 1.535 + 0.23 + 1.18 V +3 + e 2+.52 + 1.25 + 1.ELECTROCHEMICAL CELLS 235 Table 10.54 Cr2+ V+2 1 2 H2 Sn+2 Cu+1 Fe(CN)64– MnO42– Fe+2 Br– Mn+2 + 2H2O 1I 2 2 Sn+4/Sn+2 Cu+2/Cu+1 [Fe(CN)6]2–/[Fe(CN)4]4– MnO4–/MnO42– 1 I /I– 2 2 1 2 +e I– + 0.52 + + + + 1.95 V MnO42– + 4H+ + 2e MnO2 + 2 H2O.82 2.36 + 1.

95 V 1.26 V 0. in this case the comproportionation reaction Ag2+ + Ag = 2Ag+ will take place. are called skip couples and the corresponding potentials are called skip-step potentials.18 V The feasibility of disproportionation of H2O2 can be predicted by considering the change in the ∈° values for the following reactions: Overall reaction: 2H2O2 → 2H2O + O2 (a) ∴ (b) ∴ Reduction: Oxidation: H2O2 → O2 + 2H+ + 2e ∈°Ox = – . Hence. therefore dispro1.80 V . ∈° = 1. The overall ∆G° of two successive steps will be the sum of the individual ∈° values to ∆G° values by multiplying by the relevant – nF factor. the Latimer diagram is also helpful in predicting whether a particular species will undergo disproportionation or comproportionation. H2O etc.12 F Since the process is accompanied by decrease in Gibbs free energy.52 V – 1.70 V MnO4– + 8H+ + 5e Mn2+ + 4H2O. MnO4– → MnO42– → MnO2 → Mn3+ → Mn2+ → Mn In this diagram.4 F Adding (a) and (b).70) = 1.52 F 0. are not included in the diagram. 2H2O2 → 2H2O + O2 ∆G° = – 2. adding them together and converting the sum back to ∈° for the non-adjacent couple dividing by – nF for the overall electron transfer.236 ENGINEERING CHEMISTRY MnO4– + 4H+ + 3e MnO2 + 2H2O.76 = – 3.76 volt 0. we know that H2O2 disproportionates into H2O and O2 under acidic conditions. We know that ∆G° values corresponding to different steps can be added but the ∈° values cannot be so added. O 2 → H 2 O 2 −1 → H 2 O −2 0. H2O2 + 2H+ + 2e → 2H2O ∈°Red = 1.98 V portionation will be spontaneous. A Latimer diagram helps us to derive the standard potentials of such non-adjacent couples. A species will disproportionate into its neighbour species if the potential on the left is lower than that of the right species.70 V ∆G°1 = – nF∈° = – 2F × (– . ∈° = 1. The couple such as MnO4–/MnO2 or MnO4–/Mn2+ or MnO2/Mn2+ etc. for the change Ag2+ → Ag+ → Ag it can be shown by similar calculation that disproportionation of Ag+ will not take place because it will be accompanied by increase in ∆G° value. The species H+. For example.70 volt 1. Since the nF factor cancels in this way.76 V ∆G°2 = – nF∈° = – 2F × 1. On the other hand. we can write n1∈°1→ 2 + n2 ∈°2 → 3 ∈°1 → 3 = n1 + n2 Besides calculating the ∈° values of non-adjacent couples.56 V 2. ∆G° = – nF∈°.51 V The whole information can be summarised in the compact manner in a collinear diagram as follows. Again ∆G° is related to ∈° as follows. the oxidation states of Mn decrease gradually from left to right. a species will undergo comproportionation if the potential on the left is higher than that of the right species in the diagram. On the other hand.

This is due to the fact that.ELECTROCHEMICAL CELLS 237 Frost Diagram A Frost diagram for an element M is a plot of n∈° for the couple Mn+/ M against its oxidation number n where n gives the change of oxidation number from n to zero. Cu /Cu 6 5 4 nΰ (V) Nΰ Increasing 2+ + HNO3 N2O4 HNO2 H /H Zn /Zn +2 3 2 1 0 NH 3 NH2OH NH3OH N2O N2O N2 NH4 –3 –2 –1 0 +1 NO N2O4 N2 NO2 NO3 – stability Most stable oxidation state N2H4 NO N2H5 –1 Oxidation number +2 +3 +4 +5 Oxidation number Fig.3 (b) Frost diagram for nitrogen (N). however.3(a) and 10. not spontaneous as it is not kinetically favoured. An ion or a molecule in a Frost diagram will be unstable with respect to disproportionation if it lies above the line connecting two adjacent species. NH4+ – ion contains N in –3 oxidation state and in NO3 ion N is present in +5 oxidation state. on the . Under such circumstances comproportionation will be thermodynamically favoured e. A substance that lies below the line connecting two adjacent neighbours in a Frost diagram is more stable than they are because its average free energy is lower.3(b).. The Frost diagram for nitrogen in various oxidation states is as given in Fig. When the line joining two points in the diagram is quite steep. From the diagram it is seen that since NH2OH lies above the line joining NH3 and N2 it will undergo disproportionation. Hence. however. 10. Cu. 10. it can be predicted whether the oxidant or the reductant will show greater tendency for a reaction. The oxidising agent of a redox couple will show tendency to reduction if the slope is more +ve. 10. in NH4NO3..e. The diagram also indicates that the slope remains steep all the way to N2 indicating that N2 should be the product of reduction of HNO3 if excess Cu is present in the reaction. the potential of the corresponding couple is higher. An examination of this plot shows that the slope of the line connecting HNO3 to lower oxidation numbers is quite steep and hence HNO3 will function as a good oxidising agent under standard conditions i. does not reduce HNO3 to N2 due to kinetic limitations and NO is commonly the gas which is evolved when Cu is heated with dilute HNO3. A comparison of the slope of the Cu2+/Cu couple with that of the HNO3/NO couple shows that it is more +ve for the latter and hence HNO3 will oxidise Cu to Cu2+. we can make thermodynamic predictions about the reaction between any two couples by comparing the steps of the corresponding lines.3 (a) Fig.g. The disproportionation is. On the basis of this diagram. (at pH = 0). the average free energy of the intermediate species is larger than the mean free energy of the two adjacent species. The reducing agent of the couple with less +ve slope will tend to undergo oxidation.

which is intermediate between – 3 and + 5 and its – position in the Frost diagram is lower than that of NO3 ion and NH4+ ion and so NH4NO3 + + NO – → N O + 2H O. HNO2 and HNO3 lie approximately on a straight line in the Frost diagram. – 2. −1 +1 0 nΰ (V) O2 H2O2 Acidic –1 –2 H2O –2 –1 Oxidation number 0 Fig.70) = – 1. 0. n = – 2.. change in oxidation number = – 1. The difference is.238 ENGINEERING CHEMISTRY other hand N2O has an oxidation state of +1. respectively. therefore.76 = + 1.70 volt. This is due to the fact that NO. ∴ ∈° = – 1 × . NO + NO2 + H2O → 2 HNO2 3HNO2 → HNO3 + 2NO2 + 2H2O 3NO2 + H2O → HNO3 + HNO2 A Frost diagram can be constructed from a Latimer diagram e.70 volt and n∈° corresponding to oxidation number of – 2 is – 2. When the line joining three undergoes comproportionation. – 1 and – 2. H2O2 and H2O are 0.4 Frost diagram for the system O2 → O2–2 → 2O–2. let us consider the Latimer diagram.23 = – 2. n∈° for the formation of H2O = – 2 × 1. .23 V H2O The oxidation numbers of ‘O’ atom in O2.g. when O changes to H2O its oxidation number changes from 0 to – 2 and in this case. This is in accordance with the Latimer diagram. the ∈° for the couple H2O2/H2O is equal to − 1.46 – (– . then no one species will be the exclusive product e.70 = – .76 volt.g. Therefore.. Therefore.76 volt. When these values of n∈° are plotted against the corresponding oxidation numbers.70 V 1. The potential corresponding to reduction of H2O2 to H2O can be calculated as follows from the examination of the line it is obvious that at the point corresponding to – 1 oxidation number n∈° = – .46 volt. we get the required Frost diagram as follows. The change in oxidation number from H2O2 to H2O is –1. NH4 3 2 2 adjacent species becomes approximately a straight line.76 V O2 H2O2 +1. 10.46 volt. When ‘O’ changes from O2 to H2O2. Hence. oxidation of NH3 by Ostwald process to NO and then to NO2 followed by dissolution in H2O produces HNO3 and also NO as well as HNO2. oxidation number of ‘O’ changes from 0 to –1.

.106] So.00 V] 2Ag+ + H2 [E°cell = – 0. Prediction of an oxidation-reduction reaction. Prediction of feasibility of a chemical reaction.52 V The two half cell reactions are: Cu+ + e Cu+ Adding Cu+2 –e Cu+ + Cu+ Cu° [∈° = 0. 3. Predict whether the reaction will occur spontaneously or not. Prediction regarding liberation of hydrogen by a metal from a hydracid. Ag cannot displace H2 from HCl. Zn+2 + Cu Zn + Cu+2 ∈° Zn +2 / Zn = – 0. Cu+ will disproportionate spontaneously in aqueous solution into and Cu°. cell reaction is 2Cu+ Cu+2 + Cu°.798. ∈° Cu +2 /Cu + = + 0.344 Zn [∈° = – 0. Example. the E°cell value is negative. Cell reaction: 2Ag + 2H+ → 2Ag+ + H2 2Ag – 2e 2H+ + 2e Adding 2Ag + 2H+ 2 Ag+ [∈° = – 0.15 V ∈° Cu + / Cu ° = 0.344] Zn + Cu+2 [E°Cu = – 1. Example. a very interesting situation arises: .52 V] Cu+2 [∈° = 0. given ∈° Ag+/Ag = 0.ELECTROCHEMICAL CELLS 239 Highlights: Uses of standard potential (reduction) values: 1. 2.15 V] Cu+2 + Cu° [E°cell = 0.37 V] Since E°cell is positive. Example. the reaction will not occur spontaneously. Concentration Cell When a metal is dipped into two solutions of one of its salts of different concentrations.e. ∈°Cu +2 /Cu = 0. E°cell = – ve.762 The two half cell reactions are: Zn+2 + 2e Cu – 2e Adding Zn+2 + Cu Since. Find whether Cu+ disproportionate in aqueous solution into Cu+2 and Cu° i.762] Cu+2 [∈° = 0.798] H2 [∈°H+/H = 0. Sol.798] The two half cell reactions are: Since. Ag will not displace hydrogen from HCl. Given.

5 Concentration cell.240 Ag | AgNO3(C1) || AgNO3(C2) | Ag Ag AgNO3(C1) (Dilute) Salt bridge of satd. Imagine that current passes through the external wire as shown by the arrow. If C2 = 10. e. 10.f. the cell reaction is Half cell reaction (left) oxidation Half cell reaction (right) Total: Ag+ (C2) = Ag+ (C1) ∈°R = ∈°L and n = 1 E = 2.303 So. NH4NO3 ENGINEERING CHEMISTRY AgNO3(C2) [Concentrated] (C2 > C1) Ag or Ag | AgNO3(C1M) || AgNO3(C2M) | Ag Voltmeter e – NH4NO3 Salt bridge – + Electron flow Ag electrode Ag electrode Ag ® Ag + e – + Ag + e–® Ag + C1M Ag ions + C2 > C1 C2M Ag ions + Fig.m. So. of such cell depends on the relative concentration and not on the absolute values.138 × (298) RT C C log 2 = log 2 C1 C1 nF n × 96500 Ag – e +e Ag+(C2) Ag + (C1) Ag° 0. C1 The stronger solution acts as positive electrode. . We shall get silver deposited on the right hand electrode and dissolution of silver from the left hand electrode as if silver being transported from concentration C2 to concentration C1–. E= 2.f. is 59 mV.m.303 × 8.059 C log 2 1 C1 [Q n = 1] Therefore. the observed e.

Another type of concentration cell is electrode concentration cell. of the cell is 0.05 × 0.05 (M) KI) | NH4NO3 | AgNO3(0. Calculate (i) Solubility product of AgI.045 0. E= ∴ or or or log 0.m. of the cell is: H2 (p1) – 2e 2H+ + 2e H2(p1) → H2(p2) RT p1 E = 2F ln p .ELECTROCHEMICAL CELLS 241 This type of concentration cell is known as electrolyte concentration cell.. concentration of Ag+ in 0.m.045 log 1 C1 0.788 V at 25°C. we are to measure e.138 × 1013 .059 log 2 C1 n Here n = 1. E= C 0. Ag+ in AgCl can be calculated.9 each. The concentration of Ag+ in AgNO3 is 0.05M) | Ag. Cell: Ag/AgI/ in 0.9 = 0. Determination of solubility of sparingly-soluble salts. E= 0. (ii) Solubility of AgI in water at 25°.01(N) AgNO3 solution is 0. C1 i. Given e. ion l–1 is (C2).01 log 1 C1 So.33 C1 = 2.f.e.f.33 C1 0. So.f. one such cell is: Pt | H2 (p1) | H+ | H2 (p2) | pt p1 and p2 are unequal pressures of H2 The cell reaction is: Oxidation: Reduction: Overall: e.059 0.045 C1 0. of the cell is given by.045 M Let C1 be the concentration of Ag+ in AgI solution.01 g.045 M The concentration of I– in KI is 0.788 = 0.059 0. The activity coefficient (f) is 0.m. Example 1.f.05 × 0.059 0.m. If we want to determine the solubility of AgCl.788 = = 13. 2 2H+ H2 (p2) Application of the Concentration Cells H2 cell. of the following Saturated solution of KNO 3 Ag | Ag NO3 (0.9 = 0.059 log 0.01N) Saturated AgCl | Ag salt bridge e.045 = Antilog 13.

of the above cell = 0. The pH of a solution can be determined with the help of a hydrogen electrode in that case. therefore. n 0.242 ∴ ∴ Ksp = 2.059 0.m. When in use.045 ENGINEERING CHEMISTRY Solubility of AgI = − = 9.059 0. The electrode will act as if it were an electrode of metallic hydrogen.m. The platinum black surface exhibits a strong absorption power towards hydrogen gas.732 × 10–9 mol l–1 = 9.5(N) || Hg2(NO3)2 (0.5 g l–1 = 1.045 = 9. the platinum electrode is dipped into the solution whose pH is to be determined.138 × 10 13 of AgI = [Ag+] [I–] = 2. as a result. over which hydrogen gas is passed.732 × 10–9 × 143. the remainder is surrounded by pure hydrogen gas at 1 atm.029 = ∴ n= ≈ 2. pressure. The e.472 × 10 17 = 9. 2.059 0.5 log 2 = log We have.05 0. The electrode reaction is H+(aq) + e H2-Gas HCl Fig.105 × 10–15 mol l–1.396 × 10–6 gl–1 Determination of valency Hg || Hg2(NO3)2 0.029 V C 0.472 × 10–17 C1 = K sp 0. the metal surface remains in continuous contact with the hydrogen gas. of this electrode has been arbitrarily assigned to be zero. This is standard hydrogen electrode.059 0. only a part of the foil is immersed in 1(N) HCl.6 Hydrogen Electrode.f. 10. instead of 1(N) HCl and H2 gas at 1 atm passed over the platinum electrode. 1 H 2 ( g) 2 .059 log 10 = = n n 0.059 0.f. n C1 n 0.029 C2 C1 INDICATOR ELECTRODES Hydrogen Electrode It consists of a small piece of platinum foil electroplated with platinum black.105 × 10–15 × 0. E= where n is valency.05) (N)/Hg or The e.

Since electrode potential of standard hydrogen electrode is zero.7 Determination of pH by Hydrogen Electrode. The e.059 log A full cell is constructed by coupling the above half cell with a standard hydrogen electrode.059 pH ∴ pH = E Obs 0. the observed e. So.059 log [H+] = 0.f.m.f. KCl HgCl & KCl HgCl paste + H2 Salt bridge Hydrogen electrode Solution Calomel electrode Fig. But there are some difficulties with hydrogen electrode. ∈ = ∈° + RT [H 2 ]1/ 2 log F [H + ] (n = 1) 1 [H + ] ∈ = 0 – 0. of the cell gives directly the electrode potential (∈) of the half cell.ELECTROCHEMICAL CELLS 243 The electrode potential is given by. the cell is: (Pt) H2 | H+(a = 1) || H+ (a = unknown) | H2(Pt) EObs = ∈ = 0. To overcome this difficulty another electrode which is known as secondary reference electrode is used for determining standard electrode potential.059 – + H2 Trap H2 Sat. ∈ = ∈° + 0. standard hydrogen electrode is used as reference. E of the cell is then determined potentiometrically. pressure of hydrogen and to make aH+ = 1 is very difficult. To determine pH of a solution the cell constructed with the calomel electrode will be: (Pt) H2 | H+ (a) || Normal calomel electrode (Fig. Reference Electrodes For determination of standard electrode potentials (∈°). 10.m. .7). 10.059 pH at 25°C. One of such electrodes is calomel electrode. Maintaining 1 atm.

The potential of this electrode . F The standard electrode potential (reduction) of calomel electrode For 1.8 Calomel Electrode.0(N) KCl = + 0.2422 V Any electrode whose standard potential is to be determined is connected to calomel electrode by means of KCl salt bridge. It can be prepared easily and can be used for a long time. To determine pH of a solution. of the set-up cell is determined potentiometrically from which the standard electrode potential of the electrode is calculated.28 0. EObs = ∈ (calomel) – ∈ (H2 electrode) = ∈ (calomel) – 0.28 + 0.059 pH ∈ = ∈° + or pH = E Obs − 0.m. coated electrolytically with silver chloride and is dipped into a solution KCl of definite strength.1N) and over it there is a saturated solution of KCl with some crystals of KCl. we have.059 log [H+] = 0.244 ENGINEERING CHEMISTRY Calomel Electrode This electrode possesses certain advantages.059 Ag-AgCl Electrode The use of this reference electrode is very common. The e. 10. The electrode reaction is: 1 Hg + Cl– ( aCl − ) Hg 2 Cl 2 (s) 2 The electrode potential ∈ is given by RT ln aCl − ( Q n = 1).f. Mercury layer is covered with a paste of Hg2Cl2 (0. KCl HgCl + Hg Hg Fig. The electrode consists of a silver wire. The bottom of the electrode is filled with mercury. The standard electrode potential of this electrode is determined against standard hydrogen electrode.28 V Saturated KCl = + 0.

Fig. 10.1 M HCl Solution of unknown pH [H = ?] Thin-walled glass bulb + Fig. The potential of the glass electrode varies linearly with pH (Fig.303 RT pH F = ∈° – 0.9). 10.10 Determination of pH by Glass Electrode.2224 V at 25° has been accurately determined against a standard hydrogen electrode. 10.10). For good electrical contact the bulb contains a silver–silver chloride electrode immersed in a standard HCl solution. – Potentiometer + Pt wire or silver chloride coated silver wire Saturated calomel electrode Glass electrode 0. 10. The thick glass membrane serves as a solid electrode whose potential changes with pH of the solution with which it remains in contact.059 pH at 25°.ELECTROCHEMICAL CELLS 245 Ag/AgCl(s) Cl– ( aCl − = 1) || HCl (a = 1). A platinum wire may be used in place of the Ag–AgCl electrode (Fig. H2 (1 atm)/Pt ∈° = – 0. . For pH determination with the help of glass electrode the electrode is dipped into the solution where pH is to be determined and is usually combined with a reference electrode— generally calomel electrode—to form a complete cell.9 Glass Electrode. ∈glass electrode = ∈° + = ∈° – RT ln [H + ] F 2. Glass Electrode A glass electrode consists of a very thin bulb or membrane of specially prepared and pH responsive glass and which is fused on to a piece of thick high resistance glass.

Only lithium silica glasses enable pH measurements to be valid over practically the entire pH range. 10. H2SO4 Bubbles of H2 Fig. at a given temperature. E = K – 0. pH and millivolt meters A linear relationship exists between the pH of a solution. (a) Its rapid response..0592 pH ∆E i.f. Polarisation When a simple cell drives a current. • ∈° value of glass electrode can easily be determined by calibration using buffers of known pH.m. the following is the cell reaction: At Copper plate: Cu+2 + 2e Cu 2H+ + 2e H2↑ At Zinc plate: Zn Zn+2 + 2e +2 + SO –2 ZnSO4 Zn 4 Total cell reaction: Zn + H2SO4 = ZnSO4 + H2 – Zn + Cu dil. ∈ = ∈° – 0.m. (b) remains unaffected by the presence of oxidising and reducing agents. Since. however.e. of the cell comprising of glass electrode and calomel electrode gives the pH of the solution from the equation. The advantages of glass electrode.059 pH • Glass electrode is virtually hydrogen electrode.246 Highlights: ENGINEERING CHEMISTRY • e. In practice.0592 ∆pH Thus a calibration in mV can be converted into pH units when divided by 0. of a cell (E) constructed of a reference electrode and an indicator electrode. and the e.059. = – 0. (a) Its fragility and (b) its inability in the presence of high concentrations of alkali. The disadvantages of glass electrode. pH meter scales are calibrated in pH units and in millivolts (mV) and the appropriate scale and range is selected by a simple control.f. • Glass electrode is the most extensively used electrode for pH determination.11 . • ∈° value is not zero in the case of a glass electrode.

of one volt. is generated.13). the polarisation e. The effect of accumulation of hydrogen is two-fold: (i) Hydrogen layer increases the resistance offered to the flow of current by covering the Cu-plate. and hence this back e. 2H+ + 2e H2↑ If.m.f. (back e.m. The Zn-plate.m.f. 10.f. behaves as positive electrode and H2 accumulated as negative electrode. and the current stops totally. but in opposite direction to that during electrolysis. therefore.f.12). As the hydrogen bubble is generated more and more.f. Hydrogen and oxygen gases covering the two Pt-electrodes become the source of this e. we are to apply an e. H2SO4 2H+ + SO4–2 –2 + H O SO4 H2SO4 + O–2 2 At anode: The reaction is.m. the battery is removed and a galvanometer is fitted in the outer circuit.m. Decomposition Potential If we start electrolysis of dil. Polarisation effect is also seen during electrolysis: when an electric current is passed through dil. it will soon come to an end due to back e. H2SO4 using Pt electrodes applying an e. is called decomposition potential of the given electrolyte (Fig. .f.f.m. an additional e.). Galvanometer e Pt + Pt – + – dil. which is called polarisation e.m. (ii) The layer of H2 in contact with the acid solution is found to acquire a potential lower than that of Zn.f.m.f.12 Development of polarisation by the products of electrolysis.f. opposes the main e.f. H2SO4 O2 H2 (b) Polarised cell (a) Polarisation during electrolysis Fig. So. which is just sufficient to overcome the back e. or polarisation e. or back e. increases and ultimately it comptetely neutralises original e. developed by products of electrolysis is known as polarisation (Fig. and which tends to drive a current opposite to the direction of the main current flow. 10. 10. to keep the electrolysis going on. after some time. a layer of hydrogen bubbles is found to be formed on the surface of the Cu-plate.f.m. which can overcome the effect of back e.m.m. so.m.m. a current is seen to pass between the two electrodes.m.f.f. This phenomenon is known as polarisation. The minimum voltage. H2 and O2 are evolved. This phenomenon of back e.ELECTROCHEMICAL CELLS 247 When current flows from Cu-plate to Zn-plate.m. 2O–2 – 4e O2↑ At cathode: The reaction is.f.f.m. developed during electrolysis. H2SO4 using Pt-electrodes.

if the applied e. Highlights: • The decomposition potential is different for different electrolytes.f. Battery Cells are devices where electric current is generated at the cost of some physicochemical processes going inside the cell.7 V in place of 1. electrolysis continues uninterrupted. But it is seen that the value of applied e. provided the process has been conducted reversibly at constant temperature and under a given pressure is equal to (the decreasing Gibbs free energy – ∆G).m.55 V with Zn-electrodes.f. At this stage. of the reversible cell constructed with H2 (g) at 1 atm. Overvoltage Theoretical voltage required for the decomposition of an acid solution should be equal to the e.m. of the cell so.f.m. is gradually increased.m. is always higher than this theoretical value.f. of less than 2-5 V is applied between Cu-electrodes only Cu will get deposited at the cathode while Zn will remain in solution if a mixture of CuSO4 and ZnSO4 is used as electrolyte.13 Decomposition Potential. a minimum voltage must always be applied to start the electrolysis process. • The decomposition potential of CuSO4 is 1. So. In order to apply exact thermodynamic principles to cell reaction it is customary to distinguish between reversible and irresversible cells. where F = faraday and E = e. we have – ∆G = nFE or ∆G = – nFE A battery is an electrochemical cell which is used as the source of direct current of a constant voltage.m. This difference between the theoretical voltage and actual applied voltage necessary for electrolysis is known as overvoltage. Battery Primary [The cell reaction is not reversible] Secondary [The cell reaction is not reversible] Flow [The reactants. products and electrolytes pass through the battery and during the passage electric current is generated at the expense of chemical reactions as in electrochemical cells] . Since electrical work is equal to nFE. Electrolysis of dil. H2SO4 with Ptelectrodes requires 1.248 ENGINEERING CHEMISTRY Current density Decomposition voltage Voltage Fig. When an e. Because the thermodynamic principle is only applicable to reversible cells.23 V (theoretical value). Battery works on the above thermodynamic principle.5 V with Cu-electrodes and that of ZnSO4 is 2. It is well known that any chemical reaction conducted reversibly can yield some external work and the useful work available from the process. 10.f.

10. A zinc vessel serves as negative electrode.4 V.m. H2 is oxidised by MnO2 as H2 + 2 MnO2 = Mn2O3 + H2O. (Fig. When current is drawn from the cell.14 Leclanche cell.15) It is essentially a Leclanche cell.f. The cathode is an amalgamated Zn-rod (Z) dipped partially in NH4Cl solution. Since MnO2 is a very poor conductor. The anode is made of gas carbon (C) placed within a porous pot P which is also dipped partially in NH4Cl solution.ELECTROCHEMICAL CELLS 249 Primary Cells (a) Leclanche cell. 2Mn2O3 + O2 = 4 MnO2 (b) Dry cell. MnO2 and C (graphite). The seal has a hole to allow the escape of NH3 gas. of the cell is 1. charcoal is added to increase the conductivity. The e. The carbon rod is insulated at the bottom from Zn-vessel with a cardboard washer. 10. Instead of NH4Cl solution. The resulting Mn2O3 is slowly oxidised by air to MnO2. Pitch Hole C P Zn + – Porous pot Carbon rod Glass vessel Zinc rod(–) Carbon– manganese dioxide mixture NH4Cl (Sol) B Fig. The inside of the Zn-vessel is lined up with a thin sheet Cell reaction: Zn + NH4Cl = ZnCl2 + 2 NH3 + H2 Hole Pitch Paper Zinc Carbon Paste Mixture of carbon and manganese dioxide Fig. which contains a saturated solution of NH4Cl as an active liquid. It is filled at the top with a brass cap. Zn rod is used up and the MnO2 is reduced. The cell is not really dry. The space between the carbon rod and the pot is filled with a mixture of powdered charcoal and MnO2 which serves as a depolariser. 10. A carbon rod is placed at the centre to act as a positive electrode. 10. . (Fig. NH4Cl paste is used here. The paste contains NH4Cl. The top of the pot is sealed with pitch.15 Dry cell.14) This type of cell was devised by Georges Leclanche. The cell consists of a glass vessel B.

It is expensive.m.250 ENGINEERING CHEMISTRY of blotting paper. zinc is used in powder form and makes a gel with KOH. The main advantage of this battery is that. This type of cell is widely used in torches. In this type of battery. of the cell is 1. It is mainly used in camera. The paper permits the migration of ions. The cell reaction is Anode: Cathode: 2NiO . The anode and the cathode are divided by a paper.45 V. The life of alkaline battery is longer than the dry cell because zinc does not corrode. And the graphite-rod is kept surrounded by a paste of MnO2. watches etc. The cell reaction is: Anode: Cathode: Net reaction: Zn-amalgam(s) + 2OH–(aq) → ZnO(s) + H2O(l) + 2e– HgO(s) + H2O(l) + 2e– → Hg(l) + 2OH–(aq) Zn-amalgam(s) + HgO(s) → ZnO(s) + Hg(l) The entire cell is covered in a stainless steel case. The e. Use: It is used in calculators. the top of the cell is sealed with pitch. The size is small. Alkaline Battery It is a modification of dry cell where NH4Cl has been replaced by KOH and acts as an electrolyte. hearing aids. Fuel + O2 → Combustion products + electricity . Mercury Battery This type of battery is constructed of zinc-amalgam (a solution of Zn in mercury) as anode and a paste of KOH. Fuel Cells In these cells combustion of the fuel is employed as chemical reaction to generate electricity. OH(s) + 2H2O(l) + 2e– → 2Ni(OH)2(s) + 2OH–(aq) Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e– Net reaction: 2NiO. electronic flash units etc. digital watches etc. This type of battery is portable and reachargeable. it undergoes no deterioration as no gases are produced during charging and discharging. signalling equipments.f. A small hole is at the seal. telephone etc. Nickel-Cadmium Battery These battery is constructed of cadmium anode and a paste of NiO(OH)(s) cathode. calculators. Use. Use: It finds its use in pacemakers. transistors.OH(s) + Cd(s) + 2H2O(l) → Cd(OH)2(s) + 2Ni(OH)2(s) Here the reaction products adhere to the electrode surfaces and the reaction can be easily reversed. The cell reaction is Anode: Zn(s) + 2OH–(aq) → Zn(OH)2(s) + 2e– Cathode: 2MnO2(s) + H2O(l) + 2e– → Mn2O3(s) + 2OH–(aq) Net reaction: Zn(s) + 2MnO2(s) + H2O(l) → Zn(OH)2(s) + Mn2O3(s) Advantage. To prevent drying of the paste. Zn(OH)2 and HgO as cathode.

solar energy is utilised to generate electric current in a photovoltaic cell. The cell reaction is: At anode: Al(s) → Al3+(aq) + 3e– (Oxidation) Al3+(aq) + 3OH–(aq) → Al(OH)3(s) Al(s) + 3OH–(aq) → Al(OH)3(s) + 3e– At cathode: Net reaction is: O2(g) + 2H2O(l) + 4e– → 4OH– (aq) (Reduction) 4 Al(s) + 3O2(g) 6H2O(l) → 4Al(OH)3(s) In such a battery the anode is very very pure aluminium and air is bubbled through the solution at cathode. The electrodes are totally immersed in 20% dilute H2SO4. The electrolyte is aqueous solution of NaCl (or NaOH). power stations etc. Solar Battery In this type of battery. p-type semiconductor is connected with n-type . The positive pole of the generator is joined to the positive pole of the battery and the negative terminal is attached to the negative pole of the battery. The common example of storage cell is lead-acid storage cell. The cell can be again charged when both the anode and the cathode get covered with PbSO4. It is constructed of electrodes made of lead and the other electrode in PbO2. Reaction at cathode: PbSO4 + 2e– → Pb + SO4–2 Reaction at anode: PbSO4 + 2H2O – 2e– → PbO2 + 2H+ + SO4–2 Net reaction: 2PbSO4 + 2H2O + Energy → Pb + PbO2 + 4H+ + 2SO42– After charging the cell restores its original condition and is again used. The two types of electrodes are separated by strips of wood or glass fibres. In this type of photovoltaic cell. Storage Cells A storage cell can operate both as a voltaic cell and as an electric cell. Use: This type of battery is used in electrical vehicles. It is expected that this type of battery will find its application in automobiles as source of energy replacing fuels. automobiles. The cell loses its function as a voltaic cell.ELECTROCHEMICAL CELLS 251 Aluminium-Air battery It may be considered as a combination of a battery and a fuel cell. The cell reaction is At anode: Pb → Pb2+ + 2e– At cathode: Pb2+ + SO42– → PbSO4↓ PbO2 + 2H+ + 2e– → Pb2+ + 2H2O Pb2+ SO42– → PbSO4↓ Net reaction: Pb + PbO2 + 4H+ + 2SO42– → 2PbSO4↓ + 2H2O + Energy It is worthwhile to mention that PbSO4 gets precipitated at both the electrodes.

0296 × (– 1.314 J. Example 3. Example 2.314 × 298 log [Cu +2 ] 2 × 96500 = 0.015 M. Calculate the voltage at 25°C of a cell formed by dipping silver in silver nitrate (0. Calculate the single electrode potential of copper metal in contact with 0.34 + = 0.1) = – 1.296 V when [Cu+2] = 0.05398] V = 0.015 2 = [0.762 + 0. Sol.34 V (R = 8. K–1 mol–1. ∈ = ∈° + = ∈° + ∴ ∈° = ∈ – 0.34998 V.1 M) || ZnSO4 (0.0592 log [Cu +2 ] 2 0.34 + 2.8239)] V = [0. Due to this contact. (–) (+) The cell ⇒ Ag/AgNO3 (0.0592 log 0. a limited number of electrons can flow and cross the junction between the two types of semiconductors. Calculate the standard potential of Cu+2/Cu if the electrode potential at 25° is 0. T = 298 K). Sol.314 × 298 log 0.2 M) and connecting them without liquid junction potential.15 2 × 96500 = 0. ∈ = ∈° + RT ln [M + n ] nF 2.296 – 0.296 + 0.252 ENGINEERING CHEMISTRY semiconductor.798 + 0.2) – (0.1 M) and zinc in zinc sulphate (0.059 log 0. SOLVED EXAMPLES Example 1.522 V. ∈° for copper = + 0. . Sol.303 × 8.0296 log 0. R = Right hand electrode and Reduction L = Left hand electrode undergoing oxidation) 2Ag – 2e 2Ag+ Zn+2 + 2Ag ∴ Ecell = ∈°Zn + Zn Zn + 2Ag+ FG H F = G ∈° H RT RT ln [Zn +2 ] − ∈° Ag + ln [ Ag + ]2 2F 2F RT ln [ Zn + 2 2F Ag + IJ FG K H I F ]J − G ∈° K H + RT ln [ Ag + F IJ K I ]J K = (– 0.303 × 8.2 M)/Zn The cell reaction ⇒ Zn+2 + 2e Zn (Ecell = ∈R – ∈L = ∈+ – ∈–.3156 V.0592 log [M + n ] n 0.15 (M) Cu+2 solution.

ELECTROCHEMICAL CELLS 253 Highlights: • If after calculation of Ecell it comes negative.1 + 0.P of Ag-electrode is higher than that of Zn-electrode.m. of a Daniel cell at 25°C. We can write Ecell = (∈° − ∈° ) + + − = E°Cell + RT [Cu +2 ] ln nF [Zn +2 ] 0. Write down its cell reaction. Cu = Zn/Zn+2 (a = 1)/Ag+ (a = 1)/Ag+ According to ‘2R’ convention reduction will take place at right hand electrode (cathode). but the table of ∈° values and the above procedure will help to calculate Ecell of any reversible cell. respectively. of the cell: Ni | Ni+2 1(M) || Pb+2 1(M) | Pb at 25°C. Ecell would come out negative.1 M.e. Calculate the e. The standard potential of cell is 1.11 V. So here S. Also find out the standard emf of the cell. Sol.76 V and ∈° Ag/Ag + = 0.8 V at 25°C. Sol. given that ∈° Zn/Zn +2 = 0.76 V Ox ∈° = ∈° Ag / Ag + = – 0.24) = 0.0592 0. Cell reaction ⇒ At cathode: 2Ag+ + 2e At anode: Zn – 2e 2Ag+ + Zn+2 2Ag (Reduction) Zn+2 (Oxidation) 2Ag + Zn+2 . +ve electrode.e. when the concentrations of ZnSO4 and CuSO4 are 0..8 V Ox i. Cell reaction: At anode: Ni – 2e Ni+2 (Ox) +2 + 2e At cathode: Pb Pb (Red) Ni + Pb+2 Ni+2 + Pb Example 6.13) – (– 0. Calculate the e..001 = 1. • If we cannot make right choice during construction of a cell. Sketch the electrochemical cell and write down the cell reaction. Example 5.f. ∈° = ∈° Zn / Zn +2 = 0. Sol. ∈°Red = ∈Zn +2 / Zn = – 0.1592 V.001 M and 0. Given ∈°Ni = – 0. half cells are to be reversed to get positive value of Ecell.13 V at 25°C. ∈°Red = ∈° Ag + / Ag = 0.e.0296 log 100 = 1.m. if Zn and Ag electrodes are dipped in respective solutions.76 V i.1 + 0.f.0296 × 2 = 1..R. So. Example 4. E°cell = ∈°right – ∈° left = (– 0. Here if Ag-electrode is made positive electrode (one half cell) and Zn-electrode is made (negative electrode) (the other half cell) then Ecell would become positive.1 volts. Ag-electrode will form right hand half cell i.24 V and ∈°Pb = – 0.8 V.1 log [Q E° = ∈° – ∈° ] cell + – 2 0.

.0592 [ Zn +2 ] log 2 [ Zn ] 0. Cell = Cu/Cu+2 (0.0592 [Zn +2 ] 0.56 V.337 – (– 0.337 V Cell = Zn/Zn+2 || Cu+2 /Cu Cu+2 + 2e Cu . = 0.102 V..102 = 0..0296 log .76) = 1. here C2 = 0.P. 2 0.0296 log = = 0.0592 [Zn +2 ]/[Zn] log 2 [Cu +2 ]/[Cu] [Zn +2 ]/[Cu] [Cu +2 ]/[Zn] 1. Sol.1 M)/Cu Ecell = Ecell = data. Therefore.01 log 10 Example 8. Two copper rods are placed in copper sulphate solution of concentration 0.337 V Zn – 2e Zn + Cu+2 K= Zn+2 .e.254 E°cell = ∈°Right – ∈°Left ENGINEERING CHEMISTRY = 0.e. S. at 298 K.01 M) || Cu+2 (0.765 V Zn+2 + Cu (E°cell = ∈°Red + ∈°OX) = 1. ∈° Zn / Zn +2 = 0.∈° = 0. Sol.. i.1 0.1 M and C1 = 0. [Zn +2 ] [Cu] [Zn] [Cu +2 ] 0.059 [Cu + ] log 2 [Cu] ∈Zn +2 / Zn = ∈° Zn +2 / Zn + ∈° Cu +2 / Cu = ∈°Cu +2 / Cu + At equilibrium..0592 [Cu +2 ] log log − 2 [Zn] 2 [Cu] ∈° Cu +2 / Cu − ∈° Zn+2 / Zn = or 0.337 V Half cell reactions Cell reaction: ∴ ∈°Cu +2 / Cu = 0..0592 [Cu +2 ] = ∈° Cu +2 /Cu + log log 2 [Zn] 2 [Cu] 0. Example 7.0592 0.0592 log 2 . (Ox) for Cu electrode = – 0..337 i.765) = 0. Write the scheme of the cell and calculate its e.765 V F = 96.∈° = 0.E.500 C..316 J.0592 [Zn +2 ] 0.. these two electrode potentials will be equal. Calculate the equilibrium constant for Daniel cell at 25°C from the following R = 8.01 M C1 n 0.f.P. ∈° Zn +2 / Zn = – 0.1 M and 0.E.8 – (– 0..01 M separately in the form of a cell.m.765 V and ∈°Cu / Cu +2 = – 0.0296 V.765 V and S. C 0. (Ox) for Zn electrode. ∈° Zn +2 / Zn + 0.

ELECTROCHEMICAL CELLS 255 = 0. Sol.0592 pH = 0. Ecalomel = 0.0296 log K ∴ log10 K = 1. Sol.0592 pH K sp ∈° Ag + / Ag = + 0. Example 9.9.2415 – 0.3 × 10–17 (M). Ecell = ∈°H – ∈H = 0 – (– 0.123 = (0. Ksp (AgI) = 8. The e.29 ≈ 4.2223 E°cell = 0.65 .3 × 10 −17 = 8. 8.102 = 37. Cell reaction Ag+ + e Ag + Cl– We have.2297 = 1.m.3 × 10–17.2415.2297 0.3345 = 5.697 × 1037.0592 Example 11.6990 – 0.3345 0. 0.6990.f. ∈° Ag + /Ag = 0.798 ∈° = – 0.2415 – 0. [Ag+] = = E cell 0. Find out the pH of a solution in a quinhydrone half cell.2223 Sol. Calculate the potential of an Ag-electrode in a solution that is saturated with AgI and has an iodide concentration of exactly unity. Sol. ∴ pH = Ecell = ∈Q/ H 2Q − ∈calomel or or 0.123 + 0. which is coupled with standard calomel electrode. ∈Q/H2Q = 0.0592 pH) = 0. Calculate Ksp of AgCl from the following data: pH = ∈°Ag–AgCl(s) = 0. of the combined cell was determined to be 0.6990 = – 0. = 0.798 at 25°C.0592 0.0592 Example 12. Highlight: • The high value of K indicates the spontaneity of the reaction.0592 pH) – 0.0296 K = Antilog 37.5757 Ag + Cl– AgCl(s). – ∆G° = nFE° nFE° = – RT ln K .123 V at 25°C.799 V. The potential of a hydrogen gas electrode in a solution of an acid of unknown strength is 0. Calculate the pH of the solution. Ag AgCl(s) + e ∈° = 0. I 1 Example 10.29 V at 298 K as measured against normal hydrogen electrode.

It is a simple device of producing electrical energy by chemical reaction. e V Salt bridge 2– e SO4 Zn Cu ZnSO4 CuSO4 Zn → Zn+2 + 2e– Cu2+ + 2e → Cu Fig.5757 =– = – 9. It is an inverted U-tube containing an electrolyte (e.g.. What is the E.M. 3. SHORT QUESTIONS AND ANSWERS Q. What do you mean by electrode potential (E)? Ans. What is an electrolytic cell? Ans.F.2754 2. It is defined as the potential difference between the two terminals of the cell when no current is drawn from it. KCl. Daniel cell. It is a device used for converting electrical energy into chemical energy. What is a salt bridge? Ans. Q. 5.2754 = 1. Reduction potential is the tendency of an electrode in a half cell to gain electrons and oxidation potential is the tendency of an electrode in a half cell to lose electrons. Q. What are reduction and oxidation potentials? Ans. Q. 7. 10.886 × 10–10 mol2 l–2.. 6. It connects (acts as a bridge) the solutions of the two half cells. of a cell? Ans. 4. What is galvanic cell or voltaic cell? Ans. 1. Q.7246 = – 10 + 0.0592 Here K = Ksp = Antilog 10. Q.g. . Such a cell is also known as electrochemical cell. KNO3). It is the electrode potential of a metal in contact with its ions when the concentration of ions is 1 M (1 molar). 2.303 RT 0. It is the tendency of an electrode in a half cell to lose or gain electrons when it is in contact with the solution of its own ions.256 or or log K = – ENGINEERING CHEMISTRY nFE° 1 × 0.16 (oxidation) (reduction) In the above cell Zn-electrode is anode and Cu-electrode is cathode. e. Q. What do you mean by standard electrode potential (E°)? Ans.

17. Apparatus for measuring the standard electrode potential of a redox system is given in Fig. It is a reference or standard reference electrode. 9. Saline bridge H2 (1 atm) Inert electrode (Pt) Pt A H (a=1) + Redox system B Fig. Saline bridge has the function of bringing into physical contact the two solutions without mixing them. dipped in solution having 1 M H+ ion concentration and hydrogen gas at 1 atmospheric pressure constantly bubbled over it.F. ∆∈ = ∈°Redox – ∈° H ∴ ∴ ∈° H 2 2 /H+ / H+ = 0 ∆∈ = ∈° Redox B A D C G Fig. named potentiometer. E.g. A = Solution of H+ ions of unit activity B = Redox solution of unit activity.ELECTROCHEMICAL CELLS 257 Q. Q. . How is electrode potential measured? Ans. Define normal hydrogen electrode. H2 (1 atm) || H+ (1 M) 1 Reaction: H+(aq) + e– → H 2 ( g) 2 1 H 2 ( g) → H+(aq) + e– or 2 Q. of a cell is measured by means of a device. A normal hydrogen electrode generally consists of a Pt-foil coated with platinum. How is the E. it consists of a strong electrolyte (e. KCl).F. 10.18 Diagram for Potentiometer.M. It can be represented as: Pt. Its electrode potential is taken as zero at all temperatures.M. 10. Ans. 8.17 A cell constructed with standard hydrogen electrode. 10. of a cell measured? Ans. 10..

∈ = ∈°Redox + 0. where. of the oxidised form in moles dm–3 . [Red] = Conc. Give the hemistry the different indicating electrodes. Ans. (a) First Class ⇒ Metallic electrodes in contact with a solution of their own ion (an electrode which is reversible in relation to the cation) Mn+ + ne– M. Pt/Ox.059 log [Ox]/[Red] n Pt ⇒ Platinum [Ox] = Conc. 0.059 log a n where. ∈ = ∈° M / M n+ + n n where Ksp = solubility product of the salt which is not readily soluble.246 V) and the silver-silver chloride electrode (∈ = + 0. Q.059 log K sp − K sp [ A − n ] And. What is an indicating electrode? Ans. ∈ = ∈r + . 11. And. What do you mean by potentiometry? ENGINEERING CHEMISTRY Ans. of the anion in moles dm–3 . Red 0. Q. ∈ = ∈° M / M n+ + (c) Redox = Electrodes which are inert in contact with a redox couple in solution. Q. 14. A–n where. 13. (d) Membrane type = Selective electrodes specific to certain ions. 12.222 V). The best known of this type is glass electrode.059 0. Potentiometry is an electrochemical method of analysis based on measuring the potential difference (e.m. of the reduced form in moles dm–3. These are the electrodes whose potential is constant and independent of the composition of the contacting solution. What are reference electrodes? Ans. ∈r ⇒ Constant potential linked to the choice of the reference electrode and the internal solution.258 Q.059 log [M n ] n (b) Second class ⇒ Metallic electrodes in contact with one of their not readily soluble salts and with the anion of this salt: M | MA(s). The most widely used are saturated calomel electrodes (∈ = + 0. They consist of a membrane which in presence of particular ions assumes a potential which is dependent on the activity of the ions in relation to those of which the electrode is selective. of cation in moles dm–3 + 0. [Mn+] ⇒ conc. [A–n] = Conc. M ⇒ Metal MA(s) ⇒ the salt which is not readily soluble.) between two half cells. one of which is an indicating electrode and the other is a reference electrode. the potential of which is given by Nernst equation. a ⇒ activity of the ion in relation to which the electrode is selective. It is an electrode in balance with an redox couple.f.

the series so obtained is known as electrochemical series. Q.ELECTROCHEMICAL CELLS 259 Highlight: The potential of reference electrodes is determined as referred to the standard hydrogen electrode. 18.303 RT [Reduced form] log nF [Oxidised form] 0. 17. Reaction during recharging the battery PbSO4(s) + 2H2O(l) ⇔ Pb(s) + PbO2(s) + 4H+ + 2SO42– Q. R ⇒ molar gas constant. F = Faraday (96500 Coulombs) At 25°C the value of the term 2. 16. So at 25°C ∈ = ∈° – Highlight: The concentration of metal is taken as unity. Define the electrochemical series? Ans. Q. ∈° = standard reduction electrode potential. Reactions: Anode: Cathode: PbO2 + SO42– Pb + SO42– → PbSO4 + 2e– + 4H+ + 2e– → PbSO4 + 2H2O 2. Nernst proposed the fundamental electrode relation between the formal (or observed) potential and the standard electrode potential for the redox reaction: ∈Red = ∈°Red – where. What is lead storage battery? Ans. What is the reaction in nickel-cadmium battery? Ans.059. Anode: Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e– Cathode: NiO2 + 2H2O + 2e– → Ni(OH)2 + 2OH– (aq) . 15.303 RT/F comes out as equal to 0. n ⇒ number of electrons involved in the redox reaction. When the standard reduction potentials of the electrodes are arranged in an increasing order. Q. ∈Red = observed reduction electrode potential.059 [Reduced form] log n [Oxidised form] Net reaction: Pb + PbO2 + 4H+ + 2SO42– → 2PbSO4 + 2H2O. It consists of six voltaic cells connected in series. What is Nernst equation? Ans. T ⇒ absolute temperature.

∈° = 0. 21. Classify corrosion. ∈° = – 0. Ans. 22. Give the reaction in H2–O2 fuel cell. (c) Electrical protection. (d) Use of anti-rust solutions. (b) Electrochemical corrosion ⇒ it involves deterioration of metal due to flow of electric current from one point to another.3H2O (rust) Q.44 V +3 + e +2. rusting of iron. (d) Wet corrosion ⇒ it involves flow of electric current from one point to another through some perceptible distance in the presence of liquid or moisture in air. 19.. 2Fe+2 + H2O + O → 2Fe+3 + OH– 2Fe+3 + 6OH– → 2Fe(OH)3 or Fe2O3. State the electrochemical theory of rusting. . Q.260 Q. Reaction: Anode: Cathode: OH– Fe → Fe2+ + 2e– 2H2O + O2 + 4e– → 4OH–.77 V (ii) Fe → Fe Represent the data in the form of Latimer diagram. Anode: Cathode: Net reaction: {H2(g) + 2OH–(aq) → 2H2O(l) + 2e–} × 2 O2(g) + 2H2O(l) + 4e– → 4OH–(aq) 2H2(g) + O2(g) → 2H2O(l) Highlight: Such a cell is used to generate electrical power such as in Apollo space programme.. What are fuel cells? ENGINEERING CHEMISTRY Ans. i. The Fe+2 ions formed at anode are oxidised by O2 to Fe+3 ions which then combine with ions to form hydrated ferric oxide. Given (i) Fe+2 + 2e → Fe. Ans. 24. Q. e. It generally refers to the slow and continuous deterioration of metals and alloys by chemical or electrochemical actions of environments. rust. What measures ought to be taken to prevent corrosion? Ans.e. Q. 23. What do you mean by corrosion? Ans. (a) Chemical corrosion ⇒ it involves direct chemical action between metals and gases. 25. (b) Sacrificial protection.g. Q. 20. Q. (a) Barrier protection. Fuel cells are the devices that convert chemical energy of a fuel directly into electrical energy. Ans. (c) Dry corrosion ⇒ it refers to the corrosion of metals involving direct chemical action between metals and dry gases.

95 V 3∈°(Mn+3.30 – + 0.77 F Ans.04 V −n F −3F The Latimer diagram of the above system is Fig.77) = – 0. ∆G°I = – (+ 0. Fe +3 0.77) F = + 0.04 Fig.44 Fe –0.85 V 4∈°(MnO2.77 Fe +2 –0. 27. Fe+3 + 3e → Fe ∈° = ∆ G° + 0. ∈ Ans.ELECTROCHEMICAL CELLS 261 ∆G°(i) = – nFE° = – 2F (– 0. ∈°(Mn+3.42 F ∆G°II = – (+ 1. Mn) = 0. ∈º(Mn+2. ∆G°(iii) = ∆G°(i) + ∆G°(ii) = 0. ClO– → Cl–.11 F = = – 0. Mn) = – 0. 26.37 – + 0. 2 2 Adding total ∆G for the reaction = – 1. Mn) = – 1.36) F = – 1. ∈° = + 1.89 V = − nF −2F 2∈° = – 2. 10. We have Adding the above two equations.68 – + 0.36 – 1 +e Cl → Cl–.78 F From the relation.36 V.42) F = – 0. 2 2 ∈° = + 0. ClO– → +e – + 0. In alkaline solution (pH = 14) the Latimer diagram for chlorine is ClO4 ¾¾® ClO3 ¾¾® ClO2 ¾¾® ClO ¾¾® Cl2 ¾¾® Cl ? Calculate from the above diagram ∈° value for the reaction. Use the following data to draw a Frost diagram.11 F So ∆G°(iii) is the value for the reaction. 10. Q. It is conventional to put highly oxidised form of the element on the left and the elements with lower oxidation state are put successively in the Latimer diagram.88 F ∆G°(ii) = – nFE° = – F(0.44) = 0. Mn) = – 1. = 0.36 F ∆ G I + ∆ G II − 178 F .18 V ∈°(MnO2. ∈°(Mn+2.19. Mn+3) = 0. ∆G° = – nFE° ∈° (ClO–/Cl–) = 1 Cl .42 V.10 V .19 Latimer diagram for Fe species.88 + (– 0.51 V.36 V ∈ Q.42 + 1. Ans. Mn+2) = 1.18 V.

• A state is unstable with respect to disproportionation if it lies above the line connecting two adjacent oxidation states. • The steeper the line joining two points.. + 1 and 0.34 V. Since both these products involve one electron transfer.262 +6 +5 +4 +3 +2 nΰ(V) ENGINEERING CHEMISTRY Mn 6+ 7+ Mn Mn 5+ +1 0 –1 Mn –2 –3 Mn 2+ Mn° Mn 3+ 4+ 0 +1 +2 +3 +4 +5 Oxidation number +6 +7 Fig. • Mn+3 is likely to disproportionate to Mn+2 and MnO2. so.25 Tl + –0. • The minimum at Mn+2 suggests this to be the common product of reduction of MnO4– [Mn(VII)] in acidic solution and it is the most stable oxidation state of Mn. • The point for Mn(VI) similarly suggests disproportionation to Mn(VII) and Mn(IV). Most species that reduce MnO4– should also reduce MnO2. Q.20 Frost diagram for Mn in acidic pH. Tl +3 +1. Tl+1 → Tl0. the process is likely to be rapid. the higher the potential of corresponding couple. Construct a Frost diagram from the Latimer diagram for Tl. 10. in the three species. here n = 1.34 Tl +1. .23 Ans.34 V. The oxidation states of Tl are + 3. 28. For the change of oxidation number from + 1 to 0 i. Highlights: • Plot of n∈° vs n for Mn (n = oxidation state) such diagram are called Ebsworth diagram or Frost diagram. • MnO2 is also a strong oxidizing agent—its slope to Mn+2 is greater than the slopes to higher oxidation states. n∈° = – 0. ∈° = – 0.e.

Distinguish between electrolytic and electrochemical cells. 3. 4 3 2 1 0 Tl +3 nΰ(V) Tl° –1 –2 –3 Tl +1 0 +1 Oxidation number +2 +3 Fig. Prove that ∈ox = – ∈red. 5. 14. 12. Write notes on: (i) Weston standard cell. Why is a voltmeter is not used for the measurement of e. What is a calomel electrode? Describe its construction: Why it is used as reference electrode in place of a standard hydrogen electrode? What is an electrochemical series? Why are standard potentials of Zn/Zn +2 and Cu/Cu+2 electrodes opposite in sign? Describe the construction and working of H2 – O2 fuel cell. What is a standard hydrogen electrode? What is its potential? What is overvoltage? What is the cause of overvoltage? Give the reason: the hydrogen overpotential falls with rising temperature. 6. What is standard electrode potential? State the peculiarity of a concentration cell.ELECTROCHEMICAL CELLS 263 For the change of oxidation number from + 3 to 0 (Tl+3 → Tl0) ∈° value = + 1. 11. Tl+1 is the most stable oxidation state of Tl as the species lies lowest in the Frost diagram.f. 18. Define the electrode potential. 19.23 V = + 3. Give the cell rotation for a concentration cell. (ii) significance of standard electrode potential. 17. EXERCISES 1. 10. Describe the construction of a glass electrode. 4.m. .69 V.21 Frost diagram for Tl species. 9. 13. for n = 3. n∈° = 3 × 1. 2. 8. 16. 15. 7.23 V So. Explain how the pH of a solution is determined using the glass electrode. of a cell? What is a storage cell? Name some of its types. What are primary and secondary reference electrodes? Write a note on decomposition potential. 10.

(iii) Fe+3/Fe+2 Pt. 24.5] [Ans. 28. when the concentrations of ZnSO4 and CuSO4 are 0. 27. if E°cell = + 0. 37.1 V (1. Explain the construction and working of lead storage battery. (0. (i) Zn | ZnSO4 || CuSO4/Cu (ii) (Pt) H 2 (1 atm) | HCl/AgCl(s).f.44 V (– 1.01 (M) ZnSO4 solution at 25°C.001 M and 0. 2Cu+ Cu2+ + Cu 35. What is fuel cell? Give detail of one such cells.34 V and –0. The reaction H2 + Cl2 + 2H2O 2H2O + 2Cl– has an equilibrium constant K = 1046 at 25°C. Given the electrode potentials of Cu and Fe are 0.m. Calculate the e. The standard potential of the cell is 1. both at the same temperature. Calculate the pH of the solution. Also give the expression for their e. The potential of the normal calomel electrode is 0.6996 V.763 V (0.0592 V] . (ii) Calculation of solubility product of AgCl. respectively. 6.f of the following concentration cell: Ag/Ag+ (0. 29. Zinc rod is dipped in 0. Give the equilibrium constant for the reaction.264 20.212 V.m. What are reversible and irreversible cells? 25.78 V). of voltaic cell: Fe | Fe+2 (aq) || Cu+2(aq) | Cu. (iv) 2H+/H2(g) Pt.530 V. Give the use of Ag-AgCl electrode. Give the single electrode potential of Znhalf cell.f. [Ans. Give the cell reaction of the following: (i) Zn+2/Zn. 0. (ii) AgCl(s). How is single electrode potential measured experimentally? ENGINEERING CHEMISTRY 31. Describe the potentiometric methods for (i) Determination of pH of a solution. 26.13 V). of the cell at 25°C Hg(l) | Hg2Cl2(s). Calculate the e. 39.f. Derive an expression for electrode potential of an M/Mn+ electrode? 23. respectively.239 V) 38.8192 V) 36. Describe the construction and working of Daniel cell. Calculate E° at 25°C for cell: (Pt) H2/HCl (aq)/Cl2 (Pt). Will a reaction take place if an Ag-bar is placed in a solution of FeSO4? Explain using the following data: ∈°Ag + / Ag = 0. Distinguish: (i) a reversible cell from an irreversible cell (ii) a galvanic cell from a concentration cell. 22.0 N)| Quinhydrone | Pt is 0.m. Ag 32. Explain the construction of Ni-Cd cell.1 M) || Ag+ (1M) | Ag 40.m. 33. Write down the electrode reactions and overall cell reactions for the following cells. KCl(sol) (1. 21.1 M respectively.2812 V and E° for the quinhydrone electrode is 0. The standard potentials of Cu/Cu +2 and Cu/Cu+ system are 0.f.337 and 0. What is Nernst equation? State its utility. and ∈°Fe +2 / Fe = 0. Cl–/Ag. 34.44 V. The e. Calculate the e.m. 30.799 V. of a Daniel cell at 25°C.

to calculate ionic product of water.036 V ∈°I(s)/I – ⇒ 0. Find the equilibrium constant of the reaction at 25°C.f.5622 V. [Ans. 2 Fe+3 + Sn+2 2 Fe+2 + Sn+4 from ∈° values given in the Table 10. E. [Ans.001 N) in 0. Calculate the valency of mercurous ions with the help of the following cell: Hg | HgNO 3 (0.5355 V. H 2-electrode || O2-electrode] 45. (i) 6.2. 5. 43. gives e. Fe+3 + I– from the ∈° (reduction) values Fe+2 + [Ans.664 V.16 × 10–7] . Calculate the pH of the solution.ELECTROCHEMICAL CELLS 265 41.01) | Hg+ 42. When calomel electrode is connected to H2-electrode at 18°C. value ⇒ 0. 2] [Ans. K = 1021] 1 I(s) 2 ∈° Fe +2 / Fe ⇒ 0. Calculate its (i) pH and (ii) H+ concentration. ∈°Fe +3 / Fe ⇒ 0.m.44 V.m. at 25°C in 0.4] 46.f.5. [Ans. Suggest a cell. K = 166] 44. of the cell. (ii) 3. [Ans. which is constructed by connnecting H2-electrode to normal calomel electrode.1 N HNO3 | HgNO3 (0. Calculate the equilibrium constant of the reaction at 25°C.

components and degrees of freedom—need to be explained. Thus mixture of H2 and O2 constitutes single phase. 2. there will be some vapors of the liquids. in terms of which the composition of each phase can be expressed in the form of a chemical equation. (b) Mixture of two completely miscible liquids has single phase. (d) If two liquids are immiscible. ( g) At freezing point. So. Component.. G in thermodynamics) in 1876. (f ) If we keep a mixture of miscible liquids in a closed vessel. the terms—phases. mechanically separable from other parts by definite boundary surfaces”. (e) Except solid solutions all different kinds of solids form different phases. solid. (b) A salt solution will be a two-component system. Before stating the rule. Van’t Hoff and others. H2O. gases being mutually miscible in all proportions will constitute one phase only.e. 266 11 . it is a one-component system. and it was later on developed by Ostwald. We all know that a homogeneous system is one in which both the reactants and products are of one phase (i. so the system will have two phases. the composition of each phase can be expressed by a single component i.Phase Rule INTRODUCTION The phase rule was deduced by Willard Gibbs (who introduced the free energy function. liquid or gas) and a heterogeneous system is one in which they are in different phases. (a) Thus. they form two phases such as chloroform and water. above the liquid mixture. Component is defined as the smallest number of independently variable constituents.. (c) Solution of a solute in a solvent constitutes single phase such as salt solution in water. This concept of component can be explained in connection with phase rule with the help of the following examples. 1. “Phase is defined as any physically distinct portion of matter which itself is homogeneous and uniform in composition. Phase. (a) In ice-liquid water-water vapor system. water consists of three phases: Ice(s) CaCO3(s) Water(l) Water vapor( g) (h) A heterogeneous mixture of the type CaO(s) + CO2( g) consists of three phases—two solid and one gaseous.e.

However. The composition of each of the three phases can be expressed in terms of at least any two of the three constituents. the volume of the gas is known. so the system is a two-component system. F=C–P+2 where C is the number of components. Degrees of Freedom or Variance. Thus. NaCl(s) NaCl-Water(aq) H2O(g) the solubility at the saturation point is fixed by either temperature or pressure. so the system is univariant. the number of component is one.PHASE RULE 267 (c) In the thermal decomposition of MgCO3. If temperature or pressure is altered. 10H2O. various phases may exist like Na2SO4. P the number of phases and F is the degree of freedom. (a) A system consisting of pure gas or gas mixture. It is a one component. ice. . The composition of each phase can be expressed in terms of Na2SO4 and H2O. MgCO3(s) MgO(s) + CO2(g). (b) The system ice(s) Water(l) vapor(g) is one-component. 7H2O. Fe(s) + H2O(g) FeO(s) + H2 the minimum number of components required to express the composition is three and hence is a three-component system. one-phase system. The number of degrees of freedom of a system is the minimum number of the independent variables of a system. (d) For the simple system water (l) Water vapor (g) temperature or the pressure is required to define the system. 3. So this system will have no degree of freedom i.e. the system becomes a two-component system. it is a nonvariant or invariant system. (e) In the system of sodium sulfate-water. such as temperature. pressure and concentration and not influenced by gravity. hence the system is univariant. one of the phases will disappear and the three phases will not be in equilibrium. magnetic or electric forces. HCl) is exactly the same as that of the undissociated substance (NH4Cl). Na2SO4. then the composition of any one phase can be represented as Phase: Phase: Phase: MgCO3 = MgCO3 + OMgO MgO = O MgCO3 + MgO CO2 = MgCO3 – MgO So it is a two-component system. The Phase Rule The rule can be stated as “the sum of the number of phases and the degrees of freedom of any system exceeds the number of components by two.. if NH3 or HCl is introduced in the system in excess. provided that the only significant external factors acting are temperature. (d) Suppose a solid dissociates into a number of gaseous substances in a closed vessel NH4Cl(s) NH4Cl(g) NH3(g) + HCl(g) The overall composition of the dissociated vapour (NH3. Hence the degree of freedom is two. (c) For the system. pressure and concentration. If the temperature and pressure are specified. Na2SO4. which can completely define the equilibrium of a system. ( f ) In the equilibrium. three-phase system and all these three phases can co-exist at the freezing point of water at a particular temperature and pressure. solution and vapor. surface action.

Phase rule is applicable to both physical and chemical equilibria. The point B has a natural limit of – 273°C. 4. The equilibrium system requires no information regarding its molecular nature or micro structure. (a) Water(l) Vapor ( g) Hence F = 1 – 2 + 2 = 1. (c) For CaCO3 (s) C = 2. Phase diagram The conditions of equilibrium between different phases of a substance can be shown by plotting temperature and pressure as variables and the diagram is called the phase diagram. boiling point. For both of these curves OA and OB. triple point can be found. 1. . 5. The nature or quantities of the components do not have any role. water. hence if a trace amount of a phase is present and not taken into account. we find that curve BO is the vapor pressure curve of ice which indicates that ice has a small but definite vapour pressure. the critical temperature of +374°C above which distinction between liquid and vapor vanishes. P = 3.268 Examples 1. they are one-component systems with two phases (C = 1. 2. the properties like melting point. Limitations of phase rule 1. Water (l) Vapor ( g) C = 1. vapor and one-component H2O. From the phase diagram. 3. Different systems behave in a similar fashion if they have same degrees of freedom. also called the vaporisation curve. This rule can be applied only to systems that have attained equilibrium. The rule considers only the number of phases and not their amounts present. The Water System This system consists of three phases—ice.1. 11. From Fig. OA is the vapour pressure curve of water. the rule is inapplicable. P = 2. Advantages of phase rule ENGINEERING CHEMISTRY (b) For water at critical point Hence F = 1 – 3 + 2 = 0. P = 2). The OA curve terminates at A. beyond which the two phases merge. The nature of the system can be predicted under different sets of variable conditions like whether different substances can co-exist or be interconverted under different sets of conditions. Ice (s) C = 1. P = 3. so it is of no value for systems which may attain equilibrium very slowly. It states that all the phases must be present under the identical conditions of temperature and pressure. 3. 2. CaO (s) + CO2 ( g) Hence F = 2 – 3 + 2 = 1.

. Hence F = 0 i. all other properties are also fixed. AB is the vapor pressure curve of rhombic sulfur which is stable upto 95°C (0. because the three phases. The curves OA. 11.e.1 The phase-diagram for water (not to scale). Since F = 1 there is only one degree of freedom i. OB and OC divides the whole region into three portions AOC. The inclination of OC towards the pressure axis shows that melting point of ice is decreased by increasing pressure.0098°C under 4. Sulfur at low temperature is in the rhombic form and at high temperature in the monoclinic form.PHASE RULE 269 C 218 atm A X Water Pressure Y 1 atm Ice 4. 11. if the temperature is fixed.e.e. at this point neither temperature nor pressure can be altered without the disappearance of one of the three phases.e. BC is the similar curve of monoclinic sulfur and the point B is the transition point between the two allotropes of sulfur.. P = 3. The curve OC represents the change of melting point of ice with pressure.0075 °C Temperature Fig.2). This curve OD runs above the vapor pressure curve for ice for the above reason and on slight disturbance the supercooled water immediately changes to the stabler form i.. rhombic and monoclinic sulfur have same vapor pressure and co-exist with sulfur vapor.. Sulfur system is another one-component system with a slight more complexity. . called the triple point. ice. it is actually the melting point of ice i.579 mm D B O Water vapour 100 °C 374 °C Z .e. In the phase diagram for sulfur (Fig. This curve represents a metastable system. i. 0. BOC and AOB in which only one phase is present and so the system becomes bivariant and to locate any point in these areas. The point of intersection of these two curves is point O.006 mm) at B. The other two modifications are liquid sulfur and sulfur vapor.. The dotted portion OD.579 mm pressure and at this point C = 1. Sulfur System. which is the continuation of the curve AO below 0°C is the vapor pressure curve of supercooled water below 0°C. temperature as well as pressure is to be known because the degree of freedom F = 1 – 1 + 2 = 2. At B. ice-water-vapour are in equilibrium.

B is actually the triple point. The lines BE and CE represent changes in transition temperature and melting point. pressure. 1288 atm) which is again a triple point where rhombic. which can completely define the equilibrium of a system. Hence. 0. 0. 0.e. Component (C): Component is defined as the smallest number of independently variable constituents in terms of which the composition of each phase can be expressed in the form of a chemical equation. the system is univariant and either temperature or specific volume determines the system completely. . 1.270 F SR Pressure (not to scale – schematic) ENGINEERING CHEMISTRY E(151 °C.2 The sulphur system. At the triple point F = C – P + 2 = 1 – 3 + 2 = 0 i.6 °C. concentration. These metastable systems are represented by dotted curves. 11.288 mm) SL G(115 °C. respectively.. BC.04 mm) monoclinic sulfur melts and CD is the vapor pressure curve of liquid sulfur. CD. with pressure. mechanically separable from other parts by definite boundary surfaces. Degrees of freedom (F): It is the minimum number of independent variables of a system. such as temperature. BE. Highlights: The Phase rule: “The sum of the number of phases and the degrees of freedom of any system exceeds the number of components by two provided that the only significant external factors acting are temperature. zero variant and three phases coexist. i. pressure and concentration.04 mm) Sv B(95.03 mm) D C(120 °C.006 mm) B¢ A Temperature (not to scale – schematic) Fig. Again at C (120°C. There are three stable and one unstable triple points and four phases co-exist nowhere in the curve in equilibrium. 0. The conversion of rhombic to monoclinic is slow and hence if rhombic sulfur is heated quickly it bypasses the transition point B without change and finally melts to liquid sulfur at G. These two lines meet at E (151°C. Along the lines AB..e. monoclinic and liquid sulfur co-exist in equilibrium.” F=C–P+2 Phase (P): Phase is defined as any physically distinct portion of matter which is itself homogeneous and uniform in composition. CE and EF two phases co-exist and F = C – P + 2 = 1 – 2 + 2 = 1. Curve BG is the metastable vapor pressure curve of rhombic sulfur.

e. the highest degree of freedom F = C – P + 2 = 2 – 1 + 2 = 3 i. 11. F = C – P + 1 and the system is called condensed system.3 (a). the behaviour of a system may be represented by a three-dimensional diagram of pressure. a solid phase appears.. When a solid solution is cooled at freezing point. 11. The system becomes invariant. When the pure liquid is cooled it reaches its freezing point b when the pure solid makes its appearance and the temperature remains constant until the total liquid is solidified (bc) and then again temperature falls along cd. From the cooling curve of any mixture of definite composition freezing point and eutectic temperature both can be obtained. . The freezing point of a system varies with the composition but the eutectic point remains constant. If the mixture becomes eutectic the temperature falls until the eutectic point is reached. temperature and composition which cannot be drawn on a paper.3 Cooling curves. The temperature decreases continuously but at different rate than before freezing point. Thus now the system is present at atmospheric pressure and it remains constant. The cooling curve of a mixture of solid is represented by Fig.3 (b). cooling of liquid sulfur leads to solid monoclinic variety along CE but under high pressure.e. The variables reduce to temperature and composition and hence the diagrams are represented on temperature-composition equilibrium. temperature remains constant until total solidification occurs (along cd) and again temperature falls uniformly along de. which will reduce the degrees of freedom by one i. In the case of a two component alloy system there is a solid-liquid equilibrium of the alloy and the vapor phase is practically absent and hence the effect of pressure can be considered to be negligible. 11.. rhombic sulfur separates on cooling liquid sulfur along EG. Eutectic Systems The cooling curve of a pure substance can be represented as Fig. Phase Rule for Two-Component Alloy Systems For a two component system. a a Freezing point Temperature Temperature b c Eutectic temperature Time d c b Freezing point Time (a) d e (b) Fig. the rate of cooling is altered and there is a break in the cooling curve. Thus actual observation can be explained perfectly in terms of phase rule.PHASE RULE 271 From the diagram it is also found that under ordinary pressure.

solution of Ag + Pb and vapor. AO represents the curve along which the melting point of Ag falls gradually on addition of Pb till the lowest point (303°C) is reached when the solution gets saturated with Pb and hence any extra Pb added gets precipitated as solid phase and so also melting point of Ag cannot be lowered any further. as Ag is added the melting point gradually falls till the lowest point O is reached with the above mentioned composition. . A is the melting point (961°C) of Ag.4 T-C diagram of Pb-Ag system. the vapour phase is absent and the condensed phase rule is applicable as F = C – P + 1. solid Pb. F = 3 – P = 3 – 3 = 0 i. invariant. T-C curve is obtained for alloy system.6 Ag 97. the system is univariant along AO and BO and at point O. A solid solution of two or more substances having lowest freezing point than all the mixture of the components is called “eutectic mixture” and the minimum freezing point attainable corresponding to the eutectic mixture is “eutectic point”. Similarly. another curve BO is obtained starting from the melting point of pure lead (327°C) at B.e.272 ENGINEERING CHEMISTRY If the composition of the mixture coincides with the eutectic composition. According to reduced phase rule equation.6 % Ag and 97. which is the eutectic temperature and a lead-silver mixture can never have a melting point below the eutectic temperature.. A binary system consisting of two substances which do not react chemically but is miscible in all proportions in liquid phase is called “eutectic system”.4 % Pb) and the whole mass at this point crystallizes out with the above fixed composition.4 Pb O 327 °C Solid Pb + Liquid Eutectic + Solid Pb 100% Pb Fig. The composition corresponding to a freezing point gives the composition of the alloy. This point O is the eutectic point (2. By plotting freezing point against composition. 961 °C A Liquid P B Temperature Solid Ag + Liquid P¢ 303 °C Eutectic + Solid Ag 100% Ag Composition 2. Lead-Silver-Sample (Eutectic System) It is a two-component system with four possible phases—solid Ag. automobiles etc. Curve AO represents the freezing point curve of Ag. 11. At constant atmospheric pressure. there is no double break but the curve mimicks that of pure component. It is also necessary to know the freezing points of the pure components. The eutectics are applied for constructing safety devices in boilers.

At R the composition of the liquid and the solid phase is the same. 11. The melting points and the eutectic points P. At the eutectic points the solid compound is in equilibrium with either solid tin or solid Mg. Thus along QR from molten alloy only solid compound crystallizes out in equilibrium with the liquid. S are invariant and the areas in between the lines are univariant. 800° a1 a2 R a3 a4 a5 783° w T 500° C+L B+L U S Z 651° 565° C+L P 232° A+L 210° X 100° 0 B+C Q A+C 50 Mg (mole percent) Y 100 Fig. which is Mg2Sn. Q. W. L—liquid.PHASE RULE 273 The region above the curve AO and BO represents solution of Pb and Ag and below the curve AO represents solid eutectic with crystalline Ag and below the curve BO represents solid eutectic with crystalline Pb.5. Tin-Magnesium System The equilibrium diagram of tin (Sn) and magnesium (Mg) is shown in Fig. R. Further increasing the magnesium. Iron-Carbon Alloy System The equilibrium diagram of Fe-C is especially useful to understand the heat treatment of steel. The phase-diagram of iron-iron carbide system is used upto 6. At O (210°C) a new solid phase of a compound of Sn and Mg begins to separate alongwith Sn. the freezing point decreases along RS and reaches the second eutectic point S (565°C). The compound formed is stable and has its melting point at the maximum. B—Mg crystals. . Pure iron exists in three allotropic modifications α. Further addition of Mg raises the melting point along QR and the maximum is reached at R.5 Phase diagram of the system Sn-Mg: A—Sn crystals. γ and δ. This temperature (783°C) is the congruent melting point of the compound. When Mg is added to Sn.67% weight of carbon. C atoms being small compared to iron atoms form only interstitial solid solutions and the solubility of C in these allotropes is quite different. 11. Again on increasing the Mg the freezing point rises along SW. the melting point of Sn (232°C) lowers along PQ. The hump in the diagram indicates the formation of a compound. C—compound Mg2Sn. So Q is the invariant eutectic point.

0 4 4.67% C content and it is called cementite. The transformation of one solid phase into another takes place at the critical temperatures indicated on the diagram..0 Hypoeutectoid Hypereutectoid Cast iron Steels x Weight %C 6 6.130°C) C H 1100 1000 900 800 700 600 500 I A2 L 0.3% C by weight. For an iron-C alloy (cast iron) containing 3% C. On further addition of C. austenite) only.274 A E P d+g Austenite d+L x B Aus tenit ENGINEERING CHEMISTRY Liquid D y e+ Liqu id 1600 1539 1500 1400 1300 1200 Temperature °C Liquid + Fe3C G (1.e.5 0. Hence further removal of heat leads to total solidification of the liquid to ledeburite. freezing point increases upto 6. AEB area represents δ-iron and liquid. then at 1130°C. Pure iron changes from δ to α form at a temperature of 910°C. On further cooling.088% C is commercially pure iron.4 0. which are formed when the cooling rate is slow i. all the ledeburite is transformed into pearlite and cementite mixture. austenite separates out from the liquid. Area BCGP represents austenite and liquid and finally PGKI represents δ-iron (i. when equilibrium is attained. . The phase diagram indicates that upto 0. Cooling further leads to the decomposition of the eutectic mixture of cementite and finally at 723°C the residual austenite transforms to pearlite and at temperature below 723°C.088% to 2% C content is steel and C content above 2% represents cast iron.0 2.e. a mixture of austenite and cementite.3 5 0. In the phase diagram. freezing begins at 1270°C.6 Fig. The Fe-C phase diagram shows the phases.008% 0 Austenite + Ferrite A3 K Eutectoid (pearlite) Acm ite en st + tite Au en m Ce Austenite +Ledeburite +Cementite (723 °C) Cementite + Ledeburite M Eutectic (Ledeburite) A1 Pearlite + Cementite Cementite + Pearlite +Transformed Ledeburite Wrought iron N 3. 11.8 1.025% Ferrite Pearlite + Ferrite 0.6 Equilibrium diagram for Fe-C system. the mixture is austenite containing 2% C and liquid has eutectic composition. From the curve. Above the liquidus there is only liquid phase whereas below the solidus there is only solid phase and between the two lines both phases are present. whereas 0. the curve ABCD is the liquidus line and AEPGCH is the solidus line. But with faster cooling rates metastable phases like martensite and bainite are formed which are not shown in the phase diagram. Area DCH represents cementite and liquid. On dissolving C in molten iron (δ form at 1535°C) the freezing point is lowered until at eutectic temperature of 1130°C corresponding to 4.

A = 40 % = 400 gm and B = 60% = 600 gm. Find the mass of eutectic in 1 kg of the alloy. . 40 % is Cd and hence 60 % is Bi. liquid and solid phases of a substance can co-exist in equilibrium. Problem 2.e. Define the following terms: (a) Phase (b) Component (c) Degrees of freedom. See page 267. In the eutectic system. In 1 kg of AB. State Phase rule. 250 gm. Ans. 1.7) gm = 333. SOLVED PROBLEMS Problem 1. In 1 kg alloy content of Cd is 25%. 3. It is the point of a system at which the gaseous. the content of Bi in eutectic is 250 × 60 gm = 375 gms. F=C–P+1 Triple point. Eutectic point. Congruent melting point. i. AB on cooling forms eutectic containing 60% A and 40% B and the rest of B. 40 ∴ The mass of eutectic in 1 kg alloy is (250 + 375) gm = 625 gm. At triple point the system is nonvariant. Q. if the eutectic system contains 40% Cd. ∴ Corresponding to 400 gm A. What is condensed phase rule? Ans. So the system is considered to be under atmospheric pressure which reduces the degrees of freedom by one and hence..7 gm 60 ∴ Amount of B separated out = (600 – 266. The eutectic mixture contains 60 % A and 40 % B. An alloy AB contains 40% A in 1 kg. See page 272.PHASE RULE 275 Highlights: Condensed phase rule. An alloy of Cd and Bi contains 25% Cd. 2. Q. A compound possesses congruent melting point if it melts to give a liquid having the composition same as the solid.3 gm. ∴ Corresponding to 250 gm Cd. SHORT QUESTIONS AND ANSWERS Q. For two-component alloy systems it is considered that there is practically no gas phase and the effect of pressure is negligible. Ans. Sol. Ans. What is the amount of B formed during eutectic formation? Sol. the content of B = 400 × 40 = 266. A solid solution of two or more substances having lowest freezing point is the eutectic mixture and the minimum freezing point attained is the eutectic point.

Q. 6. A system in which the degree of freedom is zero is called an invariant system. 4. (c) See page 267. State (i) number of phases and (ii) number of components for Fe(s) + H2O(g) FeO(s) + H2(g). (i) Phase rule can be applied only for a system which is in equilibrium. Hence degree of freedom is one. one phase of the substance disappears and the system becomes univariant from invariant. (a) See page 266. By suitable choice. very low melting alloys can be selected for preparing safety devices like fire sprinklers. 9. Q. It is constant for a substance at a set of temperature and pressure conditions. State limitations of phase rule. 10. Ans. So there are three phases in equilibrium. 11. If temperature or volume is altered. Q. Example: Triple point of water is where ice. plugs in automobiles etc. 8. For a two-component alloy system of Pb and Ag. What is the significance of triple point? Ans. See page 269. What is triple point? Ans. state the degrees of freedom (i) as per phase rule and (ii) as per condensed phase rule. 5. Ans. (b) See page 266. (ii) Phase rule helps to predict the behaviour of a system under different sets of conditions. A triple point for a system is invariant. 7. (ii) The minimum number of components required to express the composition of each phase is three. ENGINEERING CHEMISTRY Q. so the system has two degrees of freedom. water and water vapour are in equilibrium. What do you mean by eutectic? What is the eutectic composition of Pb-Ag System? Give one application of eutectics. (ii) For the gaseous mixture of H2 and O2 both the pressure and the temperature are to be specified to define the system completely. (ii) Phase rule conditions that all phases of the system must be present simultaneously under similar set of conditions.276 Ans. Ans. Eutectic is a solid solution of two or more substances having the lowest freezing point of all the possible mixture of those components. . Eutectic composition of Pb-Ag system → 97. 12. Q. (i) For Water(l) Water vapour(g) system either temperature or pressure is to be specified to define the system completely. State two important merits of phase rule. How many degrees of freedom are there for the following systems? Water vapour(g) (i) Water(l) (ii) Gaseous mixture of H2 and O2 Ans. Ans. Q. 26% Ag. Ans.4 % Pb. (i) There are two solid phases—Fe and FeO— and one gaseous phase of a mixture of H2O(g) and H2(g). Q. What is an invariant system? Give an example. This signifies that no condition is required to define the system at that point. (i) Phase rule is applicable to both physical and chemical equilibria. Q. Q.

The maximum number of degrees of freedom for a two-component alloy system is (a) 3 (b) 1 (c) 2. 3. Write down the limitations of phase rule.PHASE RULE 277 Ans. Objective Type Questions MCQ Gibbs phase rule is: (a) F + P = C + 2 (b) F – C = P + 2 (c) P + C = F + 2. metastable state. Draw and explain the phase diagram of ice-water-water vapor system and show the variation of melting-point of ice with pressures. In the thermal decomposition of CaCO3(s) CaO(s) + CO2(g) the system is a (a) one component (b) two component (c) three component. Heterogeneous mixture of CaCO3(s) CaO(s) + CO2(g) consists of (a) one phase (b) two phases (c) three phases 7. EXERCISES State phase rule. 10. 7. 9. component. Define the following terms: phase. Eutectic mixture has: (a) highest melting point. 2. 6. Condensed phase rule has two variables. The composition of the eutectic mixture of Pb-Ag system is (a) 2. 8. 3. What are the merits and the limitation of phase rule? 10. (i) For a two-component alloy system of Pb and Ag when P = 1. 1. degree of freedom according to phase has the highest value of F = C – P + 2 = 2 – 1 + 2 = 3. 97. (b) temperature and pressure (c) pressure and concentration 9. practically no gas is present and hence at atmospheric condition the pressure remaining constant. Condensed phase rule equation is: (a) F = C – P + 2 (b) F = C – P + 1 (c) F = C + P – 2. Discuss the application of phase rule to sulfur system with special reference to triple points and metastable equilibrium. (ii) As per condensed phase rule: For solid-liquid equilibrium of alloy. 2. What is “phase diagram”? Explain (a) triple point and (b) eutectic point with reference to phase diagram. 74% Ag. What is triple point? 5. What are meant by invariant and bivariant degrees of freedom? 12. What is condensed phase rule? 4. .4% Ag (b) 2. Number of components of the system Fe(s) + H2O(g) FeO(s) + H2(g) (a) two (b) three (c) four.4 % Pb (c) 26% Pb. degrees of freedom. 6. 5. namely (a) temperature and concentration. 11. 1. In the water system at triple point. 97. (b) variable composition (c) lowest melting point. Write a brief note on: eutectic point. 4. degrees of freedom reduces by one and F becomes F = C – P + 1 = 2 – 1 + 1 = 2.6% Pb.6% Ag. Draw and explain the phase diagram of a binary alloy system with simple eutectic formation. the system is (a) univariant (b) trivariant (c) invariant. 8.

Shoe polish. Cheese. gelatin. Rubber. bases and salts and many organic compounds like urea. Curd. Starch paste. Cloud. Paints. Insecticide spray. Fog. Lava. In a colloidal solution there exists a discontinuous phase called the dispersed phase and the continuous dispersion medium. Milk of Magnesia. Glue. proteins and other amorphous substances. Thus we now define colloidal state as: a two phase heterogeneous system in which one phase is dispersed in a fine state of subdivision having diameter of 10–4 to 10–7 cm in another medium termed the continuous or dispersion medium. Alloys. Gold sol. Fume Foam.Colloids INTRODUCTION Thomas Graham (1861) while doing his classical researches on liquid diffusion observed two classes of substances. Other members are starch. Pearl (CaCO3 with water). Smoke.1 Types of colloidal systems Dispersion medium Gas Liquid Dispersed phase Liquid Solid Gas Liquid Solid Colloidal system Liquid aerosol Solid aerosol Foam Emulsion Sol Examples Mist. Whipped cream. Styrene foam. Butter. Gems. and also a stabilizing agent which does not allow the dispersed phase to coalesce and settle. Cream. 12 Classification of Colloids (a) Classification based on dispersed phase and dispersion medium which may be either solid or liquid or gas and so the following types (Table 12. FeO3 or AgCl sol in water Pumice stone. Lemonade Milk. Graham called them crystalloid as most of them were crystalline. To this class belonged almost all inorganic acids. Minerals Solid Gas Liquid Solid Solid foam Gel Solid sol 278 . Solution of some substances could readily pass through animal and vegetable membranes. Graham’s view has undergone changes since it has been seen that every substance can exhibit colloidal properties under suitable conditions. Mayonnaise. they were called colloids (from the Greek word Kolla meaning glue. albumin. S. sugar etc. Table 12. which is a member of this class). Jelly. As2O3. The other class of substances are diffused very slowly in solution and the solution could not pass through the membrane.1) of colloids are formed. Froth. bread dough.

2. (i) Unstable (ii) The particles are charged and hence move towards electrode in an electrical field. (iii) Viscosity is much higher than that of the medium. albumin are lyophilic colloids. They move freely in an electric field and the solution has high conductivity. (vii) They are coagulated easily by adding electrolyte. (x) Prepared by indirect methods. The main differences between these two classes of colloids are summarised in Table 12. metallic sulfides are lyophobic colloids. They are lyophilic and have gold numbers. (v) They are self-stabilized due to the strong attraction between two phases. (ii) Macromolecular colloids: A large number of small molecules combine to form a giant molecule held by covalent bonds having a colloidal dimension are called macromolecular colloids. (v) They are much less stable. Example: Soaps and synthetic detergents. Lyophobic sol (c) Classification based on nature of dispersed phase (i) Multimolecular colloids: When the dispersed phase consists of aggregates of atoms or molecules and the main attractive force between them is the van der Waals force of attraction.COLLOIDS 279 (b) Classification based on affinity for solvent When there is a strong affinity between the dispersed phase and the dispersion medium the colloid is known as lyophilic colloid.2 Characteristics of lyophilic and lyophobic sols Lyophilic sol (i) Stable (ii) The particles may or may not migrate in an electrical field. (vi) Surface tension is same as that of the medium. (viii) Starch gelatin. the solute molecules or ions come closer to form aggregate spontaneously of colloidal dimensions. Gums. such as water insoluble dyes are solubilized in soap solutions. (iii) Association colloids: On increasing concentration. for stabilization. (iv) They are reversible sols. . the hydrocarbon portion inside the micelle. Sodium oleate forms micelles and contains a lyophobic group (C17H33+) and a lyophilic group (—COONa). (viii) Colloidal metals. (iv) They are irreversible. stabilizer is reqd. Table 12. Polysaccharides. Nylon etc. called micelles are associated colloids. (vi) Surface tension is much lower than that of the medium. (iii) Viscosity is same as that of the medium. (x) Prepared simply by direct dissolving. Synthetic rubber. while the ionised groups are at the surface. gum. (vii) They are not easily precipitated by the addition of electrolytes. while if there is no apparent affinity it is called lyophobic colloid. Examples: Gold sol and Sulfur sol. They are lyophobic in nature. Examples: Proteins. These colloids play very important role in solubilizing solvent repellant substances. The minimum concentration at which the micellization begins is called the critical micellization concentration (cmc). (ix) Not visible under ultramicroscope. (ix) Visible under ultramicroscope.

The space in between the metal discs breaks down the particles to colloidal size. the bigger or large particles are broken down to colloidal dimension and dispersing them in a medium to form colloidal solution.280 ENGINEERING CHEMISTRY Preparation of Colloidal Solutions The main methods of preparation of colloidal solutions are (a) Condensation method (b) Dispersion method. (b) By reduction: Colloidal solutions of metals such as Ag. hydrolysis of FeCl3 takes place with the formation of deep red colloidal sol of ferric hydroxide. If an alcohol solution of S or P is poured into water. The methods used are: (i) By mechanical dispersion: Many substances of large size are ground and dispersed in a medium to get a coarse suspension which is then passed through a colloid mill. a large number of particles of molecular size are allowed to coalesce or condense to form bigger particle of colloidal dimension. carbon monoxide. Black ink. until saturation. hydrazine etc. On adding a freshly prepared saturated solution of FeCl3 dropwise on boiling water. Sols of insoluble inorganic salts are prepared in this way. Ammonium citrate is added to stabilize the solution. paints. As2O3 + 3H2S → As2S3 + 3H2O. (iii) By controlled condensation: Prussian blue sol is obtained by precipitating it in presence of a protective colloidal system like starch. which is essentially two metal discs rotating in opposite directions at high speed with a very narrow clearance. Pt in water can be prepared by reducing aqueous solution of their salts by reductants like formaldehyde. (c) By hydrolysis: Colloidal solutions of many oxides and hydroxides of iron. The various processes used are: (i) By exchange of solvent: Sulfur or phosphorus is not directly soluble in water. which is washed free of Cl– and finally dissolves on further addition of water. (B) Dispersion method: In this method. (iv) Chemical methods: (a) by double decomposition. on filtration. (A) Condensation Method: In this method. Au. The solution on boiling with saturated NaCl solution precipitates out S. . varnishes.3 %). aluminium can be prepared by this method. colloidal solution of arsenious sulfide is made by passing H2S gas. 2AuCl3 + 3HCHO + 3H2O → 2 Au(sol) + 3HCOOH + 6HCl The liberated acid is neutralized by K2CO3 to stabilize the sol. through a suspension of As2O3 in water. ointments dyestuffs are prepared by this method. FeCl3 + 3H2O → Fe(OH)3 (sol) + 3HCl (d) By oxidation: Sulfur sol is prepared by passing H2S through a solution of SO2 in water until the smell of SO2 is removed. Thus gold sol is obtained by treating a solution of gold chloride with formaldehyde (0. colloidal solution of S or P is formed. (ii) By changing physical state: Hg or S sols are produced by allowing their vapours to pass through cold water.

COLLOIDS 281 (ii) Bredig’s arc method or electro dispersion: (Figure 12. Ag. Pt etc. The trace of alkali stabilizes the colloidal solution and finally the solution is cooled by cooling mixture. The colloid-mill consists of two discs made of metal. which are finally stabilized by addition of a suitable protective colloid. 12. The heat of the spark converts the ends of the metal rods to form vapours of metal which immediately condense to give metal colloids. Cu. . which constitutes the dispersion phase. This coarse suspension is then passed through colloid-mill which mechanically grinds the coarse particles. 12. The clearance between the discs is very small that apparently determines the size of the colloidal particle. 12. Metal rods Arc A little KOH containing solvent (water) Cooling mixture (ice) A High voltage Rheostat Fig. when an electric arc is produced between the tips of two closely placed electrodes of these metals. which rotates in opposite direction at a very high speed. Suspension Metallic disc Colloidal solution (discharge) Driving belt Fig. The coarse particles which come in between the two rotating discs get teared to smaller colloidal particles.1 Bredig’s arc method. are obtained by this method. (iii) Mechanical dispersion method: (Fig.2) this technique consists of finely pulverising the substances to be dispersed in the medium.1) Colloidal solution of metals like Au. Pb. An electric current is passed through water containing traces of alkali.2 Colloidal mill.

The process is allowed to continue until most of the ions are eventually removed and the retained colloid gets stabilized. (i) Dialysis. (a) Thus freshly precipitated Fe(OH)3. The crystalloids from the sol move out through the cellophane while some amount of water or solvent from outside may enter the bag. Al(OH)3 etc. Thus. The foreign electrolyte is known as the peptizing agent and the process is called peptization. Ag+ (Sol/Colloid) Peptizing agent Peptizing agent (c) Al(OH)3 Precipitate Al(OH)3 . Dispersion is also sometimes carried out by the use of an atomiser e.3 Dialysis. can be converted into colloidal state by the addition of small amount of a foreign electrolyte solution. the process of separation of crystalloids from colloids by diffusion through the animal or vegetable membrane is called Dialysis. in the dispersion of a liquid in a gas. H+ (Colloid) Though there is no rule. if shaken with a dilute solution of FeCl3.. So. The following methods are commonly used for purification. would give rise to ferric oxide sol. Fe3+ (Colloid/Sol) Peptizing agent (b) Freshly precipitated AgCl can be peptized by shaking with a dilute aq sol. Hence.g. In certain sols such as Al2O3 hydrosol. they become unstable.282 ENGINEERING CHEMISTRY (iv) Peptization: A freshly prepared precipitate such as AgCl. which is partly immersed in water or the dispersion medium. the disperse phase is too small to be retained by cellophane and hence the system needs controlled heating whereby the particles grow bigger in size. The semipermeable membranes like cellophane parchment paper. The solvent is renewed from time to time. The sol to be purified is taken in a parchment or cellophane bag. Fe(OH)3. of AgNO3 AgCl(s) Precipitate + + Ag+ H+ → → AgCl . Fe(OH)3(s) Precipitate + Fe3+ → Fe(OH)3 . water Sol stand Fig. 12. but it is common that the peptizing agent which are most effective contains a common ion with the precipitate forming colloid. it is essential to purify these colloidal sols. animal membrane have pore sizes which allow the free passage of only the dissolved molecules or ions of a true solution but retains the bigger colloidal particles. . Purification of Colloidal Solutions The colloidal solutions prepared by the above methods contain several impurities of electrolytes and other soluble substances.

Such a filter paper is called ultrafilter paper. and the process is called electrodialysis.COLLOIDS 283 To accelerate this slow process of purification and also to achieve a higher degree of purity the dialysis is carried out in a direct current electric field. Colour and appearance depend on the size. sulfur sols may be colorless to faint and deep yellow in reflected light and reddish in transmitted light. (d) Adsorption. (c) Shape. but in sickle-cell anaemia they become new-moon shaped. 12. (ii) Ultra-filtration. RBCs (red blood corpuscles) normally are double concave plates and give red color. – H2O A D Sol B n E + H2O C Fig. so they attach to a variety of molecules on their surfaces. This process of purifying colloids from the crystalloids using ultrafilters is called ultrafiltration. (b) Colour. But when ordinary filter paper is impregnated with a solution of gelatin or collodion and hardened by formaldehyde the pores become smaller. Vanadium pentoxide particles are rod-shaped. The slime when brought in contact with water. . The sol when poured over the ultrafilter. so that colloidal particles cannot pass through it. but the colloidal particles are retained and form a slime over it. Properties of Colloidal Solutions below: Colloidal solutions possess some characteristic properties. refractive index and some other properties of the dispersed phase. Electrodialysis is of no use in separating non-electrolytic impurities. By using impregnating solutions of different concentration graded ultrafilters can be prepared which is capable of separating impurities of different sizes. This property of colloid has been utilized in dyeing fabrics where the fabrics are first treated with colloidal suspension which adsorbs dye. disperses freely and forms colloidal solution. Important ones are described (i) Physical properties (a) Colloidal systems are heterogeneous. Although the most common shape of the particles are spherical. shape. but highly asymmetrical shape is also found. electrolytes can pass through. Generally colloidal particles are either positively or negatively charged.4 Electrodialyser (diagrammatic). Colloidal particles can pass through ordinary filter papers. Gold sol of very fine particles is red and of coarser particles is blue in colour. Colloidal particles are readily filterable through ordinary filter paper. intermediate between true solution and suspension and contain two phases—dispersed phase and dispersion medium.

mount. In this machine sedimentation is effected under enormous centrifugal force of rotation. observed under a microscope that pollen grains dispersed in water executed a ceaseless random motion. Larger colloidal particles settle slowly by the effect of gravity and is called sedimentation. In a colloidal solution. The phenomenon of Tyndall effect can be explained by the scattering of light by the colloidal particles. Large particles do not show Brownian movement. remount again.284 ENGINEERING CHEMISTRY (ii) Colligative properties. becomes self-luminous and scatter this absorbed light. independent of their nature. in 1927. including colloidal particles suspended in a gaseous medium. which does not happen for true solution. descent. Brownian motion also increases with increase in temperature. colloidal particles move from a region of higher concentration to a region of lower concentration until uniformity is attained. The colloidal particles are constantly hit from all sides of the surrounding molecules. (c) Sedimentation. The intensity of the scattered light depends on the difference between the refractive indices of particle and medium. . start again. (b) Diffusion. depression of freezing point. But the diffusion process is slower than diffusion in true solution due to higher mass and lower speed of colloidal particles. the number of moles present is very low. stop. (iii) Mechanical properties (a) Brownian movement. The true cause of Brownian movement was suggested by Wiener in 1863 as molecular collision of colloidal particles with liquid molecules. (iv) Optical properties or Tyndall effect. smaller particles executing a more rapid and brisk motion than the larger ones. The colloidal particles after impact with solvent molecule move in a straight line until its speed and direction are not altered by another impact. When a beam of light is passed through a colloidal solution. without in the least tending towards immobility”. the path of light becomes illuminated due to the scattering of light by the colloidal particles. This perpetual zigzag motion is called Brownian motion. These colloidal particles can be viewed through a microscope placed at right angles to the path of light and is called the ultramicroscope. an English botanist. This phenomenon is called Tyndall effect. The intensity of Brownian motion is less with increase in size of the colloidal particles and also with the increase in viscosity of medium. High molecular weight is the characteristic of colloidal particles and hence in a solution. lowering of vapour pressure depend on the molarity of the solution and hence these values are very low for colloidal solution. Robert Brown. This motion is described by Perrin as “they go and come. Colloidal particles constantly exhibit Brownian motion and remain suspended in solution. Diffusion is used to separate colloidal particles of different size. thereby stabilizing the colloidal solution. Tyndall effect was first studied by Zeigmondy in 1903 and this effect can be applied for viewing the colloidal particles quantitatively. This random zigzag motion is also executed by all colloidal particles. Svedberg increased the rate of sedimentation with centrifugal sedimentation by employing a high-speed centifuge called ultracentrifuge. The particles absorb the incident light energy. Colligative properties like osmotic pressure.

the phenomenon is called cataphoresis. so they repel each other and become stable. the dispersion medium begins to move in the electric field.7 Hence the pH of the dispersion medium at which the dispersed particles are neutral and hence they do not migrate when subjected to an electric field is called isoelectric point. 12. 12. Positively charged particles are Fe(OH)3. containing a colloidal solution. Fig. In a U-tube. (v) Electrical properties (a) Electrophoresis. When electric current is passed through a colloidal solution such that the dispersed + – phase is prevented from movement. .COLLOIDS 285 – Microscope + Powerful beam of light Path is invisible Colloidal solution Path is visible True solution Electrophoresis Fig. organic sols move towards cathode. Lyophilic and lyophobic colloid particles are either positively or negatively charged. they lose their charge and coagulate there. when a potential gradient is applied the colloidal particles move towards oppositely charged electrode. (c) Isoelectric Point. Fig. This Diaphragm phenomenon is called electro-osmosis (Fig. pH of the medium will dictate the Endosmosis migration of the colloidal particle to any electrode. As2S3 metallic sols. the particles approach each other to form aggregates and settle down. basic dyes etc. When the negatively charged particles like CdS. The movement of the colloidal particles in an electric field is called electrophoresis.6 Electrophoresis. This can be achieved by (i) Adding oppositely charged: Two oppositely charged colloidal solutions when mixed.7).5 Tyndall effect exhibited by a colloidal solution. (ii) Electrophoresis: In electrophoresis the electrically charged colloidal particles migrate towards the oppositely charged electrode and finally coagulate. 12. The isoelectric point of protein depends on pH and ionic strength in the medium. The precipitation of colloidal solution is called ‘coagulation’ or flocculation. Al(OH)3. The colloidal sols of protein are either positively or negatively charged in acidic or alkaline solution and hence when electrolysed in a medium. After reaching the electrode. Proteins are least soluble in isoelectric point and hence coagulate at isoelectric point. Coagulation of Colloids Colloid particles are electrically charged. (b) Electro-osmosis. 12. mutual coagulation of the two sols takes place. The speed of the colloidal particle under the potential gradient of 1 volt/cm is called electrophoretic mobility. When the charge is neutralised.

0053 to 0. the coagulating power increases in the series Na+ < Ba+2 < Al3+ or Cl– < SO 2− < PO 3− .1 to 0. the coagulating power of trivalent ion is 500–1000 times greater than bivalent ion which is 100-500 times greater than monovalent ion. Table 12. (iv) Protective colloids.0058 % gold) containing also 1 ml of 10 % NaCl solution to just prevent its coagulation. the latter becomes more stable even to the action of electrolytes. This is indicated by the change of colour from red to blue.01 to 0. The smaller the gold number the greater is the protective power of lyophilic colloid. Thus.003 to 0. through which the oppositely charged ion of the electrolyte cannot penetrate to neutralize the charge for coagulation.015 0. like NaCl. Thus.2 0.2 10 to 15 0.e. (iii) Protective agents.005 to 0.286 ENGINEERING CHEMISTRY (iii) Adding electrolytes: By addition of oppositely charged ion i. (ii) Solvation. The process by which lyophilic colloid protects the lyophobic sol is called protection and the lyophilic colloid is called the protective colloid..02 0.1 to 0. Protection of Colloid The stability of colloids can be achieved by any of the following: (i) Electrical charge. the former acts as protective colloid and prevents coagulation of the latter even against addition of high concentration of an electrolyte. Protective agents are added to some colloidal systems. These sols are very stable. When a lyophilic colloid is added to a lyophobic colloid. by adding electrolytes the charges of the colloidal particles are neutralised and precipitated. Colloidal particles are surrounded by a layer of solvent molecules which resists the dispersed phases from forming large aggregates and coagulate. which get adsorbed on the surface of the colloidal particles and by coating them prevents coagulation. greater is the coagulating power—this is known as Schulze-Hardy law. This mutual repulsion prevents them from coalescing and coagulating.40 0.3 Gold numbers Protective colloid Gelatin Casein Albumin Gum Starch Sodium oleate Haemoglobin Gold number 0. which when added to one ml of standard gold sol (containing 0. The higher the valency of the ion. 4 4 Generally. Lyophilic colloids are much more stable than the lyophobic colloids—since the former are extensively solvated. Zsigmondy introduced the term ‘gold number’ to measure the protective power of lyophilic colloids. the solvent layer forms a protective envelope. if a little albumin (lyophilic colloid) is added to a gold sol (lyophobic sol). This protection is due to the formation of a protective thin layer surrounding the particles of the lyophobic colloid. Thus. It is defined as “the minimum weight in mg of a protective colloid. All the colloidal particles of a colloidal solution bear similar charges and hence they repel each other. Coagulating power of an ion increases with the increasing valency of the coagulating ion.07 .

and hence they are not stable and easily separate into two immiscible layers.g.. A part of this opposite charge is fixed on the particle and another part is mobile and distributed throughout the medium. jellies. which do not allow the particles to come closer and coalesce and hence bring stability to the system. e. The familiar examples are–milk. Reversible colloid. hence they are used as stabilizers for oil-in-water-type of emulsion whereas heavy metal soaps of palmitic and oleic acid are soluble in fat and hence used in water-in-oil-type emulsion. solid fuel of alcohol with calcium oxalate. e. + + – + + – + – Liquid + + – + + – + – + – Fixed Fixed Movable Helmholtz double layer Diffuse double layer Fig. The charge is embedded in the colloidal particle and an equivalent amount of opposite charge remains outside and these two layers form a double layer. cheap soaps. solution of gelatin can be reconverted into sol by heating. This is formed by entrapment of the dispersion medium inside the loose network of the dispersed particle. Gels have high viscosity and swell if placed in the dispersion medium and some shrink in volume. e. jelly. Emulsions are prepared merely by shaking one liquid with the other.. gelatin etc. – – – – – – – – – – – – – – – – – – + + + + + Liquid + + + + Movable – – – – – – – – – – – – – – – – – – + + + + + + Surface of solid Surface of solid zeta pot. Gel: Many lyophilic sol and few lyophobic sol when coagulated under certain conditions form semi-solid mass. soaps and detergents are the common emulsifiers. agar-agar. Gel formation is utilized for preparation of shoe polish. casein. are more soluble in aqueous phase. Emulsions are stabilized by adding a third substance (emulsifier) as stabilizer.g. Albumin.. Emulsifiers are selected according to the type of emulsion. In lyophobic colloids. Emulsions have properties similar to those of lyophobic colloids like Tyndall effect. butter. e. When a colloid can be reversibly converted from a sol to gel and vice versa. gum. (v) Zeta potential. . The emulsifier also decreases the surface tension of the two liquids. Such a product is called gel and the process is called gelation.g. which consists of liquid fat dispersed in water (oil in water type). particles are of similar charge. curd etc. Other colloids which cannot be reversibly transformed are called irreversible colloid. Brownian movement etc. soaps of alkali metals. curds. jam.8 Zeta potential. which consists of water dispersed in liquid fat (water in oil type). cheese.. 12. it is called a reversible colloid. This substance forms a thin layer around the dispersed phase thereby preventing it from coalescing and coagulating.COLLOIDS 287 Emulsion and Gel Emulsions are colloidal systems in which both dispersed phase and dispersion medium are liquids (immiscible). normal Au colloid.g.

Gold number. Blood coagulation is effected with alum or FeCl3. which is treated with negatively charged colloidal solution of tannin. Schulze-Hardy Law. By neutralizing the charge.0058% gold) also containing 1 ml of a 10% NaCl solution to just prevent its coagulation. polluted air. When a beam of light is passed through a colloidal solution. Bancroft rule. (iii) Removal of dirt from sewage. (v) Laundry. This phenomenon is called Tyndall effect. This is called Schulze-Hardy law. which when added to 1 ml of standard gold sol (containing 0. The phase in which the emulsifier is more soluble becomes the outer phase. Purification of colloidal solutions can be done by dialysis. Ca2+ present in the sea water are responsible for the deposition of colloidal particles where river meets sea. the greater is its precipitating action.. Application of Colloids (i) Purification of water. Different types of colloidal systems and emulsion are used in cosmetics. Impure water is treated with alum.0053 to 0. which is passed through tanks fitted with oppositely charged electrodes. Smoke is negatively charged colloidal suspension consisting of carbon particles. which adsorb greasy materials. K+. Colloidal system of medicines are better assimilated. The raw material skin is positively charged colloidal system. Al3+ ions of alum precipitate negatively charged clay particles. Suspended particles. dirt by emulsion formation and remove dirt from clothes. Sewage contains charged dirt particles. Brownian motion. The random zigzag motion of the colloidal particles in the suspending medium is called Brownian motion. (iv) Leather tanning. (vii) Cosmetics. smoke etc. ultrafiltration. the path of light becomes illuminated due to the scattering of light by the colloidal particles. there is a potential difference between the particle and the medium. and higher the valency of the active ion. Tyndall effect. (viii) Analysis. Negatively charged sand particles of the river water and Na+. This potential is called the zeta potential which is responsible for the stability of the colloid. Soaps in water form colloidal solution. dirt is coagulated. (ii) Purification of polluted air. Highlights: Dimension of colloidal particles range from 10–4 to 10–7 cm. (vi) Medicine. . (ix) Artificial rain are made by throwing charged sand on clouds. colloidal particles and the impurities. The motion is rapid for smaller particles and also for a less viscous medium. bacteria. whereby mutual coagulation of oppositely charged colloids takes place. It is the minimum weight in mg of a protective colloid. Noble metals are detected by formation of their colloidal solutions and observing their colours.288 ENGINEERING CHEMISTRY Hence. Air is passed through Cottrell precipitator where the charge is neutralised and carbon settles down while the hot air passes out through chimney. The coagulating power of an electrolyte depends predominantly on the valency of the ion bearing a charge opposite to that of the colloidal particles. (x) Delta formation.

Explain the action of gelatin as protective colloid. 3. What are the sizes of particles forming a solution and a colloidal solution? Ans. A colloidal system is a two-phase heterogeneous system in which one phase is dispersed in a fine state of subdivision (from 1 to 50 mµ) in another medium termed the continuous or dispersion medium. 6. Q. it forms a very thin protective shell. Why are “Brownian movement” and “Tyndall effect” shown by colloidal solutions but not the true solution? Ans. surrounding each particle of the lyophobic colloid and protects the penetration of oppositely charged ions. 4. Q. Ans. 5. 1. Large particles of the colloid solution do not settle down and scatter the light falling on the solution. Sol is a colloidal solution of a solid dispersed in a liquid medium whereas emulsion is a liquid dispersed in another immiscible liquid in the form of droplets. Write short notes on the following: (a) Brownian movement (b) Tyndall Effect (c) Dialysis (d) Gold number. Ans. which neutralize the charge and precipitate the lyophobic colloid. The solute particles in true solution are of dimension 1 to 10 Å. Write notes on (i) Electrophoresis (ii) Peptization (iii) Zeta potential (iv) Protection of hydrophobic colloids. Which of the following electrolytes will be most efficient for the precipitation of As2S3 sol and why? (i) KCl (ii) CaCl2 (iii) AlCl3.COLLOIDS 289 SHORT QUESTIONS AND ANSWERS Q. Ans. Q. (i) See page 285 (ii) See page 282 (iii) See page 287 (iv) See page 286. 2. 7. Particles of colloidal system have dimension in the range from 10 to 1000 Å. Describe a colloidal system. Q. . Gelatin is a lyophilic colloid and when it is added to lyophobic sol. (a) See page 284 (b) See page 284 (c) See page 282 (d) See page 286. whereas in true solution there are no such particles. Q. Q. What is the difference between sol and emulsion? Ans.

The sizes of the colloidal particles fall in the range (a) 10–2 to 10–4 cm (c) 2. (b) Absorbed completely Light passing through a colloidal solution is (a) Reflected (c) Scattered. See page 288. See page 288. Smoke coming out from the chimneys of different factories is led to charged metallic plate—explain. Q. Ans. and Al3+. Q. 6. 10–7 to 10–9 cm. Mention some important applications of colloid chemistry to industries. Ca2+. What happens when a sol is filtered through a filter paper? Ans. the positive ions obtained are K+. Explain: Electrophoresis and Electro-osmosis. Q. If a sol is filtered through an ordinary filter paper. (d) Protective colloids. 4. Why is alum used to remove impurities from water? Ans. 5. Explain how deltas are formed where rivers meet the sea. (b) 10–4 to 10–7 cm . Since Al3+ possess highest positive valency. 9. Write a note on application of colloid chemistry in (i) pollution control and (ii) industries. (b) Brownian movement. Ans. Differentiate between lyophilic and lyophobic solutions. See page 279. Q. the colloidal particles will pass through the pores of the filter paper since the pore-size of ordinary filter paper is larger than the size of the colloidal particles. Q. Ans. Q. See page 286. Q. 15. 8. EXERCISES 1. 14. 2. Ans. See page 288.290 ENGINEERING CHEMISTRY Ans. 13. From the above three electrolytes. The pH of the medium at which the dispersed colloidal particles are neutral and hence do not migrate when an electric field is applied to the colloidal solution. What do you mean by isoelectric point? Ans. (c) Gold number 3. What are the different ways of protecting a colloidal solution from coagulation? State Schulze-Hardy rule and explain with an example. as per Schulze-Hardy rule. Q. State Schulze-Hardy law. As2S3 sol is a negatively-charged sol and it can be precipitated by positively charged ions of the added electrolyte. Ans. What are lyophilic and lyophobic sols? Explain the following: (a) Tyndall effect. 10. AlCl3 will be the most efficient electrolyte to ppt As2S3 sol. OBJECTIVE QUESTIONS 1. See page 288. 11. 12.

Bancroft rule states that (a) Colloidal particles are always charged (b) Light falling in the medium is scattered by the colloidal particles. 8. Which one is the most efficient in coagulating a ferric hydroxide sol? (a) K4 [Fe(CN)6] (c) KCl. 7. (c) The phase in which the emulsifier is more soluble is the outer phase.COLLOIDS 291 3. . Which process is used for the purification of a colloidal solution? (a) Dialysis (b) Peptization (c) Dissolution. 12. The random zig-zag movement of colloidal particles in a dispersion medium is called (a) Tyndall effect (b) Brownian movement (c) Dialysis. Soaps and detergents act as (a) Stabilizers (b) Emulsifiers (c) Coagulating agents. Milk is an emulsion of (a) Casein dispersed in water. 5. Which is a protective colloid? (a) K4[Fe(CN)6] (b) NaCl (c) Gelatin. 11. 10. (b) Lactose dispersed in water. (b) K3[Fe (CN)6] 4. Smoke is a colloidal sol of (a) Solid dispersed in gas (b) Gas dispersed in solid (c) Liquid dispersed in gas. (c) Fat globules dispersed in water. Haemoglobin in blood is (a) Hydrophobic colloid (b) Hydrophilic colloid (c) Gel. This can be demonstrated by (a) Peptization (b) Electrophoresis (c) Dialysis. Colloidal particles are electrically charged. 9. 6.

Scandium is excluded because it only produces compounds in the +3 state and it loses all its three outer electrons when it forms Sc+3 cation. respectively. the definition holds good for all the element excepting scandium and zinc. They are stated below: All are metals with useful mechanical properties with high melting points. All act as catalysts. Zn on losing two electrons produces Zn+2 cation with an electron configuration (1s2 2s2 2p6 3s2 3p6 3d10) in which all the d-energy levels are full. Many transition metal salts are paramagnetic because of the presence of unpaired electrons in the partially-filled inner d-energy levels.. Transition metals have a number of common features. The chemistry of titanium (Ti). manganese (Mn). as metals or as compounds. + 3 and + 2. All form coloured compounds.Transition Metal Chemistry TRANSITION METALS Transition metals are d-block elements having partially filled d-energy levels in one or more oxidation states. +7 +6 +5 +4 +3 +3 +4 +3 +3 +2 +4 +3 +2 +3 +2 +2 +2 +1 Sc Ti V Cr Mn Fe Co Ni Cu Zn +2 13 • • • • • Fig. Zinc is excluded because all its compounds are in the +2 state. chromium (Cr). 292 Oxidation states . It is to be noted that Sc and Zn form ions in one oxidation state i. cobalt (Co). All form compounds in more than one oxidation states. iron (Fe) and copper (Cu) provide many examples of the above-mentioned features.1 Main oxidation states of the elements Sc to Zn (first transition series).e. vanadium (V). All form a variety of complex ions. 13. In the d-block series from scandium (1s2 2s2 2p6 3s2 3p6 3d1 4s2) to zinc (1s2 2s2 2p6 3s2 3p6 3d10 4s2).

8 × 10–8 1. The theory is known also as co-ordination theory. like ionisation of weak electrolyte. K+. K2SO4.0 × 10–21 5. and ‘Y’ is trivalent cation as Al+3. where ‘X’ is monovalent cation. A complex salt does not give all the ions of its constituents in solution. The dissociation constant is called instability constant (Kins) and is a measure of stability of a complex. So.6H2O.24H2O which is the general formula of a common alum. and the salt crystallises as X2SO4Y2(SO4)3. (NH4)2 SO4.24H2O in solution gives the reactions of K+. Fe+3 etc. The postulates of his theory may be summarised as follows: • Metals possess two types of valencies: (i) Primary or principal or ionisable valencies (ii) Secondary or subsidiary or non-ionisable valencies. follows the law of mass action. like NH4+. FeSO4 + 2KCN = Fe(CN)2 + K2SO4 Fe(CN)2 + 4KCN = K4[Fe(CN)6] The solution of K4[Fe(CN)6] does not respond to the tests for Fe+2 or CN– ions. viz. Examples of complex salts [Ag(NH3)2]Cl      [Cu(NH3)4]SO4   K[Ag(CN)2] [Ag(NH3)2]++ + Cl– [Cu(NH3)4]++ + SO4 K+ + [Ag(CN)2]– Instability Constants of Complex Salts The dissociation of a complex ion. it loses its entity in solution. A complex salt K4[Fe(CN)6] is prepared by adding KCN solution of FeSO4 solution and boiling.FeSO4. the higher is the stability of the complex and vice versa. . Al+3 and SO4–2 ions.    Kins = Complex ions [Ag(NH3)2]+ [Ag(CN)2]– [Cu(CN)4]–3 [Cd(CN)4]–2 Ag+ + 2NH3 Ag+ + 2CN– Cu+ + 4CN– Cd+2 + 4CN– [M + ] [L− ] [ML] Instability constant 6. The double salt is characterised by complete dissociation in solution and gives the reactions of all the ions formed by the salts in solutions. Cr+3. but responds to a test for a new ion [Fe(CN)6]–4 (ferrocyanide ion). the complexions. it can be said.4 × 10–17 Werner’s Theory for Formation of Complex Compounds Werner put forward a theory for the formation of complex compounds. are quite stable in the solid state as well as in solution.Al2(SO4)3. the lower the value of Kins. Na+.TRANSITION METAL CHEMISTRY 293 Double Salts and Complex Salts A double salt is formed generally when molar proportions of a monovalent cation sulphate solution in water is mixed with trivalent cation sulphate solution in water and evaporated to remove excess water. Another important double salt is Mohr’s salt. This ion remains intact even in solution K4 [Fe(CN)6] 4K+ + [Fe(CN)6]–4 and gives its distinctive reactions. like ferrocyanide ion. A complex salt is different from a double salt in respect of its distinctive character even in solution. A double salt exists as a distinct entity only in the solid crystalline state.0 × 10–28 1.

bidentate. Again. This type of ligands are known as complexones. This gives rise to various types of isomerism.e. for metals.) of the central metal atom must be fulfilled. • Primary valencies of the metal are satisfied by negative ions.N. • The secondary valencies are directed in space about the central metal ion. but secondary valencies may be satisfied by negative groups (CN– . etc.N. as for example en (ethylene diamine).N. Werner could isolate even optical isomers. H2O Bidentate ligands—H2NCH2CH2NH2 (en stands for ethylene diamine) Cu (II) has C.294 ENGINEERING CHEMISTRY • Every metal atom has a fixed number of secondary valencies or co-ordination number (C. = 6.). Chelates are formed by bidentate and polydentate ligands.) or even sometimes some positive groups. Ligands The ions or molecules thus attached to the central metal atom by co-ordinate bonds are called ligands. The main drawback for Werner’s theory is: there is no theoretical reason to have a central atom of the complex ion to possess two kinds of valencies. the six valencies are directed to the apices of a regular octahedron.N.N. Chelation increases the stability of co-ordination complex i. The maximum number of ions or molecules thereby the central atoms could form co-ordinate bonds is known as co-ordination number (C. edta (ethylene diamine tetra-acetic acid). the four such valencies are either directed to the apices of a regular tetrahedron or a square (planar). tridentate etc. chelate complexes are generally more stable than complexes formed by monodentate ligands.). neutral molecules (H2O.N. Types of Ligands Unidentate ligands—F–. Cl–. Co (III) and Pt (IV) has C. NH3 etc. For metals with co-ordination number (C.). Chelate Compounds Chelate compounds are complex compounds containing a ring structure in which a ligand molecule or ion forms more than one dative covalent bonds (co-ordinate bonds) with the central metal ion. = 4. depending upon the number of co-ordination centres in the ligand. Cl–. ++ Chelate complex with en .N. In every complex formation the coordination number (C. = 4 . The ligands may be unidentate.. = 6). edta or EDTA The ligand molecules which occupy two or more co-ordination centres are usually organic molecules. with C. Powerful chelating agents trap metal ions and effectively trap them in solution.

possess a neutral donor atom as well as an acidic group. Generally. (iv) In [PtIV(NH3)4Cl2]2+ [PtII(Cl)4]2–.2 Chelate complex of edta with a bivalent metal. Nomenclature of Coordination Compounds (IUPAC) Complex compounds are of the following types: (i) Cationic. (ii) anionic. (ii) In naming the anionic complexes like K2[PtCl6] the K+ is written first then the name of the complex anion. Naming of the ligands Neutral ligands (C2H5)3N NH2-NH2 CH3NH2 NO — — — — Triethylamine Hydrazine Methylamine Nitrosyl Dimethylamine CO CS H2O NS NH3 — — — — — Carbonyl Thiocarbonyl Aquo or aqua Thionitrosyl Amine (CH3)2NH — . (iii) non-ionic and (iv) a combination of cationic and anionic complexes. the acid group of the ligand satisfies the primary valency of the central metal ion (which therefore does not appear as an ion i.. Such non-electrolytic cyclic complexes are known as inner metallic complexes or simply inner complexes. which have very low solubility in water but high solubility in organic solvents.e. (iii) If the complex compound is non-ionic (neutral) the name of the complex compound like [Pt (NH3)4Cl2]0 is written as one word. 13. It is to be noted in chelate complexes that the rings formed are five or six membered. which act as chelating agents. (i) In naming cationic complexes like [Co(NH3)5Cl]Cl2. net charge on the complex molecule is zero). They form very stable cyclic complexes. the name of the complex cation is written first then the complex anion is named. Inner Metallic Complexes Many well-known organic ligands.TRANSITION METAL CHEMISTRY 295 O CO CH2 COCH2 N M O CO CH2 +2 O CH2 CH2 N CH2 CO O Fig. the name of the cation is considered first and then the name of the anion.

The name of the ligands or organic molecule is written in the bracket. I.for two. Examples of complex ligands are—Ethylene diamine (en) etc. tetrakis. These ligands can co-ordinate to the metal atom through any of the their donor atoms. tris. tri.for three.for two. their number is indicated by di. Order of Naming the Ligands If the co-ordination sphere of a given complex compound contains various types of ligands. • If a complex contains two or more complex ligands or organic molecules and which already have di-. Br– etc. For example: Cr — Chromate Cu — Cupreate Pt — Platinate Co — Cobaltate Al — Aluminate Ni — Nicklate .for four. For anionic complexes the name of central metal atom ends in ‘ate’ and the oxidation state of the metal is written in Roman numerals (0.for four before the names of the ligands. tetra.in their names their number is indicated by putting the prefixes bis. these ligands are named alphabetically. tri.for three. For example: [Co(NH3)4Cl(NO2)]+ ion is named as tetra-amine chloro nitro cobalt (III) ion. Example: − (i) NO 2 ion (−) (ii) SCN– ion → → O—N— O named as Nitro-O  or  Nitrito when donor atom is ‘O’ – O 2N named as Nitro-N  or  Nitrato when donor atom is ‘N’ Thiocyanato-S (SCN–) Thiocyanato-N (NCS–) Indication of the Number of ligands • If a complex contains two or more simple ligands like Cl–.296 Anion ligands F– Br– Cl– I– NH2– NC– ONO– S2O32– — — — — — — — — Fluoro Bromo Chloro Iodo Amido Iso-Cyano Nitrito Thiosulphato CH3COO– NH 2– OH– S2– CN – NO2– SCN – NO3– ENGINEERING CHEMISTRY — Acetato — Imido — Hydroxo or hydroxyl — Thio — Cyano — Nitro — Thiocyanato — Nitrato Ambident ligands Ambidentate or ambident ligands are those which have two or more different donor atoms in their structures. II).

but differ in the arrangement of ligands in space. [Cr(H2O)4Cl2]+ [Co(NH3)5H2O]Cl3 — Pentamine mono aquo cobalt (III) chloride — Tetraamine dichloro cobalt (III) chloride [Co (NH3)4Cl2]Cl Examples of Anionic Complexes K4[Fe(CN)6] — Potassium hexacyano ferrate (II). is denoted by the prefix µ. For example 1. NH2 2. the complex [Co(NH3)5 Br]SO4 (I) gives white precipitate of BaSO4 when treated with BaCl2 solution and indicates that SO42– ion is outside the co-ordination sphere. (H2O)4Fe 3+ OH OH – – Fe (H2O)4 (SO4)2 3+ is called: Tetra-aquo iron (III)-µ-dihydroxy tetraquo iron (III) sulphate.TRANSITION METAL CHEMISTRY 297 Examples of Cationic Complexes [Ag(NH3)2]Cl — Diamine silver (I) chloride. 3.Co OH Co. For example. This is of two types: (a) Geometrical or cis-trans isomerism (b) Optical or mirror image isomerism. (en)2.before its name. which links two metal atoms. Isomerism in Metal Complexes Isomerism in complex molecules arises due to difference in attachment of the groups or ions to the central metal iron or due to their different spatial arrangements about the central metal ion. namely (a) ionisation isomerism. — Tetraaquodichloro chromium (III) cation. [Pt(NH3)2Cl4] — Diamine tetrachloro platinum (IV). (e) hydrate isomerism. (c) co-ordination isomerism. (i) Structural isomerism. Ionisation Isomerism In this case. (b) linkage isomerism. they are said to be stereoisomers of each other and the isomerism of this type is called space-isomerism or stereoisomerism. Bridging Ligands A bridging ligand.(en)2 (SO4)2 is named as: Bis-(ethylene diamine) cobalt (III)-µ-amido-µ-hydroxo-bis (ethylene diamine) cobalt (III) sulphate. positions of groups inside and outside of the co-ordination sphere are interchanged and so the compound yields different ions in the solution. (ii) Stereoisomerism or space isomerism. When two compounds containing the same ligands are co-ordinated to the same central metal ion. This is also classified under six heads. And the complex [Co(NH3)5SO4] Br (II) . [(NH3)5Co—NH2—Co(NH3)4(H2O)]Cl5 is named as: Pentammine cobalt (III)-µ-amido-tetrammine aquo cobalt (III) chloride. Generally. two types of isomerisms are exhibited by metal complexes. (d) ligand isomerism. 3– [Co(Cl)6] — Hexachloro cobaltate (III) ion.

3 Co-ordination Isomerism This type of isomerism arises from the difference in distribution of the co-ordinating groups in the cations and anions of two compounds of identical composition.. The complexes with NO2– ion as with ligand NO2– may get attached to the central metal ion either through O-atom or N-atom acting as donor. thiosulphate (S2O32–) ions. With S2O3–2 acting as ligand the central ion may be coordinated with the ion either through S-atom or O-atom.Cl]SCN and Linkage Isomerism This type of isomerism is exhibited by those molecules in which the ligands can coordinate with the central metal ion either of its two atoms. .(NO2).e.(SCN)]Cl [Co(en)2. The ligands of this type are nitro (NO2–). indicating the Br– ion is outside the coordination sphere.(en)2. ligands when coordinated through different atoms are given below: Nitro-O or Nitrito (ONO ) – Nitro-N or Nitrito (NO2 ) – NO2 – SCN – O For example: 2+ NH3 H3N Co H3N NH3 NH3 H3N NH3 ONO H3N Co NH3 NH3 NO2 2+ Pentaamine nitrito (or Nitro-O) cobalt (III) ion (red) Pentaamine nitrato (or nitro-N) cobalt (III) ion (Yellow) Fig. The names of the above ions i. 13. in case of SCN– ion as ligand.298 ENGINEERING CHEMISTRY gives a light yellow precipitate of AgBr when treated with AgNO3 solution. Pentaamine monobromo cobalt (III) sulphate (red-violet) Pentaamine monosulphato cobalt (III) bromide (Red) [Co(NH3)5Br] SO4 + BaCl2 → [Co(NH3)5 Br]2+ + BaSO4 ↓ + 2Cl– (White) [Co(NH3)5 SO4]Br + AgNO3 → [Co(NH3)5 SO4]+ + AgBr ↓ + NO3– (Light yellow) Other examples for the same are: [Pt(NH3)4Cl2]Br2 [Co(NH3)4Cl2]NO2 and and [Pt (NH3)4Br2]Cl2 [Co(NH3)4(NO2)Cl]Cl [Co. Similarly. thiocyanate (SCN–). the donor site may either be through N– or through S-atom.(NO2).

[Cr(H2O)5. 13. Thus. and thus enters into the co-ordination sphere of a metal ion.Cl].5 .Cl2]. 13.Cl.TRANSITION METAL CHEMISTRY 299 For example: (i) [Cr(NH3)6]3+ [Cr(SCN)6]3– and [Cr(NH3)4 (SCN)2]+ [Cr(NH3)2 (SCN)4]– are co-ordination isomers. NH3 H3N Co H3N NH3 (a) cis-form NO2 H3N NH3 (b) trans-form NO2 O2 N Co NO2 NH3 NH3 Fig. forming aquo-complex.2-diamine (pn) and propane-1. The number of possible isomers is different for these two spatial arrangements. propane-1. In six co-ordinated complexes the six groups are arranged about the central metal ion in a regular hexagonal pattern or at the six corners of an octahedron. Hydrate isomers are generated due to variation in number of water molecules in the co-ordination sphere. Cisform is known as cisplatin and is an anticancer drug. Cl Pt Cl (a) cis-form NH3 Cl Pt NH3 NH3 H3N (b) trans-form Cl Fig.H2O.3-diamine (tn) also called trimethylene diamine have the structures: They form isomeric complexes as [Co(pn)2Cl2]Cl and [Co(tn)2Cl2]Cl Hydrate Isomerism Water molecule is a very effective co-ordinating agent and may replace NH3. Ligand Isomerism Some ligands themselves may exist as isomers and are so co-ordinated in the complexes.4 Diamine dichloro platinum [Pt(NH2)Cl2] exists in two isomeric forms (Fig. 13.2H2O Geometrical Isomerism Geometrical isomerism originates due to the different arrangements of the co-ordinated groups in space around the central atom in a definite geometrical pattern.4). Cl2 etc.6H2O are [Cr(H2O)6]Cl3.5). (ii) [Co(en)3]3+ [Cr(C2O4)3]–3 and [Co(en)2(C2O4)]+ [Cr(en)(C2O4)2]– are co-ordination isomers.Cl2. Thus for [Co(NH3)4(NO2)2]NO3 two types of geometrical isomerisms may develop (Fig. 13. [Cr(H2O)4. For example: three isomers of CrCl3.

This overlapping results in a σ-bond or possibly a π-bond.7. In this context.6 and 13.6 – (–) H3C As H5C2 (a) C6H4COO S OOCH4C6 As S (b) CH3 C2H5 Mirror plane Fig. Valence Bond Theory This theory was developed by Pauling and deals with hybridisation of the complex. 13.and 4-co-ordination complex compounds is shown in Fig. • The empty orbitals of the metal ion hybridise to give an equal number of equivalent hybrid orbitals.7 Optically active arsenic compound with co-ordination number 4. 13. It depends on the following assumptions: • The central metal atom provides a number of empty orbitals that are equal to its coordination number for forming the covalent bonds with ligand orbitals. the first two theories have been discussed. (ii) Crystal field theory. The complex [Cr(en)2Cl2] with co-ordination number 6 exhibits optical isomerism. . (iii) Molecular orbital theory and (iv) Ligand field theory. Mirror plane en Cl Cr Cl en (a) Cl Cl en Cr en (b) Fig.. Ag+ + 2 N H3 → [Ag(NH3)2]+ • An orbital of the ligand containing an unshared electron pair overlaps the hybridised orbitals of the metal ion and this is regarded either as partial donation of the ligand electrons to the metal ion or a sharing of that pair of electrons between the metal ion and the ligand. These are: (i) Valence bond theory.300 ENGINEERING CHEMISTRY Optical or Mirror Image Isomerism Optical isomerism of 6. . • Ligands are groups which can donate electron pairs to metal ions which appear as electron pair acceptors. Theories of Bonding in Co-ordination Compounds There are four distinct approaches to the theoretical treatment of bonding in co-ordination compounds. 13.

Another example of sp3d2 configuration is [FeF6]3– complex. This is often referred to as spin paired complex. 3d 4s ) sp d 3 2 5 2 3d Electronic configuration of Fe 3+ 4d in sp d configuration sp d 3 2 3 2 Electronic configuration of Fe ion in [FeF6] configuration 3+ 3– 4d ×× ×× ×× ×× ×× ×× F – F – F – F – F – F – Six sp d hybridised orbitals having lone pairs of electrons – donated by six F ligands. In Fe2+ ion..4s ) (c) Electronic configuration of Fe ion in d sp hybridised state (d) Electronic configuration of Fe ion in [Fe(CN)6] 4– 2+ 2 3 2+ ×× ×× CN CN – – ×× CN – ×× ×× ×× CN CN CN – – – The ground state electronic configuration of Fe is . . So. The complex formation is as follows: 3d (a) Electronic configuration of Iron in ground state (. Let us site an example of an octahedral complex [Fe(CN)6]4–.. 3d64s2.TRANSITION METAL CHEMISTRY 301 Octahedral complexes result from d2sp3 or sp3d2 hybridizations.. The formation of this ion is as follows: Electronic configuration of Fe 3+ 3d 4s 4p 4d (.. this is often called inner orbital complex. Because of presence of five lone electrons in 3d level the compound is highly paramagnetic and often referred to as sp high spin complex. The shape of the complex molecule is octahedral and due to the absence of unpaired electrons... This complex uses the inner d-orbitals.3d .. six d2sp3 hybrid orbitals are generated which are filled by electron pairs donated by six CN– ions acting as ligands.3d . it is called outer orbital complex. In d2sp3 hybridisation.4s ) (b) Electronic configuration of Fe 6 0 2+ 6 2 4s 4p ion in ground state (. the complex is diamagnetic. hence [Fe(CN)6]4– complex is formed. the two 4s electrons move out leaving 4s orbital vacant. 3 2 Such complex is octahedral in shape and since outer d-orbitals are involved..

Example is [Ni(CN)4]–2. it is paramagnetic in nature and the tetrahedral structure is shown below in Fig.8 Tetrahedral shape of [Ni(NH3)4]2+ ion resulted from sp3 hybridisation. 13.. Atomic number of Ni is 26. On the basis of VBT [Ni(NH3)4]2+ is formed as follows: 3d (a) Electronic configuration of Ni in ground state (. So four lone pairs are donated of four ammonia molecules.302 ENGINEERING CHEMISTRY Tetrahedral Complex As is implied the tetrahedral complexes are sp3 hybridised. The formation of the complex is shown below: . Complex cation is produced from Ni2+ ion.. 3d 4s ) (b) Electronic configuration of Ni in ground state 2+ 8 2 4s 4p sp3 (c) Electronic configuration of Ni in sp hybridised state (d) Electronic configuration of Ni in [Ni(NH3)4] 2+ 2+ 3 2+ ×× ×× ×× ×× NH3 NH3 NH3 NH3 sp hybridised orbitals are filled with paired electrons donated by four NH3 ligands 3 complex The shape of the molecule is tetrahedral. [Zn(NH3)4]2+. NH3 Ni H3N 2+ NH3 NH3 Fig. The co-ordination of nickel is four.8. [Ni(Co)4]0 are also the examples of tetrahedral complexes. 13. The formation of such complexes can be illustrated by the formation of tetramine nickel (II) sulphate complex. Square Planar Complexes These are formed by dsp2 hybridisation.

13.9.. That is an attraction between a positively charged metal ion (µn+) and the negative charge of the ligand or the partial negative charge of the ligand.9 Square planar complex resulted from dsp2 hybridisation. Crystal Field Splitting of d Orbitals This theory considers only the effect of the ligands on the energy of outermost d-electrons in the central metal ion. . the central metal ion is hexa co-ordinated i.TRANSITION METAL CHEMISTRY 3d (a) Electronic configuration of Ni 2+ 303 4s 4p in ground state dsp 2 4p (b) Electronic configuration of Ni 2+ in dsp state dsp2 4p 2 (c) Electronic configuration of Ni 2+ in [Ni(CN)4] –2 ×× ×× ×× ×× – – – – CN CN CN CN 2 Four dsp hybridised orbitals containing four electron pairs – donated by four CN ligands The structure of the complex is square planar. If the ligand (L–n) is neutral molecule (L) the negative end of the dipole is attracted towards the central positive metal ion. The shape of [Ni(CN)4]–2 is given below in Fig. 13. CRYSTAL FIELD THEORY (CFT) The postulate of this theory is: bonding between a central metal ion and its ligands simply arises from purely electrostatic force of attraction. In an octahedral complex. CN – – 2 – CN Ni 2+ NC – CN – Fig. complex is diamagnetic in nature.e. This theory does not consider the ligand electrons to enter into the orbital of the metal ion. six ligands occupy the six corners of an octahedron.

• The strong ligands i. (b) Hypothetical degenerate d-orbitals at a higher energy level if all the ligands approach the metal ion at an equal distance from each of the d-orbitals. This repulsion force raises the degenerate d-orbitals of the metal to a higher energy state as shown in Fig. The following is the arrangement of ligands with the splitting power of increasing order.... so the resultant .4 Do dz2 dx2–y2 dxy dyz dzx (a) (b) (c) dxy dyz dzx Fig. Strong and Weak Ligands Strong ligands can split the five d-orbitals into t2g and eg sets strongly i.e. ∆o when high.10 Crystal Field Splitting in an octahedral complex. the d-electrons are repelled by lone pair of electrons of the ligands.4∆o while that of eg set is increased by 0. This order is known as spectrochemical series.6 Do – 0.10 (a). OH– X-donor = F– > Cl– > Br– > I– Distribution of d-electrons in t2g and eg sets of orbitals—low spin and high spin complexes. The separation of five dorbitals in the t2g and eg sets of different energy states is known as crystal field splitting. ∆o is called crystal field stabilisation energy (CFSE). (a) The five degenerate d-orbitals in the isolated central metal ion. NH3 O-donor = H2O.6∆o as shown in Fig.e. 13. the electrons in these orbitals experience a greater force of repulsion exerted by the electrons of the ligands than that by the electrons of the dxy. y and z axes. Hence. there splitting power is weak. there splitting power is high whereas the weak ligands can split the set of orbitals weakly i. (c) Crystal field splitting of d-orbitals into t2g and eg sets by electrostatic field of the six approaching ligands. C-donor > N-donor > O-donor > X-donor Examples of C-donor = CN– N-donor = NO2–.10 (b) which is considered as a hypothetical state. It can be shown that when an octahedral complex is formed the energy of the t2g set is decreased 0. under the influence of the approaching ligands the orbitals dx 2 − y2 and dz2 exist in the higher energy levels compared to dxy. When the six ligands approach the central metal atom along the axes they exert an electrostatic force of repulsion on the d-electrons of outermost shell i. dyz and dzx. force the electrons to form a pair in the lower t2g set of orbitals and thus the number of unpaired electrons is reduced. In the free metal ion all the five d-orbitals are degenerate (orbitals of same energy) as shown in Fig. 13. d y and dzx orbital called as t2g set of orbitals which are directed in space 2 along x.10. Strong ligands confer higher value of ∆o and weak ligands confer lower values to ∆o. 13. Since the lobes of dz2 and dx 2 − y2 orbitals called as eg set of orbitals fall directly at the path of the approaching ligands..304 dz2 dx2–y2 Energy Increasing ENGINEERING CHEMISTRY eg Do or 10 Dq t2g + 0. 13. The energy difference between eg and t2g sets of orbitals is denoted by ∆o or 10Dq where ‘o’ indicates an octahedral arrangement of ligands around the central metal ion.e.e.

) or spin paired complexes.e. Bµ Table 13. S = resultant spin) dz ion d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ Distribution of d-electrons in t2g set _ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ _ _ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ eg set – – – – – – ↑ ↓ ↑↓ ↑↓ – – – – – – _ ↑ ↑ ↑↓ n 1 2 3 2 1 0 1 2 1 0 S = n/2 1/2 2/2 = 1 3/2 1 1/2 0 1/2 1 1/2 0 CFT and Magnetic Properties of the Complex Formed One of the greatest achievements of CFT is: with the help of this theory prediction of the magnetic properties of the complexes formed is possible. • The weak ligands i.S. so the spin value ‘s’ gets lowered.TRANSITION METAL CHEMISTRY 305 spin ‘s’ is also reduced. first force the electrons to occupy all the five d-orbitals singly and then get paired.1: Distribution of d-electrons in t2g and eg sets in strong octahedral ligand field (n = number of unpaired electrons..) or spin free complexes.S. Table 13. The magnetic moment µ is related to the unpaired electrons n by the relation µ = n(n + 2) . Thus weak ligands produce higher number of unpaired electrons and so the higher value of ‘s’. so therefore are diamagnetic. The complexes having no unpaired electrons should not exhibit any magnetic property.2: Distribution of d-electrons in t2g and eg sets in weak octahedral ligand field dx ion d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ Distribution of d-electrons in t2g set _ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ _ _ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ eg set – – – ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ – – – _ ↑ ↑ ↑ ↑ ↑ ↑↓ n 1 2 3 4 5 4 3 2 1 0 S = n/2 1× 1 2 = 1 3/2 2 5/2 2 3/2 1 1/2 0 1 2 . These types of complexes produced by weak ligands are known as high spin (H. so they are paramagnetic complexes. The complexes having one or more unpaired electrons should show magnetic properties. These types of complexes are known as low spin (L. So. ∆0 when lower. the complexes formed with strong ligands have minimum number of unpaired electrons.

Mention the main oxidation state of the first transition series. OH S CO—CH = C—CF3 (TTA) A combination of chelating agent and a masking agent e. 4. 2. 3. H2N C  C NH2     S S Rubeanic acid (iii) In complexometric titrations. Nickel ion in alkaline medium can be estimated as well as identified with dimethyl glyoxime acting as chelating ligand.g. (c) Vitamin B12 itself is a chelate compound in which the central metal ion is cobalt. Some of these are given below: (i) In gravimetric analysis. Some metal ions like zirconium and hafnium can be separated from solution by chelation with thionyltrifluoro-acetone (TTA). SHORT QUESTIONS 1. aluminium. are estimated by complexometric titration. Differentiate between double salt and complex salt. oxin and EDTA. Using EDTA (ethylenediamine tetraacetic acid) as complexing agent many metal ions like calcium.. HOOCH2C N—CH2—CH2—N HOOCH2C EDTA CH2COOH CH2COOH – (iv) In the separation of metal ions and solvent extraction. NO CH3 CH3 C C NOH NOH N ONH4 Cupferron (ammonium salt of nitroso phenyl hydroxylamine) Dimethylglyoxime (ii) In qualitative analysis. . Copper ion in faintly acidic or ammoniacal medium is detected with Rubeanic acid or dithioxamide as chelating complex. (d) Cisplatin is an anticancer drug. What are transition metals? Mention the common features of the transitional metals.. magnesium. etc. The ferric cupferron complex is ignited to ferric oxide and weighed. greatly increases the selectivity of extraction processes. Cupferron gives a precipitate with ferric ion in acid medium. (v) For medicinal purpose: (a) EDTA is used to inhibit heavy metal poisoning.306 ENGINEERING CHEMISTRY Application of Ligands Ligands are widely used in different fields of chemistry. (b) Thiosulphate is used as a preventing agent of cyanide poisoning.

5. 16. 1. Give one example of each type. . 18. 7. What is the main postulate of CFT? What do you mean by crystal field splitting of d-orbitals? What is CFSE? What is spectrochemical series? What are low spin and high spin complexes? What is the main outcome of CFT? Give some uses of ligands. Discuss the geometrical as well as optical isomerism in complexes with co-ordination number 4 and 6. 3. 4. 4. (b) Pt(NH3)2Cl2. Mention the types of isomerism found in complex compounds. [Ans.87. Give the state of hybridisation of a square planar complex. 7. What are chelate compounds? Give examples.TRANSITION METAL CHEMISTRY 307 5. 24. On the basis of this theory predict whether the complexes [CoF6]–3 and [Co(NH3)6]+3 are paramagnetic or diamagnetic. 25.9. Give IUPAC nomenclature of the following: (a) CoCl2. Draw the structures of the following: (a) Tetraaquo dihydro aluminium ion. Show the hybridisation of an octahedral complex. State the postulates of Werner’s co-ordination theory and discuss the structure of K4Fe(CN)6 on the basis of this theory. 13. 26. 6. What is a ligand? What is co-ordination number? Mention main drawback of co-ordination theory. 8. 6 and 7 unpaired electrons. 23. Give an example of bridging ligand complex. 17. 14. 11. 5.732 Bµ] Calculate the magnetic moment µ for 2. Calculate the magnetic moment µ for one unpaired electron. 5.92. Give an expression for Kins and state its significance. [Ans. 10. 6. State the postulates of crystal field theory. 19. 6. 3.6NH3. Explain geometrical and optical isomerisms of octahedral complexes. ( f ) [Cr(H2O)5 Cl]2+ ( g ) [Cr(H2O)4 Cl2]+ (h) [Cr(H2O)6]Cl3 (i) [Pt(NH3)4Cl2]Br2 ( j ) [Pt(NH3)4 Br2]Cl2 (k) [Co(NH 3)4Cl2]NO2 8. What are inner metallic complexes? What do you mean by ambident ligands? Give examples of each: (a) Cationic complex (b) Anionic complex. 12. 2. 22. 21. Give main postulates of Werner’s theory. 15. 3. (c) [Co(en)2Cl2]+ (d) (en)2Co II NH2 O2 Co (en)2 IV (e) [Fe(CN)6]–3. Cite some fields of application of ligands in our daily lives. 20. 4. 9.93 and 7. Explain with example the valence bond theory regarding complex molecules. 2.93 Bµ respectively] EXERCISES 1. (b) Ammonium diamine tetrathiocyano chromate (III) (c) Triamine aquo dichloro cobalt (III) chloride (d) Sodium hexa nitrito cobaltate (III).83.

• Form solid ionic chlorides. 14 Metals Metals are the elements. which occupy the left hand side of the periodic table with one. 308 . and producing bronze dates back to 300 B. • Generally solids are with high m. Metallic Bonds Metallic bonds are strong bonds in metal crystals. In history we find ‘stone age’ followed by ‘bronze age’ and ‘bronze age’ followed by ‘iron age’. Only elements with low first ionisation potential form metallic crystals. Each metal atom in a metal crystal contributes electrons from its outermost shell to form a “sea of delocalised electrons”. Major Chemical Properties of Metals Chemically. • Form basic or amphoteric oxides.Metallurgy INTRODUCTION TO THE STUDY OF METALS The gold and silver among the metals are probably the first used by man.e. the greater is its “metallic character”. Iron in the form of steel.p.p.C. The art of reducing copper ores and tin ores. Today we find the metals are very extensively used in art and industry. Rb. dams. metals tend to: • Lose electrons to form cations or positive ions i. wrought iron and cast iron is used in constructing bridges. • Malleable and ductile. Nowadays almost all the metals have some specific uses. The more an element exhibits these properties. pipes. Physical Properties of Metals Metals are: • Shiny when freshly polished and free of corrosion. When a metal atom looses electron it becomes positively charged. So. two or three electrons in the outermost shell that takes part in bonding and chemical reactions. it is quite likely that a metal crystal consist positively charged metal atoms embedded in a sea of shared electrons.. Copper is another important metal being used mainly in electrical articles. • Good conductors of heat and electricity. Cs). metals are reducing agents. and b. tubes and machine parts. K. (only six metals melt below 100 °C—Hg which is a liquid and four group I metals: Na.

These naturally occurring inorganic compounds are known as minerals. These metallic compounds generally occur in the form of hard stones either in the underneath or in the earth surface. CaSO4.2H2O] for Calcium — [Chile saltpetre. The most important among the mineral products in India is coal. India occupies the first place in producing mica in the world. which are found in India.METALLURGY + – + – + – + – – – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + + – + 309 Fig. MgCO3] for Magnesium • Sulphide • Sulphate • Nitrate — [Zinc blende.1 Simplified picture of metallic bonding. Mineral Resources of India The sound economy of a country depends upon its mineral wealth. oxygen. We can say that these metals are not readily attacked by the moisture. Mumbai and Tamil Nadu. CaCO3] for Calcium [Magnesite. A metal is said to occur native or free when it is found in nature in the metallic state. Chromite is found in Mysore and Orissa. Manganese ores are found in Chotanagpur. Metals can bend without breaking because metallic bonding is not highly directional. The percentage of gangue in a mineral is always higher than the mineral itself. As for example gold and platinum occur in nature in the metallic state. The next important mineral is manganese. Iron ores occur abundantly in India. and carbon dioxide of the air. ZnS] for Zinc [Galena. 14. oxygen and carbon dioxide occur in the combined state or as a compound. Keonjhar and Mayurbhanj. The deposits of huge iron ore are in Singhbhoom. kaoline. The bauxite deposits are largest in India. NaNO3] for Sodium . Borax. Fe2O3] for Iron • Carbonate — [Limestone. Occurrence of Metals in Nature Some metals occur in nature in ‘native’ or ‘free state’. Lines or layers of metal atoms can shift their positions in a crystal without breaking the metallic bonds. Metals conduct electricity because these shared bonding electrons can drift through the crystal structures from atom to atom when there is an electrical potential difference between the two ends. limestone. about 58% of the total output is available from Jharia and Raniganj. gypsum. Mysore. monazite sand are other minerals. While those metals which are readily attacked by moisture. Al2O3 2H2O] for Aluminium [Hematite. PbS] for Lead — [Gypsum. soil or other impurities. Copper is chiefly found in Chotanagpur and Sikkim. Common Minerals • Oxide — [Bauxite. These impurities are known as Gangue. pitch-blende. Minerals are always associated with sand.

Dolomite (CaCO3. Dolomite (MgCO3CaCO3) Manganese spar (MnCO3) Cerussite (PbCO3 ) Calamine (ZnCO3 ) Gypsum (CaSO4.H2O) (ii) Cuprite (Cu2O) (iii) Zincite (ZnO) (iv) Pyrolusite (MnO2) Braunite (Mn2O3) (v) Chromechre (Cr2O3 ) (vi) Tin stone or cassiterite (SnO2) (vii) Felspar (K2O.Sb2S3 Siderite (FeCO3) Malachite (CuCO3 Cu(OH)2 ) Calcite (CaCO3). Ca3(PO4)2] for Calcium Some minerals of common metal are listed below in tabular form: Form Metal (i) Aluminium (Al) Oxides and hydrated oxides (ii) Copper (Cu) IB (Coinage metal) (iii) Zinc (Zn) IIB (Amphoteric metal) (iv) Manganese (Mn) VIIB (Transition metal) (v) Chromium (Cr) VIB (Transition metal) (vi) Tin (Sn) IVA (Amphoteric metal) (vii) Potassium (K) (Alkali metal) (i) Copper (Cu) IA (Coinage metal) (ii) Zinc (Zn) Sulphides (iii) Lead (Pb) IVA (Amphoteric metal) (iv) Mercury (Hg) IIB (Liquid metal) (v) Tin (Sn) (vi) Iron (Fe) (vii) Silver (Ag) IB (Best conducting metal) (i) Iron (Fe) (ii) Copper (Cu) (iii) Calcium (Ca) IIA (Alkaline earth metal) Carbonates (iv) Magnesium (Mg) IIA (Bridge metals) (v) Manganese (Mn) (vi) Lead (Pb) (vii) Zinc (Zn) (i) Calcium Sulphates (ii) Lead (iii) Aluminium (iv) Barium IIA (Alkaline earth metal) Name of ores and minerals (i) Claysilicate (Al2O3. FeS) Zinc blende (ZnS) Galena (Pbs) Cinnabar (HgS) Stannite (Cu2S. Al2 (SO4)3. CaF2] for calcium — [Mica.Al2O3.2SiO2.310 • Halide • Silicate — [Fluospar. Copperpyrite (CuS. KHMg2Al2(SiO4)3] for Magnesium ENGINEERING CHEMISTRY • Phosphate — [Phosphorite.24H2O) Heavy spar (BaSO4) . FeS.6SiO2 ) Copperglance (Cu2S).2H2O) Diaspore (Al2O3. Rubby silver 3Ag2S. SnS2 ) Iron pyrite (FeS2 ) Silver glance (Ag2S).MgCO3) Magnesite (MgCO3).2H2O) Anhydrite (CaSO4 ) Anglesite (PbSO4 ) Alum (K2SO4.

the ore is enriched with the desired metallic compound. This is effected in grinding and pulverising mills (Figs. 14.H2O) Rocksalt (NaCl) Sylvine (KCl) Horn silver (AgCl) Fluoropalite (3CaF2 (3COCl2. Chloropative Carnallite KCl. The main steps for the extraction of metals are generally as follows: 1. the minerals from which metals can be extracted easily and cheaply are known as ores. Reduction 5.3). haematite is the ore of iron. Concentration of the Ore Almost all ores are associated with gangue or matrix. There are several processes of the concentration of ores. the concentration and further treatment of some ores demand their reduction of size into a very fine state of division. AlF3 ) Willemite (ZnSiO2) Felspar (K2O. Before the proper extraction of the metal the ore is freed from gangue or matrix to get it in the concentrated form. Jaw crusher. Crushing and grinding 2. As for example.Ca3(PO4)2 ) Ca3(PO4)2).Al2O3. which are described below.. An ore is naturally occurring substance or mineral from which the metal can be extracted economically. Metallurgy The process by which the metals are extracted from their respective ores is known as metallurgy. This process of removal of gangue is known as the concentration of the ore. Purification Crushing and Grinding. As a matter of fact.Al2O3.6SiO2) Ores Generally all minerals cannot be considered important for extraction of metal from them.METALLURGY 311 (v) Magnesium (i) Sodium (ii) Potassium (iii) Silver IB (Conductive metal) Epsomite (MgSO4. This process of concentration of ore makes the extraction of the metal easier and cheaper. . Particularly. MgCl2 6H2O Halides (iv) Calcium (v) Magnesium (vi) Aluminium (i) Sodium (ii) Potassium Silicates (iii) Zinc (iv) Aluminium Cryolite (3NaF. The process of extraction though costly may not be impossible from these minerals. Concentration of the ore 3. Gyratory crusher etc.2 and 14. The step provides breaking of big masses of rocks containing the ore into small lumps by conventional crushing and grinding with machines viz. Calcination/Roasting 4.7H2O) Kisserite (MgSO4. bauxite is the ore for aluminium etc.6SiO2) Sodium silicate (Na2SiO3 ) Felspar (K2O. This is one of the crucial steps of concentration process. Sometimes.

Generally some xanthates are used with pine oils. The pulverised sulphide ore is taken in a tank and some pine oil and water are used. Fig. Air is made to bubble through a perforated pipe from the underneath of the tank. .312 Lumps (ore) ENGINEERING CHEMISTRY Crushed ore Stamp Crushed ore Pulverised ore Fig. 14. 14. Oils have just the opposite effect. Concentration of the Ore (i) Washing. But the sand and soil are settled down. do not get wet as do silica and most oxides when treated with water. The concentrated ore is collected from foam (Fig. Oils form a film over the sulphide ore. they are attracted by sulphide ores. A foam is produced and floats along with the sulphide ore over the surface of water. Therefore. as a rule. Sulphide ores. (iii) Oil floatation process.4 Concentration of ore by oil floatation. (ii) Floatation. 14.2 Crushing. 14. This process includes all methods of concentrations in which water in motion is used. From the pulverised ore in stream of water the lighter particles float away with water and thus some gangues are removed. Froth Stirrer Concentrated ore Air Fig. sulphide ores will float on the surface while silica and other materials will sink.3 Pulverisation. Here concentration of the pulverised ore is effected by taking the advantage of the difference in its behaviour towards oil or water.4).

. As for example. As for example.x H2O MCO3 → → ∆ ∆ (Calcined) M2O3 + x H2O ↑ (Calcined) MO + CO2 ↑ Fluxes Before the extraction of metals from their ores and in their subsequent purification. somewhat interchangeable. below the point of fusion but always in presence of air with a view to oxidising the material.. gangue must be removed. 14. The tungsten or tin ore is separated by this method. The term is usually applied in case of oxidising the ores. Gangue + Flux → Slag (fusible) heat . metallic sulphides are roasted to oxides before reduction to extract the metal. which when added to an ore and heated gives a fusible mass known as slag. They are often refractory in nature and remain unfused which may disturb efficient extraction of the metal. Calcination and roasting. though a distinction exists between them. They become easily fusible when heated with other substances. 2MS + 3O2 = 2MO + 2SO2 MS + 2O2 = MSO4 • Calcination: To calcine a material is to heat it very strongly but at a temperature insufficient to melt it. flux is a material. Ferromagnetic ores can be separated by passing the ore through a strong magnetic field. M2O3. CO can enter into pores and make reduction complete. So. among the metallurgists.5 Magnetic separation. • Roasting: To roast a material is to heat it at a temperature insufficient to melt it i. with a view to driving of volatile matters leaving some pores on the rocky ore to facilitate the reduction process.METALLURGY 313 (iv) Magnetic separation. whereby ferromagnetic substances are separated from the ore. Non-magnetic particles Magnet Crushed ore Rubber belt Magnetic particles Fig. These two terms are used.e. So. so that reducing gas viz. the impurities (gangue) present in the ores are to be removed. those substances are known as fluxes.

made of refractory materials. Furnaces • Reverberatory furnace. 14. In this furnace.6 Reverberatory furnace. It is a type of furnace consisting of an enclosed chamber. 14. from which the fuel and its products of combustion cannot come in contact with the materials heated in it (Fig. Large scale industries. basic flux is to be used viz. . lime. Charge (Hopper) Chimney Hearth Ore Air Flame fuel Fig. If it is acidic. There are three kinds of fluxes: • Acidic (SiO2) • Basic (CaO. magnesia etc. but by the hot gases produced in the fire place (Fig. the material is heated not directly over fire.6). • The other furnaces are blast furnace (for iron extraction). then an acid flux like sand (SiO2) must be employed.7). This is a special type of furnace much used in metallurgy. MgO) • Neutral (fluorspar) Fuels Almost all industries require a fuel. need economy of fuel consumption. • Muffle furnace.7 Muffle furnace. 14.314 ENGINEERING CHEMISTRY Selection of Flux The nature of flux to be used depends on the nature of gangue. open hearth furnace (for steel manufacture) and electric furnace (for Phosphorus extraction). If the gangue is basic in character. like metal extraction. 14. Fig.

sand & rock CO Carbon electrodes Fig. 14. 14. .9 Electric arc furnace. The process by which a metal is extracted in the fused state is called smelting. Smelting.METALLURGY 315 Limestone (CaCO3).8 Blast furnace (displaying reactions of iron extraction in various zones of the furnace). SiO2 + 2C ® Si + 2CO F4OIC + 10C ® TP + 10CO Waste gases exit Upper zone (250 °C–700 °C) Middle zone (800 °C–1000 °C) Lower zone (1200 °C–1600 °C) Tuyer for hot air (form Cowper’s Stoves) Molten slag CO2 + C + 2CO C + CO2 ® CO Fusable slag Molten iron Fig. ore (Fe2O3) & cock are added at the top Cone Charging holes 250 °C 2Fe2O3 + CO ® 2Fe3O4CO2 Fe3O4 + CO ® 3FeO + CO FeO + CO ® FeO + CO2 Spongy iron CaCO3 ® CO2 + CaO—13K Cal C + CO2 ® 2CO­ SiO2 + CaO ® CasiO3 Slag Fe Metal & Mixed with C2P4Si2Mn etc. Feed hopper P & CO Coke.

• Duralumin. It is used in making rolls. So. • By compression. the alloy is called an amalgam. Si. • Molybdenum and Tungsten steel or High speed tool steel are mainly used for high speed machines. can be used to join metals.. Ni. an alloy may be considered as solid solution or an intermetallic compound or both. Fe. harder. alloys are classified as: • Non-ferrous alloys • Ferrous alloys Non-ferrous alloys do not contain iron as one of the constituents of the alloys. is mainly used in making household furnitures. Alloy. It is the operation of joining the two pieces of a metal either by pressure or by fusion to one compact mass. • Bronze. Component metals are mixed together in the desired ratio and melted followed by cooling. • to lower the melting and boiling points of individual metal. An alloy of iron with carbon (0. • Stainless steel (Chromium steel) (10-15% Cr. • Ferro-titanium is used as deoxidisers to avoid formation of ‘blow holes’ from molten steel. Cr. An alloy of 95% Al with 4% Cu and smaller amounts of Mg.g. • Wrought iron (C = 0. it is stronger.25%). an alloy of copper (Cu:Zn = 60:40). It is relatively cheap. e. Finely divided metals are compressed in the desired ratio. can be easily rolled into sheets. An alloy of Pb and Sn that melts at low temperature. hard wearing and resistant to corrosion. more resistant to corrosion than pure Al. General methods of preparation of alloys • By fusion. used mainly in making the body of aeroplanes. Examples of important alloys are • Mild steel. e. • Manganese steel contains Mn 12-14% and the rest is iron. Steel is an alloy of iron and carbon. • Solder. It is mainly used in making utensils as well as reactors in industries. Generally. a non-metal.. • Brass. Stainless steel contains Fe.1-0.1-0.25%). an alloy of copper with upto 12% tin (Sn). and can be pressed into shape. When one of these metals is mercury. 90-85% Fe).g. . Brass which is composed of Zn and Cu. An alloy is a mixture or compound or both of two or more metals. • By reduction of the mixture of oxides to get mixture of metals in the proper ratio. An alloy is often more useful than a pure metal. a strong. Controlling the composition of an alloy makes it possible to vary its properties. Whereas ferrous alloys always contain iron as one of the constituents of the alloys. Importance of alloy preparation • to increase the hardness and tensile strength • to improve the casting property • to increase the resistance to corrosion • to decrease the thermal and electrical conductivities. has a gold colour and does not corrode.316 ENGINEERING CHEMISTRY Welding.

hydroxide. sulphides. the powder is slowly absorbed by the metal without melting whereby the property of the metal changes to a certain extent. or carbonate it is first calcined to get porous oxides and then the calcined ore is reduced to the metal. General Methods of Extraction of Metals from their Ores • Metals like gold (Au). Methods of Reduction of the Processed Ore Metal extraction involves two main types of processes for the reduction of the metallic compounds. This process is called cementation and the powder is called the cement. it is first heated in the presence of air i. • When the ore is a sulphide. hydroxides. (Composition—Steel:Al:Ni:Co = 5:2:2:1) Used for making permanent magnets. The principle and processes of reduction will be discussed later on..e. carbonates. • But. So their method of extraction practically consists of separating them efficiently from the rocky and other impurities. Then we can say. • When the ore is an oxide. by carbon reduction process. Scheme I: Sulphide ore Roasted Oxide C-Reduction Metal • When the ore is a carbonate or hydroxide: Scheme II: Carbonate ore Calcined Oxide C-Reduction Metal • When the ore is a sulphate: Scheme III: Sulphate ore + C Reduced Sulphide Roasted Oxide C-Reduction Metal • When the ore is a halide or metallic oxide or is not reducible by carbon. platinum (Pt) etc. roasted to get metallic oxide and then reduced to get the metal. there are two broad steps in their extraction process: (i) Preliminary calcination and roasting (ii) Reduction. most of the metals occur as their compounds such as oxides. . Cementation When a metal is heated in contact with a powder. are obtained in nature in the free state.. An alloy of Al and Mg (98:2) used in making light machine parts. halides etc.METALLURGY 317 • Magnalium. • Alnico. generally. electrolytic process of reduction is followed.

(a) Electrowinning at low temperature in solution in water (for example. lead) MO + C → M + CO (c) Chemical reduction by a more reactive i. using iron to displace copper from a solution of CuSO4) CuSO4 + Fe = Cu + FeSO4 ∆ ∆ Goldschmidt Thermit Process The metallic aluminium has a strong affinity for oxygen at 1000°C. Goldschmidt Thermit process is nowadays mostly used for welding rails and machine parts (Fig. Zn extraction for ZnSO4 solution).g. . Al).. a mixture of aluminium powder and iron oxide in the ratio 3:1 by weight.10 Goldschmidt Thermit process. 2Al + Fe2O3 = Al2O3 + 2Fe + 199 kcal The liquid iron is dropped on the two pieces directly to the joint to be welded. Fig. electropositive metal (for example.. Cr2O3 + 2Al → Al2O3 + 2Cr (Goldschmidt Thermit process) (ii) Hydrometallurgy: It means. when a violent reaction takes place producing molten iron at 2500°C. Thermite. (b) Cementation using a displacement reaction (for example. MnO2 or Cr2O3 and for the separation of molten metals. chromium and titanium extraction). (a) Electrolytic reduction at high temperatures of the fused salts especially halides (for example Na.e. is ignited in a crucible by a ribbon of magnesium. which is utilised in Goldschmidt Thermit process or Aluminothermic process for the reduction of metallic oxides e. 14. reactions at low temperature in solution in water. (b) Chemical reduction by coke at high temperatures (for example. The combination of oxygen with aluminium at that temperature evolves much heat. iron. 14.318 ENGINEERING CHEMISTRY (i) Pyrometallurgy: It means reactions at high temperature often above 1000°C.10).

p. cadmium.12). contains about 2% of lead and traces of iron. The impurities are to be removed to get the pure form of metal. This process of purification is employed effectively in some special cases. The crude zinc. At last the molten zone containing all the impurities Sl op ing he ar th Pure molten metal .p. The impure metal containing infusible impurities is heated on the sloping hearth of a special type of furnace (Fig. Thermal refining • Oxidation of impurities by air poling. An easily fusible metal such as tin or lead can be refined by this process. 2800°C). as a result of which the easily oxidisable impurities are converted to oxides. 14. The distillate i.METALLURGY 319 Purification of the Metals Extracted Almost all metals obtained by reduction processes contain some impurities. molten mixture of zinc and cadmium is redistilled in another retort at a temperature slightly above 767°C when more volatile cadmium (b.11 Refining of metal by Liquation. • Liquation. • Fractional distillation. Easily volatile metals can be removed with the help of fractional distillation. 14. The purification processes are: 1. which is removed with the help of a laddle. Electro-refining 1. Impure metal Impurities Furnaces Fig. Thermal refining and 2. • Zone refining (Fig. 767°C) distils out and 99.e. When zinc together with cadmium distils over leaving behind lead (b.. The actual process is: a narrow rod of impure metal is taken and a small portion of it at one end is almost melted by application of heat. 1620°C) and iron (b. which is known as spelter. The spelter is at first heated in a retort at a temperature slightly above the boiling point of zinc (920°C). This small molten zone is gradually and slowly shifted to the other end of the rod by gradual shifting of the source of heat.9% of zinc is left in the retort. The volatile oxides escape and a non-volatile oxide forms a scum over the molten metal. as a result the metal melts and the molten metal flows down the sloping hearth leaving behind the infusible impurities on the top. 14. The impure metal is melted and a stream of air is purged through the bottom. arsenic as impurities.p. The advantage is taken out of the fact that the impurities are more soluble in the molten metal than the solid metal and the molten metal on resolidification crystallises out as a pure metal.11).

14.13 Electrolytic refining of copper. pure metal from the electrolyte gets deposited on the cathode and the equivalent amount of metal from the anode passes into the solution. The rod is allowed to cool and the impure zone is cut off and removed. 2.12 Zone refining.13). and (v) Sintering (vi) Finishing operation. the metal powders or alloy constituents are compacted in a die with melting or no melting followed by sintering. Molten zone Resolidified portion Source of heat Most impure zone to be cut out Fig. The electrolyte used is an aqueous solution of a suitable salt. In this technique. . H2SO4 as electrolyte Impure Cu anode Pure Cu cathode Fig. Sometimes some valuable metals are recovered from anode mud. During electrolysis. The simultaneous method of compacting and sintering is called pressure sintering. Electro-refining. 14. This deposit is known as anode mud. The article is made into the desired shape by powder metallurgy in the following steps: (i) Pulverisation of metallic powders (ii) Mixing and blending (iii) Compacting (iv) Pre-sintering. This method is widely used. The remaining portion of the rod consists of the pure metal. A typical example of electrolytic refining is of copper (Fig. 14.13) is a technique or operation or process to produce metallic or alloy articles. The impurities either remain in solution or are deposited down the anode. 14.320 ENGINEERING CHEMISTRY reach the other end. Usually an electrolytic cell is set up using thin sheets of pure metal as the cathode and comparatively thick impure metal slag as anode. POWDER METALLURGY Powder metallurgy (Fig. 15% CuSO4 solution in dil.

High pressure Guide pins ∆ Top moulding part (Male joint) Bottom moulding part (Female joint) Alloy ingredients Extraction pin Fig. Pb. Time and temperature of sintering depend upon the nature of the metal. The solid in this stage is known as ‘green compact’. For pulverisation ball mills can be employed. This step is essential for tungsten. They are uniformly mixed in right proportions. to get accurate shape of the work pieces. For pulverisation of metals techniques adopted are: (a) Mechanical: This method may be adopted in the case of Mg. Zn.METALLURGY 321 (i) Pulverisation of metallic powders. (ii) Mixing and blending. (c) Chemical: 1. (iii) Compacting. (vi) Finshing operations. This step increases the strength of green compact as well as removes the lubricant if used. This operation is required when a combination of metallic powders are used. Zn. (b) Atomisation: This method involves forcing molten metal through a nozzle or spinnerette in a stream of water or compressed air.14 Technique of powder metallurgy adopted in a die. when fine powder of metals are obtained. Cd. ∆ WO2 + 2H2 → W + 2H2O 2. The sintered articles require operations like machinery. (iv) Pre-Sintering. and Pb. By reduction. Lubricants may be added if necessary. 14. (v) Sintering. Sn etc. It involves heating the green compact to a temperature below the sintering temperature. preferably in an atmosphere of hydrogen. The metal powder in right proportions is then taken in a die into the cavity (female joint) of accurate dimensions and then compressed (100–1000 N/m2) by the male joint of the die.. This method is commonly employed for metals like Mg. This method requires control of pressure and temperature and the oxidation of metal into an atmosphere of inert gas. plating etc. Ni(CO)4 → Ni + 4CO↑ The metals are obtained in a state of fine powders in both cases. By decomposition. Al. . whereby metal particles sinter to a coherent mass. Compacted pieces are heated to a temperature below and very close to the melting point of the metal in a furnace.

Disadvantages SOME SPECIFIC EXAMPLES OF EXTRACTION OF METALS Titanium (Ti) Titanium is a very strong metal and has a density much less than that of steel. it is not widely used.. +3 and +4. the reaction is exothermic and so temperature rises. .. (i) Dies of desired precision are required which are very much expensive. but only +4 oxidation state is common. The chloride of the metal is then allowed to react with molten sodium or magnesium at 800 K in an inert argon atmosphere. the titanium (IV) chloride condenses as a liquid that can be purified by fractional distillation. Titanium is an element of d-block in the periodic table and its electronic configuration is [Ar] . (v) 100% raw material is consumed with no loss. (iii) Metals and non-metals can be mixed to give the desired property to the article as for example W and C can be mixed to produce W2C (tungsten carbide) for cutting tools. But as the extraction process is difficult and expensive. Advantages (i) Articles of any intricate shape can be produced with desired accuracy and smooth finish. It melts at a very high temperature of 1675 °C. Extraction The ores of titanium used for extracting metal are rutile (TiO2) and ilmenite (FeTiO3).322 ENGINEERING CHEMISTRY Uses In making: (i) Porous bearings . Titanium (IV) chloride is a colourless liquid produced as an intermediate in titanium extraction and is used in the manufacture of titanium (IV) oxide. Smoke grenades produce dense clouds of titanium (IV) oxide due to rapid hydrolysis of titanium (IV) chloride. The metal is being protected like aluminium by a thin oxide layer formed on the surface of the metal. breaks etc. (ii) Ejection of the articles from the die is necessary. which limits the production of very very intricate articles. (ii) Tungsten filaments for electric bulbs . It can exhibit three oxidation states +2. TiO2 + C + 2Cl2 → TiCl4 + CO2 In Kroll process. (iv) Articles with impregnated lubricants can be produced which would be self-lubricating for ever.4s2. it is heated with carbon in a steam of chlorine gas at about 1100 K. 3d2. (iii) Sewing machines (iv) Gears . After the purification of the ore. (ii) Clean and smooth operations. Among the most abundant metals in the earth’s crust Titanium achieves the fourth place. (v) Clutches.

Chromium-vanadium steel is very hard and is used in axle.4s2 [Ar]... Uses (i) Nickel is so unreactive that it is used to make spatulas and crucibles. Cr2O3(s) + 2Al(s) → 2Cr2(s) + Al2O3(s) Carbon can reduce Cr2O3 but the produced metal then contains carbon as impurity. Nickel (II) salts. Chromite contains other metals like iron besides chromium. . Chromium (Cr) Chromium is mainly extracted from Cr2O3 i. Chromium (III) oxide in a batch process employing aluminium as the reducing agent. A mixture of the oxide with powdered aluminium is then ignited in a reaction vessel. which dissolves the sodium chloride. Extremely pure Ti can be obtained by decomposition of TiI4 vapour on an electrically heated tungsten (W) filament in vacuum. shafts. 3d8. is protected from corrosion by a thin layer of oxide on the metal surface. The presence of carbon in the metal makes the metal brittle and less resistant to corrosion. Electroplating with chromium gives a shiny. Steels with 18% Cr and 7–8% Ni are superior corrosion resistant. (ii) Other major uses are the production of chemical components of chemical plants such as heat exchangers. corrosion resistant finish to metals.. (ii) Nickel is a constituent of many alloys including some alloy steels and the ferromagnetic alloy and also of Alnico which is used in making permanent magnet. The first step is to convert the ore to pure Cr2O3. (ii) Chrome steels are employed in the form of alloy “ferrochrome” containing 60–70% Cr. Uses (i) Titanium is used mainly for making aircraft engines and airframes. This is very hard and used in making cutting tools. The main use of chromium is to make alloys with iron (stainless steels). The common oxidation state of nickel is +2. (iii) Chromium plating unlike nickel plating is resistant to sulphur compounds of the atmosphere. Nickel (Ni) Nickel is a hard. The solid product is then crushed and leached with dilute hydrochloric acid. The commercial ore is chromite. The exothermic reaction produces pure metal (99 %).METALLURGY 323 TiCl4 + 4Na → Ti + 4NaCl The reactor is kept hot for about two days then the mass is removed from the furnace and is allowed to cool. grayish but shiny d-block metal with the electronic configuration . Stainless steel is ordinary steel with 14% Cr. like aluminium. Uses (i) The chief uses of chromium are in the manufacture of chrome steel and chromium plating. Chromium.e. leaving behind the metal Ti which is then washed and dried. like nickel sulphate (NiSO4) are green. locomotive wheels etc.

e. — the purple manganate (VII) ion. In solution cobalt forms ions in the +2 and +3 oxidation states.. (iv) An alloy of copper. Manganese (Mn) Manganese is a hard.. shiny d-block metal and is less reactive than iron. (ii) The metal is mainly used in steel industry in making alloy steels and as a deoxidant. (vi) The radio-active isotope Co-60 is a strong γ-radiation emitter.. (iii) Cobalt may be used for electroplating iron. It occurs in the form of compounds. The important ores of uranium are: (i) Pitchblende (uranite—U3O8) (ii) Carnolite—K2O. It has the electronic configuration . aluminium and manganese (Heusler’s alloy) is ferromagnetic. (v) Some cobalt salts with organic acids are used as driers in paints and varnishes. Cobalt-60 capsules are used to kill cancer tissues by radiation. steel and brass etc. known as Manganin. 3d7. brittle d-block metal having electronic configuration . manganese and nickel. in making blue glass and blue enamels for coating iron. (iv) Cobalt oxide is used as a colouring agent in the glass and ceramic industry i. (ii) Steels containing about 35% cobalt is used for permanent magnet.3d5.. — an insoluble black compound and acts as an oxidising agent in acid solution. state. (iii) Manganese steel containing 13% Mn is extremely hard and tough and is used in making jaws or rock crushers. which is a strong oxidising agent in acid medium. Cobalt (Co) Cobalt is a hard.4s2 [Ar]. .V2O5. Cobalt (II) is a more stable Uses (i) Cobalt is used in making the so called ‘hard alloys’ which are superior to high speed tool steel as regards the life of the tools..324 ENGINEERING CHEMISTRY (iii) Nickel in finely divided form acts as a good catalyst in hydrogenation reactions. is used for resistance coils since its electrical resistance is very slightly affected by temperature.4s2 [Ar]. Uranium (U) Uranium is not obtained in free state in nature. — the pink manganese (II) ion in salts such as manganese (II) sulphate.2UO3. gray. (iv) It is a heterogeneous catalyst and is used to harden unsaturated vegetable oils by addition of hydrogen across the double bond.3H2O. The main oxidation states of manganese are: +7 in MnO4– +4 in MnO2 +2 as Mn2+ Uses (i) Manganese is added in steel to modify its mechanical characteristics. (v) An alloy of copper.

METALLURGY 325 Uranium is extracted from pitchblende and a flow diagram for the extraction of uranium is shown below: Ore Crushing and grinding Residue Iron hydroxide Leaching with 1:1 H2SO4 in the presence of MnO2 Aluminium hydroxide Boiled with excess of Na2. U235 + 1 n = Ba140 + Kr92 + 200 meV. SiO2 etc. PbSO4. Zirconium (Zr) Occurrence The main ores of zirconium are: (i) Zircon—Zr SiO4 (ii) Baddeleyite (ZrO2) . RaSO4.CO3 solution Filtrate Filtration Filtration Residue Filtrate HCl H 2S UO2Cl2 NH4OH Filtrate Filtration Residue (NH4)2U2O7 Ignited U3O8 Filtration Filtrate UO2Cl2 BaSO4. PbS Na4 [UO2(CO3)3] Residue CuS Metallic U Carbon reduction Uses (i) Its principal use is as atomic fuel in nuclear reactors. U235 releases 200 meV per fission with neutrons. 0 (ii) In ceramics uranium compounds are sometimes used to form coloured glasses (yellow or orange). (iii) Uranium steels are also important technically.

What do you mean by minerals and gangue? Give relations between them. The most important oxidation state of the metal is +4. What do you mean by metallic bonds? Explain electrical conductivity of metal in the light of metallic bonds.. So Hf content of Zr is reduced to less than 100 ppm. Uses (i) Zirconium has a high corrosion resistance and it is sometimes preferable to stainless steel in certain chemical plants. is not detrimental at all and may even improve the property of Zr. H2. Zirconium also occurs in alluvial sands of Kerala and Sri Lanka. This filament decomposes ZrI4 to pure Zr which is deposited on the filament. which is almost always present with zirconium. self-heating oxide film over the metal surface. EXERCISES 1. silvery metal with m.p. Define metal and mention some of its characteristics. zirconium reacts directly with most non-metals viz.326 ENGINEERING CHEMISTRY The ores are found in the USA. Chemical: If heated to high temperatures. N and C make the metal brittle. Brazil and Australia. (iii) The small percentage of hafnium (Hf). a notable superconducting alloy is with niobium which retains its superconductivity even in strong magnetic fields.) (ii) Van Arkel-de Boer process. the metal is pyrophoric. The traces of impurities like O. 3. (ii) It is used in a variety of alloy steels. when finely divided. the metal has got outstanding resistance to corrosion. Distinguish between ores and minerals. 2. With the exception of HF. crude zirconium is heated with a little iodine under vacuum at 200 °C when ZrI4 volatilizes. other mineral acids react at elevated temperatures with the metal. Extraction (i) Zirconium is produced commercially by Kroll process. So. Zirconium’s major use is as a cladding for uranium dioxide fuel rods in water-cooled nuclear reactors for its low absorption of ‘Thermal’ neutrons. 1857 °C. 4. as Hf is a powerful absorber of ‘Thermal neutrons’. (See extraction of Titanium. care should be taken during machining and the production waste chips should be avoided. Here the presence of Hf is disadvantageous. O2. In this process. . Despite this inherent reactivity. ZrI4 = Zr + 2I2 Properties Zirconium is a lustrous. A tungsten or Zirconium filament is heated to 1300 °C in the same vessel. which is due to the formation of a dense. Zirconium is a good conductor of heat and electricity.

20. 8. 16. (a) How is metal powder prepared? Describe any two applications of powder metallurgy. What is an alloy? Write (a) the importance of preparation of an alloy (b) general methods of preparation of alloys. 6. 18. 21. Mention four advantages of powder metallurgy. Briefly describe the methods involved in purification of metals extracted. Write a short review on powder metallurgy. Write short notes on: (i) Smelting (ii) Welding 13. What do you mean by the study of metallurgy? What is the concentration of ore? Write down the different steps involved in the extraction of metals from corresponding ores. Give general method of extraction of metals from their ores. 10. What is flux? State the factors on which the selection of flux is based. Write notes on: (i) Pyrometallurgy (ii) Hydrometallurgy (iii) Goldschmidt thermit process (iv) Electro-refining (v) Zone refining 17. 7. Give the composition and uses of the following alloys: (i) Mild steel (ii) Stainless steel (iii) Manganese steel (iv) Duralumin (v) Alnico (vi) Wrought iron (vii) Magnelium (viii) Brass (ix) Bronze (x) Solder 14. Write short notes on: (i) Crushing and Grinding (ii) Oil floatation process (iii) Calcination (iv) Roasting 9. What is cementation? 15. 11.METALLURGY 327 5. Discuss the various steps involved in powder metallurgy and mention its application. Describe different types of furnaces with their uses in metallurgy. 19. Briefly discuss the stages involved in concentration of ores. (b) What is sintering in powder metallurgy? . 12.

(a) State the electronic configuration of titanium. (b) With a net flow chart represent the process of uranium metal extraction. Give an account of zirconium with special reference to its important ores and one method of extraction. (c) Give some uses of titanium. 26. Indicate its position in the periodic table. 24. (c) State some uses of uranium. (a) Write down some of the ores of uranium with chemical formula. (a) How is chromium extracted from Cr2O3? (b) Give some uses of chromium. . 23. Write notes on: (i) Nickel (ii) Manganese (iii) Cobalt 25.328 ENGINEERING CHEMISTRY 22. (b) Describe the extraction procedure of titanium from its ore.

g. The after-finishing process in case of bonding is not required as in the case of welding. properties and their bond strength decreases with rise in temperature. Adhesive bonding can be utilised to make the material leak-proof for liquids and gases. 329 . Bonding of dissimilar metals with adhesives prevents galvanic corrosion as the metal to metal contact is avoided. 9. metal and plastic etc. Bonding has several advantages 1. The adhesive layer of an adhesive joint can have a vibration-dampening effect. Some adhesives set even in relatively thick layers. 3. Better composite materials having improved properties than the adherends can be designed by the adhesive bonding e. soldering etc. 4. so any unevenness of the adherends can be smoothed out during bonding. 8. 11. The usability of adhesives can be restricted when stringent requirements are imposed on the thermal stability on adhesive point. 2. The process of adhesion can be carried out very rationally. Adhesives based on organic polymers show a dependence on temperature in their strength. Adhesives are capable of joining numerous materials which cannot be joined by other techniques even those differing widely in type such as glass and metal. The process of this adhesion is called bonding and the bodies are called adherends. 7. metal-faced plywood. quickly and economically. The common feature of all adhesive joints is the highly uniform distribution of forces over the entire joint area and free from any residual stresses which leads to optimal utilization of material strength compared to rivet and screw joints.Adhesives Adhesives 15 Adhesive is defined as a material that is capable of joining bodies together by surface adhesion and internal strength without the structures of the bodies undergoing any changes. 5. Adhesives can introduce electrical and heat insulating layers between the adherends. 6.. Limitation and Restrictions of Adhesive Bonding 1. 10. Many adhesives can be applied at room temperature hence the adherends are not exposed to high temperature as in the welding of plastics with metals. 2.

By pressure application: Tacky substances in solvent-free form adhere spontaneously to the surfaces of most materials. The solvent gets evaporated and thereby gelling and finally hardening takes place leading to strong bonding between the surfaces. By cooling: Thermoplastic materials are applied to the adherend surfaces in a molten and hot condition which on cooling solidifies developing bonding strength. crosslinked three-dimensional polymers with high bond strength. Adsorption theory regards adhesion as essentially a special property of phase interfaces.. Physical factors influencing adhesive strength: 1. Surface tension: The wetting characteristics of an adhesive depend on its (a) viscosity and (b) surface tension. welding etc. Diffusion theory explains that adhesion is obtained by the mutual penetration of adhesive and substrate. 7. Bonding strength is low compared to other joining methods like rivetting. when the interfacial boundary energy is lower than the sum of the surface energies of the adhesive and the adherend. The bonding between the surfaces is better when the surfaces can be . leather etc. By solvent evaporation: The adhesive is dissolved or dispersed in a solvent and applied to the surfaces to be bonded and they are brought in contact with each other. mono and/or oligomeric ingredients of thermosetting adhesives are converted by chemical reaction into high mol. Electrostatic theory explains that by contact of the adherend and the adhesive. transfer potentials are build up which sets up an electrical double layer and the corresponding coulombic attraction forces develop between the two components. Mechanical theory of adhesion is based on the anchorage of the adhesive in the porous rough surface of the adherends and hold the surface by interlocking action. 6. only under pressure. 3. Adhesives are generally susceptible to higher humidities. permanent adhesion occurs. 5. contact in molecular dimensions takes place. By wetting the surface of the adherend with the adhesive. 4. 4. Some adhesives when subjected to heavy static stress for long periods show a tendency to creep even at room temperature. Latest theories consider that bonding of adherend and adhesives takes place due to the chemical or physical forces of attraction. Smoothness of the adherend surfaces: For wood surfaces smoothness of the surfaces adds to the bonding strength of adhesives. 2.. 2. Adhesives require appreciable time for developing their full strength bonding for better performance. Adhesive Strength Development 1. In the case of other porous materials like paper. Adhesion Theories Several different theories have been developed that explain the mechanism of adhesion. The forces that are responsible for adhesion are the so called secondary valence or van der Waal’s forces. None of the above theories explain all the aspects of bonding. By chemical reaction: The reactive low molecular wt. wt. There is not available any single adhesive for joining all types of materials and hence judicial selection is of great importance in bonding process. the large number of capillaries preferentially enclose the liquid portion of the adhesive and disturb the equilibrium distribution of the adhesive on the adherend surface leading to weak joint formation.330 ENGINEERING CHEMISTRY 3.

Thickness of the adhesive film: Very viscous adhesives produce thick film but do not wet the surfaces properly leaving many voids and hence the bonding becomes weak. for cellulose derivatives partially degraded low molecular weight products give higher adhesive action. shear strength and compressive strength of the film: These three characteristics influence the bonding strength in a positive way. Less pressure is required in case the adherend surfaces are smooth but in the case of porous surfaces. in the case of cellulose esters the optimum chain length of fatty acid is from 6 to 14 for better bond strength.. Similarly. Degree of polymerization best suited for adhesive action is different for different adhesives e. Chemical Factors Affecting the Adhesive Strength 1. the surface is better wetted.g. Application modes of adhesives: The mode of application of adhesive on the surface to be joined also influences the bonding strength. wt. addition of polar molecules to the non-polar adhesives increases the adhesive power. pH: Strong acids and strong alkalies affect the bond strength of adhesives negatively. There are certain general steps involved in common bonding processes.ADHESIVES 331 uniformly wetted by the adhesive sol which is guided by the interfacial tension between the two. Similarly.. But the effects of pH are different in the case of different type of adhesives. products have greater adhesive action.g. temperature and time are the factors that affect this strength after the application of the adhesive. Degree of polymerization: Bond strength of the adhesive is affected by the extent of polymerization of the monomers. Pressure. Physical characters of the adhesive film: The bonding strength of the adhesive film is influenced by the following physical characteristics of the film. Complexity of the adhesive molecule: Complexity and chain length influence the adhesive action. slightly alkaline pH gives better bond strength in the case of Glue which are protein in nature. pressure should be applied to join the surfaces together. differing bonding processes give rise to different types of bonding. temperature also affects the process of bonding by allowing the solvent to evaporate. Thus. The bonding strength can also be increased by adding solvent and/or plasticizer to decrease the viscosity. Sufficient time is to be allowed so that the curing time be enough to establish a strong bonding. (a) Tensile strength. (b) Creep rate—Highly plasticized adhesives have higher creep rates under stress conditions than the rigid thermosetting materials. 3. Technique of Bonding Different type of adherend surfaces. . Polarity of adhesives: For organic contacting surfaces polar-group containing adhesives provide better bond strength than non-polar adhesives. This bond strength can be improved by applying pressure. 3. (c) Difference in thermal coefficients of expansion of adherends and adhesive—When this difference is high the bonding strength weakens under temperature variations. 2. different type of adhesives. When this tension becomes minimum. Creep rate under stressed condition should be lower for better adhesives. whereas acidic pH increases the bond strength of vulcanized rubber. 4. 4. e. Substance can be added to the adhesive to alter the thermal coefficient of expansion to match with that of the adherend and hence increasing the bond strength. In the case of phenol-aldehyde resin the higher mol. 5.

Loose dirt and oxide layers can be removed by brushing. (h) Cyanoacrylate adhesives and anaerobic reactive adhesives are applied by means of special metering units that delivers small metered quantities at specified time intervals. very viscous adhesives are thinned with solvent. (e) Dry adhesives are laid as film or sheet. one component is the thermosetting resin. casting knives. (c) By rollers. For wooden surfaces. added in proper proportion. so the method of application is very important. (b) Thin-flowing sprayable adhesives are distributed uniformly over large areas with spray guns (Fig. For certain plastics. For metals. ( g) For immediately reacting and hardening adhesives. Very uneven surfaces and others are rubbed with emery paper or sand blasted to remove firmly anchored layers that may interfere with the bonding process. 15. (d) Highly viscous adhesives applied as coatings. oil and lubricant are removed by solvent washing or immersion in acid or alkali bath or electrolytic methods. plasticizers.1). the components are applied to the adherend surfaces immediately before joining by double spray. b c a Fig. pretreatment processes are used to increase the affinity for bonding.332 ENGINEERING CHEMISTRY Cleaning and Pretreatment of Adherend Surfaces Layers of grease. 15. the adherend surfaces are machined to bring smoothness for better bond strength. Sometimes pressure and temperature are also used for these plastics. Developing on the size and nature of the surface and rheologic properties of the adhesive. Uniform addition of calculated quantity of adhesive is required for proper bonding strength. acidic pickling baths are used to remove low cohesive strength materials. Solid adhesives are melted. blades etc. spatulas. different methods of application are used as follows: (a) By manual application with brushes. hardners etc. surfaces are modified by chemical treatment to increase the surface tension and wettability. catalysts. For plastics which are difficult to bond. ( f ) For chemically reactive systems.1 Adhesive application by means of a spray gun (a) Adhesive (b) Compressed air (c) Atomized adhesive. which is applied to one surface and the other being the catalyst applied to the other surface to be bonded. . Adhesive Application Adhesives are dissolved in proper solvents.

Addition of water to this resin helps in forming continuous film with cross linkages and with rapid setting properties. Polycondensation adhesives must be heated with the application of external pressure higher than the vapour pressure of the cleavage products formed during condensation. Classification of Adhesives Adhesives may be classified on the basis of chemical nature. Use: This is available as solid.ADHESIVES 333 Joining. adhesion mechanism etc. generally with acid hardness to improve reactivity for bonding. syrupy compound. Thus to allow the time for evaporation of the solvent and tackiness to develop the assembly is to be kept for a long period. the applied pressure is to be released immediately after the bonding. This class has high adhesive properties by forming a network of three dimensional cross-linked structures. Similarly. the adherends are joined by different methods which vary with the type of adhesive applied and the surfaces to be joined. The necessary pressure is generally applied by using presses. Here we classify them on the basis of their chemical nature: 1. This is a pressure sensitive type of adhesive. pressure rolls. Drying and Hardening After assembling the adhesive-applied adherend surfaces some pressure is to be applied to ensure the uniform distribution of the adhesive on the whole surface and also to keep the whole surface in close contact for the appropriate time to develop highest bond strength. (b) Urea-formaldehyde resin. used in the form of aqueous solution or spray dried powders. Thermosetting synthetic resins. (b) For pressure sensitive adhesives. drying cabinets. heat and fungi proof. (d) For chemically reacting adhesives the adherend surfaces are kept in contact and the joint is allowed to remain for the required period to allow the chemical reaction to be complete to obtain high bond strength. Fixing of Adherends Following application of adhesives. (b) Adhesives or rubber solutions in organic solvents require longer period for air-drying. Some members of this class are: (a) Phenol-formaldehyde resins. (a) For slow reacting and setting adhesives the time of application of pressure is longer to ensure completion of the chemical reaction or complete evaporation of the solvent to develop bond strength. (c) For bonding of the metal surfaces. For warm-setting adhesives heating is required for a specified period. liquid or impregnated film and used for bonding wood and metal. radiant heaters. the assembly of the adherend metal surfaces is required to be heated in an oven which is called ‘pre-curing’. heat treatment is also necessary for selective adhesives. It is a transparent. Though this adhesive . The bonding of these are moisture. The adherend surfaces after being coated with this adhesive is subjected to curing by heat and pressure. setting mechanisms. heatingpresses etc. (a) For immediately drying type of adhesives the adherends are held close to each other immediately completing the assembly. For molten adhesive. cooling under pressure is required. The heat required for the hardening processes are supplied by recirculating-air ovens.

particularly to produce plywood and chipboard. Epoxy resins are also combined with phenolic resins and poly vinyl acetate resins and used as adhesion promoters. insects and chemicals. Uses. Polyacrylates are used both in the form of solutions and in the form of synthetic resin emulsions and are important raw materials for pressure sensitive adhesives. Cellulose acetate has less adhesive strength than cellulose nitrate but it is more resistant to heat. Cellulose ethers and cellulose esters. OH etc. Bonding wood. (c) Polyesters. As multipurpose adhesive. metals etc. glass. (e) Silicon resins. Cellulose nitrate is used as a raw material for solvent adhesives. metals etc. polyvinyl chloride. For wall paper paste and also as thickener. Used for bonding metal in aircraft industry and also for silicate containing materials and plastics.. They set under the effect of atmospheric moisture. Uses. Uses. Cellulose nitrate mixed with alcohol is well known as ‘collodion’. polyethyl. moisture etc. fungi. For bonding of silicate containing materials. They are stable to all conditions but costly. Copolymers of various esters (polymethyl. For bonding of paper. They possess good moisture resistance but low heat resistance. polyvinyl propionate form hard films resistant to atmospheric conditions and chemicals. 2. Polyvinyl acetate. . Uses. leather etc. Araldite which is available in the market comes under this class of resin. modifiers. Thermoplastic synthetic resins: (a) Cellulose derivatives. smooth surfaces and also in sealing of food materials. Polyvinyl acetate in combination with phenolic resins forms special adhesives. rubbers. Unsaturated polyesters dissolved in styrene or methacrylates are used as reactive adhesives. The adhesive film developed by cellulose nitrate is resistant to water but affected by strong acids and alkalies and aging. Epoxy compounds are available both in liquid and solid forms. It can also be cured without the application of heat. Uses. polybutyl-acrylate) contain functional groups like —NH2. For bonding of glass. resistant to temperature. Modified urea resins are important for labeling adhesives. (b) Acrylics. Uses. laminates. —COOH. Uses. plastics.334 ENGINEERING CHEMISTRY forms bond which is resistant to temperature. which are utilized for crosslinking and form better adhesives. On frequent contact with skin liquid epoxy resin causes irritation and allergies. (d) Epoxy resins. shoe adhesive. for aircraft and in ship industries. The thin film of epoxy resin remaining after the evaporation of the solvent acts as good adhesive having good chemical and electrical resistance. (c) Polyvinyls.. Used for making laminated glass and cloth. it deteriorates by acids and alkalies. dicarboxylic acid anhydrides etc. Usually they are used in combination with amines. The film is moisture resistant but inflammable. Uses. It is inflammable and in recent years it is replaced by others. Ethyl cellulose/methyl cellulose are used as aqueous solution with plasticizers.

For making envelopes. (b) Asphalt–Used for bonding metal. Uses. can be applied in cold and hot states but bond strength is low and susceptible to moisture. The solid cake or powder is boiled with water to form the adhesive solution. stamps. 6. . Testing of Adhesives Testing of adhesives mainly encompasses: • Solid content • Rheologic properties • Shelf life • Flammability and inflammability • Risks involved in transport and application • Measurement of the mechanical properties like tensile strength. solvent free adhesives whereas reduction in demand is expected for solvent containing adhesives and animal and vegetable glues. Uses. For making conveyer belts. Continued growth is expected in construction adhesives. Sodium silicate alongwith litharge (lead monoxide) and MnO2 etc. The bonding strength of the adhesive is high but susceptible to heat and moisture. breaking elongation of the films or test specimens made with the adhesives. books etc. 7. 4. Uses. treated with lime. Vegetable glue. Animal wastes obtained from slaughterhouses etc. Starch and dextrin adhesives. A suspension of starch is heated for sometime to obtain the adhesive which is cheap. These protein glues are obtained from soyabean. For manufacturing cardboard boxes and furnitures. paper etc. transport and electronics. which is hard. corn starch etc.ADHESIVES 335 3. The oily or the fatty matter is extracted or precipitated from soyabean or milk and then the protein is treated with lime and the water solution form a jelly-like adhesive. 5. albumin etc. The product obtained is hydrolysed with hot water to form liquid glue. corn. This gel has adhesive properties. For cardboard boxes making. This is bleached and mixed with preservatives and concentrated to form solid glue. Growth Rates of Different Adhesives The highest growth rate is expected in automotive industry. Inorganic adhesives. and hide scraps from leather industries are degreased with solvent. casein. The raw materials used for various types of starch and dextrin based adhesives are potato starch. Similar to starch adhesive. Natural resin adhesives: (a) Shellac–Hot shellac sol is an oldest known adhesive. The bond is moisture and high temperature sensitive but fungus resistant. They are very cheap but of poor bond strength. Uses. Animal glue. forms gel when suspended in water. Use.

Q. Write a brief note on natural and synthetic adhesives. EXERCISES 1. esters and also acrylics are used for binding paper. (ii) Polyesters dissolved in styrene etc. (i) Urea-formaldehyde and phenol-formaldehyde resins are used for joining wooden surfaces. The theories explaining the mechanism of adhesion are: (a) Mechanical theory (c) Adsorption theory (i) Wooden surfaces (iv) Papers (b) Electrostatic theory (d) Diffusion theory (ii) Glass and cloth (v) Plastics and rubbers (iii) Metals 3. Mention the types of adhesives used for joining Ans. Adhesive is defined as a substance capable of joining bodies together by surface attachments. Discuss the physical and chemical factors that influence adhesive action. rubber etc. 3. 4. Describe the different steps of the bonding processes of adhesives.336 ENGINEERING CHEMISTRY SHORT QUESTIONS AND ANSWERS Q. 6. 7. 2. What are adhesives? Explain the different mechanisms of adhesive action. What are the different theories that explain the mechanism of adhesion? Ans. 1. (iii) Epoxy resins are used for joining metals in aircraft industry. Mention a few important advantages and limitations of adhesives. What is an adhesive? Ans. 2. are used for joining glass and cloth. (iv) Cellulose ethers. (v) Silicon resins are used for bonding of plastics. 5. (i) Adhesive action of a polymeric adhesive is influenced by (a) Polar character (c) Complexity of molecule (ii) Adhesive used for bonding metals is (a) Epoxy resin (c) Acrylics (a) Phenol formaldehyde resin (c) Polyvinyls (a) Urea-formaldehyde resin (c) Silicon resins (b) Polyesters (d) All these (b) Acrylics (d) Polyesters (b) Polyesters (b) Degree of polymerization (d) All these (iii) Adhesive used for bonding leather for shoes (iv) Adhesives used for manufacturing furnitures of wood .

(a) Araldite (c) Polyesters (vi) Adhesive used in aircraft industry is (a) Starch (c) Shellac (vii) Araldite is (a) Animal glue (c) Thermosetting resin 8. Which of the following is fungus resistant? (a) Inorganic adhesives (c) Animal glue 9.ADHESIVES 337 (v) Natural adhesive used for stamps and envelops etc. (a) Leak proof (c) Electrically insulating 10. Adhesive having least bonding strength is (a) Starch (c) Epoxy resin (b) Cellulose derivatives (d) Acrylics (b) Vegetable glue (d) Starch adhesives (b) Heat insulating (d) All these (b) Cellulose derivative (d) Polyester (b) Asphalt (d) Araldite (b) Starch (d) Polyvinyl Adhesive bonding can be utilized to make a material .

this energy can be utilized to propel a projectile. The amount of power available from a given weight of explosive is known as “power to weight ratio”. only very safe explosives with lowest possible detonation temperature are used. The decomposition rate of an explosive should be very fast and large volume of hot gases should be liberated exothermally leading to large increase in volume. bombs etc. Once initiated. 338 . The reactions of explosives are exothermic. It should explode immediately after the application of the stimulus. electrical discharge and other sources of heat. quarrying limestone to be used in road construction. 2. 5. 3. In coal mines.Explosives and Propellants Explosives Explosives are pure substances or mixtures which on being subjected to specific stimulus like mechanical impact. These explosives usually contain a large amount of NH4NO3 and NaCl. for blasting holes in mountains for tunnels and roads. 4. The minimum quantity of energy required for initiation has a characteristic value that depends on the chemical and physical properties of the material. The explosive should be sensitive towards specific impacts. Explosives should not be volatile or hygroscopic but should be stable chemically so that they do not decompose on keeping or react with the storage container. The oxygen-balance of an explosive molecule should be higher which indicates that more oxygen is available in the molecule to oxidize C and H to CO2 and H2O. The other main area is in military and ammunition for war as well as tackling regular social problems. frictional forces. as well as in the preparation of torpedos. 1. grenades. The lesser the stimulus required better is the sensitivity of the explosion. Lastly. The explosive molecule should have a low energy of dissociation. 16 Characteristics of Explosives Following are the characteristics required for an explosive. digging earth. explosives should be cheap. blasting rocks and other social and useful works. 6. spacecrafts etc. the heat evolved is sufficient to cause the reaction to continue and become self-sustaining. The products at hot and high pressure and when confined to a closed space lead to explosion but if the reaction is controlled at slower rate. high pressure shock waves initiate an oxidation reaction producing large volume of hot gases. seismic prospecting. Another area is in the launching of rockets. In industry explosives are used for blasting ores of different metals. Uses of Explosives The principal non-military use of explosives is in mining.

The product obtained is washed and recrystallized from hot acetone. shock and electrostatic energy. It is an orange-yellow compound and prepared from picramic acid [NH2(NO2)C6H2OH]. The burning proceeds from the surface inwards at a slow rate. They are applicable wherever a well controlled force is to be generated for a short period. It is stable and non-corrosive. It is the most sensitive of initiating agents to impact and friction. They are: 1. Black powder or gun powder. 2. It is more effective than lead azide and is used as an initiator in commercial blasting caps. impact. Tetrazene. Black powder ignites and burns fast and has reproducibility and high heat flux. It is a mixture of 74% potassium nitrate. 4.4% sulphur. Only few compounds can act as primary explosives for military and industrial requirements. (A) Primary explosives. friction. Typical examples are: 1. The compound is stable upto 75°C. Lead azide tends to hydrolyse at high humidity and forms hydrazoic acid. Diazo dinitrophenol. The azides are among the very few useful explosive compounds that do not contain oxygen. It can be stored many years if dry. Lead azide. Mercury fulminate or mercuric cyanate is a grey-white powder. It is non-hygroscopic and sensitive to friction and impact. Lead azide is made in small batches buffered by the reaction solutions of lead nitrate or acetate with highly toxic sodium azide. The decomposition reaction is 10KNO3 + 3S + 8C → 2K2SO4 + 2K2CO3 + 6CO2 ↑ + 5N2 ↑ . It has high explosion energy and is used as a detonator. It is slightly toxic and its use is limited. 3. It deteriorates at humidity.6% carbon and 10. low and high explosives. sodium carboxy methyl cellulose (CMC) or dextrin may be added during precipitation to yield free flowing crystals or rounded agglomerates. They are used to initiate the explosion of high explosives which consist of explosives of increasing mass and decreasing sensitivity. 6-trinitro resorcinate is used to start ignition process in the explosive sequence. It is extensively used as primary explosive in military detonators. Lead azide is less sensitive to ignition than mercury fulminate. 4. namely primary. It is pale-yellow crystalline compound. 15. which reacts with Cu and its alloys to produce very sensitive cupric azide. reacts with metals in presence of water. It is prepared by treating 1-aminoguanidine hydrogen carbonate in dilute acetic acid with sodium nitrate. They should be handled with great care. Lead styphnate. It is prepared by intimate mixing of the thoroughly milled powdered ingredients. predetermined rates. It is prepared by mixing of solution of one part of mercury with eleven parts of 57% nitric acid and poured into ten parts of 95% ethyl alcohol when mercury fulminate forms as fine crystals of 99% purity. Of the four polymorphic forms (α to δ) the α is the most common. Lead 2. 5. The hygroscopicity of it is due to the presence of carbon and impurities in KNO3. with sodium nitrite and HCl. Addition of graphite improves its electrical conductivity in systems using electrical initiation.EXPLOSIVES AND PROPELLANTS 339 Classification of Explosives Explosives are classified under three broad groups. Low explosives do not explode but burn and produce large volume of gas at controlled. they are dense. metallo-organic compounds. Primary explosives are the most sensitive to heat. It decomposes when stored at elevated temperature. Mercury fulminate. (B) Low explosives or propellants. Pb(NO3)2 + 2NaN3 → 2NaNO3 + PbN6 Nucleating agents like polyvinyl alcohol (PVA).

N2. and (d) non-reactive towards metals to form unstable compounds. water vapour and no smoke. This product is stored as pressed cylindrical rods. When nitration is complete. (iv) 2. Its comparative excellence has made it useful for military consumption. It is a high explosive and used as self-filling explosives. two universally available cheap raw materials. Consist of only one chemical compound such as: (i) Ammonium nitrate: It is a powerful explosive compound when once initiated by an external detonation impulse of sufficient magnitude and in sufficient amount. TNT is widely used as shell-firing explosive and under-water explosions. It is used for blasting of coal. Nitrocellulose or smokeless powder: It is prepared by treating purified cellulose with mixed acid. It is also used as an explosive salt to replace a portion of the nitroglycerine used previously. The raw material toluene is derived from coal tar or synthetically from petroleum products. The nitrocellulose so formed is dissolved in alcohol and ether and the solvent evaporated when it forms a jelly-like mass. 22% HNO3 and 15% H2O. It is used to prepare binary explosives. It is readily prepared by the neutralisation of HNO3 with NH 3. Trinitrotoluene (TNT): This high explosive is prepared by nitration of toluene. It is stabilized by adding a stabilizer like diphenyl amine which can react with the liberated acid. the nitrocellulose and the spent acid are centrifuged.8°C) it is suited for loading in containers. 1. . storage and transportation. which in turn is made by condensation of formaldehyde with acetaldehyde. (c) violent-disruptive explosive.340 ENGINEERING CHEMISTRY This excess carbon and sulphur undergo slower reduction leading to more gaseous products 4K2CO3 +7S → K2SO4 + 2K2S2 + 4CO2↑ 4K2SO4 +7C → 2K2CO3 + 2K2S2 + 5CO2↑ This large volume of gaseous products is responsible for its explosive action. stable and cheap. It produces CO. (b) nonhygroscopic. The acid is sent to mixing tanks for fortification and subsequent re-utilisation. 2. CO2. (ii) Picric acid: Chemically picric acid is trinitrophenol. It is very safe to handle under ordinary condition. 6. because of its objectionable character as it reacts with metals to form picrates which are dangerously sensitive. CH2OH CH2OH C CH2OH CH2OH CH2ONO2 CH2ONO2 C CH2ONO2 CH2ONO2 + 4HNO3 ¾¾® + 4H2O This explosive compound has become important since the First World War as powerful military explosive. Because of its low melting point (80. It cannot be stored near inflammable materials and contact with alloys of copper is to be avoided as it detonates. in the aspects like (a) being safe explosive for manufacture. having an approximate composition of 63% H2SO4. 4. it is known as smokeless powder. Other uses include blasting in shells. It is largely replaced by TNT. igniters and primer assemblies for propellants etc. (C) High explosives: This group consists of six types of compounds. Single compound explosives. So. (iii) Pentaerythritol tetranitrate (PETN): It is obtained by the nitration of the irregular tetrahydric alcohol pentareythritol.

They can be made into flexible sheets. It is an explosive mixture of TNT with ammonium nitrate. TNT is the most important ingredient due to its lower melting point. Important uses of this class are blasting of hard rocks. Binary explosives are made by mixing. It is a mixture of 80% TNT and 20% Al flakes.EXPLOSIVES AND PROPELLANTS 341 (v) Cyclotrimethylene trinitroamine RDX or cylonite : This highly powerful explosive has become important for military use as well as industrial use since World War II. to a solid which is relatively insensitive to ordinary shock but capable of detonating by a blasting cap. 4C3H5 (NO3)3 → 10H2O↑ + 6H2↑ + 12CO2↑ + O2↑ 1 vol. The detonation products can undergo further combustion. They are used for both industrial and military applications. by Alfred Nobel. Binary explosives. The strongest known industrial explosive is the ‘blasting gelatin’. (ii) Gelatin dynamites. which contain nitroglycerine as the principal ingredient. minerals etc. The invention of dynamite dates back to 1866. of explosion The various types of dynamites are: (i) Straight dynamites. . Antacid material like CaCO3 to neutralize the acidity of nitroglycerine is to be added also. TNT is deficient in oxygen so the combustion is incomplete. But 80:20 mixture of ammonium nitrate and TNT is an evenly balanced composition with respect to oxygen with resulting increased strength and improved fumes. Tetryl has important use as commercial explosive as a base charge for blasting caps. Because of its too much sensitivity.000 vol. The combination includes a high explosive mixed with wax oil (that gives the plastic nature) and lower sensitivity. 10. Sodium nitrate is added as an oxidising agent that adds on good fume properties and good blasting execution. he converted a liquid. 2. which detonates by shock or pressure above 50°C. 4. (iv) Tropex. Nitroglycerine is an oily liquid. It is used as blasting charges in large caliber shells. 3. Gelatin dynamites are made by partly gelatinising the nitroglycerine by nitrocotton. The most important ones are: (i) Amatol. (v) Titronal. (vi) Tetryl or tetranitromethylaniline. which is dangerous to handle and transport. It is made by nitration of dimethylaniline and its melting point is around 130°C. It is a mixture of 70% tetryl and 30% TNT. (ii) Tetrytol. Plastic explosives. heating to liquify and pouring into containers to solidify. who conceived the idea of mixing the nitroglycerine with highly absorbent materials. fixed to a metal with adhesives and made to special shapes. The term dynamite has been limited to those commercial explosives. These are mixtures of TNT with other explosives. All these mixtures have some advantages over TNT alone by having higher energy or by being cheaper. it is used as a booster charge intermediate between ignition charge and bursting charge for military use but not used for main shell firing. which can finally be cut into pieces. It is a mixture of 1:1 TNT and PETN. In this way. starch and other low-density fibres. Its advantages are less toxicity but greater sensitivity than TNT. It is a mixture of 40% RDX. Dynamites. The amount of absorbent added varies the relative strength of dynamite. coal. The disadvantage compared to TNT is its hygroscopicity. 15 to 60% nitroglycerine are absorbed in combustible materials like wood pulp. 40% TNT and 20% Al powder. These are combinations of explosives having a plastic state with many different shapes that can be produced without risk by hand moulding or press loading. (iii) Pentolite.

It explodes very sharply if set on fire. It is incapable of detonating under the influence of blasting cap but once initiated by booster charge it can propagate explosion indefinitely. blasting of hard rocks. It is prepared by steeping cotton for 30 minutes in a cooled mixture of conc. Disadvantage is that they are costly compared to others. insensitiveness to shock and friction. Commercial High Explosives Containing No Nitroglycerine (i) Ammonium nitrate explosives. Blasting gelatin is a solid. It is made by 65 parts of gun cotton. They excell others by four important properties—high bulk density. Dry gun cotton is used in torpedos. (c) fibrous combustible material to utilize the excess oxygen of ammonium nitrate and absorbing nitroglycerine. This paste is rolled and cut into pieces of different sizes Vaseline acts as a stabilizer and cooling agent on the powder. H2SO4 and conc. After the evaporation of the acetone. artillery shells. These are— effectiveness. underground blasting like deep-well shooting. They possess some attractive properties for which they have wide use. so they are not fit to be used in wet condition.5% nitroglycerin. (b) low percentage of nitroglycerine as sensitizing agent. Composition is approx. Rate of explosion of it can be controlled by mixing other substances. elastic material. This is mainly used for blasting in wet conditions. (v) Cordite. It is used for under-water works. 30 parts of nitroglycerine and 5 parts of vaseline in acetone. This powerful explosive is a mixture of 65% blasting gelatine and 35% absorbing powder. Ammonium nitrate is highly deliquescent salt. This type of explosive. They are mainly used for submarine blasting. but this disadvantage can be overcome . where inflammable gases are present. tunnel driving etc. Permissible dynamites. highest water resistance among dynamites. non-inflammability. The gelatinous type of permissible dynamites contains a higher percentage of nitroglycerine and lower content of ammonium nitrate along with a small percentage of nitrocotton. called Notramon. These are dynamites in which a portion of the nitroglycerin has been replaced by ammonium nitrate. submarines.5% CaCO3. (iv) Ammonia dynamites. The only disadvantage is their low water resistance. as a propellant in rifles. stick well to holes into which they are loaded because of their plastic nature and lastly they excell from the point of view of fumes. Lower ratio of nitrocotton in nitroglycerin gives viscous liquid instead of the solid mass. is a safe but high-velocity agent. These are high explosives specially used for gasy coal mines etc. Gun cotton controls the explosive reaction of nitroglycerine and it can be safely used for large caliber naval guns. 91. (iii) Gun cotton or cellulose nitrate. The common permissible contain (a) about 80% ammonium nitrate. (vi) Gelignite. 8% nitrocotton and 0. They are not sensitive to shock and hence are preferred for use under wet conditions. Their strengths are equivalent to straight dynamite but of lower velocity.342 ENGINEERING CHEMISTRY belonging to this class. cheapness. HNO3 C6H7O2(OH)3 + 3HNO3 → C6H7O2(NO3)3 + 3H2O Dry gun cotton can be ignited by shock. dynamites. the horny cordite remains.

it is the safest high-velocity agent. Carbonaceous absorbent materials like lampblack or other carbon black are packed in a porous container and this cartridge is dipped into liquid oxygen to get saturated. charcoal. nitroglycerine being on the top. But though being cheap. CH 2 − ONO 2 CH 2OH   Conc. The yield is around 230. the former separating out the mono-nitro compound first. The strength does not remain constant since the liquid oxygen steadily evaporates and hence they cannot be stored for long. having a composition of 76% H2SO4. sulfur etc. 7% HNO3 and 17% H2O are run to a separator. .8°C. Sodium or potassium chlorate mixed with oxidisable materials like sugar. a desensitizing material or liquid ingredient is added to this mixture to overcome the above disadvantage. They are highly sensitive to shock. (iii) Liquid oxygen explosives.H2SO4 is taken in slight excess of HNO3 and is absolutely free from water. The formation of these isomers and oxidation products leads to the formation of undesirable impurities. continuous process has been developed. (ii) Chlorate explosive. the mixed acid is taken and nitroglycerine is added and nitration is done at a very low temperature under stirring. Recently. These liquid oxygen explosives are of high strength and velocity but they have several disadvantages. calculated on the basis of glycerine as 100. washed with water.. Either a two or a three-step process is used. which is cooled externally by brine.EXPLOSIVES AND PROPELLANTS 343 by enclosing the material in a waterproof metallic container. becomes highly inflammable and sensitive to impact. In recent years. H2SO4 CH3 NO2 + 3H2O NO2 Six isomers are possible for the trinitro compound. The liquid product containing TNT is taken out. HNO3 and H2SO4. The nitroglycerine is drawn off. This nitroglycerine is then converted to dynamites by absorbing in different inert materials. friction and shock. It is very important that to avoid any accidental explosion a close control of the temperature is to be done during nitration. Manufacture of Important Explosives (i) Nitroglycerine: The raw materials are 99% pure glycerine. CH3 O2 N + 3HNO3 Conc. they form separate layers. The resulting nitroglycerine and spent acid. Because it is not sensitive to impact. which is finally dried and stored. TNT is crystallized and the purified material melts at 80. then preparing bi and tri compounds in one step. After about 3/4 of an hour. the acid is neutralised with a weak solution of Na2CO3 under vigorous stirring. In a steel nitrating vessel. they are not popular. washed with ammoniacal solution of Na2SO3 and finally with cold water. H2SO 4 CHOH + 3HNO 3 → CH − ONO 2 + 3H 2 O   CH 2OH CH 2 − ONO 2 (ii) Trinitrotoluene (TNT): TNT is prepared by nitration of toluene using 1:1 mixtures of H2SO4 and HNO3 in a stirred tank reactor.

These fuses are used for exploding charges of explosive in deep holes. Detonating fuse has a velocity of detonation over 5000 metres per sec.1. On passing electric current this bridge wire is heated and becomes incandescent and fires the ignition charge. by using these delays. . There are three types of blasting caps as shown in Fig. The line of the fuse (cordean) is in contact with the charge throughout its length and hence causes instantaneous detonation of the whole charge. It consists of a charge of high velocity explosive like TNT in a small diameter lead tube. Blasting caps are used for initiating the explosion of dynamites and are inserted into the explosive at the time of use. So when a fuse is used for blasting. Squibs are used for this purpose. electric squibs are used. Blasting Caps Blasting caps are small cylindrical shells of copper or aluminium containing a detonating charge of explosives. In electric blasting cap. inserted in the cap to delay the detonation of the cap charge. In the delay electric blasting cap. application of flame is insufficient for firing. Squibs may be in metal or cardboard tubes and may be open or closed at the firing end. (b) Detonating fuse. The composition of the delays has been improved so that no gas is given off on combustion. This time interval can be varied from 15 to 20 sec. A recent type of detonating fuse contains pentaerythritol tetranitrate in a non-metallic wrapping and the velocity is as high as 7000 metres per sec. It has an approximate burning speed of 30 or 40 sec per ft. Squibs When deflagrating explosives like black powder are used. 16. It consists of a small-diameter core of black powder enclosed in a wrapper of water-proof fabric. there is a delay charge of a slow burning composition. The end of the fuse which is away from the cap is lighted and the spit of flame from the fuse in the cap fires the ignition charge leading to detonation. a length of safety fuse is inserted into the open end and the metal wall is crimped about the fuse. a sufficient length is used so that the shot-firers get time to reach to a point of safety.344 (iii) RDX: Bechman process: (80% yield) ENGINEERING CHEMISTRY NO2 CH2—N—CH2 Hexamine + HNO3(98%) + NH4NO3 + (CH3CO)2O → O2N—N N—N2O CH2—N—CH2 NO2 Fuses Fuses are of two types: (a) Safety fuse: Safety fuse is employed where electrical firing is not used. two leading wires are connected within the cap by a fine wire of high electrical resistance. Preferably. In ordinary fuse cap.

(ix) Nitroglycerine explosives should not be handled in unwrapped condition as it causes headache etc.1 Three types of blasting caps. (iv) The boundary of the explosive store should be protected by fencing and watchman with proper ‘Caution Boards’. and they should not be handled during thunder storm. (ii) They should be handled only by experienced and properly instructed persons. (vii) All electrical fitting of the store should be properly insulated and only torch light allowed inside in case of power failure. (x) Contact or inhalation of vapors of aromatic nitrocompounds should be avoided due to their inherent toxicity. (vi) Jerks and drops of explosives are prohibited. (iii) They should be stored under favourable conditions and at positions sufficiently isolated from any working furnace or kiln. 16. (v) Smoking/fire should be strictly prohibited within 50-m radius from explosive store. (xi) Magazines containing explosives should have lightning conductors. on contact. (xii) Magazines should be at safe distance from buildings. Handling and Storage of Explosives There are many rules to be observed in handling and storing of explosives to avoid different hazards.EXPLOSIVES AND PROPELLANTS Insulated wire Sulphur seal Waterproofing Insulated wire Plug Ignition powder Air chamber Plug Bridge wire Regular electric blasting cap Waterproofing Ignition powder Base charge Base charge Delay electric blasting cap Delay tube Delay powder Capsule Shell Crimp Bridge wire Shell Fuse Ignition powder Primary charge Base charge Ordinary blasting cap 345 Shell Sulphur seal Fig. Propellants Propellants are defined as substances or mixtures of substances of an explosive nature in a solid to liquid state that burn exothermally without contact with atmospheric oxygen and . (i) Explosives should be treated with care. rail roads and highways. (viii) Different explosives to be stored separately.

30% nitroglycerine. General composition is 50–55% nitrocellulose and 40–45% nitroglycerine. single and double-base propellants are used. empty tanks. Gun powder is the oldest composite propellant. 1. non-hygroscopic and should not produce any corrosive or objectionable product on combustion.346 ENGINEERING CHEMISTRY form a large volume of gas. In these propellants. Aluminium powder in rocket propellant produces large amount of smoke due to Al2O3 formation. explosive plasticizers (nitroglycerine etc. 1% diphenylamine is also added as stabilizer. Ammonium perchlorate is replaced by ammonium nitrate to reduce HCl generation. rockets. Energetic substances (RDX or HMX). Heterogeneously formulated solid propellants that consist of a polymeric binder in which crystalline oxidizers are incorporated in amounts upto about 90% by weight. Since propellants burn without atmospheric oxygen. of hot gases exit through a small opening at a large velocity (as per Newton’s third law of motion) which can be used for several purposes like charges for guns. inflate air bags etc. The fuel burn and the large vol. Other compositions are 65% nitrocellulose. Solid propellants may be again categorized into ‘homogeneous’ and ‘composite’. (b) Double-base propellants. Composite propellants are used as gun and rocket propellants. 5% petroleum jelly. The generated gases can also be used to drive pumps. For small charges. Composite propellants. nitroglycerine is replaced by explosive plasticizers like diethylene glycol dinitrate or butanetriol trinitrate which have low heat of explosion. They can be used only as gun propellants or in bulk powder fillings for gas generators. the propellant system must contain the oxidizer along with the fuel. launching missile. 80% ammonium perchlorate + 20% resin binder. propelling rockets. It gives of a flame temperature of 800-1500°C and the volume of gases is 400 times the volume of the original. having a low flame temperature is used as ‘cold powders’ for triple-base propellants to reduce the flame temperature. where the last one functions as plasticizer. Classification of propellants Propellants can be classified into solid and liquid propellants broadly. plasticizers like dibutyl phthalate. (c) Triple-base propellants. They are used as gun propellants and rocket propellants. Different composite solid propellants contain 75% potassium perchlorate + 25% asphalt oil. Flame temperature reaches about 2700°C and gases liberated at about 1500 times the original volume. viz. (A) Solid propellants. Composite type have low binder content and the crystalline fillers on burning produces lager amount of gases and also the flame temperature is comparatively low. Nitroguanidine. It is a type of homogeneous solid propellant consisting of mainly plasticized nitrocellulose. Propellants for larger gas generators are generally of the composite type. . actuate valves. lead or copper salts are used as ballistic modifiers to reduce pressure. 2. ammonium perchlorate produces HCl on combustion which is corrosive. For rocket propellant. 5% diethyl pthalate as plasticizer giving a smooth mass. gas generators.) and energyrich binders (GAP) are used to improve the performance. They contain stabilizers like diphenylamine. Homogeneous solid propellants are mixed homogeneously in a colloidal state—it is homogeneous solid propellant (a) Single-base propellants. The oxidizers are selected which should be stable.

Conventional rocket propellants contain H2O2.EXPLOSIVES AND PROPELLANTS 347 (B) Liquid propellants. Bipropellants consist of an oxidizer and a fuel that are injected in two separate phases to the combustion chamber. ethyl alcohol. Monopropellants should be stable on storage and smooth on burning. Examples of monopropellants are 80-99% H2O2. But unfortunately H2O2 is highly reactive and decomposition occurs though stabilizers are added. A remote control is necessary with all processes in which explosive materials are involved and exposed to thermal or mechanical stresses. Commonly used oxidizers are ozone. liquid H2. NO2 or liquid O2 as oxidizer and hydrocarbons.2% hydroxylammonium nitrate (HAN). liquid fluorine or a mixture of fluorine and oxygen (FLOX). HNO3. (ii) Bipropellants. are toxic and explode at high concentration. hydrazines and alkyl derivatives as fuel. Metallic storage tanks are generally avoided for H2O2 as metal oxide catalyzes its decomposition. There are several problems with these combination. mixtures of nitromethane and isopropyl nitrate or methanol. Type of liquid propellants are: (i) Monopropellants. Monopropellant for guns have compositions like 63. conc. liquid O2. ethylene oxide. amines. They are more advantageous for use than the solid propellants and so their uses are more versatile. Liquid propellants contain the fuel and oxidizer as a single substance or mixture of substances (mono) or in two separate phases (bipropellants).8% water. propyl nitrate etc. alcohols. 20% triethylammonium nitrate (TEAN) and 16. Liquid fluorine or FLOX is used in aerospace application with improved performance. Production Propellants are energetic materials and hence are to be manufactured and transported with great care. hydrazine and its derivatives. kerosene. though powerful oxidizers. amines. Common fuel used are hydrazine. aniline. . The production processes are: (a) Solvent process (b) Solventless process—Role and extrusion process (c) Screw extrusion process (d) Ball powder process (e) Casting process Testing for propellant includes (a) Burning behaviour (Ballistic Bomb) (b) Burning rate (Crawford Bomb) (c) Heat of explosion The environmentally-safe disposal and toxicological effects of propellants are also of concern and are coming under strict regulations. Monopropellant has fuel and oxidizer as the same compound or a solution containing both. Ozone and liquid fluorine. Solid propellants are located in a chamber for combustion but the liquid propellants are injected into the combustion chamber from a storage tank by metering device and hence the engines using liquid propellants are more delicate. nitromethane. Also they are difficult to handle and store.

348 Highlights: ENGINEERING CHEMISTRY Explosive: Explosives are pure substances or mixture. 2. respectively. Positive oxygen balance is an important characteristic of a good explosive. What are dynamites? Ans. Nitroglycerine is usually mixed with an inert absorbent like wood pulp. SHORT QUESTIONS AND ANSWERS Q. 2. 5. What are explosives? Ans. 4. High explosives: High explosives have higher energy content compared to primary explosives but they are quite insensitive to external stimuli. Q. which when subjected to specific stimulus initiate an oxidation reaction producing large volume of hot gases. Dynamites are high explosives containing nitroglycerine as the principal ingredient. Fuses: Fuse is a thin water-proof canvas length of tube which contains gun-powder that burn at a given speed for setting off charges of explosives. What is a rocket propellant? Ans. Explosives are substances or mixtures. Q. It is expressed as the difference between the oxygen contained in the molecule and the oxygen actually required to oxidise the total C and H contained in the molecule. What are fuses? Ans. 1. Propellants: Propellants are pure substances or mixtures in liquid or solid state that burn exothermally without contact with atmospheric oxygen and form large volume of gaseous products. Dynamites: Explosives containing nitroglycerine as the principal ingredient. starch meals. lead to rapid oxidation exothermally to produce large amount of gaseous products of greatly increased volume and also a large amount of energy. Q. Q. (ii) detonating fuse. with varying amount of nitroglycerine that determines its relative strength. Fuses are of two types: (i) safety fuse. which will be utilized to oxidize the C and H of the molecule to form CO2 and H2O. which explode on receiving a slight shock or fire. Fuses are thin water-proof canvas length of tube containing gun-powder or TNT. RDX: Powerful explosive consisting of cyclotrimethylene trinitroamine. It indicates the oxygen contained in the molecule. Rocket propellant is either a high oxygen containing fuel or a fuel with an oxidant which is burnt under controlled condition with the evolution of a large volume of gas. saw dust etc. What are explosives? What are rocket propellants? How are explosives classified? . EXERCISES 1. which burn at a given speed for setting-off the charges of explosive. which when subjected to mechanical or thermal shock. 3. What do you mean by “oxygen-balance of an explosive”? Ans. Primary explosives: They are highly sensitive explosives.

6. 8.EXPLOSIVES AND PROPELLANTS 349 3. 7. 11. 4. What are dynamites? State the procedure of its manufacture. Name two for each class: (a) Primary explosive (b) Two low explosive (c) High explosive (d) Monopropellants and bipropellants What are the requirements of a good explosive? Why are detonators required for high explosive? What are the uses of explosives? What are propellants? How are propellants classified? State the requirements of a good propellant? What is gun-cotton? What is RDX? What are fuses? Explain the term “oxygen-balance of an explosive”. 5. 10. Write notes on the following: (a) Modern explosives (b) Nitroglycerine (c) Rocket propellant (d) Cordite (e) TNT (i) RDX is (a) Trinitrotoluene (b) Cyclotrimethylene trinitroamine (c) Lead azide (d) Nitrocellulose (ii) TNT is a compound of (a) Cellulose (c) Toluene (iii) Characteristic of a good explosive is (a) High energy of oxidation (c) Positive oxygen balance (iv) Example of high explosive is (b) Glycerol (d) Phenol (b) Slow and controlled oxidation rate (d) Decomposition rate should be slow (c) Lead azide (c) Lead azide (a) TNT (b) Gun powder (v) Example of primary explosive is (a) Ammonium nitrate (vi) Gum powder is (a) Primary explosive (c) High explosive (vii) Smokeless powder is (a) Tetracene (a) TNT (a) 1 m sec–1 (x) Black powder is (a) Nitrocellulose (b) Mercury fulminate (b) Nitrocellulose (b) Dynamite (b) 1 cm sec–1 (b) TNT (b) Low explosive (c) Picric acid (c) Nitrocellulose (c) 100 m sec–1 (c) Gun powder (viii) Binary explosives are mixtures of other explosives with (ix) Burning speed of safety fuse is . 9.

Water is also used for all domestic purposes like bathing. bicarbonates and bromides of sodium. SO2. washing. magnesium etc. Other salts present include sulfates. gets contaminated by the following processes: (a) Dissolution. which pollute the atmosphere. 2. potassium.e. gypsum (CaSO4. while percolation. bicarbonates. Lake water. The rainwater and other surface water percolate down through the soil and rocks and get filtered and finally collected on rocky surface or again come out as spring.5% dissolved salts of which about 2. 3. soils etc. CaSO4 + 2H2O → CaSO4.2H2O) and other soluble salts get directly dissolved in the percolated water. River water while flowing through the land collects lots of organic matters from falling trees and nearby habitats and also other soluble and suspended matters from the lands.. microorganisms and other pollutants from the habitats and become unsuitable for direct human consumption and other usage.6% is sodium chloride. potassium and magnesium. irrigation etc.e. It is the most impure form of water containing about 3. Though it contains less suspended matter but the dissolved mineral content is quite high and is of high organic purity. 4. for air conditioning. water causes hydration of the minerals like anhydrite. dissolved impurities are less but contains lots of organic matter. water is essential for the survival of all the living beings on earth i. but it is also used for the operation in a large number of industries as coolant. Other impurities are carried to sea through rivers. The sources of river water are the springs and the rainwater. It is much purer than river water. Thus we can say that the surface water collects lots of suspended materials. viz. Effect of Water on Rocks Water. The dissolved matters include the salts like sulfates. animals and plants. man. 5. fire-fighting etc. Underground water. sanitary. olivine which leads to increase in volume and disintegration of such rocks. It is the purest form of natural water. (b) Hydration. and other solids. Sodium chloride. Sea water. solvent. Water is not only essential for the survival of life. Sources of Water 1. drinking..Water Treatment 17 The nature’s most abundant supply i. for steam generation. Rainwater. While percolation. But unfortunately it dissolves the toxic gases like CO2. River water. bromides of sodium. NO2 etc.2H2O Anhydrite Gypsum 350 .

Mg and Fe alongwith silicates of Na. Fe. Mg2+ and Fe2+ make water hard. Other limits include French degree of hardness. water becomes soft and forms lather. viz. Insoluble carbonates of Ca. Ca. Permanent hardness cannot be removed easily on boiling. etc. Units of Hardness Both temporary and permanent hardnesses are expressed in ppm as CaCO3.WATER TREATMENT 351 Mg2SiO4 + xH2O → Mg2SiO4. This hard water on treatment with soap which is stearic or palmitic acid salts of sodium or potassium causes white precipitate formation of calcium or magnesium stearate or palmitate.2SiO2. is 100 and equivalent weight is 50 and it is the most insoluble salt in water. (Insoluble) CaCO3 + CO2 + H2O → Ca(HCO3)2 (Soluble) K2O.Al2O3. 2C17H35 COONa + CaCl2 → (C17H35COO)2Ca + 2NaCl Sodium stearate (soap) Calcium stearate (insoluble) Thus the cause of hardness is the precipitation of the soap and hence prevents lathering at first. The choice of CaCO3 is due to the fact that its mol.6SiO2 + CO2 + 2H2O → Al2O3. Equivalent of CaCO3 (Mass of hardness producing substance) × (Chemical equivalent of CaCO3 ) Chemical equivalent of hardness producing substance Mass of hardness producing substance × 50 = Chemical equivalent of hardness producing substance Hardness is principally expressed in ppm unit. (i) Temporary hardness is due to the bicarbonates of Ca2+ and Mg2+ and carbonate of Since bicarbonates readily get precipitated on boiling the water.2H2O + K2CO3 + 4SiO2 Hardness of Water Hardness of water is the characteristic of preventing lather formation of water with soap. K.2H2O Haematite Limonite Oxidation (d) Action of carbon dioxide. and Fe are converted into soluble bicarbonates and soluble carbonates. English degree of hardness or Clark. Mg. wt. viz. USA degree of hardness and German degree of hardness.xH2O Olivine Serpentine Hydration (c) Oxidation. Generally salts like chlorides. The hardness is of two types: Fe2+. Magnetite 2Fe3O4 → 2Fe2O3 → 2Fe2O3 . 1 part of hardness 1 ppm = 10 6 parts of water = . the temporary hardness can be easily removed. When the hardness causing ions are removed as insoluble soaps. bicarbonates and sulfates of Ca2+. Ca(HCO3)2 → CaCO3↓ + H2O + CO2 insoluble heat (ii) Permanent hardness is due to the presence of chlorides and sulfates of Ca. Dissolved oxygen brings about oxidation alongwith hydration.

000 grains 5. body. • For steam generation in boilers. Due to the presence of hardness producing salts in hard water. the salts present in the hard water gets saturated and are finally deposited in the areas where the flow is slow. degree of hardness = 1 Clark = 1 USA degree of hardness = 1 part of hardness 10 5 parts of water 1 grain of hardness 1 = 1 gallon or 70. (ii) corrosion.3 ppm = 10 mg/l Disadvantages of Hard Water (a) In domestic uses. For textile industry and dyeing industry. hard water creates many problems like (i) scale formation. hard water creates difficulties. the salts responsible for hardness create difficulties in sugar refining and crystallization of sugar and the sugar becomes deliquescent.1° Fr 1 mg/l 1° Cl 1° Fr = 1 ppm = 1. (iii) priming and foaming and (iv) caustic embrittlement.352 1 Fr. (b) In industrial uses. Drinking of hard water is also problematic since it affects the digestive system and at the same time the possibility of deposition of calcium oxalate crystals in the urinary tract is alarming.000 grains 7 × 10 4 ENGINEERING CHEMISTRY 1 grain 1 grain 1 = = 1 USA gallon 58. • In laundry.83 × 10 4 1 German degree of hardness = 1 grain 1 grain 1 = = 1 German grain 56. Taste of tea. on continuous evaporation. do not cook in hard water. • For sugar industry.3 mg/l = 0. The stains of iron salts also are undesirable on fabrics. until all the Ca/Mg salts get precipitated. Hard water also hampers the economy by wastage of soap as it does not form good lather.6 × 10 4 = 0. clothes etc. • Calcium and magnesium salts also interfere with the smooth and glossy finish of the papers in the paper industry. boiling point gets elevated and during cooking a lot of fuel is wasted. When . coffee becomes unpleasant.1° Fr = 14.7° Cl. For washing and bathing. • Hard water is not suitable for preparing drug solutions in pharmaceutical industry. Thus a lot of soap get wasted also. • The hydration of cement and final hardening of cement are affected by use of hard water in concrete making. since it does not form lather freely with soap. It also creates sticky precipitates that deposit on bath tub. For cooking hard water creates similar difficulties by producing scum on the bottom of the vessels. hard water causes the usual problem of deposition of insoluble salts that interfere with the proper dyeing and printing of the fabrics.07° Cl = 14. Iron salts interfere with the colour of the paper.300 grains 5. Relation between various units of hardness 1 ppm = 1 mg/l = 0.07° Cl = 0.43° Fr = 10 ppm = 0. Sludge and Scale Formation in Boilers When hard water is used for boilers. Pulses etc. hard water causes wastage of costly soap and also interferes with the coloration due to the staining of iron salts.

particularly the high pressure boilers. i.25 mm to 12 mm leads to increase in fuel consumption from over 50% to 150%.e. This scale formation takes place due to the following reasons: (a) In low pressure boilers scale formation occurs due to the formation of CaCO3 from Ca(HCO3)2. But here CaSO4 forms the hard scale. . Removal of sludges. Disadvantages of scale formation are similar to sludge formation but the severity is more. Disadvantages of sludge formation are (i) poor heat conduction due to the presence of sludge on the surface. Since the solubility of CaSO4 decreases with increase in temperature. it is called sludge whereas when these precipitates are hard and they adhere strongly to the inner surface of the boilers. which involve alternate heating and cooling to make the scales brittle. Scales are the hard deposits on the inner surface of the boilers which are difficult to remove. (iv) Chemical treatment with 5-10% HCl for carbonates and EDTA treatment for Ca/Mg salts forming complexes. (iii) Valves and condensers of the boilers are chocked due to scale formation and boiler efficiency decreases. suitable for removing loose scales. CaCl2 etc. MgCl2. The increase in thickness of the scale from 1.. since its removal is more difficult. Removal of scales can be done by: (i) Wooden scraper or wire brush. (ii) Due to the overheating of the boiler. (iii) Giving thermal shocks. (ii) difficulty in the operation of the boiler.WATER TREATMENT 353 these precipitates are loose and slimy in nature. Sludge formation can be prevented by (i) using soft water for boiler operation and (ii) removing the concentrated salty water from time to time so that deposition of sludge is prevented. Dissolved magnesium salts also precipitate as Mg(OH)2 forming soft type of scale. Sludge is formed by the presence of MgCO3. different parts of the boiler become weak and distorted and so the operation of the boiler becomes unsafe. they are called scale. These salts are more soluble in hot water. The thick scales may sometimes lead to explosion due to sudden development of high pressure. and at high temperature the precipitated CaSO4 forms hard scale. (ii) Blow down operations for loose scales. The operation actually involves the removal of very hard water from a tap at the bottom of the boiler and replenishing the water with softened water called ‘make up’ water. Sludge can be easily removed by scrapping with a brush. MgSO4. These calcium or magnesium silicate scales are very difficult to remove. Ca(HCO3)2 → CaCO3↓ + H2O + CO2 Scale (b) In high pressure boilers this CaCO3 gets converted to soluble Ca(OH)2. Disadvantages include (i) Poor heat transfer from boiler to water leading to increase in fuel consumption. It deposits as CaSiO3 or MgSiO3. (iii) if sludge is formed along with the scale and is trapped within the scale formed and so it is difficult to remove and (iv) it clogs the pipe lines and other connections to the vessel near the places where water circulation rate is slow. Similar hard scales are formed when SiO2 is present in the hard water.

tannin. This Mg(OH)2 and Al(OH)3 are flocculent and entraps the colloidal as well as the finely divided impurities like silica in the boiler water and the loose precipitate is finally removed by blow down operation. 3CaCl2 + Na3PO4 → Ca3(PO4)2 + 6NaCl (c) Carbonate conditioning: Sodium carbonate is added to the water of low pressure boiler whereby the scale forming CaSO4 gets converted to loose sludge of CaCO3. when they are formed. . NaOH attacks and dissolves out iron of boiler forming sodium ferroate. (b) Different sodium phosphates like NaH2PO4. Na2CO3 are added and it gives rise to NaOH at elevated temperature according to the following reaction.e. The NaOH formed reacts with magnesium salts to precipitate Mg(OH)2. (a) Colloidal Conditioning: Organic substances like kerosene. reacts with scale forming CaSO4 and forms soluble complex compound. so that scale formation can be avoided. NaAlO2 + 2H2O → NaOH + Al(OH)3↓ MgCl2 + 2NaOH → Mg(OH)2↓ + 2NaCl ( f ) Electrical conditioning: Rotating mercury bulbs on heating by the boiling water emit electrical discharges that prevent scale formation by the particles.354 ENGINEERING CHEMISTRY These are methods for the removal of the scales. Internal treatment Internal treatment involves addition of chemical to the boiler water either to (i) precipitate the scale forming impurities in the form of sludges. which can be easily removed by blow-down operation. agar-agar are added to form gels and form loose non-sticky deposits with scale-forming precipitates.. CaSO4 + Na2CO3 = CaCO3 + Na2SO4. This finally causes the stressed parts like bends. This cracking is not due to corrosion and the cracks appear like brittle fracture and hence called caustic embrittlement. Na2CO3 + H2O → 2NaOH + CO2 Steam boilers are made by rivetting constructions rather than welding and are particularly liable to damage by caustic alkali solutions. sodium hexa meta phosphate when added to boiler water. which can be easily removed or (ii) convert the impurities to soluble compounds. Important internal treatments involve. which can be easily removed by blow-down operations in low pressure boilers. In steam boiler operation. Caustic Embrittlement Embrittlement is the name that has been given to boiler failures due to development of certain types of crack resulting from excessive stress and chemical attack. which prevent scale formation. 2CaSO4 + [Na4P6O8]2– → [Ca2P6O18]2– + 2Na2SO4 (e) Sodium aluminate conditioning: Sodium aluminate is hydrolysed yielding NaOH and gelatinous Al(OH)3. (d) Calgon conditioning: Calgon i. ( g) Radioactive conditioning: Tablets of radioactive salts placed inside a boiler emit radiations. rivets to lead to the boiler failure. the chemicals that are believed to be responsible are NaOH and silica. joints. Na2HPO4 and Na3PO4 are added to high pressure boilers to react with the hardness forming impurities to form soft sludge of calcium and magnesium phosphates and finally this can be removed by blow down operation. During softening processes. There are also some methods for the prevention of scale formation by internal or external treatment.

desorption. whereby the deposition of Na2SO4 prevents the penetration of NaOH into the cracks and stops caustic embrittlement in high pressure boilers. (ii) Chemical treatment–oxygen concentration is virtually made zero by using reducing agents like hydrazine. sodium sulfite etc. joints etc.01 ppm.2H2O] Dissolved oxygen can be removed by: (i) Mechanical deaeration methods using distillation. (iii) Ion exchange techniques also reduce oxygen concentration to very low level. also prevents cracking similar to sodium sulfate in low pressure boilers. (c) Mineral acids: Water from industrial areas contains acidic wastes or inorganic salts which on hydrolysis produce acids. MgCl2 + 2H2O → Mg(OH)2 + 2HCl Fe + 2HCl → FeCl2 + H2 FeCl2 + 2H2O → Fe(OH)2 ↓ + 2HCl . Concentrated NaOH Solution Dilute NaOH Solution Fe at – plane Surfaces Prevention of Caustic Embrittlement (i) Addition of sodium phosphate as softening agent instead of Na2CO3. These acids cause corrosion in boilers. querbracho etc.5. higher the dissolved O2 content.WATER TREATMENT 355 Concentration cell develops between the boiler and the NaOH of different concentrations as + Fe at rivets. lignin. Corrosion in Boilers Boiler corrosion occurs by chemical or electrochemical attack of the contents of water. (iii) Heating. (iv) Use of crack-resisting steels: Certain steels containing Al added during manufacture appear to be resistant against caustic cracking. (ii) Addition of sodium sulfate to ensure a weight ratio Na2SO4/NaOH > 2. (b) Dissolved CO2: Water contains some CO2 and the decomposition product of bicarbonates present in water also produces CO2. The acids react with iron in chain reactions producing acids again and again and also produce H2 causing hydrogen embrittlement which leads to boiler failure. 2Fe + 2H2O + O2 → 2Fe(OH)2 ↓ 4Fe(OH)2 ↓ + O2 → 2[Fe2O3. (ii) Adding lime or NH3. which reduce O2 concentration to about 0. flashtype deaeration. Fe + CO2 + H2O → FeCO3 + H2 4FeCO3 + O2 + 10H2O → 4Fe(OH)3 + 4H2O + 4CO2 4Fe(OH)3 → 2Fe2O3 + 6H2O Removal of CO2 is done by: (i) Mechanical deaeration. As the water is heated in the boiler the dissolved oxygen is liberated and iron is corroded. Greater the pressure. This CO2 dissolves in water forming carbonic acid which causes local corrosion called pitting. steam scrubbing. (iii) Addition of organic agents like tannin. Main types are of chemicals: (a) Dissolved oxygen: Oxygen is dissolved in water to the extent of 8 ml/l at room temperature and it is responsible for corrosion in the boiler.

(iii) Dissolved impurities • Temporary hardness is due to Ca(HCO3)2 and Mg(HCO3)2 and can be removed by boiling. Actual height of the water column cannot be judged due to foaming hence creating difficulty in the maintenance. For the removal of temporary hardness the reactions are: Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓ + 2H2O Mg(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓ + MgCO3 + 2H2O MgCO3 + Ca(OH)2 → Mg(OH)2 ↓ + CaCO3 ↓ Hence. Foaming can be reduced by (i) removing oil from boiler-feed water and (ii) adding antifoaming agents. Lime-soda process. Cold and hot lime-soda process. • Hard water cannot be used for steam generation in boilers due to the problems like scale and sludge formation. • Hardness expressed in equivalent amount of CaCO3 Mass of hardness producing substances × 50 = Chemical equivalent of hardness producing substances • 1 ppm hardness ≡ 1 part of CaCO3 equivalent hardness in 106 parts of water. (ii) avoiding rapid change in steam rate. • Impurities present in water: (i) Suspended. boiler corrosion and failure. Softening of water means the removal of calcium. This wet-steam formation is called priming. Priming and Foaming Softening of Water . Priming can be controlled by (i) maintaining low water level in boiler. (ii) high steam velocities. The insoluble precipitates of CaCO3 and Mg(OH)2 are removed by filtration. Ion-exchange or demineralization process. Foaming is the production of bubbles and foams which do not break easily. which would form insoluble metallic soaps. soluble calcium and magnesium salts are rendered insoluble by adding calculated amount of lime [(CaOH)2] and soda [Na2CO3]. Priming occurs due to (i) presence of large amount of dissolved solids.356 ENGINEERING CHEMISTRY During rapid steam production. By this method. rainwater. Foaming occurs due to the presence of oil in the water. The three important industrial methods employed for softening of water are: 1. priming and foaming. to remove equivalent quantities of Ca and Mg hardnesses the amount of lime necessary is in the ratio of 1:2. By this process. 2. Highlights: • Chief sources of water: Sea water. some liquid water drops are also carried along with the steam. both temporary and permanent hardness are removed. Priming and foaming occur together and they are undesirable since they wet other mechanical parts of the boiler and reduce their efficiency. 1. • Permanent hardness is due to chlorides and sulfates of Ca2+. (iii) sudden boiling and (iv) sudden increase in steam production. iron salts and similar other metallic ions. (iii) softening of boiler water and (iv) using mechanical device for steam purification. 3. (ii) Colloidal. ground water and surface water. Fe2+ and other heavy metals. Permutit or zeolite process. magnesium. Mg2+.

for softening of cooling water etc. calculated quantity of chemicals and water. alum etc. along with accelerators and coagulators are added to a tank fitted with a stirrer (Fig. So calculated quantities of lime and soda are to be added after the determination of actual hardness. 17. Motor Chemicals (soda + lime + coagulant) feed inlet Driving belt Raw water feed inlet Filtered softened water outlet Wood-fibre filter Stirrer paddles Outer chamber Inner chamber Stirrer Sedimented sludge [CaCO3. sludge of the previous operation is added.1 Continuous cold lime-soda softener. but it is necessary for Mg salts. Cold lime soda process is used for partial softening of municipal water. In the actual process the water is thoroughly mixed with the chemicals and allowed to react for sufficient time. Extra addition of Ca(OH)2 causes hardness. After softening the soft water rises upwards and the heavy sludges settle down. In actual purpose. lime is not necessary. Cold Lime-Soda Process In this method. Mg(OH)2] Sludge outlet Fig. which supplies the nuclei for the precipitation. magnesium hardness is brought down to almost zero but calcium hardness remains about 40 ppm. thorough mixing takes place. The reactions are: CaSO4 + Na2CO3 → CaCO3 ↓ + Na2SO4 MgSO4 + Na2CO3 → MgCO3 + Na2SO4 MgCO3 + Ca(OH)2 → Mg(OH)2 ↓ + CaCO3 ↓ Hence.1). for the removal of permanent hardness due to Ca-salts. To avoid after-precipitation of CaCO3. 17. On vigorous stirring. The softened water passes through a filtering media ensuring complete removal of the sludge and finally the filtered water flows out through the top. .WATER TREATMENT 357 Again for the removal of permanent hardness. are added as coagulants. Activated charcoal is added as activator.

The soft water from this process is used for feeding the boilers (Fig. 17. no coagulant is needed. the sludge settles rapidly. (ii) Due to residual hardness. which reduces the content of pathogenic bacteria. . water is not suitable for high pressure boiler. Advantages Include: (i) Lime soda process is economical. (iv) pH of the water rises. Raw water feed inlet (i) (ii) (iii) (iv) (v) (vi) (vii) Super heated steam inlet Chemicals (lime + soda) feed inlet Softened water Fine sand layer Reaction tank Conical sedimentation tank Precipitated sludge [CaCO3. Mg(OH)2] Coarse sand layer Sand filter Gravels layer Precipitated sludge outlet Filtered softened water outlet Fig. the reaction takes place faster. Hot lime-soda process consists of three parts: (a) ‘Reaction tank’ in which complete mixing of the ingredients takes place. (b) ‘Ionical sedimentation vessel’ where the sludge settles down and (c) ‘Sand filter’ where sludge is completely removed. (ii) The process improves the corrosion resistance of the water. As the reaction takes place at high temperature.2). Here the chemicals alongwith the water are heated near about the boiling point of water by exhaust steam. Disadvantages Include: (i) Huge amount of sludge is formed and disposal is difficult. (iii) Mineral content of the water is reduced. there are the following advantages: the precipitation reaction becomes almost complete. viscosity of soft water is lower. Residual hardness is low compared to the cold process. dissolved gases (which may cause corrosion) are removed. 17.2 Continuous hot lime-soda softener. hence filtered easily.358 ENGINEERING CHEMISTRY Hot Lime-Soda Process This process is similar to the cold lime-soda process.

Common zeolite is Na2O Al2O3. These are porous and glassy and have greater softening capacity than green sand.. Hard water in Top distributor Injector Zeolite sand Gravel Soft water out Salt storage Waste Fig. Others gluconites. 17.yH2O. green sand etc.e. (v) Easy to regenerate. Disadvantages. Artificial zeolite used for softening purpose is permutit. the hardness causing cations i. (iii) It requires less time for softening. hence the process is clean. (i) Coloured water or water containing suspended impurities cannot be used before filtration. are used for water softening. feldspar and soda ash.xSiO2.WATER TREATMENT 359 Permutit or Zeolite Process Zeolite is hydrated sodium alumino silicate capable of exchanging reversibly its sodium ions for Ca2+ and Mg2+. The water softened by this process can be used for laundry purposes. Advantages. CaZe or MgZe + 2NaCl = Na2Ze + CaCl2 (Or MgCl2) The washings containing CaCl2 or MgCl2 are wasted.Al2O3. (ii) Water containing acid cannot be used for softening since acid may .2H2O and is known as natrolith. They are prepared by heating together with china clay. having the general formula Na2O. Ca2+ and Mg2+ are exchanged for Na and it is converted to CaZe and MgZe. (ii) The equipment used is small and easy to handle. (i) Hardness of water can be removed completely upto about 10 ppm.3 Softening of hard water by permutit process. (vi) Any hardness can be removed without any adjustment of the process.3SiO2. Reactions taking place are: Na2Ze + Ca(HCO3)2 = 2Na HCO3 + CaZe Na2Ze + Mg(HCO3)2 = 2NaHCO3 + MgZe Na2Ze + CaSO4 = Na2SO4 + CaZe Na2Ze + CaCl2 = 2NaCl + CaZe Regeneration of Zeolite: The process is also commercially successful since the Ca/Mg zeolites formed by passing hard water through the bed can be easily regenerated into Na2Ze by passing brine through the bed of inactivated zeolite. Method of Softening: Hardwater is passed through a bed of zeolite at a specific rate at ordinary temperature. (iv) There is no sludge formation.

CH2¾CH¾¾CH2¾¾CH¾¾CH2¾¾CH¾CH2 CH2NMe+OH 2 – CH2NMe+ OH 2 CH2¾CH¾CH2¾CH----CH2 – ----CH2----CH CH2NMe+ OH 2 – CH2NMe+ OH 2 – Anion exchange resin Method: The hard water is passed first through cation exchange resin similar to the permutit process whereby the cations like Ca2+. Ca2+ and Mg2+. which causes corrosion in the boilers and hence this soft water is not suitable for boilers. Cl– etc. this on heating liberates CO2. The resin on treatment with NaOH solution is capable of exchanging the OH– with different anions of water i.e. (i) Cation exchange resins (RH+) are phenol-sulfonic acid-formaldehyde resin. (iii) Since on removal of Ca2+ and Mg2+ the soft water contains large amount of NaHCO3.360 ENGINEERING CHEMISTRY destroy the zeolite.e. . present in the water with OH– ROH– + Cl– → R+Cl– + OH– These H+ and OH– combine to form water molecule. styrenedivinyl benzene copolymers which exchange their H+ ions with the cations present in the water i.. SO42– etc. which exchanges all the anions like SO42–. Mg2+ are removed from the hard water and exchanged with H+ as follows: 2RH+ + Ca2+/Mg2+ → R2Ca2+/R2Mg2+ + 2H+ After this the hard water is again passed through anion exchange column. Cl–. Ion Exchange or Demineralization Ion exchange resins are organic polymers which are crosslinked having microporous structure and the functional groups are attached to the chains which are responsible for the ion exchange properties.. ¾CH¾CH2¾¾CH¾CH2¾ SO3H SO3H n cation exchange resin (ii) Anion exchange resins (ROH–): The styrene divinyl benzene or amine formaldehyde copolymers contain quaternary ammonium tertiary sulphonium or amino group in the resin. Thus the water coming out finally from the two exchangers is ion free and called deioinized or demineralized water.

17. .M .WATER TREATMENT 361 Injector Cation exchanger gravel Pump Anion exchanger gravel Injector Waste Acid regenerator liquor Waste liquor Alkaline regenerator Fig.5 Demineralisation of water showing the ion exchanges. W ate r HO–H H–N–C H HOH – – C C–N–H C H–OH H C–N–H C OH C C H + SO4 –– H–N–C H H H H C O O C Na O O C ++ O Ca O C O + H–OH OH H C–N–H Cl – H–N–C C SO4 –– –– H C SO4 H C–N–H H–N–C –– C H H H SO4 H C C–N–H C H–Cl –1 H–N–C H C – SO4 Hard water Cation exchange reaction: 2R H + Ca – + +2 –– H + Anion exchange reaction: CaR2 + 2H + + RNH2 + H2O – – RNH3OH + – + – – RNH3OH + Cl RNH3Cl + OH Fig. 17.4 Demineralisation of water. H + H Cation exchange + H C C C C Filter bed C C C C C C C C ONa+ Cl – + Anion exchange O C OH O C O Ca O C O O C O H HO C O HO + C C C C C C C C C C C Cl H + C Cl – H D.

• • • • • • • . • Coagulants or flocculants are generally added in the form of solution and mixing is carried out by stirring. Hence. • Settling in a large tank to remove suspended impurities. • The gelatinous precipitates mainly contain aluminium hydroxide.362 ENGINEERING CHEMISTRY Regeneration: The inactivated or exhausted cation exchange resin is regenerated by dil. Lastly. Natural water from river. it is actually equivalent to a series of cation and aninon exchangers. pH should be about 8. Al2(SO4)3. R2Ca2+ + 2H+ → 2RH+ + Ca2+ Similarly. lakes. • These partially clarified water is filtered through sand gravity filters. It should be devoid of heavy metals and arsenic. which is suitable for drinking and it must satisfy the following requirements: Requirements for Drinking Water: It should be clear and odourless. Advantages of ion exchangers include (i) Easy regeneration. canals are treated for the domestic purpose. • Sedimentation through coagulation of the colloidal particles by adding a suitable coagulant. Thus. Suspended matter should not exceed 10 ppm. Chemical coagulants are generally (i) Alum [K2SO4. H2SO4/HCl. It should be devoid of any unpleasant taste. Content of dissolved salts should not exceed 500 ppm.7H2O]. it should be free from pathogenic (disease causing) microorganisms. ferrous and ferric hydroxides (ferrous hydroxides are converted to ferric hydroxide by the dissolved oxygen of water). the exhausted anion exchange resin is regenerated by dil. NaOH R2SO42– + 2OH– → 2ROH– + SO42+ The columns are finally washed with deionized water and the washings are discarded. • These heavy flocculant precipitates contain also some bacteria making the water free of some of the microorganisms. Mixed Bed Deionizer It is actually a single cylinder containing and intimate mixture of cation exchanger and strongly basic anion exchanger. (iii) residual hardness is very low and hence the water is suitable for high pressure boilers also. The steps are as follows: • Aeration of the raw water by passing compressed air to remove mainly the obnoxious odour and iron as Fe(OH)3. Treatment of Water for Domestic Use Municipalities supply potable water. (ii) both acidic and alkaline water can be softened.24H2O] (ii) Green vitriol [FeSO4. It needs prior filtration. water while passing through the column comes in contact with the two exchangers for a large number of times and the hardness is reduced to a very low level (1 ppm). Disadvantages are (i) the equipment and the process is costly and (ii) turbid water cannot be directly charged for softening.

5. Here also HOCl is liberated. Cl2 + NH3 → Cl.5 meter thick. Sterilization (i) By addition of bleaching powder (1 kg per 1000 kiloliters). The treated water should contain chlorine less than 0. Excess chlorine imparts unpleasant taste and odour to the treated water. Cl. Disadvantages. This is due to the consumption of chlorine in oxidising some oxidisable organic matter present in water at first. • It prevents the growth of weed in water in future. (ii) By direct chlorination: Here also the generated HOCl kills the pathogenic bacteria.NH2 + HCl Chloramine is much more effective than chlorine in its bactericidal (bacteria killing) action.3-0. Disadvantages of this process: (i) Bleaching powder makes water unnecessary hard and sometimes imparts a bad taste to the water. Advantages of break point chlorination • Organic matters present in water are completely oxidised leaving behind odour-free water and sometimes colour-free water. Advantage of using Chlorine.2 ppm. Then available chlorine again increases due to decomposition of chloro-organic compounds.WATER TREATMENT 363 • These filters are rectangular tanks. at middle of coarse sand of 0. This free chlorine is responsible for destruction of pathogenic bacteria in water. The point at which the residual chlorine begins to appear is known as break point and at this point water is devoid of bad taste and odours and is bacteria free. (iii) Sterilization by Chloramine When chlorine and ammonia are mixed in the ratio 2:1 of volume chloramine is formed. Dissolved chlorine causes irritation to mucus membrane and lowers the pH of water below 6. . (ii) Break-point Chlorination It is seen that when liquid chlorine is added or chlorine gas is passed through water the consumption of chlorine makes the available chlorine less and after some time the available chlorine increases. 0.5 ppm chlorine is sufficient. Here sterilization is effected by the HOCl generated by the following reaction: Ca(OCl)Cl + H2O → Ca(OH)2 + Cl2 Cl2 + H2O → HCl + HOCl and this HOCl kills the germs.5 meter thick and at bottom a gravel of 0.NH2 + H2O → HOCl + NH3 HOCl itself is bactericidal and here the liberated nascent oxygen is also bactericidal HOCl → HCl + [O]. chlorine does not make water hard and requires a little space for storage. It is effective and economical. which contain layers of fine sand at the top of one meter thick. Liquid chlorine is the most effective reagent. • Pathogenic bacteria are destroyed completely.

364

ENGINEERING CHEMISTRY

The use of chloramine for sterilization is gaining importance as it does not impart any irritating odour and does not affect the taste of the treated water. (iv) Sterilization by Ozonization Ozone is an unstable gas and decomposes to give nascent oxygen. This nascent oxygen kills bacteria and oxidises the organic matter present in the water. The ozone treatment plant consists of a tower made of enamelled iron, separated by perforated celluloid partition into a large number of compartments, ozone is passed through bottom and the water is allowed to percolate through the celluloid partition. The perforated partition makes the water into minute bubbles resulting in a counter-current contact with ozone. This makes the treatment most effective. Advantages of ozone sterilization are (a) Sterilization, bleaching, decolourisation and deodourisation take place at the same time. (b) Ozone does not impart any unpleasant taste or odour to the treated water and does not change its pH appreciably as it simply decomposes into oxygen. So it does not cause any irritation to the mucus membrane as is the case with chlorine or bleaching powder treatment. (c) Time of contact is only 10-15 minutes and dose strength is only 2-3 ppm. The only disadvantage of this process is that it is comparatively costly. Sterilization through Physical Methods (i) Boiling, (ii) Exposure to the sunlight, (iii) Sterilization with UV light.

Dechlorination
When during chlorination, break point chlorination is reached, it becomes sometimes necessary to remove the excess chlorine from the treated water, this process is known as dechlorination. Sulphur dioxide is very common as an antichlor. Other common antichlors are: sodium bisulphite, sodium thiosulphate and hydrogen peroxide. Cl2 + H2O = HOCl + HCl H2O + SO2 = H2SO3 HOCl + H2SO3 = HCl + H2SO4 SO2 + Cl2 + 2H2O = 2HCl + H2SO4 H2O2 + Cl2 = 2HCl + O2↑

Dechlorination is needed to avoid the harmful effects of treated water.

Desalination of Brackish Water
The water containing dissolved salts and having very salty taste is called brackish water, like the sea water and it is not suitable for drinking. The process of removal of common salt from this brackish water is called desalination. Desalination can be done by the following methods. (a) Electrodialysis. This method involves the removal of ions from the brine solution by applying direct current and employing pair of plastic membranes through which ions can pass. From Fig. 17.6 we can find that when direct current is passed through saline water, the Na+ ions move towards the cathode while Cl– ions move towards the anode through the membrane and collect in the two side compartments while the central compartment contains pure desalinated water.

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365
Sea water – Sea water Sea water + Anode

Cathode

Negative ions Positive ions

Membrane

Membrane

Concentrated brine

Pure water

Concentrated brine

Fig. 17.6 Line diagram of electrodialysis.

To make this process more effective, ions sensitive membranes are used that allow the passage of either specific cations or specific anions. These membranes are selective as they are made up of materials containing fixed functional groups. An electrodialysis cell as shown in Fig. 17.7 contains a large number of pair of membranes and saline water is passed under pressure in electric field applied perpendicular to the direction of flowing water. Cations and anions pass through the membrane pairs and we obtain alternate streams of pure water and concentrated salt solution.
Sea water feed

Cation selective membrane

C

A

C

A

C

A

Anion selective membrane

Cathode

Anode

C Pure water outlet Concentrated sea water outlet

A

C

A

C

A

Fig. 17.7 Electrodialysis cell.

366

ENGINEERING CHEMISTRY

(b) Reverse osmosis. Osmosis describes the flow of solvent from dilute to concentrated solution through a semipermeable membrane. Whereas Pressure reverse osmosis describes the flow of solvent in opposite direction i.e., from concentrated solution to dilute solution across a semipermeable membrane by applying hydrostatic pressure in excess of osmotic pressure. The cellulose acetate and the more recently used polymethacrylate and polyamide membranes do not allow the solute pass, while the solvent is forced through and Sea water Stout semicollected as a pure solvent in a direction as shown in permeable membrane Fig. 17.8. There are many advantages of using reverse osmosis as the purification process for water which include (i) removal of ionic, non-ionic, colloidal and high Pure water Pure molecular weight solutes from water, (ii) regeneration of water out the process involves the easy replacement of the semipermeable membrane, (iii) easy maintenance and Fig. 17.8 Reverse osmosis cell. economical, as the membrane lifespan is high, (iv) uninterrupted supply of large volume of water for industrial or domestic purpose can be obtained. Reverse osmosis is largely used for purification of sea water for domestic use.
Piston

Chemical Analysis of Water
1. Estimation of free chlorine. The residual free chlorine remaining after the municipal processing of domestic water is injurious to health and hence estimation of this free chlorine is essential. The principle is the treatment of water containing free chlorine with KI solution. The chlorine present liberates an equivalent amount of iodine which can be estimated with standard thiosulfate solution using starch as an indicator. Cl2 + 2KI → 2KCl + I2 I2 + 2Na2S2O3 → 2NaI + Na2S4O6 I2 + Starch → Deep-blue complex Method: To 50 ml of water sample in a iodine flask, 10 ml of 10% KI solution added, shaken and waited for some time in the dark and finally titrated with N/50 sodium thiosulfate solution using starch solution as indicator towards the end. The end point indicates a change from deep-blue to just colorless solution. Calculation: Volume of N/50 Na2S2O3 required = V ml ∴ Strength of free chlorine =

V × 35.5 × 10 6 ppm. 2500 × 1000

2. Alkalinity. The alkalinity of water is estimated by estimating (a) OH– and CO32– ions – and (b) HCO3 ions. (a) OH– + H+ → H2O – CO32–+ H+ → HCO3 – (b) HCO3 + H+ → H2O + CO2

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367

These estimations are done by (a) titrating against standard acid solution using phenolphthalein as an indicator and (b) using methyl orange as an indicator. Method: 100 ml of water sample is taken in a flask and few drops of phenolphthalein added and titrated against N/50 H2SO4 solution to colorless end point. The same solution is further titrated with 2 to 3 drops of methyl orange indicator. Calculation: Vol. of acid upto phenolphthalein end point = V1 Extra volume of acid added to get methyl orange end point → V2 ml. ∴ Phenolphthalein alkalinity (equivalent CaCO3)

V1 × 50 × 10 6 ppm 50 × 100 × 1000 Methyl orange alkalinity (equivalent CaCO3)
P= M= 3. Hardness (a) Estimation of temporary hardness. Temporary hardness is due to Ca(HCO3)2 and Mg(HCO3)2 which cause alkalinity in water. Temporary hardness is determined by finding the alkalinity of water before and after boiling, since temporary hardness is removed on boiling. Ca(HCO3)2 → CaCO3 + CO2 + H2O Mg(HCO3)2 → Mg(OH)2 + CO2 Method: Into 50 ml of water sample taken in a conical flask, add 2 to 3 drops of methyl orange and titrate with N/50 HCl. Let the volume of acid be V1. Now take 100 ml of water sample in a beaker, evaporate to dryness. Add 100 ml of distilled water to the beaker and dissolve the residue left. Then, take 50 ml of this water sample and titrate with N/50 HCl using a few drops of methyl orange as an indicator. Let the volume of acid required be V2 ml. ∴ alkalinity due to temporary hardness in CaCO3 equivalent
Boiling

(V1 + V2 ) × 50 × 106 ppm. 50 × 100 × 1000

(V1 − V2 ) × 10 6 ppm 50 × 1000 (b) (i) Determination of permanent hardness. The estimation is done by adding excess of standard Na2CO3 solution to a given volume of boiled water containing permanent hardness. The chlorides and sulfates form insoluble carbonates. The residual Na2CO3 is titrated against standard acid and the difference of Na2CO3 equivalent gives permanent hardness. Method: 50 ml of the water sample is taken in a beaker. 50 ml of N/50 Na2CO3 solution is added and boiled for 15 minutes. Cool and filter the solution, wash the residue on filter paper and add it to the filtrate and titrate the N/50 Na2CO3 left in the flask with N/50 HCl using methyl orange as indicator. Let titre vol. be V.
= ∴ Permanent hardness =

(50 − V) × 10 6 ppm. 50 × 1000

(ii) Complexometric determination of permanent hardness. Disodium salt of ethylene diamine tetra acetic acid (EDTA) is used as a complexing agent for Ca2+, Mg2+.

OOC · CH2 OOC · CH2

CH2COO N¾CH2¾CH2¾N CH2COO

368

ENGINEERING CHEMISTRY

Erichrome black T is used as an indicator and pH is maintained at pH 10 using NH4OH/ NH4Cl buffer. Erichrome black T forms unstable complex with Ca2+, Mg2+ giving wine red colour. When EDTA added and the total Ca2+, Mg2+ forms complex with it and the indicator becomes free, the colour of the solution changes from wine red to blue at the end point. Method: Indicator solution 0.5 gm. Erichrome black T dissolved in 100 ml alcohol. Standard EDTA solution (N/100): 4 gm of EDTA dissolved with 0.1 gm of MgCl2 in 1000 ml water.

M Zinc acetate solution (primary standard) is taken, to it 5 ml of NH4Cl– 100 NH4OH buffer and a few drops of EBT indicator are added and titrated to blue end point with EDTA and the strength of EDTA is calculated. This same procedure is repeated with 50 ml water sample. Let the volume of titrant be V ≈ (f) M/100 EDTA solution.
An aliquot ≈

0.001 × V × f × 106 ppm. 50 The EDTA method for the determination is preferred to other methods since the method has greater accuracy, simplicity and rapidness. Buffer solution: A mixture of 142 ml of conc. NH4OH and 17.5 gm NH4Cl is diluted to 250 ml distilled water.
∴ Permanent hardness = Highlights: • Softening methods include: (i) Hot and cold lime soda process. (ii) Zeolite or permutit process. (iii) Ion exchange or demineralization. • Micro-organisms from potable water can be removed by: (i) Boiling for 10 to 15 minutes (ii) Bleaching powder treatment (iii) Chlorination with Cl2 (iv) Chloramine treatment (v) Ozonization. • Desalination of brackish water done by: (i) Electrodialysis (ii) Reverse osmosis. • Exhausted ion-exchange resins are regenerated by: (i) Cation exchangers regenerated by passing strong acid solution through the bed (ii) Anion exchangers regenerated by passing strong base solution through the bed. • Hardness of water can be estimated by: (i) Permanent hardness determined by titrating with standard Na2CO3 solution. (ii) Complexometric titration by EDTA • Units of hardness are: (i) ppm (ii) mg/litre (1 ppm = 1 mg/litre) (iii) Clark’s degree (1 ppm = 0.07° Cl) (iv) degree French (1 ppm = 0.1° Fr). (Contd.)

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369

• Hard water does not easily lather with soap, instead it forms a greasy scum. • Water is hard if it contains calcium or magnesium ions. • Scum is a precipitate formed when soap comes in contact with hard water containing above mentioned ions.
– Ca2+(aq) + C17H35CO2 (aq) → Ca(C17H35CO2)2 ↓

insoluble precipitate

• Temporary hard water contains bicarbonates or hydrogen carbonates of calcium or magnesium. • Temporary hardness is removed by boiling. Ca(HCO3)2(aq) → CaCO3 ↓ + H2O(l) + CO2↑.
boiling ∆

• The solid calcium carbonate is precipitated as scale, which affects heating element of boilers and gradually blocks the pipes in heating system. • Permanent hardness is not removed by boiling. • The mineral gypsum (CaSO4) is slightly soluble in water and makes water permanently hard. • Ion exchange resin and other methods of softening of water by removing calcium and magnesium ions is known as water treatment.

PROBLEMS
Problem 1. Calculate temporary hardness and total hardness of a sample of water containing: Mg(HCO3 )2 = 7.5 mg/l . Ca(HCO3 ) 2 = 16 mg/l MgCl2 = 9 mg/l . CaSO4 = 13.6 mg/l

Sol. Temporary hardness = 7.5 ×

L 100 + 16 × 100 OP mg/l M 146 162 Q N L 100 + 13.6 × 100 OP mg/l. Permanent hardness = M9 × 136 Q N 95
(56 + 16 + 64)g of FeSO4 ≡ 100 g CaCO3

Problem 2. How many mg. of FeSO4 dissolved per litre gives 200 ppm of hardness? Sol. For 100 ppm hardness FeSO4 required per 106 parts of water is 136 parts. ∴ For 200 ppm hardness, FeSO4 required =

136 × 200 ppm 100

= 272 mg/l.
2− Problem 3. A sample of water has a CO3 concentration of 15.6 ppm. What is the molarity 2− of CO3 in the sample of water?

370 Sol. ∴ 15.6 ppm = 15.6 × 10–6 g/l of CO 2− 3 CO32– molarity =
15.6 × 10 −6 mol/l. 60

ENGINEERING CHEMISTRY

= 2.6 × 10–5 M. Problem 4. A sample of water has been found to contain the following salts: Ca(HCO3)2 = 10.5 ppm; Mg(HCO3)2 = 12.5 ppm; CaCl2 = 8.2 ppm; MgSO4 = 2.6 ppm; CaSO4 = 7.5 ppm.

M EDTA required 100 for titration of the 100 ml of the sample to determine the total hardness of the sample.
Calculate (i) temporary and permanent hardness and (ii) the vol. of Sol. (i) Ca(HCO3)2 = 10.5 ppm = 10.5 × Mg(HCO3) = 12.5 ppm = 12.5 × CaCl2 = 8.2 ppm = 8.2 ×

100 = 6.481 ppm CaCO3 162 100 = 8.562 ppm CaCO3 146

100 = 7.387 ppm CaCO3 111 100 MgSO4 = 2.6 ppm = 2.6 × = 2.167 ppm CaCO3 120 100 = 5.515 ppm CaCO3 136 ∴ Temporary hardness = (6.481 + 8.562) ppm
CaSO4 = 7.5 ppm = 7.5 × = 15.043 ppm Permanent hardness ∴ Total hardness = (7.387 + 2.167 + 5.15) ppm = 15.069 ppm = (15.043 + 15.069) = 30.112 ppm

(ii) The volume of sample taken = 100 ml.

30.112 × 100 = 3.11 ml. 1000 Problem 5. Calculate the amount of lime and soda required for softening 50,000 litres of hard water containing
∴ Volume of M/100 EDTA required = MgCO3 = 144 ppm; CaCl2 = 111 ppm; CaCO3 = 25 ppm; Fe2O3 = 25 ppm; MgCl2 = 95 ppm; Na2SO4 = 15 ppm.

Sol. MgCO3 = 144 ppm = 144 × CaCO3 = 25 ppm. MgCl2 = 95 ppm = CaCl2 = 111 ppm =

100 = 171.4 ppm CaCO3 84

95 × 100 = 100 ppm CaCO3 95 111 × 100 = 100 ppm CaCO3 111

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371

∴ Lime required = =

74 [2 × MgCO3 + CaCO3 + MgCl2] × volume of water 100

74 [2 × 171.4 + 2500 + 100.0] × 50,000 mg 100 = 17,309,000 mg = 17.31 kg. Problem 6. A water sample on analysis gives the following data : Ca2+ = 20 ppm, Mg2+ = 25 ppm, CO2 = 30 ppm, HCO3– = 150 ppm, K+ = 10 ppm. Calculate the lime (87% pure) and soda (91% pure) required to soften 1 million litres of water sample.
Sol. Ca2+ = 20 ppm = Mg2+ = 25 ppm =

20 × 100 = 50 ppm CaCO3 40

25 × 100 = 104.65 ppm CaCO3 24 30 × 100 CO2 = 30 ppm = = 68.18 ppm CaCO3 44 150 × 100 = 122.95 ppm CaCO3 122

HCO3– = 150 ppm = ∴ Lime requirement = =

74 [Mg2+ + CO2 + HCO3– ] × vol. of water 100

74 [104.65 + 68.18 + 122.95] × 106 100 = 218.9 × 106 mg = 218.9 kg.
=

Soda requirement

106 Ca 2+ + Mg 2 + − HCO3 − × vol. of water. 100

106 [50 + 104.65 − 122.95] × 10 6 100 = 33.6 × 106 mg = 33.6 kg. Problem 7. An exhausted zeolite softener was regenerated by passing 150 litres of NaCl sol. having a strength of 150 g/l of NaCl. If the hardness of water is 600 ppm, calculate the total volume of water that has been softened in the softener.
= Sol. 150 litres of NaCl solution contain = 150 × 150 = 22,500 gm NaCl = 22,500 × If the hardness of water is 600 ppm ∴

100 CaCO3 117 = 1.932 × 104 g CaCO3

Vol. of water =

Problem 8. 10 ml of 0.85

standardization. 50 ml of a water sample required 20 ml of the above EDTA solution. Calculate the total hardness of water in ppm.

FG M IJ H 100 K

1.932 × 10 4 × 1000 litres 600 = 3.129 × 104 litres

Zn (OAC)2 required mol of an EDTA solution for

372 Sol. Strength of EDTA solution = 1000. ml ∴
M 10 × 0.85 = 0.94 100 9
3

ENGINEERING CHEMISTRY

L M O EDTA solution ≡ 1 g CaCO M 100 P N Q F M IJ EDTA solution = 1 × 20 × 0.94 g CaCO 20 ml of G H 100 K 1000

FG IJ H K

3

= 0.019 g CaCO3.

∴ 50 ml of the water sample contains 0.019 g CaCO3 ∴ 106 ml of the water sample contains =
0.019 × 10 6 = 377.8 gm CaCO3 50

∴ Hardness of water = 377.8 ppm. Problem 9. A sample on water on analysis has been found to contain the following : Ca(HCO3)2 = 10.5 ppm. Mg (HCO3)2 = 12.5 ppm CaSO4 = 7.5 ppm CaCl2 = 8.2 ppm MgSO4 = 2.6 ppm.

Calculate the temporary and permanent hardness in degree French.

10.5 × 100 = 6.481 ppm 162 12.5 × 100 Mg(HCO3)2 = 12.5 ppm = = 8.562 ppm 146 7.5 × 100 CaSO4 = 7.5 ppm = = 5.515 ppm 136 8.2 × 100 CaCl2 = 8.2 ppm = = 7.387 ppm 111 2.6 × 100 = 2.167 ppm MgSO4 = 2.6 ppm = 120 ∴ Temporary hardness = (6.481 + 8.562) = 15.043 ppm = 15.043 × 0.1° Fr = 1.504° Fr Permanent hardness = (5.515 + 7.387 + 2.167) ppm = 15.069 ppm = 1.5069° Fr.
Sol. Ca(HCO3)2 = 10.5 ppm =

SHORT QUESTIONS AND ANSWERS
Q. 1. What is the need for “Desalination of water” programme? ? Ans. Virtually there is population explosion in the modern world. So for drinking, domestic and irrigation purposes river water and other sweet water sources seem to be insufficient. So for the exploitation of the vast source of sea water, desalination programme is required, specially in the sea-side area. Q. 2. What are the causes of corrosion of boilers? ? Ans. The causes of corrosion are: • Oxygen corrosion if boiler water is not properly deaerated.

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• Electrochemical corrosion, also known as out of service corrosion, when boiler is shut down. ? Q. 3. What are the disadvantages of scale formation in a boiler? Ans. • Scales and sludges are bad conductors of heat, as a result fuel consumption increases. • Tubes and plates are clogged as a result the efficiency of the boiler is decreased. • Tubes of the boiler are corroded by the scales deposited and they may crack and lead to boiler failure. MgCl2 + Fe + H2O = Mg(OH)2 + FeCl2 + H2 Q. 4. Why is demineralisation preferred to zeolite softening? ? Ans. Demineralized water is practically free from all the ions whereas the zeolite softened water contains sodium salts which are sources of caustic embrittlement. ? Q. 5. Why is chloramine preferred to Cl2 for sterilization of drinking water? Ans. It is because chloramine does not impart any repulsive odour to the treated water. Q. 6. What are the criteria for drinking water? ?

Ans. It should be devoid of any suspending matter, and harmful dissolved matter of organic or inorganic matter and pathogenic organisms. ? Q. 7. Why is UV radiation superior to other methods of sterilization of water? Ans. UV radiation does not impart any unpleasant taste or odour to the water and the process is simple. Q. 8. What is pitting? Ans. Pitting is corrosion of the boiler. Dissolved gases like O2, CO2 , H2S corrode the iron surface of the boiler particularly near the rivet, bends and leads to leak or boiler failure. ? Q. 9. What are boiler compounds? Ans. When the boiler water is difficult to soften or purify, some chemical substances are added to the boiler water that makes the scale in the boiler loose and easily removable. These compounds are called boiler compounds and examples of these are flour, kerosene, tannin, agar-agar etc. Q. 10. What is plumbo solvancy? How can it be prevented? ? ? Ans. Water transported through lead pipes are contaminated with Pb2+ due to solubility of metallic lead in water. 2Pb + 2H2O + O2 = 2Pb(OH)2 The hydrolysis of Ca2+ and Mg2+ salts dissolved in water may lead to the formation of lead salts like PbSO4 and PbCl2. MgSO4 + 2H2O = Mg(OH)2 + H2SO4 MgCl2 + 2H2O = Mg(OH)2 + 2HCl 2Pb + H2SO4 + O2 = 2PbSO4 + 2H2O 2Pb + 4HCl + O2 = 2PbCl2 + 2H2O

These lead salts are somewhat soluble in water. This phenomenon is known as plumbo solvancy. The Pb2+ salts are poisonous and is the source of lead poisoning. Lead poisoning can be prevented by treatment of the water with alkali silicate and phosphate followed by filtration.

374 Q. 11. Differentiate between sludge and scale.

ENGINEERING CHEMISTRY

Ans. Sludge is soft, loose, slimy deposit formed inside the boiler, which is easier to remove, while scale is a hard, sticky, adherent deposit on the inner surface of the boiler which is difficult to remove. Q. 12. What is break-point chlorination? ? Ans. See text page 362. Q. 13. State the harmful effects of silica present in water. Ans. Presence of silica in the water leads to the formation of calcium and magnesium silicates and these silicates form sticky scales in the boiler which are very difficult to remove. Q. 14. What is the difference between hard water and soft water? ? Ans. See text page 350-355 Q. 15. Alkalinity of water cannot be due to the simultaneous presence of OH–, 2– and HCO –. Why? CO3 ? 3
– Ans. OH– and HCO3 ions react to form CO32– ions: OH– + HCO3– = CO32– + H2O. Q. 16. Why do we express hardness of water in terms of CaCO3 equivalent? ?

Ans. This mode permits easy addition and subtraction of concentration of hardnesscausing constituents, since its mol. wt. is 100. Moreover, it has also been adopted as standard for expressing hardness. Q. 17. What are the salts responsible for temporary and permanent hardness of water? ? Ans. Temporary hardness ⇒ Ca(HCO3)2 and Mg(HCO3)2 Permanent hardness ⇒ Chloride and sulphate of Ca2+ and Mg2+. Q. 18. Mention the units of hardness. Define them. Ans. (i) ppm, (ii) degree. ppm is defined as the parts of hardness salt present in 106 parts of water expressed in terms of calcium carbonate. Degree hardness is defined as the parts of hardness salt present in 105 parts of water expressed in terms of calcium carbonate. Q. 19. A water sample contains lithium chloride or zinc acetate as dissolved solids. Do you think that water will be hard? ? + and Zn2+ both form insoluble soaps. Ans. Yes, as Li Q. 20. Calculate the hardness of Ans. MgSO4 = CaCO3 120 g = 100 g
4

FG M IJ MgSO H 1000 K

4

solution.

FG M IJ MgSO H 1000 K

solution contains =

120 100 g, MgSO4 = CaCO3 in 1000 ml water. 1000 1000

0.1 × 106 = 100 ppm. 1000 0.1 Again, hardness in degree = × 105 = 10 1000
So, hardness in ppm

WATER TREATMENT

375

Q. 21. The presence of carbon dioxide is avoided in boiler feed water. Explain. Ans. Dissolved carbon dioxide forms carbonic acid and attacks boiler pipes and corrodes. Q. 22. Why does hard water consume a lot of soap? ? Ans. When hard water comes in contact with soap Ca2+ and Mg2+ ions react with soap and scum is formed when the reaction is overconsuming much of soap, lather is then formed. That is why hard water consumes a lot of soap. Q. 23. Why is calgon conditioning better than phosphate conditioning? ? Ans. Calgon conditioning forms soluble complex salt Na2[Na4(PO3)6] + CaSO4 = Na2[Na2 Ca(PO3)6] + Na2SO4
Calgon Soluble complex

whereas phosphate conditioning i.e., treatment with sodium phosphates, precipitates calcium and magnesium phosphates causing scale in boiler pipes. Q. 24. Why is water softened before using in boiler? ? Ans. Natural or hard water when fed in boiler produces scale, sludge and causes priming and foaming and boiler corrosion. That is why water is softened before using in boiler. Q. 25. Why is caustic embrittlement controlled by adding sodium sulphate to boiler-feed water? ? Ans. Sodium sulphate when used blocks hair cracks thus prevents infiltration of caustic soda through the cracks. Thus sodium sulphate prevents embrittlement in boilers. Q. 26. State two harmful effects of silica in water. Ans. Silica reacts with Ca2+ and Mg2+ ions forming calcium silicate and magnesium silicate in boiler. This type of scales are difficult to remove.

EXERCISES
1. 2. 3. 4. Explain the various steps for the purification of water for municipal supply. What is desalination? Name the different methods of desalination and describe any one. What are boiler troubles? Why are they caused? What are the methods of their elimination? Distinguish between: (a) Temporary and permanent hardness. (b) Sludge and Scale. (c) Softening and demineralization. 5. 6. 7. 8. 9. Write notes on: (i) Caustic embrittlement, (ii) Reverse osmosis, (iii) Priming and foaming, (iv) Hot lime-soda process, (v) Boiler corrosion. What is the principle involved in the determination of total hardness of water by EDTA method? What are the functions of lime and soda in hot lime-soda process? Give equations. Why coagulants are not used in hot lime-soda process? Why does hard water consume more soap? During deionization process, water is first passed through cation exchanger and then through anion exchanger, why?

10. Describe the methods of disinfection of water. Why is chloramine better than chlorine for sterilization of water?

. 9. 8. 15. 10. 19. (a) MgSiO3 A semipermeable membrane allows the flow of (a) Solute molecules (ii) Solvent molecules (b) Both solute and solvent molecules. 3. 4. 11. Hard water can be softened by passing through (a) Calgon (b) Sodium silicate (c) Ion exchange resin. What do you mean by caustic embrittlement? What measures can be taken to control the caustic embrittlement? What factors are responsible for boiler corrosion. The most ideal disinfectant in water works is (a) Chlorine (b) Bleaching powder (c) Chloramine. 7. 5. 18.376 ENGINEERING CHEMISTRY OBJECTIVE TYPE QUESTIONS 1. (a) What are scales? What are the ill-effects of scales? (b) How can scale formation be prevented by (i) Phosphate conditioning and (ii) Calgon conditioning? Distinguish between: (a) Purification and softening of water (b) Boiler scales and sludges (c) Internal and external treatment of water. 13. 17. 12. Write down the disadvantages associated with using of hard water. Calgon is the trade name of (a) Sodium hexametaphosphate (b) Sodium zeolite (c) Calcium silicate. Brackish water can be purified by (a) Reverse osmosis method (b) Lime-soda process (c) Calgon treatment. How can the factors can be eliminated? Describe the process of water softening by permutit process. 2. 14. 6. 16. Pure water can be obtained by (a) Lime-soda process (b) Boiling (c) Demineralization. A sample of water containing NaCl is (a) Hard water (b) Soft water (c) Pure water. Correlate the various units of the hardness. 20. 21. Write a short note with a proper sketch diagram on “reverse osmosis” process for desalination of brackish water. The chemical that gets dissolved in high pressure boilers (b) CaCO3 (c) CaSO4. Why treatment of water is essential? Write down the possible sources of water? Give reasons for why water becomes hard. Temporary hardness of water can be removed by (a) Filtration (b) Boiling (c) Coagulation Permanent hardness of water is caused by (a) Calcium chloride (b) Magnesium sulfate (c) Both.

10 ppm] A sample of hard water has a hardness of 510 ppm. 6.000 litres of a sample of hard water was completely removed by passing through a zeolite softener. 24. 6.WATER TREATMENT 377 22.07 ppm.110 of calcium oxalate (CaC2O4. Find the temporary and permanent hardness of the water sample. Write different methods of sterilization. [Ans. 64. 25.7° Clark and 51° French] 3. Calculate the hardness of the sample water. 26.4 grain. (c) Write short notes on aeration. FG N IJ Na CO solution is added to it = 20 cc. 5. 27.5 ppm] 4. 28. 1 g = 15. The bed on exhaustion required 500 litres of NaCl solution containing 15 g l–1 of NaCl on regeneration. the following results are obtained: Volume of sample water = 100 cc. [Ans. 15. 120 ppm] Analysis of a sample of water revealed the content of dissolved salts in the following data: Mg(HCO3)2 = 22 mg l–1 MgCl2 = 30 mg l–1 CaCl2 = 85 mg l–1 [Ans.07° Clark = 0. In an experiment for the determination of hardness of a sample of water. (a) What do you mean by carbonate and non-carbonate hardness of water? (b) State harmful effects of silica present in water. Given. What is desalination? Name the different methods involved in desalination? Describe any one in detail.H2O) was obtained from a 250 ml of water sample. Briefly describe the different steps involved in the treatment of water for domestic purpose. 2 3 2. Write short notes on break point chlorination. How free chlorine in water can be estimated? Write down the method for determination of alkalinity of water. [Ans. 31.99 grain of CaCO3] CaSO4 = 28 mg l–1. The hardness of 1. Express the content of calcium in ppm. [Ans. Express its hardness in °Clark and °French. H 50 K FG N IJ H SO required the back titre the unreacted Na CO H 50 K 2 4 2 3 = 10 cc. What are the methods involved for determination of temporary and permanent hardness of water? PROBLEMS 1. 200 ml of a sample of water required 5 ml of (N/20) sodium carbonate solution for complete precipitation of calcium ion (Ca2+) and calcium carbonate.1° French] [Ans. Calculate the hardness in ppm. A precipitate of 0. 29. Write down the requirements for drinking water. 62. 128.00. 23. Briefly discuss the process of softening of water by means of ion-exchange process. 30. 35. [Hints → 1 ppm = 0. From these data calculate the hardness of water in grains per gallon.75 ppm] .

200 per metric ton and that of soda of 90% purity is Rs. MgSO4 = 120 mg l–1. The cost of lime of 80% purity is Rs. Lime = 3. MgCl2 = 9. whose strength is equivalent of 1.000 per metric ton. Calculate the hardness of a water sample. Calculate the hardness of water. CaSO4 = 68 mg l–1.6 kg] mg l–1 as CaCO3. Soda = 5. [Ans. Mg(HCO3)2 = 73 mg l–1. 9.3 mg l–1.7 kg. Calculate the amounts of lime and soda to be required for softening the water. whose 10 ml required 20 ml of EDTA.000 litres of water sample having calcium hardness = 450 mg l–1 as CaCO3.3 kg] 8. magnesium = 150 mg l–1 as CaCO3 and total alkalinity = 400 [lime = 1.5 g of calcium carbonate per litre required 30 ml of EDTA solution.000 litres of water contain the following: ENGINEERING CHEMISTRY HCl = 7. The zeolite softener required 30 litres of NaCl solution. 12. 1. [Ans. Calculate the cost of lime and soda required for softening 1 million litres of a water sample containing. [200 ppm] 11.00.6 ppm] Calculate the lime and soda required to soften 10. The total hardness of 1. . NaCl = 29.25 mg l–1. 20 ml of calcium chloride solution. CaCl2 = 111 mg l–1.2 mg l–1.11 kg soda = 10. Al2(SO4)3 = 34.000 litres of water was completely removed by a zeolite softener.378 7. 10. containing 15 g l–1 of NaCl for regeneration.5 mg l–1. 384.

The fuels commonly used contain carbon as the main constituent and some common fuels are wood. and the difference in the energy of reactants and the products are liberated as large amount of heat energy which is utilized. the original material and the final products of combustion being at a reference 379 . which on combustion produces a large amount of heat. (ii) Net calorific value (NCV) is the quantity of heat evolved when a unit quantity of fuel is burnt in oxygen. the original material and the final product of combustion being at a reference temperature of 25°C and the water obtained in the liquid state.Fuels and Combustion INTRODUCTION Fuel is a combustible substance. hydrogen etc. The fossil fuels are coal. The process of combustion involves oxidation of carbon. of the fuels to CO2. kerosene. charcoal. Fossil fuels are non-renewable energy resources which were stored up millions of years ago by photosynthesis. diesel. which can be used for various domestic and industrial purposes. producer gas etc. Gross or higher calorific value is the quantity of heat liberated by combusting unit mass of fuel in oxygen. Classification of fuels Fuels 18 Natural Derived Solid Wood Coal Dung Liquid Crude oil (Petroleum) Gaseous Natural gas Solid Coke Charcoal Petroleum coke Coalbriquette Liquid Tar Kerosene Diesel Petrol Fuel oil LPG Synthetic gasoline Gaseous Coal gas Water gas Oil gas Biogas Coke oven gas Blast furnace gas CALORIFIC VALUE There are different expressions for calorific values: (i) The quantity of heat evolved by the combustion of unit quantity of fuel is its gross calorific value (GCV). crude oil and natural gas. represented by GCV or HCV. H2O.

formed = HCV – Mass of hydrogen × a × Latent heat of steam since 1 part by mass of hydrogen produces ‘a’ part by mass of water. The calorific value is expressed in either calorie/gm (cal/gm) or kilocalorie/kg (kcal/kg) or British thermal unit/lb (B. The initial and final temperatures of the calorimeter are noted.e. The apparatus consists of a cylindrical stainless steel bomb.U/lb) in the case of a solid and a liquid fuel. 18. An electrically heated magnesium wire touches the sample. which is surrounded by an air jacket and water jacket which minimises the heat loss due to radiation. 6V battery Oxygen valve Electrically operated stirrer Beckmann's thermometer Electrodes to which a ring is attached Copper calorimeter Mg fuse wire Weighed pallet of given fuel sample Air jacket Water jacket Stainless steel bomb Stainless steel crucible Fig 18.T.e. Determination of Calorific Value Bomb calorimeter. ∴ NCV = HCV – Latent heat of water vap. Units of calorific value.380 ENGINEERING CHEMISTRY temperature of 25°C and the water obtained from the fuel being at the vapor state.. 587. The apparatus which is used to determine the calorific value of solid and liquid fuels is known as Bomb calorimeter (Fig. There is a stirrer and a Beckmann’s thermometer which can accurately measure the temperature upto n/100th of a degree.T. the heat liberated is taken by calorimeter and water. In the bomb there is nickel crucible attached to a ring. the units are kcal/m3 or B./ft3.U. The sample of fuel is placed in the crucible. The net calorific value is hence always less than the gross calorific value by the amount corresponding to the heat of condensation of water vapours i. the lid of which is screwed to the body to make it air-tight.1).1 Bomb calorimeter. Through the lid there is one oxygen inlet valve and two electrodes. A weighed mass of a fuel placed in the crucible is allowed to burn in oxygen by electric spark across the electrode and the heat liberated is measured by the principle of calorimetry i.. Calculation: m = mass of fuel pellet (g) W = mass of water in the calorimeter (g) . The bomb is placed in a copper calorimeter.0 kcal/kg. In the case of gaseous fuels.

(iii) Cooling correction. the heats of formation of H2SO4 and HNO3 should be subtracted (as the acid formations are exothermic reactions). The correction factors used to get accurate results include: (i) Fuse wire correction. 100 OP Q . N = 0. m The approximate calorific value of a fuel can be determined by knowing the amount of constituents present: Gross or higher calorific value (HCV) from elemental constituents of a fuel. The fuels used in the above purpose are benzoic acid (GCV = 6325 kcal/kg) and naphthalene (GCV = 9688 kcal/(kg). dt°/min) and the actual time taken for cooling (t min) then correction (dt × t) is called cooling correction and is added to the (t2 – t1) term. From this rate of cooling (i. The rate of cooling of the calorimeter from maximum temperature to room temperature is noted. LM N 9 H × 587 kcal/kg. hydrogen. Calculate the percentage of H and GCV.5% and ash = 2. H = 34500 kcal/kg. Available Η in combustion of the fuel is = Total hydrogen – Fixed hydrogen ∴ L= 1 mass of oxygen in fuel.. C = 8080 kcal/kg.09 H × 587] kcal/kg. O. t2 = final temperature of calorimeter. ∴ LCV = HCV − LM N FG H IJ K OP Q = [HCV – 0. 8 Dulong’s formula for calorific value from the chemical composition of fuel is.5%. A coal has the following composition by weight C = 90%. (Q 1 part of H gives 9 parts of water and the latent heat of steam is 587 kcal/kg). S = 0.e. Net calorific value of the fuel was found to be 8490. H.FUELS AND COMBUSTION 381 w = water equivalent of calorimeter (g) t1 = initial temperature of calorimeter. Fuels containing Sulphur and Nitrogen if oxidised. L = HCV = HCV = gross calorific value of fuel. oxygen and sulfur in the fuel. Heat liberated during sparking should be subtracted from heat liberated. S = 2240 kcal/kg Oxygen present in the fuel is assumed to be present as water (fixed hydrogen). Example 1. (W + w) (t2 − t1) cal/gm.5%. = Total hydrogen – HCV = 1 0 + 2240 S kcal/kg 8080 C + 34500 H − 100 8 where C. Oxygen is assumed to be present in combination with hydrogen as water. (W + w) (t2 − t1 + Cooling correction) − (Acid + fuse correction) . (ii) Acid correction.5 kcal/kg. m The water equivalent of calorimeter is determined by burning a fuel of known calorific value and using the above equation. O = 3%. S are the percentages of carbon.

2) known volume of gas is burnt at a uniform rate by a burner.5 kcal/kg.638 – 0.9 × 0. water equivalent of calorimeter and latent heat of steam are 385 and 587 cal/g.5 + 52. (W + w) (t2 − t1 ) (385 + 3500) (29. In the apparatus (Fig. 18.8 H.3) Sol. If the fuel contains 0.601 cal/g. Around the burner there is a chimney containing coils wherein water at a constant rate is passed.382 Sol.5 + 0. respectively.83 m = 12. Example 2. 18.9 H × L) cal/g = (12. calculate HCV and NCV.5°C to 29.7% H.8 + 345 H = 8490.8 + 345 H = kcal/kg.8 H.2). the temperature of 3500 g of water was increased from 26.09 H + 587) kcal/kg [Q H = % of hydrogen] = (8490.83 g of a solid fuel in a bomb calorimeter.5 + 52.2 Boy’s gas calorimeter.8 + 345 H = 8490.575% ∴ HCV = (8490.5 + 52. LM N FG H IJ K OP Q Exhaust gases Rubber tubing Inner Cu coil Outer Cu coil Air Air Condensed steam Meter Water inlet Insulated container Gaseous or liquid fuel Fig.2 − 26.8 H) kcal/kg. ∴ 7754.8 kcal/kg. It is used for measuring the calorific value of gaseous and liquid fuels (Fig. Separate thermometers measure the incoming and outgoing water temperatures (t1 and t2) . ENGINEERING CHEMISTRY HCV = net calorific value + (0. .638 cal/g. NCV = (HCV – 0. On burning 0.09 H + 587) kcal/kg = (8490. HCV = 1 3 + 2240 × 0. Boy’s Gas Calorimeter. or 292. HCV = = 0. 18.575) = 8731. = 7754.7 × 587) cal/g = 12. 8080 × 90 + 34500 H − 100 8 = 7754.2 H = 1335% ∴ H = 4.8 × 4.5 + 52.2°C.

. O = 43% and ash = 1%. H2 = 40%.23 m3 2 CH4 + 2O2 = CO2 + 2H2O Volume of O2 required = 0.2 + 0. Wood contains lignocellulose—wood pulp mainly consists of α cellulose and a very small amount of β cellulose.2 m3 H2 + 1 O 2 = H2O 2 1 = 0.2 + 0.2 × = 0. C2 H2 = 2%. Sol. The average composition of wood on moisturefree basis is C = 55%. t1 and t2 = Incoming and outgoing water temperatures m = mass of steam condensed in time t. W(t2 − t1) V Mass of H2O condensed per m3 of gas = m/v kg.68 × 100 3 m = 3. V OP Q 1 O = CO2 2 2 1 Volume of O2 required = 0.1 × 2 = 0.05 2 Total O2 required = (0. L = HCV.23 + 0. 21 SOLID FUELS Wood Wood is derived from trunks and branches of trees.05) m3 = 0.238 m3.2 m3 2 Volume of O2 required = 0. Latent heat of steam per m3 of gas We get L = = ∴ NCV = L − Example 3. W = mass of cooling water used in time t. resins and proteins. Let the gaseous fuel be 1 m3 CO + LM N m × 587 kcal V m × 587 kcal/m3. N2 = 1% and the remaining being CO2. Calculate the volume of air required for complete combustion of 1 m3 of a gaseous fuel having the composition: CO = 46%.68 m3 ∴ Volume of air required = 0. Calorific value varies from 4000 to 6400 Btu/lb. CH4 = 10%. its use as engineering fuel is restricted. It contains about 15% moisture after airdrying. H = 6%.FUELS AND COMBUSTION 383 Let V = volume of gas burning.4 × C2H2 + 2 1 O = 2CO2 + H2O 2 2 5 Volume of O2 required = 0. Wood is largely used as domestic fuel.46 × = 0.

It is used as domestic fuel. Rajasthan and Tamil Nadu. It is powdered. volatile matter = 10–15%. possesses no coking power. O = 20%. dried and pressed into briquettes and used for domestic purpose. Lignite is compact in texture. N. Analysis of Coal Ranking of coal is done on: (a) Proximate analysis: It consists of determination of percentages of (i) volatile carbonaceous matter. The continuity can be proved graphically by plotting oxygen and C percentages of coal at different stages of formation. 2. (iii) ash and (iv) moisture of the airdried coal. then to lignite then into bituminous coal and finally to anthracite. containing 20–60% moisture. railway locomotives and thermal power stations. By carbonisation and gasification it is converted to coke. calorific value is from 8000 to 8500 kcal/kg). gaseous fuels like producer gas. Calorific value is 8400–8600 kcal/kg. It ignites more easily than anthracite. Bengal. Vegetable matter is first transformed into peat. volatile matter content decrease whereas carbon content. the moisture. O. industrial furnaces and boilers. Kashmir. lowest volatile matter and moisture. Origin. The composition and properties of peat widely vary from place to place. . It is an uneconomical fuel since it contains about 80–90% moisture. Its chief use is for combustion in household. calorific value and hardness increase. 3. in steam boilers.Chhattisgarh and Orissa. 1. Classification of coal. N. Bituminous coals are black and usually banded with alternate very bright and dull layers. When air-dried moisture content is 1–2%. On the basis of carbon content bituminous is classified as: (a) Sub-bituminous coals. domestic ovens and metallurgical furnaces. (c) Semi-anthracite is intermediate between bituminous coals and anthracite. lignites occur in Assam. 4. used for gaseous fuel production. H 4–5% and O 20%). Calorific value is 6800–7600 kcal/kg. Its calorific value is 6500–7000 kcal/kg. Anthracite is the highest rank coal having highest percentage of C (92–98%). Peat is easy to ignite and burns freely to give a long pleasant flame . power stations and gas producers. Occurrences. (C content 70–78%. H. It ignites easily and if low in S content. The transformation period extends over millions of years through a continuous process. Coal is highly carbonaceous and composed of C. Calorific value is 8500–8800 kcal/kg. S. Bituminous coals are found in Bihar. It burns without smoke but ignites with difficulty. liquid fuels like coal tar fuels. Its chief uses are in boilers. Madhya Pradesh. Peat is also used as a fertiliser. (b) Bituminous coal (C content 78–90%. (ii) fixed carbon. It is extracted by hand cutting. depending on nature of the original plant material. Various types of coal are ranked according to the degree of coalification from the parent material wood as follows: Wood → Peat → Lignite → Bituminous coal → Anthracite With the progressive transformation of wood. Airdried lignite contains C = 60–70%. It burns with a smoky flame. Low temperature carbonisation of peat is used for getting peat coke and byproducts. Peat is regarded as the first stage of coalification of coal. The airdried material has moisture content of 10–20%. Peat deposits are found in Nilgiri hills. for boilers and for production of producer gas. brown coloured coal. and O and non-combustible inorganic matter.384 ENGINEERING CHEMISTRY Coal Coal is the most important solid fuel and derived from prehistoric plants. Lignite or brown coals are soft. water gas. coal gas. Anthracites are found in Kashmir and eastern Himalayas. H.

Low volatile matter also reduces coking property of coal. Loss in weight × 100. 111 g 237 g ∴ Percentage of C = Increase in wt. of coal taken (iv) Fixed carbon: Percentage of fixed carbon = 100 – % of (moisture + volatile matter + ash) Significance: By taking away the latent heat of evaporation moisture content lowers the calorific value of coal.7H 2O . (b) Ultimate Analysis: (i) Carbon and hydrogen: Accurately weigh 1–2 gm of the coal sample and burn in a current of O2 in combustion apparatus whereby CO2 and H2O are formed. CaCl 2 × 2 × 100 . refractive index etc. Similar is the effect of volatile matter content. KOH × 12 × 100 . Hence. reduces the calorific value of coal.M. left in the desiccator and weighed till constant weight. Wt. C + O 2 → CO2 ∴ Percentage of ash = 12 44 112 g 138 g H2 + 2 1 O → H 2 O 2 2 18 and CaCl 2 + 7H2O → CaCl 2 . higher is the calorific value and better is the quality of coal. Higher the percentage of fixed carbon. Percentage of moisture = Loss in weight × 100. CO2 and H2 O are absorbed by previously weighed tubes containing KOH and anhydrous CaCl2. lower the moisture content. of ash left × 100 . of coal taken (ii) Volatile matter: The dried sample left in the crucible along with the lid is heated in a muffle furnace at a 250°C ± 20°C for 7 minutes and then cooled. Wt. Other chemical and physical properties are specific gravity.FUELS AND COMBUSTION 385 (b) Ultimate analysis: Consisting of determination of percentages of C. and again weighed after desiccation till constant weight. of coal sample × 44 Increase in wt. O. Ash being non-combustible. Volatile matter percentage (V. of coal sample taken (iii) Ash: The residual sample after the two above experiments in the crucible is heated in the furnace at 700°C ± 50°C for 1 or 2 hours without the lid. of coal sample × 18 and percentage of H = . Wt. The increase in weight gives the C and H content as follows: and 2KOH + CO2 → K 2CO3 + H2O. N and S. which escapes unburnt so volatile matter content lowers with better quality of coal. Wt. Then it is cooled. better the quality of coal. H. Ash deposition also causes problems in the furnace walls and the ultimate disposal of ash is also a problem. (a) Proximate Analysis: (i) Moisture: 1 g of finely powdered airdried sample taken in a crucible and heated in an electrically heated hot air oven at 105°C–110°C for 1 hr. surface area and porosity.) = Wt. weighed after desiccation till constant weight. Wt. (c) Calorific value: The coking properties are of importance for bituminous coals only.

K2SO4 and heated. Wt. washed with water and heated to a constant weight. Coke Carbonisation or coking bituminous coal leads to the formation of coke. The excess acid is back-titrated with standard NaOH solution. Coke and Coal • Coke possesses much strength and porosity compared to coal.4 . HCl and BaCl2 solution. and from a mixture of high and low volatile coking bituminous coal (non-swelling) in coke ovens hard coke is obtained. which precipitates BaSO4 which is filtered in a sintered glass crucible. namely. A smokeless fuel or semicoke is obtained from low temperature carbonisation. Also. of coal taken (iii) Sulfur: While determining the calorific value of a coal sample in a bomb calorimeter. . Percentage of S = Wt. H2SO4. Coarsely powdered coal taken in a closed retort and heated out of contact with air leads to the breakdown of coal with the formation of water. (v) Oxygen content = 100 – % of (C + H + S + N + ash) Significance: Higher percentage of C and H increases the calorific value of coal and hence better is the coal. is undesirable due to its polluting properties as it forms SO2 on combustion. All these properties of coke make it suitable for metallurgical processes compared to coal. of BaSO 4 × 32 × 100 . Finally the washings containing sulfate is treated with dil. O when combined with H in the coal. This process is called the carbonisation of coal or coking of coal. Coke obtained from coal with high volatile matter forms swelling coke which is soft coke. Then it is treated with excess of KOH and the liberated NH3 is absorbed in known excess of standard acid solution. gases and coke. ammonia. S. the S in the coal is converted to sulfate. of coal sample in bomb × 233 (iv) Ash content: Ash content is determined similar to proximate analysis. H available for combustion becomes unavailable. Both soft and hard cokes are obtained by high temperature carbonisation. other volatile matters. • By coking the undesirable sulfur content of coal is removed from coke and due to lower volatile matter content of coke it burns with a short flame. lower is the calorific value and lower is the coking power. Wt. although contributes to calorific value. Higher the percentage of O. (i) Low temperature carbonisation (LTC) and (ii) High temperature carbonisation (HTC).386 ENGINEERING CHEMISTRY (ii) Nitrogen: About 1 g of accurately weighed coal sample taken in a Kjeldahl’s flask along with conc. Carbonisation of Coal Depending on the operation temperature there are mainly two types of carbonisation processes. From the volume of acid consumed N content is calculated as follows: Percentage of N = Volume of acid consumed × Normality × 1.

Low temperature carbonisation yields a very complex mixture of higher phenols.2: Products (by fractional distillation) Light oil Middle oil Heavy oil Anthracene oil Benzene. The calorific value is lower. Xylene. (ii) High temperature carbonisation (HTC). .FUELS AND COMBUSTION 387 Table 18. Phenanthrene. Pyridine etc. As all the volatile matters are driven off. Toluene. Xylene. The gas and tar yields are lower. Naphthalene. In this process. the yield of coke is 65–75% containing 1–3% volatile matter. Quinoline etc. The crude spirit corresponds to crude benzol of HTC but contains greater amount of paraffins. Cumene etc. naphthalene and olefin. Naphthalene etc. substituted aromatic hydrocarbons and other N and O containing compounds. The coke obtained is not mechanically strong but highly reactive and can be easily ignited to give smokeless flame and used as a domestic fuel. purity and strength and can be used in metallurgy. Anthracene. It is carried out at 900°C–1200°C producing coke of good porosity. Disinfectants are made from this tar. The coal gas obtained has calorific value of 6500 kcal/m3 and is richer in hydrocarbons and poorer in hydrogen compared to the gas produced by HTC. hardness. The yield of coke is 75–80% and it contains 8–12% volatile matter. about 4500 kcal/m3. coal is heated in steel retorts at 500°C–700°C. Cresol. The retorts used are made of brick. (i) Low temperature carbonisation (LTC). Cresol. Phenol.1: By-products of carbonisation of coal Coal Carbonisation Residue coke Volatile part Coal tar Fractional distillation Ammoniacal liquor Coal gas Gas carbon 200°C Residue Pitch (62%) C–56% Light oil (5%) 250°C Middle oil (17%) 300°C Heavy oil (71%) 350°C Anthracene oil (9%) Distillates Table 18.

tars.) at a glance: • Temperature ⇒ L. At the end of carbonisation.T. Heat is supplied by the burning of the volatile matter and hence no byproducts are recovered.C.T.C. • Physical characteristics of tar ⇒ H. Coal forms a layer of 60–90 cm depth.5 m Door for air supply for coke discharging Fig. tars are darker in colour and more viscous than that of L. • Nature of other products ⇒ The amount of ammonia formed greatly increases with the rise of temperature showing that nitrogenous complexes are broken at higher temperature.T.T. = 1000–1400°C • Economy ⇒ In L. . The hot exhaust gases are utilised to run waste heat boilers to increase the heat efficiency.T.C. on the other hand the quantity of gaseous products is greater in the case of H. tar.T.1 and 18. • Yield of tar ⇒ The yield of L. • Nature of tar ⇒ The liquid volatile products are larger in quantity in the case of L.. less costly steel retorts are used whereas in the case of H.T. 18.C.C. as the working temperature is less. The yield of coke is 80% of the coal charged (Fig.T. one at the top for charging the coals and the other on one side for the entry of air and also for removal of coke. Carbonisation proceeds from the top to bottom and completes in 2–3 days.C.C.T. There are two main types of oven for the manufacturing of coke: (a) Beehive oven: It is a batch process and now obsolete.C.C.T.T. the coke is quenched by water and raked out through the side door.C.5 m diameter and form the shape of a beehive.C.C. The Tables 18. 18. retorts made of fire bricks are used.C. than that of H.T. The formation of lower amount of paraffin and alicycilc compounds and higher amounts of aromatic compounds in the case of H. = 400–600°C H.3 Beehive coke oven.388 ENGINEERING CHEMISTRY Distinction between high temperature carbonisation (H.T.C.2 show the amount and nature of various products. Heat radiated from the roof to the coal bed Coal 0.3).T.) and low temperature carbonisation (L. The firebrick chambers are of 2 m height and 3.T. indicates that the process of aromatisation is greater in the case of H. tar per ton of coal is much greater than that of H.C. There are two openings. leaving the oven hot enough to start the next batch. The expenditure due to fuel is also less in the case of L.T.C.6 m 4m Coal charging door Refractory lining Zone of combustion 2.

Finely crushed coal is charged through the hole at the top and in a closed system it is heated to 1200°C.4 Otto Hoffman’s byproduct coke oven with regenerators. air is excluded so that no burning takes place within the oven. The coke ovens are made of silica bricks and the temperature is about 1350°C to 1450°C. heat is supplied from the hot flue gases and 40% of the oven gas (coal gas) generated is burnt to heat the battery of ovens and the rest is used for domestic fuel locally.FUELS AND COMBUSTION 389 The limitations of the process are (i) no recovery of byproducts. It is heated externally by a portion of coal gas produced by the process itself or by producer gas or by blast furnace gas. (iii) the exhaust gases cause pollution. after which the doors are opened and the glowing coke mass is discharged by machine driven coke-pusher into coke-quencher. The hot coke is quickly quenched by water spraying. (b) Byproduct coke oven: In this process coal is heated in combustion chambers. • Beehive coking is obsolete. It is a batch process causing a large amount of pollution. This cycle continues till the volatile matter lasts.4). There is a charging hole at the top. The flue gases produced during combustion pass their sensible heat to the checker brick-work. The oven consists of number of narrow silica chambers (10 m × 3 m × 0. Chambers loaded with coal Coal gas C oal Coal bunker Coal gas Tar Coke oven Space between chambers for flow of burnt gases Gas burns here Hot regenerators Outgoing waste gases heat regenerators before escaping to chimney Air Producer gas Waste gases to chimney Coal charging cars Ram (Coke pusher) Coke chamber Regenerators Coke ovens with regenerators Waste gases to chimney Fig. • In byproduct coking. (ii) coke yield is low. ‘Dry quenching’ is also done by circulating flue gases over hot coke and the hot gases are utilised to run waste heat boilers (Fig. The batch process is made continuous by building ovens in a battery. Carbonization takes about 11 to 18 hours. separate from carbonisation chambers. which is raised to 1000°C.4 m) erected side by side with vertical flues in between them. The thermal efficiency has been increased and the valuable byproducts are recovered. a gas off take and a refractory lined cast iron door at each end. A portion of coal is burnt inside the retort to generate heat for coking. . 18. (iv) process is not flexible. 18. Highlights: • There are two main types of coking of coal: (i) Beehive and the (ii) by product coking. The flow of heating gases is then reversed and the hot checker bricks heat the inlet gas.

This crude oil is sent to the refineries for further processing and refining of the crude oils (Fig. About 90% crude produced at present fall in this last category. called waxes.390 ENGINEERING CHEMISTRY Recovery of byproducts: The gases coming out at 600°C–700°C get a spray of flushing liquor at the goose-neck of the standpipe and the temperature is reduced to 80°C. (b) Asphalt-base crude contains mainly naphthenes and cycloparaffins with smaller amounts of paraffins and aromatics. the most common are Si. (i) Coal tar is condensed in the tank below. whereby the oil is forced out through the inner pipe. Durgapur. The ‘Coke oven gas’ is composed of NH3. Practically all metals are found in petroleum. H ⇒ 11–14%. Ni. Raniganj. By the hydrostatic pressure of natural gas the oil is pushed up or it is pumped up by means of a pump. S ⇒ 0. Rourkela. Two coaxial pipes are lowered to the oil reservoir. whereby most of the organic compounds are destroyed and the remaining unsaturated fatty oils and fatty acids undergo polymerization. LIQUID FUELS Petroleum or crude oil is a deep brown oil consisting of mainly hydrocarbons. Al. The dead organic matter settles down to the bottom of shallow seas and lagoons. Bokaro-Ramgarh in large numbers in India whereas byproduct coke ovens are on large numbers in Giridih. naphthenes and aromatics in varying proportions. Fe.5). (c) Mixed base crude contains both the above type of compounds but rich in waxes. Classification of petroleum. Bhilai. Tar and steam get condensed. H2O. 18. Sulfur. (ii) Ammonia is recovered partly as aqueous solution and partly as sulfate. The settled debris is attacked by anaerobic bacteria. Jamshedpur. The average ultimate analysis shows C ⇒ 83–87%. paraffins. (v) H2S is recovered by passing the gas through moist Fe2O3 as: Fe2O3 + 3H2S → Fe2S3 + 3H2O Fe2S3 is again regenerated by exposing to atmosphere Fe2S3 + 4O2 → 2FeO + 3SO2 4FeO + O2 → 2Fe2O3 Beehive ovens are located in Jharia. Mg. . N ⇒ 0. (iv) Benzene is recovered similarly by spraying petroleum.1% and O ⇒ 2–3%. Bokaro etc. through the outer pipe compressed air is forced. benzene. Petroleum Drilling: Oil is brought to the surface by drilling holes upto the oil bearing surface. (iii) Naphthalene is recovered by passing the gas through a tower where water is sprayed at very low temperature which condenses the naphthalene. moisture etc. nitrogen and oxygen are present in the form of derivatives of hydrocarbons in the oil. tar contains naphthalene. Occurrence: The crude oil has been derived from the organic matter originally present in marine sediments.5–3%. Ca. There are three main types petroleum according to chemical nature: (a) Paraffin-base crude composed of saturated hydrocarbons upto C35H72 which are semisolids.

All these steps are under petroleum refining which include: 1.6) (Table 18. the crude oil is separated into fractions by distillation and the fractions obtained are subjected to simple purification procedures or complex treatments to yield different petroleum products. Refining: After removal of dirt.3). These are separated in a fractionating column consisting of a tall tower where the higher boiling fractions condense first. water and natural gas.6 Petroleum distillation. Coltrell’s process.FUELS AND COMBUSTION 391 Compressed air Oil Natural gas Natural gas Brine Fig. The water is separated from the oil by passing the emulsion through Coltrell’s electrostatic precipitator. Crude oil is intimately mixed with water forming an emulsion. Sulfur compounds have objectionable properties of pollution so they are removed prior to distillation as copper sulfide by treatment with copper oxide. Condenser Refinery Straight run gasoline Crude tower Bubble tower Strippers Gasoline storage Refinery Cracked gasoline Crude petroleum Reforming Condenser furnace Cooler Refinery Solvent naphtha Gas oil reduced crude Refinery Kerosine oil Fig. . Petroleum distillation. The crude oil is subjected to distillation to about 400°C temperature in an iron retort whereby all volatile components except the solid residue are distilled out. 18. 2. 18. 3. This distillation is a continuous process and the following fractions are obtained (Fig. Removal of objectionable compounds.5 Mining of crude oil and use of air-lift pump. 18.

isomerization and polymerization. diolefins after refractionating. The paraffins decompose to lower mol. which is passed back to the main fractionating column. As a motor fuel solvent and dry washing As a solvent As fuel for domestic and industrial uses As a fuel for diesel engine For different fractions Petroleum ether Gasoline or petrol Naphtha Kerosene oil Diesel oil Heavy oil 30°C–70°C 90°C–200°C 200°C–250°C 250°C–300°C 300°C–350°C 320°C–400°C C5–C7 C5–C9 C9–C10 C10–C16 C10–C18 C17–C30 Cracking Process Cracking is the process in an oil refinery by which heavier fraction from the fractional distillation converted into useful lighter fractions by the application of heat.250 kcal/kg and is used as a fuel for internal combustion engines in automobiles and aircrafts. . This contains some gasoline. 1. Its calorific value is 14. it is called thermal cracking. with or without catalyst.3: Common fractions from crude Fraction Uncondensed gas Boiling range Within 30°C Composition C1 to C4 Uses As domestic or industrial fuel under the name LPG (Liquefied petroleum gas) As a solvent. petroleum. The chief application of commercial cracking in all the refineries is for the production of gasoline from gas oils. (e) The residual liquid coming out from the bottom on subsequent treatment yields lubricating oil. (c) Kerosene oil is obtained between 250°C–300°C. Thermal Cracking: When cracking is carried out without any catalyst at high temperature from 450°C–750°C at pressures ranging from 1–70 atms. There are two methods of cracking. (d) Gas oil is obtained between 300°C–350°C. This is passed through a cooler and then extracted with liquid SO2 to remove sulfur. like paraffin and an olefin. grease. (i) Petroleum ether boiling between 40°C–70°C and (ii) Benzene boiling between 70°C–90°C and (iii) Gasoline boiling between 90°C–200°C all are obtained. asphalt-bitumen. The surplus of heavier petroleum fractions are also cracked to get petrol. compounds. Table 18.. wt. vaseline. The lower boiling fraction mixed with it is returned to the main column.392 ENGINEERING CHEMISTRY (a) Gasoline is obtained upto 200°C. The important reactions are decomposition. (b) Solvent naphtha is obtained as a side steam between 200°C–250°C. dehydrogenation. Bottom liquid is refined and finally can be used as domestic fuel having calorific value of 1100 kcal/kg. coke etc. It is used as a diesel engine fuel with calorific value of 11000 kcal/kg. Naphtha contains 6-10 carbon atoms. The naphtha is condensed and subjected to refining for the removal of sulfur. paraffin wax. Other uses include the production of olefins from naphthas and gas oils. i. cracking is a process by which larger molecules break up into smaller ones.e.

zeolites in the form of beads or pellets. When the cracking oil is vaporized and then cracked at 600°C–750°C at a low pressure. Catalyst used are synthetic composition of silica and alumina. The catalyst becomes deactivated by a deposition. The bottom liquid is reboiled and recycled to the fractionating column and ultimately gas oil is obtained having high octane value. Catalytic Cracking. 18.7).FUELS AND COMBUSTION 393 CH3(CH2)8CH2 → CH3(CH2)4CH3 + CH3CH2CH = CH2 n-decane n-hexane butene-1 The olefins formed isomerizes and polymerizes.8). . The use of catalyst during cracking accelerates the reactions and at the same time modifies the yield and the nature of product.7 Fixed-bed catalytic cracking. it is called vapour phase thermal cracking. through which the hot oil (500°C) flows from the top and passes down. At the top of the tower a cyclone separator is active to separate the cracked oil vapour and passes it to the fractionating column. The products are separated by fractional distillation. 2. The products have better anti-knock properties. which is reactivated by burning away the deposits with compressed air in a regenerator (Fig. The carbon deposits on the catalysts are burnt by compressed air in one chamber for reactivation while the other catalyst chambers are active (Fig. This carbon deposits on the catalyst beds. The catalyst powder is retained and sent back. 40% of the charge is converted to gasoline and 2–4% carbon is formed. 18. (b) Moving bed or fluidized bed catalytic cracking: The finely powdered catalyst behaves as a fluid when suspended in gas or oil vapour. The gasoline is stripped off dissolved gases and purified. 18. Cracked vapour Cooler Stabilizer Gases Catalyst Vapour Gasoline Heavy oil charge Heavy oil Heater Pre-heater (425°C – 450°C) Catalyst chamber (425°C – 450°C) Fractionating column Gasoline + some dissolved gases Fig. CH3 CH3   CH3—CH2— C — C = CH 2  CH 3 2CH3CH2CH = CH2 This cracking taking place at 475°C–530°C temperature leads to liquid phase thermal cracking. The preheated heavy oil is forced through tower along with the fluidised catalyst. There are two main types of catalytic cracking: (a) Fixed-bed catalytic cracking: The catalysts are fixed in towers.

the anti-knocking properties are higher.. • Oil refineries use catalytic cracking to make gasoline.394 Flue gases Cyclone Catalyst regenerator Regenerated catalyst Cracked vapour Light fraction ENGINEERING CHEMISTRY Cooler Gases 600°C 500°C Gases Stabilizer Reactor Spent catalyst Heavy oil Fraction matching column Gasoline + gas Gasoline Feed oil Air Catalyst + oil +s pe nt ca tal ys t Blower Air Fig. • Enough gasoline is not produced during purified petroleum distillation.E. (Tetra Ethyl Lead) • Leaded fuel is now avoided and the oil companies produce high octane fuel by increasing the proportions of both branched alkanes and arenes and blending some oxygen compounds. (vii) Gum-forming compounds are very low. (ii) External fuel is not necessary since the coal embedded in the catalyst supplies the heat. (viii) In presence of specific catalysts preferentially the cracking of naphthenic materials takes place. (iv) Byproduct gas evolution being low. (ix) Only the high-boiling hydrocarbons and the side chain of the aromatics are decomposed preferentially. (v) Due to higher aromatics content.e. (contd.8 Moving-bed type catalytic cracking. (vi) Greater portion of S escapes as H2S so residual S content of the oil is low. yield of petrol is higher. gasoline has to burn smoothly without knocking. T. (iii) Operating pressure is lower. Advantages of catalytic cracking: (i) The quality and yield of petrol is better.) . • Gasoline contains alkanes C5—C10 atoms. so it becomes richer in paraffinic compounds. • For smooth running of the motors. Highlights: • Gasoline is the fuel for motor engines.L. • The octane number scale was devised by Thomas Midgley (1889-1944) and he discovered anti-knocking additives based on lead i. 18.

These compounds undergo polymerization either in presence of catalyst (catalytic polymerization) like phosphoric acid. Reforming.FUELS AND COMBUSTION 395 • The four main approaches are: (i) Cracking not only makes small molecules but also forms branched chain hydrocarbons. Polymerization. alkylation and isomerization. alkylation in presence of HF or H2SO4 gives iso-paraffins. All these processes supply excellent high volatile gasoline components. (ii) Isomerisation converts straight chain alkanes to branched chain by passing over Pt-catalysts. the naphtha fractions of gasoline. 2. By this process superior quality gasolines are obtained. . H2SO4 or by heating at temperatures of 500°C– 600°C and pressure (thermal polymerization) to yield products rich in branched-chain hydrocarbons. (iv) Addition of alcohols and ethers. The cracker gases in the refinery are rich in olefins. (iii) Reforming turns cyclic alkanes into arenes such as benzene and toluene. Actually these aromatics and the iso-paraffins are the best gasoline components. CH 3 CH 3 + 3H 2 methyl cyclohexane toluene CH 3 CH 3 + 4H 2 n-heptane toluene The other reactions are the isomerization of n-paraffins to iso-paraffins and hydrocracking of higher paraffins to lower ones. Compounds such as MTBE (Methyl Tertiary Butyl Ether) now known as 2-methoxy-2-methyl propane. This upgrading is a result of reforming of molecules without disturbing their average molecular weights. This process also helps in preparing high quality gasoline by heating with or without a catalyst. Isomerization converts n-paraffins to iso-paraffins in presence of anhydrous AlCl3 catalyst. CH3C(CH3) = CH2 → CH3C(CH3)2CH2C(CH3) = CH2 iso-butene di-isobutene Similarly. CH3  CH3 C  O  CH 3  CH 3 MTBE Petroleum Processing 1. like formation of aromatics from naphthene and paraffins.

chromia supported on alumina.9 Fixed-bed catalytic reforming process. (i) Objectionable odour forming mercaptans and H2S make the oil sour. . platinum on silica or alumina. but gets poisoned easily by the impurities like S. The catalysts used are molybdena. The former leads to gum and sludge formation and the latter leads to corrosion of engines and pollution of atmosphere. As. pressure 5–45 kg/cm2) (Fig. reforming is also thermal and catalytic. H 2 compressed and recycled Low boiling (to avoid explosive reaction with H 2 ) Diethanolamine (DEA) Gas Reformed or stabilized gasoline Compressor (25 atm) H2S scrubber Fractionator Gasoline feed stock Fractionator Heater Reactor at 500°C containFraction b. (iii) The storing quality of the refined gasoline is improved by adding different inhibitors of oxidations to it. Refining of Gasoline The straight-run gasoline obtained from the fractionation of crude petroleum contains undesirable constituents like unsaturated straight chain hydrocarbons and sulfur compounds. Reforming is a once through process. 100–170°C ing catalytic bed (Pt–Al 2 O 2 ) Reactor (Pt– Al 2 O 3 ) Reactor (Pt– Al 2 O 3 ) Condenser To solvent DEA recover Residue Heater at 500°C Heater at 500°C Fig.9). These are removed by refining processes. (iv) Refined gasoline is blended with suitable fractions of catalytically cracked gasoline to impart good combustion qualities. 18. 18. The latter is more active. 2RSH + Na2PbO2 → Pb(RS)2 + 2NaOH Pb(RS)2 + S → PbS + RSSR disulfide (ii) Gasoline is percolated through “Fuller’s earth” which absorbs the olefins and coloring matters present in it. The black PbS precipitates and the other disulfides are extracted with a suitable solvent.396 ENGINEERING CHEMISTRY Similar to cracking. N etc. Thermal reforming has been almost completely replaced by catalytic reforming. rendering the foul smelling stock to sweet smelling or odourless stock and the process is called sweetening process. Fluid bed and moving bed processes are run at higher temperature and lower pressures and fixed bed processes are run at higher pressures (temperature 450°C–520°C. Oil sample treated with sodium plumbite and a little sulfur converts the sulfur compounds into disulfides (Doctor’s process).p.

but it is not yet competitive with petroleum refining. n-hexadecane is given cetane number 100 and α-methyl naphthalene given cetane number zero. ditertiary butyl peroxide and metal organic compounds.2. Cetane Number There is a delay period between the injection of diesel fuel and its ignition. Bergius-Pier Process: Destructive hydrogenation of coal in presence of a catalyst yields oil.4-trimethyl pentane) in a mixture of n-heptane and iso-octane having the same knocking tendency compared to the sample of gasoline being tested. Liquid Fuel from Coal and Coal Tar The conversion of coal into oil is essentially raising the H:C ratio. diethyl telluride. iso-octane has the best antiknocking properties and assigned an octane number of 100 whereas n-heptane has poor antiknocking property and assigned an octane number of zero. The paste is preheated and treated with H2 at 250–350 atm. carbamates. which react with any hydrocarbon peroxide molecules formed in the engine cylinder thereby solving down the chain oxidation reaction and preventing knocking. If a given fuel matches in quality with the blend having 40/60 blend of cetane and α-methyl naphthalene. This is known as knocking. Yield of gasoline is 60% of the coal dust. pressure and 450°C–500°C temperature. This delay period if becomes large. the rate of oxidation sometimes becomes so great that the unburnt fuel may burn rapidly with the formation of explosive violence. tin or molybdenum compound. The anti-knock quality of a fuel is expressed as its octane number. Coal is ground and made into a paste with a heavy recycle oil and a catalyst like iron. 1. which decompose at high temperature yielding low-boiling hydrocarbons. Other antiknocking agents are tetramethyl lead (TML). The cetane number of diesel can be improved by adding amyl/butyl nitrate. 1.FUELS AND COMBUSTION 397 Knocking Octane Number. it is assigned a cetane number 40. Increasing delay period occurs in the series: n-paraffins < olefins < naphthenes < isoparaffins < aromatics. Middle oil is hydrogenated in vapour phase with catalyst to yield more gasoline.0–1. The unreacted coal is filtered-off and the liquid product distilled. The fuel which has same knocking tendency with the mixture having 80% iso-octance has octane number 80. Hydrogen combines with coal to form saturated hydrocarbons. The hydrocarbons present influence the knocking properties of gasoline which vary according to the series: straight chain paraffin > branched chain paraffin > olefin > cycloparaffin > aromatics. TEL functions by being converted to a cloud of finely divided lead oxide particles. Knocking results in loss of efficiency of the engine and also leads to its short life. The most effective antiknock agent added is tetraethyl lead (TEL) along with ethylene dibromide which prevents the deposition of lead by forming volatile lead halides. Maximum power is derived from gasoline when it burns silently and uniformly in an internal combustion engine. Due to presence of certain constituents in the gasoline. Octane number is equal to the percentage by volume of iso-octane (2. tertiary butyl acetate. too much fuel accumulates in the cylinder and burn very rapidly and causes “diesel knock”. The order is the reverse for gasoline anti-knock quality. . The crude oil is fractionated to get (i) gasoline (ii) middle oil and (iii) heavy oil which is recycled.5 ml of TEL is added per litre of petrol. This delay period is connected to the type of hydrocarbons present in the diesel.

produced by passing steam over heated coke is mixed with hydrogen. 18. The gas is purified by passing over Fe2O3 to remove H2S. The gasoline contains straight chain hydrocarbons and hence have low octane number. Fischer-Tropsch Process. 18.10 Bergius process of hydrogenation of coal to gasoline. The process is based on the catalytic hydrogenation of carbon monoxide leading to the following reaction: nCO + (2n + 1)H2 → CnH2n+2 + H2O Paraffin nCO + 2nH2 → CnH2n → CnH2n + nH2O Olefin Water gas (CO + H2). . 18. 8 parts magnesium and 200 parts keiselguhr. which are cracked to yield more gasoline.398 Powdered coal Heavy oil Catalyst (Sn or Ni oleate) Paste H2 Gases Condenser ENGINEERING CHEMISTRY Gases Gasoline Middle oil H2 Gasoline Heavy oil Converter at 450°C and 200 – 250 atm Crude oil Fractionating column Fig. The exothermic reaction leads to the formation of straight-chain saturated and unsaturated hydrocarbons.11).11 Fisher-Tropsch method. then passing over a mixture of Fe2O3. Catalyst (Co + Th + MgO + Keiselguhr) Fe 2 O 3 Fe 2 O 3 + Na 2 CO 3 Cooler Gasoline Cracking Water gas (CO + H 2 ) H2 Purification of gas Compressor (5–25 atm) Heavy Gasooil line Fractionating column Fig. 2. 5 parts thorium.Na2CO3 to remove organic sulfur compounds. so needs reforming before use (Fig. The purified gas is compressed to 5 to 25 atm. The crude oil on fractionation yields (i) gasoline and (ii) heavy oil. at 200°C–300°C passed through a converter containing catalyst which is a mixture of 100 parts cobalt.

Its octane rating ranges between 87 and 90. Non-petroleum Fuels 1. kerosene. coke. diesel fuel. Octane number is high as 114 and 99.FUELS AND COMBUSTION 399 Important Petroleum Products The main products of refinery are motor and aviation gasoline. It is a good fuel for internal combustion engines but its initial boiling point is high (80°C). GASEOUS FUELS (a) Fuel gas from nature: (i) Natural gas (ii) Methane from coal mines. Wide range of liquid fuels used in boilers and furnaces are covered by this term. Diesel fuels are prepared from heavy distillate obtained from catalytic cracking units. Motor gasoline is a mixture of low boiling hydrocarbons (215°C) and made by blending— (i) Straight run gasoline (direct distillation of crude oil). space heaters for jet engines. They are n-butane. Gasolines. Ethyl alcohol is not used as a prime fuel but used as blends with gasoline upto 25% alcohol and the mixture is called “gasohol”. butylene. Diesel fuel. Refined benzol is essentially a mixture of 70% benzene. Volatility is improved by blending with light fractions. Cycle gas oil is the light variety and needs a number of treatments for purification. respectively. isobutane. Cost considerations prohibit their use. Kerosene is used for domestic purpose. It requires about 36 hrs. It is used in reciprocating spark-ignition internal combustion engines. LPG contains hydrocarbons which are gaseous under atmospheric pressure but can be liquefied under pressure. Alcohols. the low cetane number is improved by additives. so it can be used only when blended with gasolines. Liquefied petroleum gas is obtained as a byproduct during the cracking of heavy oils or from natural gas. It is used as domestic and industrial fuels and in future it may be used as motor fuel. the cetane numbers should be more than 45 whereas for low speed engines it should be in the range of 25 to 35. (ii) cracked gasoline. propane etc. LPG. fuel oils. . Benzol. wax. 18% toluene and 6% xylenes. TEL and other additives. so it cannot be used in cold countries. (iii) reformed naphtha and other fractions. LPG etc. (b) Fuel gas from solid fuels: (i) Producer gas (ii) Water gas (iii) Coal gas (iv) Blast furnace gas (c) Fuel gas from petroleum: (i) Refinery gases (ii) LPG (iii) Gases from oil gasification. (d) Fuel gas made by fermentation of organic wastes. The importance of ethyl alcohol as a fuel lies in the fact that it can be produced from naturally available carbohydrates by fermentation. Colours are added to identify different grades. But their calorific values are low. Methyl and ethyl alcohols can be used in gasoline engines. bitumen. No additives are required. Kerosene. 10% butane for easy starting of engines. Aviation gasolines have higher volatility and higher percentages of TEL and isoparaffin. It is rich in aromatics and iso-paraffins. In a high-speed diesel engine. to complete whereby the fermented liquid contains 18-20% alcohol which is then fractionally distilled to recified spirit containing 90-95% alcohol. Purification involves removal of sulphur. Fuel oils. from which absolute alcohol can be obtained after treatment with lime and distillation. It is obtained as a straight-run distillate from crude oils. The heavy fuel oil produced from the cracking units are the heavy variety. other products include lubricating oils. It serves to increase the octane rating. The other defect is its high freezing point (55°C).

Its calorific value is around 5000 kcal/m3. though wood waste. Tar and ammonia are first removed by cooling the gas and water scrubbing. 4% N2 and 1% CO2. Water. (ii) as a fuel. At the base there is inlets for air and steam and an outlet for the ash. 7% CO.400 ENGINEERING CHEMISTRY Natural Gas Natural gas is a mixture of paraffinic hydrocarbons and methane is the principal component. peat etc. 2Fe(OH)3 + 3H2S → Fe2S3 + 6H2O Coal gas is used (i) for illuminating towns and cities. H2S. Natural gas is used (i) as a domestic fuel. Coal Gas Coal is produced by the high temperature carbonisation of coal in gas retorts and coke ovens. The coke oven gas is purified in steps to obtain the coal gas finally. naphthalene are removed by creosote oil scrubbing. can be used.12 Gas producer. 32% CH4. CO2. Natural gas when found to occur with petroleum in oil wells is called ‘wet gas’ and when it is associated with crude oil the gas is called ‘dry gas’. CO2 etc. 18. (iii) as a raw material for NH3 production and (iv) in metallurgical operations to provide reducing atmosphere. It is a fuel of low calorific value (1300 kcal/m3) but its advantage is its cheapness and ease of production.000–14000 kcal/m3. The gas producer consists of a steel vessel with inner lining made up of refractory bricks. (ii) for manufacture of various chemicals (iii) as raw material for the manufacture of H2 and carbon black and (iv) for synthetic protein preparation from methane. then benzol. dirt. The calorific value is 12. It is prepared by passing air and steam over an incandescent bed of solid carbonaceous fuel in a reactor called “gas producer” or simply a “producer”. H2S is finally removed by passing it over moist ferric oxide. . Coke Cup and cone feeder Producer gas outlet Refractory brick lining Coal at 1000°C Exit for ash Distillation zone Reduction zone Combustion zone Air mixed with a little steam Fig. N2 and heavier hydrocarbons are removed from the gas and finally it contains from 50 to 95% methane. 5-10% ethane. Producer Gas It is a mixture of combustible gases like CO and H2 and large amount of non-combustible gases like N2. 3% H2 etc. It contains 40% H2. The dimension of the vessel is about 4 m height and at the top there is a cone feeder and a side opening for producer gas outlet. 2% C2H2. 3% C2H5. It burns with a long smoky flame. The carbonaceous fuel used is generally coal or coke.

Water gas is a gaseous fuel of medium calorific value (2800 kcal/m3) generated by gasifying solid incandescent source of carbon in superheated steam. combines with steam to liberate H2 and from oxides of C. The water vapor and the volatile matter are added to the escaping gas which results in production of enriched gases. . where red hot coke. C + O2 → CO2 + 97 kcal 1 C + O2 → CO + 29. CO2 forms at the expense of O2. (ii) the endothermic reaction of steam and C prevents localised overheating of a fuel bed and leads to diminished clinker formation. Its concentration reaches a maximum at the top when CO begins to appear. 18. only air can be used. The topmost zone serves to preheat the precarbonised fuels coming in. CO2: 3%. For the production of producer gas. The oxygen is consumed within 75 to 100 mm of the bed. N2: 52-55%. steam used along with air is advantageous since (i) it raises the content of combustible components (CO + C2) compared to noncombustible thereby increasing calorific value. and in metallurgical operations.5 kcal 2 (c) Reduction zone.13 Water gas production.12 where the following reaction takes place which is endothermic C + H2O → CO + H2 – 29 kcal Cup and cone feeder Coke Water gas outlet Red hot coke at 900°C–1000°C Grate Steam supply Refractory brick lining Air supply Ash outlet Ash Water Gas Fig. muffle furnaces for coal gas production. (b) Oxidation zone. H2: 8-12%. Other reactions are also endothermic. The temperature at this zone is about 1100°C. 18. which then undergoes reduction into CO and the reaction is endothermic and is called Bondonard reaction. The equipment is known as water gas generator and is more or less similar to that shown in Fig. The average composition of the producer gas is CO: 22-30%. which constitutes the zone. The temperature of this zone is from 400°C-800°C. CO2 + C → 2CO – 36 kcal C + H2O → CO2 + H2 – 29 kcal C + 2H2O → CO2 + 2H2 – 19 kcal As long as O2 is in excess.FUELS AND COMBUSTION 401 Reaction Zones in a Gas Producer (a) Ash zone. CO2 is formed. The temperature is around 1000°C (d) The uppermost layer of the bed is the drying and carbonisation zone. The fuel bed in a normal producer is on metallic grate. Producer gas is used for heating the furnaces for the production of steel and glass. Its equilibrium constant greatly increases with rise in temperature. The air-steam blast is preheated by the ash zone which also protects the grate from intense heat. This is just next to the ash zone.

402

ENGINEERING CHEMISTRY

This gas burns with a blue flame owing to high carbon monoxide content and hence known as blue water gas. The bed of coke in the reactor is at 1400°C to 1000°C. As the reaction is endothermic temperature gradually falls and when it comes to 1000°C the blast of steam is stopped and air blast is passed and the following exothermic reactions occur. C + O2 → CO2 + 97 kcal 2C + O2 → CO + 59 kcal

The reaction again rises and these cycles alternately take place to maintain the temperature. After the production, ash is removed and the generator recharged. The water gas passing through the superheater is cooled and then purified. The average composition is H2: 51%, CO: 41%; N2: 4%, CO2: 4% Blue water gas is used as a source of hydrogen, as a fuel gas. The calorific value of water gas can be enhanced by adding gaseous hydrocarbons (obtained from cracking crude oils) to get carburetted water gas (Calorific value 4500 kcal; CO2 → 3%(m3)); composition of carburetted water gas is 35% H2, 25% CO, 35% saturated and unsaturated hydrocarbons and 5% N2 + CO2.
Products of combustion Purge steam Steam Oil spray

Blast of air

Tar separator Cooler Purifier

Fig. 18.14 Manufacture of carburetted water gas.

Biogas Production
Aquatic plants, organic wastes from domestic, agricultural and industrial sectors with high B.O.D. value (Feed stock) are digested anaerobically to produce biogas. The biogas is totally used as fuel. The chief constituent of biogas is methane, so the process is also called biomethanation. Composition of biogas is given below:
Component CH4 CO2 H2S H2 N2 O2 CO NH3 Volume% 52-95 9-45 0.001-2 0.01-2 0.1-4 0.02-6.5 0.001 Small

FUELS AND COMBUSTION

403

Conditions for Biomethanation • Temperature = 35° • pH = 6.8-8.2 • Anaerobic condition. • Trace elements = Na+, Co+3, Ni+2 etc. Arrangements for Biomethanation Feed stock is mainly cowdung.
Gas Gas

Excess feed stock

(Batch process) Feed stock (a) (b) Feed stock

Fig. 18.15

Better quality of coal should have low nitrogen and sulphur content. Higher percentage of oxygen is also undesirable as an increase in 1% oxygen content decreases the calorific value by about 1.7%. Method of Analysis of Flue Gas Analysis of flue gas will indicate the complete or incomplete combustion of a fuel; which is very essential in respect of efficient utilization of the fuel. The analysis is done in Orsat’s apparatus and is based on the principle of absorption of • CO2 in KOH solution (500 gl–1, 500 ml) • O2 in alkaline pyrogallic acid (25 g of pyrogallic acid in 400 gl–1 KOH solution, 500 ml) • CO in ammoniacal cuprous chloride solution (100 g Cu2Cl2 + 125 ml liquor ammonia + Rest water to make up the volume, 500 ml). Description of the Apparatus It consists of a water jacketted measuring burette, connected in series with the absorption bulbs containing the above three solutions successively as depicted in the Fig. 18.16. The water jacket maintains the temperature of the gas constant. The absorption bulbs are filled with glass tubes for better absorption of the gases.

404

ENGINEERING CHEMISTRY

Filter

Stop cock

Water reservoir

Gases tube

Flue gas Bulb containing AM.Cu 2 Cl 2 Bulb containing Alkaline pyrogalic acid Bulb containing KOH solution

Graduated Burette

Fused CaCl 2

Rubber tube

Fig. 18.16

Procedure • The apparatus is tested for its air-lightness. • The flue gas (100 ml) is taken in the apparatus in the measuring burette by adjusting the volume by water reservoir atmospheric pressure. • The stopper (1) is opened for CO2 absorption and water reservoir is raised to force the gas inside the bulb. The gas is finally taken in the burette and the volume of the gas is measured by making the levels of water inside the burette and water reservoir equal. The decrease in volume gives the percentage by volume of CO2 in the flue gas.

• The stopper (2) is opened and provided as usual to get the percentage by volume of O2 in the flue gas. • The stopper (3) is opened and proceeded as usual to get the percentage by volume of CO in the gas. • The sequence of the bulbs should be strictly followed. Implications of the Analysis • If the flue gas contains greater percentage of CO it is implied that considerable wastage of fuel is taking place due to incomplete combustion and the O2 supply is insufficient. • The greater percentage of O2 in the flue gas indicates that O2 supply is in excess. • Result of the analysis will help to control the combustion process.

SOLVED EXAMPLES
Example 1. A sample of coal contains: C = 93%, H = 6% and ash = 1% Calculate the gross and net calorific V value of the coal from the following data: Weight of coal burnt (m) = 0.92 g Weight of water taken (w) = 550 g

FUELS AND COMBUSTION

405

Water equivalent of bomb calorimeter (W) = 2,200 g. Rise in temperature (t2 – t1) = 2.42°C; Fuse wire correction = 10 cal. L = 580 cal/g–1. Sol. HCV = =

(W + w) (t2 − t1 ) − [acid + fuse] correction m

(2,200 + 530) × 2.42 − [50 + 10] cal/g –1 0.92 = 7168.5 cal/g Net Calorific Value (NCV) = (HCV – 0.09 H × L) cal/g–1 = (7168.5 – 0.09 × 6 × 580) cal/g–1 = 6,855.3 cal/g. Example 2. A sample of coal was analysed as follows: Exactly 2.5 g was weighed in a silica crucible, after heating for 1 hr. at 110°C the residue was weighed to be 2.415 g. Next the crucible was covered with a rented lid and strongly heated for exactly 7 mins. at 1000°C. The residue was weighed to be 1.528 g. Then the crucible was heated without cover until a constant weight to 0.245 g was obtained. From the above data calculate the proximate analysis of coal. Sol. Moisture in the sample = (2.5 – 2.915)g = 0.085 g 0.085 × 100 = 3.4 2.5 So, amount of volatile carbonaceous matter (VCM) in the sample = (2.415 – 1.528) g = 0.887 g.
So, % moisture = So, %

0.887 × 100 = 35.48 % 2.5 Weight of ash × 100 % Ash = Weight of coal
VCM = =

Fixed carbon % Fixed carbon

0.245 × 100 = 35.48% 2.5 = (1.528 – 0.245)g = 1.283 g

1.283 × 100 = 51.32%. 2.5 Example 3. On burning 0.83 g of a solid fuel in bomb calorimeter, the temperature of 3,500 g of water increased from 26.5°C to 29.2°C. Water equivalent of calorimeter and latent heat of steam are 385 g and 587 cal/g, respectively. If the fuel contains 0.77% H, calculate HCV and NCV.
= Sol.

(W + w) (t2 − t1 ) m (385 + 3500) (29.2 − 26.5) = 12638 cal g −1 = 0.83 NCV = (HCV – 0.09 H × L) cal g–1 = (12638 – 0.09 × 0.7 × 587) cal g–1 = 12601 cal g–1.
HCV =

406

ENGINEERING CHEMISTRY

Example 4. An ultimate analysis of 1 g coal for nitrogen (N) estimation is the Kjelldahl method, the evolved NH3 has collected in 25 ml

excess acid, 15 ml of 0.1 (N) NaOH was required. Calculate the % of nitrogen in the given sample. Sol. In the Kjelldahl method organic compounds containing nitrogen are heated with concentrated H2SO4 to convert to (NH4)2 SO4. This (NH4)2SO4 during soiling with alkali liberates NH3 that is absorbed in H2SO4

FG N IJ H SO H 10 K
2

4

acid solution. To neutralise the

FG N IJ . Excess acid is titrated with NaOH. H 10 K

The volume of H2SO4 consumed by NH3 (25 ×.1 – 15 × .1) ml (N) = 1 ml (N) Now, 100 c.c(N) H2SO4 ≡ 17 g NH3 ≡ 14 g N.

14 gN = 0.014 gN 1000 Again 0.014 g Nitrogen is present in 1 g coal. 0.014 × 100 = 1.4%. So, % of N in the coal sample = 1 Example 5. A gaseous fuel has the following composition of volume: H2 = 24%; CH4 = 30%; C2H6 = 11%, C2H4 = 4.5%; C4H8 = 2.5%; CO = 6%; CO2 = 8%; O2 = 2% and N2 = 12%. Calculate (i) air to fuel ratio and (ii) volume of dry products of combustion using 40% excess air. Sol. Basis: 1 m3 of gaseous fuel.
∴ 1 c.c(N) H2SO4 =
Volume of combustible gases (m3) H2 = 0.24 CH4 = 0.30 C2H6 = 0.11 C2H4 = 0.045 C4H8 = 0.025 CO = 0.06 H2 + Reaction Volume of O2 m3 Volume of products of combustion on dry basis (m3) – CO 2 = 0.3 CO 2 = 0.11 × 2 = 0.22 CO2 = 0.045 × 2 = 0.09 CO2 = 0.025 × 4 = 0.1 CO 2 = 0.06 × 1 = 0.06 Total = 0.77 m3 CO2 in fuel = 0.08 m3 Net CO 2 = 0.85 m 3

1 O2 = H2O 2 CH4 + 2O2 = CO2 + 2H2O
C2H6 + 3

1 = 0.12 2 0.3 × 2 = 0.60
0.24 × 0.11 ×

1 O2 = 2CO2 + 3H2O 2

7 = 0.385 2

C2H4 + 3O2 = 2CO2 + 2H2O C4H8 + 6O2 = 4CO2 + 4H2O CO +

0.045 × 3 = 0.135 0.025 × 6 = 0.15 0.06 ×

1 O = CO2 2 2

1 = 0.03 2
m3

Total = 1.42 m3 Less = 0.02

Net need = 1.4 m3 (O2)

FUELS AND COMBUSTION

407

Volume of air required (when 40% excess)

100 140 × = 9.333 m3 21 100 ∴ air: fuel = 9.333:1 Total volume of dry products = CO2 + N2 (from fuel + air) + O2 (excess)
1.4 × = 0.85 + 0.12 +

...(i)

Composition of product of combustion on dry basis. CO2 =

L M N

FG 79 × 9.33IJ OP + FG 9.33 × 21 − 1.4IJ m K 100 H 100 K Q H

3

= 8.782 m3

0.82 × 100 = 9.337% 8.782 7.373 × 100 = 83.95% N2 = 8.782 .559 × 100 = 6.365% . O2 = 8.782 Example 6. Calculate the volume of air required for complete combustion of 1 m3 of a gaseous fuel having the composition CO = 46%, CH4 = 10%; H2 = 40% C2H2 = 2%; N2 = 1% and the remaining being CO2. Sol. Basis: 1 m3 of the gaseous fuel.
Combustible gases in the fuel (m3) CO = 0.46 CH4 = 0.10 H2 = 0.4 C2H2 = 0.02 CO + Reaction Volume of O2 required (m3)

1 O = CO2 2 2 CH4 + 2O2 = CO2 + 2H2O 1 O = H2 O 2 2 1 C2H2 + 2 O = 2CO2 + H2O 2 2
H2 +

1 = 0.23 2 0.1 × 2 = 0.20
0.46 × 0.4 ×

1 = 0.20 2 5 0.02 × = 0.05 2

Total O2 = 0.68 m3 required

As air contains 21% of O2 by volume ∴ Volume of air required = 0.68 ×

FG H

100 m 3 = 3.238 m3. 21

IJ K

SHORT QUESTIONS AND ANSWERS
Q. 1. What is a coke? Ans. It is a carbonaceous residue obtained from the destructive distillation of coal, petroleum and coal tar pitch. Petroleum yields coke during cracking processes. The main source of coke is coal. Petroleum coke is used as metallurgical coke since it is pure.

408 Q. 2. What is a fluidised bed?

ENGINEERING CHEMISTRY

Ans. Finely divided solids suspended in a moving gas or liquid behave like a fluid. Catalyst in this form is used for catalytic cracking. Q. 3 What is petroleum? Ans. It is a highly complex mixture of paraffinic, cycloparaffinic (naphthenic) and aromatic compounds with traces of N, O and low percentage of S and is obtained from underground. Q. 4. What is Naphtha? Ans. It is a refined petroleum product 90% of which distils below 240°C and 10% distils below 175°C. It is obtained by cracking of petroleum and mainly used as thinners for paints and varnishes. Q. 5. What is flash point? Ans. It is the lowest temperature at which the vapour of a volatile liquid or solid gets ignited by a small flame e.g., flash point of kerosene is 90°F. Q. 6. What is an anti-knocking agent? Ans. They are organometallic compounds that increase the octane number of gasoline when added in low percentage to it. Most common is TEL (-tetraethyl lead). They can increase the octane number over 100%. Q. 7. What are Octane Number and Cetane Number? Ans. See text page 396. Q. 8. What is aviation gasoline? Ans. It is a variety of gasoline having high octane number i.e., 100 and high volatility and hence used for aircraft. The main components of aviation gasoline are isoparaffins and some TEL. Q. 9. What is straight run gasoline? Ans. Gasoline obtained by direct distillation of petroleum without using other conversion processes like cracking is known as straight run gasoline. Its octane number is low. Q. 10. (a) What is LPG? (b) What is LNG? Ans. (a) LPG or Liquefied petroleum gas is obtained from ‘Wet Natural gas‘ from underground, by washing it with gas oil and fractionating the useful fraction. (b) LNG is Liquefied Natural gas. Q. 11. What is reforming? Ans. See text page 395. Q. 12. What is the difference between gross and net calorific values? Ans. See text page 378. Q. 13. Mention the basic reactions or conversion processes for petrochemical industry. Ans. Petroleum offers a fertile field both for gasoline and for petrochemicals. The following examples are a few of the more important basic reactions. • Cracking
C 7 H 15 .C 15 H 30 .C 7 H 15 D C 7 H 16 + C 6 H 12 = CH 2 + C 14 H 28 = CH 2 gasoline antiknock gasoline

FUELS AND COMBUSTION

409

• Polymerisation
C ¾C ¾ C = C ¾ + ¾ C ¾ C = C ¾ D or cat. C ¾C ¾ C ¾ C ¾ C = C ¾ C 82% C

• Alkylation
C ¾C = C ¾ C ¾ C ¾ + ¾ C ¾ C ¾ C ¾ ¾C¾ 1-Butene Isobutane ¾C ¾ C ¾ C ¾ C ¾ C ¾ C C

Isooctane

• Isomerisation
C ¾C ¾ C ¾ C ¾ C ¾
Straight chain 300°C Anh. AlCl 3

¾C ¾ C ¾ C ¾
Branched chain

• Hydroforming or Aromatisation
(i)
CH 3 CH 3 + 3H 2

( ii )

CH 3 (CH 2 ) 5 CH 3 n-heptane

D cat

CH 3

+ 4H 2

Q. 14. What is Benzol? Ans. Benzol is a coal tar distillation fraction (b.p. 70-150°C) containing 70% benzene, 18% toluene and 6% xylenes. It is blended with petrol. It has octane rating 87-90. The blended petrol is a good motor fuel. Q. 15. What is power alcohol? Ans. Ethyl alcohol when blended with petrol to be used as a fuel for internal combustion engine, is known as power alcohol. Q. 16. What is gasohol? Ans. It is a mixture of gasoline and alcohol. gasoline + alcohol = gasohol. The use of grain alcohol as a blending agent with petrol is a controversial issue in the world. Though blending will reduce 10% petrol consumption but alochol production by fermentation will make use of food grains which is not desirable. Moreover, rectified spirit (95% alcohol) is not suitable for blending, 99.5% alcohol is to be produced which will make the cost higher. That is why now-a-days butanol is tried for the purpose.

410 Q. 17. What is oil gas?

ENGINEERING CHEMISTRY

Ans. Oil gas is mainly obtained by cracking of kerosene oil. But other oils like diesel and heavy oils and petrol may also be used for cracking. A device is set up where a plate is heated specially electrically and the oil is allowed to drop on the hot plate. The oil is cracked to lower gaseous hydrocarbons. C12 H26 → CH4 + C2H6 + C2H4 + C2H2 + etc. + tar The resulting gases are passed generally through a hydraulic main and collected in a gas holder by displacement of water. The composition of oil gas is Calorific value = 54000 kcal/m3. CH4 = 25-30%, H2 = 50-55%, CO = 10-12%, CO2 = 3%,

The gas is mainly generated for laboratory use. Q. 18. What are the advantages of a gaseous fuel? Ans. • Can be distributed over a wide area by pipeline. • Smooth combustion without smoke and ash. • The temperature of heating can be controlled by controlling the gas flow to the burner. • Higher calorific values. Q. 19. Mention the disadvantages of a gaseous fuel. Ans. • Danger of explosion • Larger scale fire risk. Q. 20. What is an anti-knocking agent? a fuel. Ans. The organometallic compounds like TEL or TML, which increase octane number of Q. 21. What is an aviation gasoline? Ans. The variety of gasoline specially suitable for aircraft having octane number well over 100. Q. 22. Why is sulphur content controlled below 0.1%? Ans. Sulphur and sulphur compounds greatly reduce effectiveness of TEL to increase the octane number of a fuel. Q. 23. What is a natural gasoline? Ans. A mixture of butane, pentane, and hexane obtained from natural gas. Q. 24. What is HDA process? Ans. Gasoline produced, for the manufacture of ethene, as a byproduct is known as pyrolysis gasoline. This gasoline is mainly used to produce benzene by Hydro-DeAlkylation (HDA) process. CH3(CH2)8CH3 → C8H18 + CH2 = CH2
octane ethene
700 K

C8H18 → C6H6

HDA

FUELS AND COMBUSTION

411

Q. 25. What is white gasoline? Ans. It is unleaded gasoline used for motor boats. Q. 26. Why is calorific value of coal gas higher than that of producer gas? Ans. Coal gas contains all the combustible gases like CH4, C2H4, C2H2, CO and H2, whereas producer gas contains CO, H2 and N2. N2 acts as inert diluent. So calorific value of coal gas is higher than that of producer gas. Q. 27. Producer gas is made by passing air and steam through a thick bed of coal. Why? Ans. The primary purpose of steam is to use up the heat developed during exothermic reaction of coal and O2 of air to maintain the temperature of producer. Q. 28. Why is NCV greater than GCV? Ans. Gross calorific value GCV includes the latent heat steam during combustion of a fuel, but Net calorific value NCV excludes the latent heat of steam. Q. 29. Why a good solid fuel must have low ash content? Ans. Ash is inorganic in nature. So high ash content decreases the calorific value of a fuel. Q. 30. What is CNG? Ans. CNG is compressed natural gas used in motor engines now-a-days instead of gasoline fuel causing less pollution. Q. 31. What is synthesis gas or syn gas? Ans. Modern processes produce a mixture of CO and H2 from coal and steam more efficiently than the old water gas and producer gas plants. Two varieties of gas are obtained: (i) Low heat gas (ii) Medium heat gas. Low heat gas contains 50% N2. These gases are known as synthesis or syn gas. The gasification is done in fixed bed: (i) Fluidised bed.(ii) Entrained bed. Reactions: (i) C + H2O = CO + H2 (ii) CO + H2O = CO2 + H2 (iii) C + CO2 = 2CO Q. 32. What is SNG (Substitute Natural Gas)? Ans. (i) During the production of syn gas, at sufficiently high pressure i.e., during hydrogasification H2 liberated converts carbon to CH4. C + 2H2 = CH4, CO + 3H2 → CH4 + H2O The gas produced was known as synthetic natural gas. But the synthetic product cannot be known as natural; so now it is called substitute natural gas (SNG). The operating pressure may be atmospheric to 7 MPA and temperature 800°C-1650°C for gasification. The higher pressure and lower temperature result in the formation of larger amount of SNG.
cat

412
Coal

ENGINEERING CHEMISTRY

Distillation zone Pyrolysis zone

Coal = C + ash + tar + H 2 O C n H m = CH 4 + C + H + Tar C + 2H 2 = CH 4 C + CO 2 = 2CO

Gas 120°

Gas 600°

Gasification zone

C + 2H 2 O = 2H 2 CO 2 CO + H 2 O = H 2 + CO 2 C + H 2 O = H 2 + CO 1100°

Combustion zone

C + O 2 = CO 2 2C + O 2 = 2 CO Ash bed

Air and steam blast

Fig. 18.17 Showing gasification reactions involved in a gasifier.

EXERCISES
1. 2. 3. 4. 5. 6. 7. 8. 9. What is sweetening of petrol? What is flue gas? How is it analysed? Describe the fluidized bed cracking of pertroleum mentioning the catalysts used. Describe the manufacture of producer gas? What are its uses? What is leaded-petrol? Write the difference between proximate and ultimate analyses. Describe the manufacture of biogas from waste materials. How is the calorific value of a fuel determined? Write notes on: (i) Bomb calorimeter. (ii) Octane number (iii) Catalytic cracking (iv) Proximate analysis. 10. What is carbonization? Write the advantages of high temperature carbonization. 11. What is power alcohol? 12. Write a brief note on: (i) Synthetic petrol (ii) Blue water gas.

FUELS AND COMBUSTION

413

13. (a) What are fuels? How do you classify them? Describe methods employed for ultimate analysis of coal. (b) Explain the terms (i) Knocking (ii) Octane number (iii) Cetane number. 14. (a) What is sweetening of petrol? Name the various fractions obtained during the fractional distillation of crude petroleum oil. (b) What is the flue gas? How is it analysed? 15. What is meant by cracking of petroleum? Describe various methods used for cracking of petroleum. 16. Write a short note on biogas. 17. Describe fixed bed catalytic cracking. 18. How are gross and net calorific values of a solid fuel determined using a Bomb calorimeter? 19. Give a detailed account of petroleum refining. 20. Give at least four advantages of catalytic cracking over thermal cracking. 21. What is L.P.G.? Give its uses. 22. What do you understand by cetane number of a fuel? Distinguish between high speed diesel and low speed diesel. 23. Mention advantages and disadvantages of a gaseous fuel. 24. What is the difference between claking coals and coking coals? 25. What is power alcohol? Mention its merits and demerits? 26. Give the constituents and uses of Gobar gas. 27. Discuss giving equations, sketch, manufacture and composition of: (a) Producer gas 28. Write a short note on: Orsat’s method of flue gas analysis and its significance. 29. Write short notes on: (i) Catalytic converter (ii) Octane and cetane numbers. 30. Write a short note on: Carburetted water gas. 31. What is ultimate analysis of coal? 32. What is the difference between H.T.C. and L.T.C.? 33. Mention the byproducts of coking of coal. (b) Water gas (c) Oil gas.

OBJECTIVE TYPE QUESTIONS
1. 2. Which of the fuel gases has highest calorific value? (a) Water gas (a) Moisture content is high (b) Volatile matter is high (c) Fixed carbon is high. 3. 4. Calorific value of coal is decreased due to presence of (a) Carbon (a) Peat (b) Sulfur (b) Lignite (c) Hydrogen (d) Oxygen. (c) Bituminous coal (d) Anthracite. Which of the following contains highest percentage of volatile matter? (b) Coal gas (c) Producer gas. The calorific value of a coal sample is higher if its

15. Bomb calorimeter is used to measure (a) Calorific value (b) Carbon content ENGINEERING CHEMISTRY (c) Boy’s gas calorimeter. ash and volatile matter (b) C. Anthracite is a coal of (a) Highest calorific value (b) Lowest rank (c) High volatile matter. (c) More than 100. (c) Knocking properties. 8. (c) Water gas. 6. 7. (c) CO + N2 (c) Diesel. S (c) C and H. 14. (c) Isooctane. H2O. 11. N. 13. Fuel gas used as a source of hydrogen is (a) Natural gas (b) Producer gas Isooctane has an octane rating of (a) Zero (b) 100 Better diesel fuel is determined by (a) Octane rating (b) Cetane number Producer gas is a mixture of (a) CO + H2 (b) CH4 + H2 Fuel for jet plane is (a) Aviation gasoline (b) Kerosene Natural gas is composed of: (a) n-butane (b) Methane Proximate analysis of fuel determines the percentage of (a) C. H. (c) C content. 10.414 5. Analysis of flue gases is done by: (a) Bomb calorimeter (b) Orsat’s apparatus Alcohol-blended petrol possesses (a) Better calorific value (b) Reduced antiknock properties (c) Better antiknock properties. 9. 12. .

– – – – – – – – – – – – – – Fig. e — Silicon atom. The structural pattern of silicates are important in different ceramic products which have been shown in following figures: In a silicate unit silicon atom is symmetrically surrounded by four oxygen atoms to form a tetrahedral unit. humus (decayed vegetable matter) and various other minerals. d — Oxygen atom. Ceramic products are made of clay which are silicates. transparent or translucent.2). – – – – – – – – – – Fig. Soil is infact a mixture of clay. Basically most of these are hydrated silicates of aluminium. 19. Chain silicates.1). Clay is a mixture of variety of minerals like bentonite. These tetrahedral units remain joined in the silicates (see Fig.1).2 Structure of [(Si4O11)n]6n– ion (double chain). Clay and soil are different products.. while double chain silicates contain [(Si4O11)n]–6n as the primary unit (Fig. all these industries fall under silicate technology. rigid super supercooled liquid of infinitely high viscosity comprising of metallic silicates one of which is usually of an alkali metal. Soil is the thin outermost layer of the earth. Silicates are chemical compounds of silicon and oxygen with metals. 19. hauoysite etc.1 Structure of [(SiO3)n]–2n ion (single chain). sand. kaolinite. cement is also a mixture of silicates and other compounds.Silicate Technology INTRODUCTION 19 Glass and Pottery are the earliest products of man made chemical industry. 19. Glass is an amorphous. single chain silicates and double chain silicates. 19. Single chain silicates contain [(SiO3)n]–2n ion as the primary unit (Fig. Clay must not be confused with soil. 415 . Glass was known to the ancient Egyptians 6000 years ago. 19. These silicates are of two types viz. So.

3). . do not contain any negative charge. Bentonite is an example: BaTiSi3O9. do not carry any negative charge. forming a bridge between SiO44– tetrahedral units. O-atoms. i. forming no bridge.3 Structure of Si3O9–6 and Si6O18–12 ions (ring). These silicates have cyclic structure and contain [(SiO3)n]–2n ion as the primary unit. – – – – – AND – – – – – Si 3 O 9–6 (ion) – – – – – – – – Si 6 O 18–12 (ion) Fig. These silicates are formed when each SiO44– tetrahedron shares two O-atoms (bridging O-atoms). – – – – – – – – – – – – – – – – – – – Fig.4 Structure of sheet silicates (layered structure). 19.. carry negative charge.416 ENGINEERING CHEMISTRY It may be noted that O-atoms.e. 19. which are shared by SiO44– tetrahedrons. O-atoms. 19. Cyclic or ring silicates (Fig.

in YBa2Cu3 O7–y (see Fig.SILICATE TECHNOLOGY 417 Clay or silicates are common raw materials for Ceramic industries Refractory industries Glass industries and Cement industries. 19. For example. The property of super-conductivity in these compounds is dependent on a particular characteristic of arrangements of constituent atoms. 19. some new types of ceramics are discovered with electrical and magnetic properties.5) successive horizontal layers of copper-oxygen sheets are separated by ribbonlike chains of copper-oxygen. . ground well and finally heated to 1000°C for 12 hrs.5 The crystal lattice of YBa2Cu3O7–y. The square copper-oxygen sheets are the pathways of superconducting electrons in these compounds. These properties depend on their unit structure. These ceramics are called high performance ceramics. The individual solid metal oxides were mixed in the proper ratio. For that reason the technologies of these industries fall under the common name silicate technology. at this high temperature the individual oxides are converted into the mixed oxide compound. Now-a-days. • • • • Oxygen Copper Ba Ba Y Y Ba Ba Ba Ba Y Y Ba Ba Fig. The preparation of superconducting ceramic therefore. Even slight alteration of the arrangement of atoms destroys superconductivity. Generally silicate materials are bad conductor of heat and electricity. is an exacting piece of work.

65 Fe2O3) should not be more than 1. patented an artificial cement made by the calcination of an argillaceous lime stone (argil-clay). CaO ≤ 1. viz. The rocks on calcination gave a product that hardened on the addition of water. He called this ‘Portland’ as concrete made from it resembled a famous building stone obtained from the Portland island near England. SiO2 (CaO)4Al2O3 . The present day civilization very much depends upon lime. The raw materials should be so proportioned as to produce a cement in which the ratio of the amount of CaO to the amount of (2. This is an example of application ceramic superconductor like YBa2Cu3O7–y. The hard clinkers (Brick type) resulting from the burning of argilaceous limestone is known by the term Portland cement to distinguish it from natural or Pozzuolana and other cements.66 ≤ 2. The Greek and Romans used volcanic tuff for cement and a number of these structures are still standing. Cement was first used by the Egyptians in constructing the pyramids. The cement will set under water and therefore it is known by the name of Hydraulic cement. • Roman cement • Portland cement. SiO2 or 2CaO . Fe2O3 Abbreviation C3A C3S C2S C4AF CEMENT . superfast floating train. A cement is a substance.65 Fe 2O 3 The Portland cement is a mixture of the following compounds: Compounds (i) Tricalcium aluminate (ii) Tricalcium silicate (iii) Dicalcium silicate (iv) Tetracalcium alumino ferrate Formula 3 CaO . Al2O3 or (CaO)3 . an Englishman. The tremendous application of these products is due to their: • Convenience • Cheapness • Adaptability • Strength • Durability Man had early discovered certain natural rocks. In 1824. Portland cement is now manufactured on a large scale.. Portland cement is made by mixing calcareous (lime-stone) and argilaceous materials in the proper ratios and heating to the point of incipient fusion in a kiln and grinding the resulting clinker. tunnels. SiO2 (CaO2) ..8 SiO2 + 1.418 ENGINEERING CHEMISTRY These types of superconductors are used in superfast magnetically leviated (maglev) train i. which sets to a hard mass in presence of water.e. reinforced-concrete walls and girders (a chief beam). Two types of cements are in use. Al2O3 3 CaO . mortar and cement products.02 and not less than 0. Of these.2 Al 2 O 3 + 0.66 i. This was the start of the Portland cement industry as we know it today.8 SiO 2 + 1. Al2O3 .e. SiO2 or (CaO)3 . Fe2O3 or 4CaO .02 0.2 Al2O3 + 0. Joseph Aspdin. dams and roads etc.

Limestone is partly replaced by the CaCO3 mud obtained as by-product during clarification of sugarcane juice at the sugar factory of the same company. In India. • Pozzuolana cement. precipitated calcium carbonate and misc. • Special or corrosion resisting cement. Rohtas Industries Ltd. SiO2. can be put into service more quickly than if regular cement had been employed.C.. MgO etc). A concrete of better chemical resistance contains high proportion of C4AF. clay and shale. White cement contains less ferric oxide. The complete process involves a combination of (1) grinding. (2) classification.S] is made from a raw material with a high lime to silica ratio. cement rock and marl (mixture of CaCO3 ) and clay are used. It is characterised by a very rapid rate of development of strength and superior resistance to sea water and sulphate carrying water. gypsum. Raw Materials Formerly a large proportion of cement was burned from argilaceous limestone known as cement rock.. Low heat portland cement contains high proportion of C4AF and C2S. iron material.SILICATE TECHNOLOGY 419 Small amount of MgO derived from the raw materials is also present. In making these differential separations. Si.E. Gypsum (2-3%) is added to prevent rapid setting of the C3A. Sand. cement rock. Dalmianagar.S. The regular Portland cement contains medium amount of CaO. Roads constructed from H.E. The collecting agent must selectively wet or ‘film’ the mineral to be removed and act with the air to cause the particles to be lifted to the surface making a froth. It contains a higher proportion of C3S than regular Portland cement and hence hardens much more quickly. In industries for CaO of cement. Varieties of Cement • Portland cement. the purpose is to ‘benificiate’ available raw materials and hence the process is named beneficiation process.e. very small quantities of collecting reagents are employed. List of Raw Materials: Limestone. waste bauxite and iron ore are sometimes consumed in small amounts to adjust the composition of the mix. It is mainly used for the fabrication of corrosion proof linings for chemical equipment such as storage tanks. (3) floatation and (4) thickening operation. marl. sandstone.C. That is. Al and Fe essential for cement manufacturing and discard useless constituents. the artificial ones are burnt clays and shales. High early strength cement [H. Bihar company to manufacture cement. i. chalk. In addition to natural materials some plants use artificial products such as blast furnace slag and precipitated CaCO3 obtained as a by-product in alkali and synthetic ammonium sulphate industry. the froth floatation process is used to remove the undesirable material in the froth and oleic acid . Some cement contains gypsum or plaster of paris. sand. which is not cementitious in itself but becomes so upon mixing with lime. The natural pozzuolana are volcanic tuffs. A pozzuolana is a material. It is manufactured by fusing a mixture of limestone and bauxite (contains Fe2O3. absorption towers. A processing of available raw materials is necessary to correct the proportions of the mineral sources of the four oxides of Ca. Example: phenolic cement–phenol formaldehyde resins. acid digesters etc. the byproduct precipitated CaCO3 from Sindri Fertilizer Corporation of India was utilised by A. This may involve the raising of the lime content of the raw materials or it may be for the elimination of the greater part of the silica as compared to the alumina. Delhi uses (1) Laterite (red clay) and (2) limestone. • High alumina cement. which is added in small quantities to increase the plasticity of cement. blast furnace slag.

6). the solid material after dry crushing is reduced to a fine state of division in wet tube or ball mills and passes as a slurry through the bowl classifiers or screens. although Portland cement clinker itself is satisfactory for the purpose. The internal diameter is usually 8 to 15 ft.. Heat is provided by burning oil. Frothing aids in separation of desired materials from the undesired ones. The dry process is especially applicable to natural cement rock and to the mixtures of limestone and shale or slate.p. The moisture content of the feed is 40%. Al2O3 3CaO + Al2O3 → 3CaO . xH2O → Al2O3. Manufacturing Procedure Two methods of manufacture are used: • Wet process • Dry process The wet process was the original one. But the wet process is now being adopted largely for new plants for more accurate control and mixing of the raw mixture. 300-500 ft kilns are not uncommon. high alumina bricks and high magnesia bricks are widely used for the lining of the kiln. taking from 2-3 hrs (Fig. sized and more finely ground in tube mills. the choice of refractory linning is difficult. For a time it was gradually displaced by the dry process. For this reason. SiO2 . but in the wet process.. In order to obtain greater heat economy. The kilns are rotated at from 1/2 to 2 r. In this process. In the wet process. gas or pulverised coal. the materials are roughly crushed in jaw crushers followed by gyratory mills.420 ENGINEERING CHEMISTRY may be employed as the collector. Waste heat boilers are used to conserve heat..m. 3Al2O3 2CaO + SiO2 → 2CaO .SiO2 + xH2O CaCO3 → CaO + CO2↑ *5CaO + 3 Al2O3 → 5 CaO . SiO2 3CaO + SiO2 → 2CaO . Al2O3 Heat change Endothermic Endothermic Endothermic U | V | W Exothermic (Contd. This slurry is filtered in a continuous rotary filter and fed into the kiln. This dry powdered material (moisture content 2%) is fed directly to the kiln. The kilns are slightly inclined so that materials fed in at the upper end and travel slowly to the lower end. Reactions at various temperatures in the kiln Temperature 100°C > 500°C > 900°C 900°C to 1200°C Reactions Evaporation of water (H2O↑) Al2O3 . The tendency in recent years has been to lengthen the rotary kiln in order to increase its thermal efficiency. The slurry is pumped to correcting tanks where rotating arms make the mixture homogeneous and allow the final adjustment in composition of raw materials to be made. Because the lining of kiln has to withstand severe abrasion and chemical attack at the high temperatures in the clinkering zone. using preheated air from cooling the clinker. unit operations are used for removing the part of the water from slurry by slurry filters. 19. 80-160 lbs of fuel are necessary per barrel (376 lbs) of cement. Dry process kilns may be as short as 150 ft. depending on size. A concentration of 0. SiO2 2CaO + Al2O3 → 2CaO .04 lb per ton of rock suspended in 4 tons of water has given good results. then dried.) .

Endothermic Endothermic 1250°C – 1280°C > 1280°C Oversize Crushed shale limestone Mills Water Filtrate Filter Screen Correcting tank Slurry mixers Kiln Fuel Hot air Gypsum Air Clinker storage C o o le r Shale – 500 lbs Limestone – 2400 lbs Gypsum – 70 lbs Mills Per ton of cement Water – 750 gal Coal – 600 lb Power – 90 kwh Labour – 2. Pulverising followed by the fine grinding in tube ball mills and packaging complete the steps to the finished cement. 19. CaSO4 ⇒ 1.46%. called clinker. The clinker falls through openings in the stationary firing ring of the kiln into rotating coolers. Unchanged clay and sand ⇒ 2.27%. During fine grinding the following materials are added to the finished cement. which simultaneously preheat the combustion air. bagging Fig.75%. MgO ⇒ 0.SILICATE TECHNOLOGY 421 Commencement of liquid formation Further formation of liquid and compounds *Main reactions between lime and clay. The final product formed consists of hard grannular masses from 1/8 to 3/4 inches in size.1 man hr Storage. Potash ⇒ 1.92%. Al2O3 and SiO2. Al2O3 ⇒ 8% Fe2O3 ⇒ 5. • Retarders such as gypsum • Plaster or calcium lignosulphate • Air entraining agents • Dispersing agents and • Waterproofing agents .06%. Lime produced combines with main constituents of clay viz.13% Soda ⇒ 1.77%.7%.6 Wet process for cement manufacture. The analysis of typical samples of cement gives the following composition: Lime ⇒ 55. SiO2 ⇒ 22.

xH2O (amorphous) C3S + xH2O → C2S . The liquid glass is cooled until thick enough to mould and then shaped and cooled further slowly (annealing) until it sets to a solid mass. Glass may be considered as supercooled liquid of infinitely high viscosity. which takes the Al2O3 as C4AF. Due to this interlacing of crystals the setting of cement occurs. 3CaSO4 . 2H2O) + 25 H2O → C3A . (x – 1) H2O (amorphous) + Ca(OH)2 C3A + 6H2O → C3A . bottles. This is followed by a slow crystallisation of the gel.3CaSO4. Another theory suggests that due to hydration. Lower clinkering temperature GLASS Glasses are Ceramic materials that are rigid like solids but which are not crystalline. the structure may be cooled during setting by circulating cold water. Compounds C3A C3S C2S and C3S Fe2O3. If this was not true. Most glass is made from silica mixed with other oxides that melt at a lower temperature than glass made from pure silica. The following table displays the functions of various compounds of cement. (x – 6) H2O MgO + H2O → Mg(OH)2 The various compounds contribute to the heat of setting as follows: C3A > C3S > C4AF > C2S Lower heat of setting of cements are made low in C3A and C3S but high in C2S by adding more Fe2O3. thereby diminishing the amount of C3A and by decreasing the CaO/SiO2 ratio. 6H2O(c) The hydration products have very low solubility in water. windows. On addition of water. The following equations represent these reactions: C2S + xH2O → C2S . To hold up the ‘flash set’ caused by C3A. The following equations represent these reactions: C3A + 6H2O → C3A .Al2O3). and the cause of setting has been the subject of much discussion. and drinking water glasses are made of . 31H2O C4AF + xH2O → C3A .422 ENGINEERING CHEMISTRY Setting or Hardening of Cement Setting of cement is a complicated process. concrete would have been rapidly attacked in contact with water. the calcium compounds are decomposed with the formation of free Ca(OH)2 and hydrated crystalline silicate and calcium aluminate. while others believe that the gypsum gives free Ca(OH)2 by reaction with alkali and this in turn forms the more stable C4A(4CaO. Glass is made by melting one or more oxides in a furnace. 6H2O(c) C3A + 3(CaSO4 . the crystals of which form an interlaced mass. Fe2O3 . But it is generally agreed that this takes place by hydration and hydrolysis. Mg and alkalies Function Responsible for initial set (flash set) Responsible for 1st strength (after 8 days) Responsible for final strength (at 1 yr). This low heat of setting cement is used for construction of dams to avoid cracking the structure from heat stresses during setting and cooling. 6H2O with absorbed water. Al2O3. The rapid increase in strength and hardness during setting of cement is mainly due to the partial hydrolysis of C3S to form needles of Ca(OH)2 in the hydrated silicate gel.3H2O. 6H2O(c) + CaO . As an additional safeguard. some investigators assert that the gypsum added as retarder causes the temporary formation of C3A. cement is converted into a gel of composition C3A.

Coloured glasses • Colour is produced by the absorption of certain light frequencies by agents in solution in the glass. • Lead glass [Potash lead glass. refractive index.). window and plate glass.V. Mn. Different varieties of glass • Vitreous Silica (quartz glass).CaO. SiO2.5) Uses. radiation (ordinary glass is not transparent to U. K2O . Flint glass] (K2O.7-1. Compostion of glass Glass is not a single compound.78 (higher than that of common glass. Special glasses 1.6SiO2). Uses. Used beyond the temperature ranges of other glasses.SILICATE TECHNOLOGY 423 soda lime glass. V. for preservation of eggs. low expansion coefficients. Wide and ever increasing uses for these properties for laboratory glassware. sp.6SiO2) fuses easily. high electrical resistance. excellent chemical stability. Transparent to U. A glass made by fusing pure silica without a flux and is very resistant thermally and chemically. . higher. Cr. Co.36(SiO2 + B2O3). The colouring agents of this group are the oxides of transitional elements. Uses. µ = 1. Borosilicate glass is used to make ovenware and laboratory glassware.CaO. µ = 1. When part of SiO2 in glass formulation is replaced by B2O3 the glass formula becomes 7Na2O. in the manufacture of artificial stones. Ni and Cu. gr. SiO2)] used in soap manufacture. specially combustion tubes. K etc. Uses.6SiO2) are easily fusible.4CaO. Pb etc. Fusion temperatures high. 3ZnO. Hard glass] (K2O. especially the first group: Ti. soft glass (Na2O. Laboratory apparatus.) M = bivalent metal (Ca. SiO2 = 80-83%. soda glass. It is difficult to write any chemical formula for it. Lead glass is used for decorative cut glassware.V.) x and y = number of molecules. • Borosilicate glass. • Alkali silicates [Soluble glass (Soda). 6SiO2 where R = alkali metal (Na.PbO. soluble glass (Potash). Generally the formula for glass may be represented thus. usually contains B2O3 = 10-13%. (b) Potash lime glass [Bohemian glass. Chemical apparatus withstanding high temperatures. Water glass (Na2O . • Lime glass (a) Soda lime glass. superior resistance to shock. low softening temperature. Fe. xR2O. yMO. (a) decoration and optical effects (b) manufacture of lens and prism (c) artificial gems (d) electric bulbs.

It can resist HF. When the glass is broken the fragments are held in place by inter layer. Selenium rods (SeO2) used in traffic lights. glass capable of transmitting UV light could be manufactured. SiO2 + 6HF → CaF2 + SiF4 + 3H2O (b) Ordinary glass attacked by alkali solutions.424 ENGINEERING CHEMISTRY • Colour is produced by colloidal particles precipitated within an originally colourless glass by heat treatment. Fibre glass • Glass wool is impregnated with various binders and used for insulation. (b) Vitrifies easily. 5. but devitrifies by formation of crystals under suitable conditions. Sight glasses for the handling of uranium hexafluoride in separation of uranium isotopes are made of phosphate glass. acids. Glass is then said to devitrify. • It can be spun into yarn. or sand and water. Opal. translucent or ground glass (ghosa kanch) Soft glass made translucent by rubbing the surface with emery powder and turpentine. wholly or partially displacing SiO2. • Colour is produced by microscopic or larger practicles. Na2O . water. 2. High silica glass 96% SiO2. This glass has high chemical durability and is extremely stable to all acids except HF. (b) Fe2O3: Inability to transmit UV is due to the presence of FeO or Fe2O3 in glass. Using iron free raw materials. Only attacked by HF readily. SiO2 + 6HF → 2NaF + SiF4 + 3H2O CaO . Functions of different constituents of glass (a) K2O: increases the softening point. 3. Safety or laminated glass Two layers of glass with an interleaf of plastic. oxidising agents. On long standing or very slow cooling during annealing some of metallic silicates crystallise out. Example is the precipitation of gold (colloidal) producing gold ruby glass. Phosphate glass It contains P2O5 as a major ingredient. 4. which attacks more slowly than others. Properties of glass • Physical: (a) Transparent (usually) amorphous solid. . (c) Hard and brittle (d) No fixed melting point (e) Bad conductor of heat and electricity ( f ) Can incorporate colour maintaining transparency • Chemical: (a) Not attacked by air. 6. 3% B2O3 and the rest Al2O3. using HF.

The latter is useful in oxidising iron and accelerating the melting. • In window glass molecular ratios are approximately 2Na2O.Al2O3. • Soda. SnO2 etc. Feldspars supply Na2O or K2O. • The compounds may be of the type Na2O. 3. Fe3O4 for green colour.SILICATE TECHNOLOGY 425 (c) PbO: increases the refractive index of glass.g. c SiO2 + SO2 + CO. Devitrification means slow crystallisation. The green colour due to ferrous silicate being changed to yellow colour due to ferric silicate. BaO. Various decolourising and opacifying agents like MnO2. The latter introducing MgO into the batch. like soda. PbO etc. • Potash is always used in the form of K2CO3. • Boric acid as such or as B2O3.1.Al2O3 serves to lower the melting point of the glass and to retard devitrification. Cr2O3. Substances of an acid character.. Zn-compounds. • Feldspars having the general formula R2O.6SiO2. Substances of basic character. CuO for blue colour. Cu2O for ruby or red colour. a SiO2 + CO2 CaCO3 + b SiO2 → CaO . It facilitates melting and utilises waste. lime. Pb3O4. . • Silica is used in the form of sand. • Cullet is crushed glass from imperfect articles. • H3PO4 is used as an opacifying agent.5SiO2.8SiO2. B2O3. Certain colour producing oxides are used for producing coloured glass. Other sources are salt cake and NaNO3. It is almost pure quartz (white sand) of which iron content should not exceed 0. potash. MnO2 for violet colour etc. nitre. It may be as low as 10% of the charge or as high as 80% of the charge. • ZnO is sometimes used to replace lime. Na2O is principally supplied by soda ash. • It should be noted that the ratios Na2O/SiO2 and CaO/SiO2 need not be 1:1 molecular ratios. CaCO3. MnO2 is added to the charges which oxidises Fe+2 to Fe+3. Chemical reactions of the formation of glass in a furnace Na2CO3 + a SiO2 → Na2O . (d) B2O3: increases the hardness or refractory characters of glass and lowers expansion coefficient. • For decolourisation. • PbO in the form of Pb3O4.045%. (CaO) are limestone and burnt lime from dolomite. MgO.(R2O) and SiO2. like SiO2. • BaO as such or as precipitated BaCO3. Na2CO3. ZnO. • The important sources for lime. b SiO2 + CO2 Na2SO4 + c SiO2 + C → Na2O . MgCO3.CaO. 2. e. Raw materials The raw materials employed in the manufacture of glass can be classified under three heads: 1.

The glass articles are shaped either manually or by machine. Two types of furnaces are in use: (a) Pot furnaces (b) Tank furnaces Pot furnaces are employed principally in the manufacture of optical glass. The material of the pot is attacked by prolonged action of molten glass and hence has to be changed after a number of operations except when platinum is used. All types of glass articles must undergo certain finishing operations. cutting. high alumina fire clay such as mulite (3Al2O3 . (ii) Cooling the mass to room temperature slowly. The operation is continuous. . Annealing involves two operations: (i) Holding a mass of glass above a certain critical temperature. grinding. In either of the cases the heat from the hot gases is utilised in preheating the air. batch materials are charged into one end of a large ‘tank’ built of refractory blocks. art glass and plate glass and in the small scale units. It is allowed to stand vertically on a stand. Sometimes water cooling pipes are used to cool the furnace wall. At present every stage of shaping has been mechanised. In order to produce a sheet glass first a cylinder of approximate size is blown into shape. for combustion of the fuel. The larger part of the heat is lost by radiation from the furnace walls. polishing. Otherwise the furnace wall will corrode. Although all these are not required for every glass object. The pots are really crucibles made of selected clay.426 ENGINEERING CHEMISTRY This yellow colour is rectified by the pale violet colour due to manganese silicate and a perfect white glass results. it is necessary to anneal all glass objects. The annealing oven is nothing more than a carefully designed heated chamber in which the rate of cooling can be controlled. one or more is almost always necessary. (ii) Shaping or forming. In a tank furnace. To reduce strains. long enough to reduce internal strain by plastic flow. This sort of heat loss is necessary to reduce the action of the molten glass on the furnace wall. Once the furnace has been heated. Manufacturing procedure The manufacturing procedure is divided into four major phases: (i) Melting (ii) Shaping (iii) Annealing (iv) Finishing (i) Melting. The ‘formed’ glass is worked out of the opposite end of the tank. a temperature 1205°C is maintained all the time. The walls of tank furnace gradually wear away under the action hot glass. 2SiO2) or platinum. The blowing is done by compressed air. The furnaces may be of either regenerative or recuperative design. The tank measures 125′ × 30′ × 5′ with a capacity of 1400 tons. enameling etc. These include cleaning. The cylinder is cut open by running a sharp knife lengthwise. (iv) Finishing. (iii) Annealing. The glass forms a pool in the hearth of the furnace across which the flames play alternately from one side to the other.

. sometimes enamelled or glazed. coherent mass without losing its original colour. Mn. 6SiO2 + CO2 + 2H2O → K2CO3 + Al2O3 . it sinters together forming a hard. porcelain wares. The use of clay in ceramics depends upon its following important properties: (i) It is plastic enough to be moulded when it is wet. Mg etc. Geologically. When fired. clays are regarded as the products of disintegration and weathering of granite rocks. pottery articles. 2SiO2 . Kaolin or China clay It is a pure white burning clay of low plasticity and is formed by weathering of feldspar. (ii) It retains its shape when dried and. Composition— Al2O3 . Al2O3 . electric insulators. and vegetable matters. Clays are used in the manufacture of bricks. in which feldspar was a original mineral but the term is also applied to most minerals which possess the property of being plastic when mixed with a suitable amount of water. 2SiO2 . Weathering reaction: K2O .SILICATE TECHNOLOGY 427 Flow diagram mentioning manufacturing sequences for glass Transportation of raw materials Sizing of raw materials Storage of raw materials Weighing and feeding the raw material to furnace Heat saving by regeneration Annealing of glass products Shaping of glass Reacting in the furnace to form the glass Finishing of glass products Burning the fuel to secure the temperature needed for glass formation POTTERY AND PORCELAIN Clay They are generally clay fired products. Ca. drain pipes and other sanitary goods etc. 2H2O + 4SiO2 feldspar kaolinite Common clay It is principally aluminium silicate mixed up with a large number of substances viz. (iii) When the moulded mass is heated to a high temperature. 2H2O Fire clay. tiles. It contains a good deal of SiO2 and very little Fe. it forms a material of high fusing point (1550°C and upwards). compounds of Fe.

. . The glazed product is obtained by applying glaze on the unglazed body. It is not always white because the ingredients contain Fe2O3. CaO = 1%.2H 2 O ¾¾® 6H 2 O ­ + 3Al 2 O 3 China clay 600°C (amorphous) + 6SiO 2 (amorphous) (Crystal) SiO 2 ¬¾¾ 4SiO 2 + 3Al 2 O 3 . Feldspar. K2O = 6%. Quartz (SiO2). Quartz etc. Al2O3 = 18%. For glazing the shaped material is covered with a coating of mixture of powdered feldspar. It is made from Borax. Common fluxing agents. (iv) high class sanitary goods. cryolite. borax etc. This is a kind of porcelain. The three main raw materials are: (1) clay (kaolinite). Ball clay 3. The thin coating melts and forms a glaze on the surface of the body. (ii) basin. crucibles. Flint (Pure SiO2 + CaCO3) 4. CaCO3. SiO2. It is used for making jars suitable for storing acids. and heated at higher temperature for longer time. Marble (CaCO3) 6. Cornish stone (Potash feldspar. TiO2. Common refractory materials. Chemical stoneware. iron oxides.2SiO 2 . therefore is looked upon as partly glass and partly stoneware. It is glazed with salt. (iii) electrical insulators.428 Pottery: (articles made of clay) Pottery ENGINEERING CHEMISTRY Non-porous (1) China and Porcelain (2) Earthenware (3) Stoneware Porous (4) Unglazed pottery (3) Terracotta. Both glazed and unglazed clay products are manufactured. Na2CO3. SiO2 = 75%) 5. (2) feldspar. K2CO3. tiles etc. (3) sand. CaO. Porcelain. boric acid. bricks. The raw materials for unglazed product 1. ZnO2. the unglazed product is to be made. are: In all cases.2SiO 2 ¬¾¾¾ g -3Al 2 O 3 Mullite 1400°C 1000°C ®¾¾ + 900°C Silicate Crystal line formation (amorphous) 6SiO 2 Porcelain is used for making– (i) dinner and tea sets. Borax. Raw materials. floor and wall tiles. It is used for sewer pipes. China clay 2. Raw materials for glaze Frit. It is a sort of glass. Stoneware. The reactions of porcelain formation are: 3Al 2 O 3 . fluorspar.

3. Storage Water Vac Cutter Brick Clay Screen Crusher (a) Clay Vac Screen flint water Feldspar Jigger Extruder Mag. 4. Usual maximum temperature is 1400°C. The firing is done in a tunnel furnace.7 Flow diagram: (a) Brick manufacture (b) Dinner plate manufacture. 5. But in most cases. The residual cake contains 10-30% water. Slurry preparation: The mixture of weighed ingredients is taken in a blunger and stirred well with water to form a creamy liquid known as clay slip. blanks are fired to produce biscuits. 6. separator Cutter Slurry Agitation Slurry Blunger Dinner plate Drager Filter press Press (b) Fig. 2. In few cases glaze is put on the blanks before firing. The cakes are dumped for some days. Glazing: The dried articles known as blanks are glazed. . Ageing: The slip is filter-pressed.SILICATE TECHNOLOGY 429 Process: It consists of the following steps: 1. 19. Deairing: The aged cakes are deaired in a pug mill by slicing with knives and putting under vacuum. Shaping. This improves the plasticity of the clay mixture because of uniform hydration and gelation. Trimming and drying: The shaped articles after airdrying are trimmed and then dried in hot air.

magnesite.430 ENGINEERING CHEMISTRY Glazing: The glazing ingredients are finely powdered and mixed. chromite (FeO. magnesia (2250°C) and zirconia (2200 °C) etc. Whenever very high temperatures are involved as in furnaces. kilns. Examples–Chromite bricks. chemical and physical effects without softening or suffering a deformation in shape. silica. The fusion temperatures of the usual refractories in use vary from 1600°C to 2700°C. (v) They should be able to withstand spalling. Refractories are sold in the form of bricks. . CrO2).. the refractories do provide the linings or bricks. Annealed bricks can better withstand spalling. All ceramic bodies undergo a certain amount of vitrification or glass formation. Examples–alumina (2050°C). The mixture is mixed with water to make the slip. refractories are materials which are used to withstand high temperature. The alkali portion of feldspar and most of the fluxing agents becomes a part of the glassy or vitreous phase of the ceramic body. to resist the heat loss) and at the same time to resist the abrasive and corrosive action of molten metals. chromite bricks. slags and gases at high operating temperatures. which is applied on the surface to cover the pores. Examples–Magnesite bricks (magnesia). Glaze is a sort of glass. Classification Refractories are classified broadly under three heads depending on the chemical properties of their constituent substances. kilns and electrical heating apparatus. liquid metals and slags produced in its immediate contact in furnaces. These are self bonded and have high fusion points. and zirconia refractories etc. Broadly speaking. They are not attacked by acidic materials. At present some single oxide bricks have been developed. Examples–silica bricks and fire clay bricks. silicon carbide. clay-silica mixtures and of pure silica.e. cracking and flaking of the bricks due to uniform expansion or contraction. supports and other filaments. retorts. (iii) Neutral refractories: They are made up of weakly acidic or basic materials like carbon. Properties Refractories should possess the following general properties: (i) They must be able to withstand high temperature. The slip is next applied to dry blanks or more frequently to the biscuits by dipping or pouring or spraying or brushing very carefully and then heated at 1400°C. These are (i) Acid refractories: They are made of clay. Thus refractories are those materials which are used for the construction of furnaces. silicon carbide and graphite. bauxite bricks. ovens. REFRACTORIES The word refractory means resistant to melting or fusion.e. The main objective of a refractory is to confine heat (i. zirconia (ZrO2) etc. (ii) Basic refractories: They are made up of large proportion of lime or magnesia or a mixture of these bases or other metal oxides. (iii) They should be chemically inert towards the corrosive action of gases.. (iv) They should be able to withstand sudden change of temperature. (ii) They should be infusible at the temperature to which they are liable to be exposed. converters etc. i. crucibles.

35% alumina. thermal conductivity and chemical strength. 2% lime).e. The reason for such incidence is due to the absence of air in the void space. quartzite. the quartzite converts to crystobalite.SILICATE TECHNOLOGY 431 (vi) They must be able to withstand abrasion or erosion of the furnace charge and also the pressure of the load. (vii) Porosity of a refractory is a deciding factor of the degree of penetration by molten fluxes and gases and thus the refractory material easily disintegrates. quartzite is not converted to tridymite and crystobalite the bricks will expand during use in the furnace and the refractory structure will break and fall. Temp. Fire clay-bricks: Raw material is fire clay (clay–Al2O3. Decrease in porosity increases the refractory’s strength and also increases its heat capacity. . i. During slow cooling. Basic fire clay bricks contain 55% alumina and 40% silica. Manufacturing of refractories The steps can be displayed schematically as follows: Crushing in jaw crushers to 25 mm size of raw materials Grinding in a grinding machine to 200 mesh Screening to remove unwanted materials by settling or magnetic separation or chemical method Moulding 1. 1480–1870°C Common Refractory Bricks 1. Manual 2. FeO.–avg.2SiO2..2H2O) Generally fire clay bricks contain 55% silica. the greater the porosity. Mechanical Mixing. rest consists of K2O. During heating. To attain the right composition 12 hours heating at 1500°C of the bricks is very much essential. MgO. So silica brick contains a mixture of tridymite and crystobalite. During manufacture. sandstone etc. (viii) Least porous bricks have highest thermal conductivity. The cooling of the bricks takes about 1-2 weeks. the greater is the susceptibility of the refractory to chemical attack by molten fluxes and gases. This is acidic fire clay brick. crystobalite is converted to tridymite. the main raw materials are—quartz. uniform mixing causes moulding easy Storage in storage bins Deairing by applying vacuum Drying carried out very slowly in tunnel driers Firing in tunnel kilns or rotary kilns. Uses Main applications of silica bricks are: • In open hearth furnaces • In coke-oven walls • Glass-furnaces 2. CaO. silica bricks are heated to about 1500°C within a span of 24 hours. If during heating of silica bricks. Silica bricks: Silica bricks contain (92-95% silica.

. 5. Uses • For linings for Portland cement rotary kilns • Furnace hearths and walls • In reverberatory furnaces • In combustion zones of oil-fired furnaces.5 kg/cm2 • They possess good crushing strength. MgO is powdered to a proper size and then mixed with caustic magnesia or iron oxide as binding material and then ground. • Cheaper than silica bricks. 3.432 Properties • Light yellow-reddish brown in colour • Low porosity and lower refractoriness than silica bricks • Fusion temperature 1350°C • Crushing strength 200 kg/cm2 • Better resistance to thermal spalling than silica bricks. The bricks are then slowly heated to 1500°C and kept for about eight hours at this temperature and cooled then slowly. Dolomite bricks: They are made by mixing calcined dolomite (i.. silver and platinum etc. good resistance to basic slags and very little shrinkage • Their resistance to abrasion is poor. The prepared powder is pressed into bricks in hydraulic presses.e. Uses • In blast furnaces • In kilns • Charging doors etc. Properties • They are generally grey or brown in colour • They can be used upto 1500°C under a load of 3.e. mixture CaO + MgO) in equimolar proportion with silica as binding material. ENGINEERING CHEMISTRY 4. High alumina bricks: Composition—50% or more alumina. copper convertors • In reverberatory furnaces for smelting lead. Uses • For the lining of basic converters and open hearth furnaces in steel industry • They are used in hot mixer linings. Other binding materials used . Magnesite bricks: Magnesite is naturally occurring magnesium carbonate (MgCO3) and is the raw material for the magnesite refractories. Properties • Low coefficient of expansion • High porosity • Little tendency to spall • Excellent wear resistance and stability. Calcined magnesite (at 1600°C) i. copper • In refining furnaces for gold.

more porous and have more softness and shrinkage than magnesite bricks • They can withstand a load of 3. The firing temperature is 2000°C. iron oxide. The crushed chromite ore (FeO.5 kg/cm2 at 1650°C. Salt reacts with iron and similar impurities present in the raw materials to form volatile chlorides. Carborundum or silicon carbide bricks: They are prepared from coke and sand. resistance to acidic as well as basic slags • They can withstand upto 1800°C under a load of 3. Sand (60%) and coke (40%) are properly mixed and is followed by addition of some sawdust and a little salt. At this temperature interlaced crystals are formed. silicon nitride are mixed.SILICATE TECHNOLOGY 433 for the same are tar. • They possess good crushing strength • They have moderate thermal conductivities. They are then fired at 1500°C for about 24 hours. • They are not very much resistant to thermal shock • They are more resistant to slags and spalling than magnesia bricks • They wear out quickly. Properties • They are neutral in colour • They possess high density. Uses • For repairing materials • In Bassemer converters.5 kg/cm2.17-3. Reaction SiO2 + 3C → SiC + 2CO Composition of silicon carbide bricks is: • Silicon = 65% • Carbon = 30% • Impurities = 5% Properties • Colour–dark grey to black • • • • • Hardness–high Fusion point – 2500°C Coefficient of thermal expansion is very low Specific gravity 3.Cr2O3) is fired at 1500°C–1700°C after mixing with a little clay as binding material. Sawdust when burned evolves gases. open-hearth furnaces. 6. clays etc. The silicon carbides obtained from the furnace are interlocked tridiscent crystals. dried and fired. quick lime. Bonding agents like clay. Chromite bricks: Chromite is a neutral refractory. 7. Properties • Dolomite bricks are less strong. which by circulation increases the porosity of the charge.2% Resistance to abrassion–high . The mixture is then shaped. The mixture is then fired at 1500°C in an electric furnace. These volatile chlorides make the final products porous. laddle-linings etc.

The use of organic plasticizers makes the brick less porous. magnesia (MgO). they are used in electric arc furnaces. Zirconia brick is prepared by heating zirconite (ZrO2). viz. Properties • They are the combination of ceramics and metals • They have high refractoriness of ceramics . colloidal zirconia or alumina in a mill. Zirconia bricks: Zirconia bricks fall under pure oxide refractories. 8. • They are resistant to basic slags. and thoria (ThO2). Properties • High melting point (2550°C) • Low electrical conductivity • High thermal conductivity • Good resistance to thermal shocks • Inertness to carbon dioxide and carbon monoxide upto 2000°C. Refractory oxides do not possess plastic properties. zirconia (ZrO2). Cermets: Cermets are hot pressed or sintered materials comprising ceramic and metallic components. Uses • Beryllia is used in making crucibles to melt uranium and thorium. The powdered zirconia is kept under water for sometime and the wet zirconia is mixed with binding material. Properties • Zirconia refractories fall under neutral refractories • They can withstand a temperature upto 2600°C. First zirconia is calcined and powdered. Organic plasticizers such as dextrin and resins may also be used.434 ENGINEERING CHEMISTRY • Resistance to spallation–high • Oxidising action–in presence of air at 1000°C silica bricks tend to oxidise to silica. 10. The moulded bricks are dried and fired at about 1750°C. • As radiation shields in carbon resistant furnaces. owing to its low neutron absorption capacity. The materials are then moulded into bricks by hand moulding or pressing. Beryllia bricks: Beryllia minerals are used to prepare the bricks which are fired at 2000°C. Refractory oxides of common use are alumina (Al2O3). Uses • Zirconia bricks are very costly • Specially used when high temperature is used 9. • Owing to their high electrical conductivity. That is why clays and bentonites are to be used to prepare the pure oxide refractory bricks. 2SiC + 3O2 = 2SiO2 + 2CO • Mechanical strength–very high Uses • Owing to its high thermal conductivity they are used in muffle furnaces.

they form a glass comprising sodium. Q. A cement is a substance which sets to a hard mass in presence of water. sand and water is known as mortar. when melted. What is cement? Ans. Ans. 2. calcium borosilicate. 1. Uses • In rocket and jet engine parts. SHORT QUESTIONS AND ANSWERS Q. Raw materials used for the manufacture of enamels are: (i) Refractories (ii) Fluxes (iii) Opacifier (iv) Colours (v) Floating agents (vi) Electrolytes. The enamels used to coat metallic surfaces are known as porcelain enamels. They are usually fabricated by the techniques of powder metallurgy. potassium. borax etc. then articles are fired at 800°C.C. walls. 4.SILICATE TECHNOLOGY 435 • They have high thermal conductivity of metals • They have high thermal shock resistance of metals etc. • Most cermets contain about 80% of ceramic materials and 20% of the metal. The product formed after setting of lime. Q. roads etc. R. Application of the enamel—a thin coating of the enamel thus obtained is applied on the metal either by dipping or by brushing or by pumping. What is a mortar? Ans. . Q. soda ash. 11. Enamels: Enamelling means to impart a hard and glossy coating applied on wares for decorative and protective purposes. Concrete made with sand. 3. What is RCC? Ans. dams. stone chips and cement when reinforced with iron rod for an extra strength of the concrete is known as reinforced concrete cement (RCC). feldspar. For making the enamel at first frit is made from glass forming materials such as sand. • Spinning tools for hot metals. Mention the areas of application of cement. Uses In making: (i) refrigerators (ii) food processing equipments (iii) motor cars (iv) sanitary wares. molybdenum carbide and tungsten carbide. • Refractory ceramics used in the manufacture of cermets are zirconium carbide.C.

(iii) Silicon carbide. furnaces. Mention some refractory metals. Clay materials are known as ceramics. 9. Building. . Glass may be defined • Physically as an amorphous. Ans. What is a hydraulic cement? ENGINEERING CHEMISTRY Ans. Mention some important refractories. See text page 418. roads. What are ceramics? Ans. The cement sets under water. Q. Q. What are primary uses of refractories? Ans. 6. 14. Q. 13. • Glass has almost 100% elastic recovery. The primary uses of refractories are for lining (i) Steel furnaces (ii) Coke ovens (iii) Glass wares. That phenomenon is known as devitrification of glass. What is vitrification? Ans. kitchen wares. 10. Q. Glass-wares left unused for a long time gradually loose their transparency and become opaque due to the crystallisation of some of metallic silicates of glass. 8. (vi) Mullite (Clay sand). The process of not forming crystals during cooling of glass is called vitrification. • Chemically as a mixture of a number of metallic silicates. What are refractories? Ans. The greatest uses of advanced ceramic products are in • Aerospace industry due to their lighter weights compared to metal alloys • Heat shields for space vehicles • As bio materials like false teeth. 7.436 Q. 5. Q. artificial hip joints etc. (i) Fire clay (aluminium silicates). 12. What is glass? Ans. Ans. that is why the term hydraulic came. Ans. laboratory wares are made of ceramics. (ii) Silica. Q. bone replacement. (v) Magnesite (MgO). Tungsten and tantalum (W and Ta) are refractory metals capable to withstanding high temperatures. Even at the present time ceramics remain important in many spheres of life. (iv) High alumina (70-80% Al2O3). transparent or translucent. Refractories are earthy ceramic materials of low thermal conductivity capable of withstanding extremely high temperature without any change. Give general composition of cement. (vii) Zirconia (ZrO2). one of which is an alkali metal. rigid supercooled liquid of infinitely high viscosity. Q. 11. Q. What is devitrification of glass? Ans. Q.

Describe the setting of mortar and lime. C. the overall fundamental reaction of heating of clay is 3(Al2O3. a common example is Kaolinite. Ans. Describe various types of cement.2H 2 O ¾¾® Al 2 O 3 + 2SiO 2 + 2H 2 O ­ amorphous mixture 600°C ¯ The amorphous form of alumina changes to γ-alumina. Q. 5.2SiO 2 . Al 2 O 3 .2H2O) Kaolinite → ∆ 3Al2O3. fire clay) (b) Basic (magnesite. 10. • Magnesia • Chromite • Forsterite. Pure zirconia undergoes (i) a change from monoclinic crystal to tetragonal form at 980°C and (ii) also volume change on inversion by adding certain oxides like MgO. 11. Discuss the structural pattern of silicates. clay undergoes elimination of water of hydration at 600°C. 2SiO2). 18. As the temperature increases. 15. 17. 4. What is the importance of zirconia as refractory? Ans. SiC).2SiO2. Discuss the composition of Portland cement. Ans. Clay is the common ingredient of all ceramic products. 12. . (a) Acidic (silica. more SiO2 is converted to cristobalite. At 1000°C. dolomite) (c) Amphoteric (Al2O3. Q. Mention some basic refractories. Describe the rotary kiln used in cement manufacture. 7. So. 16. What do you mean by silicate technology? What do you mean by superconductive ceramics? Mention its uses. Discuss the effect of heat on clay. Q. a crystalline form at 940°C. 9. 6. What are silicates? Define clay and soil. 8. 3. This type of zirconia possesses a working temperature of 2600°C.SILICATE TECHNOLOGY 437 Q. Mention classification of refractories. At the early stages of heating. 13. How is portland cement prepared by wet process? Explain the setting and hardening of cement. CaO. Al2O3 and SiO2 combine to form mullite (3Al2O3 . Ans. 2. How are cements classified? Give the various physico-chemical reactions responsible for the setting and hardening of Portland cement.2SiO2 + 4SiO2 + 6H2O Mullite Cristobalite EXERCISES 1. Distinguish between (a) Pozzuolanic cement and (b) Portland cement.

35. 23. 21. What are refractories? How are they classified? Give examples. What is glass? Write the raw materials used in the manufacture of glass. 34. What are fire clay bricks? Describe the manufacture. Briefly describe its manufacture. What are refractory materials? Write a brief note on chromite bricks. What are basic refractories? Explain magnesite refractory in detail. Write short note on soda lime glass. What is glass? Discuss the physical and chemical properties of glass. 30. Describe the manufacture of: (i) Fire clay bricks (ii) Silica bricks (iii) Magnesite bricks. Give the reaction involved in porcelain formation. 38. Discuss the manufacture of ordinary glass with the help of flow diagram. What are refractories? Give an account of any four characteristics of a good refractory material. 20. 25. 33. 29. 26. Give reactions involved. 32. ENGINEERING CHEMISTRY What are the criteria of the Portland cement raw materials? What do you mean by wet and dry processes in cement manufacture? How is Portland cement manufactured? Describe with the help of a neat diagram of rotary kiln for the manufacture of Portland cement by wet process. 15. Write notes on (i) Coloured glass (ii) Plate glass (iii) Shaping of glass (iv) Safety glass (v) Chemical action in glass making (vi) Fibre glass (vii) Annealing of glass (viii) Glass laminates (ix) Phosphate glass 24. Explain the significance of the following properties of refractory materials (i) Porosity (ii) Dimensional stability. Write notes on (i) Carborundum (ii) Silica refractories. 31. 36. properties and uses of fire clay bricks. 28.438 14. properties and applications of the following materials: (i) Magnesite (ii) Fire clay (iii) Zirconia (iv) Silica. 19. 17. What is cement? Describe the composition of any cement. 22. . Describe the manufacture of glass by pot furnace process. State composition. 18. 16. Classify glasses with composition and illustrations. Write notes on (i) Clay and common clay (ii) China clay (iii) Fire clay (iv) Uses of clay (v) Pottery. 27. Describe the process of manufacturing of porcelain. Explain the theory underlying the manufacture of refractory products. 37.

g. i. Addition or chain polymerization. Monomers (M) having the general formula. The first step of which involves two reactions. H H H H H H C¾C¾C¾C H H H H polythene 20 nC = C H H ethylene There is no limit to theoretical length of the polymer. CO2R.CHYCH2CH2---(iii) Random type —CHYCH2 CHY. tertiary butyl hydroperoxide etc. 439 . The number of repeating units in a polymer is called the “degree of polymerization”. COOOOC 2 COO ..e. polyethylene is made up of the monomers ethylene.CH2 CH2CHYCH2 CHY---Mechanism of addition polymerization: (a) Free radical polymerization is the first type which involves the following steps: Initiation. these monomers having double or triple bonds polymerize without the liberation of small molecules. Types of polymerization 1. There are three ways of addition polymerization: (i) Head to tail type —CH2CHYCH2CHYCH2CHY---(ii) Head to head type —CHYCH2CH2CHY.. e. CH2=CHY (Y=X.. The first is the spontaneous decomposition of an initiator into free radicals. but the polymer ceases to grow for many practical reasons.Polymers POLYMERIZATION Polymers are macromolecules of high molecular weight which are formed by linkage between large numbers of small molecules called monomers. A variety of peroxides act as initiator such as benzoyl peroxide. CN etc.) undergo polymerization.

propagation and termination but here. Terminations. More rarely. → H H   —CH2— C  C  CH 2    Y Y (ii) Collision of a growing chain with an initiator radical when the latter is proportionately in excess. H H   • —CH2— C • + C  CH 2    Y Y H H H    CH2— CH + C = C    Y Y → (b) Ionic polymerization is an important class of addition polymerization which also involves the steps of initiation. Sometimes the chain length of the polymer is controlled by deliberately adding inhibitors.440 ENGINEERING CHEMISTRY The next part of initiation involves the addition of this radical to the monomer molecule (M) to initiate the chain. 2R• + Free radical M → M* Monomer The M* is the initiator radical or primary radical. The most common terminations are the effect of (i) Collision between two growing chains H H   C • + • C  CH 2  —CH2—   Y Y i. instead of free radicals. Cationic Mechanism Initiation X+ + CH2 = CH  Y → X – CH2 C H  Y + The initiators are Lewis acids like AlCl3.e. M* + CH2 = CHY → M-CH2CHY* Continuous addition of new monomer in this manner will finally produce a polymer chain in which the substituents are located on alternate atoms. (iii) Collision between a growing chain with impurities. . H2SO4 etc.BF3... The mechanism of propagation is the reaction of the radical M* with its own monomer M. Propagation. in presence of water. the unstable intermediates are either cations or anions. by disproportionation an H atom of one radical is transferred to another resulting in two polymers–one saturated and the other unsaturated.

(c) Co-ordination polymerization or Ziegler-Natta polymerization. sodium ethoxide takes place via this mechanism. Anionic polymerization mechanism: Initiation: Z(–) + CH2 = CH → ZCH2 – C H   Y Y Carbanion (–) Propagation: ZCH2¾CH + CH2 = CH ¾¾® zCH2¾CH¾CH2¾CH Y Y Y Z¾CH2CH¾CH2¾CH Y n (–) (–) (–) Y nCH2 = CHY Y Termination: H Z¾CH2CH¾CH2¾CH: ¾¾¾® Z¾CH2CH¾CH2¾CH2 Cation (–) + Y n Y Y n Y polymer Polymerization of olefins with metallic sodium. the overall effect leads to an increased polymerization rate and also increased degree of polymerization. . ZrBr3. It was observed by Ziegler and Natta that in presence of a combination of transition metal halides (TiCl4. since better charge separation of ion and counter ion occurs.POLYMERS 441 Propagation: Termination: X¾CH2¾CH¾CH2¾CH ¾¾® Y n + Z– Anion X¾CH2¾CH¾CH2CH Z Y Polymer n Y Y If the medium is of dielectric strength.

Stereochemistry of polymers (i) Isotactic polymers have all the groups in one side of the polymeric backbone and the monomers are joined in a regular head to tail arrangement. Mo etc. rubbery. Mechanism of Ziegler-Natta polymerization: Initiation: Propagation: Cat R′ + CH2 = CHR → Cat CH2CH(R)R′ Cat ¾CH2CHR¢ + nCH2 = CHR¢ ¾¾® Cat ¾CH2CH¾CH2¾CH¾R¢ R R R n Termination: Cat ¾CH2¾CH¾CH2¾CH¾R¢ + HX ¾¾® Cat ¾X + CH3CH¾CH2CH¾R¢ R R n polymer R R n By earlier free radical polymerization of ethylene. elastic. Ziegler-Natta polymerization yielded stereospecific structure of high mechanical strength.) along with organometallic compounds (triethyl/trimethyl aluminium) polymerization of olefins leads to stereospecific polymerization. H C H Y C H C H Y C H C H Y C H H H (ii) Syndiotactic polymers have similar head to tail arrangements but here Y groups appear on opposite sides of polymer backbone alternately. H C H H C Y H C H Y C H H C H Y C H H C H . high melting and highly crystalline polymer like HDPE (high density polyethylene). unbranched. propylene yielded polymers of low density having highly branched chain polymer of low crystallinity and mechanically weaker structure like LDPE (low density polyethylene).442 ENGINEERING CHEMISTRY and halides of V. H C H C H C Y C H C H C H C Y H Y H H H H (iii) Atactic polymers have Y groups arranged randomly along the polymeric backbone and the material is soft. Zr. Cr.

HCl etc. are soft and gummy but brittle. 20.1). 20. such as polypropene in which the side groups along the polymer chain are randomly orientated. In this type of polymerization. Presence of polar groups along the chain length also increases the intermolecular forces and increases the strength of polymer.POLYMERS 443 Spatial arrangement of an atactic polymer: It is a form of addition polymer. when any monomer may contain two or three functional groups cross-linked polymer structure will be formed. CH3 H H CH3 H CH3 CH3 H H CH3 CH3 H Fig. three dimensional structure and they are strong and tough as the movement of inter molecular chains are totally restricted. rubbery polymer of little value unlike isotactic polypropene (Fig. wt. the units are linked by interchain covalent bonds forming giant. Condensation polymerization It is the type of reaction occurring between monomers containing polar groups which form polymer along with the elimination of small molecules like H2O. Polymers of low mol. Co-polymerization Two or more monomers undergoing joint polymerization is called copolymerization reaction such as the production of SBR (Styrene butadiene rubber). . Atactic polypropene is an amorphous. But higher-chain length polymers are tougher and more heat resistant.1 Part of a chain of atactic polypropene. Strength of straight chain polymers depends on the chain length. as it takes place through the functional groups. CH = CH2 n(·CH2 = CH—CH = CH2) + n butadiene styrene Copolymerization —CH2CH = CH—CH2—CH—CH n SBR (GRS-rubber) Influence of structure of polymer on its properties Strength of polymer In cross-linked polymer.

even for very high molecular weight. The amorphous nature of polymer provides flexibility. non-polar group containing polymers are chemically resistant to polar solvents but are soluble in non-polar solvents. fibres..e. form random arrangement and show rubbery character. . (c) Co-ordination polymerization (Ziegler-Natta polymerization). Solubility and chemical resistance Polymer containing polar groups are more soluble in polar solvents like water. Similarly.g. If the internal forces are high they ultimately give rise to orderly arrangement and form fibrous nature. particularly the greater the degree of cross-linking. Intermediate forces lead to plastic nature. Hence. toluene. alcohol but are chemically resistant to non-polar solvents like benzene. As for example SBR. greater rigidity. polythene from ethene. Three-dimensional polymer molecules are insoluble in any conventional solvent and are thermosetting. (b) Ionic mechanism. Very long chain polymers having free rotating groups form irregularly coiled and entangled snorts. Plastic deformation Polymers consisting of linear-chain molecules are always soluble and thermoplastic.. Physical state Random arrangement of molecules in the polymer leads to amorphous state whereas regular arrangements of molecules or chains in a polymer lead to crystalline state. • Mechanisms of addition polymerization are: (a) Free radical mechanism. The regular arrangement increases the intermolecular forces of attraction and leads to higher softening point. molecules become bulky. less is the solubility of the polymer in a solvent. Artificially creating crosslinking converts thermoplastic material into thermosetting. thermoplastic and thermosetting qualities of polymer depend on structure of the polymers.444 Highlights: Types of polymerization • Addition polymerization: ENGINEERING CHEMISTRY The product polymer is exact multiple of the original monomeric molecule e. brittleness and strength of the polymer. CCl4 etc. plastics and rubbers. Shapes and forms—mechanical properties The internal arrangement of the long-chain molecules provides the forms in which the polymer may form i. which can be stretched and again returned back to its original state giving rise to elastic character to the polymer. • Copolymerization: Joint polymerization of two or more types of monomers. • Condensation polymerization: Combination through different functional groups of monomers with elimination of small molecules like H2O. If the internal forces between the molecules are low.

This hardened material cannot be softened again. hence the setting is permanent and irreversible. 2. brittle polymers Rigid and high impact thermoplastics Polymer fibres Rubbery polymers Strain Fig.2. Compounding Plastics for manufacturing of finished articles are always mixed with 4-10% of other materials. Resins are actually the binders used for plastics and these two terms are used synonymously. 1. which do not have melting point have softening points. On increasing strain continuously ultimately the polymer chains are uncoiled and fully stretched called necking and after this point the polymer reaches its break point and yields. which actually form crosslinking during the moulding process in presence of catalyst. hence repeated heating and cooling also does not alter its nature. Thermoplastic resins soften on heating and harden on cooling and this change is not chemical but physical in nature. Amorphous polymer becomes rubbery and then gummy and on further heating it liquefies. Effect of heat Behaviour of polymer is controlled by the temperature. 20. But the crystalline polymer on heating above Tg shows thermoplastic behaviour and finally liquefies. . At very low temperature both the crystalline and amorphous polymers behave like glass and on heating.POLYMERS 445 Stress Hard. Amorphous polymers. These materials are known as additives which not only impart some properties to plastics but also make the processing easy. which binds all the additives together. which impart some durable properties to the moulded material. 20. the glass transition temperature is reached (Tg) after which they soften. There are two classes of plastics or resins. Thermosetting resins are added as linear low molecular weight polymers.2 Four types of stress-strain curves illustrating how polymers of different types behave (the lines end where the sample breaks). The process of mixing these additives to virgin plastics is called Compounding. Strength of a polymer is estimated from typical stress-strain curves for different polymers as shown in Fig. Additives and their functions are discussed below: (i) Resin is the binding constituent. PLASTICS (RESINS) Plastics are a class of high polymers which can be moulded into any desired form by heat and pressure. The strength of the polymer is controlled by the length of the polymer chains and its cross-linking. Thermosetting resins are those which are heated during moulding and heating is continued until is set and hardened.

are added to dissipate the electric charge developed by conducting it away. FRP is very strong and can be used to make gates of dam. Percentage of fillers may vary and can be upto 50%. jeep bodies. (iii) Film casting. Stabilizers like Pb.446 ENGINEERING CHEMISTRY (ii) Fillers. (v) Colouring materials. are added to accelerate the cross-linking of the thermosetting plastics while they are in the moulds. Processing of plastics (i) Calendering. ZnO. Fibrous fillers such as wood flour. phenol and urethans. safety helmets. To improve the appeal and to impart beauty to the finished materials. Pb-silicate. Catalysts like H2O2. amides etc. A compounded solution in a suitable solvent is continuously dropped on a moving belt. Sometimes antioxidants are added to prevent oxidative degradation of polymers. (vi) Other additives. .. This cheap technique is used for acrylics. finish and workability. Pb etc. better hardness. Cu. oils. asbestos increases heat resistance. cotton fibre. Solidified filaments of glass are bundled into strands. plasticizers act as an internal lubricant and improve the plasticity and flexibility of the polymer. polyesters. chopped rags impart improved mechanical strength to the plastic. Plasticizers are small molecules which penetrate into the polymer matrix and neutralize a part of the intermolecular forces of attraction between macromolecules and increase the mobility of the polymer segments so that chains can slide over each other. compressed to produce a glass mat. Ag. Thus. (iv) Waxes. Fillers can modify the properties of plastics to give the final plastic. Compounded material is poured into die cavities made up of metals or plaster of paris and it is heated when the crosslinking takes place and finally the finished material is cooled. benzoyl peroxide. stearates and soaps are used to improve the finish and reduce the sticking tendency of the plastic to the moulds. Soluble organic dyes are added to the transparent variety and inorganic pigments are added to the nontransparent plastics. corrosion-resistant pipes and tanks. While passing through the gap between the rollers the sheet is formed. Engraved rollers offer beautiful designs of embossed plastics. mica or slate powder improves electrical properties. Commonly used plasticizers include vegetable oils. The compounding material is run between two highly polished metallic rollers rotating in opposite direction. Pb chromate etc. the solvent evaporates and films are obtained. NH3. (iii) Plasticizers. (ii) Die casting. To give UV protection to the colours some compounds are added which preferentially absorb UV light.. Plastics embedded with these mats are known as fibre reinforced plastics (FRP). Antistatic agents like amines. whose thickness varies with the gap. Cellophane papers and photographic films are produced by this process. are added to improve the thermal stability of polymers during processing. colours are added to them. tensile strength. PVC laminated to steel or aluminium are called ‘Composites’. camphor. dibutyl/dioctyl phthalate etc. For production of continuous films or sheets this process is adopted.

two halves are closed slowly. . are made by this process. which are moved relative to each other. Furniture handles. 20. telephone parts etc. The whole process is automatic. The mould consists of two halves. bowls. Finally curing is done by heating (for thermosetting) and cooling (for thermoplastic). The compounding material in definite proportion fills the gap between the two pieces of mould. This process is applicable for thermoplastics only. Heat and pressure applied. (iv) Compression moulding. Plastic powder is fed into a hot cylinder and then injected by a piston plunger into a tightlylocked mould with the help of a screw arrangement. (v) Injection moulding. furniture parts are made by this process. 20.3 A schematic representation of the film casting machine.POLYMERS Polymer solution Wind-up roll 447 Polymer solution spreads as a film Control valve Solvent evaporates Continuous polymer film Endless metallic belt Fig. Pressure Guide pins Top moulding part (male die) Bottom moulding part (female die) Moulding plastic ingredients in cavity Extraction pin Fig. The cavities get filled with fluid plastic. Buckets. This method is applicable for both thermosetting and thermoplastic materials. The mould is cooled for curing and finally the half of the mould is opened for the ejection of the article.4 Compressing moulding of plastics..

6 Moulding of insulated electric cable by vertical extrusion moulding. Plastic feed Metallic wire Plastic Hopper Heater Plastic coated cable Screw conveyer Fig. A hot softened tube of thermoplastic is placed between the two halves of mould and compressed air is blown whereby the thermoplastic takes the shape of the mould to form hollow articles like bottles. Sometimes. The mould is cooled and the article taken out.5 Injection moulding of plastics. (vii) Extrusion moulding. vacuum is also applied so that the sheet sticks to the shape of the mould. (viii) Thermoforming. . 20. The sheet is compressed between the die to the desired shape. This process is used to obtain three-dimensional articles from two-dimensional sheets. jerrycans etc. (vi) Blow moulding. The powder compounded material is introduced and electrically heated. The thermoplastic sheet is heated and softened and placed between two halves of a metal die.448 Plastic feed Hopper Nozzle ENGINEERING CHEMISTRY Top moulding part (cold) Hinge Moulding powder Bottom moulding part (cold) Heater Fluidized plastic Extraction pin Archimedian screw Fig. 20. This process is used for continuous moulding of thermoplastics. it is pushed by screw conveyer into a die whose shape is acquired by it and finally cooled. In plastic condition.

POLYMERS 449 Heating Vacuum off Vacuum on Moulded Article Fig. Two types of polyethylenes are available—LDPE (Low density polyethylene) and HDPE (high density polyethylene). Polyethylene is manufactured by gas-phase polymerization. a waxy solid. Ethylene is polymerised into polythene.01%) or peroxides act as catalyst.7 Vacuum forming process. Important Thermoplastics Polyethylene Polythene is polymerised ethylene. Ethylene is colorless gas at ordinary temperature. Properties. The ethylene gas is compressed to 1500 atmosphere and passed through a reactor maintained at 200°C in the upper and 120°C in the lower parts. * C2H4 → (C2H4)n Polymerize . which comes out from the perforated bottom of the vessel. 20. HDPE is produced by using low pressure methods (31 kgf/cm2) using ionic catalysts whereas LDPE is produced by using high pressure methods (1050-2000 kgf/cm2) using free radical initiator. It has good chemical resistance against acids. The unreacted gas is recycled. O2 (0. It is prepared in the lab by dehydration of ethyl alcohol at 160°C with concentrated H2SO4. alkalies and salt solutions. Industrially dehydration of ethyl alcohol is the process for ethylene production*. Polyethylene is a rigid. particularly kerosene. good insulating property but it is susceptible to organic solvents. waxy. translucent non-polar material. white.

Polyethylene has highly symmetrical structure so it crystalizes easily. LDPE has a branched structure and hence is flexible and tough. 20. higher softening point. greater rigidity but low impact strength and it is opaque and relatively brittle. bags for packing. it has better chemical resistance. bottles.450 Recycle ethylene ENGINEERING CHEMISTRY Ethylene Primary compressor Hypercompressor Catalyst Cooling tower High-pressure separator Low-pressure separator Cold water Water Polyethene Dryer pellets Separator Extruder and pelletizer Quench cooler Fig.. It has low hardness i. Polythene sheets. The degree of crystallinity varies from 40-95% depending on degree of branching. about 1/10th of bakelite. gr. Compressor Fluid-bed reactor Cycle cooler Compressor 690 to 2100 kPa 100°C Ethylene Comonomer Catalyst Lock Purge Separator and product discharge Nitrogen Ganular polyethylene Fig. HDPE is a completely linear polymer. 20. tubes are manufactured. insulator parts. It is also used to prepare toys.9 High-density polyethylene by low-pressure resins (HDPE). It has low sp. which are used for domestic purpose. . caps.e.8 Low-density polyethylene by high-pressure processing (LDPE). coated-wires and cables. Uses.

Polytetrafluoroethylene (TEFLON) It is obtained by polymerization of water-emulsion of tetrafluoro ethylene. highly crystalline polymer. CH3CH = CH2 ¾¾¾¾® [CH3CHCH2— ]n Polymerize Properties. washing machine parts.. 13. carpets. It has high rigidity and chemical resistance but brittle. benzyl benzoate etc.p. light. chemically-inert powder. Uses. petrol etc. odorless. for making sterilizable hospital equipments. rain coats. pipes. colorful furniture etc. It is lightest among all high polymers. Increased solubility of the polymer is also attained by solution polymerization at high pressure and temperature. Uses. Polypropylene is also an isotactic. toys. F Polymerize F n(CF2 = CF2) ¾¾¾¾® —C—C— F F n Properties. O2. Polyvinyl Chloride (PVC) Vinyl chloride is the monomer for PVC and the monomer is produced by direct addition of HCl to acetylene at 60°C-80°C. apparels etc. cycles and motor cycle mudguards etc. moulded luggage.e. oil. pipes of petroleum industry. under pressure and in presence of benzoyl peroxide as catalyst. The polymer is obtained in the form of fine powder and is soluble only in special solvents like dibutyl phthalate. blankets. bags. Fibres of polypropylene are very strong and hence fibres are used for making ropes. emulsion and in suspension. nCH2 = CHCl ¾¾¾¾® —CH2CHCl— ( )n PVC Polymerize HgCl Properties: PVC is a colorless. refrigerator components.. organo metallic halide with transition metal halide.r. resistance to chemicals. floor covering. tyres. inorganic acids and alkalies. moisture proofing quality etc. It is also used for packing of pharmaceutical and cosmetic products.t.9°C) can be done in solution. It contains 53-55% Cl2 and softens at around 80°C. water hoses. It is resistant to water. Due to the presence of highly electronegative fluorine in the regular polymer structure of TEFLON strong interchain forces are present which give the material extraordinary . non-flammable.POLYMERS 451 Polypropylene Polypropylene is obtained by polymerizing propylene in presence of Ziegler-Natta Catalyst i. its use is mainly in making cables. It is superior to polyethylene w. hardness. rexin. strength. but soluble in hot chlorinated hydrocarbons. CH ≡ CH + HCl → CH2 = CHCl The polymerization of the gaseous monomer (b. It is the most widely used plastic. TV. so. radios.

which have a structure similar to that of polypeptides. spongy known as ‘U-foam’. A coating of polyurethane is applied over leather. high softening point (350°C). Due to all these qualities. non-lubricating bearings and to make non-reactive coating. low coefficient of friction and waxy touch. Polyurethane (i) O (ii) CH3—CH2—CH2 OH – CH3 CH3 CH3 HOCH—CH2—O—CH2—CH—O—CH2CHOH Poly(oxypropylene) glycol Polyurethanes are a varied range of crosslinked polymers made from two liquids—a polyol and an isocynate. It softens at about 350°C. Nylon-66 Polyamides are synthetic polymers. Due to its spongy nature. pipes and tubes for chemical industry. transformers. wires etc. Uses. It is used as insulating material in refrigerators. pump parts. it is used for making pillows and matresses. hence at this high temperature it can be moulded applying high pressure. Nylon belonging to this class is used for making fibres. cables. good mechanical and electrical properties. It can also be used for making gaskets. the polymeric material can be machined. It is also used to make chairs etc. which improves the appearance and quality of the leather and hence the bags made of these look attractive and the shoes feel comfortable. It can be foamed like polystyrene but unlike thermocoal. is soft. high chemical resistance. Its greatest advantage lies in the fact that it can be made where they are needed without any complex machinery—the two liquid ingredients can be mixed and moulded. Uses. tank linings. It has low thermal conductivity.452 ENGINEERING CHEMISTRY properties like extreme toughness. Properties. It can be used for insulating motor. . having recurring amide groups. Non-stick cookware coatings are made of TEFLON.

The compounds react to form nylon salt in solution. Nylon fibre is obtained by melt spinning process. tough. The polymer can be remelted to spin into fibre and can be used for extrusion of molded objects.POLYMERS 453 Nylon 66 is obtained by the polymerization of adipic acid with hexamethylene diamine. . It possesses high temperature stability and also high melting (160°C-264°C). It is insoluble in common organic solvents but soluble in phenol. Nylon possesses high abrasion resistance and is chemically stable. the first step leads to the formation of o-and p-hydroxy methyl phenol. undergarments. formic acid. Important Thermosetting Resins Phenolic resins The most important of this class is bakelite or phenol-formaldehyde resin. In presence of acid catalyst. Uses: The polymer can be run directly to spinning machines to produce fibre. carpets etc. in an atmosphere of nitrogen which is chilled and chipped. elastic and can be dyed easily. NH2(CH2)6 · N H H + HO O C—(CH2)4COOH —HNCH2NHC(CH2)4C— + 2nH2O O O n Nylon can be extruded as a heavy ribbon. Properties: Nylon is strong. dresses. which forms linear polymer. Hexamethylene is made by final hydrogenation of the adiponitrile. which find use in making socks. Nylon salt is then heated at 265°C with Dow therm vapours to remove water and molten nylon results. HOOC(CH2)4COOH + 2NH4OH = H4NOOC—(CH2)4COONH4 Distilled with P2O5 H2N(CH2)6NH2 ¬¾¾ NC—(CH2)4—CN + 4H2O Hexamethylene diamine Adiponitrile Adipic acid and hexamethylene diamine mixed in equimolecular proportions in aqueous solution in an autoclave and heated at 100°C. hence nylon 66 is primarily used for fibres. Adipic acid is commercially produced by oxidation of cyclohexane derived from either benzene or petroleum. It is prepared by condensing phenol with formaldehyde in presence of acid-alkaline catalyst in an aqueous solution.

Solubilities and melting point of the resin gradually change with rise of molecular weight. As an inert material it can substitute for glass. hard. water resistant. These phenolic resins are rigid. organic solvents but are susceptible to alkalies. They are resistant to non-oxidising acids. which crosslinks the structure. It can be used for making insulator parts like switches. as cation exchanger resin for water softening. in paper industry as propeller shafts. Epoxy resin Epoxy resins are obtained from a poly condensation of epichlorohydrin with polyphenols or polyalcohols.454 OH + HCHO OH CH2OH + ENGINEERING CHEMISTRY OH CH2OH OH CH2·OH + H OH H + HOCH2 OH H + HOCH2 OH H OH CH2 OH CH2 OH CH2 Novolac In the second step a small amount of hexamethylene tetramine added and at the steam temperature. the chain length increases and also three-dimensional resin is formed. the soluble novolac gets converted to insoluble bakelite. Uses. plugs. It can be moulded to cabinets for TVs and radio and telephone parts. It is used as adhesive also used in paints and varnishes. OH CH2 OH CH2 OH CH2 CH2 CH2 OH CH2 OH bakelite CH2 OH CH2 Properties. Thus. These resins possess electrical insulating properties. It can be widely used as metal substitute where high tensile strength is not necessary. heater handles. .

2-(bis)-4-hydroxy phenyl propane [bis-phenol] Preparation of bisphenol CH3 2 HO Phenol + CH3—COCH3 Acetone NaOH 50 °C HO C Bisphenol A OH CH3 (ii) Epichlorohydrins CH2 = CH—CH3 + Cl2 Propylene 400 °C —HCl CH2 = CH—CH2Cl Allylchloride 300 °C H2O + Cl2 CH2 = CH—CH2Cl + HCl Epichlorohydrin 200 °C CaO Cl.CH2—CH—CH2Cl OH O (iii) Structure of epoxy resin CH3 CH2—CH—CH2— O O C CH3 CH3 —O C CH3 Flow diagram for the production of epoxy resin: Epichlorohydrin Brine OCH2CHOH.POLYMERS 455 Monomers are: (i) 2.CH2 n O—CH2—CH—CH2 O Bisphenol A Reaction Kettle Purification of resin washing with water Resin Water NaOH dry or in solution Recovered epichlorohydrin .

For the above properties. Terylene is the British name of Dacron. HNO3 (50%) at about 100°C to give terephthalic acid. Ethylene is oxidised at high pressure and temperature in the presence of Ag as catalyst and the ethylene oxide is hydrolysed by dilute HCl to ethylene glycol. the epoxy resins are used as the major constituents of adhesives in paint industry and as insulator in electrical industry. CH2 1 O (a) CH2 = CH2 + – O2 ¾¾® 2 CH2 O CH2 CH2 + H2O ¾¾® CH2—OH ethylene glycol CH2—OH (b) Paraxylene obtained from coal tar fraction is oxidised by neutral permanganate solution or conc. Better yields are obtained with dimethylterephthalate.. The fibre has high tensile strength and resiliency and is stable to hydrolysis. Uses. quilts etc. women and children. Polyester Polyesters are the condensation products of dicarboxylic acid with dihydroxy alcohols. which are finally used for making garments for men. blankets. It can be blended with wool and used for making carpets. The fabric made from the fibre is crease resistant. It is mostly used for making synthetic fibres like terylene. Since the structure of the polymer is symmetrical and a number of polar groups are present it forms fibre easily. Properties. CH2—OH + Condensation polymerization —OCH2OC— —C— . dacron etc.456 ENGINEERING CHEMISTRY Properties and Uses Epoxy resins possess outstanding properties of • Adhesion to various materials • Flexibility • Chemical inertness • Toughness • Stability at high temperature • Low shrinkage during cure. CH3 COOH esterification COOCH3 CH3 COOH Terephthalic acid COOCH3 Dimethylterephthalate COOH (c) n CH2—OH O n O COOH Polyester The equilibrium of the reaction is not favorable for the formation of ester hence to get high yield the byproduct must be continually removed from the reaction mixture. which is obtained by condensation of ethylene glycol and terephthalic acid. upholsteries.

R R R    Cl  Si  Cl + Cl  Si  Cl + Cl  Si  Cl    R Cl R R Cl R    Cl  Si  Cl + Cl  Si  Cl + Cl  Si  Cl    R R Cl OP PP PP PP PP PP Q → H2 O . it leads to long chain polymers but when there are three OH groups.SiMe 2 – [OSiMe 2 ]n – OSiMe 2OH Silicone Di-alkyl-di-chlorosilicane and alkyl trichloro silicone undergo hydrolysis and condensation polymerization to give a cross-linked silicone polymer. the OH groups of Si are involved in polymerization hence when there is one or two —OH groups in Si. paratroop. Silicones Silicones have alternate silicon-oxygen bonds and organic radicals attached to the silicon atoms. crosslinked polymers are formed. Terylene has several advantages over cotton in respect of (i) Resistance to acids (ii) Strength (iii) Crease resistance and (iv) Gives better finish and blendable with cotton or wool. wire insulators.POLYMERS 457 It can be reinforced with glass to form safety helmets. The monomers are prepared as (i) RCl + Si → R2SiCl2 (ii) From Grignard reagent SiCl4 + RMgCl → RSiCl3 + MgCl2 The monomer is obtained by fractional distillation of the reaction products whereby different organo-silicon chlorides are obtained. fighter parachute etc. Reactions: (i) 2RCl + Si → R2SiCl2 (ii) From Grignard reagent SiCl4 + RMgCl → RSiCl3 + MgCl2 (iii) Me2SiCl2 → Me2Si(OH)2 Structure of Silicone Polymers H 2O Cu HO. In the next step the chlorides are polymerized by hydrolysis involving the following steps– ≡ SiCl + H2O → ≡ SiOH + HCl Cu ≡ SiOH + HOSi ≡ → ≡ Si – O – Si ≡ + H2O Thus. aeroplane parts.

siliconeglass laminates for high temperature application. Different Types of Silicones Depending on the proportion of various alkyl silicon halides used the final silicones may be liquids. thus a mixture of monomers (containing one or more —OH groups) along with sufficient water for hydrolysis is heated for polymerization.458 ENGINEERING CHEMISTRY R R R    HO  Si  OH + HO  Si  OH + HO  Si  OH    R OH R R OH R    HO  Si  OH + HO  Si  OH + HO  Si  OH    R R OH R R R    — O  Si  O  Si  O  Si  O      R R R O R    Si Si Si  O   O  O  O    R R O  (Cross-linked polymer) OP PP PP – H O PP → PP PP Q 2 Complete condensation of all the —OH give rise to hard. (i) Silicone fluids. low surface tension and show low change in viscosity with temperature. Uses. for different electrical and electronic equipment parts manufacturing. They are of relatively low molecular weight. They have good resistance to heat and oxidation. viscous liquids. These are formed from the oils by adding silica. Used for high voltage insulators. carbon black etc. They are used as lubricants particularly for very high and low temperature applications. in cosmetics. ZnO. insoluble product. high temperature insulating foams. (iii) Silicone resins. Silicone rubbers are formed by reaction of dimethyl silicone fluid with peroxide and appropriate inorganic fillers like TiO2. (iv) Silicone rubbers. (ii) Silicone greases. sparkling clear fluids with an oily feel. . semi-solids and solids. heat resistance and good dielectric properties. They are used as autofoam agents. SiO2 etc. Their properties and uses also differ accordingly. possess good insulating properties. insoluble in water but soluble in aromatic and chlorinated solvents. They are highly cross-linked polymers. as damping and hydraulic fluids and to give water repellant finish to textiles and leathers. Uses. high temperature lubricants.

protective coatings etc. as adhesives for artificial heart valves. for special boots to be used at very low temperature. Mw = Now. Thus Mn = w Σ N iM i = ΣN Σ Ni where Ni is the number of molecules of mass Mi . viscosity measurements. For tyre manufacturing of fighter aircrafts. Mn can be determined by measuring the colligative properties like lowering of vapor pressure. M w can be determined by light scattering measurements. Degree of polymerization The number of recurring units of monomers in a polymer chain is known as degree of polymerization (DP). the overall rate of polymerization is proportional to the concentration of the monomer and the square root of concentration of the initiator. we use the term average degree of polymerization ( DP ). for making lubricants. good resistance to dilute acids and alkalis. actually the chain length varies. They are flexible in wide range of temperatures. since the chain length varies. good heat transfer properties. as insulators of electric wires in ship. Uses. Mw = Σ ci M i Σ ci M i Σ N i M i 2 = = Σ ci c Σ NiMi where ci = weight concentration of Mi molecules and c = total concentration of all polymer molecules. Hence. (ii) Weight-average molecular weight Weight average molecular weight ( M w ) can be defined by the following relation: Σ wi M i Σ wi where wi is the weight fraction of molecules having mass Mi.POLYMERS 459 They retain rubbery properties over a much wider temperature span. transfusion tubings. M w /M n is used as a measure of the molecular-mass distribution or “index of polydispersity” and it is 1. In a free radical polymerization. In a polymer. depression of freezing point etc. in case all the polymer molecules are of identical molecular weight. diffusion measurements. There are the following types of molecular weights for polymers. Also.5 or larger for natural and synthetic polymers. paints. M w = M n . M w is always greater than Mn . (i) Number average molecular weight The number average molecular weight ( M n ) is defined as the total mass (w) of all the molecules of polymer divided by the total number of molecules present. some may contain 100 to 200 monomers while others may contain 1000 or more. Molecular weight of a polymer Polymers are mixtures of molecules of different molecular masses. d(M) − = K[M][C] 1/2 M = concentration of monomer dt C = concentration of initiator .

Coagulation of the latex. Latex is diluted to contain between 15-20% of rubber. • Cellulose derivatives • Polythene. Natural rubber. The coagulum is allowed to drain and the absorbed serum is squeezed out through steel rollers upon which water is sprayed. Polytetrafluoro ethylene (Teflon) • Polyamides (nylon) • ABS polymers.[M] RUBBER Rubbers are high polymers. (ii) Melamine obtained by condensing melamine with formaldehyde. Natural rubber came into market first in early 19th century. filtered to make it free from dirt. Examples of this class include (i) Bakelite obtained by polymerization of phenolic derivatives with aldehydes. which have elastic properties and can be stretched upto about 300 percent.460 ENGINEERING CHEMISTRY At a certain stage of polymerization it is found that the number of active centres for polymerization is equal to the number of chain terminators. In releasing the stress the chains revert back to their original coiled state. (iii) Terylene (Polyester) are condensation products of dicarboxylic acids with dihydroxy alcohols (iv) Epoxy resins (araldite) (v) Silicone resins. The latex is collected from the mature Havea tree by making deep cuts on the bark.000-150. Coagulation is then effected by adding acetic acid (1 to 2% on weight basis). DP = K . The unstretched rubber is amorphous and the polymer chains are in a coiled state. .000 and is made from the latex of different plants like Havea brasillians and gangule found in tropical and subtropical countries. At this stage the average degree of polymerization is [ c]1/ 2 This equation relates average degree of polymerization with monomer concentration as well as initiator concentration. Polyvinyl chloride. Highlights: Classification of plastics • Thermoplastic resins soften on heating and harden on cooling reversibly. The molecular weight of raw rubber is about 100. Tapping is done at intervals of about 6 months. which on stretching gets aligned causing crystallization. Rubber coagulates as soft white mass which is washed and further processed. Polystyrene. The degree of polymerization influences the tensile strength of the polymer. The coagulum is converted to a sheet with uneven rough surface resembling crepe paper and called crepe rubber. Polypropylene. • Thermosetting plastics are permanent setting resins which harden on heating during moulding and they cannot be softened again. Natural rubber is polymerized isoprene. and by allowing the latex stream to collect in a pot attached below the cuts. which occurs in the latex of various trees.

reacts with HCl. it has very good electrical insulation property.   CH 3 H During the process of linking. For each C5H8 unit in rubber molecule. But for decomposition product of rubber i. O3 and HCl reacts. it is oxidised by air. impervious to gases. To overcome these limitations rubber is vulcanized. elastic in nature.. whereby the sheets get dried within 4 days. Also on excessive streteching it gets permanently deformed.POLYMERS 461 Smoked rubber sheets are made from thicker sheets than crepe rubber. Vulcanization of rubber During 1839. The embossed sheets are then hung up in a smoking house. sulfur content is from 3-5% whereas for tougher variety like ebonite. head and tail linking of isoprene molecule occurs. when the sulfur enters into the double bonds of rubber forming crosslinks between the chains and this gives the structure toughness. Natural rubber is an amorphous solid. non-polar solvents. Vulcanization is a process which is essentially compounding rubber with different chemicals like. When the destructive distillation is carried out at higher temperature the condensate contains mostly the isoprene dimers. one molecule each of Br2. oxidising agents. Smoking is done at a temperature of 45°C-50°C. The tough slabs are passed through rollers (embossed or ribbed) to obtain ribbed pattern. wood or coconut husk is burnt to produce heat. it is attacked by acids. thus there is only one double bond. . Structure of natural rubber (cis-polyisoprene) H O L H M   M  C  C — C  C  PPP M     P M H CH H H P M N Q 3 n Rubber is attacked by strong alkalies and oxidising agents. sulfur. Ebonite is so tough that it can be machined. translucent. Rubber slowly oxidises when exposed to air. It is actually polymerized cis-isoprene. The crude rubber obtained is translucent and amber in colour and is not attacked by micro-organisms. On destructive distillation rubber first softens and then decomposes producing white fumes. it decolorizes bromine water. Limitations of natural rubber Natural rubber softens at high temperature and becomes brittle at low temperature. On heating it softens and liquifies. benzoyl chloride etc. For flexible tyre rubber. The method is basically heating raw rubber with sulfur at 100° C-140°C. where on the floor. It burns to form CO2 and H2O. Raw rubber powder catalytically reacts with H2 gas. Charles Good Year developed the method of vulcanization of rubber by which the properties of natural rubber can be improved to a large extent. isoprene there is two double bonds CH2= C  C =CH2 . The toughness or the stiffness of vulcanization depends on the amount of sulfur included.e. content of S is 32%. Strong HNO3 attacks rubber. Coagulation is carried out in large tanks and finally allowed to settle for 16 hours. H2S. forms ozonide with ozone. Properties.

6. 8. for insulating wires and cables. Tackiness 10. 7. It can be vulcanized as natural rubber. Elasticity Tensile strength Useful temperature range Chemical resistance Water absorption tendency Resilience Insulation property Resistance to organic solvents 9. mainly ozone. Raw rubber very high 200 kg/cm2 10°C-60°C very poor high good ” Low marked less inherent Vulcanized rubber low. as adhesives and lining for vessels. Some important examples are: (i) GR-S or Buna-S. 4. 3. Durability 11. Properties. Uses. It is a copolymer of butadiene and acrylonitrile xCH2 = CH—CH = CH2 + nCH2 = CHCN → Copolymerization  CH 2  CH = CHCH 2  CH 2  CHCN  x n LM N OP LM QN OP Q . This variety is the most important synthetic rubber and it is obtained by copolymerization of butadiene and styrene. It possesses high resilience and good and tough mechanical properties. But unfortunately it is easily attacked by oxidising agents. SBR is similar to natural rubber in processing character and also as finished product. (ii) GRA or Buna-N. It is mainly used for the manufacture of tyres. It is also used as soles and other components of shoes. depending on percentage of sulphur 2000 kg/cm2 40°C to 100°C higher low much better ” much higher but swells low better can be controlled by vulcanization Synthetic Rubbers Synthetic rubber is artificially produced rubber-like polymers which can be stretched to at least twice its length and on releasing the stress. 5. It also swells in organic solvents. Quality 2.462 ENGINEERING CHEMISTRY Comparative study between natural and vulcanized rubber Property 1. it returns to its original shape and size.

floor mats etc. Reclaimed Rubber It is obtained from the waste rubber articles by the process of reclaimation. tubes. Uses. Reclaimed rubber is used for making tyres. adhesives. Process. sunlight. elasticity etc. compared to natural rubber but has improved ageing properties.. Uses. aircraft. Compounding of rubber Compounding is mixing of raw rubber with different chemicals to impart special properties for application.) . antioxidants like amines and phosphites. as linings for reaction vessels and for making pipes to carry corrosive gases and oils. It is washed. It is made by polymerization of chloroprene or α chlorinated butadiene. It is then repeatedly passed through hot roll mills rotating in opposite directions to soften and break down and the process is called mastication. gaskets etc. It is also used for making conveyer belts. It is highly resistant to heat. devulcanization takes place. It can be vulcanized by heating alone. atmospheric change and to oils. footwares. (Contd. it is much more susceptible to alkali than natural rubber. dried and finally reinforced with carbon black etc. Finally the material forms soft plastic mass. but due to the presence of —CN group. The unwanted ferrous materials are separated by electromagnetic separator and then charged to an autoclave and digested with caustic soda solution at 200°C under pressure for 8-15 hours. plasticizers like vegetable oils. shoe soles. waxes etc. The good qualities increase as the proportion of acrylonitrile is increased and it can be vulcanized to better heat resistant variety. The only difference of the structure of chloroprene and natural rubber is a single chlorine atom instead of an H atom which brings about marked resistance to temperature. Properties: Reclaimed rubber has inferior tensile strength. It is used for making conveyer belts. Its use is versatile. Uses. It is used to manufacture parts for automobiles. The fibres get hydrolysed i. belts. fillers like C-black. mercaptans. oils etc. Synthetic or natural rubber is mixed with vulcanizing agents like sulfur.. tubes. and coloring matters.e. The waste rubber articles like tyres. Highlights: Rubber • Natural rubber is cis-polyisoprene • Gutta percha is trans-polyisoprene. (iii) GR-M or Neoprene. Vulcanization • The process discovered by Charles Good Year in 1839 to improve the quality of rubber by introducing sulfur at 100°C-140°C to the double bond of rubber. Its properties can be changed by compounding to ZnO or MgO. Sulphur is removed as sodium sulfide. It is cheaper and easier for fabrication. adhesives and oil resistant foams.POLYMERS 463 Properties. gaskets. acids. accelerators like benzothiazole. are cut and powdered in a cracker. Cl Polymerize Chloroprene Cl n nCH2 = C—CH—CH2 ¾¾¾¾® —CH2C = CH—CH2— Properties. Process.

(a) Plywood. Conducting polymers are made by special powders and are classified as (a) π-electrons conducting polymer. then they are cut into suitable size and then subjected to curing in a hydraulic press at about 180°C and pressure. They are machineable and chemical resistant.464 ENGINEERING CHEMISTRY Synthetic rubber • An elastomer produced artificially. are impregnated with thermosetting resin like phenol-formaldehyde or urea-formaldehyde solution in solvent and dried at a temperature much lower than the curing temperature of the resin. it is called parallel laminate and when they are at right angles to each other. — Styrene rubber (GR-S) — Nitrile rubber (GR-A) — Neoprene (GR-M) — Thiocol (GR-P) — Hypalon — Polyurethane Compounding of rubber • Mixing of raw rubber with plasticizers.. (b) Laminated Plastics. Laminate. For transparency. false-ceilings and in other house building purposes. cabinets. The finished laminated plastics are light but strong and impermeable to water. By this process the plywood produced has uniform properties. metal etc. They are used for electrical and insulating materials. MISCELLANEOUS POLYMERS 1. when the resin becomes hard. asbestos fibre. length and widthwise. fillers. Plywood is used for making railway coach. Bullet proof or splinter proof laminated glass is obtained by curing the laminates in an oven under heat and pressure. pump parts etc. vulcanizing agents. Uses. Conducting Polymers Polymers obtained by the usual methods of polymerization are mainly insulators. glass. shrinkage etc. are minimised and becomes more strong compared to wood of equal thickness. Uses. to impart specific properties to the finished products. it is called cross laminate. Paper. thus splitting of wood. oil etc. If the grains of the layers are parallel to each other. They are also used for decorative purposes on table tops and wall panellings etc. colours etc.. Two glass sheets are joined by a plastic sheet in between to form laminated glass. antioxidants. It is obtained by joining two or more layers of solid materials with the help of an adhesive. which can be stretched to twice its length. polyvinyl-butyl resin can be used as adhesive. cloth. . In these polymers the backbone of the polymer is made up of molecules that contain conjugated π-electrons which extend the entire polymer and make the polymer conducting. but returns to its original shape. Odd numbers of layer of wood (0. (c) Laminated glasses.5-10 mm thick) are bonded such that grains of alternate layers are at right angles to each other (cross-laminate).

The polymer is made conducting by exposing the surfaces to charge transfer agents in gas or in solution place. Industrially important conducting polymers are: Polyquinoline.POLYMERS 465 (b) Conducting element-filled polymer. Nylon 6 is an additional polymer whereas nylon 66 is a condensation polymer. polybutadienylene etc. fillers etc. Conducting polymers are used for making (i) button cells. Q. metal oxides. metallic fibres that conduct electricity. In this type of polymer the polymer acts as binder. Ageing is the autooxidation of rubber with time due to the presence of double bond and due to this rubber becomes hard. 4. The cause of gelation is the formation of an infinite network of polymer and at this phase the resin becomes tough and less extensible. polyanthrylene. 7. (c) Inorganic polymer. Differentiate between a homopolymer and copolymer? Ans. polythiophene. This point of transformation is the gel point. Vulcanized rubber is used in vehicle tyres. Addition polymerization is a reaction that gives a polymer. Uses. Ans. Ans. Differentiate between addition and condensation polymerization. Q. hose. electrical insulation. which binds the conducting elements like carbon black. SHORT QUESTIONS AND ANSWERS Q. (iii) sensors and (iv) biomedical devices. When is vulcanization done? Mention some of the uses of vulcanized rubber. antioxidants. which is an exact multiple of the original monomers. The monomers of alkyl resins possess functionality greater than two. 2. The shaping is done with raw rubber along with suphur and other ingredients like accelerators. . the composition of the monomer is the same as that of the polymer. Q. which is a charge transfer complex is bound to the polymer to make it conducting. Q. A metal atom with poly dentate ligand. Vulcanization is done after shaping the article. (e) Blended conducting polymer. Uses. Q. (d) Doped-conducting polymer. 3. conveyer belt. 1. 5. In nylon 6. What is ageing of rubber? Ans. 6. What is functionality of a monomer? Ans. What is gel point? Ans. What is the basic difference between nylon 6 and nylon 66? Ans. During condensation polymerization it gets transformed from viscous material to a gel and the transformation is sudden. (ii) photovoltaic devices. A homopolymer consists of many identical monomer units whereas a copolymer consists of monomers of different chemical structures. but nylon 66 is formed with the elimination of water molecules. This type of polymer is made by blending a conventional polymer with a conducting polymer. Q. It is the number of bonding sites of monomer.

which cannot be broken on heating. 17. so. What changes take place with polymers near glass transition temperature? Ans. What is copolymerization? Ans. 8. Polydispersity index (PDI) of a polymer is a measure of the molecular mass distribution of a polymer.. thus. In teflon the most electronegative element F contributes to the strong attractive force within the chains and hence is non-reactive towards other chemicals. Q. antioxidants. Q. 12. . Q. filler. In thermosetting plastics. Any rubber-like elastic polymer. Q. Vulcanization. 9.e. 11. Polymers are different from other small sized molecules as they are mixtures of molecules having different molecular masses. Q. which can be stretched to thrice its size and after removal of the stretching force it returns to its original shape is called an elastomer. colorant etc. packing efficiency is low and hence density is low. In PVC the molecular chains are bonded to each other by Van der Waal’s forces and hence these long chains are flexible and can slip or twist on applying force but in the case of bakelite the thermosetting polymer chains are crosslinked by covalent bonds. poor chemical resistance. poor strength. e. 16. improves all the above properties. Why is natural rubber vulcanized? Ans. Q. it is hard and no deformation can take place on applying force. What is polydispersity index of a polymer? Ans. butadiene and styrene to yield GR-S rubber. large water absorption capacity etc. Natural rubber is long-coiled chains of polycisisoprene and gutta-percha is horny and tough form of polytransisoprene.g. Why is natural rubber compounded? Ans.. 13. HDPE is completely a linear polymer and hence packing of the chains is efficient and hence its density is high.466 ENGINEERING CHEMISTRY Condensation polymerization takes place through different functional groups of monomers with elimination of small molecules like H2O etc. the monomers are bound to each other by strong covalent bonds. due to its branched structure. When the force becomes too large the covalent bonds are broken and it becomes brittle. Vulcanization i. Q. 10. Q. Why thermosetting plastics cannot be reused? Ans. Natural rubber possesses many undesirable properties and so to improve its properties it is usually compounded with different ingredients like plasticizers. Raw rubber has high elasticity. 15. Why is the density of HDPE different from LDPE? Ans. tackiness. Q. 18. Q. the polymer is brittle and above it. Q. Why is teflon highly chemical resistant? Ans. they would deform but not break. adding some sulfur at 100°C-140°C causes saturation of the double bonds by S and hence stiffening of the polymer takes place. What is natural rubber and what is gutta-percha? Ans. Why is PVC soft and flexible but bakelite is hard and brittle? Ans. What is an elastomer? Ans. Below the glass transition temperature. 14. But for LDPE. Copolymerization is the point polymerization of two or more monomers. Thus by heating it cannot be softened to reshape and reuse.

glycerol. Q. The final cross-linked polymer is shown below: O=C O CH2 C=O O CH2 O C C=O O CH2 CH O C=O O=C O CH2 C=O OH CHOR CHOR CH2OH CH2 O O O CH2—O—C O HO—C C—O—CH Alkyd resin (R = fatty acid chain) Uses: • As insulators • As film formers in emulsion paints • Automobile parts manufacture • Switches manufacture. What are alkyd resins? Ans. 20. Q. How can cross-linked silicone be produced? Ans. The basic reaction of alkyd formation is esterification. Cross-linked silicone can be produced by adding a calculated quantity of trifunctional methyl silicon trichloride to the condensing polymer. What is polymethyl methacrylate (Trade name: Perspex)? Ans. 21. Phthalic anhydride is used instead of an acid and alcohol is polyfunctional alcohol. Here monomer is: Methylmethacrylate CH 3  CH2 = C  COOCH3 Methylmethacrylate . 19.POLYMERS 467 Q.

(ii) co-polymerization. What is polyvinyl (Trade name: Fevicol) alcohol? Ans. 5. (ii) Neoprene rubber (iii) SBR (iv) Silicone rubber. 3. What do you mean by biodegradation of polymers? Ans. Explain its significance with suitable examples. Write short notes on: (i) Rayon (ii) Synthetic rubber (iii) Types of plastics. table lamp shades.468 Polymer is: ENGINEERING CHEMISTRY Properties and uses It is a glass-like plastic. 8. Write the structures of five addition polymers and five condensation polymers. (a) Write short notes on (i) addition polymerization (iii) thermoplastic and thermosetting plastics (ii) condensation polymerization (iv) number average and molecular weight. 2. (a) Discuss the effect of structure of polymers on their physical properties in detail. two properties and uses of: (i) PE. Monomer is: CH2=CHOH (Vinyl alcohol) Polymer is: — CH2—CH(OH)—CH2CH(OH)—CH2 ]n [ — It is a water soluble polymer which is soft and gummy. EXERCISES 1. (iii) vulcanization of rubber. It is used for making transparent sheets. Q. (iv) PTFE. It is a component of emulsion paint. (a) What is a heterochain polymer? Give one example. Biodegradation is a process by which refuse mixes with environment by microorganisms. with their respective monomers. 6. 7. (b) Give the preparation and properties of (i) Nylon 6. Polyhydroxybutyrate is a ‘biopol’ which degrades within a few months in soil but it is too costly to be used very soon. Development of biodegradable polymer ‘biopol’ is now a challenge to scientists. (d) What are the functions of fillers and plasticizers in plastic industry? 9. (v) Nylon 66. . (ii) PP. It is used as an adhesive. and also for making binoculars. Explain with example: (i) addition polymerization. 23. 22. Discuss briefly the application of plastic in engineering and industry. (iii) PVC. (b) Define the term functionality of monomers. 4. Q. (b) Write the structures. rods etc. This biodegradation process is completely absent in the case of high polymers. (c) Discuss the preparation of bakelite and PVC plastic. Discuss various methods of plastic processing. Write short notes on (i) free radical polymerization (ii) cationic polymerization (iii) silicone resin. camera lenses.

(a) What is latex? How is natural rubber isolated from it? (b) What is vulcanization? How does it improve the property of natural rubber? 22. (a) What do you understand by vulcanization of rubber? What are the advantages and disadvantages? Give the structural unit of vulcanised rubber. 11. How is it related to the chemical structure? 16. 19. (b) What is the effect of polymer structure on the strength and crystalline nature of polymer? . 12. 17. Mention their uses. graft polymer. Write short notes on bakelite. Distinguish between the following with examples: (i) Natural and synthetic rubber (ii) Addition and condensation polymerization (iii) Thermo plastic and thermosetting plastic. (b) Give an account of one (i) Crepe rubber. copolymer. (a) Outline the general method of preparation of urethanes and state their applications. (c) Give four uses of rubber. (a) Define the terms (i) Degree of polymerization. (b) Give the manufacture and uses of (i) teflon (ii) nylon 66. (ii) Silicone rubber (iii) Polyethylene. (c) How are the following produced: (i) Buna S (ii) thiokols? Mention their properties and uses. thiokol. 13. 20. Define the term crystallinity of polymer. (b) List out the difference between HDPE and LDPE. (b) Discuss the methods of preparation of urea-formaldehyde resin and polyurethane and mention their uses. homopolymer. Give the structure of bakelite. (c) Write note on glass reinforce plastic. (d) What are silicones? Draw the polymer obtained by hydrolysing dichlorodimethyl silicone and give its use.POLYMERS 469 10. (a) Explain the terms with example (i) addition polymerization (ii) co-polymerization (iii) condensation polymerization. (a) Discuss the mechanism of addition polymerization. (b) Give the preparation and industrial application of PVC and neoprene. (ii) butyl rubber. (ii) Co-polymerization. (c) What is an Epoxy group? Give the preparation and uses of a common Epoxy resin. List the difference between addition and condensation polymerization. (b) Define monomer. (c) Write note on silicone. Write preparation. (c) Describe the methods of preparation of neoprene and silicone rubber. 21. How does it compare with injection moulding? 18. properties and uses of (i) Phenol-formaldehyde resin. (a) Discuss the preparation of natural rubber. 14. (d) What is meant by compounding of plastic? 15. Describe with a neat sketch the process of compression moulding. 23. (a) Give a brief account of vulcanization of rubber.

(ii) nylon 66. (c) Explain–Injection moulding with a diagram. (ii) Compounding of rubber. (ii) PVC. (b) Write short notes on (i) Plastic deformation. 41. 26. . (iv) silicone resin. 38. 44. 28. 43. 33. (ii) epoxy resin. (a) What are bakelite and PTFE? Name any four commercial thermoplastics. (ii) nylon. What is Zeigler-Natta polymerization? Give the structures of syndiotactic. 30. (b) Explain how the polymers are classified on the basis of their thermal behaviour and method of polymerization. 34. properties and uses of (i) nylon 6. 32. 31. properties and uses of (i) bakelite. How do the properties of polymer change with Zeigler-Natta polymerization? (a) Mention the technical tests of polymers. (d) Explain the chemical resistant and thermal resistant polymers. (a) Define and give examples for ENGINEERING CHEMISTRY (i) Monomer (ii) Functionality (iii) Degree of polymerization (iv) Co-polymer.470 24. and (iii) Plexi glass. 46. isotactic and atactic polymers. Write note on thermoplastic and thermosetting resin. 27. 37. properties and uses. Write a note on reclaimed rubber. Give preparation. Give a brief account of (i) Vulcanization of rubber. Distinguish between (i) Thermoplastic and thermosetting plastic. (ii) Moulding techniques. 40. (ii) Teflon. What is biodegradation of polymers? 29. (b) Name a polymer containing fluorine. (a) What is meant by co-ordination polymerization? Explain with two examples. (iii) polyester or dacron. (b) Mention the influence of molecular characteristic on the properties of polymers. (b) Explain–Vulcanization of rubber. Give the representative formula and two important uses of each of the following: (i) Plexi glass. 35. (a) How is natural rubber obtained from latex? (b) Explain compounding and vulcanization of rubber. Write short notes on (i) Polypropylene (ii) Plexi glass. Give example of each class. What is the difference between-plastic. 45. Distinguish between nylon 6 and nylon 66. Give its structure. 42. 25. method of preparation and uses of (i) HDPE. Write short notes on structure. (iii) PVC. (ii) Addition and condensation polymerization. rubber. Write short notes on (i) Teflon (ii) Cellulose acetate (iii) Silicone (iv) SBR. and (iii) dacron. 36. 39. (b) What are the materials from which an epoxy adhesive is prepared? (a) Bring out the differences between thermoplastic and thermosetting plastic. and fibre? Write short notes on (i) rayon. What is an elastomer? (a) Write short notes on preparation.

471 . mustard oil) may be used. water. rapeseed oil. • It should possess a good covering power. They not only reduce the cost of paint but also extends its durability. which hold the pigment to the surface by forming a smooth plastic film as the paint dries and sets. The solvent is known as thinner. A paint has three main ingredients. The oil contains a long unsaturated fatty acid chain. so that the paint covers up the surface underneath and decorates it with colour. which scatter and absorb light. • It should be opaque. (ii) a solvent and (iii) an organic or inorganic pigment. Some sort of atmospheric oxidation and polymerisation occur due to the presence of unsaturation and a film is formed on the surface. • Polymers. • Pigments. In gloss paints a vehicle is traditionally a hydrocarbon solvent.21 PAINTS Paints Paint is a uniformly dispersed mixture having viscosity ranging from a thin liquid to a semisolid paste and consisting of (i) a drying oil. In emulsion paint it is In case of synthetic resins a drying oil (linseed oil. in emulsion paints they are latex polymers. A paint is a product formulated to protect and decorate mainly metallic and wooden surfaces. The binder and the solvent are collectively called a vehicle. Here film forming mechanism is different. tung oil. which is a liquid in which the other ingredients are dissolved or dispersed. Pigment extenders are generally called fillers. In gloss paints the film forming polymers are alkyd resins. • A vehicle. CH2OCO(CH2)7CH = CH—CH2—CH = CH—(CH2)4—CH3  CHOCO(CH2)7CH = CH—CH2—CH = CH—(CH2)4—CH3  CH2OCO(CH2)7CH = CH—CH2—CH = CH—(CH2)4—CH3 Drying oil (A glyceride of linolenic acid) Characteristics of pigments A pigment is any substance that imparts colour to another substance. The film forming substances are known as binders. synthetic resin or other film forming components.

(vi) Metal paints.1: Range of PVC in a given paint Name (i) Flat paints (ii) Semi gloss paints (iii) Gloss paints (iv) Exterior house paints (v) Metal primers (vi) Wood primers %PVC 50–75 35-45 25-35 28-36 25-40 35-40 . Importance of emulsion paints (Latex paints) (i) It can be employed on both interior and exterior surfaces.472 • It should be inert. (iii) It does not have any disagreeable product.e. ENGINEERING CHEMISTRY Characteristics of an ideal paint • It should be chemically inert. (v) Emulsion paints or latex paints. PVC (Pigment Volume Concentration) PVC is defined as : PVC = Volume of pigment in paint Volume of pigment in the paint + volume of non-volatile vehicle in the paint The concept of PVC is very much important in case of paints as PVC controls—gloss. The concept of PVC is extremely useful to a paint formulator for determination of different pigment or vehicle combination i. rheological properties. • It should be non-toxic.. a range of PVC shown in the table below: Table 21. washabilities and durability of a paint. (iv) Marine paints. • It should have a suitable consistency which is generally determined by PVC. • It should be non-toxic. (ii) Application of emulsion paint over a surface is an easy task. (iv) It is non-inflammable. • It should be weather resistant. Special types of paints (i) Fire resistant paints (ii) Chemical resistant paints (iii) Luminous paints. And above all.

e. Amyl acetate. zinc yellow. Dehydrated castor oil. methylated naphthalene White lead. casein. naphthenates. Butyl acetate.. 21. Tints and Thinners Resins Feed Tank Oils Weight Tank Pigments Mixer Tinting & Thinning tank Labelling machine Filling machine Belt conveyer Grinding mill Hopper Carton Packaging Shipping Platform scale Fig. Lithopone. Acrylics. (ii) Volatile i. Dri