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Copyright © 2007, New Age International (P) Ltd., Publishers
Published by New Age International (P) Ltd., Publishers

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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 impos-
sible 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 attach-
ing 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

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...................................................................... 584 Noise Pollution.......................................................................................................................................................................................................................................... 519 Infrared Spectroscopy . 586 Short Questions and Answers ....................................................................................... 571–589 Air Pollution ........................ 585 Thermal Pollution.......................................................................................................................................................................................................................................................... 565 Electron Transfer ............................................................................................................. 562 Copper ............ 554 Photosynthesis ................................................................................................................... 570 27 Pollution Prevention and Waste Minimisation .......................................................................... 563 Manganese ...........................................................................................548–560 Singlet and Triplet States .................. 512–547 Introduction ........................................................................................ 565 Electron Transport and Oxidative Phosphorylation ...................... 525 Shielding............................... 537 Short Questions and Answers ...................................................................................................................................................................................................................................................................................................................... 560 26 Role of Metals in Biology ............................................................................................................................................... 513 Beer-Lambert’s Law ............................................................................................................................................... 563 Zinc ............................................. 564 Cobalt ............................................................... 564 Nickel ................................................................................................................................................... 556 Exercises ................................................................................................................................................................................................................................................................................. 522 Some IR Spectra .................................................................................................................................................................................................................................................................................................... 547 25 Photochemistry ....................................................................................... 569 Exercises ............................................. 549 Photolysis ............. 550 Types of Photophysical Pathways .......................................................................... 579 Soil Pollution ................................................................................................ 583 Radioactive Pollution ... 529 Mass Spectrometry ...... 512 Some Terms Concerning UV ........ Deshielding and Chemical Shift ........ 587 Exercises ..................................................... (xii) 24 Instrumental Methods of Analysis ....................................................................................................... 552 Photochemical Processes for Excited Molecules .................................................................................................................................................................................................................................................................................................................... 589 C8—d:\N-engche\TITLE.. 540 Exercises ............................................................................. 561–570 Iron ....................... 567 Short Questions and Answers ....................................................................................................................................... 564 Calcium and Magnesium .......................... 571 Water Pollution....................................................................................pm5 viii .......................................................................................................... 549 Properties of the Excited States ........................................

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

etc. then 2πr = nλ. Charge Density Distance K L M N O Fig.2). These waves form stationary waves with their nodes and antinodes. The New Atomic Picture In Bohr’s atomic model.. it is still customary to talk of orbits and shells for the simple reason that even according to the new picture of the atom. nucleus of an atom is surrounded by particles known as electrons. the whole of electron mass and charge is spread out uniformly throughout the space immediately surrounding the nucleus of the atom (Fig. i. At nodes where the motion is practically zero. i.2 ENGINEERING CHEMISTRY If r is the radius of the circular orbit. there is assumed to be a little or no charge while at the antinodes the amount of charge is maximum. This model has been replaced by wave mechanical model. 3. M. Since ‘mvr’ is the angular momentum of the electron as a particle. which revolve in defined shells or orbits. replaced by de-Broglie’s electron wave. New wave model accepts the electron distribution to be three dimensional. 1.1 Bohr’s postulate that the angular momentum is an integral multiple of h/2π. Old Bohr’s model is represented by orbits of an atom (Z = 37) (Fig. Other quantum conditions can also be derived similarly.e. electrons are found to distribute their charges in such a way that something analogous to shells is formed.PM5 2 . 1.2 Old and new models of an atom. Hence. we see that wave mechanical picture leads naturally to Fig.2) and the new wave model is represented by a graph of spherically symmetrical electronic charge with several maxima corresponding to the discrete K.. 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. nh r ∴ 2πr = mv or mvr = nh/2π where n = 1.e. Now. 2. instead of being localised at a point. C-8\N-ENGCHE\ECH1-1. the angular momentum is quantised. 1. N shells. 1. However. L. Moreover. λ = h/mv.

In an ordinary material wave the displacement of whatever is vibrating about its mean position is given by x FG IJ y = a sin 2π ft − λ H K .. 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. ∆p = change in momentum and h = Planck’s constant. It is for this reason the classical concept of Bohr’s model of atom has been replaced by probability approach. Let us now see how this equation can be applied to specify an electron in motion. ∆ x. Schrödinger Wave Equation It is a differential equation capable of describing the motion of an electron. Uncertainty Principle and Bohr’s Theory—Concept of Probability Bohr had postulated that electrons revolve in well defined orbits with fixed velocities (energy). The above expression is known as uncertainty relation where ∆ x = change in position. On the basis of this principle therefore Bohr’s model of atom no longer stands. y varies periodically with frequency f. y = displacement at time t and at distance x from origin. As we know. it becomes d2y 4π 2 .(1) where. it is impossible to determine its position and momentum simultaneously. Its solution is y = a sin 2π x/λ which defines a standing wave. a = maximum displacement from mean position.. the total energy E of an electron is partly kinetic and partly potential. 1 E= mv2 + V 2 ∴ mv = 2m(E − V) .(3) dx 2 The above equation involves only distance as the independent variable..∆p ≥ h/2π... Thus the uncertainty principle which gives the wave nature of the electron only provides probability of finding an electron in a given space.(2) + y=0 dx 2 λ2 d2 y or + k2 y = 0 . λ = wavelength.PM5 3 . C-8\N-ENGCHE\ECH1-1. When differentiated twice with respect to x. At each point along the wave in space. f = frequency of vibration.. The Heisenberg uncertainty principle states that l It is impossible to determine simultaneously both the position and the momentum of a particle with accuracy. But according to uncertainty principle since an electron possesses wave nature. 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).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.

.dz. Schrödinger wave equation is time independent.. Generally its solutions are only attained for certain energy values called characteristic or eigen values. d 2 ψ d 2 ψ d 2 ψ 8π 2 m + + + (E − V)ψ = 0 dx 2 dy 2 dz 2 h2 8π 2m or ∇2ψ + (E − V)ψ = 0 . Schrödinger equation can be employed for determining the total energy of an electron. Like other differential equation. ψ = a + ib and its conjugate ψ* = a – ib and their product.(5) h2 This Schrödinger equation is a basic equation of wave mechanics.. Significance of ψ and ψ2 l ψ denotes the amplitude of a three dimensional stationary electron wave.. |ψ2|dx represents the probability of finding an electron within a range of x and x + dx... we can write. Because of the spherical symmetry of an atom the wave functions are most satisfactorily expressed in terms of C-8\N-ENGCHE\ECH1-1.(4) dx 2 h2 The equation (4) is known as the time-independent Schrödinger equation in one dimension.. ψ. As. mv 2m(E − V) Substituting this value in equation (1) and replacing y by ψ as is customary. which is real. l According to the Heisenberg’s uncertainty principle.dy. The total probability of finding an electron in space extending to infinity is expressed as follows: z +∞ ψ2d V = 1 −∞ where dV = dx. So.(6) h2 So.PM5 4 . the Schrödinger wave equation is also governed by boundary conditions. i. This is known as the condition of normalisation and the corresponding wave function ψ is said to be normalised. this equation becomes. de-Broglie wavelength is given by h h λ= = . The corresponding wave function ψ which is generally complex is called characteristic or eigen function.ψ* = (a – ib) (a + ib) = a2 + b2. we get d 2ψ 8 π 2m + (E − V) ψ = 0 . The potential energy V of an electron is specified in terms of space co-ordinate not on time. p = mf is a starting point of classical mechanics.e. This mathematical expression displays how the probability of finding an electron varies in space. 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.4 ENGINEERING CHEMISTRY Now. It is seen from equations (3) and (4) that 8 π 2m k2 = × (E − V) . But in three dimension system |ψ2|dV represents the probability of an electron within the volume range of V to (V + dV). For three-dimensional motion of an electron. For a one dimension system.

ATOMS AND MOLECULES 5 spherical polar co-ordinate system with nucleus at the origin. θ and ϕ are the polar co-ordinates of the electron with respect to the nucleus (N) as origin [see Fig.. ∂θ H + 8π 2 µ(E − V) = 0 K . FG 1 ∂ 2 ∂ψ IJ 1 ∂2 ψ 1 ∂ ∂ψ FG IJ 2 r ∂r r H ∂r + 2 K2 r sin θ ∂ϕ 2 + 2 .. the Schrödinger wave equation assumes the following form. changing from the Cartesian co-ordinates to polar co-ordinates.3 (a) and (b)]. 1. m e m e r N E . r sin θ ∂θ sin θ.(A) where r.

φ). This is also same for d-orbital.PM5 5 . Φ(φ) is a function of ϕ which depends on magnetic quantum number (ml).e. φ) can be expressed as ψ (r. The total wave function ψ(r. The function Θ(θ) is function of θ depending on azimuthal quantum number (l) and magnetic quantum number (ml). θ. Φ(φ) where. (i) radial wave function and (ii) angular wave function. 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.. which depends on the quantum number n. φ) is denoted as a product of two functions. l (the principal and azimuthal quantum numbers. The angular dependence of p-orbital is also not influenced by the principal quantum number. θ.3 It can be shown mathematically that each permitted solution of the wave equation (A) i. θ.) C-8\N-ENGCHE\ECH1-1. which gives the total probability of finding an electron is called the atomic orbital. r E N  (a) (b) Fig. For any s orbital (1s.. respectively).). 2s. etc. θ.e. 3s. (contd. Θ(θ) . it represents the variation of ψ in the same direction. Highlight: For a small particle like an electron moving in three dimension in the field of nucleus.. the angular part of the wave function is always the same whatever be the principal quantum number n. 1. ϕ) = R(r) . The radial wave function R(r) shows the variation of wave function with r keeping θ and ψ constants i. R(r) is a function that depends on the distance from nucleus.. The wave function ψ(r. wave function ψ(r. the Schrödinger wave equation is ∂ 2 ψ ∂ 2 ψ ∂ 2 ψ 8π 2 m + 2 + 2 + (E − V)ψ = 0 ∂x 2 ∂y ∂z h2 where m = mass of the electron.

ψ function must be zero for all values x > l. Alternatively.6 ENGINEERING CHEMISTRY V = potential energy of the electron. Alternatively. it is found that the equation can be solved when E assumes certain values which are related by integers. E = total energy of the electron. ψ function has to be zero at x = 0 and for all negative values of x. ψ(x) = 0 at x = 0 or ψ(0) = 0 0 = a sin 0 + b cos 0 or b = 0 Also ψ(x) = 0 at x = l C-8\N-ENGCHE\ECH1-1. So.PM5 6 . A general solution of Schrödinger equation is: ψ(x) = a sin kx + b cos kx For boundary conditions.   n=3 n=2 n=1 2 [x] || n=1 V V 0 L 0 L V=0 n=3 n=2 x=0 x=L (a) (b) (c) Fig. inside the box V = 0. the quantised or allowed or permitted energies of electrons and ψ is the wave function.4. we have. Similarly. 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. Hence. x. h = Planck’s constant. z = co-ordinates of the electron. the solution of the above equation produces the electron distribution in space as well as the allowed energy state of the electron. When this equation is applied to hydrogen atom. 1.4 The potential energy V of the electron at the bottom of the box is constant. y. 1. The solution of the above second order differential equation furnishes the values of E. it can be stated that the particle is confined to the box and cannot exist outside. since the particle is not allowed over the walls of the box. Hence. ψ = wave function or the eigen function of the electron representing the amplitude of the wave associated with the electron. Let the potential energy be infinite for x < 0 and x > l. may be taken as zero. the concept of quantised energy levels and quantum numbers are the consequences of the wave theory.

Substituting this value in eqn. So. p= 2l 1 ( mv ) 2 p2 Now. (2p) = h or.. 3 .e.e. 8ml 2 The above equation means that the particle in a box does not possess any arbitrary amount of energy. can easily be deduced from the above equation. ∞. So we can write... ∞... C-8\N-ENGCHE\ECH1-1. of the electron.. its energy is quantised. n 2h 2 ∴ En = where n = 1. A few energy levels are given below: n=3 h2 E3 E1 = 8ml 2 Energy 4h 2 E2 = n=2 E2 8ml 2 n=1 E1 9h 2 E3 = 0 8ml 2 x=0 x=L The reason why a particle in a box i. we get. (E. Highlight: Calculation of minimum energy of a particle in a box from Heisenberg’s uncertainty principle. rather it possesses discrete set of energy values i.ATOMS AND MOLECULES 7 ∴ a sin kl + b cos kl = 0 It can only be possible when. ∆p = 2p because the momentum changes from + p to – p continuously. 2. 8ml 2 PROBABILITY DISTRIBUTION The directional properties of an election in an orbital of the hydrogen atom cannot be represented in one diagram. and the particle bounces back in the box. nπ kl = nπ or k= l where x is called quantum number and is equal to 1. Here ∆ x = l. Two separate diagrams are required to meet the demand. 1. h ∆ x × ∆p = l . 4 and also putting V = 0. 3 .E. 2. E= mv2 = = 2 2m 2m h2 ∴ E= . n2π2 8π 2 m = E l2 h So. bound particle possesses Fig.PM5 7 .5 a quantised energy whereas a free particle does not. the total energy of the electron) = K.

the distance from the nucleus does vary. C-8\N-ENGCHE\ECH1-1..7 below. (i) Angular probability distributions of orbitals i.. how r. y-z plane in this case is nodal plane with zero electron density. there is an equal chance of finding it in any direction around the nucleus.e. A p-level has an accommodation for six electrons distributed over three p-orbitals to each value of the principal quantum number. This is graphically shown in Fig. In the presence of external magnetic field these vary in their energy content depending on the magnetic quantum number. how the angular position θ varies from nucleus with respect to a fixed axis and (ii) a radial probability distribution i. in the case of py and pz orbitals the electron will be found along y and z axes. y z + x Fig. y y y z z z + + – + x x x – – px py pz (a) (b) (c) Fig.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. The different shapes are shown in Fig.6 In this diagram.8 ENGINEERING CHEMISTRY These are namely (i) an angular probability distribution i. Similarly. 1.e. py and pz orbitals. 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..PM5 8 . 1. shapes or boundary surfaces of orbitals gives the probability of finding an electron in a particular direction.6 below. An s-electron has no preferred direction in space i..e.. 1.e. In the absence of magnetic field these orbitals are equivalent in energy content and are said to be triply degenerate.e. 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. 1.

C-8\N-ENGCHE\ECH1-1. e.. y y y z z z + – – + + – x x x + – – + – + dxy dyz dxz (a) (b) (c) y y z z Negative dough nut in – + x + + x x-y plane + x-y plane – dz2 px2–y2 (d) (e) Fig.e. The probable distances of an electron are given by radial probability distribution diagram which are given in Fig.PM5 9 . dyz. e.g. dx2 − y 2 . dzx have their lobes lying symmetrically in between the co-ordinated axes indicated by the subscripts to d. dz2 .9. 3s.g. 2p. 1. (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. 2s. the lobes of dxy orbital are pointing or lying in between the x and y axes. These are shown in Fig.8 below. 1.8 All the d-orbitals are equivalent in energy in the absence of magnetic field and are said to be five fold degenerate. This set is referred to as t2g set. The set of the three orbitals namely dxy. dxz. The lobes of dx 2 − y2 orbital lie along the x and y axes while those of dz2 orbital lie along z-axis. 1. The set of two orbitals i.ATOMS AND MOLECULES 9 The angular probability distribution of five d-orbitals that can accommodate ten electrons is quite complicated. In these diagrams. the probability of finding an electron at a distance r from the nucleus is plotted against r (distance from the nucleus) to get 1s. dyz. These five orbitals are named as dxy. 3p and 3d orbitals of hydrogen atom. dx 2 − y2 and dz 2 orbitals form eg set having their lobes along the axes.

2s. Probability Probability 1s 2s r0 1 2 Å 0 r1 2 r2 4 6 8 Å Distance r Distance r (a) (b) Probability Probability 3s 2p 0 2 4 6 8 Å 0 2 4 6 8 10 12 Å Distance r Distance r (c) (d) Probability Probability 3p 3d Distance r Distance r (e) (f) Fig. All these facts are based on the proper interpretation of Schrödinger wave equation. 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.9 Radial probability distribution of 1s.PM5 10 . 3s. This means the electron can never be at nucleus. 2p.10 ENGINEERING CHEMISTRY Highlights: l The probability of finding an electron at the origin is zero which is the nucleus. 1.528Å). l 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. C-8\N-ENGCHE\ECH1-1. l The distributions vary according to the principal quantum number.

6. 14. 3p. Give the new picture of an atom. Write Schrödinger wave equation for one dimension. Write the Schrödinger wave equation using polar co-ordinates. 7. Correlate Bohr’s postulate of angular momentum with the wave mechanical model.ATOMS AND MOLECULES 11 EXERCISES 1. 8. Give the probability expression for finding an electron in the volume range of V and V + dV.PM5 11 . What do you mean by wave nature of an electron? 2. 4. 5. What are eigen values and eigen functions? 10. Draw angular and radial probability distributions of 2s. C-8\N-ENGCHE\ECH1-1. 3d orbitals. 12. Write how the uncertainty principle leads to probability approach. Write Heisenberg’s uncertainty principle. 13. Write Schrödinger wave equation for three dimension. Give the de-Broglie’s wave equation? 3. Apply Schrödinger wave equation for particle in one dimensional box illustrating energy quantisation. 11. Mention the significance of ψ and ψ2. 9.

Kr. have eight electrons in their outermost shells except He. Na atom can attain inert gas structure by losing one electron and Cl atom can attain inert gas structure by gaining that electron. 2 Valency and Chemical Bonding Atoms of elements combine to form molecules of compounds. Other electrovalent compounds have been represented as follows by dot-cross method. M and N shells in the atoms. During chemical combination. viz. L. This is a very common nature of the atoms and for this sake. 2. 8. Ar. + + – Na Cl Na Cl Fig. 12 . There are three types of valencies — (i) Electrovalency or Ionicvalency (ii) Covalency (iii) Co-ordinate covalency. the electrons of the atoms rearrange to form the molecule of the compound. He.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. Ne. The electrons remain in the K. 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.1. 7. Rn and Xe. The electrons of the outermost shell of an atom take part in a chemical combination and are called valence electrons. 2. The phenomenon can be represented pictorially as in Fig. atoms either lose or gain electrons or share and this idea of electronic arrangement is the basis for electronic theory of valency. 8. These ions remain combined due to electrostatic force of attraction between the so-formed ions. 1 and Cl atom has got electronic structure ⇒ 2. Electrovalency: Na atom has got electronic structure ⇒ 2. The inert elements. 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.

The atom which donates a pair of electrons is known as ‘donor’ atom and the atom which C-8\N-ENGCHE\ECH2-1. (vi) They are non-polar in nature. and b. 8 ) Mg + 2F = µg ++ 2F − (MgF2) ( 2. (iii) m. The other atom contributes no electron towards the bond. 8 . combine to form molecules of a compound they share the electrons to fill up their octets in their outermost shells. Co-ordinate Covalency In covalency the bonding atoms contribute equal number of electrons to form a bond. 8) Highlight: Electrovalency is seen in the case of atoms with a marked difference in electronegativity values when they combine. 18. × . of same or more or less same electronegativity values. ×× Cl × × × × × × × × × × + × × Cl × × × × × × Cl ×× Carbon tetrachloride × × molecule Comparison of electrovalent and covalent compounds: Electrovalent Compounds Covalent Compounds (i) They are Non-directional. 2) 2(2.p. 2) 2(2. This sort of combining of atoms is known as covalency.C. Br × × × × × Br ×× × × × × × × × Ca : ++ + Ca (CaBr2) . 8) Similarly 2K + S = 2K + S − − (K2S) 2( 2. are high. + × Cl × × . 8. (ii) They cannot exhibit isomerism. 7) ( 2. Cl . After combination the bond acts as a purely covalent bond. (vi) They are polar in nature. 1) ( 2. Covalency When atoms. 8. 7) (2. and b. 2Br − (2. 8) ( 2. 8.p. Examples of covalent compounds : × × × × × × × × × × Cl × + × Cl ×× × Cl ×× Cl ×× × × × × × × × × × Chlorine molecule × × × × Cl ×× × × × × × +. 8 . In some cases during chemical combinations. (iv) They are conductors of electricity (iv) They are nonconductors of electricity in solution or in their molten state. 8. CCl4). a pair of electrons is being contributed by a single atom. (iii) m. in solution or in molten state. (i) They are directional in nature. and insoluble in non-polar solvents generally insoluble in water. (C 6H6. 18. 8. (ii) They can show isomerism.p. 8.VALENCY AND CHEMICAL BONDING 13 Some examples of electrovalent compounds : . × × × × × Br ×× × Br ×× × × × × Ca + 2Br = Ca + + . 8) 2(2.× × Cl . (v) They are soluble in polar solvents (H2O) (v) They are soluble in organic solvents. 8) 2(2. 8. This sort of bond formation is known as co-ordiate covalency.p.PM5 13 . C × × × × × × × × × × × × × × × Cl + . 8. 8. . 6 ) 2 ( 2. are low.

.0 2.0 1.0 4 K Ca Ga Ge As Se Br 0.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 ‘→’.6 1.9 1.8 1.7 1.0 2.H H .5 3.. × ×  (BF4) × × F F Electronegativity The attraction and repulsion powers of atoms of different elements are not same.. F – × × .B . H + + × × H .O . Table 2.8 5 Rb Sr In Sn Sb Te I 0.7 0. ..1 2. – .5 3..14 ENGINEERING CHEMISTRY accepts the pair of electrons is known as ‘acceptor’ atom.. In comparison.5 6 Cs Ba Ti Pb Bi Po At 0.+.1 2 Li Be B C N O F 1.0 1. As for example.7 0.. F .8 2.B F .8 1.N .9 2. The power of attracting electrons of one of the atoms in a covalent bond is known as its electronegativity.1 2.8 2.O . 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. F .9 C-8\N-ENGCHE\ECH2-1. . The donor atom should have a lone pair of electrons. .8 1.N . × H ×  (NH4) × × H H Ammonium ion + .0 3. ..5 1. H .0 1.. .2 7 Fr Ra 0. .PM5 14 .9 1.1: Electronegativity values (L.0 2.2 1. Pauling Scale) Group → I (1) II (2) III (13) IV (14) V (15) VI (16) VII (17) Period↓ 1 H 2.4 2.5 4. H .F .5 2. The phenomena can be represented as follows: A.1 below. H atom has less tendency of this sort.0 2.H .F . H + + × H ×  (H3O) × × H H Hydronium ion – . .8 1.1 is given in Table 2. . Comparative values of electronegativities of different elements taking the electronegativity value of H as 2.. Some examples of coordinate bond formation: + .9 2.0 3 Na Mg Al Si P S Cl 0.

. F.5 (xA – xB)2 Calculation of partial ionic character of HF molecule: % ionic character in HF molecule = 16(4. HCl..1) + 3... As a result.PM5 15 . Greater the difference (xA – xB). greater is the ionic character of the bond. xA = xB. Hydrogen Bondings There are two types of hydrogen bonding: (a) Intermolecular (b) Intramolecular. This sort of bond is known as ‘hydrogen bond’.. The bond energy is less than that of covalent bonds.e.0 – 2. (ii) The atomic radius of the electronegative elements should be small. the hydrogen will gain the positive charge partially but the electron will not be detached totally from the hydrogen atom.. like O.. When xA ≠ xB. H – F . the bond gains partial ionic character and the molecule AB becomes polar.... (ii) HO HO HO HO Covalent H H H H bond Hydrogen bond C-8\N-ENGCHE\ECH2-1.VALENCY AND CHEMICAL BONDING 15 This sort of attractions give the covalent bond between two atoms a partial ionic character...0 – 2.1)2 = 43%. If the second atom is electronegative. due to its greater electron attraction power.5(4. when atomic radii are small). Example of hydrogen bonding in HF molecules: + – + – + – + – H – F . In this condition. H–F . i.. Partial ionic character of a covalent bond is calculated as follows: When electronegativity values (x) of the two atoms A and B are same. (a) Examples of intermolecular hydrogen bonding : (i) . N and F (i. the bond A – B is 100% covalent.. This type of bond is not very strong.e.. • Hydrogen bond is seen when hydrogen is attached to electronegative elements.... i. Hydrogen Bond Hydrogen atom has got only one electron... H–F . H–F . The relation is represented by the equation — LM RS 1 ( xA − xB ) 2 UVOP % ionic character = 100 1 − exp 1 − N T 4 WQ = 16(xA – xB) + 3. H –F hydrogen bond Highlights: • Conditions of hydrogen bond — (i) Hydrogen should be attached to an electronegative element of a covalent bond.. it can combine with one atom of a monovalent atom...e.. 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. if the charged hydrogen atom comes in contact with strongly electronegative element of the other molecules (hydrogen of HF)... H–F.... then electron pair of the bond is shifted towards the other atom. viz F.. viz. H – F ..... So.

they develop a moment. When they fall in different places i. C-8\N-ENGCHE\ECH2-1. the charge is expressed in ‘e.. If the magnitude of the charge at the centre of action is e and distance between them is d.e.’ unit and the distance in ‘cm’ unit. So the unit of dipole moment is ‘e.s.PM5 16 . dipole moment. The molecules containing the dipole moment are called polar molecules. 1 × 10–18 esu-cm is known as 1 Debye. the boiling points of the molecules become high. 2. HO HO R H Dipole Moment Every atom has got nucleus and requisite number of electrons. (ii) Solubility of the molecules in water arises out of hydrogen bonding with water molecule. then. i. volatility becomes less. So within a molecule there is a centre of action of positive charges as well as centre of action of negative charges.e. known as dipole moment. So within a molecule two or more positive nuclei are surrounded by electrons at different places. two charges (+ve and –ve) are separated by a distance. These two points in a molecule may fall at the same point or at different places in the molecule. µ = e × d d + e e– Fig.2 Generally.s.16 ENGINEERING CHEMISTRY + – + – HO O N O HO O N O (iii) + – + – O N O H—O O N O H—O (b) Examples of Intramolecular hydrogen bonding: O + O H C H O N H O 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.u-cm’. And this Debye unit is used to express the dipole moment..u.

its dipole moment is 1. CO2... If R is zero. E A ) Electron affinity is represented by the ‘–ve’ sign as energy is liberated in this case.0 kcal U0 . are non-polar molecules.8 D. C6H6. 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 1 Cl (g) Q = –98. A ( g) + e − ( g) → A − ( g) + Energy released Neutral gaseous atom Anion (Electron affinity of atom A.0 kcal 2 Determination of electron affinity of Na atom. H2. • 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.VALENCY AND CHEMICAL BONDING 17 Highlights: • The dipole moment of H2O molecule is 1. d ⇒ 0. and in those molecules centre of positive charge action and centre of negative charge action are at the same place. ∴ µ ⇒ 0.9 kcal S = +26.. µ1 and µ2 = dipole moments of the different bonds of the molecule.e. i. i. NH3. H2O. 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.2 kcal NaCl(s) Na(s) + 2 2 Crystal 1 D = +28. etc.8 × 10–18 esu-cm.e. R = Resultant moment of the molecule. CH3OH are polar molecules i.e. CH4. Na(g) Cl(g) I = +118. • HCl. their centre of action of positive charges and centre of action of negative charges are not same and the molecule is not symmetrical. the molecule becomes non-polar and if R has got a positive value the molecule becomes polar. When energy is supplied it is represented by ‘+ve’ sign and called second electron affinity (E2). • Cl2. The molecules are symmetrical.

PM5 17 .2 = + 26 + 28. Cl(g) → Cl–(g) C-8\N-ENGCHE\ECH2-1.4 ∴ E = – 90.9 + 118 + E – 180.4 kcal 1 Q=S+ D + I + E + U0 2 – 98. + – Na (a) Cl (g) U0 = –180. Lattice energy of E = ? (+e) (– e) NaCl crystal.7 kcal/g atom of Cl Negative sign indicates that energy is released in the formation.

In this connection. C-8\N-ENGCHE\ECH2-1. Both the theories admit that — (i) A covalent bond is formed as a result of overlapping of the atomic orbitals. • We have utilised Born-Haber cycle in determining the electron affinity of ‘Cl’ atom.18 ENGINEERING CHEMISTRY Highlights: • 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. 2. • The lattice energy for NaCl is –780 kJ mol–1. • A Born-Haber cycle can also help to determine whether the bonding in a compound is truly ionic. (iv) Each covalent bond requires overlapping of a pair of orbitals. 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. that for KCl is –711 kJ mol–1 and that for AgCl is –905 kJ mol–1 calculated as per Born-Haber cycle.PM5 18 . 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. Valence-bond theory 2.4 (a) Formation of HFmolecule. two main approaches are — 1. 2. Molecular orbital theory. H2O molecules (i) HF molecule H + H F F Fig. • The cycle is an application of Hess’s Law (see Chapter 4).3 Formation of H2 molecule by the overlapping of two 1s atomic orbitals of two H atoms. Molecular orbital theory is gaining much importance. 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. (iii) Maximum overlapping gives a strong bond known as sigma (σ) bond. NH3. (ii) When the overlapping takes place along the axes of the atomic orbitals maximum overlapping of atomic orbitals can occur. H H H : H Fig. (v) The overlapping orbitals must be valence orbitals and must contain an odd electron. The application of wave mechanics gives a satisfactory explanation of some of these problems.

But actually bond angle in NH3 is 106° 45′. But the actual bond angle in water molecule is 104° 27′. So some other concept becomes essential to explain the formation of NH3 molecule. That concept is the concept of hybridization. py pz py pz px + px F atom F atom F2 molecule Fig. This fact also leads to the idea of hybridization of orbitals. 2. C-8\N-ENGCHE\ECH2-1. If it were the case. (iii) Water molecule x x 1s + + y y + + + + + 1s + z z – – – – H2O molecule Fig.PM5 19 .VALENCY AND CHEMICAL BONDING 19 (ii) NH3 molecule z 1s H y + + 1s + + + + N + + + + z – z + + 2pz 1s – – 2py 2px NH3 molecule Fig. 2. Here the overlapping takes place between the three (2p) orbitals of nitrogen atom with 1s orbital of each hydrogen atom. then bond angle in NH3 should be 90°. 2. (iv) Fluorine molecule : p-p overlapping to form a σ-bond.5 Formation of H2O molecule. In this case also the bond angle appears to be 90°.6 px-px overlapping along the axis to form F2 molecule.4 (b) Formation of NH3 molecule.

then bond angle and bond energies in CH4 molecule can satisfactorily be explained as follows: 1s 2s 2p C-atom (ground state) ⇒ C-atom (excited state) ⇒ Now this one s-orbital and three p-orbitals of a carbon atom mix to give four hybrid orbitals of equal energies. but in CH4. the axes of hybrid orbitals are directed towards the vertices of a regular tetrahedron (Fig. + + + . Hybridization: Carbon has electronic configuration: 1s2 2s2 2p2. (a) Overlapping of two px orbitals along the axes leads to the formation of a sigma bond.20 ENGINEERING CHEMISTRY (v) N2 molecule: p-p overlapping to form σ and π bonds py py py py pz pz pz pz -bond px -bond Fig.8). 2. C atoms form four identical bonds with H-atom with equal energy.7 σ and π bonds in N2 molecule. (b) Lateral overlapping of two py and pz orbitals leads to the formation of two π bonds. This can be explained only by the Concept of hybridization. 2. 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.

2.8 sp3 hybridised C atom.PM5 20 . + + + s px sp3 sp3 sp3 sp3 hybrid orbitals py pz 3 sp 109° 28 3 3 sp sp C 3 sp Fig. C-8\N-ENGCHE\ECH2-1. 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.

sp2-hybridization Electronic configuration of : 1s 2s 2p C in the ground state . 2.9 CH4 molecule.VALENCY AND CHEMICAL BONDING 21 H C H H H Fig.

Four unpaired C in the excited state .

electrons 2 sp hybridization One 2s and two 2p electrons 2p hybridize to give .

PM5 21 .10 Ethylene molecule.10). Residual 2p orbitals of each sp2 hybridised C-atom overlap laterally to form a π-bond (Fig. 2.10). Three sp2 hybrid orbitals of each C-atom form three sigma bonds in ethylene molecule. 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. 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. • Four sigma bonds are formed due to overlapping of sp2-s orbitals and one out of sp2-sp2 overlapping. The hybrid orbitals lie in a plane and the axes are directed towards vertices of an equilateral triangle and so. bond angle in this case is 120°. C-8\N-ENGCHE\ECH2-1. 2. Highlights: • Ethylene molecule contains five sigma bonds. 2. H H C C -bond H H -bond -bond Fig.

sp-hybridization Electronic configuration of: 1s 2s 2p C in the ground state . 2s and 2p hybridise electrons to produce three sp2 hybrid orbitals directed towards the vertices of an equilateral triangle.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. 1s2 2s2 2p1. F sp2–p (–bond) B sp2–p (-bond) F sp2–p (-bond) F Fig.11).11 Formation of triangular planar BF3 molecule. 2. 2. Boron atom has electronic configuration. (Another example of sp2 hybridization).

px py pz Four unpaired C in the excited state .

electrons sp hybridization 2p Electronic configuration of sp hybridized C-atom .

Then two C-atoms possess total four unchanged p-orbitals. In BeF2 molecule the central atom Be has electronic configuration ⇒ 1s2 . Since. the Be atom cannot form any covalent bond. there is no unpaired electron. 2. So triple bond of acelylene molecule contains one σ-bond and two π-bonds.   H H HC CH    Fig. two sp-hybrid orbitals overlap along the axis to give a σ-bond. They overlap laterally to give two π-bonds. 2s2 in its ground state. In the structure of acetylene sp-hybridization takes place. During combination with H-atom. C-8\N-ENGCHE\ECH2-1.PM5 22 .12 Structure of acetylene. In the excited state of C-atom there are two hybrid orbitals (sp) and two unchanged p-orbitals.

Electronic configuration of: 2s 2p Be in ground state . 2px1 2py0 2pz0.VALENCY AND CHEMICAL BONDING 23 In the excited state one of the 2s2 electrons jumps to 2p-orbital before forming any bond. 2. the Be atom has the configuration ⇒ 1s2 2s1.13). 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.

Two unpaired Be in excited state .

electrons sp hybridization with two unpaired electrons. 2p sp hybridized Be atom .

there are lateral overlapping and due to this lateral overlapping the π-bonds are formed. axes of which are directed towards the C-8\N-ENGCHE\ECH2-1.13 Structure of BeF2 (example of sp hybridisation). the overlapped charged cloud is parallel to internuclear axis. Hence. sp hybridized orbitals 180° F F F Be F Be Fig.54 1.PM5 23 . In this type of bonding. • π-bonds are comparatively weaker than σ-bonds.52 1. Table 2. Highlights: • When orbitals overlap along the axes. two p-orbitals (px and py) and one d-orbital ( dx 2 − y2 ) mix to give four equivalent hybrid orbitals. as they form by lateral overlapping.21 1. 2. there is σ-bonding. • In double bonds and triple bonds. In this type of bonding.2: Displaying bond lengths and bond energies Bond C—C C=C C≡C N—N N≡N Bond length (Å) 1.34 1. • When the number of bonds between the atoms increase the bond energy increases and bond length decreases. the π-bonds open easily and take part in the chemical reactions. charge cloud exists symmetrically.10 Bond energy (Kcal) 83 144 196 38 225 dsp2-hybridization In this type of hybridisation one s-orbital.

px s py pz 2 dz 3 dsp Fig.14). 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. But in this case. The shape of the molecule will be trigonal bipyramidal (Fig. the hybrid orbitals are not equivalent.24 ENGINEERING CHEMISTRY corners of a square. Example of sp3d hybridization: Electronic configuration of: 3s 3p 3d P-atom in ground state . 2.15).3).14 sp3d hybridization. The hybrid orbitals consist of one group of two equivalent oppositely directed orbitals and the second group of three equivalent orbitals. 2. 2. the shape of the molecule becomes square planar and the bond angle is 90° (see Table 2. So.

P-atom in the excited state .

Five unpaired electrons sp3 d hybridization 3d .

15). 2. C-8\N-ENGCHE\ECH2-1.PM5 24 . 2.15 Trigonal bipyramidal structure of PCl5. Cl Cl Cl P Cl Cl Fig. These sp3d hybrid orbitals of one P-atom overlap with five p orbitals of five Cl atoms to form PCl5. The shape of the molecule is trigonal bipyramidal (Fig.

VALENCY AND CHEMICAL BONDING 25 d2sp3 or sp3d2 hybridization Electronic configuration of: 3s 3p 3d S-atom in ground state .

S-atom in excited state .

Six unpaired electrons 3 2 sp d hybridization .

When the central atom contains one or more lone pairs (lp) of electrons in the valence shell with bond pairs (bp) the C-8\N-ENGCHE\ECH2-1. Table 2. 2.3 No. or sp3d2 Co(NH 3)6 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.PM5 25 . of electron pairs Hybrid Shape of Bond angles Example in outer shell orbital the molecule of the atom 2 sp Linear 180° BeF2. (NH3)2 Cl22– 90° 5 dsp3 Trigonal bipyramidal 120° and 90° PCl5. the molecule then acquires a regular geometry. SiF4 90° 4 dsp2 Square planar 90° 90° 90° [Ni (CN)4]2–. F F F S F F F Fig. These sp3d2 hybrid orbitals of one S-atom overlap with p-orbitals of six F-atoms to form SF6. or sp3d Fe(CO)5 ` 6 d2sp3 Octahedral 90° SF 6. bp) in the valence shell. C2H4 4 sp3 Tetrahedral 109° 28′ CH4. C2H2 3 sp2 Trigonal planar 120° BF3.16 Octahedral structure of SF6 molecule.

Fig. the orbitals containing lone pairs as well as the bond pairs are so arranged that there is maximum repulsion between them. there is sp3 hybridization and one hybrid orbital contains lone pair of electrons. In all the above cases there were only bond pairs in the molecules and the molecules have a regular geometry. 2. The bond angle is 180°. 105 b.e.96 O l. 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. 2.p. It is again greater than the bond pair-bond pair repulsion i. The other two corners of the tetrahedron is occupied by the two sp3 hybrid orbitals containing unshared pairs of electrons.19).17 H2O molecule: Here O-atom is sp 3 hybridized and only two H-atoms occupy the two corners of a tetrahedron. the shape of H the molecule becomes pyramidal (Fig.p. So the bond angle is reduced (107°) and if we overlook the fourth corner of tetrahedron occupying H an orbital containing an unshared pair of electrons. l. Central atom surrounded by two bonding pairs: The two bonding pairs remain as apart as possible. Å O 0. In NH3.p H H Fig.18 sp3 hybridized ‘O’ atom. Case I. Molecule containing lone pair and bond pair: Example ammonia molecule: The geometry of the molecule is distorted tetrahedron.p. The central atom surrounded by three bond pairs: They remain as apart as possible and the bond angle is 120°. we can write lp-lp repulsion > lp-bp repulsion > bp-bp. This is the basis of Valence Shell Electron Pair Repulsion (VSEPR) theory.20). Here the bond angle is 105°. Central atom surrounded by four bond pairs: Example methane. 2. Example: BeF2. Now. C-8\N-ENGCHE\ECH2-1. . 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. if the distribution of the orbitals about the central atom of the molecule can be predicted. H ° H b. N But the bond angle here is 107°. the shape of the molecule and bond angle may be predicted. The bond angle becomes more reduced (Fig. Overlooking those two corners of the tetrahedron the H2O molecule becomes ‘V’ shaped (Fig. Fig.PM5 26 ..26 ENGINEERING CHEMISTRY shape of the molecule becomes distorted for minimum energy and for maximum stability. Here lp-bp repulsion is 107° H greater than the bp-bp repulsion.. Case II. 2.17). Here there are four bond pairs and the shape of the molecule is tetrahedral. repulsion. 2.19 V-shaped water molecule. Case III. Case IV.

Such attraction is known as van der Waals force of attraction. + – displaying dipole-dipole interaction (in HCl molecule) – + As a result of dipole-dipole interaction. Intermolecular forces: In a crystalline solid. they can solidify. So energy requirement for melting is less compared to ionic compounds. we can say. ions of molecules are arranged in a symmetrical way. Molecular orbital theory [linear combination of atomic orbitals.O. There are two kinds of intermolecular forces: (a) dipole-dipole interaction.. There must be some forces between the molecules of a non-polar compound. Thus. lp-lp repulsions. Highlight: NH3 and H2O molecules are examples of distorted molecules due to the presence of lone pairs in the hybrid orbitals and lp-bp. when the distance between the nuclei is equal to the sum of the van der Waals radii.O. These van der Waals forces have very short range. van der Waals forces are weak intermolecular forces which are responsible for weakest attractions between nonpolar molecules. (b) van der Waals forces.20 Showing repulsions. Then expression for two molecular orbitals (M.O lp – bp repulsion . if the atoms are forced to come still closer then van der Waals attraction will be replaced by van der Waals repulsion. LCAO] Homonuclear diatomic molecule: Let. i. polar molecules are held to each other more strongly than non-polar molecules (purely covalent molecules).. both attractive and repulsive van der Waals forces are important for our understanding of molecular structure.e.. the intermolecular forces are very weak. 2.) will be one bonding (φB) and the other antibonding (φA): C-8\N-ENGCHE\ECH2-2. lp – lp repulsion H H Fig.PM5 27 . the attraction between them steadily increases and reaches a maximum when they are just “touching”. Every atom has an effective ‘size’. Since. 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). non-bonded atoms strongly resist crowding. When two non-bonded atoms come closer. the particles act as structural units. They act only between the portions of different molecules that are in close contact. In non-ionic compound (covalent compound) where the atoms are held by covalent bonds. two H-atoms designated by HA and HB containing two 1s-atomic orbitals overlap to form M.VALENCY AND CHEMICAL BONDING 27 bp – bp repulsion . This difference in strength of intermolecular forces is reflected in their physical properties. This is called van der Waals radius. Thus.

2. E HA HB Atomic orbitals . Linear combination of 1s-atomic orbitals (σ-symmetry) of two H-atoms to give bonding and antibonding molecular orbitals (σ-symmetry). + +. diagram.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.22 Representation of M.21 Bonding and antibonding orbitals.O.PM5 28 . . 2.23 Linear combination of two 2px orbitals to form σ2p (bonding) and σ*2p (antibonding) molecular orbitals (σ-symmetry). Molecular orbital Antibonding 1s Atomic Atomic Energy orbital 1s 1s orbital 1s Bonding Fig. (ii) Molecular orbitals from p atomic orbitals: (a) End-end overlap + – – + 2p (Antibonding) E – + + + – – + – 2p (Bonding) Fig.21) + . A) +. Energy level diagram (Fig. + * is (Antibonding. 2.  is (Bonding B) Fig.28 ENGINEERING CHEMISTRY φB = ψA(1s) + ψB(1s) φA = ψA(1s) – ψB(1s) (i) The two conditions can be represented pictorially (Fig. + . 2. C-8\N-ENGCHE\ECH2-2. 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. *z2p 2p z z 2p z y y x *y2p.B.). − N. of electrons in antibonding molecular orbitals. 2. *2p *y2p. ⇒ no.O. (Energy level diagram of molecular orbitals for a homonuclear diatomic molecule) So.VALENCY AND CHEMICAL BONDING 29 (b) Side-by-side overlap (Fig. ⇒ 2 N.24): + – 2* 2p – + + + A(Antibonding) E + – – + 2 2p Bonding – Fig. Linear combination of two 2pz orbitals to form πz2p (bonding) and πz2p* (antibonding) molecular orbitals (π-symmetry). 2.24 π-Bonding. A.O.) of a molecule is calculated as follows: N. of electrons in bonding molecular orbitals. N. 2.B. y2p 2p *2s Energy 2s 2s 2s Fig.O.): Bond-order (B.A.O.PM5 29 . C-8\N-ENGCHE\ECH2-2. ⇒ no. B.25 Order of energy of molecular orbitals (M.

the electrons will first fill them singly and when both of them have been filled singly. • Rules for filling up of molecular orbitals with electrons: (i) The molecular orbitals are filled in the increasing order of their energies. Significance 0 molecule is unstable and does not exist. 2. In N2 molecule there will be all total 14 electrons of which 4 will be in the K shells which is denoted by KK. 2.. greater is the stability of the molecule.4 B. allowing s-p interaction.PM5 30 .e.O. –ve unstable and does not exist. In a similar fashion πy*2p and πz*2p antibonding degenerate molecular orbitals are filled just like degenerate bonding orbitals. (iii) According to Hund’s rule of maximum multiplicity. if there are two molecular orbitals having the same energy (i. • Energy level diagram for N2 molecule: The electronic configuration of N-atom is 1s2 2s2 2p3.30 ENGINEERING CHEMISTRY Table 2. pairing of electrons will occur.27 Molecular orbital diagram 2s and 2p atomic orbitals. 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.26 Molecular orbital diagram from Fig. C-8\N-ENGCHE\ECH2-2. *Greater the value of B. degenerate molecular orbitals). +ve *stable and exists. *2px *(sp) 2 * * 2pz 2pz 2pz 2pz 2py 2py 2py 2py 2px 2px 2px 2px (sp)  2 2px  *2s *(sp) 1 2s 2s 2s 2s 2s (sp) 2 Fig. (ii) The maximum number of electrons that can fill a molecular orbital is two.O. Thus mo- lecular orbital posses3ing the lowest energy will be filled first and that possessing the highest energy will be filled up in the last.

VALENCY AND CHEMICAL BONDING 31 So. diagram for N2. A.O.O. *2p y*2p z*2p A. 2.28 M. the electronic configuration of N2 molecule will be KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) [KK denotes (σ1s2) (σ*1s2)] M. O. • Energy level diagrams of other molecules: *2px (sp)2 *2py *2pz *2py *2pz .O. 2px 2py 2pz 2pz 2py 2px y2p z2p 2p B.O. = 8 – 2 = 3 E 2 N2 molecule has triple bond (N N) *2s 2s 2s 2s Fig.

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2px 2py 2pz 2pz 2py 2px 2px 2py 2pz 2pz 2py 2px 2py 2pz (sp)2 .

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2px 2py 2pz .

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*2s *(sp)1 .

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2s 2s 2s 2s .

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B2 (with s-p interaction). 2. 2s (sp)1 B B2 B B B2 B Fig.30 Molecular orbital diagram of of B2 (without s-p interaction). 2.29 Molecular orbital diagram Fig.PM5 31 . C-8\N-ENGCHE\ECH2-2.

32 ENGINEERING CHEMISTRY • Electronic configuration of B2 molecule: KK(σ2s2) (σ*2s2) (σ2p2) *2px *sp)2 .

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*2py *2pz *2py *2pz .

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2pz 2py 2px 2pz 2py 2px 2pz 2py 2px 2pz 2py 2px .

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2py 2pz (sp)2 .

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2px 2py 2pz .

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*2s *(sp)1 .

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2s 2s 2s 2s .

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2s (sp)1 O O2 O O O2 O Fig. • Electronic configuration of O2 molecule: KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) (π*y2p1) (πz*2p1) *2px *sp)2 . O2 (with s-p interaction).31 Molecular orbital diagram Fig. 2. 2.32 Molecular orbital diagram of of O2 (without s-p interaction).

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*2py *2pz *2py *2pz .

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2pz 2py 2px 2pz 2py 2px 2pz 2py 2px 2pz 2py 2px .

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2py 2pz (sp)2 .

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2px 2py 2pz .

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*2s *(sp)1 .

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2s 2s 2s 2s .

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2.34 Molecular orbital diagram of of NO (without s-p interaction). 2.PM5 32 . NO (with s-p interaction).33 Molecular orbital diagram Fig. C-8\N-ENGCHE\ECH2-2. 2s (sp)1 N NO O N NO O Fig.

O. Aromatic compounds a2e benzene or the compounds that resemble benzene in chemical behaviour. have no longer their significance. The word aliphatic came from ‘fatty’ and the word aromatic came from ‘fragrant’. (ii) Heat of hydrogenation of benzene is lower than that expected. C-8\N-ENGCHE\ECH2-2. They may be cyclic also but they resemble the open chain compounds in their properties.VALENCY AND CHEMICAL BONDING 33 [Energy level diagram for heteronuclear diatomic molecule] Table 2. Aliphatic compounds are mainly open chain compounds.5: Electron Distribution in Molecular Orbitals of some Simple Molecules shown in above M. The idea of resonance could explain all the three above anomalies and established the structure of benzene as put forward by Kekule. diagrams Molecule σ(sp)1 σ*(sp)1 π(2p) σ(sp)2 π*(2p) σ*(sp)2 unpaired electrons B2 ↑↓ ↑↓ ↑ ↓ 2 C2 ↑↓ ↑↓ ↑↓ ↑↓ 0 N2 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 0 O2 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ 2 CO ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 0 NO ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ 1 Aromatic Character Organic compounds have been classified into two broad subdivisions: (i) aliphatic and (ii) aromatic. (iii) The C—C bond lengths in benzene are equal and intermediate between a single and a double bond. Kekule established the structure of benzene as follows: or According to the Kekule’s structure there should be four isomeric di-substituted benzenes. .PM5 33 . 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 .

benzene possesses chemical properties that are not intermediate between compounds containing single or double bond.. • As a result of this resonance stabilisation. which is substitution in which the benzene ring system is retained.PM5 34 .36 Delocalised π clouds in benzene. we get a regular hexagon with a bond angle 120°. -clouds Benzene ring -clouds Fig. If we fit the six sp2-hybridized carbon atoms. it is an intermediate in length. which has 36 Kcal mole–1 extra stability.36). i. 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. • We see that addition will lead to a less stable product by destroying the resonance stabilized benzene ring system. • Benzene is more stable than expected. with overlapping. 2. And there still remains six electrons in the six p-orbitals with two equal lobes.6 Kcal mole–1 to be converted into cyclohexadiene. known as aromatic properties. Orbital Picture of Benzene Benzene is a flat molecule. Fig.39Å) between a single and a double bond. one lying above the plane and the other lying below the plane of paper.e. H  H  C C H C 120° C H 120° C C H 120° H (ii) The six p-orbitals are shown (i) Only -bonds are shown. The 36 Kcal of resonance energy is responsible for a new set of properties. which is a new type of bond. When overlapping is not restricted between two nuclei and it occurs between more than two nuclei. (2.35 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. Because the resonating Kekule’s structures have a resonance hybrid structure. the phenomenon is known as delocalisation. (1. hydrogenation of benzene requires 5. This delocalisation energy is frequently used instead of resonance energy. benzene follow an entirely different path. 2. The delocalisation in benzene molecule gives π-clouds above and below of the plane of the ring as shown in the Fig. As for example.34 ENGINEERING CHEMISTRY Highlights: • The idea of resonance explains six identical bonds in benzene. C-8\N-ENGCHE\ECH2-2. So. as its six carbon atoms are sp2 hybridised.

Benzenoid aromatic compounds: naphthalene antenacene (Anthracene) 10  electrons 14  electrons phenanthrene 14  electrons Non-benzenoid aromatic compounds: (+) : N N : H (–) pyridine pyrrole cyclopentadienyl tropylium ion 6  electrons 6  electrons anion 6  electrons 6  electrons SHORT QUESTIONS AND ANSWERS Q. etc. When a group of atoms of same and different elements stay together with a definite combination (of atoms). necessary and sufficient conditions for aromaticity are: (i) The molecule should be cyclic and flat.VALENCY AND CHEMICAL BONDING 35 So. What is a chemical bond? Ans. Q. 3.PM5 35 . What is a molecule? Ans. 2. What is the special feature of an electrovalent bond or ionic bond? Ans. Mention the types of bonds. anthracene (n = 3). possessing properties entirely different from constituent atoms is known as a molecule. tropylium ion. Q. (ii) The molecule should contain delocalised π-cloud. 3. Q. Ans. phenanthrene (n = 3) • Heterocyclic compounds: pyrrole (n = 2). Benzene molecule is flat. Most important types are: (i) Electrovalent. It refers to the bonding force that holds together the constituent atoms in a molecule. In that sense benzene is an ideal aromatic compound and forms the foundation stone of aromatic chemistry. Thus ions are formed. 1. (iii) The π-cloud must contain a total of (4n + 2) π electrons where n = 0. Here Hückle number corresponds to n = 1. Such a bond is formed by complete transfer of electrons from one atom to the other. 1. Benzene has six π-electrons (known as aromatic sextet). 4. C-8\N-ENGCHE\ECH2-2. • Non-benzenoid aromatic compounds: cyclopentadienyl anion. Highlights: • Benzenoid aromatic compounds: naphthalene (n = 2). 2. pyridine (n = 2) etc. Ionic bonding is the result of electrostatic forces of attraction between the positive metal ions and negative non-metal ions. This requirement is called (4n + 2) π rule or Hückle rule. Such electron transfer occurs from metals to nonmetals. (ii) Covalent and (iii) Co-ordinate bonds.

H  H—C—H × H H (ii) Double covalent bond. 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. Ans. 7) (2. Na. Q. 8. H ×. 8) ions (2. 2. (a) N.. . 8) (2. (iii) Triple covalent bond. 8. 8) Q. 7. (a) :Cl . + 4H ×  H ×..C:. (b) .  H . What is a covalent bond? Ans. 5. 2) (2. 8) – Ans.36 ENGINEERING CHEMISTRY Q. 8.C. 8. + 2H ×  H×. . 7) Calcium ion two fluoride (2. × × (b) 2. + . C ::C× H  × + 4H H—C = C—H . Give dot and cross diagrams for NaCl and CaF2 molecule formation.PM5 36 . double and triple covalent bonds by dot and cross diagrams. Give examples of single. H . 8.C.H  H—C C—H Q. ×.× .: C×. H. 6. 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. ××× × F ×× × F× Ca++ ×× Ca : + ××  + × ×– ×× F × . Attraction Proton in + + nucleus Shared electrons Fig.:N  N N Triple bond . (i) Single covalent bond. × × × ×F× ×× ×× Calcium atom (2. 8.C. + .×Cl ×× ×× – + × Cl ×× × ×  Na+ + ×× × × Sodium atom Chloride atom Sodium ion Chloride ion (2. 8.37 (a) Forces of attraction during H2 molecule formation. (b) 2.C . ×× . 1) (2.Cl : : : : : : : : :  : Cl : Cl :  Cl—Cl Single bond H . . : : : : : : : : (a) O: + :O  O ::O  O=O Double bond H H . How are the atoms held together in a covalent bond? Ans.N : : : : : :  N:. C-8\N-ENGCHE\ECH2-2.

What are polar and non-polar covalent bonds? Ans. Q.VALENCY AND CHEMICAL BONDING 37 Q.141 nm sum of covalent radii HCl Fig. Br—Br. 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. What is the special feature of a covalent bond? Ans.190 nm. H+δ → Cl–δ Q. etc. van der Waals radii determine the effective size of a molecule. between similar atoms during bond formation. one of the participating atoms in the bond formation donates both the electrons for bond formation. van der Waals radius is the effective radius of an atom when held in contact with another atom by weak intermolecular forces.e. When two atoms of the element (same or different) are joined by a single covalent bond. 10. (b) Molecules have a definite shape because covalent bonds have a definite length and direction. Fig. e. C-8\N-ENGCHE\ECH2-2.g..37 (b) Forces of attraction during H2 molecule formation. Q. Covalent radius of an atom is half of the distance between the nuclei of two like atoms bonded together by a single covalent bond.037 nm H2  0.. The covalent radius of an element is half the bond length.e. Covalent radius = 0.104 nm Cl2  0. between dissimilar atoms during bond formation viz. Mention special types of bonds. 2. (i) Metallic bond. 2. Covalent radius Covalent radius Bond length  0. O = O. Ans..37 (c) Covalent and van der Waals radii for bromine. H—H. 11. 9. A nonpolar bond is formed when sharing takes place between the atoms of same electronegativity i. 13. Q. A polar bond is formed when sharing takes place between the atoms of different electronegativities i. What is the special feature of a coordinate bond? Ans. 12. The coordinate bond is indicated by an arrow to express this unequal sharing. Cl—Cl. (ii) van der Waals bond.PM5 37 .. (iii) Hydrogen bond. (a) Covalent bond holds together the atoms of nonmetals in a molecule and giant structures. This type of bond is formed by unequal sharing of electron pair.114 nm van der Waals radius  0. What is covalent radius? Ans.

Ans. A single bond is always a σ-bond. Q. In H—O—H (g) molecule. What do you mean by dipole moment? Ans. In water molecule. Bond breaking is endothermic. Calculate the C–H bond energy in CH4 molecule. 15.PM5 38 . CH4 → CH3 + H° D ⇒ 102 Kcal mol–1 CH3 → CH2 + H° D ⇒ 105 Kcal mol–1 CH2 → CH + H° D ⇒ 108 Kcal mol–1 CH → C + H° D ⇒ 83 Kcal mol–1 Total D ⇒ 398 Kcal mol–1 C-8\N-ENGCHE\ECH2-2. sp2-s. sp3-p. sp-s. Q. A double bond contains one σ and one π bond and a triple bond contains one σ and two π bonds. 19. Energy is needed to break covalent bonds. π-bond is formed by sideway overlapping of mainly p-orbitals of different atoms. So the bond dissociation energies of two or more bonds between similar atoms are not the same. Mathematically dipole moment is expressed as: µ=e×d where. double and triple bonds? Ans. What is a sigma bond? Ans. p-p or sp orbitals and also sp3-s. HCl (g) ⇒ H(g) + Cl(g) ∆H ⇒ + 432 kJ mol–1. d = distance in cm. µ = dipole moment. 14. Q. Q. Q. What do you mean by bond energy? Ans. 18. What is a π-bond? Ans. so enthalpy change is always positive. This type of bond is formed by axial overlapping of s-s. 16. of different atoms whereby maximum overlapping of orbitals is possible. The dipole moment in a molecule develops due to the separation of positive and negative charges by a distance. the energy needed to break the first O—H bond is 498 kJ mol–1. Bond dissociation energy is the energy (or enthalpy) for breaking one mole of a covalent bond in a gaseous molecule. Q. as the centre of action of positive charge due to nuclei and centre of action of negative charge due to electrons do not coincide. the energy needed to break the second O—H bond is 428 kJ mol –1. 17. 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. are the two bond dissociation energies same? Ans. What are special features of single. 20. e = magnitude of charge separated in esu.38 ENGINEERING CHEMISTRY H LMH OP +  MM  H  N : + H+ ⇒ H  N → H PP  MM  PP H HN Q Q. sp2-p etc.

The bigger the difference in the electronegativity of the elements forming a bond. 2.PM5 39 . + – H Cl polar bond. The stronger the pulling power of an atom. Nb ⇒ number of bonding electrons. in turn. Bonding M. Bond order zero and negative indicates that molecule does not form or exist. stabler is the molecule. This happens in compounds like NaCl. 25.O.. MgO.e.O. 22. But in this case.120nm Q.) are obtained by the overlapping of atomic orbitals of the atoms linked by a covalent bond.. 398 E(C—H) ⇒ = 99. M. 24. Q.) is given by the expression.21 and 2. Ans.21 and 2. Bond order (B. In a simplified form.157nm 0. Give the concept for antibonding molecular orbitals. it may be stated that molecular orbitals (M.O. Na ⇒ number of antibonding electrons.O. Molecular orbitals are the solutions to the Schrödinger wave equation like atomic orbitals. 23. When does a bonding in a covalent compound become fully ionic? Ans. 26..23). Q. Give the conception of a bonding molecular orbital. 2. Q. B B B 0. C–C C=C C≡C . Nb − N a B. are shorter than single bonds.VALENCY AND CHEMICAL BONDING 39 C—H bond energy in CH4 is mean value of D values i. 21. Ans.) overlap along the internuclear axis (see Figs.O. Q.O. 4 Q.e. Higher the bond order. What do you mean by bond length? Ans.5 Kcal mole–1. Bond length is the distance between the nuclei of atoms bonded by one or more covalent bonds. the more polar the bond. by the overlapping of + – regions of the atomic orbitals (see Figs. Ans.134nm 0. What do you mean by electronegativity? Ans. CaF2 etc. (φB) is obtained when ++ regions of both the atomic orbitals (A. φA results from subtraction of the two atomic orbitals (φA = ψA – ψB) i. is produced by addition of two atomic orbitals (φB = ψA + ψB). For the same two atoms triple bonds are shorter than double bonds which. Interpret the idea of bond order.e. The bonding molecular orbital is a region in space where the probability of finding the bonding electrons is maximum. 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. Antibonding orbitals (φA) are also solutions to the Schrödinger wave equation like the bonding molecular orbitals. = 2 where. 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.23) i. C-8\N-ENGCHE\ECH2-2. the higher its electronegativity.

O2 molecule is paramagnetic. N − Na 2−0 Ans.. The molecule does not exist. Explain. 2−1 1 (iii) B. so it is less acidic. 28. = =0 2 Here the number of electrons in σ-orbital = the number of electrons in σ*-orbital.O. (ii) sp2. (iv) He2 and interpret the result. Ans. the number of electrons in s-orbital is greater than the number of electrons in s*-orbital. 29. What do you mean by hybrid orbitals? Ans. Q. 2−2 (iv) B. = = 2 2 He2+ also has transient existence. (vi) d2sp3. Q. 1− 0 1 (ii) B. Q.PM5 40 .O. 27. (i) sp3. (ii) H2+.O. +δ +δ +δ +δ Ans. O2 molecule contains double bond (O = O). (v) sp3d.40 ENGINEERING CHEMISTRY Q. That is why.32).31 and 2. (iii) He2+.. H− F −δ Due to hydrogen bonding. ⇒ ⇒ =2 2 2 So. 30. Here. one is σ and the other is π-bond. H− F −δ . 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) Nb − N a 8−4 B. Hydrogen bond in HF inhibits release of H+ partially in aqueous solution. HCl is gas and HF is less acidic than HCl. H− F − δ . According to Hund’s rule two unpaired electrons fill the degenerate (orbitals of same energy) πy*2p and πz*2p orbitals (see Figs. C-8\N-ENGCHE\ECH2-2.. (i) B. 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. What is hybridisation of atomic orbitals? Ans.. The intermixing the atomic orbitals of slightly different energies so as to redistri- bute their energies and to give a new set of orbitals (known as hybrid orbitals) of equivalent energies and shape is known as hybridisation.O. Mention the types of hybridisation.. = = 2 2 H2+ has a transient existence. So He is monoatomic. H− F −δ . (iii) sp. (iv) dsp2. Ans. 31. 32.. 2. Calculate the bond orders of: (i) H2O. = b = =1 2 2 H-atoms are held together by one covalent bond. O2 molecule is paramagnetic.O. Q. Q. Here the number of bonding electrons exceeds the number of electrons in antibonding orbital. 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. Explain why HF is liquid.

But there is no H-bonding in dimethyl ether molecule as H here is not attached to O-atom. when ice melts its volume Fig. Due to tetrahedral structure. Dimethyl ether There is H-bonding in ethyl alcohol and due to molecular association H is attached to O-atom in every molecule of ethyl alcohol. 6. bond angle and shape of the following molecules: (i) BeF2. Explain sp. Ans. 8. 34. When ice melts. (a) Explain the structure of benzene. So. 7. O Ans. (v) NH3. So O H O a crystal of ice is not a single molecule but an associated molecule. there is some void H O H space in ice. reduces and density increases. 31 above. (ii) BF3. (iv) CH ≡ CH. Q. Explain the bond order of N2 molecule. Q. By X-ray crystallography. a molecule of water is H surrounded by four water molecules and every molecule of H H water form hydrogen bonds giving a tetrahedral structure. sp2 and sp3 hybridisations with examples. Due to loss of this void space. this tetrahedral structure is H destroyed.38 H-bonding in ice. C2H6O. every oxygen atom is connected Covalent bond to two hydrogen atoms as covalent bonds. H H Ans. 3. there is no molecular association due to H-bonding in dimethyl ether. 35. 33. Give the state of hybridisation. 2. Discuss hydrogen bonding and explain why density of ice is less than that of water. C-8\N-ENGCHE\ECH2-2. And each oxygen atom contains two lone pairs. ethyl alcohol is less volatile than dimethyl ether though both have the same mol. it has been Hydrogen O bond established that in a crystal of ice. H——O– – –H——O– – –H——O H—C—O—C—H C 2H 5 C 2H 5 C 2H 5 H H H-bonding in ethyl alcohol. H——O– – –H——O– – –H——O– – –H——O H H H H The reason is same as in Q no. 2. EXERCISES 1. Write a short note on ionic bonding. Write a note on co-ordinate bond.PM5 41 . (b) Give a concise account of delocalisation of benzene. Explain H2O is a liquid and H2S is a gas.VALENCY AND CHEMICAL BONDING 41 Q. The density of water is greater than that of ice. (vi) H2O. (iii) CH2 = CH2. 5. so it is more volatile than ethyl alcohol. formula. Explain. And the water molecules are hydrogen bonded in a chain. In H2O molecule. These electrons can form H hydrogen bonds. 4. What is hybridisation? Give different types of hybridisations with examples. H H Explain.

Discuss Born Haber cycle with an example. C-8\N-ENGCHE\ECH2-2. (b) Give the characteristics of covalent bond. 15. 16. 12. Explain inter and intramolecular hydrogen bonding with examples. 10. Give its name also. What is dipole moment? How is dipole moment of a molecule calculated? 13. What is VSEPR theory of molecular model? Explain with suitable examples. combine to form a compound. 14.PM5 42 . 11. (e) Delocalization. (c) Explain sp3- hybridisation. Two elements having the atomic numbers 11 and 17. respectively. Give the molecular orbital diagrams of H2 and O2 molecules. Write short notes on: (a) Intermolecular forces. (b) Molecular orbital theory. (f) Aromaticity. (c) Resonance.42 ENGINEERING CHEMISTRY 9. (a) Explain hydrogen bonding. State the nature and formula of the compound so formed. (d) Hund’s rule.

3
Nuclear Chemistry

Nuclear Chemistry is the branch of chemistry that deals with the changes in the nuclei. It is
quite obvious that the conventional energy sources, such as coal, petroleum will be exhausted
in near future. So scientists are searching for non-conventional energy sources such as–solar
energy, nuclear energy etc. The idea of exploiting nuclear energy came after the discovery of
radioactivity. So we are to discuss, in brief, the idea of radioactivity before going to discuss the
source of nuclear energy which is the main feature of nuclear chemistry.

RADIOACTIVITY
Becquerel in 1896 observed that uranium or its compounds emit a kind of rays spontaneously.
These rays can affect photographic plate. He named this phenomenon of emission of spontaneous
radiation by uranium as radioactivity. The atoms of some of the elements were found to exhibit
radioactivity, such as—radium, thorium, polonium etc. As compounds of those elements exhibit
radioactivity, so it can be said that radioactivity is a nuclear phenomenon. Radioactive elements
emit the radiation and create new elements. Radioactivity is an irreversible process and emits
more heat than that of any of the chemical processes (109 cal mol–1). The rays emitted are
4
classified as alpha [ 2 He++], beta (uninegative charge), and gamma (neutral). A comparative
study of the rays emitted during radioactive disintegration is displayed in the following table.

Table 3.1: Comparison among α, β, and γ Rays

Property α-Rays β-Rays γ-Rays

(i) Nature (i) Streams of positively (i) Streams of fast (i) It is similar to X-
charged particles moving negatively rays and neutral
which are merely charged particles in nature. They
nuclei of He atoms, which have the same have very small
each consisting of 2 e/m value as the wavelengths of
protons and 2 cathode rays. the order of 10–10
neutrons. to 10–13 m.

(ii) Representa- (ii) [2He4]+2 or α (ii) –1e° or –1 β° or β. (ii) γ
tion

(Contd.)

43

44 ENGINEERING CHEMISTRY

(iii) Mass (iii) 4 a.m.u. 1 (iii) No mass (0)
(iii) of hydrogen
1836
atoms or 0.000548
a.m.u.
(iv) Charge (iv) Possess positive (iv) Possess negative (iv) No charge (0)
charge of 2 units charge of 1 unit
= 9.6 × 10–10 e.s.u. or = 4.8 × 10–10 e.s.u. or
3.2 × 10–19 coulomb. 1.6 × 10–19 coulomb.
(v) Velocity (v) Nearly 1/10 the speed (v) 2.36 × 108 to 2.83 × (v) Nearly same as
of light or 20,000 to 108 m/sec. light 3 × 108 m/sec.
30,000 km per sec.
(vi) Penetrating (vi) Low (vi) Medium (vi) Maximum
power

It has been observed that heavier elements in which neutron-proton ratio (N/p) exceed
1.5 show radioactivity. These nuclei are unstable and emit spontaneously α, β, or γ-rays to give
daughter elements.
Nuclear Stability
1. Nuclei with 84 or more protons are radioactive.
2. Nuclei containing 2, 8, 20, 50, 82 and 126 protons or neutrons are more stable than
other nuclei containing different number of protons and neutrons. These numbers
are magic numbers.
3. Nuclei with even numbers of protons and neutrons are more stable than that with
odd numbers.
240

200

160
Mass number, A

120

80

40

0
10 30 50 70 90
Atomic number, Z

Fig. 3.1

C-8\N-ENGCHE\ECH3-1.PM5 44

NUCLEAR CHEMISTRY 45

The graph (Fig. 3.1) is a plot of proton number (Z) vs mass number (A). The graph is
more or less linear. When the value of Z is less, then the ratio A/Z for a nucleus is 2 i.e., light
elements possess equal number of protons and neutrons and the nucleus is stable; 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. As the
difference of Z and A increases the nucleus becomes totally unstable. So it can be said that
radioactivity is a phenomenon to stabilize the nucleus by decreasing the ratio A/Z of the nucleus.
Radioactive Decay
The radioactive decay follows an exponential law. At any instant of time, the rate of
disintegration is proportional to the number of atoms (N) present, i.e.,
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.
The ‘negative sign’ indicates that with passage of time ‘t’ the number of atoms decreases.
dN
So, = − λdt
N
Integrating we have, loge N = – λt + C [C = integration constant]
If ‘N0’ be the number of atoms present initially, i.e., when t = 0
then loge N0 = C
∴ loge N = – λt + loge N0
N
or loge = – λt
N0

∴ N = N0.e–λt

When M0 = original mass and M = mass at time t, the equation is

M = M0.e–λt
Hence, the decay curve is exponential in nature (Fig. 3.2).
Fraction present

t=T

t = 2T
t = 3T

Time t

Fig. 3.2 Decay curve of radioactive substances.

C-8\N-ENGCHE\ECH3-1.PM5 45

46 ENGINEERING CHEMISTRY

If T is the half-life of the radioactive element, then we can write,
N 1
= = e −λ T
N0 2
log e 2 0.693
∴ =
T= .
λ λ
The above equation is a relation between half life (T) of a radioactive element and its
disintegration constant (λ).
Half-Life
Half-life of a radioactive element is the time required for half of the atoms to decay
away. Half-lives for radioactive isotopes can be as short as a fraction of a second or as long as
millions of years.
Units of Radioactivity
The unit of radioactivity is ‘curie’. The curie is defined as that quantity of any radioactive
substance which gives 3.7 × 1010 disintegrations per second. The curie is a very large unit.
Hence for all practical purposes millicurie [1 mCi = 10–3 Ci] and the microcurie [1 µCi = 10–6 Ci]
are used.
Radioactive Disintegration Series
Number of naturally occurring radio isotopes is about forty. Naturally occurring radio-
active disintegration series are shown below. The series are 4n or Thorium series; 4n + 2 or
Uranium series and 4n + 3 or Actinium series. The term 4n means mass number is divisible by
4; whereas 4n + 2 and 4n + 3 means mass number when divided by 4 gives a remainder of 2 and
3, respectively.
232
In the 4n series starting element is 90 Th and through a chain of successive
208
disintegration it produces ultimately 82 Pb .

238 206
Starting element of (4n + 2) series is 92 U and end product is 82 Pb
.

235 207
For (4n + 3) series starting element is 92 U and end product is 82 Pb.

An artificially made disintegration series is Neptunium series (4n +1). It starts
237 200
with 93 Np and ends at 82 Bi .

Details of disintegration chart of (4n + 2) series is given below:
238 α 234 β 234 β 234 α 230 α
92 U → 90Th → 91 Pa → 92 U → 90Th →
226 α 222 α 218 α 214 β 214 β
88 Ra → 86 Rn → 84 P o → 82 Pb → 83 Bi →
214 α 210 β 210 β 210 α 206
84 Po → 82 Pb → 83 Bi → 84 Po → 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, in the periodic table i.e., atomic number of the daughter element
decreases by two units. When a β-particle is emitted the daughter element formed shifts to one
column forward (right side) in the periodic table i.e., atomic number of daughter element is
increased by one unit.

C-8\N-ENGCHE\ECH3-1.PM5 46

NUCLEAR CHEMISTRY 47

Artificial Radioactivity
If an atom of a non-radioactive element is bombarded by a powerful particle, it is converted
to a radioactive atom, e.g. if we bombard 27
13 Al
with an alpha (α) particle, we get radioactive
phosphorus which is ultimately converted to silicon.
27
13 Al + 42 He → 30
15 P + 01n
30 30
15 P → 19 Si + 01e .
This phenomenon is known as Artificial Radioactivity.
Atomic Mass Unit
Masses of atoms are usually expressed in atomic mass units (a.m.u.).
1
1 a.m.u. = × 126 C
12
1 12 1
So, 1 a.m.u. = × g= g
12 N N
where N (Avogadro number) = 6.023 × 1023
1
1 a.m.u. = 23
= 1.66 × 10 −24 g.
6.023 × 10
Mass–Energy Equivalence
In 1905, Einstein established from theoretical standpoint that mass and energy are
mutually convertible. The famous equation in this regard is
E = mc2
where E = energy ; c = velocity of light.
The year 2005 has been declared as year of physics to observe the centenary of this
famous equation.

Highlight:
E = mc2
= 1 × (3 × 1010)2 g cm2 sec–2
= 9 × 1020 g cm2 sec–2
= 9 × 1020 ergs
= 9 × 1013 joules.
So, 1 g of matter is equivalent to 9 × 1013 J of energy.

Mass-Energy conversion factor
We know that, 1 eV = 1.6 × 10–12 ergs.
So, 1 MeV = 1.6 × 10–6 ergs
and 1 a.m.u. = 1.66 × 10–24 g.
1.6 × 9 × 10 20
∴ 1 a.m.u. = ≈ 931 MeV.
1.6 × 10 −6

Nuclear Fission
In 1939, German scientists Hahn and Strasman bombarded uranium atom with neutrons and
obtained two elements with atomic numbers 56 and 36.

C-8\N-ENGCHE\ECH3-1.PM5 47

48 ENGINEERING CHEMISTRY

235
+ 01n → 266
92 U
141 92 1
92 U → 56 Ba + 36 Kr + 3 0 n.
This phenomenon of splitting a nucleus into two approximately equal fragments is called
nuclear fission or simply fission. 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.
This process of repeated fission is known as chain reaction (Fig. 3.3) and as a result it can
generate a huge amount of energy, 1 g of U-235 will generate 2 × 107 kcal, and this amount of
energy will be generated within 10–6 second. So, the generation of huge amount of energy
leads to an explosion with a temperature of one crore degree. This nuclear fission reaction is
the principle of an atom bomb.
1
0n

(Secondary neutrons)
Neutrons
Fission Fragments
235
92U

Fig. 3.3 Chain reaction as a result of bombardment of 92U235 with one
neutron and perfission three secondary neutrons are released.
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. A small fraction of mass is lost and is
converted to energy according to the equation: E = mc2.
For the reaction,
235 1 141 92 1
92 U + 0 n → 56 Ba + 36 Kr + 3 0 n.
Initial masses Final masses
235 ⇒ 235.0439 a.m.u. 141 ⇒ 140.9139 a.m.u.
92 U 56 Ba
1 92
0n
⇒ 1.0087 a.m.u. 36 Kr
⇒ 91.8973 a.m.u.
236.0526 a.m.u. 301 n ⇒ 3.0261 a.m.u.
235.8373 a.m.u.

C-8\N-ENGCHE\ECH3-1.PM5 48

NUCLEAR CHEMISTRY 49

So, the mass lost is 0.2153 a.m.u., which is equivalent to an energy of 0.2153 × 931
≈ 200 MeV.

Highlight:
It can be shown that when 1 kg of uranium is completely fissioned, the energy released
would be 8.2 × 1013 J, which is sufficient to supply energy at the rate of 2.2 megawatt
continuously for one year.

To utilise the energy released during the fission, we are to control the chain reaction to
get the heat energy according to necessity. Now-a-days, in an atomic reactor, the motion of
neutrons are retarded by graphite or heavy water to control the chain reaction. So, 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.
Atomic Fusion
At a very high temperature, two nuclei combine to give a comparatively heavy nucleus,
i.e., two nuclei combine to give a new atom. This phenomenon is known as atomic fusion. And
during this fusion reaction some mass is destroyed, that means such a fusion process would
also lead to liberation of huge amount of energy which causes explosion.
2
1H + 21 H → 42 He + Energy
2 × 2.0162 → 4.00389
∴ ∆m = 0.02863 a.m.u.
which is equivalent to 0.02863 × 931 MeV
= 26.6545 MeV. (Energy released due to above fusion)
The difficulty is to attain the high temperature for such fusion process. But it is believed
that such condition is attained for preparing thermonuclear bombs such as hydrogen bomb.
The transformations for fusion reactions are:
(i) 31 H + 21 H → 42 He + 10 n + 17 MeV
(ii) 31 H + 11H → 42 He + 20 MeV etc.
Mass Defect and Binding Energy
After the discovery of isotopes, Aston examined the atomic weights of various elements
and concluded that the atomic weights of all the elements would be a whole number. But due
to the presence of isotopes in unequal amounts, the atomic weights become fractions. Besides
that, the atomic weights of the different elements depend upon another factor: in a.m.u. the
atomic weights are calculated from number of protons, electrons and neutrons. The calculated
mass (M) and actual weight (A) is determined considering the contribution for the presence of
isotopes. The difference of these two quantities is called mass defect (∆) or ∆m
∴ ∆ = M – A.
For a 73 Li atom, the atomic weight will be
3 × 0.0005486 + 3 × 1.00758 + 4 × 1.00893
= 7.0601058 a.m.u.
But actual atomic weight of 73Li is 7.01818 a.m.u. (in 16O scale)
So, mass defect (∆) = 7.0601058 – 7.01818
= 0.0419258 a.m.u.

C-8\N-ENGCHE\ECH3-1.PM5 49

50 ENGINEERING CHEMISTRY

When protons and neutrons unite a small fraction of mass is converted to nuclear binding
energy, and this is the reason for mass defect.
So, the nuclear binding energy will be
0.0419258 × 931 = 39.03 MeV.
When mass defect is divided by mass number, a fraction is obtained which is known as
packing fraction (f)
m−A 0.0419258
f= × 10 4 = × 10 4
A 4
= 104.81
Therefore, packing fraction is average mass defect for any particle. The value of packing
fraction is very small, so it has been expressed by multiplying 104. A small value of packing
fraction indicates greater stability of the nucleus, a higher value indicates looseness of packing
of protons and neutrons in the nucleus and as such lower stability of the atom (Fig. 3.4).

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. 3.4 The graph is a plot of binding energy/nucleon vs. mass number (A).

NUCLEAR REACTORS
“A nuclear reactor is an apparatus in which nuclear fission is produced in the form
of a controlled self sustaining chain reaction.” In other words it is a device where controlled
nuclear fission of 235U, 233U or 239Pu and also chain reaction takes place and produces, heat,
neutrons and radio-isotopes. Nuclear reactors may be looked upon as a nuclear furnace where
fuel is 235U, 233U etc.
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, they are rapidly
slowed down and brought to rest due to collison with other atom of the metal. In doing so
energy is converted to heat.
Nuclear reactors are of various types depending on their neutron spectrum, construction,
composition and the purpose for which they are used. The reactors are differentiated by the
following features.
• Neutron energies:
(a) High energy—as in fast reactors
(b) Intermediate energy
(c) Low energy—as in thermal reactors.

C-8\N-ENGCHE\ECH3-1.PM5 50

NUCLEAR CHEMISTRY 51

• Types of fuel:
(a) Natural uranium (238U = 99.28%; 235U = 0.714%)
(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.
(b) Heterogeneous–where moderator remains separated from the fuel.
• Moderators:
(a) Heavy water (D2O) (b) Ordinary water (H2O)
(c) Graphite (d) Beryllium
(e) Beryllium oxide.
• Types of Coolants:
(a) Gaseous (air, CO2) (b) Water or organic liquids
(c) Liquid metals.
• Purposes:
(a) For research (b) For production of 239Pu
(c) For power generation.
Depending on the above factors, the nuclear reactors are:
(i) Thermal, natural uranium, graphite moderated, Heterogeneous, air cooled, research
reactor.
(ii) Fast, enriched uranium, heterogeneous, liquid metal cooled, power breeder reactor.
A nuclear reactor is constructed of the following components:
1. Reactor Core: Reactor cores are generally a right circular cylinder with dia. 0.5 m to
15 m. The cylinder is enclosed in a pressure vessel. The cylinder with the pressure vessel is
considered as reactor core. The reactor core consists of an assembly of fuel elements, controlled
rods, coolant and moderator. In the reactor core, the fission chain reaction takes place and the
energy is liberated in the form of heat.
The fuel elements are either in the form of plates or rods of uranium metals. They are
usually clad in a thin sheath of Zr or Al stainless steel. This provides retention of radioactivity
and corrosion resistance. For the passage of the coolants, enough space is provided between
the individual rods (Fig. 3.5).
Reactor
Control rods

Steam to
turbine

Coolant
Moderator

Water

Core Shielding
Pressure
uranium fuel vessel
Fig. 3.5 Nuclear reactor.

C-8\N-ENGCHE\ECH3-1.PM5 51

52 ENGINEERING CHEMISTRY

2. Reflector: A reflector is usually made of the same material as the moderator (not
shown in the figure). It is used to reflect back some of the leaking neutrons from the reactor
core.
3. 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.
(ii) To keep power production steady.
(iii) To shut down the reactor normally or under emergency condition.
The control system also plays an important role to control the chain reaction, so that
violent and damaging consequences may be avoided. 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. The advantage is, they do not become radioactive
due to neutron capture. Three rods are sufficient for any amount of excess neutrons. To shut
down a reactor the control rods are inserted to a considerable depth so that the chain reaction
ceases. To start up the reactor it is necessary to carefully withdraw the control rods and adjust
them. Movement of control rods can be made mannual or automatic.
4. Moderator: Function of moderator is to slow down the fast moving fission neutrons.
A moderator should have the following characteristics:
(a) low mass number elements to have a high flowing capacity.
(b) a low cross-section is used for better neutron absorption.
The excellent moderator is D2O because it slows down the neutrons efficiently and it
can be used as coolants as well. The following are the drawbacks of D2O:
(i) Low boiling point,
(ii) necessitating the use of pressure
(iii) It is very expensive but its advantage outweighs its high cost.
Beryllium (Be) can withstand high temperature, being very expensive it is used in special
cases. Reactor grade graphite is not good as a moderator but it is cheaper than Be.
5. Coolants: Function of the coolants is to remove the heat produced in the reactors.

Categories

H2O, D2O Liquid metals Organic liquids Gases
(Na, K) (polyphenyles) (CO2)

Highlights:
• D2O, H2O are good coolants. They can act also as the moderator. Their boiling points
are low. They need pressurisation. Water is corrosive at high temperature.
• Molten metallic Na or K are excellent coolants. However, Na is highly reactive to O2
and H2 and becomes radioactive by capturing the neutron. So it needs shielding.
• Use of polyphenyls are advantageous for—(i) they do not require pressurisation,
(ii) they do not become radioactive by neutron capturing, (iii) they are not corrosive
and (iv) stable at high temperature. The only disadvantage is they are inferior to H2O
or liquid metals as coolants.
• Air cooling is suitable for low power reactors.

C-8\N-ENGCHE\ECH3-1.PM5 52

NUCLEAR CHEMISTRY 53

6. Shielding: It is an important consideration for a reactor installation. 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, two shields are used.
(a) Thermal Shield: It is kept very close to the reactor core, it is a thick steel or iron
covering.
(b) Biological Shield: It is a layer of concrete of few decimeter thick surrounding the
thermal shield. It is used to absorb γ-rays and the neutrons leaking through the
inner thermal shield.
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”. In general type of
reactors the conversion factor is 0.9. A reactor with the conversion factor above unity is known
as breeder reactor. In the breeder reactor, 235U is fissioned by the slow moving neutrons. In
this case, per nuclear fission, 2.5 neutrons remain in the reactor and 0.5 neutrons escape out of
the reactor. Among which one neutron is used to maintain the steady chain reaction. The
residual 1.5 neutrons is used up as follows:
(i) 238U captures 0.9 neutrons
(ii) Moderator, coolant absorbs 0.6 neutrons.
235 U produces 239Pu by capturing those 0.9 neutrons and it is noteworthy to mention
that 239Pu is a manmade nuclear fuel.
Uses of Radioisotopes
Radioisotopes provide a powerful tool for the solutions of enormous problem in chemistry,
industry, physics, biology and physiology. The application of isotopes depends on the fact that
the chemical properties of the isotope of a given element are essentially identical. The detection
of a radioisotope is made on the basis of its radioactivity and a stable isotope by means of a
mass spectrometer. 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. The element which is ‘labelled’ or ‘tagged’ is called a
‘tracer element’. A few example of the use of radioactive tracers are given below:
(a) Photosynthesis in plants: When plants come in contact with sunlight, they can
take up CO2 and water, which are then converted into sugar and starches. At the same time,
O2 is liberated. The O2 produced may come from CO2 or H2O molecules or from both. By
performing experiments with labelled oxygen in CO2 or H2O, it was found that O2 came only
from water.
6CO2* + 10H2O → C6H12O6* + 6H2O* + 6O2
6CO2 + 12H2O* → C6H12O6 + 6H2O + 6O2*
(b) Agriculture: During growth, plant absorbs elemental P both from the soil and from
the added fertilizer. How much of the P is consumed from the fertilizer by the plant can only be
determined by tracer technique.
(c) Medicine and diagnosis: (i) Radioisotopes are used to locate the presence of tumours,
particularly brain tumours.
(ii) 59Fe is used to diagnose the blood disorder.
(iii) 131I is used to diagnose malfunctioning of liver, kidney, etc.
(iv) 60Co (γ-radiations) is used in cancer therapy.

C-8\N-ENGCHE\ECH3-1.PM5 53

54 ENGINEERING CHEMISTRY

(d) Industry: (i) In steel industry to test whether P is removed completely from cast
iron radiophosphorus is used. The disappearance of radioactivity indicates that all the P have
been removed. (ii)The wear and tear of engines can be determined by making the metal of the
piston rings radioactive. The appearance of radioactivity in engine oil or in lubricants shows
that the process of wear and tear of the pistons has started.
(e) Research: Reaction mechanism can be ascertained with radioactive tracer technique.
In ester hydrolysis, the acyl oxygen cleavage or alkyl oxygen cleavage can be determined as
follows:

O O

CH3

C.

O—C2H5 + H2O* → CH3— C —OH + C2H5*OH (alkyl oxygen cleavage) O O  CH3.

C.

A similar relation holds good for U235. The radioactive decay equation is. In mitosis.OC2H5 + H2O* → CH3— C —*OH + C2H5OH (acyl oxygen cleavage) (f ) Biological research: Isotopic tracers have been widely used in cellular biology. so we have U235 = (U235 + Pb207) e − λ ′ t where λ′ = decay constant for U235. U238 = (U238 + Pb206)e–λt where.PM5 54 . amount of Pb206 present in the mineral = N0 – N So. Since all U238 has been decayed to Pb206. (g) Isotopic dating in Geology: The age of a rock or mineral containing uranium can be determined by its radioactive decay. t = lapse of time (age of rock). N = N0e–λt where. we can write. λ and λ′ can be determined from the half-lives of two isotopes of U. behaviour of cells has been studied with the help of labelled DNA molecules. N0 = amount of U238 in the rock when it was formed. U238 = amount of U238 in the rock Pb206 = amount of Pb206 in the rock λ = decay constant t = age of the rock. Pb 206 U 238 (e λt − 1) = Pb 207 U 235 (eλ ′ t − 1) The present ratio of U238 to U235 is 139. From the above two equations. N = amount of U238 still left. C-8\N-ENGCHE\ECH3-1. we have.

Pb206 represent their respective masses. In radio-carbon dating ratio C14 to C12 is assumed constant in the plant. the age of a rock can be determined as follows.693 GH log 1 + 238 U JK (h) Radio-carbon dating technique: The age of a piece of wood or animal fossil can be determined by radio-carbon dating technique. C 12 C-8\N-ENGCHE\ECH3-1. λ= 2. Alternatively.693 a− x C 14 Here. 2.303 t1/2 F Pb 206 I.303 a λ= log t a− x a = amount of U238 originally present in the rock at the time it was formed.PM5 55 . a = ratio in the fresh plant C 12 C 14 (a – x) = ratio in dead plant. 0. U238 present in the rock at time t is: a = U238 + Pb206 and (a – x) = U238 where. the age of the rock can be calculated. C14 is formed in the atmosphere as follows : 14 + 0n1 (from cosmic rays) → 6C14 + 1H1 7N This is present in atmosphere as C14O2 with C12O2. no more CO2 is assimilated so ratio C14 to C12 in the plant changes.303 U 238 + Pb 206 So. 2.730 yrs) age of the wood (t) can be calculated. The radioactive decay follows the first order rate law. After the death of the plant. λ = decay constant of U238. provided the ratio Pb206 to Pb207 is determined with the help of a mass spectrometer. U238. as the plant assimilates CO2 with C14O2 during photosynthesis. 2. λ= log t U 238 F Pb 206 I. (a – x) = amount of U238 still left after the lapse of time (t). the decay constant of U238 is known from the relation 0.303 t GH log 1 + 238 U JK Since. 2. values of Pb206 and U238 can be determined experimentally.693 λ= t1/ 2 Thus. by measuring C14 to C12 ratio and t1/2 of C14 (5.303 t1/ 2 a t= log . age of the rock (t) can be calculated. t= 0.NUCLEAR CHEMISTRY 55 Hence.

478 × 106 years.00387 a.66 × 10–24 g = 6. N0 λ N = N0 e = N0e–1 = e N0 = 0. λ 1 − λ. Sol.37 N0. M 1 × 10 −6 0.56 ENGINEERING CHEMISTRY So.464 × 10–24 g = 14. in all directions. We have..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.8672 × 10–15 sec–1. Sol.693 0. Example 3. (t1/2 of radium is 1620 years).368 N0 ≈ 0. = 4.D.u. Total time = (8378 – 1898) = 6480 yrs.D. C-8\N-ENGCHE\ECH3-1. Assuming that it were to remain undisturbed since 1898 A. 6480 No.8672 × 10–21 g dM As − = λM dt − d M/ dt − 14. λ 14.8672 × 10 −15 = 1. then the above equation will take the form.867 × 10 −21 / 1 So λ= = = 14. Example 2.m. Estimate half-life of Pu239 from this data. A radioactive source contains one microgram (µg) of Pu239.37 N0. Mass of one α-particle = 4. calculate how much of Madam Curie’s 200 mg of radium would be left in the year 8378 A. N = N0e–λt 1 when t = . age of the wood (t) can be calculated. Sol.646 × 10–24 g Mass of 2300 α-particles = 2300 × 6. This source is estimated to emit 2300 α-particles/sec.693 Half-life (t1/2) of Pu239 = = sec.00387 × 1. by measuring the ratio C14 to C12 in the fresh and dead plants. Example 1. Prove that N ≈ 0.5 mg.PM5 56 . 2. of half-lives (t1/2) = =4 1620 F 1I Mass of radium left = M G J n H 2K0 F 1I = 200 G J 4 H 2K = 12.

0 mg of 92U234.189 M M0 or. N = N0e–λt N0 or.000 yrs.88 × 10–14 × 62000 × 365 × 24 × 3600 = 0.28 × 10–4 year–1. t1/2 1620 Let. The half-life period of radium is 1620 years.88 × 10–14 × 234 = 7. The mass of radium would be left behind at the end of time t = 1 – 0. (a) We know. 1.01 = 0. (a) Let. M = M0e–λt 0. 0.69 × 105 disintegrations/sec.364 × 10 −3 × 6. as follows: λt = 8. M= 1. e0. λ = 8. We have.PM5 57 .693 0..173 ∴ M = M0e0.693 0.28 × 10–4 × t × 0.000 years ? (b) What will be its activity at the end of that time? (t1/2 = 2. M0 = Initial mass of 92U234 M = Mass at the end of 62. Now.173 = 1.NUCLEAR CHEMISTRY 57 Example 4.189 (b) Activity of 234 92U is: 3. N0 1 (b) Here = = 100 N 0.4343 99 ∴ t = 23.48 × 105 yrs. Example 5.01 C-8\N-ENGCHE\ECH3-1. Sol.173 t1/2 2.364 mg.189 234 4 ∴ Mass of 92U left unchanged = = 3. In how many years will one gram of pure element (a) lose one centigram (b) be reduced to one centigram? Sol.48 × 10 5 λt may also be calculated.693 λ= = = 4.88 × 10–14 s–1).68 years. time during which one centigram of radium is lost due to disintegration be = t. log10 = 4. M0 = M . = eλt N N0 or.99 g.023 × 10 23 A = λN = 8. log10 = λt × 0. (a) How much of it will remain unchanged after 62. A radioactive sample initially contains 4.4343 N 100 or.173 or.693 × 62000 and λt = ×t= = 0.

98.31 × 10–4 × 214 ∴ m = 3. − = λN dt m × 6.31 × 10–4 × 214 ∴ m = 8.5 × 109 years) is: m × 6. s −1 dt m × 6. the mass of 238 (λ = 0.28 × 10–4t × 0. Example 6.7 × 1010 dis/s.5 × 109 × 365 × 24 × 3600 and 92 U t1/2 = 4.s–1. Example 7.PM5 58 .3 × 10–13 g.7 × 1010 = 4. Calculate the mass for RaB for 1 rd activity. For 1 rd activity. • For one rutherford. Calculate the mass of RaB in gram which gives 3. = 10 6 dis.023 × 10 23 ∴ 106 = 4. One Ci is defined as that quantity of a radioactive material which gives 3.5 × 109 years) Sol.02 × 10 23 ∴ 3. The number of atoms of RaB contained in mass (m) m × 6. estimate its age. The ratio of mass of Pb206 to the mass of U238 in a certain rock specimen is found to be 0.023 × 10 23 3. Assuming that the rock originally contained no lead. Highlights: • For one curie.5. We know that.2 × 106 g. The unit for measuring radioactivity is curie (Ci). Example 8.58 ENGINEERING CHEMISTRY ∴ log10 100 = 4. • Smaller units like millirad (mrd) and microrad (µrd) are also used.4343 ∴ t = 10.02 × 10 23 = 214 dN Now. (t1/2 for U is 4. dN Sol.760 years.1 × 10–8 g.023 × 10 23 106 = 4.7 × 1010 = 4. One rutherford is de- fined as that quantity of a radioactive substance which gives 106 dis.9 × 10–18 × 238 ∴ m = 3. Sol. U238 = (U238 + Pb206) e–λt C-8\N-ENGCHE\ECH3-1.7 × 1010 disintegrations/sec. Highlights: • A new absolute unit of radioactivity is rutherford (rd).693/4.9 × 10–18 × 238 ∴ m = 80. the mass of 238 92U is m × 6.

05 IJ = 0. The amount of 6C14 isotope in a piece of fresh wood is found to be 1/6th of the total carbon.23 × 0. Sol.5 × 109 years) 11.303 × 5760 1 t= log 0. What is the age of the old piece of wood? Sol.9 g of U238 and 10. Mole of U238 = = 0. 2. Calculate the age of the ore.693 2. Example 9. Calculate the age of wood. A sample of U238 is found to contain 11.1761 4.05 206 2.693 log 1 + 0.5 or.63 × 109 years.3 Mole of Pb206 = = 0.6021 = = 11. (t1/2 = 4.7782 = = 20. 0.05H K 2.5 e–λt ∴ eλt = 1.303 × log10 1.5 × 10 9 = log 2 = 4. 1 = 1+GH U 238 JK e –λt or.693 ∴ t = 0. We have.693 1/ 6 2.5) e–λt = 1.5 × 10 9 ∴ t = 2.693 Example 10.1761 0.303 × 4.693 C-8\N-ENGCHE\ECH3-1.9 Sol.5 × 10 9 FG 0. t= 0.303 t1/2 FPb 206 I We have. Half-life period of C14 is 5760 years.303 t1/2 1 t= log 0.303 × 5577 = log 6 0. 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 × 109 years. 1 = (1 + 0.3 g of Pb206. 0.693 1/ 4 2.303 × 5577 × 0.693 GH log 1 + 238 U JK 2.NUCLEAR CHEMISTRY 59 F Pb 206 I or. We have.303 × 4.525 yrs.05 238 10.3 × 0.5 = 2. λt = 2. 2.PM5 59 .170 yrs.303 × 5760 × 0. (t1/2 of C = 5577 yrs). 0.693 Example 11.

13 hrs. so the reaction is endoergic.u.u.948 x≈3 1 ∴ the fraction of the Sample = . the reaction is 4 + 7N14 = 8O17 + 1H1 + Q 2He ∴ Q-value of the reaction is = – 0.693 1/ x 2.693 10 × 0.0045 14 1 7N 14.01264 – 18. the reaction is accompanied by liberation of energy.303 × 6.PM5 60 .15 MeV So. and such reaction are called endothermic or endoergic. 2.u. = – 1. On the other hand. Sol.01264 Increase in mass = 18.00387 8O 17.m.693 or log x = = 0. 3 Example 13. there is absorption of energy.m.00124 a.u.u. if Q-value is negative. Calculate the fraction of the sample of this substance present at the end of 10 hrs. The half-life of Ac222 is 6.60 ENGINEERING CHEMISTRY Example 12. there is decrease in mass in the reaction.4696 2. 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. If Q-value is positive. there is gain of mass in the reaction.01140 Total = 18. there is increase in mass and absorption of energy. C-8\N-ENGCHE\ECH3-2.13 or 10 = log x 0.303 × 6. (a) The overall energy liberated or absorbed in a nuclear reaction is called nuclear reaction energy. ∴ Q-value = 0. such a reaction is exothermic or exoergic.) Product particles Mass (a. (a) What is Q-value for a nuclear reaction? (b) Calculate the Q-value for the following nuclear reaction: 14 + 2 He4 → 8O17 + 1H1.01140 = 0.) 4 17 2He 4. 7N Sol.m.00814 Total = 18.4696 = 2. = 931MeV] = 1.15 MeV The Q-value for the reaction is negative.00124 × 931 MeV [Q 1 a.m. (b) Interacting particles Mass (a.13 ∴ x = Antilog 0.00753 1H 1.m.00124 a.303 t1/2 1 t= log 0.

) Product particles Mass (a. and the mass of neutron is 1. the reaction is accompanied by liberation of energy (decrease in mass).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 235.124 + 1. Q value is positive.m.u.00387 Total = 8. ∴ Energy released = 0. (energy released/fission of U 235 MeV = 200 MeV).NUCLEAR CHEMISTRY 61 Example 14.2151 a.PM5 61 .) 7 4 3Li 7.02636 Total = 8.01474 + 6. 40 = 8. Example 15.00814 2He 4.03387) = 0. 6 + 1D2 = 2 He4 + 2 He4 + Q 3 Li where isotopic masses are.00774) = 0. 92 U Sol.m.01702 a.0099) = 0.u.m.0099) – (94. Q = (2.954 + 2 × 1.975 a.m.0086) – 39.353 a. = 0. Sol.67 MeV.975 a.00774 ∴ 7 + 1H1 = 2He4 + 2He4 + Q 3Li ∴ Q = Decrease in mass = (8.u. Example 17.m.03402 × 931 = 31.u.u.945 + 138. = 0.m. The reaction is 92U235 + 0n1 = 36Kr95 + 57Ba139 + 2 0n1 + Q or Q = (235.2151 × 931 MeV = 200. Mass defect ∆m for Ca-atom = (20 × 1. Interacting particles Mass (a. So the reaction is exothermic of exoergic. 0. Example 16.m.01822 2He 4.u. Calculate the limiting energy per nucleon 20Ca40.m.01474 2 He = 4.u. 3 Li6 = 6. 2 4 1D = 2.01862 a.216 MeV.258 MeV.02636 – 8.m. The mass of proton is 1. which has atomic mass of 39.u.01702) – (2 × 4.3 MeV. Calculate the energy released in the following fission reaction: 235 + 0n1 → 36 Kr95 + 57 Ba139 + 2 0n1.m.0086 a. Sol.00387 1 4 1H 1.00387 a.03402 a. 3 Li Sol.0078 a. C-8\N-ENGCHE\ECH3-2. Show the following reaction is exoergic 7 + 1H1 = 2 He4 + 2 He4.u.353 × 931 ∴ Binding energy per nucleon = MeV.01862 × 931 = + 17. Here.m. = 0.0078 + 20 × 1. Calculate the energy released from the fusion of 3 Li6 and 1D2 by the reaction. Example 18.m.u.u. From the above equation.

PM5 62 .2 × 1013 J. calculate the amount of fuel required for one day’s operation.2 × 10–11 J or W.5 × 1023 atoms of U235 are present in 235 × 13.s. 3.5 × 10 23 = kg 6. energy released per 1 kg of U235 200 × 6.e.6 × 10–13 J = 3. Energy required to be produced in a day 864 × 10 10 = = 432 × 10 11 J 0. ∴ No.023 × 1026 atoms or nuclides. What do you mean by nuclear chemistry? Ans.6 × 10–13 J = 32 × 10–12 J. of U235 atoms to be fissioned 432 × 10 11 = = 13.023 × 1026 atoms of U235 are present in 235 kg ∴ 13.025 × 10 26 = 530 × 10–3 kg = 0. C-8\N-ENGCHE\ECH3-2. SHORT QUESTIONS AND ANSWERS Q.023 × 10 26 = MeV. (Q 1 MeV = 1. Nuclear chemistry is concerned with changes of the nuclei i. 1. etc. Sol. Energy consumed in the city in a day = 100 × 106 × 24 × 3600 = 864 × 1010 J Since efficiency of the reactor is 20%.5 × 1023 32 × 10 −12 6. So.2 Energy released/nuclide = 200 × 1. Hence.2 × 10 −11 (ii) 1 kg atom of U235 = 235 kg = 6.62 ENGINEERING CHEMISTRY Sol. If this is to be supplied by a nuclear reactor of efficiency 20%. disintegration. 235 = 8. fission rate for generation of 1 watt 1 = = 3. using U 235 as the nuclear fuel. (i) Energy released per fission of U235 nuclide = 200 MeV = 200 × 1.. its stability.6 × 10–13 J) Example 19.53 kg. A city requires 100 MW of electrical power on an average. Given that energy released per fission of U 235 is 200 MeV.1 × 1010 fissions sec–1.

7.and β-particles are emitted from the nucleus. So it appears strange. How does a nuclear reaction differ from a chemical reaction? Ans. Q. 3. (ii) The nuclei of radioactive elements disintegrate forming atoms of new elements called ‘daughter elements’. (iv) γ-rays are the secondary effects of the nuclear disintegration. (i) The nuclei of radioactive elements are unstable. 6. Q. The phenomenon of spontaneous emission of radiations from the nuclei of heavy elements is called radioactivity. A β-particle is a single negatively charged particle and positive nucleus does not contain any electron. The emission of a β-particle from a radioactive element is known as β-emission. A γ-decay has been depicted in the following figure. Thus. The transformation of UI to UXI by α-emission may be represented as follows: 238 −α 92UI → 2He4 + 90UXI234.NUCLEAR CHEMISTRY 63 Q. nucleus gains a proton at the cost of a neutron. 2. What is β-emission? Ans.PM5 63 . the atomic number of the daughter element increases by one unit. (iii) α. What is the theory behind radioactivity emission? Ans. What is radioactivity? Ans. What is α-emmision? Ans. γ-rays have been proved to arise from the transition of a nucleon from one energy state to the other. on emission of a β-particle. Q. The emission of an α-particle from a radioactive nucleus is designated as α-emission. nuclei of the atoms remain unaffected in a chemical reaction. 210 82Pb RaD E = 65 KeV -ray 210 83Bi E = 47 KeV -ray RaE E=0 210 83Bi C-8\N-ENGCHE\ECH3-2. Q.  Q. Nuclear reaction involves the changes of the nucleus whereas ordinary chemical reaction involves the changes in extranuclear electrons of the atoms. 5. β-particle is generated in the nucleus as follows: 1 → –1e0 + 1H1 0n So. Rutherford and Soddaz postulated that. What is γ-decay? Ans. 4.

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

.

92U 54Xe + 38Sr + 2 0n 144 90 1 55Cs + 37Rb + 2 0n A huge amount of energy is released during nuclear fission according to famous Einstein’s equation E = mc2. and this reaction is the principle for atom bomb.PM5 64 . C-8\N-ENGCHE\ECH3-2.

Q. combining of two lighter nucleus into lighter ones with release of nuclei into a heavy nucleus with release of large amount of energy. (iii) During fusion. EXERCISES 1. 2 + 1H2 → 2He4 + energy 1H 1 + 1H3 → 2He4 + energy. (v) Fusion does not give rise to chain reaction. positrons are emitted. Ans. Why the elements with even proton numbers are more abundant than other elements? Ans. Apart from atom bombs and alternative energy sources. the following fusion takes place. (ii) Fusion takes place at very high temperature (106 K). 14. Ans.NUCLEAR CHEMISTRY 65 Q. (iv) Fission gives rise to chain reaction. 15.13. It is also the process that accounts for the origin of all the elements.PM5 65 . 4 1H1 → 2He4 + 2 positrons + 109 kJ. The pressure and temperature at the centre of very large stars is high enough for 4 nuclei to fuse to form heavier elements such as C. how can you determine by simple experiments if the mineral is radioactive? C-8\N-ENGCHE\ECH3-2. If you are given a piece of mineral. Nuclear reactions are the changes affecting the nuclei of atoms. Si. since 2He4 has even number of 2He nucleons. 1H Nuclear fusion is the source of energy of the sun and the other stars. Compare fission and fusion reactions. Q. Fission Fusion (i) Fission involves breaking up of a heavy (i) Fusion involves. 238 β β 92 U + 0n1 → 92U239  → 93Np239  → 94Pu239 Nuclear reactions are used to give birth to radioactive isotopes to be used as tracers. When two light nuclei combine with release of a huge amount of energy. How are nuclear reactions carried out? Mention the uses of nuclear reactions. What is radioactivity? Give an account of the discovery of radioactivity? 2. they fuse to produce elements with even proton numbers. the phenomenon is known as ‘nuclear fusion’. Nuclear reactions are brought about by bombarding nuclei with high energy particles in particle accelerators or with beams of neutrons from nuclear reactors. How will you show that radioactivity is nothing but a nuclear property? 3. 16. (iii) During fission. (ii) Fission takes place at ordinary temperature. at a temperature of ten million degrees. with higher proton numbers than uranium. neutrons are emitted. Fe. In the sun. Q. large amount of energy. What do you mean by nuclear fusion? Ans. nuclear reactions can be used to make elements that do not occur in nature.

.04 1 amu = 931. β. What is a nuclear reaction? Discuss some uses of nuclear reactions. 26.. range and velocity. 6C Given: Mass of H-atom = 1. 22. 19. 10. 25.00866 a. + 74 Be. Actual mass of C-atom = 12. What are α-. 8.u. [Ans. What are the causes of nuclear instability? Explain with suitable examples.76 MeV] 28. 9. 24. Calculate the binding energy in MeV per nucleon of 12 . Write a short note on nuclear fusion. Calculate the amount of energy released during the bombardment of 10 n on 235 92 U . [Ans. 2385 yrs. Given the t1/2 of thorium = 1. + 11H 7 3 Li + 11H → . What is nuclear fission? Show how nuclear fission is a chain reaction. Why is natural radioactivity mostly limited among heavier elements? 14. Write a short note on nuclear transmutation..1 g? [Ans. Mass of neutron = 1. Write notes on: (i) Radioactive equilibrium (ii) Atomic weight of lead in radioactive minerals (iii) Tracer technique.4 MeV. State and explain the law of radioactive disintegration. 10 5B + 42 He → .93 × 10–5 yrs. Explain artificial radioactivity with suitable examples. 5.00782 a. Complete the following nuclear reactions: 9 4 Be + 42 He → 12 6C + . Derive a relation between mass defect and nuclear binding energy. 15. What informations are available from these curves? 18... 20. What are the units of radioactivity? 7. 17.] 27. What is nuclear binding energy? 16. 13. 6.66 ENGINEERING CHEMISTRY 4. What is radioactive displacement law? 12.. 24 24 11 Na → 12 Mg + . 21.and γ-rays? Compare their ionising power.. Give a brief account of the nuclear reactors.. The half-life of radium is 1590 years... 54.m. 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. Explain the terms: (i) Disintegration constant (ii) Half-life period 6.m. Where is the radioactive displacement law invalid? 23. How long will it take for 1 g of the element to lose 0. 11. Calculate the time required for 10% disintegration of a sample of thorium. What are radio-isotopes? How are they prepared? Mention their uses. Write a short note on radio-carbon dating. 238 239 92 U → 90Th + .u.PM5 66 .] C-8\N-ENGCHE\ECH3-2.4 × 1010 yrs. Give a relation between half-life and the decay constant of a radioactive substance. Give a comparative account of the nuclear binding energy curve and packing fraction curve.

[Ans. Given the t1/2 of cobalt = 5.m.5 × 109 yrs. 40 days] 33.m. [Ans. C-8\N-ENGCHE\ECH3-2.u. Mass of 2H = 2.u.u.00812 a. Distinguish between nuclear fuel and a chemical fuel. Given: Mass of neutron = 1. Mass of electron = 9 × 10–28 g.016 a.NUCLEAR CHEMISTRY 67 29. [Ans. Mass of proton = 1.m.114 MeV] 34.33. 16. 9. = 931 MeV. An old wooden article shows 2. [Ans.m.01605 a. Mass of 31 H = 3. Calculate the decay constant of 60Co. 4. A fresh sample of wood shows 15. Calculate the approximate life period when the plant died.82 days.5 × 10–6] 32.9 g of 238U and 10. Half life of 222Rn in 3.u. Mass of 11B = 11. 6. [Ans. 1 a. A radioactive element disintegrates to 1/16th of its original mass in 160 days.u. Calculate the energy released in MeV from the reaction: 10 5B + 21H → 11 5B + 11H Given: Mass of 10B = 10. 14 Given: t1/2 for 6C = 5. 2970 years] 30.862 years] 38. Calculate the energy produced in MeV. [Ans.003 a.m. Mass of 1H = 1. 16.0 counts min–1 g–1. [Ans.760 yrs. [Ans. 0. of 206Pb.m.u.6725 × 10–24 g.m.2 counts min–1 g–1. Calculate the age of the rock. Write short note on components of a nuclear power reactor and their functions.009 a. A piece of wood was found to have 14C/12C ratio 0.6747 × 10–24 g.76 MeV] 37.01472 a.13 yr–1] 36.u. 39. A neutron breaks into a proton and an electron.m. Mass of 42 He = 4. Mass of 10 n = 1. Calculate the weight of 1 curie of 222Rn. Calculate the age of the wooden article.01286 a.014 a. 0.PM5 67 . What is its half- life period? [Ans. Given t1/2 = 5760 years. Calculate the energy released in the nuclear fusion reaction: 2 1H + 31H → 42 He + 01n Given: Mass of 21 H = 2.u.m.73 MeV] 35. Given t1/2 of uranium = 4.5 × 109 years] 31.u.3 years. A sample of uranium ore is found to contain 11.7 times that in a living plant.

.. State of a system. viscosity. pressure and temperature are the fundamentally important properties. etc. • Before beginning with the laws of thermodynamics following terms are needed to be defined. Thermodynamic systems. The set of thermodynamic variables such as pressure. 1. volume. When one or more of these variables undergo change. refractive index. 2. The physical characteristics which are experimentally measurable and which enable us to define a system are called thermodynamic parameters or properties of the system. Properties like volume. 4 Thermodynamics Thermodynamics is concerned with the flow of heat and therefore deals with the quantitative relationship between heat and work. which can exchange both mass and energy across the boundary. which is capable of exchanging only energy with the surroundings but no mass transfer across the boundary is permitted. are dependent upon the mass of the system and are called extensive property. An open system is a system. viscosity. 68 . density. etc. Hence. Extensive property. 3. Composition. Properties 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. There is no such perfectly isolated system other than our universe itself. 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. A closed system is one. the system is said to have undergone a change of state. surface tension. The rest of the universe is called the surroundings. which describe a system is called the “state of the system”. example is a sealed flask containing matter in a closed system. etc. composition. Properties like temperature. Intensive property. 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. A system is defined as any matter or its part. example is a plant or any living being. are independent of the mass of the system and are called intensive properties. specific heat. temperature. the energy and matter remain constant for the system. it will never be overthrown”. within the framework of applicability of its basic concepts. Einstein comments: “It (thermodynamics) is the only physical theory of universal content concerning which I am convinced that. Refractive index. chosen for study and separated from the rest of the universe by a real or imaginary boundary. energy. volume. surface area. Thus.. pressure. dielectric constant are also other properties.

chemical composition.e. the system returns to its initial state. Five moles of a substance in a specified state has five times the internal energy possessed by a single molecule in a similar state. rotational. All the natural processes are irreversible.1). pressure and composition. so dE is path independent and E is a state function. as a result of a series of changes. State function is a thermodynamic property. free energy change (∆G) and entropy change (∆S) are such functions. it can be stated that when a system changes from initial state (1) to a final state (2) and comes back to (1) (Fig. a system in equilibrium state has definite temperature. If a process is carried out at constant pressure. which depends only on the state of the system but not on the paths followed for the change. If a system undergoes a series of changes and returns to its initial state i. ∑∆E = 0. Otherwise. internal energy is found to return to its original value. its thermo- dynamic parameters also return to their original values. pressure and volume of the system. such a process is called a cyclic process. Internal energy change (∆E). Equilibrium state. 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. So internal energy (E) is a state function. expansion of gases from high pressure to low pressure.. if a cyclic process is completed. This energy is a function of the temperature. z dE = 0 C-8\N-ENGCHE\ECH4-1. If a change takes place in a thermally insulated system which does not permit heat exchange with the surrounding. net change in internal energy is zero i. Internal energy. etc.. Hence. A system is said to be in equilibrium when its composition is fixed.e.PM5 69 . hence the sum of the changes of internal energy for a cyclic process i. the process is called an isobaric process. A process can be made reversible by performing the change very slowly with no friction and no finite temperature differences. enthalpy change (∆H). It is an extensive property. (cyclic integration of E is 0).. The absolute value of the internal energy of a system cannot be ascertained. example. which is accompanied by volume changes. The magnitude of internal energy of a system is determined by the kinetic. Irreversible processes are all spontaneous processes. Every system within itself has a quantity of energy which is called the internal or intrinsic energy. If a change takes place at a constant temperature maintained throughout. When a system changes from a thermodynamic state 1 to a thermodynamic state 2. 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. vibrational movements of the molecules of the system. the process is called an adiabatic process and the temperature of the system may increase or decrease. 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. If a change takes place in which the volume of the system remains constant the process is called an isochoric process.e. it is called an isothermal process.THERMODYNAMICS 69 If. 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. 4. heat flowing from a hotter to a colder body.

PM5 70 . it completes a cyclic path and the overall change of energy (E) i. Joule-Thomson effect Joule-Thomson effect states: “When a gas under high pressure is permitted to expand into a region of low pressure. dV = 0. ∴ W = – ∆E. Thus.e. is of pressure × volume type.. we can write dE = dq – dw where dE is the increase in internal energy. from first law. and it may be stated as “the energy of an isolated system remains constant and whenever a quantity of some form of energy disappears. ∆E = 0. dV for very very small changes. dE = dq – P. Hence. the algebraic sum of all the heat terms is equal to the algebraic sum of all the work terms. dq and dw represent small quantities of heat absorbed and external work done by the system. 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). For an adiabatic change. it suffers a fall in temperature”. When the volume (V) is constant.e. according to the first law Heat absorbed = Increase of internal energy + Work done by the system i. So in an adiabatic process. exclusively. it may be used up by the system as partly increasing the internal energy of the system and partly in doing mechanical work. work done by the system = decrease in internal energy of the system. q = 0. q = ∆E + W or ∆E = q – W If the above change is infinitesimally small. If the system is under a pressure P and volume increases by dV. we arrive at a very important relation that for a cyclic process. the work done becomes P dV and hence the mathematical expression of first law becomes. respectively.70 ENGINEERING CHEMISTRY Cyclic process Fig. an exactly equivalent quantity of some other form of energy must make its appearance”. 4.. Hence. ∆E = q – W = 0 ∴ q = W. Mathematical formulation of the first law Let us suppose.1 THE FIRST LAW OF THERMODYNAMICS The first law of thermodynamics is simply the law of conservation of energy. C-8\N-ENGCHE\ECH4-1. Here the work. Since heat energy cannot be lost. 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. heat supplied to a system is q.

C-8\N-ENGCHE\ECH4-1. P2V2 – P1V1 = W. not on the path followed during the change. Heat absorbed by the system is q. thus the gas while expanding does some work and hence the temperature falls. Constancy of Enthalpy (isoenthalpic) in Joule-Thomson expansion Joule-Thomson experiment is carried out adiabatically. for an ideal gas. according to the first law. q = 0.. if the process is carried out at constant volume change in enthalpy and change in internal energy are equal. 4. H is a similar state function.. when q = 0. i. Hence.e. work done by the gas is. Thus. a system at constant pressure is undergoing a change from states 1 to 2.e. 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. 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.PM5 71 . 4.. when heat does not flow out of the system nor does it come into system from the surrounding. ∆H = ∆E + PV = ∆E + W = q (heat absorbed) and at constant volume. So. there should be no change in temperature. Change in enthalpy = change in internal energy. The gas expands is passing through porous plug (Fig. ∴ ∆H = ∆E + 0 = ∆E. Porous plug V1 P1 P2 V2 Fig. Hence.2 Joule-Thomson expansion. Suppose.. ∆E = –ve.e. i.e. from first law of thermodynamics. ∆H = (E2 + P2V2) – (E1 + P1V1) = (E2 – E1) + (P2V2 – P1V1) ∴ At constant pressure.2) and the work done is P2V2 – P1V1. ∆V = 0. Hence. Hence. The work done is at the expense of the kinetic energy of the molecule while they are separated from each other. the energy of the gas falls i. The quantity (E + PV) is universally represented as H and called the heat content or enthalpy of a system. ∆E = q – W = q – 0 = q.THERMODYNAMICS 71 Joule and Thomson performed an experiment where a gas was allowed to expand adiabatically through a porous plug against a constant pressure. ∆H will depend only on the initial and final states of the system. from the first law of thermodynamics q = (E2 – E1) + W = (E2 – E1) + (P2V2 – P1V1) = (E2 + P2V2) – (E1 + P1V1) = H2 – H1 = ∆H. the gas was allowed to do no work and there was no interchange of heat with the surroundings. P1V1 = P2V2 ∴ W = 0. The volume increase is from V1 to V2. But Joule-Thomson observed that most gases cooled down by such a pressure drop. Hence. Since E is a characteristic of the system (state function). For an ideal gas. Since the expansion is carried out adiabatically i.

72 ENGINEERING CHEMISTRY Hence. thermostat at T K.. under adiabatic conditions.3 V2 V2 nRT Then. i. we can define Joule-Thomson coefficient (µ) by the relation. W= PdV = dV [Q PV = nRT] V1 V1 V V2 ∴ W = nRT ln V 1 V2 P Since. a × ∆l is the volume swept by the piston. from first law.e. The cooling effect is seen when the temperature is low. The work of expansion (W) will be given by the product of opposing force and the displacement. it is dV z z Fig. i.. 4. ∆E = q – W = 0 – (P2V2 – P1V1) i. V1 P1 C-8\N-ENGCHE\ECH4-1. then instead of cooling the gases are heated. This temperature is called the “inversion temperature. FG δT IJ µ= H δP K H µ is zero for an ideal gas (PV = nRT). E2 – E1 = – P2V2 + P1V1 ∴ E2 + P2V2 = E1 + P1V1 or H2 = H1. for a lowering of pressure dP. Ti” of the gas. if the temperature is high.e. Work done in a reversible isothermal expansion: Suppose n moles of a gas is enclosed in a cylinder by a frictionless piston (Fig. For every gas there is a temperature where µ = 0.. isothermal condition is maintained. 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. For van der Waals gas. = 2 in an isothermal expansion of a perfect gas.. At every step a minute distance (∆l) of the piston may be V1 T made so that work done (W) is.e. W = P × a × ∆l.. The gas has a volume V1 and the piston is at point A. For gases having positive µ value cools on expansion but for H2 gas µ is negative i.e. ∆H = ∆E + P∆V = ∆E + P(V2 – V1) = ∆E + w = qP (heat absorbed at constant pressure) i. W = force × displacement = force × area × distance A = P × a × l.. 4. But. change in enthalpy is equal to heat absorbed at constant pressure. The gas is to be expanded from volume V1 to volume V2. when neither heating nor cooling of the gases occurs on expansion after pasing through orifices. H2 warms up on expansion. µ becomes negative. The cylinder is kept in a constant temperature bath i. Inversion temperature If the gas in above expansion suffers a fall in temperature by dT.3).PM5 72 .e.e.

Cv = H ∂T K V . When the reaction involves gaseous contraction. ∴ P(V2 – V1) = (n2 – n1) RT. Molar heat capacity at constant volume is Cv. ∆H = ∆E + ∆(PV) ∆H ∆E ∆ (PV) or = + ∆T ∆T ∆T ∆ (PV) or Cp = Cv + ∆T C-8\N-ENGCHE\ECH4-1. or P∆V = ∆n . ∆H = ∆E. 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. When the reaction involves gaseous expansion. Relation between Cp and Cv: We know. ∴ ∆H > ∆E. dq C= dT FG ∂E IJ At constant volume condition. ∴ ∆H = ∆E + ∆n.THERMODYNAMICS 73 V2 P1 Then. PV = nRT. work done (W) during reversible isothermal expansion is. For n moles of an ideal gas. V1 Enthalpy of a gaseous reaction n1 moles of reactant gases react to produce n2 moles of gaseous products.PM5 73 . 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. for 1 mole of an ideal gas. ∆n is negative ∴ ∆H < ∆E. From first law of thermodynamics. When there is no volume change. ∆H = ∆E + P∆V.RT. V2 W = RT ln . If dq heat is required for dT increase in temperature then for 1 mole of substance. which is molar heat capacity measured at constant volume condition. Similarly. ∆n is positive. RT. Molar heat capacity at constant pressure is measured by keeping the pressure constant dq ∂H FG IJ ∴ Cp = dT = ∂T H K P . W = nRT ln = nRT ln V1 P2 So. thereby volume changes from V1 to V2 at constant temperature T and pressure P.

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. dq dE PdV = + T T T dT dV ∴ dS = Cv . • Any irreversible process is accompanied by increase in entropy. • Entropy is a measurement of randomness of a system. The energy unavailable as work is proportional to the increase of entropy. . w increases when S increases.THERMODYNAMICS 75 the disorder and irreversibility and when equilibrium is reached. T and path independent. So. Thus.e. • Gases generally have higher entropies than liquids. k = Boltzmann constant.3. The volume of the gas changes from V1 to V2. The higher the entropy. the pressure on the gas is approximately equal to the external pressure P. • It is convenient to calculate total entropy change in two parts. +R . V. the entropy of the system goes on increasing and reaches a maximum value at equilibrium. when an order to a system is brought. For example. increase of randomness enhances thermodynamic probability. (i) the entropy change of the system and the entropy change of the surroundings i. from 1st law of thermodynamics. Entropy of an ideal gas In the case of a reversible expansion of an ideal gas in a container as in Fig. it has the maximum disorder.. • Entropy is a state function dependent on P. dq = dE + dW = dE + P dV. entropy increases and vice-versa. • From experience we can say. the odour of the gas spreads all over the room randomly and equilibrium is reached when the entropy also becomes maximum. some energy is always dissipated i. Conversely. disordered form is more probable than ordered form. only a part of the total energy is made available for useful work. Since the process is reversible. w = thermodynamic probability. Thus. the container is fitted with a frictionless movable piston at constant pressure P. 4.. where S = entropy. ∆Stotal = ∆Ssystem + ∆Ssurroundings. Boltzmann expressed this idea by the relation. the entropy of the universe is ever increasing. As w is always greater than one. Hence. In any system..(III) Dividing both the sides of the equation (III) by T. the less the availability of work. T V C-8\N-ENGCHE\ECH4-1. For example. solidification of a liquid brings about orderly state and thereby entropy decreases. if a gas with strong odour is let loose at the corner of a room. As all spontaneous processes are irreversible.PM5 75 . • If system absorbs heat. • A spontaneous change occurs in the direction leading to a total increase of entropy.e. S = k ln w. the entropy of the system decreases. Highlights: • Prediction of direction of changes is possible with a thermodynamical quantity known as entropy (S). entropy signifies unavailable form of energy of the system during transformation of heat into work. wasted.

for isothermal expansion. for an ideal gas at constant temperature. let a heat reservoir at T1 (state 1) is brought in contact with a second reservoir at T2 (state 2) where T1 > T2. V1 P2 At constant pressure P. T1 V1 V2 P Since.. which is evacuated (Fig. T2 ∆Sv = Cv ln . 4. z S2 S1 dS = Cv z T1 T2 dT T +R z V1 V2 dV V T2 V or. The vessels are kept in a thermostat of the temperature T. z 1 2 When the flow of heat is irreversible. q = ∆E + W C-8\N-ENGCHE\ECH4-1. T2 ∆Sp = Cp ln T 1 At constant volume V. T1 Entropy change in irreversible process Entropy is a state function. the irreversible heat flow leads to increase in entropy.4). T1 P2 At constant temperature i.76 ENGINEERING CHEMISTRY Thus.e. The vessel is connected to a vessel of volume V2 by a tube containing stop cock. the change of entropy (∆S) is given by: dqr ∆S = S2 – S1 = T . and small quantity of heat q flows from T1 to T2. V P1 ∆ST = R ln 2 = R ln . So. Irreversible isothermal expansion of an ideal gas Let n moles of an ideal gas is enclosed in a vessel of volume V1. for a change from states 1 to 2 we have. = 1 V1 P2 T2 P1 ∴ ∆S = Cv ln + R ln . 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. we have.PM5 76 . q The decrease in entropy of state 1 = T1 q The decrease in entropy of state 2 = T2 q q T − T2 ∴ Net change of entropy = − = q. hence. ∆S = Cv ln + R ln 2 . 1 T2 T1 T1T2 The difference is a positive quantity. From the first law of thermodynamics.

S1 = Cv ln T1 + R ln V1 + S0 S2 = Cv ln T2+ R ln V2 + S0 T2 V2 ∴ ∆S = S2 – S1 = Cv ln + R ln T1 V1 For an isothermal change. of the gas. ∆Sirr. ds is a perfect differential. S = (Cp – R) ln T + R ln + S0 P or. Thus. if this expansion is carried out irreversibly at T K from volume V1 to a volume (V1 + V2) after opening the stop cock (Fig. for the irreversible expansion of gas. V1 Entropy change of a mixture of gases From first law of themodynamics. dq = dE + PdV Dividing both the sides of the above equation by T. So we have. Cp – Cv = R for an ideal gas. we have. RT So. dq dE PdV dT dV = + = Cv +R (for 1 mol of gas) T T T T V or. dS = Cvd (ln T) + Rd (ln V) or. we have V2 P1 ∆S = R ln = R ln .4). V1 P2 C-8\N-ENGCHE\ECH4-1. S = Cp ln T – R ln P + S0′ We cannot determine the absolute value of the entropy of an ideal gas. ∆Suniverse = ∆Ssystem + ∆Ssurrounding V1 + V2 = R ln +0 V1 V1 + V2 = R ln A positive quantity. We know.4 Since S is a state function.PM5 77 . 4. V1 + V2 qrev = ∆E + RT ln V1 V1 V2 T V1 + V2 = 0 + RT ln V1 . S = Cv ln T + R ln V + S0 where S0 is a constant. if the temperature of an ideal gas changes from T1 to T2 and the volume from V1 to V2 for 1 mol. As there is no thermal change.THERMODYNAMICS 77 Now. ∆Ssurrounding = 0 Hence. (system) would be same. Fig. 4. we have. But the changes in entropy can be determined.

A = E – TS For an isothermal process. they diffuse and mix-up irreversibly. Moles of gas A is nA Moles of gas B is nB Temperature is T Pressure is P Then. ∆Smix = – n R ∑xi ln xi where xi = mol. (– ∆A) gives the maximum amount of work available during isothermal process. Such a spontaneous irreversible process leads to an entropy increase. ∆Smix = (S A mix + S Bmix ) – (SA + SB) = S A mix + S Bmix – SA – SB pA p or.e. xA = . So. fraction of gas i. ∆AT = ∆E – T∆S (Q ∆T = 0) = ∆E – q = – Wmax or. change of entropy due to mixing. Work function (A) Let us define. Let. the total pressure (P) P = pA + pB. for mixing any number of gases. C-8\N-ENGCHE\ECH4-1. fraction = pressure fraction) P P ∴ ∆S = – nA R ln xA – nB R ln xB. maximum work is involved. 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.PM5 78 . xB = n n pA pB Now. hence. ∆S = – nA R ln – nB R ln B P P nA nB The total moles of mixture = n = nA + nB mol.78 ENGINEERING CHEMISTRY When two gases come in contact. LM n A nB OP or.. = xA and = xB (As mol. fraction of A. 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. – ∆AT = Wmax where Wmax is reversible. ∆Smix = – n R Nn ln xA + n ln xB Q = – n R[xA ln xA + xB ln xB] In general. work function is such a thermodynamic property of the system that decreases in work function A i.

= – nFE (n = number of electrons.PM5 79 . we have. The standard state is defined at constant pressure of 1 atmosphere and constant temperature i. Standard free energy change G is a state function. FG δA IJ FG δA IJ So. Hence.. To assign numerical values to free energy change of a system. Free energy and useful work Suppose a reversible change takes place at constant temperature T and at constant pressure P. q = ∆E + P∆V + Wuseful = ∆H + Wuseful Now. from the first law of thermodynamics. F = Faraday and E = emf of a cell. it is necessary to assign a standard value for the free energy of a system at a specified state.THERMODYNAMICS 79 A = E – TS or dA = dE – TdS – SdT = dE – dq – SdT = – PdV – SdT. 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. ∴ ∆G° = ∑G°(products) – ∑G°(reactants) Relations of ∆G (i) ∆G = Wuseful (at constant T and P). – (∆G)P. 25°C or 298 K. 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. T∆S = ∆H + Wuseful ∴ ∆H – T∆S = – Wuseful = (∆G)P. for isochoric process H δT K v = – S. since q = T∆S. decrease in Gibb’s free energy is a measure of the ‘useful work’ obtainable from the process. ∴ ∆G = ∆H – T∆S. T. which are very useful for physicochemical studies are: • Gibb’s free energy (G) and • Helmholtz free energy or work function (A). Gibb’s free energy is related to enthalpy and entropy as. Free energy (G) Two thermodynamic functions. or. G = H – TS. and for an isothermal process H δV K T = – P. This relation correlates free energy change to cell potential) (ii) ∆G = ∆H – T∆S (at constant T) C-8\N-ENGCHE\ECH4-1.e. Therefore. (at constant temperature). T = Wuseful. Therefore.

but the sum total of energy of the universe remains constant. the process will not take place spontaneously. • Free energy change is a state function and is related to enthalpy change. It is also defined as qrev “unavailable energy”. 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. ∆G. entropy change and temperature by Gibb’s-Helmholtz equation as ∆G = ∆H – T∆S. T • State function is one which depends only on the initial and final states of the system but independent of the path followed e. but it may reverse. As such. If ∆G is negative. ∆G must be negative. T = temperature in kelvin. K is the equilibrium constant of a reaction. Entropy change. both of which are corollaries of the first law. any change shall spontaneously occur. • Mathematical expression of first law: dE = dq – dW • Kirchoff’s equation: ∆H 2 − ∆H 1 (T2 − T1 ) = ∆Cp.303 RT log K. THERMOCHEMISTRY All types of chemical reactions are accompanied by heat changes. • Entropy is a measure of randomness or disorder of a system. Thus. If ∆G is zero. the net heat-content change or energy content C-8\N-ENGCHE\ECH4-1. for a spontaneous process. A. at constant T and P). etc. 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. 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.PM5 80 . The energy from chemical reactions comes from the breaking or formation of bonds.. where R = gas constant. ∆S. The reactions in which heat is evolved are termed exothermic and in which heat is absorbed are endothermic.g. Law of Lavoisier and Laplace.80 ENGINEERING CHEMISTRY (iii) ∆G° = – RT ln K = – 2. ∆S = . heat content (H) or energy content (E) of the initial reactants again returns to the same magnitude. the initial and the final states would be at equilibrium with each other and finally if ∆G is positive. The thermal changes in chemical processes are governed by two general principles. (iv) ∆G = 0 (at equilibrium.

Let us take the example of formation of CO2 in one step and two steps (a) and (b): C + O2 = CO2 ∆H = – 94.THERMODYNAMICS 81 change is zero i. heat changes in the two directions must be equal in magnitude but opposite in sign.PM5 81 . heat of transition.e. The experimentally determined values of heat of combustion are useful. “bomb calorimeter” which is a pressure vessel internally enamelled with platinum (Fig. 4. subtraction. 2 2 Summing up we get.63 Kcal.680 cal of heat is absorbed and the reaction is endothermic. Heat of reaction (∆H) is the difference between the heat contents of the products and the reactants.608 cals (exothermic) (b) H2 + I2 = 2 HI –12.. Example: C2H5OH + 3O2 = 2CO2 + 3H2O ∆H = – 325 Kcal C-8\N-ENGCHE\ECH4-1. (i) Heat of reaction.e. From first law we find that ∆HP and ∆EV will be independent of the path. 12. The principal advantage of this law is that thermochemical equations can be treated as simple algebraic equations and the heat of formation. 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. so heat of combustion is always negative.42 Kcal 2 1 (b) CO + O = CO2 ∆H2 = – 67. multiplication of the quantities i. etc. the heat of reaction for the formation of 2 moles of HCl is 43..63) Kcal which illustrates the law = – 94. • Enthalpy changes of reaction from enthalpy changes of formation. complete combustion means when these compounds are converted finally to CO2 and H2O. ∆H1 + ∆H2 = (– 26. (ii) Heat of combustion. Combustion reactions are always exothermic. B. ∆H terms algebraically. In the case of organic compounds..5 Bomb calorimeter.680 cals (endothermic) Thus. Example: (a) H2 + Cl2 = 2 HCl +43. The heat of combustion is experimentally determined in a Fig.42 – 69.5). which are difficult Highlights: Hess’s law is used to calculate: • Enthalpy changes (∆H) of formation from enthalpy changes of combustion.05 Kcal 1 (a) C + O2 = CO ∆H1 = – 26. 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.600 cal which is exothermic whereas for the formation of 2 moles of HI. to measure experimentally can be easily found out by addition. 4. • Lattice energies is the Born-Haber cycle. when molar quantities react and indicated by a balanced equation. Hess’s Law of Constant Heat Summation.05 Kcal.

The heat change taking place when 1 gm mole of the solute is completely dissolved in a solvent is called the heat of solution. one gm mole of KCl dissolved in 50 moles of water and in 200 moles of water will cause different heat changes. (v) Heat of solution and heat of dilution. The lower the enthalpy of formation of a compound. Example: HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O ∆H = – 13. the heat change becomes constant.. Heat of fusion is always positive. The value of heat of solution obtained graphically by extrapolating ∆H to infinite dilution is the integral heat of solution at infinite dilution. C(graphite) + 2 H2 (g) → CH4(g) ∆Hf = – 74. KCl(s) + 100 H2O = KCl (100 H2O) – 4391 Cal. If the enthalpy of formation of a compound is positive. they can be assumed to be completely dissociated.7 kJ indicates the HF is much more stable than HI.7 Kcal HCl(aq) + KOH(aq) → KCl(aq) + H2O ∆H = – 13.. Example: H2O(s) → H2O(l) ∆H = 6 kJ. the energy content of the corresponding compound is lower than its constituent elements and hence the compound is stable. it is needed to assume some arbitrary value for substances at a given state.7 Kcal. In order to measure the change in enthalpy. Therefore. H+ + OH– = H2O. (vi) Heat of fusion. the enthalpy of any element at 1 atm and 298 K is assumed to be ‘zero’. Thus. it means the energy content of the compound is greater than the energy content of its constituent elements and hence the compound is unstable.PM5 82 .9 kJ and ∆Hf of HF is – 161. the more stable is the compound. The standard enthalpy of formation (∆Hfo) is just the negative of the heat of formation. Whereas. If the acid and base are both strong. when the enthalpy of formation of a compound is negative.8 kJ. Example: ∆Hf of HI is + 26. 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.7 Kcal. Conventionally. the heat of neutralisation deviates considerably from 13. the stability of a compound is inversely proportional to the enthalpy of formation of a compound. The heat of solution changes with concentration. i.e. (iv) Heat of formation.e. C-8\N-ENGCHE\ECH4-1. Example: KCl(s) + 50 H2O = KCl (50 H2O) – 4276 Cal. It is the amount of heat liberated or absorbed when one mole of the compound is formed from its constituent elements. i. The enthalpy of formation is related to the stability of compound.. and this is always the equivalent of 13. 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. all in their respective standard states and at a reference temperature. But when a weak acid or a weak base is neutralized.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.e.7 Kcal of heat. H+ + A– + B+ + OH– = B+ + A– + H2O i. At high dilution.

. Taking average of the two bond energies we have 118 + 102 = 110 Kcal for O—H bonds.. the system loses energy to surroundings. • The enthalpy change (∆H) is calculated when starting temperature of the reactants and final temperature of the products are the same. Example.4 kJ. Example: H2O(l) → H2O(g) ∆H = 42 kJ. • Values measured under nonstandard conditions are corrected to give the value under standard conditions. 4 Alternatively.. • If ∆H is negative.PM5 83 . • The standard conditions for change of enthalpy (∆H) are 298 K and 1 bar (100 kPa).p. • If ∆H is positive. 2 Similarly. we can find the bond energy for C—H bonds by taking in average one-fourth of the total heat of formation of methane. towards H atoms to form stable molecules. This difference in bond energy is related to the more reactive nature of OH radicals than oxygen. we can also take the average of the four different dissociation energies of C—H bond of methane. C-8\N-ENGCHE\ECH4-1.p. Bond energy is also called the heat of formation of the bond. Example: I2(s) → I2(g) ∆H = 62. 396 = 99 Kcal/mol. to atoms or radicals in gaseous form.e. sublimation. This energy is dependent on the nature of the atoms present as well as the environment.e.THERMODYNAMICS 83 (vii) Heat of vaporization. • Enthalpy change for melting. the system gains energy from its surroundings. (viii) Heat of sublimation. It is also positive.e. • It is impossible to measure ∆H°298 directly. Bond Energy Bond energy is defined as the average energy required to break the bonds present in a molecule of gaseous compound. whereas this energy of separating the second H-atom from the residual OH group is 102 Kcal. i. for CH4 (methane) molecule. It is the heat change involved in converting 1 mole of substance from liquid to the gaseous state at its boiling point. For water the energy of separating a H-atom is 118 Kcal. 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. Highlights: • Enthalpy change is the exchange of energy between a reaction mixture (system) and its surroundings when the reaction takes place at constant pressure. the standard enthalpy change is represented by ∆H°298. the reaction is endothermic i. vaporisation are measured at m. the reaction is exothermic i. or b. Many values are determined indirectly using Hess’s law. • The present unit of ∆H is kJ mol–1.

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. H = E + PV and G = H – TS = E + PV – TS C-8\N-ENGCHE\ECH4-2. with- out producing some other effects in the system.. So. 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.5) Kcal.e. respectively. the total enthalpy change involved in these bond breaking and making gives the heat of reaction. second law of thermodynamics can be stated in some different important forms. H H   2C(g) + 6H(g) → 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 guides the conditions under which heat and work are interconvertible.3 + 6 × 98. (ii) Bond energy varies with the difference between the electronegativity of the two atoms.84 ENGINEERING CHEMISTRY Variation of bond energy (i) Bond energy varies with the size of the atoms. (b) It is impossible for a self-acting machine unaided by any external agency.1 kJ/mol. The engine must take up heat at higher temperature. For the conversion of heat into work two conditions must be fulfilled. = 670. to convey heat from a body at a low to one at a high temperature. Bond energy decreases as H—F > H—H > C—C > N—N > F—F.3 Kcal mol–1. i. (iii) Bond energy varies with the total environment of the molecule. 2. Example: Heat of formation of ethane is. (d) The energy of the universe is constant.PM5 84 . 1. From the above experience. Example: bond energy for H—F and H—Cl are 56. (a) It is impossible to convert heat completely into an equivalent amount of work. but the entropy approaches a maximum. Effect of temperature on free energy-(Gibbs-Helmholtz equation) We know. convert a portion of it into work and give up the rest of heat to a body at lower temperature. SECOND LAW OF THERMODYNAMICS Heat is readily available and man is interested to convert this heat energy to useful work. (c) All spontaneous processes tend to equilibrium. ∆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.5 and 43.

change of phase..e. the process will be spontaneous only when ∆H is greater than T∆S. 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. dq = dE + PdV ∴ dG = dq + VdP – TdS – SdT dq Again for reversible mechanical process dS = T ∴ dq = TdS ∴ dG = VdP – SdT FG ∂G IJ ∴ For an isobaric process dG = – SdT ∴ H ∂T K P =–S FG ∂∆G IJ ∴ H ∂T K p = – ∆S. the reaction attains equilibrium. vaporization. we get dG = dE + PdV + VdP – TdS – SdT We know. Hence. Imagine a very small change of a small amount of liquid vaporizing at C-8\N-ENGCHE\ECH4-2.e. (Clapeyron- Clausius equation) Change of phase taking place during freezing. the criteria for spontaneous processes are: (a) If ∆H is negative and ∆S is positive – ∆G becomes negative. etc. ∆H is neagtive. 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. which relates free energy and ethalpy changes at constant pressure.e. the reaction occurs if T∆S is positive and greater than ∆H. (b) If both ∆H and ∆S are negative and ∆H > T∆S.THERMODYNAMICS 85 Differentiating. (a) When a reaction is exothermic i. (c) If both ∆H and ∆S are positive and T∆S > ∆H. We know that if ∆G is negative the reaction takes place spontaneously and when ∆G = 0 i. ∆H is positive. (b) In endothermic process. We know G = H – TS ∴ ∆G = ∆H – T∆S FG ∂∆G IJ ∴ ∆G = ∆H – T H ∂T K p This is Gibbs-Helmholtz equation. ∆G has negative value and the reaction becomes spontaneous. and ∆S is positive.PM5 85 .. can be studied thermo- dynamically. Application of thermodynamics to phase transition i. (c) When ∆H is negative and ∆S is also negative. which are in equilibrium at a temperature T.

86 ENGINEERING CHEMISTRY equilibrium. Effect of pressure on boiling point. dT T(V2 − V1 ) Application of Clapeyron-Clausius equation 1. ∆P S − S1 ∆S or. Determination of latent heat.. = 2 = ∆T V2 − V1 V2 − V1 q Since. = .303R T1 T2 Q P2 L T2 − T1 LM OP or. P2 L 1 1LM OP P2 L LM 1 1 OP ln P = R T − T 1 1 2N Q or. dP q L ∴ = = (q = L = latent heat of vaporization) dT T V 2 T V2 RT Now. V1∆P – S1∆T = V2∆P – S2∆T. P RT 2 Assuming. the volume V1 of the liquid can be neglected as it is very small compared to the volume of vapor V2.PM5 86 .e. 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. V2) are in equilibrium.303R T1T2 . The drop in free energy of the liquid is –∆G1 and corresponding gain in free energy of the vapour is +∆G2. latent heat is constant and on integrating. 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. dP q We know = . log = N − P1 2. ∆S = T dP ∆S q ∴ = = dT V2 − V 1 T(V2 − V1 ) where q is molar heat of transition from one phase to another. as net ∆G = 0 ∴ ∆G1 = ∆G2 or. =L. i. log P = 1 2. V1) and vapor (Vol. Since the system is in equilibrium. for ideal gas PV = RT. This equation is the famous Clapeyron-Clausius equation. C-8\N-ENGCHE\ECH4-2. dT T(V2 − V1 ) When two phases of liquid (Vol. N Q Thus. dP q Thus. V = P dP LP ∴ = dT RT 2 dP dT or.

Example. 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). the energy required for the first reaction to occur is supplied by the second reaction which is coupled to it. So. 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. Planck enunciated the third law of thermodynamics as “the entropy of a solid or a liquid is zero at the absolute zero of temperature”. Mathematically.303 C p d log T (I) (II) Cp Cp T 1 2 O 10 20 30 log T T Fig.THERMODYNAMICS 87 3. THIRD LAW OF THERMODYNAMICS In 1912. Absolute value of entropy can be measured by determining the heat capacities (Cp) of a substance at different temperature.6 Graphical determination of entropy. 4. • Entropy and the third law—Third law can be used to determine the entropy of a substance. there is no disorder and hence the entropy of all pure substances at absolute zero is zero. These Cp values are plotted against T and can be extrapolated to T = 0. ∴ ST = z 0 T Cp 1 dT = z 0 T C p d ln T ∴ ST = z 0 T 2. ATP is a high energy molecule. Many reactions occur in nature which have ∆G = positive only when they are coupled with another reaction whose ∆G is much larger negative. S0 = 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. we have ST – S0 = z T 0 Cp T dT From 3rd law. Hence. so when in the C-8\N-ENGCHE\ECH4-2. At absolute zero temperature. kinetic energy of a substance is zero and it is present in a perfectly arranged crystalline state. Coupling of non-spontaneous reactions Those chemical/biological reactions only take place spontaneously for which ∆G = negative.PM5 87 .

• The entropy of the universe is increasing.PM5 88 . C-8\N-ENGCHE\ECH4-2. viscosity. • ∆G is zero for reaction at equilibrium. if the ∆G is negative the change is spontaneous. pressure. • ∆G is negative for a spontaneous reaction. Highlights: • Intensive property is independent of the amount of substance present in the system e. if ∆G is positive the process is non-spontaneous. we can calculate ∆G of the system. 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. surface tension. dT T(V2 − V1 ) 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. refractive index. • Hess’s law states: For a chemical process. etc. dS + dS′ = 0 For a spontaneous process. • Second law of thermodynamic states: It is impossible to convert heat completely into work. • A spontaneous process always has a net increase in entropy for the computation of the change of entropy. if ∆G is zero the initial and final states of the system will be at equilibrium. Thus. • ∆S for a spontaneous process is ∆S > 0. specific heat. the changes in entropy of both the system and the surrounding are to be considered when a system is in equilibrium. the amount of heat evolved or absorbed is the same whether the process takes place in one step or in several steps. temperature. • Third law of thermodynamics states: The entropy of a solid or a liquid is zero at the absolute zero of temperature.. • ∆G is positive for non-spontaneous reaction. dStotal > 0 When a reversible process is at equilibrium. the energy of glucose oxidation can be utilised to carry out other non-spontaneous reaction via ATP. • For a spontaneous process at a definite T and P.g. reactions with increasing enthalpy may also occur spontaneously. density. dStotal = 0 For any spontaneous irreversible process.88 ENGINEERING CHEMISTRY cyclic process ATP is hydrolysed to ADP. • Clapeyron-Clausius equation is: dP q = .

FG ∂G IJ µi = H ∂n K T. For the equilibrium. We have. chemical potential. dE = TdS – PdV 2. Just like temperature. dG = µ(II) dn – µ(I) dn But for equilibrium. T. It is to be noted that free energy is an extensive property but chemical potential is an intensive property. dG = – Sdt + VdP = O + VdP (at constant. (iii) G J = G (iv) G F ∂V IJ = – FG ∂S IJ H ∂T K H ∂V K V T H ∂T K H ∂P K P T . FG ∂T IJ = FG ∂V IJ . (i) H ∂V K H ∂S K S V (ii) H ∂P K H ∂S K S P F ∂P I F ∂S IJ . which have extensive applications in both physical and chemical phenomena.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 . ∴ µ(I) = µ(II) Maxwell’s Relations 1. that is why the study of chemical potential has become important. Applying the cross-derivative rule. G Therefore. we have FG ∂T IJ = – FG ∂P IJ . dA = – PdV – SdT 4. dG = 0. P . These four derivatives are very well known relations. µ = (for a pure substance). Chemical potential also has such a tendency.PM5 89 . pressure or electric potential it tends to equalise within all parts of a system. n j where nj represents the constant composition of a mixture. chemical potential of water in ice must be same in both the phases. T) ∴ ∆G = G2 – G1 = z 1 2 Vd P C-8\N-ENGCHE\ECH4-2. Thus. Chemical potential of an ideal gas at temperature. dH = TdS + VdP 3. Ice Water (I) (II) If dn moles are transferred from phase I to phase II. dG = VdP – SdT. It can be proved easily. n For a species i which is component of a mixture we can express its chemical potential µi as follows.

we increase the constituents by the same proportions ∆x.. We know. µ2 – µ1 = RT ln . n1 . T.90 ENGINEERING CHEMISTRY Applying this to one mole of an ideal gas (PV = RT).e. n .. C-8\N-ENGCHE\ECH4-2.(a) Now at constant temperature and pressure. n3 . µ1 becomes µφ0 if we apply the standard conditions i. We get. n1 . the complete differential will be given by.. n2∆ x and Ai. = ∑µi dni . the changed amounts of A1 are n1∆ x. T .. P1 Since G2 and G1 are molar free energies µ2 and µ1 respectively. FG ∂G IJ = V FG ∂G IJ = – S.. the free energy then will depend upon the quantities of the components. n j At constant temperature and pressure. ni F ∂G IJ F ∂G I dG = VdP – SdT + G GH dn JK H dn K 1 P. n 2 3 dn1 + 2 P.. T. pressure 1 atmosphere. this term is called the partial molal free energy of the component A2. n1. it is a function of T. µ = µφ0 + RT ln P or. Let us have a system containing n1 moles of A1. G = f (P. G = f (P.. G depends upon P. means that P. T . if we express partial molal free energies in terms of µ.PM5 90 . n3 . FG ∂G IJ FG ∂G IJ dT + FG ∂G IJ FG ∂G IJ dG = H ∂P K T.. T and all other moles are constant except n2. P2 G2 – G1 = RT ln P1 P2 or. n3 . T.. ni dP + H ∂T K H ∂n K P. of A2. FG ∂G IJ The term H dn K 2 P. that is.) If all the variables vary. under this convention the chemical potential µi for the ith component of the mixture is given by. then the free energy (G) of the system is given by. H ∂P K T. T) if we take an open system in which the quantities of the components may vary. ni H ∂T K P. ni∆x.. n 2 3 dn1 + H ∂n K 2 P. T and V.. n2 moles of A2. T. ni 1 P.. T .T = µ1 dn1 + µ2 dn2 + µ3 dn3 + . n2 . Gibbs-Duhem Relations The free energy G of a system is a state function. F ∂G I GH dn JK i P. G = G0 + RT ln P where µ0 is the standard chemical potential but not a constant.. etc. we have. we get. n .. n3 dn2 . n1 . dn2 + . dGP. As they are interrelated we can write for a fixed composition of a system...

therefore it will increase by the amount G∆x hence. = 0 We have thus three useful relations for chemical potentials with the composition of the system...... So.e.. free energy change for the reaction (i) is given by ∆G = Gproducts – Greactants = (cGC + dGD) – (aGA + bGB) .. G = µ1n1 + µ2n2 + .. dG = G∆x So. = ∑µn (ii) dG = µ1dn1 + µ2dn2 + µ3dn3 + . dG = µ1n1∆x + µ2n2∆x + . PC and PD are GA....(ii) 0 where G = integration constant known as standard free energy i. = ∑µdn (iii) 0 = n1dµ1 + n2dµ2 + n3dµ3 + .T P N PV = RT or V = P Q Integrating both sides. + µini + .. PB. = ∑µini Now. dni = ni ∆x Since.(b) Subtracting equation (a) from (b) n1dµ1 + n2dµ2 + n3dµ3 + .. + µini∆x + . + µini∆x + . G is an extensive property. G∆x = µ1n1∆x + µ2n2∆x + .THERMODYNAMICS 91 Therefore. B.. GC and GD.(i) We. (dG)T = V. G = H – TS = E + PV – TS [Q H = E + PV] So. or.dP – S..PM5 91 .. 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 aA + bB → cC + dD ... dn2 = n2 ∆x. we have.. Again... Free energy change for one mole of any gas at a constant temperature is given by: dP LMQ RT OP dG = V. know.dP. respectively.. dG = (µ1dn1 + µ2dn2 + µ3dn3 + ..) .. (i) G = µ1n1 + µ2n2 + µ3n3 + . GB. = ∑ndµ These relations are commonly known as Gibbs-Duhem relations.) + (n1dµ1 + n2dµ2 + n3dµ3 + . complete differentiation of this equation gives us.dP = R.. Then.. Let the energy/mole of A. Hence.dT At constant temperature.(iii) C-8\N-ENGCHE\ECH4-2. C and D at their respective pressures PA. G0 = G when P = 1 atm.... dq = dE + PdV and dS = dq/T ∴ dG = V.. dn1 = n1 ∆x... dP ∫ dG = RT P z G = G0 + RT ln P . dG = dE + PdV + VdP – TdS – S dT.

It is of great importance as it gives a quantitative relation for free energy change accompanying a chemical reaction.92 ENGINEERING CHEMISTRY Substituting the values of GA. Calculate the increase in internal energy per mol of water assuming water vapour to behave as an ideal gas. GC and GD from (ii) and (iii).(v) Combining (iv) and (v). Highlights: • ∆G° = – RT ln Keq when pressures of reactants and products are one (i..e.. at equilibrium. ∆G0 = – RT ln MN (P ) (P ) PQ A a B b eq ∆G° is a constant as G is a state function ∆G° is the difference in free energy between the products and the reactants. – ∆G is called the Affinity of the reaction. ∆E = q – w = 9648 – 746 = 8902 cal mol–1 = 8. • The above expression gives free energy change for a reaction. we have ∆G = (cGC0 + cRT ln PC + dGD0 + dRT ln PD) – (aGA0 + aRT ln PA + bGB0 + bRT ln PB) (PC ) c (PD ) d = (cGC0 + dGD –0 aGA0 – bGB0) + RT ln (PA ) a (PB ) b (PC ) c (PD ) d So. C-8\N-ENGCHE\ECH4-2. Sol. ∆G = ∆G0 + RT ln . we have (PC ) c (PD ) d ∆G = – RT ln Keq + RT ln (PA ) a (PB ) b (PC ) c (PD ) d or. One gm of water requires 536 calories of heat for conversion to steam at 100°C. q = 536 × 18 cal mol–1 or.. GB.PM5 92 . According to first law of thermodynamics q = ∆E – w Here w = PV = RT = 2 × 373 cals = 746 cals. ∆G = 0 LM (P ) (P ) OP C c D d So.. LMwhere K = (PC ) c (PD ) d OP = – RT ln Keq MN eq a (PA ) (PB ) b PQ ∴ ∆G0 = – RT ln Keq . • The above relation shows that equilibrium constant (Keq) can be calculated from a table of standard free energy values... – ∆G = RT ln Keq – RT ln .(vi) (PA ) a (PB ) b This expression (vi) is called Van’t Hoff reaction isotherm. Example 1.(iv) (PA ) a (PB ) b Now. P = 1).902 Kcal mol–1.

and ethane are 337.8 Kcal mol–1 at a definite temperature. Sol. hydrogen. (Given qv at 200°C is 97000 cals).PM5 93 . mols of gaseous reactant. Calculate the heat of combustion at constant pressure of carbon. C-8\N-ENGCHE\ECH4-2. ∆E = q – w 990 × 4. C(s) + O2(g) = CO2(g) Here qv = – 97000 cal. after absorbing 990 cals. Here. ∆n = 1 – 2 = – 1. w = P(V2 – V1) = PV2 [Q V1 = 0] = nRT = RT [Q n = 1] 8. Example 4. qp = qv + ∆nRT. Calculate the internal energy change of the system. So. 372.36 × 10 9 w = 8.314 × (273 + 27) = kJ. ∆H = ∆E + ∆nRT. Example 6. 68. qp = qv (As n2 = n1) Example 5. We have. Mg(s) + 2HCl(g) → MgCl2(s) + H2 (g) (Given ∆H = – 109 Kcal).4942 kJ. We have.836 = 3. Zn + H2SO4 → ZnSO4 + H2↑ 1 mol.314 × 300 = 8. Sol.158 – 0.36 × 109 ergs.36 × 109 ergs = kJ = 0.THERMODYNAMICS 93 Example 2.836 kJ 10 7 × 10 3 ∴ ∆E = 4. n1 = 1 mols of gaseous product. Sol. Heats of combustion of ethylene. = – 97000 + 0 × RT = – 97000 cals. n2 = 1 ∴ ∆n = n2 – n1 = 0. We know.332 kJ. Calculate the heat of reaction of C2H4(g) + H2(g) → C2H4(g) at that temperature.2 Here q = 990 cals = kJ = 4. 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. of heat. The amount of work of a system is 8. Calculate the value of ∆E for the reaction at 500 K. Sol. 1000 = 2. Calculate the work done by the following reaction at 27°C.2. Example 3.3.13 10 3 8. Here.

H2O(g) → 2H(g) + O(g). H2O(g) → H2(g) + O (g) ∆H = 58 Kcal. We know that. 2 2 1 1 (i) + (ii) – (iii) gives = H2(g) + O2(g) + H2O(g) → 2H(g) + O(g) + H2(g) + O2(g) 2 2 i. So. ∆H = 120 Kcal . Example 7..8 Kcal. Calculate O—H bond energy from the following heats of reactions. and for breaking of these two bonds energy requirement is 222 Kcal. 2 2 7 (iii) C2H6 + O → 2CO2 + 3H2O.(iii) 2 2 Sol. C-8\N-ENGCHE\ECH4-2. Given the standard enthalpies of combustion: ∆H°C (C3H8) = – 2220 kJ mol–1 ∆H °C (C) = – 393 kJ mol–1 ∆H°C (H2) = – 286 kJ mol–1. ∆H = 68. Calculate the enthalpy of formation of propane (C3H8 ) at 298 K. ∆H = 104 Kcal .7 Kcal. 2 2 1 From equation (iii). ∆H = – 337. ∆H = 222 Kcal. ∴ O—H bond energy is 111 Kcal. Example 8...94 ENGINEERING CHEMISTRY Sol.7 Kcal) ∴ C2H4 + H2 → C2H6.. (i) C2H4 + 3O2 → 2CO2 + 2H2O..PM5 94 . From equation (ii) 1 O (g) → O(g).3 Kcal. H2(g) → 2H(g). ∆H = 60 Kcal. 1 7 C2H4 + 3O2 + H2 + O + 2CO2 + 3H2O → 2CO2 + 2H2O + H2O + C2H6 + O2 2 2 2 (∆H = – 32. there are two O—H bonds in a molecule of water. ∆H = – 372. (iv) 2CO2 + 3H2O → C2H6 + O. ∆H = + 372. ∆H = – 32.e. ∆H = – 58 Kcal . for dissociation of one O—H bond energy requirement is 222 ÷ 2 = 111 Kcal. (ii) and (iv) we have..2 Kcal.(i) O2(g) → 2O(g).(ii) 1 H2(g) + O (g) → H2O(g). 2 2 Adding the equations (i). 1 (ii) H2 + O → H2O. Given.8 Kcal 2 2 7 or..

Basis = 1 g. ∆H2 – ∆H1 = ∆Cp(T2 – T1) ∆H150° – ∆H100° = – 0.1 Cp for water = 1.1 cal mol–1. Example 9.PM5 95 .THERMODYNAMICS 95 Sol. T2 – T1 = 423 – 373 = 50 K. respectively for the interval. We have. Sol. ∆H150° =?. = 3 × (– 393) + 4 × (– 286) kJ mol–1 = – 2323 kJ mol–1 ∆H3 = ∆H °C = – 2220 kJ mol–1 Hence.45 – 1 = – 0. If average Cp for water and steam are 1 cal g–1 and 8. A thermodynamic cycle is drawn: H1 3C(s) + 4H2(g) + 5O2(g) C3H8(g) + 5O2(g) 3 H H 2 3CO2(g) + 4H2O(l ) According to Hess’s law – ∆H1 = ∆H2 – ∆H3 ∆H1 = ∆H °f (C3H8) ∆H2 = 3 ∆H °C (C) + 4 × ∆H °C (H2). ∆H °f (C3H8) = (– 2323) – (– 2220) kJ mol–1 = – 103 kJ mol–1.55. Calculate the enthalpy change of transition from yellow P to Red P from the given thermochemical cycle. ∆H100° = 538 8. Example 10. 18 ∆Cp = 0. calculate the latent heat of water at 150°C.55(50) C-8\N-ENGCHE\ECH4-2. The latent heat of evaporation of water at 100°C at constant pressure is 538 cal g–1. Sol. Thermochemical cycle: HT ( H1) Yellow P Red P 3 ls 23 H H ca 86 2 13 ca 21 ls H3PO4 According to Hess’s law – ∆HT = ∆H2 – ∆H3 = 2386 – 2113 cals = 273 cals. Cp for steam = .

5 cal g–1.26 J mol–1.303 RT ln P 2 2 = 2. T2 = 100°C = 373 K.19 × 32 = = = 4.PM5 96 . Sol. (273 − 182. 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.66 kJ. Calculate change of entropy in isothermal reversible expansion of one mole of an ideal gas.303R T1 T2 N Q C-8\N-ENGCHE\ECH4-2. Given L = 12. Here.5 cal g –1. T1 = ?.5 × 18 cal mol–1 = 9819 cal mol–1.33 J mol–1.96 ENGINEERING CHEMISTRY ∆H150° = ∆H100° – 0. Given latent heat – 19. Calculate the change of molar entropy during melting of ice. Example 11. Sol. From the integrated form of Clausius-Clapeyron equation. Example 12.987 cal K–1 mol–1.55 × 50 = 510. q = W = RT ln V1 qrev V2 dS = = R ln [Positive quantity] T V1 Example 15.19 J g–1. R = 1. We know that ∆E = 0 V2 Therefore. dS = T 12.31 × 298 log 1 = 1. dS = T 19.19 × 32 12. P1 Sol.5 cal g–1 = 545. At what temperature will water boil when the atmospheric pressure is 528 mm Hg? Given latent heat of vapourisation of water is 545. P1 = 528 mm of Hg. Maximum work = 2. we have P2 ∆H v 1 − 1 LM OP log P = 1 2.55 × 50 = 538 – 0. qrev Sol.9°C).1 Example 14.14 × 18 = = 1.14 J g–1. P2 = 1 atm = 760 mm of Hg.p.303 × 8. Calculate the change of molar entropy during the conversion of liquid oxygen to oxygen gas at its b. qrev Sol. 273 Example 13.9) 90. (– 182. Hv = 545.66 × 103 J = 1.

7 J.THERMODYNAMICS 97 760 9819 LM 1 − 1 OP ∴ log 528 = 0. ∆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. 300 7 Example 19. P1 = 1 atm.7 J. Thus find the value of Kp for the following reaction at 37°C. (ii) Now. internal energy will decrease by an amount of 185 cal. Calculate q. 2 2 2 Consider the reaction to be independent of heat and temperature. q = ∆E + W or. Example 16.7 J = 1012. 363 1 ∴ ∆S = 7 ln + 2 × ln = – 2. = 10 L atm × H 0. ∆E = 0.7 J.25) cal [Q 1 lit. work done by system.PM5 97 . from 1st law. Work done in an irreversible process is given by W = P(V2 – V1) = 2(20 – 10) = 20 lit.987 N T 373 Q 1 or.303 × 1. Sol. = (20 × 24. But. Example 17.atm. atm = 24. C-8\N-ENGCHE\ECH4-2.5577 cal deg–1. A gas during expansion from 10 litre to 20 litre under 2 atmospheric pressure absorbs 300 cal. (iv) ∆H = ∆E + P∆V = 0 + 1012. ∆E = q – W = (300 – 485) cal = – 185 cal.2 Kcal. ∆E = 0 or q = W.49 × 10–2 atm–1.25 cal] = 485 cal. 1 3 N (g) + H2(g) NH3(g) + 11. W. For one mole of an ideal gas the entropy change in a reversible process is T2 P ∆S = Cp ln + R ln 1 T1 P2 Here. Pressure is increased reversibly upto 7 atm and temperature is incremented to 90°C. T1 = 363 K. Cp = Cv + R = (5 + 2) cal = 7 cal. Find the change in internal energy.0821 L atm K (iii) q = W = 1012. T1 = 27°C = 300 K. W = P(V2 – V1) = 1 atm (20 – 10) dm3 = 10 atm dm3 = 10 atm L FG 8. heat energy. The initial temperature and pressure for one mole of an ideal gas is (Cv = 5 cal) 27°C and 1 atm. for a reversible process. The value of Kp (equilibrium constant) of the reaction regarding ammonia synthesis at 27°C is 3.1582 = 2. Sol. P2 = 7 atm. From the 1st law of thermodynamics. (i) Since operation is isothermal and the gas is ideal so. Calculate the entropy change for the process. So.314 J IJ = 1012. T2 = 90°C = 363 K. Example 18.

Q. we have K P2 LM ∆H T2 − T1 OP ln K P1 = R T1T2 N Q Here. T1 = 27°C = 300 K.9038 × 10–2 atm–1. See text page 66. When does the entropy of a substance become zero? Ans. State intensive property of a system. SHORT QUESTIONS AND ANSWERS Q. they occur at atmospheric pressure. 8. it can be stated as the net energy of the universe remains constant. 5. Ans.PM5 98 . 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. See text page 71. Q. respectively. See text page 85. Derive Clapeyron-Clausius equation and mention its applications. Q. 4. K P2 = 1. R = 1. ordered state and at the temperature of 0 K. From Van’t Hoff equation. T2 = 37°C = 310 K. 3. C-8\N-ENGCHE\ECH4-2.e. Q. Why is enthalpy more useful than internal energy? Ans. See text page 84. in most of the reactions. 1.49 × 10 −2 = N 2. K P2 = ? ∆H = – 11. State First law with mathematical expressions. Q. 7. Internal energy and ethalpy of a system are measured by keeping the volume and the pressure constant..987 cal deg–1 mol–1. See text page 68. What is enthalpy? Ans. Ans. K P1 = 3.987 300 × 310 Q or. 6.303 × 1. Q. K P2 ∆H T2 − T1 LM OP ∴ log K P1 = 2. Since. Alternatively. 2.2 Kcal = – 11200 cal. Q.49 × 10–2 atm–1. The entropy of a substance becomes zero when the substance is perfectly crystalline i.303R T1T2 N Q K P2 − 11200 LM 310 − 300 OP log 3. Derive Gibbs-Helmholtz equation and mention its significance. Why? Ans. Ans. The molar heat of sublimation of a solid is always greater than the molar heat of vaporization of the corresponding liquid. so enthalpy is more useful than internal energy. Ans.98 ENGINEERING CHEMISTRY Sol.

disorder of the system.e. ∆E = 0. 9.e.. 10. (c) PV = Constant for such process. Entropy is the measurement of randomness i. W = – ∆E So. Q.. then to what extent or in which direction would the transformation take place.THERMODYNAMICS 99 Q. 1 2 Q.. Write the expression for work obtained in an isothermal irreversible reversible process. Wirr = P2(V2 – V1). Apply the first law of thermodynamics for the following cases (a) adiabatic change. dS is defined as dS = reversible . (b) Change in internal energy does not take (b) Internal energy of the system changes. What do you mean by entropy? Ans. The first law does not indicate: (i) Whether the transformation of intrinsic energy of a substance would occur at all. W = nRT ln V = nRT ln P . For cyclic process the internal energy does not change at all. V2 P1 Ans. ∆E = q – W or ∆E = 0 – W [Q q = 0] So. surrounding does not occur. T Q. Ans. from first law. Ans. Q. Isothermal change Adiabatic change (a) Temperature of the system remains (a) Heat exchange between the system and the constant. from first law. 15. i. Its change q i. So. 12. See page 69. C-8\N-ENGCHE\ECH4-2. 13. place. What are the limitations of first law of thermodynamics? Ans.PM5 99 . (ii) If it so occurs. Distinguish between adiabatic and isothermal changes. 14. (a) For adiabatic change q=0 So. the work done by the system is equal to the decrease in internal energy. 11. in cyclic process the work done by the system is equal to the amount of heat absorbed by the system. Q. (b) cyclic process. Ans. in adiabatic process. So. Ans.e. Q. ∆E = q – W or 0=q–W [Q ∆E = 0] or W = q. (c) PVγ = constant for such process. Write down the expression for maximum work done in an isothermal reversible process. Define reversible and irreversible processes.

27. 22. It means that if a mole of H2 and mole of O2 both at unit pressures at constant 2 temperature (25°C). EXERCISES 1. 25. It is based on which law? Explain.65 Kcal. Q. 20. See page 71. See page 81. See page 84. Q. 82. (iii) Define the concepts of Helmholtz free energy and Gibb’s free energy. State relation between them. (ii) Derive Clapeyron-Clausius equation and state its applications. See pages 78 and 79. (iv) What is the significance of entropy? What is the criteria for spontaneity? (v) Derive Kirchoff’s equation. What do you mean by a cyclic process? Ans. Describe a relation be- tween the two. 1 Q.PM5 100 . State with example the significance of Hess’s law. Explain that Joule-Thomson experiment is isoenthalpic. Ans. State the law of Laplace and Lavoisier. Define Cp and Cv. Ans. the decrease in free energy is 54. 18. Ans. Q. See page 70. State Maxwell’s relations. See page 80. What do you mean by ∆G° for the reaction H2 + O = H2O is – 54. 17. 19. Ans. Q. 24.65 Kcal 2 2 at 25°C? 1 Ans. Ans. 23. (b) heat of combustion. Ans. How can you measure a spontaneous system with the help of free energy? Ans. State the second law of thermodynamics. Ans. Ans. Define (a) heat of formation. Q. See page 72. (c) heat of neutralisation. See text page 79. Define work function and free energy. See page 81.100 ENGINEERING CHEMISTRY Q. Q. C-8\N-ENGCHE\ECH4-2. 21. 16. See page 89. What is inversion temperature? Ans. Q. Alternatively it can be stated as the net entropy of the universe tends to a maximum. See page 73. Q. Short Questions: (i) Derive an expression for the variation of heat of reaction with the temperature with the help of first law of thermodynamics. Q. Q. 26.

(ix) Entropy of a system changes during melting. (vii) Isothermal process. ∆H > ∆E. (viii) Adiabatic process. (iii) Extensive properties. (ii) Closed system. (ix) State Hess’s law and explain how it can be used to calculate the heats of formation. (iv) Intensive properties. During melting it (a) decreases (b) increases (c) remains unchanged. 4. (viii) All living systems are (a) adiabatic systems (b) Closed systems (c) Open system. (c) Strong acid and strong base react completely. (a) What is Joule-Thomson effect? (b) Prove the constancy in Joule-Thomson expansion. Derive an expression for entropy for an ideal gas. 7. (a) What do you mean by thermodynamics? (b) Explain the terms— (i) Isolated system. 10. Objective Type Questions: (i) Which is a state function? (a) q (b) W (c) q – W (d) q/W. (vi) The expression of first law of thermodynamics is (a) q = ∆H – W (b) ∆H + P∆V = ∆E (c) ∆E = q – W. C-8\N-ENGCHE\ECH4-2. (d) Explain the relation: S = k ln w. boiling point of water (a) remains unchanged (b) increases (c) decreases. Show that entropy change in an irreversible process is positive. (b) Define molar heat capacities. (vi) Irreversible process. (ii) Heat of combustion. (c) Give characteristics of entropy. 6. (x) On increasing pressure. (b) Only H+ and OH– ions react in each case. (v) Reversible process. (a) What do you mean by entropy? (b) Give physical significance of entropy. Derive an expression for the work done during reversible isothermal expansion of an ideal gas. 9. Derive Kirchoff ’s equation. (xi) State func- tion. (c) Give the mathematical expression for first law of thermodynamics. (iv) When is a system in equilibrium? (a) ∆G is zero (b) ∆S is minimum (c) ∆G is maximum. (a) Show that for a gaseous expansion. (vii) All naturally occurring processes proceed spontaneously to (a) increase in free energy (b) decrease in free energy (c) decrease in entropy. 3. (ix) Isochoric process. (c) What do you mean by inversion temperature? 5. (x) Why is entropy a state function? 2. (v) Heat of neutralization of a strong acid with a strong base is constant since (a) Salts are formed.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. (iii) Which is an intensive property? (a) Pressure (b) Time (c) Volume. (x) Isobaric process. (ii) Which is an extensive property? (a) Temperature (b) Viscosity (c) Volume. 8.PM5 101 . (c) Prove that Cp – Cv = R.

[Ans. 790 cals] 4. 21. 326. (vi) Heat of fusion. 22. are heated inside a gas cylinder to 100°C 3 assuming it to behave ideally and having Cv = R. cals.T. (b) Mention the applications of Hess’s law.05 and – 68. (1440.1 cals.788 × 107 ergs] 5. 133. Long Questions 1..32 Kcal. Considering the gas to be an ideal find out the work obtained in this case. During isothermal reversible expression of 4 g of helium gas at 27°C the pressure reduces from 10 atm to 1 atm. [Ans. Calculate the heat of oxidation of ethyl alcohol to carbon dioxide. Derive Maxwell’s relation and state its usefulness.. 20. 1381. Calculate the work done in calories. 15. The heat of formation of ethyl alcohol is – 66.01 × 106 ergs) 2.. [Ans. (c) Explain the terms (i) Heat of reaction. q and w per mole. Find the internal energy change of the system. lL + mM + . Entropy change for the mixture of gases can be represented by – ∆Smix = – nR Σ xi ln xi where xi = mole fraction of gas. 223. . Consider the gas to behave like an ideal. (v) Heat of solution. 17. What do you mean by Van’t Hoff reaction isotherm? Derive an expression for the reaction isotherm of the general reaction aA + bB + . (viii) Heat of sublimation. 13.102 ENGINEERING CHEMISTRY 11. heat from the surrounding.6 Kcal] C-8\N-ENGCHE\ECH4-2. The heats of formation of CO2 from diamond and graphite are – 94500 and – 94050 cal. respectively. (iii) Heat of neutralisation. (iv) Heat of formation. (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. What is the enthalpy change in the transformation of diamond to graphite? [Ans. g–1. (a) State Hess’s law. – 4. when the heats of formation of carbon dioxide and liquid water are given as – 94.PM5 102 .. – 450 cal] 7. (b) Give the significance of Gibbs-Helmholtz equation. How can you determine the bond energy and lattice energy with the help of Hess’s law? 16. Derive an expression for chemical potential at a temperature T in terms of P. When ice melts at 0°C. Calculate ∆E and ∆H if 10 litres of helium at N. (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. 1440. Derive Gibbs-Duhem relations.8. A system performs 8.36 × 109 ergs work after absorbing 990 cals. [Ans. Derive Clausius-Clapeyron equation. 12. the latent heat of fusion is 80 cals.8 cals] 6. 2. 19. (ii) Heat of combustion. 1440 cals. The density of ice is 0. (a) Derive Gibbs-Helmholtz equation. The volume of a 45 g nitrogen gas is expanded from 5 litre to 10 litre at 25°C isothermally and reversibly. (vii) Heat of vaporisation.4 Kcal.P. Calculate ∆E. [Ans. Show that entropy change for an irreversible isothermal expansion of an ideal gas is positive. 18.1 cals] 2 3. ∆H.82 and of water of unity.

39.03 LM2000 − 20000 OP ergs W = 2. ∆W. 2 ∆H f (CO2 .5 cal/°K. Calculate the free energy change of g mole of SO2 at 25°C and 10 atm pressure.1 eV] 18. [Hint. Evaluate the heat of formation of methyl alcohol. From the following bond enthalpies calculate ∆H for the reaction.p. 760 mm Hg] C-8\N-ENGCHE\ECH4-2.0 kg of benzene at 30°C. Calculate the entropy change in vaporisation of ether. Bond energy H—H = 435. [Ans. a = 3. [Ans. – 70. ∆A = – 1. What is the inversion temperature of the gas? [Ans. H2 + Br2 → 2 HBr.000 2 2 1 H2 + O = H2O + 68. – 108. Calculate the work done if a = 1. ∆A and ∆G for vaporisation of 2 moles of benzene (b. 153080 cals] 9. 0.03 + 1. [Ans.3 kJ mol–1. The average latent heat of vaporisation of water is 546 cal g –1 within the temperature range 90°C – 100°C. It was allowed to expand isothermally against a constant external pressure of one atmosphere. [Ans. Find the change in entropy when 1 kg of benzene at 10°C is mixed with 4.65 Kcal. (Ans.PM5 103 . [Ans. Br—Br bond energy = 192. [Ans.] 11. 21. respectively. Given. Calculate ∆S.75 eV] 20. ∆U. ∆S = 44.4 Kcal] 15. 1. ∆G and ∆H for a particular reaction at 127°C are – 12 Kcal and 17. = 353.043 litre mol–1. W = RT ln V2 − b +a LM1 − 1 . – 13. – 17120 cals] 10. Given.24 kJ mol–1. – 57040 cal] 14. Isothermally at 27°C one mole of a van der Waal’s gas expands reversibly from 2 litres to 20 litres. OP V1 − b N V2 V1 Q 20 − 0.9879 eV] 17.303 × 8. The heat of combustion of methyl alcohol is – 173.2 K and G = 101 cal g–1) [Ans.5 Kcal. 1.5 Kcal.42 × 1012 dynes cm 4 mol–1 and b = 30 c.THERMODYNAMICS 103 8. The vapour pressure of water at 90°C is 530 mm Hg. Find heat of formation of caustic soda from the following data: 1 Na + H2O = NaOH (aq) + H + 98.300. boiling point = 35°C. ∆G = 0. Calculate the heat of formation of benzene given that the heats of combustion of benzene. [Ans. carbon and hydrogen are 754300 cals.380 2 2 NaOH + water = NaOH (aq) + 13. Find out ∆S. ∆H. heat of benzene is 0. [Ans. g) = – 94050 cal. ∆G°298 = – 71.59 litre2 atm/mol–2 and b = 0.42 × 1012 N20000 × 2000 Q = 5677 × 107 ergs.8 Kcal mol–1.c mol–1. L = 6500 cal mol–1.43 Kcal/mol–1] 19. 0. The van der Waal’s constant for CO2. l) = – 68320 cal. Calculate the vapour pressure at 100°C. 94380 cals and 68380 cals.5 kJ mol–1.31 × 107 × 300 log 2 − 0. 0] 12.5 Kcal. [Ans. The sp.86 kJ] 13. Calculate ∆Q. H—Br bond energy = 368. 2036 K] 16. 70 g of nitrogen gas was initially at 50 atm and 25°C. Given. ∆H(H O.

Modern techniques have been developed to study the reaction rate which gets completed in milliseconds or even in microseconds. For a reaction → aA + bB cC + dD rate of reaction.. x = concentration of the product. (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 rate of a reaction can also be determined by the increasing concentration of the products in unit time. we know that the rate of reaction is dependent on the active masses of reacting substances. Actually active mass means ‘molar concentration’. we can predict how far the reaction would go. But there are several other reactions where the rate can be easily measured. When [A] = [B] = 1 then. k is a constant known as rate constant or specific reaction rate. The passage towards equilibrium takes some time which may be almost instantaneous or very long. the rate constant is called specific reaction rate. [B]b where [A] and [B] are the concentrations of the reactants at that instant.e. 104 . i. But can say nothing about how fast the equilibrium will attain. In this case. Highlights: • Higher the value of k higher the reaction rate. dc dx • Mathematically r = – = dt dt where c = concentration of the reactant. the rate constant will express the rate of the reaction. k = r. As for example: CH3COOC2H5 + H2O → CH3COOH + C2H5OH 2H2O2 → 2H2O + O2 Velocity of Reaction From law of mass action. [A]a . The velocity of a reaction is not same even at constant temperature. Every chemical reaction has a definite velocity at a definite temperature. • Reaction rate is determined by the decreasing concentration of the reactants in unit time. 5 Reaction Dynamics/Chemical Kinetics INTRODUCTION From the study of chemical equilibrium involving law of mass action.

for a reaction: aA + bB → Products rate of the reaction (r) = k . As for example 2HI = H2 + I2 For this reaction. So. [A]a . In the experimentally determined rate equation.PM5 105 . So it is a first order reaction. the molecularity is ‘two’. Molecularity of a Reaction The minimum number of molecules. C-8∴N-ENGCHE∴ECH5-1. So. atoms or ions taking part in a chemical reaction is known as molecularity of the reaction. one molecule is needed and hence the molecularity is one. [B]b. we should take into account the ‘order’ and the ‘molecularity’ of a reaction. the rate equation will involve the concentration of the reactants. [H2O2] Here we see rate is proportional to the first power of the concentration of H2O2. Therefore. Table 5.REACTION DYNAMICS/CHEMICAL KINETICS 105 To consider the rate of a reaction. Again for the reaction: 2H2O2 = 2H2O + O2 But the reaction can be written as H2O2 = H2O + O So. the order of the reaction will be = (a + b). • The order of a reaction will be determined by the power terms of the concentrations of the rate equation. [HI]2 2 (ii) H2 + I2 = 2HI r = k . As for example. for decomposition of H2O2. minimum two molecules of HI will be required. Order of a Reaction The rate of reaction will definitely depend on the concentration of the reactants. [H2][I2] 2 (iii) CH3COOC2H5 + NaOH r = k[CH3COOC2H5] [NaOH] 2 = CH3COONa + C2H5OH Highlights: • The number of molecules of the equation for the chemical change has got no relation with the order of a reaction. The experimentally determined rate equation for the decomposition of H2O2 is: r = k . • The order of a reaction may be zero or fraction. the powers of the concentration terms are added to get the order of a reaction.1 Reactions Experimentally determined Order rate (i) 2HI = H2 + I2 r = k .

106 ENGINEERING CHEMISTRY Highlights: • For the reaction 2N2O5 = 4NO2 + O2. are called first order reactions. a− x Integrating we have. Let the reaction be A → Products. where the experimentally determined rate of the reaction is dependent on the first power of the concentration of the reactant. Therefore. a = initial concentration of A. [NO]2 [O2] So. both the order and the molecularity of the reaction are three. the rate equation will be dx = k . The observed rate = k . • For the reaction BrO3– + 5Br– + 6H+ = 3Br2 + 3H2O The observed rate = k . [CO] [Cl2]1. dc If c be the concentration.PM5 106 . (a – x) x At time ‘t’. – ln (a – x) = kt + z where z = integration constant when t = 0.5 and the molecularity is 2. the order of the reaction is one and the molecularity is two. x=0 Then. – ln (a – x) = kt – ln a a or ln = kt a– x C-8∴N-ENGCHE∴ECH5-1. [BrO3–] [Br–] [H+]2 So. the order of the reaction is 2. then the rate of the reaction = – = kc. (a – x) dt dx or = k . – ln a = z So. the order of the reaction is four but the molecularity is twelve.5 So. dt where k = rate constant. • For the reaction CO + Cl2 = COCl2 Rate = k . • 2NO + O2 = 2NO2 Rate = k . dt. Mathematical Formulation of First Order Reaction The reactions. [N2O5] So. x = concentration of the product at time t.

PM5 107 . 1 a (ii) k = . it is purely a dimensionless number. 2. ln a/(a – x) k The half-life of a first order reaction can be calculated 1 a LM aOP t1/2 = k .693 = . c • If we put a – x = c i. ln a– a Nx= 2 Q 2 1 = .e.. log c = + log c0 2. k k (v) For complete reaction x = a. ln 2 k 2. k is change of fraction of reactants in unit time.303t −k ∴ log c is plotted against ‘t’ we get a straight line with a negative slope = . then the equation x = a(1 – e–kt) will be a = a(1 – e–kt) ∴ t = infinity. t a– x • The rate equation can be written as (a – x) ln = – kt a a– x or = e–kt a or (a – x) = a .303 C-8∴N-ENGCHE∴ECH5-1. for any unit of a– x concentration. t a– x So. • The above equation expresses a number of characteristics of a first order reaction— a (i) is a common ratio. log .REACTION DYNAMICS/CHEMICAL KINETICS 107 1 a or k= . we have. unit of k will be time–1. concentration at any time ‘t’ and a = c0.303 a = . So. log10 2 = . 1 t = . ln . e–kt –k Therefore. a first order reaction is never completed. dc dc / C fraction of reactants (iii) k=– C=– = dt dt time So. ln t a− x 2. (iv) From the equation. the value of k will be same. So.303 0. e–kt or x = a(1 – e–kt). kt = ln 0 c ∴ c = c0 .

108 ENGINEERING CHEMISTRY 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 (ii) Isomerisation (gas phase) (a) CH2CH2  CH3CH = CH2 propylene CH2 cyclopropane (b) CH  CH 2 → CH2 = CH—CHe = CH2   1. Let. the reaction be represented by. are called second order reaction. identical or different.PM5 108 . CH  CH 2 Cyclobutene (iii) Decomposition (solution phase) 1 (a) H2O2 → H2O + O2 2 COOH O2N NO2 O2N NO2  (b) NO2 NO2 (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. A + B → C + D Initial concentration of A = a Initial concentration of B = b C-8∴N-ENGCHE∴ECH5-1. take part and the rate of the reaction is proportional to the concentration of each of them. 3-butadien.

303 a(b – x) = log (b – a)t b(a – x) If.PM5 109 . a = b. then we can write.e. concentration of both the reactants are equal i. initially. x = 0 ∴ ln =z a b–x b ∴ ln = k(b – a)t + ln a– x a b (b – x) b(a – x) ∴ – k(b – a)t = ln – ln = ln a (a – x) a(b – x) b(a – x) a(b – x) or k(b – a)t = – ln = ln a(b – x) b (a – x) 1 a(b – x) ∴ k= ln (b – a)t b(a – x) 2.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] dx or = k(a – x) (b – x) dt dx 1 1 – 1 LM dx OP or k dt = (a – x)(b – x) = b– a a– x b– x N Q ∴ z 1 FG H 1 – 1 b– a a– x b– x IJ K dx = k dt z or 1 z FG 1 – 1 IJ dx = k dt b – a H a – x b – xK z or 1 L M z1 b– aN a– x dx – 1 zO dxP = k dt b– x Q z 1 or [– ln (a – x) + ln (b – x)] b−a = kt + z (integration constant) b–x or ln = k(b – a)t + z a– x b At t = 0.. dx dx = k(a – x)2 or = k(b – x)2 dt dt C-8∴N-ENGCHE∴ECH5-1.

2 = × = conc–1 . c a c a Characteristic of a Second Order Reaction (i) Time of half reaction 1 x 1 a/ 2 1 . z= a 1 1 1 x ∴ kt = – or k = . Examples of a Second Order Reaction (i) Decomposition (gas phase): (a) 2HI → H2 + I2 (b) 2NO2 → 2NO + O2 (c) 2NOCl → 2NO + Cl2 (ii) Displacement reaction (gas phase): (a) H + D2 → HD + D (b) Cl + H2 → HCl + H C-8∴N-ENGCHE∴ECH5-1...e.PM5 110 . mol–1 sec–1 [l = litre] dt c time conc 2 (iii) Physical significance dx k= = When c = 1 dt i. t1/2 = = = k a(a – x) k a(a – a / 2) ak i.110 ENGINEERING CHEMISTRY Taking dx = k(a – x)2 dt dx or = k dt ( a – x) 2 1 or = kt + z (integration constant) a– x 1 when t = 0. k is the rate of decomposition at unit concentration of the reactants. if we put a – x = c a–x a t a(a − x) 1 1 1 1 then. x = 0. time–1 = l . kt = – ∴ = kt + .e. 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 dx = k(a – x)2 = kc2 when (a – x) = c dt dx 1 conc 1 ∴ k= .

PM5 111 . sec–1 k Independent of concentration. t1/ 2 Independent of initial concentration. c Unit of k sec–1 l mol–1 . Third Order Reaction The rate equation for a third order reaction is A + B + C → Products dx = k(a – x)(b – x)(c – x) dt where. When. a=b=c the rate equation becomes. Initial concentration of A = a Initial concentration of B = b Initial concentration of C = c no. Dependent on concentration. Inversely proportional to 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 (v) Substitution reaction (Solution phase): (a) I– + CH3Br → CH3I + Br– (b) OH– + CH3I → CH3OH + I– (vi) Hydrolysis of an ester: CH3COOC2H5 + OH– → CH3COO– + C2H5OH (vii) Esterification: CH3COOH + C2H5OH → CH3COOC2H5 + H2O Comparison Points First order reaction Second order reaction 1 a 1 x Rate equation k= ln k= t a–x t a( a – x) 1 Linearity log c decreases linearly with time increases linearly with time. dx = k(a – x)3 dt C-8∴N-ENGCHE∴ECH5-1. of moles of each reactant decomposed at time t = x.

2 t 2 a2 k 2 a 2 k a 1 ∴ t∝ 2 a So. (ii) k is dependent on the unit of concentration.PM5 112 . x = 0 1 1 1 .. the rate of the reaction is not dependent on the concentration of the reactant or. 2 a H K 2 2 13 1 1 3 1 3 1 = ..112 ENGINEERING CHEMISTRY = kc3 [when a – x = c] = kc2(c – x) [when a = b ≠ c and (a – x) = c] dx Again = k(a – x)3 dt dx or = k dt ( a – x) 3 Integrating. or t = . =Z ∴ Z= 2 a2 2a2 1 1 1 or – = kt 2 ( a – x) 2 2a 2 ∴ kt = LM 1 1 1 – 2 OP N 2 (a – x) 2 a Q 1 L 1 O 1 x (2a – x) ∴ k= M 1 2t N ( a – x) 2 – a Q P = t 2 a ( a – x) 2 2 2 . 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. . 1 2 H a .e. Characteristics of a Third Order Reaction 1 (i) Where x = a. 2a – a 2 = 1 K a 2 – a2 4 = 1 4 a t 1 FG IJ 2 t 1 4 a t 1 a4 2a 2 . (iii) Unit of k is mole–1 sec–1. in other words. rate of the reaction is proportional to the zero power of the concentration of the reactant i.e. 2 = . 2 1 FG 1 IJ 1 3 2 k= . 1 1 . = kt + z (Integration constant) 2 (a – x) 2 When t = 0. C-8∴N-ENGCHE∴ECH5-1. the time required for the completion of the same fraction of the change is inversely proportional to the square of the initial concentration.

i. = Kc3/2 dt Usually such order involves a mechanism where atoms or free radicals are intermediates of the reaction. Examples of Fractional Order Reaction dc (i) CH3CHO → CH4 + CO.. which is equal to k (Zero order rate constant). In those reactions. dc because is constant.e.PM5 113 . The bromination of acetone in acid solution is of zero order with respect to Br2. = Kc3/5 dt – dc (iii) ortho-H2 → para-H2. the rate of reaction is proportional to fractional power of concentration of the reactant. the amount decomposing in unit time is constant.e. c0 – c k= t i. since the reaction velocity is not influenced by a change in concentration of bromine. CH3COCH3 + Br2 → CH3COCH2Br + HBr W 1 1 HI + → H2 + I2 prs 2 2 Fractional Order Reactions Not all reactions are of integral or zero order. C-8∴N-ENGCHE∴ECH5-1. – dc = Kc1/n dt where concentration of the reactant = c.REACTION DYNAMICS/CHEMICAL KINETICS 113 dc = k[ A ]0 = k – [Q [A]0 = 1] dt where concentration of the reactant A = c or – z z c c0 dc = t 0 k dt = k z 0 t dt or – [c – c0] = k[t – 0] or c0 – c = kt Characteristic of a Zero Order Reaction (i) We have..e. (ii) In zero order reactions when c plotted against t would give a straight line of slope k .. i. – = Kc 3 / 2 dt Sb – dc (ii) 2SbH3 → 2Sb + 3H2. dt Examples of Zero Order Reactions These reactions are controlled by catalyst. the reaction velocity is constant and is independent of concentration. many fractional order reactions are known. independent of concentration or time.

(a – x) is determined. The rate equation comes to – dc = k′[C12H22O11] dt dx or = k′(a – x) dt 1 a or k′ = . i. the reaction is dependent on the concentration of both the reactants. By putting the value ‘a’ and (a – x) the value of ‘k’ is determined.. 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: 1 a First order reaction ⇒ k= ln t a– x 1 x Second order reaction ⇒ k= . Such solvolytic first order reactions are called Pseudo unimolecular reactions. we see that the reaction is of the second order. The order of the reaction is determined by that equation which gives the satisfactorily constant value of ‘k’. The method is laborious and too complicated to give a satisfactory constant value. characteristics of first order reaction is seen actually in second order reaction. the rate equation of the reaction is – dc = k[C12H22O11] [H2O] dt In solution the amount of water is excessively high compared to sugar.e. So [H2O] is constant. C-8∴N-ENGCHE∴ECH5-1. Due to presence of excess water. So. the incident so happens.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.PM5 114 . ln t a– x So. t a(a – x) Third order reaction ⇒ k= 1 LM 1 1 – 2 OP N 2t ( a – x ) 2 a Q 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. the change of concentration of sugar is very negligible. After complete hydrolysis of sugar. So. But is still employed for simpler reactions.

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. 5. the rate equations for the two experiments will be dc R1 = – 1 = kc1n. plot of t1/2 vs. so the order can be determined. For the second experiment the initial concentration = c2.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. (iii) Van’t Hoff’s differential method Let. 1/a will give a straight line. dt dc2 R2 = – = kc2n. So. i.1 (a) and (b)). If t1/2 remains constant the reaction is of the first order. we can get the order of a reaction. By plotting log c vs t if a straight line is obtained the reaction is of first order.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. the order of a reaction be = n. the first experiment the initial concentration = c1. the reaction is of third order. (iv) Graphical method If we plot ‘time’ vs ‘a function of concentration’. dt Taking ‘log’ on both the sides log R1 = log k + n log c1 log R2 = log k + n log c2 log R 1 − log R 2 or n= log c1 − log c2 If the rates of reaction determined initially R1 and R2 are known.e. For.. if t1/2 varies inversely as the initial concentration the reaction is of the second order. 1/a2 gives a straight line. A Amount decomposed (x) Rate of reaction (dx/dt) dx C . If the plot t1/2 vs.

Slop = tan .

1 C-8∴N-ENGCHE∴ECH5-1. 5.PM5 115 . B = dx dt Time (t) (a – x) (a) (b) Fig.

so the interpretation of the order of a reaction from their velocity data becomes difficult. Each reaction gives a set of products. These reactions are called simultaneous reactions. B + C. But many of the reactions are not so simple. The other reactions occur simultaneously. yield 10% (side reaction) Example: CH2 = CH2 CH3. Some of these factors are given below: Simultaneous Reactions In a simple reaction. A+B C+D So. the experimentally determined rate for this reaction is a net result for the two opposing reactions.CH2OH dx C2H4 + H2O = k1c dt C2H5OH [k1 and k2 are not same] dy CH3CHO + H2 = k 2c dt (b) Opposing reaction: The reversible reactions also interfere to give the constant value of ‘k’. The reaction which gives the major product is called main reaction and the other is called side reaction. yield 90% (main reaction) A P + Q.PM5 116 . Example: k1 CH3COOH + C2H5OH CH3COOC2H5 + H2O k2 C-8∴N-ENGCHE∴ECH5-1. There are certain disturbing factors which influence the reaction and constant values for k are not obtained. Simultaneous reactions Side reactions Opposing reactions Consecutive reactions (a) Side reaction: Sometimes the reactants undergo two or more independent reactions simultaneously. But many reactions are complicated.Cl CH3.116 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. the reactants react to give products. These reactions interfere to give a constant value of k. The rate constant values are not obtained constants for a number of reactions. There are three types of simultaneous reactions.CH2.

(c) Consecutive reaction: In many reactions. These types of reactions are known as consecutive reactions. CH2 . CH2 . COOC2 H5 k1 CH 2 COOC2 H 5  + NaOH →  + C2 H 5 OH CH 2 . the products obtained change to a third product. As for example—period of induction is noted during the reaction of H2 and Cl2 in the presence C-8∴N-ENGCHE∴ECH5-1. which can be measured and that determines the order of the reaction.PM5 117 . After some time the reaction starts and proceeds as usual with normal speed. k1 k2 A → B → C Examples: k1 k2 (i) (CH3)2O → CH34 + HCHO → CO + H2 k1 (ii) 2NO + H2 → N2 + H2O2 k2 H2O2 + H2 → 2H2O (iii) CH 2 .REACTION DYNAMICS/CHEMICAL KINETICS 117 OCO k1 CH2OH . COOC2 H5 CH 2 COONa Ethyl Succinate Ethyl Sodium Succinate CH 2 COOC 2 H 5 k2 CH 2COONa  + NaOH →  + C 2 H 5OH CH 2 COONa CH 2 COONa Sodium Succinate (iv) H2O2 + 2HI → 2H2O + I2 k1 H2O2 + I– → H2O + IO– k2 IO– + 2H+ + I– → H2O + I2 Of these reactions. the first proceeds very slow. COOH CH2 + H2O k2 (Hydroxy butaric acid) CH2CH2 (Lactone) Rate equation for the first reaction is: dx = k1(a – x)(b – x) – k2 x2. Period of induction Sometimes it is seen that even though the proper conditions for the reaction are maintained the reaction does not start. This period of static state of reaction is known as period of induction. 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.

rate constant of a reaction at temperature T1 = k1 and rate constant of that reaction at temperature T2 = k2. Their values are different for different reactions. The relation can be expressed mathematically as follows: E d ln k E ln k = A – or = RT dT RT 2 where A and E are constants. Then. ln k1 =− E 1 – 1 LM OP k2 R T1 T2 N Q C-8∴N-ENGCHE∴ECH5-1. Arrhenius first related temperature T of a reaction with k. value of k will increase. Rate of a reaction gets doubled when temperature increases by 10°. E E ln k1 = A – and ln k2 = A – RT1 RT2 Subtracting the above two equations we have.PM5 118 . 5. Let. rate of a reaction will increase i. 4 2 0 –Ea –2 Gradient = R ln k –4 –6 –8 –10 8 9 10 11 12 7 1 4 × 10 T 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. 1 He established that when loge k or ln k is plotted against a straight line is obtained T (Fig. 5. induction period is observed in photochemical and polymerisation reactions.2 Plot of ln k against 1/T for a reaction. negative catalysts are responsible for this inactivity in the period of induction or sometimes slow production of an active intermediate. Generally. we can write..118 ENGINEERING CHEMISTRY of light.e.2). Keeping concentration constant if we increase the temperature. Generally.

gives a straight line so the equation of the straight line is: T b ln k = a – T where k is the specific reaction rate and T is the absolute temperature. which is known as energy of activation (Ea). − k = Ae a where. If E for a reaction is known. which take part in a chemical reaction should get activated by gaining a minimum definite amount of energy. k25° Temperature co-efficient = (usually) k35° 1 • Plot of ln k vs. 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. we can determine the value of k2 when k1 is known. the molecules should be raised to a state of sufficient energy. if we can determine the two rate constants k1 and k2 we can find out the value of E from the above equation.303R T1 T2 MN PQ So.3 C-8∴N-ENGCHE∴ECH5-1. For every reaction. 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°. k = Rate constant Ea = Energy of activation R = Gas constant T = Absolute temperature A = Another constant known as frequency factor.PM5 119 . • The exponential form of the above equation is known as Arrhenius equation E /RT . otherwise the reaction will not be Ea Potential energy A+B H C+D A+B C+D Progress of reaction Fig.REACTION DYNAMICS/CHEMICAL KINETICS 119 or log k1 =– E 1 – 1 LM OP k2 2. 5. Energy of Activation (Ea) of a Reaction: its Significance The molecules of reactants.

• There is always an equilibrium between ordinary molecules and excited or activated molecules with an energy difference Ea. which a molecule should possess to get activated to take part in a reaction. C-8∴N-ENGCHE∴ECH5-1. These activated molecules take part in the reaction. are called effective collisions. E or ln k = ln z – E/RT = A – RT This supports the experimentally derived equation. ∴ Number of collisions of molecules possessing E = z . others cannot take part in the reaction unless activated. According to Maxwell. this excess energy is liberated in the form of heat. Effective collisions are sufficiently energetic. Number of collisions per second (z) in any given volume can be obtained from kinetic theory. It is observed that the number of molecules reacted is always less than the number of molecules collided i.PM5 120 . When two gases A and B react. the molecules of the reactants collide to take part in a reaction. Highlights: • A simple collision between the reacting molecules does not necessarily cause reaction. the molecules possess an average energy. the theory of collision can be accepted. Let the total number of collisions be z. When the liberated energy is less than Ea. ∴ k = z . This energy state is different for different reactions. Ea is minimum energy which a molecule must have as a prerequisite to take part in a chemical reaction. the ratio of total number of collisions and the number of collisions giving E to the molecules is e–E/RT. At any state. Again the number of molecules reacted in one second can be obtained from rate constant k (experimentally determined). e–E/RT.e. • Not only effective collisions are responsible for a reaction. e–E/RT.. After the reaction. 5. the reaction becomes possible when molecules of A and B collide.120 ENGINEERING CHEMISTRY possible. but orientation of collision is also important. which lead to the reaction. every collision does not give rise to reaction. the reaction becomes endothermic and when the liberated energy is greater than Ea the reaction becomes exothermic (See Fig. These number of molecules will react. • The collisions. Some molecules are more energised than the others. 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. Highlights: • Energy of activation (Ea) is the critical value of energy.3). So. at a temperature T. Collision Theory According to this theory. • Theoretically. Arrhenius proposed that only the molecules attaining energy of activation Ea due to collision can take part in the reaction.

1 37. k = ln = 0. 250 cc of H2O2 solution of strength 2 (N) is taken.. k = ln = 0. Determine from the following data the value of k and establish that the decomposition is of the Ist order.PM5 121 .0 C-8∴N-ENGCHE∴ECH5-1. 5. For a Ist order reaction 1 a k= .0 Sol.044 min–1.3 1 46. SOLVED EXAMPLES Example 1.1 k= .e.8 1 46. a = 46.6 12.1 29. The titre values will give the change in concentration of H2O2 i.REACTION DYNAMICS/CHEMICAL KINETICS 121 Collision Reaction + + H2 I2 Transition state Product (effective collision) HI + HI molecules react Collision when they collide Collision in a preferential direction Ineffective Ineffective Fig. ln = 0.1 at t = 10. 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.3 5.4 Rate of a reaction = [No.1 Now.8 19. 50 5.0436 min–1 10 29. ln t a– x Here.044 min–1 30 12. x. k = ln = 0.1 at t = 50. k = ln = 0.1 1 46. In an experiment.1 at t = 20. Decomposition of H2O2 Time 0 5 10 20 30 50 Time value (KMnO4 in cc) 46. So.1 at t = 30. of properly oriented molecules per unit volume per unit time] × fraction of molecules equal to or greater than threshold energy. putting t=5 1 46.6 1 46.0434 min–1 5 37.0427 min–1 20 19.

18 32. 1 cc methyl acetate was added to a flask containing 20 ml 0. after a time t and after an infinite time.24 24. decomposition of H2O2 is of the Ist order.PM5 122 .14 1 34.03 From the above data show that the hydrolysis is of the Ist order.83 18 28.18 32.00485 min–1.. The optical rotation of this solution is measured at regular intervals and the final reading is taken after 24 hrs.303 22.4 + 17.18 18 27.71 k= log = 0.32 42.05 25.7 + 15 – 10. Here.00519 min–1 18 28.79 183 12.5(N) HCl kept at a temperature of 25°C.20 26. k = ln 0 t rt – rα 1 34. Example 3.79 Time Vα – Vt k 2. Vα – Vo = 42.83 k= log = 0.00486 min–1 7.79 Since.60 29.79 75 17.83 1 r – rα Time rt – rα. 27. the hydrolysis of methyl acetate is of the Ist order.00316 min–1 183 12. 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 7.43 k= log = 0.03 – 19.303 22. Sol. a = r0 – rα (a – x) = rt – rα where r0.71 C-8∴N-ENGCHE∴ECH5-2.e.43 2. Vt and Vα are the volumes of alkali initially. Here a = Vα – Vo a – x = Vα – Vt where Vo.79 119 15.83 7. A 20% sugar solution is taken.24 = 22.122 ENGINEERING CHEMISTRY Since the ‘k’ values are fairly constant by putting the data in the Ist order-rate equation the reaction i. r0 – rα = 24.00395 min–1 75 17.14 k= log = 0. respectively.303 22. 2 ml of aliquot (reaction mixture) was withdrawn at different intervals and titrated against a standard alkali.e.05 α Rotation (degrees) + 24.14 k= log = 0.00321 min–1 119 15. The mixture is poured in a polarimeter tube. of alkali used: 19..83 27. Example 2.14 1 34.74 Show that the reaction is of the Ist order.09 + 21. the k-values are fairly constant by putting the data in the Ist order rate equation i.74 k= log = 0. 50 cc of this solution and 50 cc of (N) HCl is mixed at constant temperature. rt and rα are initial rotation.79 = 34.05 25. The data are as follows: Time ( in minutes): 0 75 119 183 α Vol. Sol. rotation after time ‘t’ and rotation after infinite time where the reaction is assumed to be completed.09 + 10.83 2.

A Ist order reaction is 25% completed in 30 mins. Calculate the time for 80% disintegration. 0. a = 100% a – x = (100 – 75)% = 25% 2.000433 year–1 1600 2.303 ∴ t= log = log 4 = 34 minutes .e. 0.693 Sol. k 25 0.17 yrs. i.693 ∴ k= min–1 = 0. t1/2 to be determined for Ist order reaction t1/2 is k 2.303 100 k= log = 0. Time of 50% reaction.693 ∴ k= year–1 = 0.. the hydrolysis of methylacetate is of the Ist order..303 a and k= .PM5 123 .000433 20 C-8∴N-ENGCHE∴ECH5-2.303 a k= log t a–x Here a = 100 % (a – x) = 100 – 80 = 20 2.0407 Example 6. Example 4.e.303 100 2.693 ∴ t1/2 = k 0. The half-life for radium is 1600 years. Radioactive disintegration is of the Ist order 0.0095 Example 5. 0. log t a– x Here.303 100 ∴ k= log t 25 2. t1/2 = 17 mins.693 ∴ t1/2 = = 72.0407 min–1 17 Here. 0.693 ∴ 1600 = k 0. Half-life for a first order reaction is 17 mins. Sol. Calculate the rate constant and time for 75% completion of the reaction.REACTION DYNAMICS/CHEMICAL KINETICS 123 Since the ‘k’ values are fairly constant by putting the data in the Ist order rate equation i. Determine the time of 50% completion of the reaction.303 100 t= log = 37. 0.693 Sol. We know t1/2 = k Here.0095 min–1 30 75 0. t = 30 min a = 100% a = (100 – 25)% = 75% 2.9 minutes.

59 k= × = 0.32 11.0067 conc–1 sec–1 16 × 15 6.87 k= × = 0.c. An aliquot (25 cm) of the reaction mixture was titrated against a standard acid at regular time intervals.41 Since the k values are fairly constant by putting in the 2nd order rate equation i. T a–x x k 1 5. t OP N (n – 1) ( a – x) n–1 a Q C-8∴N-ENGCHE∴ECH5-2. The rate equation is – d[ A ] = k . Deduce the rate constant and t1/ 2 for nth order reaction. of acid (a – x) 16 10. [A]n dt Let a be the initial concentration and x be the concentration which has reacted in the time ‘t’. Let the reaction be nA → Products. The following is the data for the hydrolysis of ethyl acetate by NaOH solution. Sol. So the concentration of A at time t is (a – x).59 35 3.41 Show that the reaction is of the 2nd order.13 1 11.24 5.32 1 12.PM5 124 .76 k= × = 0.68 25 4.68 k= × = 0. Time (in minute) 0 5 15 25 35 Vol.007 conc–1 sec–1 16 × 5 10. Sol.0066 conc–1 sec–1 16 × 35 3.24 1 9.13 4.41 12. the hydrolysis of ethylacetate by NaOH is of the 2nd order.87 15 6.e.24 6. Example 8.32 3.76 5 10.13 9.x=0 1 LM 1 1 − n− 1 = k .0069 conc–1 sec–1 16 × 25 4. The 2nd order rate equation is 1 x k= at (a – x) Here a = 16 c.124 ENGINEERING CHEMISTRY Example 7.. – d[ A ] – d(a – x) dx ∴ = = = k(a – x)n dt dt dt dx ∴ = k dt ( a – x) n z 0 x dx (a – x) n =k z t 0 dt Q t=0.

PM5 125 .2 × 10–3 mol–1 litre min–1 a/2 1 ∴ 5. If the specific reaction rate is 5. what is the initial concentration of the reactants? Sol. Example 9. the time of half completion for a reaction is found to change from 50 sec. Calculate the time taken for the concentration to be reduced to 20% of the initial value. For a 2nd order reaction x k= at(a – x) Here. 60 × 5.REACTION DYNAMICS/CHEMICAL KINETICS 125 ∴ k= 1LM 1 1 – n–1 OP N t (n – 1) ( a – x) n–1 a Q t= 1 LM 1 – 1 OP k(n – 1) N ( a – x) n–1 a n–1 Q For t1/2. Sol. T1 = 50 sec.5 H K or 2 = 2n–1 ∴ n–1=1 or n=2 C-8∴N-ENGCHE∴ECH5-2.5 to 1 mol l–1.2 × 10–3 = = 60 . T2 = 25 sec.2 mol litre–1. a . x = a/2 k = 5. When the initial concentration is changed from 0. x = a/2 ∴ t1/2 = 1 LM 1 – 1 OP N k(n – 1) ( a / 2) n– 1 (a) n– 1 Q ∴ t1/2 = 1 LM 2 n− 1 −1 OP k(n – 1) N a n− 1 Q unit of k is (conc)–(n–1) (time)–1.5 mol l–1 a2 = 1 mol l–1 50 1 FG IJ n– 1 ∴ 25 = 0. a / 2 60a 1 a= = 3. t = 60 mins.2 × 10 –3 Example 10. t1/2’s are related to initial concentrations as T1 a FG IJ n–1 T2 = 2 a1 H K Here. a1 = 0. In a 2nd order reaction.2 × 10–3 mol–1 litre min–1. where the initial concentration of the reactants is the same half of the reactants are consumed in 10 mins. to 25 sec.

k = 0. t = ? (a – x′) = 0.5 × 50 25 k 0. the initial concentration of reactants is 0. ak 0.2)mol l–1 = 0.08 = 0.303 × 0.303 100 ∴ k= log 1 99 = 2.1 = 0. Sol.0044 min–1 = 0.1 mol l–1 x = 0. a = 0.75a = 0.1 mol l–1.126 ENGINEERING CHEMISTRY So. 1 1 1 ∴ k= = = l mol–1 sec–1 = . time required to complete 75% of the reaction. In a 2nd order reaction.01 min–1 when t = 1 hr = 60 mins 2.PM5 126 .2 Example 11. a – x = (0.5 × 0.2 a = 0.0625 × 0.1 × 40 × 0.04 l mol–1 sec–1 at1/2 0.2 × 0.0625 x′ = 0.01 = log 60 a–x C-8∴N-ENGCHE∴ECH5-2.1 – 0.625 Example 12. Here. For a unimolecular reaction 2. ak(a – x) 0.0625 l mol–1 min–1 1 k= at1/2 1 1 ∴ t1/2 = = = 160 mins.303 100 or 0.303 160 k= log 60 a– x 2.02 k= = at(a – x) 0. Sol. x 0. If one percent decomposes in the first minute in a unimolecular reaction. The reaction is found to be 20% complete in 40 minutes.075 mol l–1. calculate how much would remain undecomposed at the completion of the first hour. the reaction is of the 2nd order.075 ∴ t′ = = = 480 mins.0625 mol–1.025 mol l–1 x′ 0. a = 100 a – x = (100 – 1) = 99 2. Calculate the rate constant.1 × 0. half-life period. ak(a – x′ ) 0.1 × 0.303 a k= log 1 a–x Here.8 × 25 t= = = 200 sec.08 mol l–1 For the second order reaction.02 mol l–1 t = 40 min.

PM5 127 . 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. unit of k = mole1–n ln–1t–1 when c = mol l–1 and mole1–n ln–1 t–1 = mole1–n 103(n–1) mln–1 t–1 when c = mol ml–1 For first order reaction.303 log 4 = 1.303 log 1 a – 0. the reaction will be.204 = 16 a – x′ 2.303 a– x or log (a – x) = log 100 – 0. k1 = t–1 (k1 will remain same) For second order reaction. second and third orders when concentration is expressed in mole l–1.303 a − x′ a 100 ∴ (a – x′) = = = 12. For nth order reaction. k3 = mole–2 l2 t–1 = mole–2 106 ml2 t–1 or 10–6 k3 = mole–2 ml2 t–1 So.89.75a 0.7395 = 54. (ii) first order in A and first order in B? Sol.2605 = 2 – 0.01 100 or = log = log 100 – log (a – x) 2. If k1 = k2 = k3 for three reactions being respectively of first. At the end of one hour A is 75% reacted. Example 13. what will be the above relation if the concentration unit is mol m–1? Sol.75a 2. Example 14.2605 = 1. A certain substance A is mixed with equal moles of a substance B.REACTION DYNAMICS/CHEMICAL KINETICS 127 60 × 0.7395 ∴ (a – x) = Antilog 1.5% 16 16 C-8∴N-ENGCHE∴ECH5-2. initial concentration = [A] = [B] = a t = 1 hrs.3865 × 2 a ∴ log = = 1.303 a 1. k1 = 10–3 k2 = 10–6 k3. when time t′ = 2 hrs.25a = 2.303 a a (i) When first order in A=K= log = 2.3865 = log [where x′ = amount reacted] 2 a – x′ a 1. 2.3865 hr–1. Let.89 ∴ % undecomposed = 54. 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.204 ∴ = Antilog 1. x = 0.

128 ENGINEERING CHEMISTRY So.75a ∴ k= = = 3a–1 hr–1 (when t = 1 hr) at(a – x) a × 1 × 0. x′ k= when x′ = amount of reactants A and B reacted at(a – x′ ) x′ x′ 3a–1 = or 6 = a × 2 × (a – x′ ) a – x′ 6a ∴ x′ = 7 FG 6 IJ So. k = t1/ 2 Here. 968 cal mole–1. Calculate the activation energy of this reaction. respectively for a first order reaction. The specific reaction rates of a chemical reaction at 273 K and 303 K are respectively 2. Rate constants at two temperatures are given by Arrhenius equation.t. B) (ii) In the second case. Sol.693 As the reaction is first order. Sol.303 × 1. The values of Arrhenius factor and activation energy are 4 × 1013 s–1 and 98. 100 ≈ 14.3.. % of A and B left unreacted = a – H 7 a K 6 i. Example 16. 0. k2 = Ea T2 – T1LM OP log k1 2. C-8∴N-ENGCHE∴ECH5-2. t1/2 = 10 mins = 600 sec. mole–1 ∴ log 162 × 10 –5 = Ea 303 – 273LM OP 2.e.987 273 × 303 N Q Ea 30 1.8203 = × 2.303R T1T2 N Q Here.r. Calculate the temperature at which its half-life is 10 mins. − Ea / RT k = Ac where A is called the Arrhenius factor and Ea is the energy of activation. 100 –.987 273 × 303 ∴ Ea = 22. The exponential form of Arrhenius equation is.987 Cal K–1 .45 × 10–5 and 162 × 10–5. the over all order of the reaction is 2. % of A left unreacted = 12.45 × 10 –5 2.45 × 10–5 k2 = 162 × 10–5 R = 1.5% % of B left unreacted = 100% (Q order = 0 w.25a At t′ = 2 hrs. T1 = 273 K T2 = 303 K k1 = 2.6 kJ mol–1.303 × 1. x 0. 7 Example 15.PM5 128 .

155 × 10–3 sec–1 From Arrhenius equation we have. Let. 98600 ∴ T= F 4 × 10 I 3 K H 1. Example 17.303 × 8. K1 = 5 × 10–3 l mol–1 s–1. let us state we have a population inversion with n2 > n1.39 K1 ∴ K2 = 1.303 × 8.693 ∴ k= 600 = 1.303 log 10 (k/A) = – Ea/RT Ea or T= 2.1431 = 1.316 × 16. h C-8∴N-ENGCHE∴ECH5-2.303R log( A /K) Here. mol–1. Lasers in Chemistry Laser means “light amplification by stimulated emission of radiation”. What is the value of the rate constant at 875°C? Sol. Ea = 4.115 × 10–3 sec–1.600 J. K2 E (T – T1 ) log = a 1 K 1 2.39 × 5 × 10–3 l mol–1 s–1 = 7. the populations be n 2 and n1 and energies of the two states be E 2 and E 1.303 RT1T2 Here. We have.PM5 129 .1431 K 1 2. The use of lasers has initiated new types of spectroscopic experiments and has improved the precision of spectroscopic experiments.Ea = 98. T1 = (800 + 273) = 1073 R = 8.0 × 10–3 l mol–1 s–1 has an activation energy of 45 kJ mol–1.REACTION DYNAMICS/CHEMICAL KINETICS 129 0.0 × 10–3 l mol–1 s–1. A second order reaction. A = 4 × 1013 sec–1 k = 1.115 × 10 JK 2. When E2 > E1.5 × 104 J mol–1 T2 = (875 – 273) = 1148 K.5 × 10 4 (1148 – 1073) ∴ log = = 0.314 J mol–1 K–1 K2 4.316 J mol–1 K–1.316 × G –3 98600 = K 2.555 = 98600 = 373 K.314 × 1073 × 1148 K2 ∴ = Antilog 0. 2. R = 8.303 × 8. whose rate constant at 800°C was found to be 5. then photons of frequency E 2 – E1 1→2= are spontaneously emitted as molecules drop from the state 2 to the state 1. To achieve a laser action a Population inversion should be generated in the system.

5). An example of chemical laser: One can use the reaction: H + F2 → HF + F. The frequency emitted lies in the IR. Thus. and stimulate emission for further photons. • Chemical laser. Those photons emitted at the cylindrical axes pass out of the system and 1 have no role in the laser action. where n is an integer. Kinds of lasers • Solid-state metal ion laser. 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. Let l be the distance between the mirrors and light only with wavelength = λ. The laser system is contained in a cylindrical cavity whose ends have parallel mirrors. C-8∴N-ENGCHE∴ECH5-2. For example. the laser output is highly monochromatic and highly directional. will resonate in the cavity. 5. Thousands of different lasers exist. we can take the following two reactions: (i) H + HOD → OD + H2 (ii) H + HOD → HO + HD.PM5 130 . Then we can study the dependence of the reaction probability on the vibrational quantum states of these reactants. These properties make laser useful in spectroscopy and kinetics. the material in which the laser action can be employed may be a solid. This makes the laser nearly 2 monochromatic. • Semiconductor laser or diode laser. The presence of end mirrors makes the laser a standing wave pattern. 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. States involved in laser axis travel forward and backward between the end mirrors laser action. 5. such that nλ = l . • Dye laser. a liquid or a gas. visible or UV region. Those photons emitted along the Fig.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.5. The HF chemical laser can be used as an antimissile. 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. A few photons are spontaneously emitted when the molecules go from the state 2 to state 1. • Gas laser. laser light can be employed to control the outcome of the reaction. 3 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 2 net amplification of radiation of frequency ν1→2.

Differentiate average rate from instantaneous rate. 4. Let. similarly. By using laser light. Q. Q. What is a laser? Q. Q. 3. 2. Q. (1) Temperature. The breaking of a chemical bond in a molecule occurs within a fraction of a second (10–13 to 10 –12 second). Q. Change in concentration ∆A Ans. Chemical kinetics is that branch of chemistry which deals with the rate of a chemical reaction. 6.PM5 131 . It is the rate of the reaction when the concentration of the reactants are unity. the bond breaking process can be observed spectroscopically. (2) Order of a reaction. the reaction be A → B. What do you mean by chemical kinetics? Ans. 4. Give an example of chemical laser. Average rate = = Total time (involved for the change) ∆T C-8∴N-ENGCHE∴ECH5-2. 3. Can you break a bond preferentially by the application of laser? Q. SHORT QUESTIONS Lasers in Chemistry: Q. 5. What is specific reaction rate or rate constant (k)? Ans. 7. What do you mean by rate of a reaction? Ans. The rate of reaction is increased if the concentration of the reactants increases. This technique is called Femtosecond Transition State Spectroscopy (FTS) or laser femto chemistry. SHORT QUESTIONS AND ANSWERS Q. 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. Q. What do you mean by FTS? Q. Q. one can preferentially break the O – H bond in HOD. 2. The experiments are done using either molecular beams or gaseous molecules in a chamber. ∆A ∆B Rate of reaction = – or + ∆t ∆t Unit = Concentration time inverse. What are the factors that can change the value of k? Ans. 1. 5. Mention various kinds of lasers.1.REACTION DYNAMICS/CHEMICAL KINETICS 131 By using laser. Explain why the laser radiation is monochromatic. Give one major application of laser. Whether control of chemical reactions by lasers will ever have commercial applications is not clear. excitation of O-D stretching vibration in HOD leads to break the O–D bond preferentially. Unimolecular reactions are best studied by FTS.

fraction. temperature. The average rate approaches the instantaneous rate when ∆t becomes smaller. etc. (iii) Order changes with physical conditions like (iii) Molecularity does not depend on such → pressure. So molecularity is a theoretical approach and its value is always a whole number. Q. If we take a reaction: αA + βB + γC → Products the rate = k . zero or a (iv) Molecularity is always a whole number. [A]α [B]β determining step of the mechanism. In modern reaction.. Highlight: For elementary reaction order is necessarily equal to molecularity. 6. Compare order and molecularity of a reaction. Cγ where k = rate constant and the order of the reaction α + β + γ. For complex reactions it may or may not be equal.132 ENGINEERING CHEMISTRY Instantaneous rate is the rate of the reaction determined at the particular moment of time. What do you mean by the order of a reaction? Ans. It is equal to the total number of reacting species atoms. Molecularity of a reaction in equal to the sum of the coefficients of various reactants appearing in a balanced chemical equation i. Ans. It is not classical definition is connected with the connected with the chemical equation of the overall chemical equation. C-8∴N-ENGCHE∴ECH5-2. Order Molecularity (i) Order is a purely experimental fact related to (i) Molecularity is a theoretical concept. (ii) If a reaction is (ii) It is the sum of the stoichiometric co- A + B → Products efficients of a chemical equation. What is the molecularity of a reaction? Ans. the rate will be Modern definition is—it is the number of molecules taking part in the rate Rate = K . (iv) Order may be a whole number. it is the sum of the stoichiometric coefficients in the simplest chemical equation. definition it is related to the mechanism of the reactions. ions of molecules the concentration of which changes actually during the course of a chemical reaction. 7. Its the rate equation of the reactions.PM5 132 . Aα . What are unimolecular and bimolecular reactions? Ans. B β . Q. Q. 9. 8.e. experimentally observed fact. Q. If the reaction is: C12H22O11 + H2O → C6H12O6 + C6H12O6 The molecularity of the above reaction is two. When the molecularity is one it is unimolecular reaction and when it is two then the reaction is bimolecular. factors.

[A]2 = Rate equation for second order reaction. If the rate of a chemical reaction varies to the first power of concentration of the single reactant. For a reaction: A + B → Products Rate = k . [A] [B] or Rate = k . What is the time for the change from c/2 to c/4? Ans. Comment on half-life of a first order and a second order reaction. 2. Q. t = ∞ So. it is a constant quantity. What will be the time for the change from a/2 to a/4? C-8∴N-ENGCHE∴ECH5-2. [A] = rate equation for a first order reaction. Give examples of first order reaction. 1. For a second order reaction the integrated form of the rate equation is: 1 x k= t a(a – x) when. 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. concentration will be zero at infinite time. Ans. Q. time will be asymptotic plot. 15. For a second order reaction one hour is needed for a change of concentration a to a/2. A second order reaction is a reaction. Q. Is a first order or a second order reaction completed? Ans. ak So. 11. Integrated form for a first order rate equation is: c = c0e–kt The plot of concentration vs. 16. k 1 t1/ 2 for a second order reaction = . 0. it is known as first order reaction.REACTION DYNAMICS/CHEMICAL KINETICS 133 Q. 13. Hence. What is a first order reaction? Ans.PM5 133 . One hour. Radioactive disintegration process. Q. a second order reaction is also an incomplete reaction.693 Ans. A → Products. So. x = a. 12. For a first order reaction one hour is needed for a change of concentration c to c/2. Rate of growth of bacterial culture. Q. 14. dt Q. What is a second order reaction? Ans. – dA ∴ Rate = = k . half-life in this case is inversely proportional to the initial concentration. 10. So the reaction is not completed. t1/2 for a first order reaction = .

t = ka which is a finite quantity. t1/′ 2 ak ak / 2 2 Q. EA = ET – ER Q. It is the minimum amount of energy from zero level of the reactant molecule which must possess in order to react. The integrated form of zero order reaction is c0 – c K= . 21. the reaction will be completed and for a zero order reaction. What is threshold energy? Ans. It is denoted by EA. ak 1 When concentration changes from a/2 to a/4. 17. k t1/′ 2 1 1 1 ∴ = = or t 1/2 ′ = 2 . c = 0. It is denoted by ET. When concentration changes from a to a/2. 20. What is transition state theory? Ans. H H + I I H H 2HI Final state Initial state   Transition state Activated state I Ea Final state Energy H > 0 Initial state H < 0 II Final state Reaction co-ordinate Fig.6 C-8∴N-ENGCHE∴ECH5-2. Q. What is activation energy? Ans.134 ENGINEERING CHEMISTRY 1 Ans. c0 when. Q. t1/2 = a/ 2 . the rate is not at all dependent on the concentration of the reactants. 19.6). t1/2 = 2. Chemical reactions occur through an intermediate stage known as transition state or activated complex (Fig. t1/2 = . 5. which must be supplied to the reactants to enable them to cross-over the energy barrier between the reactants and products. How are the activation and threshold energies related? Ans. where c0 = initial concentration t c = concentration at time t. What is the special characteristic of a zero order reaction? Ans. Activation energy of a reaction is defined as the extra energy over and above the average potential energy of the reactants.1 = 2 hrs. So.PM5 134 . 5. Q. 18.

C-8∴N-ENGCHE∴ECH5-2. (ii) completion time. of acid (c. 17.24 6. From the given data. 12. Describe an accurate method for determining order of a reaction with three reactants. For. 14. 5. of the reaction mixture was titrated at regular intervals against standard acid.REACTION DYNAMICS/CHEMICAL KINETICS 135 Particles in collision react only if. Briefly develop the concept of activation energy and temperature.c.PM5 135 . EXERCISES 1.) 16 10.13 4. The half-life period of a 1st order reaction is 15 mins. the reactants A and B are at equal concentrations. 10. The study of chemical kinetics helps to determine the mechanism of a chemical reaction. Distinguish between rate and specific reaction rate of a chemical reaction. [34.0173 min–1] 15. 25 c. ∆H > 0 endothermic reaction (Curve I) ∆H < 0 exothermic reaction (Curve II) Q. ‘order of a reaction’ and ‘molecularity of a reaction’. What is meant by order of a reaction? Derive an expression for the velocity coefficient of a second order reaction. How does rate of a reaction vary with temperature? What is Arrhenius equation? 11. Explain the meaning of pseudo unimolecular reaction. 9. 5 Br– + BrO3– + 6H+ → 3Br2 + 3H 2O Rate = Constant × [Br–] [BrO–3] [H+]2. Derive the rate con- stant expression of a 2nd order reaction: k A + B → c. The volumes of acid used by unchanged NaOH are given below: Time (minute) 0 5 15 25 35 Vol. Explain the terms ‘rate constant’.c. 22. show that the reaction is of the 2nd order. 6. upon impact.32 3. Classify the statement: “decomposition of H2O2 is of the 1st order”. Calculate the rate constant and the time taken to complete 80% of the reaction. by titration of the hydroxide against standard acid at different stages in reaction.85 mins] 16. Derive an expression for rate constant of zero order reaction and discuss about its (i) half-life. 2. they attain impact. Indicate how the specific reaction rate of a first order reaction can be evaluated. 4. they attain the energy of the transition state. What is the utility of the study of chemical kinetics? Ans. Discuss any two methods of determination of order. 7. State the molecularity and order of the above reaction. 8.41 Show that the reaction is of the 2nd order. 3. Derive the rate constant for a 1st order reaction and show that it is an incomplete reaction. Discuss the various factors affecting the rate of a reaction. The hydrolysis of ethyl nitrobenzoate by aqueous NaOH was followed at 25 °C. What is the rate constant of the reaction at the same temperature? [ 0. 13. During the hydrolysis of ethyl acetate by NaOH using equivalent concentration. Half-time change for a 1st order reaction is 40 mins.

[Ans. 18.0332 atm] 20.236 × 10–3 sec–1.24 6.136 ENGINEERING CHEMISTRY 18. is 20%.32 3.314 JK–1 mol–1) [Ans.044 atm. Calculate the energy of activation for this reaction (R = 8. When log K (velocity constant for a reaction) was plotted against 1/t.0 10. Calculate the activation energy of the reaction. How long will it take to go to 60% completion? [Ans. follow first order kinetics. (ii) B → Products. Two reactions: (i) A → Products.25 × 10–4 sec–1 at 298 K and 8. The rate of the reaction (i) is denoted when the temperature is raised from 300 K to 310 K.5 kJ mol–1at 581 K. The following data were obtained in the hydrolysis of ethyl acetate. 3. A 2nd order reaction. (ii) Calculate the pressure of Cl2O7 after 100 sec. At the same temperature B decomposes twice as fast as A. 050 Cal mol–1] 23. If the energy of activation for the reaction (ii) is half that of reaction (i). The activation energy for the reaction 2HI (g) H2 (g) + I2 (g) is 209. 19. is completed in 500 seconds.5 × 10–4 sec–1 at 318 K. [Ans.4 kJ mol–1] C-8∴N-ENGCHE∴ECH5-2.c.) 16.0327 min–1] 24. 1. 0. of HCl (c.PM5 136 . 22. The half-life periods for the decomposition of ammonia (catalytically) are as follows : Pressure in mm 50 100 200 Half-life period in hrs.41 Show that reaction is of 2nd order. of decomposition at this temperature.462 × 10–19] 25. [Ans. using equal concentration of ester and NaOH: Time (minutes): 0 5 15 25 35 Vol. The half-life for this reaction at 310 K is 30 minutes. (i) After 55 seconds at 400 K the pressure of Cl2O7 falls from 0. Calculate the rate constant. Calculate the fraction of molecules of reactants having energy equal to or greater than activation energy. A 1st order reaction has rate constant equal to 1. 3000 seconds] 21. 6.13 4.92 1 Find the reaction is of which order. calculate the rate of the reaction (ii) at 300 K.52 1. The decomposition of Cl2O7 at 400 K in the gas-phase to Cl2 and O2 is a 1st order reaction. 103. where a = b. [Ans. 0.062 to 0. the slope of the line was found to be – 5400 K.

it can be said that catalysts smoothen the passage towards equilibrium. influences the velocity of the reaction by not involving itself in the reaction. The catalyst which retards the rate of a reaction is called a negative catalyst and the phenomenon is negative catalysis. A catalyst which increases the rate of a reaction is called a positive catalyst or a catalyst and the phenomenon is catalysis. DEFINITION A catalyst is a substance. a catalyst. which was not at all related to the reactants. (ii) Negative catalysis. 6 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. not related to the reactants. Berzelius named the phenomenon of acceleration of the reaction as catalysis and the substance influencing 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’. Since all reactions tend to attain equilibrium. Examples of Catalysis Positive Catalysis Reaction Catalyst (i) 2KClO3 → 2KCl + 3O2 MnO2 (ii) 2H2O2 → 2H2O + O2 Pt (iii) 2SO2 + O2 → 2SO3 Pt or V2O5 (iv) N2 + 3H2 → 2NH3 Fe (v) C12H22O11 + H2O → C6H12O6 + C6H12O6 H+ ion Negative Catalysis Reaction Catalyst (i) 2H2O2 → 2H2O + O2 H2SO4 (ii) 2H2 + O2 → 2H2O CO 137 . 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. A catalyst may also retard a chemical reaction. (i) Positive catalysis or catalysis.

so if a catalyst changes k1. (iii) Catalyst hastens the attainment of equilibrium. it also accelerates the backward reaction. • So “a catalyst is a substance that makes a chemical reaction that could happen. (iv) Catalyst has no influence on the point of equilibrium. in one single phase. it never increases the equilibrium yield. the equilibrium constant of the reaction as the two are related by – ∆G° = RT ln K. Types of Catalysis Catalysis Homogeneous Heterogeneous There is a third type of catalysis in mainly biological systems. • This means if a catalyst accelerates the forward reaction. Those catalysts are termed Enzymes or Low catalysts. So it has no influence on the standard free energy change ∆G° i. 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 H+ C12H22O11 + H2O → C6H12O6 + C6H12O6 + [H+] – (b) Decomposition of H2O2 in the presence of I I− 2H2O2 → 2H2O + O2 C-8\N-ENGCHE\ECH6-1. (v) Catalytic action is universal.e. but does not happen..PM5 138 .. happen”.e. (ii) Catalyst remains unaltered at the end of the reaction. it will also change k2 in the same k2 proportion so that their ratio K remains unchanged. the catalyst remains in the same phase with the reactants and is evenly distributed throughout the reaction phase. Homogeneous Catalysis In this type of catalytic reactions. the point of equilibrium is independent of the catalyst. • So. k1 • Since K = . This type of catalytic reactions occur in gas or solution phase i. • Catalyst only helps to attain the equilibrium rapidly. on K.138 ENGINEERING CHEMISTRY Characteristics of a Catalyst (i) A small amount is effective. • Catalyst merely lowers the energy barrier (Ea) of a reaction. Highlights: • Catalyst undergoes no chemical change in a reaction.

Pt. 6. the catalyst forms a separate phase.) C-8\N-ENGCHE\ECH6-1. This type of catalysis has a great technical importance. Important Applications of Catalysts Reactions Examples Catalyst used (i) Dehydration C2H5OH → C2H4 + H2O Alumina. Pd (Contd. Ea.PM5 139 . Schematically it is represented as follows: + Reactant Transition Product molecules state molecules Uncatalysed reaction Potential energy Ea Catalysed reaction Ea Reactants Products Progress of reaction Fig. Zirconia (ii) Hydrolysis Vegetable oil + H2O → Fatty acid Twitchel’s reagent   + glycerol (iii) Oxidation 2SO2 + O2 → 2SO3 V2O5 C6H6 + O2 → Maleic anhydride C10H8 + O2 → Phthalic anhydride (iv) Hydrogenation Oil + H2 → Vanaspati Raney Ni N2 + 3H2 → 2NH3 (Haber’s process) Fe Alkene + H2 → Akane Ni. The minimum amount of energy required to attain transition state is called energy of activation. Examples of Heterogeneous Catalysis: Pt( s) (a) 2SO2(g) + O2(g) → 2SO3(g) (Pt-Catalyst) Fe( s) (b) N2(g) + 3H2(g) → 2NH3(g) (Fe-Catalyst) Activation energy and Catalysis reaction According to collision theory: the molecules of reactants collide to give products. Catalyst lowers the energy of activation (Ea) of a reaction.1 Progress of reaction.CATALYST 139 Heterogeneous Catalysis In this type of catalytic reactions. This is usually termed contact catalysis. usually a finely divided solid either as such or supported on an inert solid such as asbestos or gas (fluidised bed).

(i) Autocatalysis—Examples of such autocatalytic reaction are: (a) Hydrolysis of ester—water formed in the reaction catalyses the reaction. may damage the efficiency of the contact catalyst and may even destroy the catalytic activity. As2O3 acts as a catalyst poison in the contact process for the manufacture of H2SO4.140 ENGINEERING CHEMISTRY (v) Dehydrogenation C6H5C2H5 → C6H5CH = CH2 + H2 Cr2O3/MoO3 (Styrene) Friedel– Craft’s reaction (vi) Alkylation C6H6 + RX → C6H5R + HX Anhydrous AlCl3. when used with iron in the Haber’s process. An important catalyst promoter is Al2O3 and alkali metal oxide. These substances are called catalyst poisons or anti-catalysts. BF3. (ii) Induced catalysis—Sodium arsenite solution is not generally oxidised by O2 but sodium sulphite is oxidised. 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. The poison acts very likely by blocking the active sites of the catalyst.PM5 140 . both of them undergo simultaneous oxidation. (Contd. This type of catalytic reaction is now widely used. (b) Decolourisation of KMnO4 by oxalic acid. If air is passed through a solution containing the two salts. This type of catalytic reaction is known as induced catalytic reaction. 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. Mn+2 ion formed initially catalyses the reaction. chain alkanes MoO3 (ix) Halogenation Benzene + Cl2 → Chlorobenzene Fe or anhydrous FeCl3 (x) Polymerisation Ethene → Polythene Zeigler catalyst or Styrene → Polystyrene Peroxides or Vinyl chloride → PVC Persalts Phase Transfer Catalyst This type of catalytic reaction may be considered as a combination of homogeneous and heterogeneous catalyses. Highlights: Two other types of catalytic reactions are to be noted. the catalytic action increases. Catalyst Poison Certain foreign substances. Catalyst Promoters Promoters are the substances which promote the catalytic activity or enhance the activity of a catalyst by its presence. when present in very trace amount.) C-8\N-ENGCHE\ECH6-1. (iii) A catalyst is more effective in a finely divided state. HF (vii) Isomerisation Normal paraffin → isoparaffin Anhydrous AlCl3 (viii) Cracking Long chain paraffin → branched Bauxite.

AlCl 4 R+ + AlCl4– . (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. 2NO + O2 = 2NO2 . Here. Mechanism of Catalytic Reactions The following two theories have been widely accepted: (i) Intermediate compound formation theory (ii) Adsorption theory. A+B Reaction: A + B C+D Catalytic reaction Rate of reaction Equilibrium Without use of a catalyst C+D Time Fig. the catalyst works by adsorption of the gas molecule on its surface.. The following examples can be given in support of the above theory: (a) NO2 acts as an oxygen carrier in Lead Chamber process.... (ii) Adsorption theory (Heterogeneous catalysis) This theory mainly explains the mechanism of a catalytic reaction between two gases catalysed by a solid. 6. 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. anhydrous AlCl3 forms an intermediate compound with RCl and finally generates R+ for the reaction. (c) In Friedel–Craft reaction. δ+ δ− RCl + AlCl3 → R . (vi) A catalyst does not change the position of equilibrium but can only shorten the time required to attain the equilibrium.2 Effect of catalyst on time to attain equilibrium. Here. The adsorption theory is compared to the intermediate compound formation theory. (vii) Change of temperature can alter the rate of a catalytic reaction as for a non- catalytic reaction.PM5 141 .CATALYST 141 (iv) A catalyst is specific in its action. (v) A catalyst cannot initiate a reaction. H2SO4 to ether. the C-8\N-ENGCHE\ECH6-1.

3 (a). (b). 6. These reactions are catalysed by certain organic compounds which are known as biocatalysts or enzymes. either plants or animals. 6. 6. 6. Enzymes are invariably protein molecules.142 ENGINEERING CHEMISTRY intermediate compound is an activated complex formed on the catalyst surface.4). Fig. ES = activated complex. C-8\N-ENGCHE\ECH6-1. It is assumed that enzymes act on a substrate to give products.4 Illustration of the lock-and-key model of enzyme catalysis. Biochemical Catalysts (Enzymes) Numerous organic reactions occur in the body of living beings. P = products. The protein molecules. (c) and (d).PM5 142 . The following figure explains the enzymatic activity: Enzymatic activity can be explained as: Enzyme + Substrate Enzyme – Substrate → Products + Enzyme [activated complex] The reaction is abbreviated as: E+S E – S → P + E. where E = enzyme. This statement can be explained by the fact that those protein molecules containing an active site are enzymes. The adsorption theory can be explained by the following Fig. S = substrate (reactant). But not all protein molecules are enzymes. to maintain the life processes. The reaction may be represented pictorially as follows (Fig. from catalyst surface. H H H H Ni Ni Ni Ni Ni Ni Ni Ni (a) Adsorption of H2 molecule (b) H–H bond weakened and broken by chemisorption H H H H C C H C C H H H H H H H + Ni Ni Ni Ni Ni Ni Ni Ni (c) Formation of activated (d) The product ethane released complex with ethene.3. S + ES E [activated complex] + E Active sites Products Fig. which do not contain those active sites cannot function as enzymes.

Q. • For its full activity.e. SHORT QUESTIONS AND ANSWERS Q. Q. What is the effect of a catalyst on the equilibrium constant of a reaction? Ans. enzyme needs help of another factor (compound) known as co-factor or co-enzyme. 5. substrate i. 4.e. A catalyst lowers the activation energy of a reaction. it only shortens the time of attaining the equilibrium. What is a catalyst? Ans. • Enzymatic reactions are generally dependent on the concentrations of enzymes. C-8\N-ENGCHE\ECH6-1. What is the effect of a catalyst on free energy change of a reaction? Ans. A catalyst does not alter the equilibrium constant of a reaction. Ans. Draw a distribution curve showing how the proportion of molecules able to react increases when a catalyst lowers the activation energy. • Enzymatic reactions not at all depend on the concentration of the reactant i. Q. 3.. A catalyst is a substance that speeds up chemical reactions without changing itself. • Enzymes lose their activity at higher temperatures.CATALYST 143 Examples of enzymatic reactions (i) Inversion of cane sugar Invertase C12H22O11 + H2O → C 6 H 12 O 6 + C6 H 12O 6 glucose fructose (ii) Fermentation Zymase C6H12O6 → 2 C2H5OH + 2CO2 Amylase (iii) Amylose → Maltose Peroxidase 1 (iv) H2O2 → H2O + O. 1. 2. enzymatic reactions are zero order reactions.. A catalyst cannot change the free energy change of a reaction. Mention the effect of a catalyst on activation energy (Ea) of a reaction. 2 2 Highlights: • Enzymatic reactions generally take place at 35°-45°C.PM5 143 . Q. • Enzymatic activity is pH dependent. • Enzymes do not act in cold conditions.

the rate of reaction increases. etc. n-propyl gallate. What is autocatalysis? Ans. Completion of reaction Rate of reaction Sigmoid curve Time Fig. Ans. An important type of negative catalyst is termed anti-oxidants.6). Why is the hydrolysis of ethyl acetate autocatalytic? Ans. Give important uses of negative catalysts of technical importance. lentoxy anisole are added to retard the rancidity of oil. Q.6 Ans. In autocatalysis reaction as the catalytic product is gradually formed. Draw a graph for an autocatalytic reaction. 7. When one of the products of a reaction itself acts as a catalyst for that reaction the phenomenon is called autocatalysis. The rate is maximum when the reaction is complete (Fig. CH3COOC2H5 + H2O → CH 3COOH + C2H5OH catalyst C-8\N-ENGCHE\ECH6-1. thiourea. As traces of moisture initiate the reaction. 8. are used as antioxidants for prolonging the life of rubber. 6.5 Give experimental evidence that different catalyst has no influence on the yield of a reaction. Q. Ans. Aromatic amines. Q. 9. 6. Widest technical use of negative catalyst is TEL as ‘antiknock’ compound in motor fuel. 6. whether the catalyst used be Pt. It has been observed that at the same temperature the yield of SO3 is the same.144 ENGINEERING CHEMISTRY Activation energy with kinetic energy (E) with a catalyst Number of molecules Activation energy without a catalyst Kinetic energy (E) Fig..PM5 144 . Q. Fe2O3 or V2O5 . CH3COOH is formed acts as catalyst. 6.

) of a metal is obtained by deducting the number of electrons lost in the metal ion formation. Ans. then adding the number of electrons gained by co- ordination i. Determination Atomic no.e. Co-ordination Electrons Electrons Metal ion of metal number lost in ion added by E.A.CATALYST 145 Q. Enzymes are highly specific.N. 13. If the catalyst is in the same phase as the reactants.e.A. 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.N. Example: (i) Homogeneous catalyst = Hydrolysis of ester. Enzymes are proteins in nature and are the catalysts for biochemical reactions. that is.N. effective atomic number rule regarding complex formation. C-8\N-ENGCHE\ECH6-1. Thus. the saturation will occur as follows: 10 (for (n – 1) d subshell) + 2 (for ns subshell) + 6 (for np subshell) = 18 electrons. (ii) Heterogeneous catalyst (contact catalyst) = In Haber’s process for manufacture of ammonia (Fe + Al2O3 + K2O).. If the catalyst is in a different phase. it is a homogeneous catalyst..) To explain the formation of a complex of a metal with a ligand.e.. 11.N. Each enzyme works best at a particular temperature and pH. it was suggested by Sidgwick that metal ions will tend to accept the electron pairs from donors. formation co-ordination Fe2+ 26 6 2 12 36 (Kr) Co3+ 27 6 3 12 36 (Kr) Cu+ 29 4 1 8 36 (Kr) Ni2+ 28 4 2 8 34 (Se) The 18-electron Rule This is another way of expressing noble gas electron number rule i. Q. What are enzymes? Ans. Q. The rule can be exemplified by the following table: E. CATALYTIC APPLICATIONS OF ORGANOMETALLIC COMPLEXES Effective Atomic Number (E.PM5 145 . The statement of 18-electron rule is that the valence shell of metal atom will attain 18 electrons by saturation of (n – 1) d. 10. Q. Do you know any use of enzymes in detergent? Ans. just right shape and size for the substrate molecules. i. it is a heterogeneous catalyst.A.A. Each enzyme catalyses a particular reaction. Some washing powders contain proteases—enzymes that remove blood stains on dirty clothes. Ans. so that a metal ion in the resulting complex has an effective atomic number of the nearest inert gas. Mention the main characteristics of an enzyme. ns and np orbitals of metals by the ligands. 12. the effective atomic number (E. So. What are homogeneous and heterogeneous catalysts? Give examples. both acid and base catalysed. Every enzyme has an ‘active site’. ligand until they have obtained a sufficient number of electrons. two electrons from each ligand having one co-ordination centre.

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. (V) undergoes reductive elimination to release the alkane and regenerate the 14-electron species. Structure and bonding in organometallic complexes. though it is a very reactive compound. Homogeneous systems are used for pharmaceutical industries. The stage IV is very very significant in the overall hydrogenation process as in this stage. The action of the Willkinson’s catalyst is represented by the following cycle. which acts heterogeneously. acts as a homogeneous catalyst for the hydrogenation of alkenes and alkynes. the substrates alkene. 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. guration of the donated by electrons in tion number central metal of ligands (n – 1) d. mostly alkenes is an important industrial reaction.e. of atom with oxida. It is dissociated (only 5%) into 14 electron species in pure solvents. The catalyst is not able to reduce other organic functional groups. Organometallic chemists made the process very popular. thus: (Ph3P)3 RhCl (Ph3P)2RhCl + PPh3 The species (Ph3P)2 RhCl is of low coordinating power.. C-8\N-ENGCHE\ECH6-1. Next step is the rearrangement of the coordination site to give V.146 ENGINEERING CHEMISTRY To illustrate. let us cite the following examples: Compounds Central metal Electronic confi.PM5 146 . of electrons Total no. No. The structure (II) is seen to possess a vacant coordination site shown by a square. (Ph3P)3 RhCl. hydrogen are now bonded to the same metal atom. ns (n–1) d subshell and np levels (i) Ni (CO)4 Ni(0) 3d10 2 × 4 (four CO 10 + 8 = 18 groups) = 8 electron valence shell configuration (ii) Fe(CO)5 Fe(0) 3d8 2 × 5 (five CO 8 + 10 = 18 groups) = 10 electron valence shell configuration The attainment of 18 electrons in the valence shell of the metal atom or satisfying 18- electron rule is one of the useful criteria of elucidating the structure of metal carbonyls. The hydrogenations of alkenes and alkynes have been studied extensively. so it can readily accept π electrons from the alkene to give (IV). Almost all large scale hydrogenation processes are carried out using Raney Ni as catalyst. The 14-electron species (II) is formed by dissociation of phosphene ligand from (I). which is generally known as Willkinson’s catalyst. This is because stable Rh(I) complexes are generally four coordinated (16-electron species). In the cycle there are four co-ordination compounds (II – V).

But among them. As this needs high pressure reactor the initial installation cost of the plant is high for an industrial process. The reaction. which takes place in presence of a catalyst is as follows: Catalyst R. • Hydroformylation The reaction of an alkene with synthesis gas i. catalysis by cobalt or rhodium compounds is of interest.. C-8\N-ENGCHE\ECH6-1.PM5 147 .e. mixture of carbon monoxide and hydrogen (CO + H2) to produce an aldehyde.CH=CH2 + CO + H2 → RCH2CH2CHO + R CH— CH 3 | CHO Several transition metal compounds are used as catalyst in hydroformylation.7 Catalytic applications of organometallics. Highlights: • Oxidative addition refers to the increase in coordination site of the central metal. Industrially cobalt carbonyl is used as catalyst at 130° – 170°C and under 200 – 300 atm pressure.CATALYST 147 L3RhCl (I) L+ –L H2 L L addition of H2 Rh Cl C—C 14e (II) H H H L H Rh Cl L 16e H L C—CH (III) Rh Cl L H C—C L H 16e (V) Rh Cl L C C PH3P = L 18e (IV) Vacant site = Fig. 6. is known as hydroformylation. • Reductive elimination refers to the decrease in coordination site of the central metal.

Give a brief account of the various theories of the mechanism of catalysis. How does a catalyst accelerate the speed of a reaction? Explain with proper energy profile dia- gram. 7.148 ENGINEERING CHEMISTRY The mechanism of hydroformylation using cobalt carbonyl as catalyst is shown in the scheme.8 EXERCISES 1. (ii) Enzyme catalysis. Define with illustrations: (i) catalysis. What will be a more effective catalyst—platinum as a lump or finely divided platinum? Give reason. (ii) positive catalysis.”—explain. 1 Co2(CO)8 2 – 1 H2 + 1 H2 2 2 HCo(CO)4 RCH2CH2CHO + CO – CO RCH = CH2 HCo(CO)3 Insertion of alkene into Hydrogenolysis Co—H of Co-acyl RCH2CH2Co(CO)3 CO RCH2CH2CCo(CO)3 O RCH2CH2Co(CO)4 O Insertion of —C into Co-alkyl Fig. What do you mean by (i) homogeneous and (ii) heterogeneous catalytic reactions? 3. What are catalyst poisons and promoters? 4. 6. 2.PM5 148 . “A catalyst doesn’t affect the final state of equilibrium. C-8\N-ENGCHE\ECH6-1. 8. 5. Write notes on: (i) Adsorption theory of catalysis. although it shortens the time required to establish the equilibrium. 6. (iii) negative catalysis. Discuss a few important catalytic processes. 9.

(ii) Specificity of catalytic action. Write an account of the kinetics of heterogeneous catalytic reaction. Write short notes on: (i) Effective atomic number (ii) 18-electron rule. 15. 14. Write notes on: (i) Catalyst and equilibrium point. 17. (ii) Catalyst and energy of activation.CATALYST 149 10. Discuss with suitable mechanisms—the processes of hydrogenation and hydroformylation. 13. C-8\N-ENGCHE\ECH6-1. Write notes on: (i) Hydrogenation catalysts and oxidation catalysts and their application in India. 16. 11. mentioning the specific catalyst used. (iii) Phase transfer catalysis. What are the chief criteria of catalysis? Describe four applications of catalysis.PM5 149 . 12. Write briefly on acid-base catalysis. Give one example of an industrially important catalytic reaction.

which has been indicated by +δ. And in this condition the bond is said to be polarised. The inductive effect is seen to exist upto third carbon atom from the electronegative atom in the chain +++d ++d +d –d C®C®C®Cl 3 2 1 But the charge on the carbon atoms gradually decreases. chloroacetic acid is more acidic than acetic acid. i. Elimination 4. If the bond is between two same atoms. carbon atom acquires a small positive charge and the chlorine atom acquires a small negative charge. If the bond is between two atoms of unequal electronegativities. 7 Mechanism of Organic Reactions REACTION TYPES Types of organic reactions may be depicted as follows: Organic reactions 1.. It will depend on the elctronegativity values of the two atoms. Rearrangement In organic compounds. This sort of bond polarisation due to the presence of electronegative element like chlorine is known as inductive effect. 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. etc. the carbon atom is attached to other atoms by covalency. 150 .55 × 10–3) molecule becomes much easier than that of acetic acid (Ka = 1. in methyl chloride. ++δ. And this effect is permanent. Substitution 2. and acquires ionic character. For example. of the same electronegativities. Addition 3. then the influence of the atoms on the bond is same. then the influence of the atoms on the bond is not the same. +++δ. One covalent bond is made of a pair of electrons.e. This phenomenon is explained as follows: Due to inductive effect of chlorine atom the release of proton from chloroacetic acid (Ka = 1. As for example. This inductive effect has a great influence on the character of organic compounds as well as on organic reactions.85 × 10–5). The displacement of the bonding electrons will be towards the atom of greater electronegativity.

. then the π electrons are transferred completely to one of the bonded atoms under the influence of attacking reagents. If an organic molecule contains a double bond. O O   CH3→ C →O→H H— C ←O←H Another phenomenon is worthwhile to mention.. C . 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. When the reaction takes place through free radical formation (Fig. CH3COOH is weaker acid than HCOOH. So organic reactions can take place through free radical formation or through the formation of carbocations and carbanions. This sort of polarisation effect is the cause of many organic reactions. It is an example of (+I) effect. Due to (+I) effect of CH3 group. on the contrary. The bond break-up may be homolytic or heterolytic. + – + – : HA + C :: C C C HA A H C C The effect is generally represented by a bend arrow. electron displacement by repulsion is known as (+I) effect. This effect is temporary and is known as electromeric effect.PM5 151 . Sometimes non-polar covalent molecules like bromine get polarised under the influence of double bond. a) the mechanism of the C-8\N-ENGCHE\ECH7-1.MECHANISM OF ORGANIC REACTIONS 151 H O H O     Cl ← C ← C ← O ← H Cl  C  C  O – + H +   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. Electron repulsion of the bonding electrons by the CH3 group in acetic acid molecule makes H+ release comparatively difficult. Free radicals are generated due to homolytic fission and carbocations and carbanions are generated due to heterolytic fission of the bond.H C H C . H : (a) homolytic (b) heterolytic (c) heterolytic bond breaking bond breaking bond breaking This type of bond breakings give rise to free radicals as well as carbocations (C+) and carbanions (C–).

e. CN–. When the reaction takes place through the formation of an ion (Figs. Nucleophiles or nucleophilic reagents Electrophiles mean electron seeking. these reagents attack at the point of highest electron density of a molecule. . . Nucleophiles may be negatively charged or a neutral molecule having an atom with a lone pair of electrons. (iii) Termination: R C C C C +R R C C C C R n n There are other ways of termination of a polymerisation reaction. i. CH 3 + CH 3 → CH 3 3 Polymerisation reactions also take place through free radical mechanism. (i) Initiation: (RCO2)2 → 2R CO2 → 2 R + 2CO2     . and alkynes. Classification of Reagents The reagents which take part in ionic reactions are categorised as: 1.. I– (a) H+ and other positive ions. ..e. C C + (RCO2)2 R C C C C. nucleophiles mean nucleus seeking.152 ENGINEERING CHEMISTRY reaction is called free radical mechanism.. It is represented as follows: heat or hν Cl2 → 2Cl• Initiation step . (b) Double and triple bonds of alkenes (b) Halogen and halogen acids. b and c above) the mechanism is known as ionic mechanism. i. they attack at the positive centre of a polarised molecule. C-8\N-ENGCHE\ECH7-1. So it is a free radical substitution reaction. On the contrary. Nucleophiles Electrophiles (a) OH–. (ii) Propagation: R C C + nC C R C C C C n . i.e.PM5 152 . substitution of methane takes place through free radical mechanism. 78 Propagation step . Cl + Cl → Cl 2 78 Termination step – CH 9 . CH 3 + Cl 2 → CH 3Cl + Cl 9 . Cl + CH 4 → HCl + CH 3 . Cl–. Free Radical Mechanism The chlorination of methane. Monomer Catalyst n . Electrophiles or electrophilic reagents 2. R + C = C → R  C  C• (free radical)     . Br–. . That means electrophiles are positively charged species. .

addition and substitution. Nucleophilic reactions Again electrophilic reactions may be of the two types viz. electron pair acceptors and nucleophiles are Lewis bases i. The minimum amount of energy that must be provided by a collision for reaction to occur is called the energy of activation (Eact). HNO3.e. etc. 7. R3N:. the reaction is called electrophilic reaction and when the attacking reagent is a nucleophile. Electrophilic reactions 2. a lone pair.PM5 153 . And so is the case with nucleophilic reactions. HNO2. electron pair donors. The potential energy at any stage of the reaction is indicated by the height of the curve (see Fig. AlCl3. The source of Eact is the kinetic energy of moving molecules. Another type of reaction is very common in organic chemistry which is known as elimination reaction. 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. Reaction: CH4 + Cl  CH3. + HCl Progress of reaction (one-step process) Fig. Conventionally. nucleophiles donate an electron pair and the electrophiles accept it and makes a bond. (d) NO2.1 Potential energy changes during progress of reaction: (One-step process) an exothermic reaction. If we take chlorination of methane for example. Classification of Reactions Broadly. And the reactions of electrophiles and nucleophiles may be considered as neutralisation reactions. (d) R2O:. CH3 + HCl . 7.1). That means electrophiles are Lewis acids i. H = 1 Kcal .. the reactions may be classified as follows: 1. Eact = 4 Kcal Potential energy CH4 + Cl .MECHANISM OF ORGANIC REACTIONS 153 (c) Compounds containing an atom with (c) H2SO4. :NH3 . etc. the reaction is called nucleophilic reaction.. BF3. if the attacking reagent be an electrophile. etc. The methane molecules must collide with chlorine molecules.e. C-8\N-ENGCHE\ECH7-1.

Ar. 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 – Br H H H + H (–) H H C C C C + Br C C H H H H H H Br Br + – Br  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 Br H H H + H – H H C C C C + Br C C H H H H H H H H + – H  Br 2. Bromine molecule gets polarised when comes in close contact with a π bond. Step 1.H + NO2 + Ar .154 ENGINEERING CHEMISTRY Examples: 1.S. Electrophilic addition.PM5 154 . that carbocation gets attached to the Br– generated. NO2 + H Progress of reaction (Two-step process) C-8\N-ENGCHE\ECH7-1. Formation of a transition state: (+) NO2 (+) NO2 H Transition state (T.S. 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.S1 T. Electrophilic substitution takes place in three steps.S2 Potential energy + H NO2 + T. Electrophilic substitution. Nitration of benzene is an example of electrophilic substitution.) (I) Potential energy diagram for nitration T. Generation of an electrophile: HNO3 + 2H2SO4 2HSO4– + H2O+ + +NO2 Step 2.

Nucleophilic substitution. Nucleophilic attack on the carbon atom of C—X bond in a haloalkane or alkyl halide. H3C H3C + – Fast H 3C C + OH H 3C C OH Step 2. leads to substitution. This is a two-step process. RX. 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–.. Nucleophilic addition. the base during reaction. Here the attack of nucleophile (CN–) occurs on a carbonyl carbon leading to an addition reaction.. H3C H3C (b) SN2 reaction: This is a one-step process. Back to aromaticity from the transition state (I). Ionisation of the alkyl halides i. this step is slow. Study of the rate equations of the reactions suggests that there are two different mechanisms: (a) Nucleophilic substitution unimolecular (SN1) (b) Nucleophilic substitution bimolecular (SN2).PM5 155 . (a) SN1 reaction.MECHANISM OF ORGANIC REACTIONS 155 Setp 3. formation of a carbocation intermediate by breaking of C—Cl bond. CH3 H 3C Slow + – CH3 C Cl H3C C + Cl CH3 H3C Tertiary butyl carbocation Tertiary butyl carbocation is stable due to the (+I) effect of the methyl groups.e. 3. Addition of HCN to a ketone is an example of nucleophilic addition. This step is rate determining step of the substitution i. Here the rate equation is rate = K [alkyl halide] . So hydrolysis of alkyl halide is an example of nucleophilic substitution. where X = Cl. [OH–] C-8\N-ENGCHE\ECH7-1. Br or I. The rate equation is: rate = K[C(CH3)3Cl] Step 1. The carbonyl group of the ketone polarises HCN and the addition takes place as follows: R R + – (a) C O C O R R (–) R + – R O + R OH (b) C O C +H C R R CN R CN – + CN H 4. (+) NO2 NO2 H + HSO4– + H2SO4 Here after the attack of the electrophile the stable aromatic system is disturbed. Then the nucleophile OH– attacks and forms a new bond.e. That is why.

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

This reaction occurs in one step process X – C C X + C C + H:B H :B Another example of elimination reaction is the removal of water from an alcohol to form an alkene.PM5 156 . H 2SO 4  H  C  C  C  H → H  C — C  C  H Heat (– H 2O)       H H H H H H C-8\N-ENGCHE\ECH7-1. C C C C + H:B H :B (b) E2 reaction. Fast Step 2. H OH H H    Conc.

1. Each of these drawn structures contributes to the resonance hybrid (Fig. This acceptance is not for the discovery of new facts about benzene but is a result of modification of the structural theory. C-8\N-ENGCHE\ECH7-1. (I) (II) The structures (I) and (II) cannot satisfactorily explain all the properties of benzene. Benzene is more stable than expected.34 Å for a C==C bond. 7. The resonance hybrid structure is more stable than any of the contributing structures.MECHANISM OF ORGANIC REACTIONS 157 This is an example of acid catalysed elimination reaction.2). (c) Only π electrons and non-bonded electrons can be shifted. (b) Position of σ-bonds cannot be changed. 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. 2.2). That theory is the concept of resonance. 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.39 Å instead of 1. So the idea needs to be discussed here: According to Kekule the benzene molecule has following two structures (I) and (II). All the C—C bond lengths in benzene is 1. 3. The Kekule structure is still the accepted structure for benzene.PM5 157 . The difference in energy of any of the contributing structures and the hybrid structure is called the resonance energy (Fig. Despite having three double bonds benzene undergoes substitution reactions more easily than addition reactions.54 Å for a single bond and 1. Thus H + H OH H H OH H H H H+ – H2 O + H C C C H  H C C C H  H C C C H H H H H H H H H H H  H C C C H H H H Resonance The idea of resonance has a major role in understanding the mechanisms of reactions. there is resonance. 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. 7.

Sign of resonance Cyclohexatriene + 3H2 Resonance energy (Resonating structures) 36 Kcal Benzene + 3H2 (Resonance hybrid structure) Potential energy Cyclohexadiene + 2H2 49. benzene to be 85. o–groups in 2. For this overlapping.. (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.2 Kcal (calc) (obs) (calc) 28. 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. the odd electron and the bond pair of the C—H bond. the hyperconjugation may be represented as follows: .. Explanation (i) We should expect from the graph that the heat of hydrogenation of cyclohexatriene i..PM5 158 .8 Kcal/mole. 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. 4. Victor Meyer attempted to explain these abnormalities by steric hindrance i. 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. 4.158 ENGINEERING CHEMISTRY Graphical representation of the idea of resonance from the heats of hydrogen- ation values.8 Kcal/mol but actually it is 49. Kekule structures. benzene is more stable by 36 Kcal/mole than expected which is resonance energy of benzene. Hyperconjugation (No bond resonance) The stabilities of tertiary.e.8 Kcal (obs) 85.2 Stability of benzene (Resonance energy)..e.6 (obs) Cyclohexane Fig. help to bind together the three nuclei i. H H H H H H H H Each of the above no-bond resonance structures appears strange. 6-tribromoaniline does not. That is. the three electrones i. C-8\N-ENGCHE\ECH7-1. two carbons and one hydrogen.4 Kcal 57. H H H H H H H H        H  C  C. 7. This type of delocalisation involving σ-orbital is known as hyperconjugation. (iii) As a resonance hybrid benzene is more stable than either of the contributing resonat- ing structures i.e..e.e. Steric Hindrance Aniline reacts to form anil with benzaldehyde but 2. ←→ H • C — C ←→ H  C — C ←→ H  C — C         .8 Kcal Cyclohexene + H2 55. In terms of resonance.

MECHANISM OF ORGANIC REACTIONS 159 6-tribromoaniline mechanically interfere the attack by the reagent i. – Nu C X Nu C X Nu C+X Crowded transition state (T. The term spatial factor is used to denote steric hindrance.From the foregoing discussion we can say..S. NH2 + OCH NH = CH Anil Br Br NH2 + OCH NO reaction Br The term steric hindrance originally considers the geometry of the molecule. 1. When a chemical reaction occurs. state of hybridisation at the attacked C-atom changes sometimes and the effect of steric hindrance becomes pronounced in T.S. The effect of steric hindrance requires a knowledge of reaction mechanism. it does so via transition state.e.. consequently. 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 CH3 . tending to shield the molecule from the attacking reagent benzaldehyde. SN1 reactions will not be affected by the influence of steric hindrance whereas SN2 reactions are very much affected by steric hindrance. the geometry of both the initial molecule and the transition state. Also.) The transition state accommodates more atoms than the initial state. In an SN2 reaction: .

CH3 . CH2 . CCH2.

. C C C C C . These are the rearrangements in which the migrating group moves from one atom to the neighbouring next atom. This shift is very much important in understanding organic reactions. C . 2-shift. (A hydride shift) . CH3 . + C . CH2 .. CH3 (Rearrangement) H Primary (1°) carbocation Tertiary (3°) 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.

.

. (An alkyl shift) . C C C C C . H H H + C ..

.

2-shifts) C-8\N-ENGCHE\ECH7-1. R R R (1.PM5 159 .

CH2 . The phenomenon is known as isomerism. Structural isomerism may be classified as: (a) Chain isomerism (b) Functional group isomerism (c) Position isomerism (d) Metamerism. Examples are displayed in the following table.CH 2 . Cl (ii) CH3— CH —CH3 1-chloropropane  Cl 2-chloropropane (Contd. CH 2 .160 ENGINEERING CHEMISTRY Isomerism Different organic compounds having the same molecular formula are known as isomers. The isomerism is of two types: (i) Structural isomerism (ii) Stereoisomerism.) C-8\N-ENGCHE\ECH7-1. Types of isomerism Molecular formula Different structures (Compounds) (a) Chain isomerism (i) Butane [C4H10] (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 (i) C2H6O (i) CH 3CH 2OH (ii) CH3—O—CH3 isomerism ethyl alcohol dimethyl ether (ii) C3H6O (i) CH3.PM5 160 .CHO (ii) CH3COCH 3 Propanaldehyde acetone (c) Position isomerism (i) C3H8O (i) CH3CH2CH2OH (ii) CH3— CH —CH3 n-propylalcohol  OH isopropylalcohol (ii) C 3H7Cl (i) CH 3 .

3) is possible about single covalent bonds but is prevented under normal conditions by double bonds or triple bonds. 7.4(a). There are many other conformers between these two extremes. They are known as ‘skew’ or ‘Gauche’ forms. n-propyl ether anic compounds) CH3 (iii) CH O CH 3 CH3 Methyl isopropyl ether Bond rotation (Fig. 7. The rotation about C2—C3 bond of n-butane gives different conformers as depicted in Fig.PM5 161 .4(b). 7. The topic has been treated later on. meta. 7.OH OH para- (d) Metamerism (i) C4H10O (i) C2H5—O—C2H5 (ii) CH 3—O—C3H7 (isomerism in the diethyl ether methyl same class of org. The two conformers of ethane are given in Fig. The lack of rotation about double bonds gives rise to geometric isomerism.4 (a) Newman projection formula for ethane.MECHANISM OF ORGANIC REACTIONS 161 OH OH OH OH (iii) C6H9(OH)2 (i) (ii) (ii) ortho. Conformational Isomerism The different spatial arrangements arising out of the rotation of a C—C single bond are known as conformations. 7. The different structures obtained due to the rotation of this C—C single bond are known as conformers. CH3 CH3 CH3 H H C C C C H H CH3 H CH3 H CH3 Fig. 4 3 2 1 CH3CH2CH2CH3 (n-butane) C-8\N-ENGCHE\ECH7-1.3 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. Eclipsed form Anti form or staggered form (I) (II) Fig.

7.4 (c) Conformers of cyclohexane. we see that the anti-conformation of n-butane is more stable (CH3-groups are as apart as possible. Any deviation from the staggered conformation is accompanied by torsional strain.4(c)].PM5 162 . Conformations of Cyclohexane Factors influencing the stability of conformations: To go deep into the chemistry i. the eclipsed conformation is least stable due to severe crowding. 180°).e.5°) are accompanied by angle strain. • Any deviations from the normal. ethane-like). And the result can be either destabilisation or stabilisation of the conformation.162 ENGINEERING CHEMISTRY 4. HA HA HA HB HB HB Chair Twist Boat Conformer Conformer Conformer Fig.4–6. the stability of the cyclic compound and its reactivity.5 Kcal Potential energy 0.9 Kcal CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 Anti Gauche Eclipsed Gauche Angle of rotation Fig. sp3 hybridised carbon (bond angle 109. C-8\N-ENGCHE\ECH7-1. 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. • Any pair of tetrahedral carbon attached to each other tend to have their bonds staggered (i. In two Gauche conformations. 7.. In the case of cyclohexane the following conformations are common [Fig.e.e. From the potential energy diagram.1 Kcal 3. • Any two atoms or groups that are not bonded to each other can interact. This non- bonded interaction can either be repulsive or attractive.4 (b) Potential energy changes during rotation about C2—C3 bond of n-butane. 7. i..

7.4 (e) The boat conformation is less stable than the chair conformation at an energy maximum. Cyclohexane (boat form) Eclipsed ethane Fig.4 (d ) Cyclohexane (chair form) staggered form of ethane. Here the three pairs of tetrahedral carbon of cyclohexane remain in staggered forms.PM5 163 . 7. For boat cyclohexane the Newman projection formula is as Fig. The twist form or skew boat form is a conformer lying at energy minimum. 7. 1. So the chair cyclohexane is more stable conformer of the cyclohexanes.5). it is thus not a conformer but a transition state between two conformers. The half chair form is a most unstable form which lies at energy maximum (see Fig. 7. Here the three pairs of tetrahedral carbon of cyclohexane remain in eclipsed forms.4(e).MECHANISM OF ORGANIC REACTIONS 163 Newman projection formula of chair conformer [Fig. 7. C-8\N-ENGCHE\ECH7-1.6 Kcal Chair Half Twist Boat Twist form chair form form form Fig. Between the chair form and twist form there are half chair forms with angle strain and torsional strain.4(d)]: Fig.5 Potential energy diagram (conformations of cyclohexane).3 Kcal Potential energy 11 Kcal 5. 7.

they also belong to the stereoisomers. Polarized light is a light beam in which all the waves are vibrating in the same plane.7 Two configurations of lactic acid. which deals with structures in three dimensions is called stereochemistry. that their atoms are oriented is space.6). Two optical isomers of lactic acid (Fig.PM5 164 .Optical isomers rotate the plane of polarised light. Optical isomers rotate the plane of polarized light (Fig. 7. Ordinary light Polarizer Plane- polarized light Fig. Since conformational isomers differ from each other only in this way.7) are molecules with no centers. Generally. a chiral carbon atom is one that is attached to four different atoms or groups. C-8\N-ENGCHE\ECH7-1. axes or planes of symmetry. 7. This part of the science. Simple test of determining chirality of a three dimensional molecule is non-superimpossibility of its mirror images (Fig. 7. (i) Optical isomerism.7). 7. Optical isomerism is shown by the compound containing at least one chiral carbon atom (asymmetric). Any carbon atom with four different groups or atoms attached to it is asymmetric.6 Arrangement for producing plane polarized light. 7. The two general types of stereoisomerism are: (i) Optical isomerism and (ii) Geometrical isomerism.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. Asymmetric molecules are chiral and can exist in distinct mirror image forms. giving rise to optical isomerism. Light is plane-polarized after passing through a sheet of Polaroid. Mirror COOH COOH H OH HO H CH3 CH3 Fig.

• A mixture of equal parts of enantiomers is called racemic modification. 3-Dichloropentane. 7. For compound containing two different chiral carbon atoms. These types of molecules rotate plane of polarised light (see Fig. (II) and (IV) are diastereomers.MECHANISM OF ORGANIC REACTIONS 165 H H C C HO2C CH3 H3C CO2H OH HO Mirror Fig. These two forms of stereoisomers (configurations) are known as enantiomers. Asymmetric Molecules If we translate the three-dimensional molecule to a two-dimensional figure. 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.8 (b) Then the test of chirality is very simple. we get Fischer projection formula of the molecule.PM5 165 .8 (c) Stereoisomers of 2. They can be separated by various physical and chemical methods. (I) and (III). CH3 CH3 CH3 CH3 H Cl Cl H H Cl Cl H Cl H H Cl H Cl Cl H C2H5 C2H5 C2H5 C2H5 (I) (II) (III) (IV) Fig.8 (a) The mirror image forms of lactic acid. the stereoisomers (I) and (II). COOH COOH H OH HO H CH3 CH3 D(–)-Lactic acid mirror L(+)-Lactic acid Fig. 7. 7. Highlights: • Number of possible stereoisomers = 2n. C-8\N-ENGCHE\ECH7-1. The prefix (±) is used to designate the racemic mixture.6) either right or left. 7. (III) and (IV) are pairs of enantiomers. The two configurations of lactic acid rotate plane of polarised light in the same degrees but in the opposite directions. where n = number of chiral carbon atoms in the molecule.

8(d)]. 7. such that 1 → 2 → 3 → 4 or a → b → c → d. 4 or a. the configuration is known as trans isomers (E-isomers). If the path provides a clockwise motion.8 (d) Optically inactive isomer (meso form). based on ‘sequence rule’. 2. Ingold and Prelog to designate the configurations of stereoisomers having chiral centres. The system is often termed as “absolute configuration” assignment as this type of specifying configuration is independent of any reference compound. 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. When similar groups are attached or the opposite side of the C = C bond.9]. If the path describes a counter clockwise or anticlockwise path. C-8\N-ENGCHE\ECH7-1. b. d.PM5 166 . 7. then the stereocentre is designated to have ‘R’ configuration. Geometrical Isomerism This type of isomerism arises out of restricted rotation about C = C bond. the configuration is known as cis-isomers (Z-isomers). c. 7. CH3 H Cl H Cl CH3 Fig. These are as follows: • The number of stereocentres in the molecule are identified. • 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 (R) or (S) designation is written in italics within the parentheses followed by a hyphen before the name of the compound. The geometrical isomerism is also a case of diastereoisomerism [Fig. then the stereocentre is said to have ‘S’ configuration [Fig. 7. H3C CH3 H CH3 C C C C H H CH3 H cis-2-butene Trans-2-butene (Z-2-butene) (E-2-butene) Fig. • The four different groups (ligands) attached to each of the stereocentres are found out and given priority 1.8 (e) R-S System of Nomenclature R-S system of nomenclature was developed by Cahn. When similar groups are attached to the same side of the molecule. etc.166 ENGINEERING CHEMISTRY Stereoisomers which are not pairs of enantiomers are known as diastereomers. 7. Another interesting phenomenon arises among the compounds containing similar chiral carbon atoms [Fig. 3. There are certain methods of assigning R-S notations to any chiral centre of a molecule. This type of isomer is known as mesoform.8(e)].

other three atoms are hydrogen i. 7. H. C H but in the case of H H —CH2CH3 the two atoms are hydrogen and the third one is carbon i. Br. Cl. As for example. in 1-bromo-1-chloroethane (CH3CHClBr). C2H5. the chiral centre is attached to 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. C-8\N-ENGCHE\ECH7-1.e. C H . Similarly. The priorities are then determined at the first point of difference. in the case of —CH2NH2 and —CH2CH3 .e. in this case. the four ligands attached to the central chiral centre are CH3. 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. with 2-chlorobutane (CH3CHClC2H5). Cl is of highest and H is of lowest priority.9 Assigning R and S notations. the atomic numbers of next sets of atoms in the unassigned groups are taken into consideration.MECHANISM OF ORGANIC REACTIONS 167 1 1 4 C 4 C 3 2 2 3 1 1 4 4 C C 2 3 3 2 1 2 3 anticlockwise 1 2 3 clockwise (S)–Configuration (R)–Configuration Fig. The atomic numbers of atoms directly attached to the chiral centre show the priority order to be Br > Cl > CH3 > H. Cl. Among these. the former will get priority over the latter. For example. H.. • When the preferences cannot be determined on the basis of the atomic number of the atoms directly attached to the chiral carbon.PM5 167 . CH3 So.. —CH2CH3 gets priority over —CH3. The two groups are viewed as follows: H In the case of —CH3.

H of —CHO attains the priority over the O. let us consider the following examples: CHO H   H  C  OH —CHO is considered as  C O   CH 2 OH O Glyceraldehyde Here O.PM5 168 . The complete priority sequence is then —OH → —CHO → —CH2OH → H. C-8\N-ENGCHE\ECH7-1. H.168 ENGINEERING CHEMISTRY • A double or triple-bonded atom X to C is considered to be equivalent to two or three X′s. O. The —C6H5 group is considered as C .  A For example : H H   —CH = CH2 means  C CH   C C C C   —C ≡ C— means CC   C C H  —CH = O means  C O  O To illustrate the above phenomenon. The priority sequence of 1-amino-2-methyl- HC C CH 1-phenyl-propane is —NH2 → C6H5 → C3H7 → H. For example   C = X means C X  X X and —C ≡ X equals C X X   But one thing to be kept in memory is that a real  C  A has priority over — C ==A. H of —CH2OH group.

Then the groups are placed across the horizontal lines and the last carbon is at the bottom of the vertical line. • If the sequence is the same i.e. Fischer projection of 3-chloro-1-pentene is: (b) CH = CH2 Cl (d) (a) * H3C5C4H2CHH2C CH2 H Cl 3-Chloro-1-pentene CH2CH3 (c) Fischer projection formula Priority sequence is: Cl→ —CH = CH2 → CH2CH3 Rotation is anticlockwise and hydrogen is on the horizontal line. C-8\N-ENGCHE\ECH7-1.e. Then the sequence rule is applied to get the priority sequence. So the configuration of carbon number ‘3’ is ‘R’.e. • To determine ‘R’ or ‘S’ enantiomer of the compound we are to draw the Fischer projection formula. • Then configuration is specified if priority sequence is a → b → c → d is clockwise and hydrogen (d) remains in the horizontal line. rotation is anticlockwise with hydrogen on the horizontal axis. • Then the asymmetric carbon atoms are to be determined. In D-alanine the priority sequence is NH2 → COOH → CH3 . (ii) Alanine —C3H3C2*H(NH2) COOH .MECHANISM OF ORGANIC REACTIONS 169 Example: (i) 3-chloro-1-pentene.. hydrogen will fall on the right hand side of 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) (b) COOH COOH (d) (a) H NH2 H2N H (a) CH3 CH3 (c) (c) D-alanine Mirror L-alanine (I) (II) In configuration (I) hydrogen falls on the left hand side of horizontal line. So configuration is ‘R’. 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.. then the configuration of the asymmetric carbon atom is assigned to be ‘S’.. Its optical isomer i. enantiomer will inevitably be L-configuration. the number ‘1’ carbon should be on the top of the vertical line. For Fischer projection formula. The configuration of the asymmetric carbon is ‘S’. i.PM5 169 .

The symbol (E) is used when the groups of higher priority are on the opposite sides of the double bond. then the symobol (Z) is used to specify the configuration. i. 3S). 3R). 4-Hexadiene (CO2H > H . Similarly.3-Dichlorobutane. (IV) (2R. (II) (2S.is for cis-somer when the groups of higher priority are on the same side of the reference plane.. the others are: (II) (2R. the configuration is ‘S’. 4E)-2. So the IUPAC nomenclature of the compound (I) is: (2S. So the configuration is ‘S’. CH3 H H3C H C C which is represented as H COOH H COOH (CH3 > H. For example: 2-Butenoic acid.C2*H(Cl). E and Z Nomenclature For the compounds of the type Cab = Cab or Cab = Cac.C1H3] the Fischer projection is CH3 CH3 CH3 CH3 H 2 Cl Cl 2 H H 2 Cl Cl 2 H Cl 3 H H 3 Cl H 3 Cl Cl 3 H CH3 CH3 CH3 CH3 (I) (II) (III) (IV) (I) and (II) are enantiomers. 3R). The priority sequence for carbon number ‘3’ is Cl → CH(Cl)CH3 → CH3. So. In the case of (I) the priority sequence for carbon number (2) is Cl → CH(Cl)CH3 → CH3.e. (III) and (IV) are known as mesoforms.3S)-2. 3-dichloro butane [C4H3C3*H(Cl). They are optically inactive due to internal compensation.PM5 170 .170 ENGINEERING CHEMISTRY (iii) For 2. double bond. (I) and (III) or (II) and (III) are diastereoisomers. Here also the sequence rule is applied.is applied for trans-isomer and Z. 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. CO2H > H) (E)-2-Butenoic acid Similarly: H CH3 H COOH H H H COOH CH3 H (Z)-Butene dioic acid (Haleic acid) (2E. COOH > H) C-8\N-ENGCHE\ECH7-1. Generally E.

Hydrolysis of tertiary halogenoalkanes viz. NH3 with unshared pair of electrons. 3. Why is the RX + KOH → ROH + KX called nucleophilic substitution? Ans. 2. and OH– is a strong base as its conjugate acid H2O is very weak. i. Q. Q. X– is a weak base as its conjugate acid HX is a strong acid.. OH–. Rate equation for the reaction is: Rate = K[C4HgBr] The suggested mechanism is: CH3 CH3 CH3 CH3 Slow + C Br C + Br – [Rate determining step] CH3 CH3 fast OH– CH3 CH3 C OH CH3 C-8\N-ENGCHE\ECH7-1. CN– etc. Obviously a nucleophilic reagent attacks a molecule at the point of low electron density.PM5 171 . 1. Nucleophilic reagents can supply an electron pair. The rate equation is.MECHANISM OF ORGANIC REACTIONS 171 SHORT QUESTIONS AND ANSWERS Q. How can you ascertain that X– is a weakly basic group and OH– is a strongly basic group? Ans. Since the attacking reagent (OH–) is a nucleophilic reagent. 2-bromo 2-methylpropane is first order. Rate equations suggest that there are two different mechanisms for nucleophilic substitution—explain. substitution of weakly basic group takes place by a strongly basic group.e. Ans. Nucleophilic reagents may be negatively charged viz. and substitution of X– takes place by OH–. bromobutane is a second order reaction. Hydrolysis of primary halogenoalkane viz. and neutral molecules like H2O. Q. What are nucleophilic reagents? Ans. R = K[C4H9Br] [OH–] The suggested mechanism is: H H CH3 CH3 ! H:O: + : Br : – : : : : C Br HO C H H In SN2 reaction two molecules are involved in the rate determining step. 4.

So. . 7. Then the nucleophile forms a bond with the carbocation formed.+ . – – O O O O + –H – CH3 C X CH3 C X : NH3 CH3 C X CH3 C+ X + NH3 NH2 NH2 Here substitution of X– takes place by nucleophilic NH3. 6. At first ethanol is protonated. + + CH3 CH2— O . : H → CH3 C H2 + H2O. SN2 is a one step process and SN1 is a two step process. this is an example of nucleophilic substitution. H H + + H C C CH2 = CH2 + H H H This reaction is an example of dehydration of an alcohol. more is the stability of carbocation. So we can write the following stability sequence.172 ENGINEERING CHEMISTRY In SN1 mechanism one molecule is involved in rate determining step. More the number of methyl groups. Q. Ans.. The mechanism shows that C—Br bond breaks first to form a carbocation inter- mediate. That is why the ionisation in the first case is possible and SN1 path is followed. H2SO4? Ans. This carbocation eliminates an H+ to give an alkene. more is the dispersal of charge and more the dispersal of charge. + + + + 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. C-8\N-ENGCHE\ECH7-2. What do you expect if ethanol is heated with conc.PM5 172 . so.:H CH3CH2—OH + H+ → CH3CH2 O then a water molecule is eliminated to give a carbocation H. why does 2-bromo-2-methylpropane follow SN1 path? Ans. H . 5. Q.. the charge is dispersed by its (+I) effect. When a methyl group is attached to a carbocation (C+). Is the following reaction a nucleophilic substitution? O  CH3— C —X + NH3 → CH3CONH2 + HX. Of the two isomeric C4H9 Br. Q. 2-bromo-2- methylpropane ionises to give most stable 3° carbocation whereas 1-bromomethane gives 1° carbocation.

CH 3 CH 3   H+ Ans. 2-Methylbutanol on dehydration gives 2-methyl but-2-ene—explain.MECHANISM OF ORGANIC REACTIONS 173 Q. First step of nucleophilic addition HCN to ethanal: H H – – O: : : CN + C O NC C CH3 CH3 To complete the reaction. 10. H CH3 CH3 CH3 C C CH3 CH3 CH C CH3 2-methyl but-2-ene H Q. Second step of nucleophilic addition of HCN to ethanal: H H – – O: + HCN : : NC C NC C OH + CN CH3 CH3 Q. CH3 CH2 CH  CH 2OH + H+ → CH3CH2 CH  CH 2 O H CH 3 –H2O  + → CH3CH2 CH C H 2 The formed carbocation is 2°. This rearranges to the most stable 3° carbocation by 1. the negatively charged oxygen acts as a base and accepts an H+ from HCN. Benzophenone does not form bisulphite compound. Ans. OH  C6H5 COC6H5 + NaHSO3 → C6H5  C  SO3 Na  C6H 5 C-8\N-ENGCHE\ECH7-2.2 hydride shift. CH3 CH3 + + CH3 CH2 C CH2 CH3CH2 C CH3 3° carbocation H This species then eliminates a proton to give 2-methyl but-2-ene.PM5 173 . Give an example of nucleophilic addition. 9. 8. Explain.

12. 14. Give the products of the reaction of ethyl bromide and AgCN. Vinyl chloride does not undergo nucleophilic substitution—explain. it can attack from both the sides of the species. so ionisation of benzyl chloride takes place and SN1 path is followed. CH3Cl C-8\N-ENGCHE\ECH7-2. CN–.174 ENGINEERING CHEMISTRY Ans. Ans. Q. Ans. Q. Indentify the products of the following reaction: Ans. CN– . C H 3 . 11. 16. Allyl carbocation is resonance stabilised + + CH2 = CH – CH2 CH2 – CH = CH2 and behaves as if the chlorine atom is ionic.. + So. N O2. C6H5 CH 2 is resonance stabilised. 15. Allyl Bromide undergoes nucleophilic substitution readily—explain. ! : + : : : : CH2 = CH – Cl CH2 – CH = Cl: : Ans. – – : : : : C N N C (Resonance) So the products of the reaction are: C2H5 Br + Ag CN → C2H5 NC + C2H5CN + Ag Br major minor Q. CH3 I. So. R—X + KNO2 → A + B + C – : : : : : : : O – N = O is an ambident nucleophile. Find out the nucleophile from the following: + . 13. 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. : Due to resonance C—Cl bond attains a partial double bond character and C—Cl bond energy increases and no carbocation is formed. Benzyl chloride undergoes SN1 reaction—explain. 17.PM5 174 . + Ans.e. as it has lone pairs C ≡ N . CH2 = CH – CH 2 + OH– → CH2 = CH–CH2OH (SN1) Q. CCl4. + CH2 + CH2 CH2 CH2 + + Q. CN– is an ambident nucleophile i. Arrange the reactivity of the following towards nucleophilic reagent: CH3F. Q. Ans. : – – : : : : : : : O–N=O O=N=O : : R—X + KNO2 → RONO + RNO2 + KX major minor (A) (B) (C) Q. vinyl chloride does not undergo nucleophilic substitution. CH3Br..

The stronger or harder as a base. 21. there are two active sites in the CN– – . Ag promotes R formation from RX by precipitating AgX and reaction takes SN1 path. SN takes place. OR–. Why do haloalkanes give cyanides with KCN– and isocyanides with AgCN? Ans. R HO C 50% R R R Slow + OH – R C Br C Fast ( ) R R R R R C OH 50% + – R (+)– Br R C-8\N-ENGCHE\ECH7-2. Discuss the stereochemistry of SN1 and SN2 reactions. Thus C—I bond is readily broken and the reactivity of CH3I is greatest.g. In SN1 reaction racemisation takes place that means (+)– and (–)– isomers form in equal amounts if we take an optically active RX. The charged species (group) that is replaced during a substitution reaction is a leaving group. CN– being ambident nucleophile. –OH. worse as a leaving group. – OC 2H 5 RCH2CH2X → RCH = CH2 Q... halide ions (X–). with Na+ [CN–] the SN2 reaction is found N ≡ C– + R – X → [N ≡ C---R---X] → N ≡ C ≡ R + X– T.. The best leaving groups are anions of strong acids e. Ans. What is the characteristic of a better leaving group? Ans. NH2– are harder bases and are the worst as a leaving group. ≡ N ←→ C . = N . Both the reagents act as nucleophilic and release CN–. CH3I > CH3Cl > CH3Br > CH3F as bond dissociation energies (D) is of the order C—F > C—Cl > C—Br > C—I.g. Q. 19. The –OC2H5 is strongly basic and preferentially help elimination. What do you mean by leaving group? Ans. Q. Aqueous KOH with RX gives alcohol whereas alcoholic KOH alkene— explain.MECHANISM OF ORGANIC REACTIONS 175 Ans. Ans. Q. RX + KOH → ROH + KX whereas in alcoholic medium C2H5OH + KOH C2H5O–K+ + H2O. + + slow fast R – X + Ag+ [CN–] → Ag X↓ + R+ + [CN–] → R – N+ ≡ C! In the absence of such promotion by Ag+ e.PM5 175 . 18.S.. Q. – C . 22. 20. In aqueous medium..

For a given HX. 23. C-8\N-ENGCHE\ECH7-2.PM5 176 . Q.-O + H2 ] → RX + H2O. The order of reactivity of halogen acids towards an alcohol is— HI > HBr > HCl.. Developing ion pair gets solvated easily and helps the process ionisation. only a slight decrease in reaction rate is observed. the order or reactivity of the alcohols follows the order 3° > 2° > 1°—explain. SN1 reaction becomes faster if the solvent polarity increases. Q. In SN2 reaction: R R R – – – HO + C Br HO C Br HO C R R R R R R T. the reaction is nucleophilic substitution and the leaving group is H2O. The change of solvent (I) affects the rate of the reaction (II) which may change the mechanistic pathway..176 ENGINEERING CHEMISTRY As the planar carbocation is formed in rate determining step and the process of formation is slow. 24.5 × 104 fold faster than the reaction CH3 I with N–3 if we change the solvent from CH3OH to HCON(CH3)2 (DMF). So. Hence the order of reactivity of HX is HI > HBr > HCl. Nucleophilicity of X– decreases in order: I– > Br– > Cl–. The solvolysis of (CH3)3 Br becomes 3 × 104 times faster in 50 % ethanol than in ethanol alone. Ans. The back side attack by the nucleophile always leads to inversion of configuration in SN2 reaction. That is. HX X– ROH → R – OH+2 → [ X − δ . Increase in solvent polarity has little effect in SN2 reaction. always racemisation takes place during SN1 reaction. The alcohol is first protonated. Discuss the effect of solvent on SN1 and SN2 reactions. 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. Whereas in DMF the hydrogen loading is absent and N3– remains unsolvated and powerful nucleophile can attack. The reaction rate becomes 4. Q. Increase in solvent polarity and ion solvating ability may change reaction pathway from SN2 → SN1.S. Because in CH3OH due to hydrogen bonding N–3 is solvated and its nucleophilic activity is reduced. Change of solvent may have marked effect on SN2 reaction. 25. Explain.-R. Transfer from protic polar solvent to polar nonprotic solvent may change the reaction pathway from SN1 → SN2 by increasing the effectiveness of the nucleophilic. there is attack by X– to give RX. Ans.

Elimination reaction is a reaction that splits off a simple molecule of a compound e. the reactivity of alcohols follow the order: 3° > 2° > 1° for a given HX. the most common elimination mechanism is the one step E2 pathway.g. 26.MECHANISM OF ORGANIC REACTIONS 177 Ans. Rate = K[RCH2CH2Br][B] H H H ! : (i) B R C C C H . By far.. Q. H2O from a molecule of organic compound to form a double bond. Since the stability of carbocation follow the order: 3° > 2° > 1°. Hence. Elimination of a molecule of hydrogen halide from a haloalkane produces an alkene. What do you mean by an elimination reaction? Ans. This reaction is known as dehydrohalogenation.

.

.

R C CH CH3 + Br – H Br H H H H CH3CH2CH = CH2 (A)  – OC H 2 5 (ii) CH3 C CH CH2 .

.

.

H Y CH3CH = CHCH3 (B) In substrates which have alternative β-hydrogen available. Q. H— C←O←H Due to electron pull. C-8\N-ENGCHE\ECH7-2. O  ) Ans. that is determined by two empirical rules. What is the origin of acidity in organic compounds? Ans. (iii) factors stabilising A–. Q.PM5 177 . and anion formed has got resonance stability. N+(CH3)3 –OEt – 95% 5% Hofmann The alkene which has least alkyl substituents on the double bond carbons. (i) The strength of H—A bond. (iv) the nature of the solvent. 28. (ii) the electronegativity of A. HCOOH is an acid—explain. H+ release is possible. Table Alkenes Substrate Y Base Name of the Rule Rule A B CH3CH2 CH CH3 Br –OEt – 19% 81% Saytzev The alkene will predom-  inate which has most Y alkyl substituents on the double bond car- bons. 27. more than one alkenes can be obtained.

Q. Phenol is (i) acidic. Justify the pKa values Acid pK a CH3COOH 4.16 Ans. HCOOH is an acid as the anion has resonance stability.PM5 178 . The electronegativity order of halogens is: F > Cl > Br > I So.e. 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. Justify the pKa values Acid pKa CH3COOH 4.86 BrCH2COOH 2. So pKa value gradually increases i. Q. Acidity order with pKa values of the following acids is: Cl Cl Cl   CH COOH (pKa = 0.66 ClCH2COOH 2. Ans. As the number of electron withdrawing groups increases acidity increases.76 FCH2COOH 2.178 ENGINEERING CHEMISTRY – O O + HCOOH + H2O H C H C + H3O O O So. 29. Explain.. 31.29) > Cl ← CH2COOH(pKa = 286) Cl Cl Justify. Q. pKa value decreases.65) > CH COOH(pKa = 1. Q. 32.05 O  Ans.86 (CH3)3CCOOH 5. (ii) o.90 ICH2COOH 3. The electron withdrawing substituents with (–I) effect has got marked influence on the acidity of simple aliphatic acids.76 (CH3)2CHCOOH 4. acidity decreases. 30. : : : : + : + : + : O H O H O H O H O H ! ! : : ! : C-8\N-ENGCHE\ECH7-2. p-orienting. acidity order will be.

62) becomes less basic than NH3. . But we see that pKa of aniline is 4. NH3 is basic. CH3  : : : NH3 CH3 NH2 NH CH3  pKa = 9. C-8\N-ENGCHE\ECH7-2. like NH2 .77 Q.e. . 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.25.77 respectively. 10.PM5 179 ..25. *This property common to other groups. the anion formed on the release of H+ by phenol molecule is resonance stabilised. The pKa values are in accordance with the above fact. Benzene having a delocalised π-cloud is susceptible to electrophilic substitution. 34. : OR . it can donate a pair of electrons. helps electrophilic substitution and are o-. due to the (+I) effect of the –CH3 group. p-orienting. The resonating structures of aniline is: + + + : : : NH2 NH2 NH2 NH2 NH2 ! : ! : ! : Example of resonance Due to resonance. o. Justify. NH 3 is a Lewis base. . .64 and 10.and p. So phenol is o-. 35.positions. CH3NH2 is more basic.. the electron density over ‘N’ atom becomes less than that over NH3. (CH 3 ) 2 NH are 9.62 respectively. So aniline (pKa = 4. 10.. pKa values of NH3. Q. p-orienting*. Justify. CH3NH2 and PhNH2 are 9. Do you expect that p-nitroaniline is less basic than aniline? Ans. This increased electron density activates the benzene ring towards electrophilic substitution SE2. it is less basic than NH3. 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. the basicity is increased.62 i.. 33. When this donation capacity is increased by any effect. Ans.and p.MECHANISM OF ORGANIC REACTIONS 179 (i) The electronegative atom ‘O’ of phenol gets positively charged due to resonance.positions of the benzene ring of phenol molecule become electron rich.64 and 4. Yes. (ii) Due to resonance. Moreover. So. Ans.25 pKa = 10. phenol can behave as an acid. So bonding electrons of O—H bond will be pulled strongly towards O-atom making release of H+ easier.. The electrophiles can attack at those positions leading to electrophilic substitution. pK a values for NH 3 . CH 3 NH 2 . 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 NH3.64 pKa = 10. Q.

36. OH OH O2N NO2 NO2 pKa = 0. Ans.62 O O – O – O pKa = 0. That is why. 37. 4. 2. —NO2 group is m-orienting—explain. it is known as picric acid.180 ENGINEERING CHEMISTRY + : : Ph NH2 NH2 NH2  N N pKa = 4.02 Q. Ans. 6-trinitrophenol exercise pronounced (–I) effect making the phenol molecule total acidic. The resonating structures of nitrobenzene are: – + : – + – – + – – + – – + : : : O.98 Q.9 pKa = 1. 4. Introduction of an —NO2 group in the phenol molecule increases its acidity due to (–I) effect of the —NO2 group. The three —NO2 groups in 2. 6-Trinitrophenol (picric acid) is a very strong acid—explain.

N O O .

N.

O O .

N.

O O .

N.

O O.

So.PM5 180 . Nitration is an electrophilic substitution and takes place easily in the case of phenol. SO3 dissolved in conc. The eletrophile SO3 is generated as follows: 2H2SO4 SO3 + H3O+ + HSO4– C-8\N-ENGCHE\ECH7-2.positions due to resonance. further electrophilic attack at nitrobenzene molecule becomes difficult.and p. Q. nitration of nitrobenzene molecule becomes difficult. —NO2 group is m-orienting.positions positively charged. 38.positions of benzene ring of nitrobenzene become electron deficient.e. —NO2 group in nitrobenzene deactivates the benzene ring by withdrawing electrons from the benzene ring and making o.N O    Due to resonance. The sulphonating agent is Oleum i. 39. Ans. The m-position of the benzene ring is comparatively electron-rich. Nitration of phenol is easier than that of nitrobenzene—explain. electron-rich centre is necessary. In phenol —OH group activates the benzene ring towards further electrophilic substitution by enriching the electron density at o. Ans. that is why electrophile attacks there and m- substitution takes place. So. So. Show that sulphonation of benzene is an elctrophilic substitution. o.. Q. For electrophilic attack.and p. H2SO4. On the contrary.and p.

. Q. RCl + AlCl3 AlCl4– + R+ + So.MECHANISM OF ORGANIC REACTIONS 181 Second step is attack by electrophile SO3 and the formation of a transition state.PM5 181 .e. sulphonation of benzene is an electrophilic substitution. the reagents are anhydrous FeCl3 and Cl2. Pinacol-pinacolone rearrangement (example of 1. 40. R acts as an electrophile during alkylation i. What are the electrophiles for (i) halogenation and (ii) alkylation reactions of benzene? Ans. Cl2 + FeCl3 FeCl4– + Cl+ + So. in Friedel–Craft’s reaction. Electrophile is thus generated. (ii) For alkylation the reagents are anhydrous AlCl3 and RCl. : O: : O: : : S O :: O: + : O: – S O : S O: : :  H OH O: : T. Q. chlorination. Ans. 2-alkyl shift) CH3 CH3 CH3 CH3 + H CH3 C C CH3 CH3 C C CH3 + OH OH OH OH2 Pinacol – H2O CH3 CH3 CH3 CH3 CH3 C C CH3  ! CH3 C C CH3 CH3 C C CH3 OH :OH CH3 :OH CH3 + : + –H CH3 CH3 C C CH3 O CH3 Pinacolone C-8\N-ENGCHE\ECH7-2.S So. Mention an organic reaction where rearrangement takes place. Cl acts as an electrophile during chlorination of benzene. (i) For halogenation viz. Electrophile is thus generated. 41.

N-dimethyl aniline (I) is more basic than N. What is electromeric effect? Is it permanent? 6. CCl 3COOH. Yes. Classify the different organic reactions. State the origin of a carbocation.Cl2COOH. CH2Cl. p-nitrosophenol is obtained. Mention the mechanism. Compare the acidity among CH3COOH.PM5 182 . the planarity. —N(Me)2 group goes out of plane of the benzene ring by free rotation about the single bond.COOH. 42. When Phenol is treated with NaNO2 and HCl at 0–5°C. CH. State the products obtained during the chlorination of CH4 in diffused sunlight. 6-Dimethyl –N. 9. here the electrophile is NO+ HONO + HCl NOCl + H2O + – NO + Cl + OH OH OH + + + NO +H NO H NO EXERCISES 1. N-dimethylaniline (II). What do you mean by polarisation? What is the reason behind it? 3. H3 C CH3 CH3 CH3 : : N N H3 C CH3 (I) (II) Q. What is polymerisation reaction? Give an example of such type of reaction with plausible mecha- nism. 2. This is an example of steric inhibition of resonance. 2. So lone pair over —N(Me)2 group in (I) is available to be accepted by a proton (H+). What do you mean by inductive effect? How does it play an important role in organic reactions? 4. 7. So primary condition of resonance. 43. Is this reaction an electrophilic substitution? Ans. carbonium ion and free radical. What do you mean by steric inhibition of resonance? Ans. 8. Due to crowding in (I). But in (II) lone pair over —N(Me)2 comes into resonance with benzene ring and not so much available for an H+. What do you mean by electrophiles and nucleophiles? C-8\N-ENGCHE\ECH7-2.182 ENGINEERING CHEMISTRY Q. 5. is affected and resonance is inhibited.

Draw Fischer projection formula of D. Draw the resonance structures of: (i) phenate ion (ii) acetate ion (iii) chlorobenzene (iv) butadiene. 2-shift. What do you mean by SN1 and SN2 reactions. 19. What does the term ‘isomerism’ refer to? Give different classifications of isomerism.PM5 183 . 3. Heat of hydrogenation value of 1. Name them as per R. 21. 25. 15. 14. 3-dibromopentane. Write notes on electrophilic addition and electrophilic substitution. S-nomenclature. C-8\N-ENGCHE\ECH7-2. . 24. 23.8 kcal/mole while that of benzene is 49. Explain with proper mechanism involved with examples. What do you mean by dehydrohalogenation? Explain with proper mechanism and example. What is resonance? State the important features of it. 5-cyclohexatriene is 85. 17. 22. 18. Electrophiles are in general Lewis acids–explain.MECHANISM OF ORGANIC REACTIONS 183 10. 20.and L-glycine (NH2CH 2COOH). 13. Name them as per R—S nomenclature. 11. Draw the energy profile of the following reaction: A + B → A --. Draw all the Fischer projection formulae of: (i) glyceraldehyde (ii) lactic acid (iii) tartaric acid (iv) 2. Write a short note on nucleophilic addition reaction. What are the significances of the terms: (i) Resonance hybrid and (ii) Resonance energy. 16. Compare the basicity among the following: NH2 NMe2 NMe2 Me Me . Write a short note on hyperconjugation. What do you mean by 1.8 kcal/mole—explain. 26. What is elimination reaction? Describe different types of elimination reactions.B → AB 12.

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

that common ion effect suppresses the dissociation of a weak electrolyte in solution. In general. the dissociation of AcOH will be suppressed.IONIC EQUILIBRIUM 185 Common Ion Effect If we add NaOAc to a solution of AcOH. C-8\N-ENGCHE\ECH8-1. The definition of acids and base needs to be extended..e.. [H+ ] will decrease i. specially in non-aqueous solvents. The strengths of the acids or bases may be determined by their tendencies to donate or accept a proton in a definite solvent. So concentration term [ OAc ] increases in the equation (3). 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. AcOH H+ + OAc . 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. 2NaNH2 + MgSO4 = Mg(NH2)2↓ + Na2SO4 (in liq. NaOAc being a salt dissociates completely in solution. For every acid. Some Acid/Base conjugate pairs are shown in the following table. there is a base known as conjugate base and for every base there is an acid known as conjugate acid. It is well known that in neutralisation reactions. undissociated [AcOH] will increase. As a result. a substance can behave as an acid or a base by not producing H+ or OH– ions.. to maintain the value k a constant. Let us see its effect on ionisation of AcOH. These species may be neutral or charged. Whether the species will behave as an acid or a base will depend upon the nature of the solvent. the ion ( OAc ) becomes common. As for example.(3) [AcOH] Now. the formation of water.e. behaviours of NH2– and OH– ions are same and OH– is derived from a base.e. NaNH2 dissolves in liquid ammonia and behaves as NaOH in water as is implied from the following equations. 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.. we can say. As for example.. so we can say NaNH2 is a base i. NH3) 2NaOH + MgSO4 = Mg(OH)2↓ + Na2SO4 (in water) So. Bronsted and Lowry defined: Acid as a species which can donate a proton and base as a species which can accept a proton. Cl– is a conjugate base of the acid HCl and HCl is the conjugate acid of the base Cl–.PM5 185 . NaOAc → Na+ + OAc [H + ] [OAc − ] Ka = . This phenomenon is known as Common ion effect. acids react with alkalies to form salts and water.

Classification of Solvents Solvent Example (i) Protophilic (Proton seeking) H2O. the solution will get enriched with OH– ions and will behave alkaline. CH3COO is a strong base as its conjugate acid. And water will remain undissociated being a weak electrolyte. seeking and generating) C-8\N-ENGCHE\ECH8-1. 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. CH3COONa → CH3COO– + Na+. HF (iii) Amphiprotic (Both proton seeking H2O. H2SO4. • 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. EtOH and generating) (iv) Aprotic (Independent of proton C6H6. acetic acid is weak. CCl4. Highlights: • HClO4. CH3COOH. H2O H+ + OH– – According to Bronsted. HCl and HNO3 are of same strengths in water. As a result.PM5 186 .186 ENGINEERING CHEMISTRY Acid Conjugate base HClO H+ + ClO– H2 O H+ + OH– HSO4– H+ + SO4= HCO3– H+ + CO3= NH4+ H+ + NH3 [Cr(H2O)6]+3 H+ + [Cr(H2O)5OH]+2 Role of Solvent Solvent makes to act the substances to behave as an acid or a base. CH3COO– ions will readily accept protons from water molecules setting OH– ions free. HBr. AcidI + BaseII AcidII + BaseI CH3COOH + H2 O H3O+ + CH3COO– HCl + CH3COOH CH3COOH2+ + Cl– CH3COOH + NH3 NH4+ + CH3COO– HF + CH3COOH CH3COOH2+ + F– H2 O + H2 O H3O+ + OH– (Autoprotolysis of water) AcidI and BaseI are conjugate pair and AcidII and BaseII are conjugate pair. NH3 (ii) Protogenic (Proton generating) H2O. Solvent behaves as a base towards acid and vice versa. Therefore.

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. It is worthwhile to mention that an aqueous solution always contains H+ and OH– ions. K[H2O] = [H+][OH–] or Kw = [H+][OH–] (Q [H2O] = constant) Kw is known as ionic product of water. [H + ] [OH − ] [H 3 O + ] [OH − ] K= or [H 2 O] [H 2O] 2 [H2O] is constant because of very feeble ionisation of water.PM5 187 . its value at 25°C is 1 × 10–14.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. So dissociation constant (K) of water is. Highlights: • We arrive at an important conclusion that in any aqueous solution. N + AlCl3 N AlCl3 Acid Base Salt CO Cl CO Cl O: + B : : Cl O B Cl Cl Cl CO CO Base Acid Salt • A substance can behave as an acid even though it does not donate a proton. Ionic Product of Water Water is very much inferior as an electrolyte. It ionises as follows: H2O H+ + OH– or more correctly. the product [H+] [OH–] is constant. this phenomenon can only be explained by the Lewis concept. though negligibly small. its value is 10–14 at 25°C. pH Scale For various experiments. Therefore. 2H2O H3O+ + OH–. • Dissociation constant of water and ionic product of water are not same. we need to know hydrogen ion concentration of a solution. Even strong acid solution contains OH– ions. Again an alkaline solution contains C-8\N-ENGCHE\ECH8-1.

Sorensen (1909) simply applied negative logarithm of hydrogen ion concentration to remove this sort of difficulty for expressing such concentrations. ∴ pKa = 3. all acidic solutions will have pH less than 7. A simple operation like this made an easy expression for hydrogen ion concentration of the solution. S.188 ENGINEERING CHEMISTRY H+ ions though in small concentration.ion l–1. C-8\N-ENGCHE\ECH8-1. As strong acid dissociates completely in aqueous solution. It is somewhat inconvenient to express the concentration of the solution in such a manner. 1 (N) solution of a strong acid contains an [H+] of 10–1 g. in any aqueous solution pH + pOH = 7 + 7 = 14 Highlight: [H+] × [OH–] = Kw.ion l–1. N Let us consider an acid solution of concentration .L. [OH–] = 10–7 – log10[OH–] = – log10(10–7) ∴ pOH = 7. or. where [H+] = 10–7 ∴ – log10[H+] = – log10(10–7) ∴ pH = 7 Again in pure water.ion l . hydrogen ion concentration of the solution will be 10–12 g. Again 0.ion l–1. So. Pure water is neutral because in pure water. Therefore. In pure water [H+] = [OH–] = 10–7. pH scale pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 [H3O+(aq)]/mol dm–3 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. and all alkaline solutions will have pH greater than 7. the solution becomes acidic. And in the solution where the [H+] becomes less than that of [OH–]. – log10 [H+] + (– log10[OH–]) = – log10Kw ∴ pH + pOH = pKw = 14 where – log10Kw = pKw. [H+] = [OH–] = 10–7. Highlight: Following such conventions we express Ka and Kb as follows: pKa = – log10 Ka. the solution becomes alkaline.01 (N) strong alkali solution contains [OH–]. so its hydrogen ion concentration 6000 –4 –1 will be 1.PM5 188 . 10–2 g. so [OH–] of the solution will be 10–13 g. So in an aqueous solution when [H+] exceeds that of [OH–]. Because [H+] × [OH–] is constant in aqueous medium and its value is 10–14.P.66 × 10 g.ion l–1 which is completely dissociated in aqueous solution. and pKb = – log10 Kb As for example: Ka for salicylic acid = 10–3. Therefore.

1.1 = 1. degree of dissociation of acid A1 = α1 Degree of dissociation of acid A2 = α2 The concentrations of the acids were same (C).63 = – 3 – 0. Calculate [H+] of a solution of pH 3.3 × 10 −3 pH = – log10 (7. So.9 × 10–4 (N) acid.0016 (N) base.76 = 11.37 = 2.34 × 10–4 g-ion litre–1.24. their strengths S1 and S2 are represented by.2041 = 2.013. If concentrations of two acids A and B are CA and CB respectively. [OH–] = 0.7 × 10–12 g-ion litre–1.7959 or 2.34 × 10–4 ∴ [H+] = 2.63.3 × 10–3 g-ion litre–1.9 × 10–4 g-ion l–1 – log10[H+] = – log10(4. C-8\N-ENGCHE\ECH8-1.9 = 4 – 0.9 × 10–4) ∴ pH = 4 – log10 4.6 × 10–3 g-ion l–1 – log10 [OH–] = – log10 (1. Such solutions are known as buffer solutions.8865 = 11. Sol. Example 3. The arrest of pH changes of these solutions is known as buffer action. As the acid and base are strong.PM5 189 .IONIC EQUILIBRIUM 189 Example 1. (b) 0.7 × 10–12) = 12 – log 7. ratio of strengths should be CA: CB.6 = 3 – 0.6 × 10–3) ∴ pOH = 3 – log10 1. Calculate pH of the following solutions: (a) 4. Given: α = 0.37 = 4.63 – log10 [H+] = 3. Sol.013 × 0. the ratio of dissociation constants of two acids compare their strengths. Both acid and base are strong.76 ∴ pH = 14 – pOH = 14 – 2. (a) [H+] = 4.1135. pH = 3. Let.63 log10 [H+] = – 3.31 (b) [OH–] = 1.37 [H+] = antilog 4. Calculate [H+]. Sol. the dissociation is complete.63 = 4 – 0.7 = 12 – 0. Example 2.1(N)]. 10 −14 [H+] = = 7. So. One such method is by comparing dissociation constants of the acids. There are several other processes for comparing strengths of acids.69 = 3. [OH–] and pH of a weak base [0. S1 α 1C α1 K 1C K1 = = = S2 α2C α2 K 2C K2 So. Relative Strengths of Acids and Bases Tendency of donating protons in any aqueous solution is a measure of acidity of the solution. Buffer Solutions Some solutions do not change their pH on addition of little acid or alkali.

[Salt] ∴ pH = pKa + log10 [Acid] This is the famous Henderson equation.PM5 190 . external H+ will be removed by BOH H+ (external) + BOH → B+ + H2O. 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) A is a strong base as its conjugate acid HA is weak. Again. As in this case. we can write [A–] = [Salt] as all the A– in the solution are due to ionisation of BA. a weak base BOH and its salt will give a buffer solution. – log10 [H+] = – log10 Ka + log10 [HA] [A − ] or. C-8\N-ENGCHE\ECH8-1. according to Bronsted concept. So we have. BA → B+ + A– (complete dissociation) BOH + B + OH – (incomplete dissociation) On addition of acid to such solution. the dissociation of acid HA is very poor. as OH– is a strong base: OH– (external) + HA → H2O + A– . So the pH of the solution will not change on the addition of a little acid or alkali. So. pH = pKa + log10 [HA] Due to common ion effect. the acid be HA and its salt be BA. If we add a little base to such a buffer solution the external KH– will be removed by the acid HA. pH of a Buffer Solution (i) Buffer solution (prepared from weak acid and its salt) Let. here the common ion is A– HA H+ + A– (weak acid) [H + ] [A − ] ∴ Ka = [HA] log10 Ka = log [H+] + log10 [A–] – log10 [HA] [A − ] log10 Ka = log10 [H+] + log10 [HA] [A − ] or. So the change of pH will be arrested.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. pH of such solution will not change on addition of little acid or alkali and that is the buffer action of the solution. So A– will readily accept H+ from – solution which comes from the added acid to the solution. So. H+ (external) + A– → HA The undissociated molecules of HA will be generated more and more. again whose dissociation is almost prevented due to common ion effect of A–. Again on addition of alkali to such solution OH– ions are removed as follows: OH– + B+ → BOH + B is an acid.

76 = 5.24. (ii) Buffer solution (prepared from a weak base and its salt) In this case: BOH B+ + OH– (weak) [B + ] [OH − ] [B + ] Kw LMQ [OH − ] = Kw OP Kb = [BOH] = × [BOH] [H + ] N [H + ] Q K [B + ] ∴ [H+] = w .PM5 191 .38 (iii) Acetic acid/Sodium acetate 3. where dpH is the increase of pH resulting from the addition of db of base.7 (ii) Phthalic acid/Potassium hydrogen phthalate 2.6 (iv) NaH2PO4/ Na2HPO4 5.IONIC EQUILIBRIUM 191 The acidity or alkalinity of mixed solution. when concentration of salt becomes 10 times the concentration of acid and vice versa. [Salt] Sol.76]. i..7-5.e.2-3. then pH = pKw – pKb. 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. Prepare a buffer solution of pH 5.2 (vi) NH4OH/NH4Cl 10 (vii) Na2HPO4/Na3PO4 11-12 Example 1.76 + log [Acid] [Salt] ∴ log = pH – 4.76 = 0. [Acid] [Salt] ∴ = antilog (0.8-8 (v) Boric acid/Borax 6. K b [BOH] As entire B+ ions in the solution is due to complete ionisation of BA and BOH is weak [B + ] [Salt] ∴ pH = pKw – pKb – log = pKw – pKb – log [BOH] [Base] where [Salt] = [Base].e.738 [Acid] C-8\N-ENGCHE\ECH8-1. Different Buffer Solutions Component conjugate acid–base pair pH ranges (i) Glycine/Glycine hydrochloride 1. The buffer action is favourable in pH ranges pKa ± 1 i. the addition of acid decreases the pH and is equivalent to a negative amount of base.00 – 4.8-9.0-3. pH depends upon the ratios of the concentration of salt and acid. [Given pKaCH3COOH at 25° is 4.. pH = pKa + log [Acid] [Salt] = 4. • The buffer capacity of a solution is defined by db/dpH.24) = 1.

[B + ] [A − ] K= [BA( s)] or K[BA(s)] = [B+][A–] The concentration of solid salt [BA (s)] is constant. BA(s) BA (solution) B+ + A– Applying law of mass action.mol l–1 and [A–] = S g.l–1.0305 gl–1 = 3.e.192 ENGINEERING CHEMISTRY Therefore. ion l–1 i. By convention it is unity. each concentration term being raised to a power representing the number of gm. Calculate its solubility product. of CaCO3 = 100) Solubility S = 0. But it can be successfully applied to the saturated solutions of sparingly soluble salts. Ksp = [B+] [A–] = S2 For a salt like BxAy: BxAy(s) BxAy (Solution) xB+ + yA– –1 + – If the solubility is S mol l then [B ] = xS. If S is the solubility of BA. the desired buffer solution of pH 5 is obtained.Sx+y It is a universally applicable equation. l–1 Mg3(PO4)2(s) Mg3(PO4)2 (Solution) 3Mg+2 + 2PO4–3 its Ksp is[Mg+2]3 [PO4–3]2 = (3C)3 × (2C)2 = 108 C5.05 × 10–4 mol l–1 Ksp = S2 = (3. So [BA (s)] = 1.3 × 10–8. • It is customary to express the concentrations of the ions in g. per litre.ion l–1. then [B+] = S g. 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. Therefore. Example 1. equiv.738 g-moles of CH3COONa is mixed with 1 g-mole of CH3COOH and the volume of the solution is made upto one litre.. CaF2 Ca+2 + 2F– C-8\N-ENGCHE\ECH8-1. Calculate Ksp of CaF2 . ions of each type formed by dissociation of one molecular formula weight of the salt. 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.05 × 10–4)2 = 9.0002 mol l–1. wt. The solubility of CaF2 is 0.mol. (mol. • The solubility product of a sparingly soluble binary electrolyte is simply the square of its solubility in pure water expressed in mol l–1.0305 gl–1. [B+] [A–] = constant = Ksp. The constant Ksp is called the solubility product of the salt BA. formula weight per litre and not in g.PM5 192 . Solubility Product The law of mass action cannot be successfully applied to the process of electrolytic dissociation except to the cases of weak electrolytes. [A ] = yS ∴ Ksp = [B+]x [A–]y = (xS)x (yS)y = xxyy. Highlights: • When the solubility of Mg3(PO4)2 is C mol. The solubility of chalk is 0. Example 2. when 1. because a heterogeneous equilibrium is set up as follows.

Therefore. [F–] = 2 × 0. For doing so. Ksp = [Ca+2] [F–]2 = 0. Let. ∴ S′ = 2. 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. B+ and A– will combine to give the solid BA(s) and the solubility of BA will decrease.ion l–1. [SO4=] = 10–5 × 10–5 = 10–10. Example. (a) [Ba++] = [SO4=] = = 10–5 g. 4 2 Sol. 3. To arrest the precipitation of Mg(OH)2.ion l–1.0004)2 = 3.12 × 10–11 ∴ [OH–] L 1.001 Q So.1) = 10–10. l–1. We know that Ksp = [Mg+2] [OH–]2 = 1.1 g. Calculate the solubility product of the salt.001 g. As a result. Effect of Common Ion on Solubility We know that. the concentration of other ion will decrease otherwise the constant Ksp will change. taking complete dissociation. 10 −10 ∴ S′ = [S′ is negligible compared to 0.12 × 10–11.00233 gl–. N 0.01 mole NH4OH and 0. (a) At 25° the solubility of BaSO4 is 0.PM5 193 .2 (b) [(NH4)2SO4] = = 0. ∴ Ksp = S′ × (S′ + 0.IONIC EQUILIBRIUM 193 [Ca+2] = 0.12 × 10 OP =M −11 1/2 = 1.33 gl–1. What will be concentration of NH4+ ion from NH4Cl? Given K b NH OH = 1.ion l–1 137 + 96 ∴ Ksp = [Ba++] .8 × 10–5. Example 4.00233 Sol. Ksp = [B+] [A–] If we add to the solution a substance. which has an ion common to the above salt then concentration of that ion will increase. [NH +4 ] [OH − ] So.1 × 10–4 g. [Ba = 137] 0.ion Mg+2.0002 × (0.2 × 10–11. 13.1 × 10–4 g. A litre of a solution contains 0. (b) Calculate the solubility of BaSO4 in a solution of (NH4)2SO4 containing 13.1 (M) 132 ∴ [SO4=] = 0. for a saturated solution of a sparingly soluble salt BA.0002 g ion l–1.1] 10 −1 = 10–9 mol. the changed solubility of BaSO4 = S′. [OH–] should not exceed 1. 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.0002 g ion l–1 .2 gl– at 25°C. [NH 4 OH] C-8\N-ENGCHE\ECH8-1.8 × 10–5 and K sp Mg(OH) = 1.ion l–1 to arrest the precipitation of Mg(OH)2. Kb = = 1.

γ Cl− [Cl − ] where γ = activity coefficient. The chlorides of Group I metals (Hg2+2. aCl − So. ionic product (CM+ × CCl–) easily exceeds the solubility products and the cations are precipitated. to reduce acidity of the medium water is added to dilute the medium. So. That is why. IIIB metallic ion (Co+2.01 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. [ Ag + ] . It may remain in saturated solution for sometime. Pb+2. Bi+3. are soluble in salt solutions due to this salt effect.e. The reagent is H2S in presence of dil. on addition of dil. Q activity (a) = Concentration (c) × activity coefficient (γ) ∴ a = cγ. Sb+3. despite low S= ion concentration. Again diluted acid medium precipitates colloidal As2S3 and SnS which creates difficulty in filtration. As a result Fe+3. Mn+2. It is also precipitated in Group II. Ag+) are insoluble. As+3. for precipitation in chemical analysis. The common NH 4+ suppresses the dissociation of weak base NH4OH thereby COH– remains low. get precipitated here i.194 ENGINEERING CHEMISTRY [NH +4 ] × 1. A salt may not get precipitated even when its ionic product exceeds its solubility product. which are sparingly soluble in water. HCl. Therefore. The metallic ions (Hg+2. Cr+3 get precipitated as hydroxides because their solubility products are exceeded. solubility of a sparingly soluble salt increases on addition of any salt without a common ion. so their precipitation is arrested here. 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. Only PbCl2 has higher solubility product and for that reason it is not completely precipitated here. Zn+2) sulphides have higher values of solubility products. the value of solubility product of the salt should always be higher than its ionic product.. [Cl–] increases in order to keep the true Ksp value constant. The common ion H+ suppresses the ionisation of H2S. CdS and PbS have comparatively higher values of solubility products.8 × 10–5 ∴ [NH4+] = 1. Ni+2. Cu+2. Sn+2). So concentration of sulphide ion CS= remains low. true expression is Ksp = γ Ag + . Group I. Al+3. The precipitation of C-8\N-ENGCHE\ECH8-1. If we add KNO3 to a saturated solution of AgCl the γ-term of the expression of Ksp decreases. HCl.6 × 10–3 g.e. whose solubility product of sulphides are low.ion l–1. Here reagent is NH4Cl/NH 4OH. To increase the ionisation of H 2S. • The effect of common ion on solubility is utilised in qualitative inorganic analysis to separate the ions present in a solution. Pb+2. For a very dilute solution γ = 1 then a = c. 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. 0.1 × 10 −4 or = = 1. the ionic products (CM+2 × CS–2) of metal ions exceed the solubility products because of low value of solubility products.. so CS= should be high for them. Group III A.PM5 194 . Highlights: • Many proteins. low acidity or higher pH is necessary. Group II. This effect is known as salt effect. Ksp = aAg + . [Ag+] .

3 = 5.3 – log10 [OH] = 11. ∴ pOH = 2.7 ∴ pOH = 14 – 2. or x2 + 10–8x – 10–14 = 0 − 10 −8 ± (10 −8 ) 2 + 4 ..5 × 10–8 ∴ pH = – log10[H+] = – log10 (10.1 Sol.5 × 10–8) = 8 – log10 10. Calculate the pH of (a) 1.0 × 10–8 + x) = (1.5 × 10 (M) [H ] = (1.3010 = 2. Mg+2 and Mn+2 as hydroxides are arrested as their solubility product values for hydroxides are comparatively higher. the [H+] of the solution = (1 × 10–8 + x) and [OH–] = x ∴ Kw = [H+] [OH–] = (1 × 10–8 + x) × x = 10–14. Ca+2. ∴ pH = 14 – 2 = 12. But when it exceeds 10–6.0 × 10 – 8 (M) HCl solution.5 × 10–8) + = 10. 20 × 0.002 = 2 × 10–3 mole l–1. [H+][OH–] = Kw = 10–14 ∴ (1 × 10–8 + x) × x = 10–14 C-8\N-ENGCHE\ECH8-1.5 = 6. [H+] = = 0. Example 3. Sr+2 are precipitated as carbonates. [OH–] and pH of a solution prepared by diluting 20 ml of 0. the contribution of H+ ions is to be counted during calculation of pH.005M Ca(OH)2 solution assuming complete dissociation.ion l–1. +2 SOLVED EXAMPLES Example 1. Ba . Sol. Sol.3 [OH] = 10–11.98. Calculate the pH of 0.7 = 11. Let the contribution of [H+] from water = x.PM5 195 . Group IV metals i.01 × 10–12 g.e. (a) When the [H+] is 10–6 or greater the ionisation of water is negligible due to common ion effect.IONIC EQUILIBRIUM 195 Zn+2. Calculate [H+]. (b) Here let the contribution of OH– ions from water be x.6990 ~ 2.0 × 10–8 + 9. NH4OH.005 = 10–2 mol.1 M HCl to 1 litre. Group IV. 1000 ∴ pH = – log10 [H+] = – log10 [2 × 10 –3] = 3 – log 2 = 3 – 0. Example 2. [OH–] = 2 × 0. l–1. So. and (NH 4)2CO 3. 1 . Here reagents are NH4Cl. (b) 1 × 10–8 (M) NaOH solution. ∴ total [OH–] = (1 × 10–8 + x) So. 10 −14 ∴ x= 2×1 –8 = 9.

Calculate the ratio of HCO3– and H2CO3 .8 × 10 −5 × 0.1 Example 6.74 + log = 4.196 ENGINEERING CHEMISTRY ∴ x2 × 1. Sol.4 = 3.02) (b) Calculate the degree of dissociation of 0.01 Example 5.02C × 0.4.004 = 0. Given Ka of H2CO3 = 4. Sol.1 = 4.45 × 10–11. According to Henderson equation pH of a buffer solution [salt ] pH = pKa + log [acid] 0.98 ∴ c= molar 0. C 0.0 × 10–8x – 10–14 = 0 ∴ x = 9. (a) Calculate the molar concentration of an CH3COOH solution. Ksp = [Ca+2] [F–]2 = [S] × [2S]2 where. A buffer solution contains 0. H2CO3 H+ + HCO3–.5 × 10 −7 ∴ = = = _ ~ [H 2CO 3 ] [H + ] [H + ] 3. Example 4. 0. The solubility product of CaF2 in water at 18°C is 3.98 ∴ pH = 14 – 6.4 ∴ [H+] = 10–7.8 × 10–5 .98 = 7.5 × 10–8 g.02) 0. α = 0. = 4S3 C-8\N-ENGCHE\ECH8-1.044 molar.24 × 10–2. [H + ] [HCO 3− ] ∴ Ka = [H 2 CO 3 ] [HCO3− ] Ka 4. Calculate the solubility of CaF2 in water. (Given Ka = 1.ion l–1 Example 7. Ka 1.5 = 6.5 × 10–8 (M) ∴ [OH–] = 9.98 × 10 −8 11 pH = 7.5 × 10 – 7. (pKa = 4. Sol.2C 0.8 × 10 −5 (b) α= = = 4.98 × 10–8 g.01 (M) AcOH.1 mole of CH3COONa per litre.5 × 10 −7 4. Calculate the pH of buffer solution. ion l–1 ∴ pOH = 8 – log 9.0004 × C = = C(1 − 0.02. Sol.PM5 196 . S = solubility.74). pH of blood is 7.74.4 ∴ – log10 [H+] = 7. CH3COOH H+ + CH3COO– at equilibrium: C(1 – α) Cα Cα [H + ] [CH 3 COO − ] ∴ Ka = [CH 3 COOH] 0.1 mole CH3COOH and 0.98 1.

Q. This sort of pairs are known as conjugate acid-base pairs. Calculate the solubility SrF2 in 0. K= C(1 − α) where. 1. So. α is negligibly small. Give an expression for the ionisation constant. Every acid has a conjugate base and every base has a conjugate acid. HCl is an acid and NaOH is a base. SrF2 Sr+2 + 2F– S mole 2S mole Initially = in 0.1)2 = 0. Example 8.1) mol. Q. What are conjugate acid-base pairs? Ans. For weak electrolytes. Thus HCl and HSO4– are acids as both of them can donate a proton and Cl– and SO4= and HSO4– are bases as they can accept a proton. 2. α = degree of dissociation of a weak electrolyte. C-8\N-ENGCHE\ECH8-1. C Q. 0.1M NaF solution.45 × 10 −11 S= mole l–1 4 = 2. Given. mol l–1. – Again HCl is the conjugate acid of Cl– and H2SO4 is the conjugate acid of the base HSO4. Thus. 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. differing by a proton. What is the Arrhenius concept of acids and bases? Ans. Sol. 3.01 SHORT QUESTIONS AND ANSWERS Q. α 2 C2 Ans. HSO4 is a conjugate base of H2SO4.01S 8 × 10 −10 ∴ S= = 8 × 10–8 mol l–1. C = concentration of the weak electrolyte. A base is a substance which in aqueous solution gives OH– ions.IONIC EQUILIBRIUM 197 ∴ 4S3 = 3. K = ionisation constant.05 × 10–4 mole l–1. Cl– is a conjugate base of – acid HCl. 1–α≈1 K ∴ K = α2C ∴ α = . ∴ Ksp = 8 × 10–10 = [Sr+2] × [F–]2 = S × (0.45 × 10–11 3 3.PM5 197 . What is the Lowry and Bronsted concept of acid and base? Ans. Ksp of SrF2 = 8 × 10–12. An acid is a substance which in aqueous solution gives H+ ions. 4.1 M NaF Solution = S mole (2S + 0.

AcidI + BaseII AcidII + BaseI Q. 6. Ans. every acid–base reaction proceeds according to the equation i. Q.. [H+] [OH–] = 10–14 and in pure water.8 × 10–16 × 55. Give Lewis concept of acids and bases. 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.ion l–1. 8. 7. Show that solvent acts as a base or an acid according to Lowry Bronsted concept. H . given K for water = 1. + – H ← : O . According to Lowry Bronsted concept acid–base reaction always follows the equation: AcidI + BaseII AcidII + BaseI CH3COOH + H2O H3O+ + CH3COO– HF + CH3COOH CH3COOH2+ + F– H2 O + H2O H3O+ + OH– So..PM5 198 . 18 Kw = K [H2O] = [H+] [OH–] = 1. what will be the [H+] or [OH–]? Ans.5555 = 100 × 10–16 = 1. In pure water.00 × 10–14..8 × 10–16. If the acid is strong. Q. As. Show that ionic product of water (Kw) is 1 × 10–14.e.. its conjugate base will be weak and vice-versa. . H H: N + .. : → H •• acid base acid H base Cl H   Cl  B ← : N  H   Cl H acid base Q. 5.5555 moles l–1. H2O + H2O H3O+ + OH– or H2O H+ + OH– [H3 O + ] [OH − ] [H + ] [OH − ] K= or [H 2 O] [H 2 O] 1000 [H2O] = = 55. NH4+/NH3 and so on.198 ENGINEERING CHEMISTRY Some conjugate acid-base pairs are: HSO4–/SO4=. conjugate acids and bases are formed during the reaction. H3O+/H2O. Ans. H2O/OH–. C-8\N-ENGCHE\ECH8-1. Ans. [H+] = [OH–] ∴ [H+] = [OH–] = 10–7 g. HNO3/NO3–.

37? Ans.699 ≈ 1. [H+] range = 100 – 10–6 g .3 or log10 [H+] = – 2. Q. 8.1 Neutralisation Curves. 13. 11. pH = – log10 [H+] = – log10 [2 × 10–2] (as the acid is strong) = – log10 2 + 2 log10 10 = 2 – 0.PM5 199 . Q. What is pH? Ans. In acidic solutions. What is the hydrogen concentration of coca cola with pH 2. What is the pH of 0. Ans. pH = 2. [H+] = [OH–] = 10–7 g .c.3 or – log10 [H+] = 2.3 or [H+] = 10–2.c. 9.) Alkali(c.3 = 5 × 10–3 mol dm–3. Ans. ion l–1. pH = – log10 [H+] pH = 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 [H+] = 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 acidic ← neutral → alkaline Q. 10. 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.. 12. Q. Explain the pH changes during acid–base titration. ion l–1 In neutral solutions. In alkaline solutions. It is negative logarithm of hydrogen ion concentration.) Strong acid–strong base Weak acid–strong base Fig. Phenolphthalein pH 7 pH 7 Methyl orange 0 0 0 25 0 25 Alkali(c.7.02 mol dm–3 HCl? Ans. pH = – log10 [H+] or [H+] = 10–pH The acidity or alkalinity of a solution is generally expressed by pH.IONIC EQUILIBRIUM 199 Q. [H+] range = 10–8 – 10–14 g .3010 = 1. i. C-8\N-ENGCHE\ECH8-1. The pH scale is a logarithmic scale for measuring the concentration of hydrogen ions in aqueous solutions. ion l–1. Explain the pH scale.e.

Q. Kb = dissociation constant of weak base. hydrolysis of salts does not take place and the solutions remain neutral at the equivalence point (pH = 7). Q.02 mol. When a salt formed at the equivalence point has either a ‘parent acid’ or a ‘parent base’ weak. 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. useful for pH calculations. It is to be noted that. At the equivalence point. Neutralisation reactions do not always produce neutral solutions—explain. H3O+ + OH– → 2H2O (l) Enthalpy change of neutralisation is same for all acid-base partners. at the equivalence point. 17. the pH is not always neutral. 1 1 (iii) pH of a weak base = 14 – p K b + log c 2 2 where c = concentration of undissociated base. Q. if acid and base both are strong.PM5 200 . 8. NaOH is a strong base [OH–] = 0. The ‘strong parent’ in the partnership wins. c = concentration of undissociated acid. strong or weak. dm–3 solution of NaOH? Ans. Weak acid/strong base end point is alkaline (pH > 7) Strong acid/weak base end point is acidic (pH < 7). (i) pKw = pH + pOH = 14 ∴ pH = 14 – pOH 1 1 (ii) pH of a weak acid = pH = pK a − log c 2 2 when Ka = ionisation constant of weak acid. – log10 Ka = pKa.7 pH = 14 – pOH = 14 – 1. – log10 Kb = pKb. Neutralisation is essentially a reaction between H+ and OH– ions in aqueous solution—explain. What is the pH of a 0.02 = 1. We know that. pK is the logarithmic form of an equilibrium constant. How can you use pK values for pH calculations? Ans. when exactly equal amounts of acid and alkali have been added. 15. 14. Ans. C-8\N-ENGCHE\ECH8-1.1). – log10 Kw = pKw Taking logarithms produces a convenient small scale of values. 16. Q.7 = 12. 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. This experimental evidence supports the above view. What is pK? Ans.02 mole dm–3 pOH = – log 0. 18. a salt is formed. Q.3. it hydrolyses to give a solution that is not neutral.

19. Ka × Kb = × = [H3O+] [OH–] [HA] [A − ] = Kw = 10–14. Kb and Kw. (i) The common ion effect can change the ionisation of weak acids and weak bases. (ii) A small variation of pH of human blood (6. K a = 1 [H 3 PO 4 ] [H + ] [H 2 PO4−2 ] (ii) H2PO4– H+ + HPO4–2. What is common ion effect? Ans. 1 a 2 3 Q. Relate Ka. Q. (i) The pH value of soil helps to decide the type of fertiliser to be used in agriculture. which help to keep pH of a solution more or less constant. K a = 3 [HPO −42 ] Ka > K > Ka . Ans. Mention the importance of pH. 22. C-8\N-ENGCHE\ECH8-1. (iii) The common ion effect alters the solubility of a sparingly soluble salt. (iii) pH value helps to determine the condition of reactions in laboratory and in industry. Q. – Ans.PM5 201 . What is a buffer solution? Ans. ∴ Ka × Kb = Kw or – log Ka – log Kb = – log Kw ∴ pKa + pKb = pKw = 14. K a = 2 [H 3 PO4− ] [H + ] [PO 4−3 ] (iii) HPO4–2 H+ + PO4–3.7) causes bodyache. Ans. H3PO4 has three Ka values–explain. Q.IONIC EQUILIBRIUM 201 Q. 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. (ii) The common ion effect influences the behaviour of buffer solution. [H + ] [H 2 PO 4− ] (i) H3PO4 H+ + H2PO4–. There are three dissociations for H3PO4 and accordingly ka values. Buffer solutions are mixtures of a weak acid and its salt or a weak base and its salt. 21. (i) HA + H2O H3O + A acid base Conjugate pair [H 3 O + ] [A − ] Ka = [HA] – – (ii) A + H2O HA + OH Conjugate pair [HA] [OH − ] Kb = [A − ] [H 3 O + ] [A − ] [HA] [OH − ] Now. 20. 23.

Deduce the Hendersen equation and state its utility. Explain (a) neutralisation. will not be obtained. The reaction HCl (aq) + KOH (aq) → KCl (aq) + H2O is neutralisation according to: (a) Bronsted-Lowry concept. 6. (MnS) = 1. 18. Deduce the relation between solubility and solubility product of CaF2 at room temperature. Deduce Ostwald’s dilution law and state its limitations. Explain the terms: (i) Buffer solution (ii) Buffer capacity and (iii) Buffer action. H2S 2H+ + S–2. Explain the following–Aqueous solution of NaCl conducts electricity while chlorine water does not conduct electricity. 2. 15. Derive an expression for pH of the buffer solutions: (a) Weak acid and its salt. What is the pH of a buffer solution containing 0.01) [S −2 ] ∴ 1. Discuss the effect of common ion on solubility product. 12. Give the Bronsted-Lowry concept of acids and bases. (b) BeCl2. 100 .4 × 10–15 So.40 = 3. Ans. 8.4 = 4. FG N IJ Mn FG N IJ H Q. Elucidate.01) 2 × [S −2 ] (0. Show that it is different from dissociation con- stant of water. 3. 13.202 ENGINEERING CHEMISTRY Q. BCl3.1 × 10–19 = 10–20 Ksp . in the light of Bronsted theory. Derive an expression for ionic product of water. 20. (b) Weak base and its salt. ppt.1 ∴ [S–2] = 10–19. (b) hydrolysis.8. C-8\N-ENGCHE\ECH8-1.PM5 202 .2. Tricovalent phosphorus compounds can serve as Lewis bases and also as Lewis acids–comment. BI3.8 + 0.0 mol dm–3 sodium methanoate? pKa(HCOOH) = 3. 17. 25. 9. ∴ [Mn+2] [S–2] = 0. K = = 1. BCl3.1M] [H 2 S] 0. (b) Lewis theory and (c) Solvent system concept. Which are the strongest Lewis acids in the series? (a) BF3.1 × 10–22 [H 2S] (0.4 mol dm–3 methanoic acid and 1.1 × 10–22 = = [Q S H 2S = 0. Will H 10 K +2 containing H 100 K + be precipitated by passing H2S? [H + ] [S −2 ] Ans. 16. 24. What do you mean by autoprotolysis of water? 11. What is a buffer solution? Explain buffer action. What is pH? Give its importance and usefulness. Give an expression for the solubility product of the salt Ax By. What do you mean by solubility product? What is true solubility product? 19. What do you mean by common-ion effect? How is it utilized in qualitative chemical analysis? 10. 7. EXERCISES 1. 4. pH = pKa + log 0. 5. What is the basic equation for acid-base reaction of Bronsted theory? 14.

00886 (N) base [Ans.95. Ksp(PbS) = 3.57.1 × 10–23. Given Kb = 2 × 10–5.IONIC EQUILIBRIUM 203 21. 5 × 10–8 g-in l–1] 30. Solubility of PbSO4 is 0. of CH3COOH and 7. What will be the pH of a solution obtained by mixing 800 ml of 0. 4. 5.1N HCl.46.PM5 203 . Solubility of Ag2CrO9 g-l–1. Calculate the [H+]. (a) 2.05] assuming complete dissociation. [Ans. [Ans. 2.69 × 10–11 moles l–1] 26. [Ag+]in a solution is 4 × 10–3 g-in l–1. [Ans.000775 (N) acid (c) 0. 10. Given Ka(H2S) = 1. .00345 (N) acid (b) 0.54 (b) 3.4 × 10–12} 29. 1.78] 25.6 × 10–8] 28. 13] 23.11. Given Ksp of AgCl = 1.038 g-l–1. Calculate the minimum concentration of Cl– to precipitate –10 AgCl.014] 24. 1.4 × 10–28. [Ans.3] 22. 11.89 (c) 11. making a volume equal to 500 ml? [Ans.5 g. pH of a solution is 10. What will be the pH of a solution obtained by mixing 5g. of CH3COONa. 12. Calculate the pH and pOH of . [Ans. Find α for NH4OH in a solution of . [Ans. Calculate the concentration of H2S required to arrest the precipitation of PbS from a solution of 0. Calculate its solubility product.001 (M) Pb(NO3)2. [Ans.05 (N) NaOH and 200 ml of 1N HCl? [Ans. 1. 2.8 × 10 .6 (M)] C-8\N-ENGCHE\ECH8-1. Calculate the pH and pOH of: (a) 0. Calculate its solubility product.1M. 27.

Table 9. 204 . Some conduct it and some do not.e. bases etc. Substances which conduct electricity are conductors. acids. Substances which conduct electricity and get dissociated in solution or in the fused states were termed electrolytes by Faraday. metals. • It involves no chemical change during • Chemical change takes place i. and which do not conduct electricity are nonconductors as for example. Electrolytes dissociate when they conduct electricity i. acids. as for example. 9. 9.. alkalies are examples of such electrolytes. The current is always passed into and out of the electrolyte by means of metal foils or plates Battery + – Anode Cathode + – Voltameter Electrolyte Fig. wood. Electrolysis Dissociation of a compound by passing electric current through a compound in solution or in fused state is known as electrolysis.e. of electricity through them. new pro- conduction of current.1.1 Set-up for electrolysis.. Again conductors can be divided into two subdivisions: (i) electrolytes and (ii) non- electrolytes. Salts. An arrangement for electrolysis is shown in Fig. asbestos etc. a chemical change occurs then. But some physical ducts are obtained during conduction of changes may occur. current. 9 Electrochemistry INTRODUCTION Substances behave differently towards electric current.1: Comparison Metallic conductors Non-metallic conductors (electrolytes) • Flow of electrons takes place during the • Flow of ions takes place during the passage passage of electricity through them. whereas when non-electrolytes conduct electricity there is no such chemical change.

the amount of positive charge being exactly equal to the amount of negative charge. c = 1 and t = 1.PM5 205 . Z is mass of ion liberated by unit quantity of electricity. W = Z i. the relative masses of ions liberated are proportional to their chemical equivalents. When Q = 1 i. The anions migrate towards the anode and cations migrate towards the cathode.. When an electrolyte (electrically neutral) is dissolved in water (or in fused state). positive and negative. This theory of electrolytic dissociation was first put forward by Arrhenius. This dissociation is complete at infinite dilution.E. + – + – + – + – 1 2 3 H2O + Acid CuSO4 solution AgNO3 solution Fig. 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. 9. If W = the mass of ion liberated in gms. which conduct electricity.e. not the undissociated molecule.e.. NaCl Na+ + Cl–. They are electrodes (cathode and anode). It is the ions. Z is called electrochemical equivalent (E. that is why the theory is known as Arrhenius ionic theory. NaOH Na+ + OH– etc.2 Different voltameters containing different electrolytes. Such a dissociation of an electrolyte is called ionic or electrolytic dissociation. Q = the quantity of electricity in coulombs. Second law: When the same quantity of electricity is passed through different electrolytes.). t = the time in secs. C-8∴N-ENGCHE∴ECH9-1. then according to first law: W ∝ Q but Q=c×t ∴ W ∝ ct ∴ W = Zct where Z is a constant. c = the current strength in amperes. An ion is an atom or a group of atoms carrying positive or negative charge of electricity. The liberation of the ions at the electrodes depends upon their discharge potentials. The ions produced exist in equilibrium with the undissociated electrolyte molecules.C. it breaks up into two or more ions of two different kinds.ELECTROCHEMISTRY 205 kept immersed in it.

the quantity of electricity = Q coulomb the quantity of Cu deposited = W1 g the quantity of Ag deposited = W2 g Then. to liberate 1 gm equiv. W ∝ Q (where E is constant) From second law.) K QE ∴ W = KQE = F From first law. of any element during electrolysis. of hydrogen.PM5 206 .008 1 So.C. This quantity of electricity is called one faraday (F).E.C. of any element = Chemical equivalent of the element × E.) = ZF E or F= Z C-8∴N-ENGCHE∴ECH9-1. equiv. of hydrogen = ZH.206 ENGINEERING CHEMISTRY That is to say.E. of any element = Z E × ZH E × ZH ∴ Z= ≈ 1. then. 9. 1 ∴ F=Q= (for 1 gm. W ∝ E (where Q is constant) ∴ W = KQE (where E and Q vary) W or Q= (K = Constant) KE 1 When W = E. the quantity of electricity is fixed.E. E. according to Faraday’s second law: W1 E 1 Z 1Q = = (from the first law) W2 E2 Z 2 Q E1 Z 1 E1 E2 ∴ = or = or E ∝ Z E2 Z 2 Z1 Z2 So chemical equivalent of an element is proportional to its electrochemical equivalent. Q = K Therefore. W = ZQ or E = ZQ (for 1 gm. equiv. E.E.C. E Z E × ZH = or Z = EH Z H EH Chemical equivalent of hydrogen = EH. If one of the elements is H.2).5/2 g Cu will be liberated in cell (2) and 108 g Ag will be liberated in cell (3) (Fig. when 1 g of H2 is liberated in cell (1). Let. 63. Combination of First and Second Laws of Faraday From first law.C. chemical equivalent of any element = E E.

0 0. then current is wholly carried by cation. We can say that the cation transport number is hundred per cent and the anion transport number is zero per cent.0003294 96494 96495 O 8. So. cations and anions present in the solution conduct current.3).ELECTROCHEMISTRY 207 for one gm equivalent of different elements E 1 E2 E = = .. So. So we can define transport number as the fraction of the current carried by an ni Z i ion.3 Concept of transport number. the transport number of anions is hundred per cent and that of cations is zero per cent. Usually both cations and anions cross the barrier (ab) but in unequal numbers owing to their unequal speeds. 1 F = 96500 coulomb.e. ni = number of the ions and Zi = valency of the ions which cross the barrier. Table 9.PM5 207 . t+ ∝ u and t– ∝ v and (t+ + t–) ∝ (u + v) But t+ + t– = 1 u v ∴ t+ = and t– = u+ v u+ v where u and v are the speeds of cations and anions respectively. a A C A N T O H D O D E E b Fig.. If 100 cations cross the barrier from left to right. if 80 cations cross the barrier (ab) towards cathode compartment and 20 anions cross the barrier (ab) towards anode compartment.. 9.0000829 ≈ 96500 The concept of transport number.. C-8∴N-ENGCHE∴ECH9-1.. Transport number is proportional to speeds of the ions. Ions of an electrolyte i.008 0. The case may be totally reversed.2: Displaying the constancy of E/Z for different elements Element E Z F = E/Z (Coulomb) H 1..78 0.0001118 96495 Cu 31.88 0.. It is to be noted that deposition at the electrodes in the above two cases will be same (Fig. so their transport numbers are unequal.0000104 96496 Ag 107. 100 units but the current carried by cations is 80 per cent and the current carried by anions is 20 per cent.e. = n = F Z 1 Z2 Zn Therefore. we can accept that. in that case. 9. transport number (t) = Σ ni Z i where. the total quantity of the current passed will remain same as above i. For example.

A and B.4) Current carried by the positive ions = I+ = (n+u)z+e Current carried by the negative ions = I– = (n–v)z–e. 9. and the valency of ions is z(±). 9. the solution contains n(±) number of ions per millilitre + – A B + – + – + v u Fig. The total current carried by the positive and negative ions = I = I+ + I– = (n+u)z+e + (n–v)z–e. 9.5). but it is not so. this phenomenon creates an idea that perhaps the ions move at the same rate during electrolysis. The number of ions liberated at the positive and negative electrodes per unit area are given by n+ u and n– v. If unit of the charge is ‘e’ (Fig. The current I is flowing. n+z+ = n–z– I+ n+ z+ eu n+ z+ eu u So. Let the two electrodes. are kept inside an electrolyte and their potential difference is E. t– = = = = I n+ z+ eu + n+ z+ ev n+ z+ e(u + v) u + v u v ∴ t+ = and t– = u+ v u+ v It is obvious that. The following model will make the idea clear (Fig.208 ENGINEERING CHEMISTRY Transport number or transference number of an ion is dependent on the speed of the ions. therefore.PM5 208 . ions are always discharged in equivalent amounts but their speeds are different. C-8∴N-ENGCHE∴ECH9-1. As every part of the electrolyte is electrically neutral. t+ = = = = I n+ z+ eu + n+ z+ ev n+ z+ e(u + v) u+v I− n− z− ev n+ z+ ev v Similarly.4 Voltameter. 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.

we get the picture (II). the number of anions and cations discharged is the same i.ELECTROCHEMISTRY 209 Anode Middle Cathode + compartment compartment compartment – I ++++ ++++++ ++++ –––– –––––– –––– II ++++ ++++++ ++++ –– –––– –––––– –– III ++ ++++++ ++++++ –––– –– –––––– –– IV ++ ++++++ ++++++ ––– –– –––––– ––– a o Fig. In this case also. The total number of cations and anions discharged is again the same three. The ‘+’ sign represents a cation and ‘–’ sign represents an anion. but the concentration of both the compartments has fallen to the same extent i.5 Scheme showing the equivalence of discharge for any relative rate of motion of the two ions. (iv) When the ions move at the different speeds. Although concentration in the cathode compartment has fallen by one mol- ecule and that of anode compartment has fallen by two molecules. (ii) When only the anions move. we get the picture (III). 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.PM5 209 . (i) 4 molecules each in the anode and cathode compartments and 6 molecules in the middle compartment. The concentration in the anode compartment has not altered while the concentration of the cathode com- partment has fallen by two molecules due to deposition of ions at the respective electrode. Let when two cations have crossed the diaphragm towards the cathode. Let two anions have crossed diaphragm towards the anode.e.. We get the picture (IV). one anion passes towards anode. four.e. by two molecules due to deposition of ions at the respective electrodes. 9. Let two cations and two anions have crossed the diaphragms towards cathode and anode. 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 C-8∴N-ENGCHE∴ECH9-1.. (iii) When the anions and cations move at the same rate. Let there be total 14 molecules in the electrolyte. The cations did not move at all.

A dilute M – + AgNO3 solution (N/20) is taken for electrolysis.01 A B to . equivalence liberated from both the compartments is proportional to (u + v). Total number of equivalence of the electrolyte liberated on the electrode Determination of Transport Number (Hittorf’s Method) Two broad vertical glass tubes A. The solution from the anode compartment is taken for analysis (Fig.02 amp. Actual weight of AgNO3 present = y g so.210 ENGINEERING CHEMISTRY The total gm. 9. A milliammeter M. e Let. No. the total weight of AgNO3 should have been present (x – y) g of water in the anode compartment = (W + z) g. = (W + Z) – y = {W – (y – Z)}g. 108 If no migration would have taken place. B are connected in the middle by a ‘U’ tube ‘e’. coulometer X are connected in series. is passed for a period of 2–3 hours through the AgNO 3 solution. t+ = Total number of equivalence of the electrolyte liberated on the electrode The number of electrolytes lost from cathode compartment t– = .6). The solution collected from anode (anolyte) = x g The amount of AgNO3 in x g anolyte =yg Fig. The three tubes are fitted with Y R stopcocks. loss due to migration. of equiv. of AgNO3 lost from anode compartment due to migration tAg + = No. y g .6. of silver deposited in the coulometer W – ( y – Z) × 108 tAg + = 170 × w ∴ tNO – = 1 – tAg + 3 C-8∴N-ENGCHE∴ECH9-1. After a definite time. A current 0. the current is stopped. The increase in weight of AgNO3 in anode compartment due to dissolution of silver from w × 170 the anode = = Wg.PM5 210 . AgNO3 = (x – y) g AgNO3 present in (x – y) g of water before electrolysis = z g. Transference number The amount of water containing determination by Hittorf’s method. 9. The tubes are fitted with silver plates which act as X anode and cathode which are introduced into A and B. of equiv. The number of electrolytes lost from anode compartment So. Weight of silver deposited on cathode in the coulometer = w g.

Calculate the transport number of Ag+ and NO3– ions when the speed ratio of the two ions is 0. Increase in wt.50 tCd + 2 0. CdI2 ionises as follows in a concentrated solution: 2CdI2 Cd+2 + [CdI4]–2 +2 i.442 0.153 and Transport number of SO4– – = (1 – tCu + + ) = (1 – 0.003 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 .153 – 0. increase of wt.12 g. of Cu+2 in the liquid per unit vol.916 during electrolysis of a silver nitrate solution.785. This abnormal transport number does indicate the formation of complex ion.91 g respectively.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 CdI2.521 1 + 0.521) = 0. due to dissolution of Cu anode during electrolysis = (0. Fall in concentration due to migration of Cu+2 ions = (0.916 Speed of NO 3 − v u 1– n 1 r= = (n = tNO 3 – ) or n = v n 1+ r 1 n = tNO 3 – = = 0.79 g. C-8∴N-ENGCHE∴ECH9-1. would have been 0. Let.444 0.10 0. Increase in wt. Speed of Ag + u = = ratio (r) = 0.05 0..PM5 211 .e. Concentration (N) 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’.916 tAg + = 1 – tNO – = 1 – n = (1 – 0.396 0.153 g.12 g.127 0. surrounding anode = 0.91 g.79 and 0. If no Cu++ had migrated from the anode. of Cu+2 in the liquid per unit vol.479. But actual increase = 0. Example 2. This is true for other complex compounds too. In an electrolysis of CuSO4 between copper electrodes the total mass of copper deposited at cathode was 0.02 0. Example 1.215) = 0.91 – 0. 0.33 ∴ Transport number of Cu++ ( tCu + + ) = = 0.12) g = 0.20 0. After electrolysis the amt.153 g and masses of Cu per unit volume of the anode liquid before and after electrolysis were 0.01 0. of Cu-cathode in the coulometer = 0. It can only be explained by the formation of complex ions. Calculate the transport number of the Cu++ and SO4– – ions. Cd ion is moving towards both cathode and anode and towards anode due to above complex ion formation.215 0. surrounding anode = 0. Before electrolysis the amt.79) g = 0.296 0.153 g.033 g.

equivalent–1. Kappa). it is the conductivity of 1 cm3 of the solution. 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. But the value of λv or λm actually increases with dilution as it is the product Kv × V and on C-8∴N-ENGCHE∴ECH9-1. l = 1 and a = 1. 1 l 1 cm × 1 K= = .V a R N Kv = . λv = KvV. l 1 LM3 l 1 OP = .e. –1 2 Effect of Dilution on Conductance The value of specific conductance (K) is expected to fall with dilution of an electrolyte solution.. Molar Conductivity (λm) It is defined as the conductance of all the ions present in one mole of the electrolyte in a solution. the specific conductivity of the solution is known as Kv. If M is the concentration in moles l–1. a R Q cm × 1 × cm 3 = cm 2 × ohm × g . the volume of the solution containing 1 g-equivalent will be 1000/C. λv = K v × C We know that.e. then 1000 K λm = M The unit of λm is ohm cm mole–1. If C is the concentration of the solution in g-equivalent l–1. When. Equivalent Conductance If one g-equivalent of an electrolyte is dissolved in V ml of the solution. its value is dependent on material of the conductor and is known as specific resistance. the conductivity of all the ions of the electrolyte present in the solution is known as equivalent conductance and is abbreviated as λv i.PM5 212 . λv = KvV. or ρ = a l where ρ = constant. i. R = ρ Therefore..equivalent = ohm–1 cm2 g .212 ENGINEERING CHEMISTRY l Ra ∴ R=ρ. The reciprocal of specific resistance is termed specific conductance or specific conductivity (K. 1000 then. = = ohm–1 cm–1 = mho cm–1 ρ a R cm 2 × ohm If a solution acts as an electrolyte. . as the number of current carrying ions per ml of the solution should gradually decrease.

2 41. no increase of λv or λm with dilution.3 0. Strong electrolyte Molar conductivity Weak electrolyte Concentration Fig. After a certain dilution there remains no more electrolyte molecule to ionise and then there is no change i.1 0.0 0.0000752 0. Such electrolytes whose λv values increase with dilution are known as weak electrolytes (see Fig.0000129 0.000041 127.2 14.4 2. 9.e.ELECTROCHEMISTRY 213 dilution more and more of the electrolyte ionises.2 1.30 0.7 Change of equivalent conductivity with dilution.0 Classification of Electrolytes (i) Strong electrolytes: Strong acid HCl.8).3 Specific conductivity (Κ) Equivalent conductivity (λv) Normality KCl CH3COONa CH3COOH KCl CO3COONa CO3COOH 1.00611 0.0 0.C. is necessary to avoid this difficulty.9 61. Such electrolytes are called strong electrolytes.0001276 0. C-8∴N-ENGCHE∴ECH9-1.01119 0.1 2.001005 102.05115 0.0247 0.0982 0.000702 0.00132 98.0412 0. The modification is necessary as the passage of current will electrolyse the electrolyte.8 107.2 41.PM5 213 . strong alkali NaOH have high conductances even at low dilutions and there is no sharp increase in their equivalent conductances on dilution. (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.001225 0.000143 122.5 0.7).. The products of electrolysis will accumulate on the electrodes which will change the effective resistance.00000768 0.0001 0.6 75.3 49.5 76.82 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∞.01 0. 9. The use of A. 9. Experimental Determination of Specific Conductance (K) The arrangement of apparatus adopted for the determination is modified Wheatstone’s meterbridge arrangement (see Fig.00024 111. Table 9.5 70.001 0.01 0.0000107 129.

Conductivity water (double distilled water) should be used throughout.002768 ohm–1 . 9. When the sound in the telephone is minimum or zero reading on the appropriate meter. 9. But the procedure is to calculate a factor for each cell known as cell constant (x). Fig.C.8 Determination of conductivity of solutions. The The cell constant is known by determining the conductance of H 50 K K value of the solution has been accurately determined by Kohlrausch to be 0.9. cm–1 at 25°C. (c) the electrolyte is taken in a cell containing platinised Pt electrodes (Fig.9 Conductivity cell. Source Fig.PM5 214 . 1 b 1 =x× =x× × ρ a R C-8∴N-ENGCHE∴ECH9-1.9). The solution whose conductance is to be measured is put into the conductivity cell (see Fig. 9. 9. C is a compensating condenser (adjustable). (b) the use of telephone detector or magic eye indicator.. the cell should be placed in a thermostat.9). The modifications are: (a) the use of A. Specific conductance K = x × Observed conductance. FG N IJ KCl solution. Calculation of Specific Conductance (K) If necessary ρ is calculated from the observed resistance. the resistance R of liquid enclosed between the electrodes is: l R=ρ× =ρ×x s where l/s = x is cell constant. Different cells are in use. Specific conductance = Observed conductance × Cell constant When l is the distance between the electrodes and s. 9.214 ENGINEERING CHEMISTRY C R R T S A a b B Platinum electrodes X A. the area of cross-section of the electrode. Connections are made by Pt wires. if the area of the electrodes and the distance between them are accurately known.C. the common form is shown in Fig. specific resistance ρ is given by the following equation: ρ a = R b Since the conductivity of a solution rapidly increases with temperature.

Highlights: l • It should be noted that cell constant (x) = where l is the distance between the s electrodes and s is the mean area of the electrodes.3 0. The cell constant being known it is easy to obtain the specific conductance of any solution by using the above relation..00076 SO4– 79. 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. the higher is the observed conductance and so for weak electrolytes a conductivity cell having a small cell constant should be used.00055 HCO 3– 44. λ∞ = λc + λa where.4 Ionic Conductance and Ionic Mobilities of some Ions at Infinite Dilution at 25°C. • According to equation: K = x × observed conductance.00062 NO 3– 71.00042 It is evident from the table that each ion contributes a certain definite quantity towards λ∞ of the solution. i.6 0.1 0.002768.00064 1 Ca++ 59.00046 2 Na+ 50.5 0. 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.PM5 215 .00079 Ag+ 61.00083 2 NH 4+ 73. U Anion λa Mobility. C-8∴N-ENGCHE∴ECH9-1.e.00074 2 1 Mg++ 53.9 0. V cm2/sec.4 0.1 0. volt cm2/sec volt H+ 349. λc = Ionic conductance of cation. Cation λc Mobility.ELECTROCHEMISTRY 215 FG N IJ KCl be l If the observed resistance with H 50 K 1 the cell constant (x) = ρ1 × 0.8 0. λ∞ = Ionic conductance of anion.00052 CH 3COO– 40.00205 1 K+ 73.5 0.8 0.9 0. This regularity was first observed by Kohlrausch and was put in the form of a law which is known as Kohlrausch’s law.5 0.00076 Cl – 76.4 0. The lower the cell constant.00362 OH– 197.

Calculate λ∞ for CH3COOH. We have (i) λ Na + + λ CH COO − = x 3 (ii) λ H + + λ Cl − = y (iii) λ Na + + λ Cl – = z. y and z. But λ∞ for weak electrolytes can be calculated from Kohlrausch’s law. HCl and NaCl are x. Example: The λ∞ values for CH3COONa.11 ohm–1 Br– = 78.PM5 216 . λ∞ association with other ions. F C C-8∴N-ENGCHE∴ECH9-1. λc ∝ u or λc = ku λa ∝ v or λa = kv where k is a constant.216 ENGINEERING CHEMISTRY Highlight: Kohlrausch’s law can be stated in another way: At infinite dilution. It 1000 Ah = t+ . So. respectively. λm + + – – where r+ and r– are numbers of cations and anions and λ +∞ and λ ∞– are molar conductances of cations and anions respectively. And λ∞ = λc + λa = ku + kv = k(u + v) λc kv u ∴ = = = t+ λ ∞ k(u + v) u+ v λa kv v And = = = t– = (1 – t+) λ ∞ k(u + v) u + v So. because they do not ionise to a sufficient extent in solu- tion. Ionic conductance possesses a constant value at a definite temperature.34 ohm–1 NH4+ = 73. λ∞ + r . when the dissociation of an electrolyte is considered complete. ( λ + + λ Na CH 3COO – + λ H + + λ Cl − ) – ( λ Na + + λ Cl – ) = (x + y – z) = (λ CH 3COO − + λ H + ) λ∞(CH3COOH) (iii) Ionic mobility (Absolute velocity of ions) We have. Its unit is ohm–1 cm–2 and is directly proportional to the speeds of the ions.40 ohm–1 NO3– = 71.22 ohm –1 Cl– = 76. the ionic conductances of cations and anions can be determined from their experimentally determined transport numbers from the above relations. Thus. except at a infinite dilution.4 ohm–1 + K = 53. (ii) Determination of λ∞ of weak electrolytes: λ∞ for weak electrolytes cannot be determined experimentally.44 ohm–1 Applications of Kohlrausch’s law (i) Determination of ionic conductances. Examples are: λm∞ (KCl) = λ ∞ K ∞ ∞ – and λm (K 3PO 4) = 3λ + + λ ′PO + λ Cl ∞ ∞ −3 K 4 Ionic Conductance of Some ions at 25°C Na+ = 50. each ion makes a definite contribution towards the molar conductance of the electrolyte irrespective of its ∞ = r .

V = . And the end point is determined. Ideally two straight lines are obtained which intersect at the equivalence point [Fig. C-8∴N-ENGCHE∴ECH9-1. • The H+ ions are about five times and OH– ions are three times faster. where V = mobility of anion in cm sec–1 under potential gradient F 1 V cm–1. Ionic mobilities can easily be calculated. Ionic conductance = Ionic mobility × F Ionic conductance or Ionic mobility = F Therefore. C = Concentration (equiv. The conductance of the solution is measured after each addition of titrant and the results are expressed graphically (conductance vs volume of titrant). h = The distance through which cation moves.10(a)]. h FG K × 1000 IJ 1 1 d i U= t = t+ HC FK × = tλ ∞ F 1 λ = λc × = c [3 t+ λ∞ = λc] F F λa Similarly. A = 1. • 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. Potential gradient = 1 V cm–1 1 1 Specific conductance K = = =I [3 V = 1 V cm–1] ρ V /I Let. 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. dm–3) It = amp × sec = Q = quantity of current (coulomb) F = Faraday. U = Mobility of cation in cm sec–1 under unit potential gradient of 1 V/cm distance h So. So.ELECTROCHEMISTRY 217 where. And the use of this conductivity change is made to determine the equivalent point of reactions involving neutralisation reactions or precipitations. when. U= = time t For very dilute solutions. 9. Highlights: • The ions move very slowly.PM5 217 . Conductometric Titration During a titration. A = Cross-section of the tube through which current passes.

10(b)]. 9.218 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. The titration of KCl solution vs AgNO3 solution satisfies the above conditions. base (NaOH) (aq). Highlight: The stronger the solution used for the titration. end point of the reaction can be determined easily.10 (c). 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. For this reason.10(a)]. Conductivity falls as OH– (aq) ions are neutralized Conductivity Conductivity rises Conductance due to excess H+ (aq) ions added Conductivity of Na+Cl– (aq) End point Volume of HCl (aq) added Volume of alkali Fig. the decrease in conductance is due to the replacement of OH– ions (molar ionic conductivity = 199) by Cl– ions (molar ionic conductivity = 76). The conductance then rises beyond the equivalence point. 9. 9. so they (CH3COOH) (aq) with a strong conduct electricity very well. In water H+(aq) during titration of a weak acid and OH–(aq) ions are very mobile. 9. 9. dissociation or solubility of the reaction products. The nature of the titration curve is as in Fig. Beyond the equivalence point. • Measurements of conductance in the region of equivalence point are of little value due to hydrolysis. So.10 (a) Changes in conductivity during titration Fig. C-8∴N-ENGCHE∴ECH9-1. there is always an initial decrease in conductance. the increase in conductivity is due to excess of H+ ions with very high ionic molar conductivity (350). The point of intersection of the two curves is sharp.PM5 218 . The precipitate should be formed fairly rapidly and should not have strong adsorbent properties. the graph shows a curvature rather than a clear intersection of the two straight lines [Fig. (b) Precipitation Reactions Conductometric titrations of this type may be performed if the reaction product is sparingly soluble salt. 9. (a) Neutralisation Reactions In the titration of a strong acid with a strong base. In the titration of HCl with NaOH.10 (b) Changes in conductivity of NaOH(aq) with HCl(aq). the sharper is the end point (Fig.10). In the titration of NaOH with HCl.

5 Sol. If the cell is filled with an electrolyte and offers a resistance of 1996 ohm. Cell constant = and R=ρ a a l R 1 or = =R× =R×K a ρ ρ l ∴ = 500 × 0. l 10. 1996 Specific conductivity = Cell constant × observed conductivity. 50 If the resistance of cell containing this solution is 500 ohms. In the region of the equivalence point. C-8∴N-ENGCHE∴ECH9-1. calculate the cell constant and specific conductivity. The equivalence point is located by extrapolating the straight lines.0002765 cm–1 a = 0. due to hydrolysis the titration curve shows a marked curvature (Fig.10(b)). Specific conductivity of an KCl solution at 25°C is 0. They are 10. N Example 2. A conductivity cell contains two electrodes of area of cross-section 1.4 cm–1 a 1. 9.0002765 mhos cm–1.5 cm.10 (c) Titration curve of KCl solution by AgNO3 solution.2 × 10–3 ohm–1 cm–1. Cell constant = = = 8. Titration of a very weak acid with strong base or a very weak base with strong acids results in a small initial conductance. what is the cell constant? l l Sol. 1 1 = 8. SOLVED EXAMPLES Example 1.4 × 1996 1996 = 4.25 cm2. 9.PM5 219 .4 × = 8.138 cm–1. The conductance increases as the concentration of the salt increases. apart.ELECTROCHEMISTRY 219 Conductance Volume of AgNO3 Fig.25 1 Observed conductivity = ohm–1.

02109 ohm–1 cm–1 72.5224 × = 0.9 ohm cm .5224 cm–1 Again.2 = 105. C 0.58 ohm.4 cm2 in area was found to be 32 ohms. Cell constant = R × K = 550 × 0.4 K = 0.02109 λm(molar conductivity) = = M 0. the observed resistance of the cell is 4364 ohm. Calculate the equivalent conductance (λv ) of the solution.18 ohm. A conductivity cell containing 0. If the cell is filled with another solution the observed resistance is 3050 ohm. Calculate specific resistance of the solution.1 –1 = 210. l l Sol.1 C-8∴N-ENGCHE∴ECH9-1. 2 Example 5. Calculate the cell constant. Example 4. R=ρ or = = × a ρ R a 32 5.2 N ZnSO4 . Specific conductivity of a conductivity cell containing 0.010416 ohm–1 cm–2 1000 K 1000 × 0.02 N KCl solution offers a resistance of 550 ohm at a definite temperature. Cell constant = R=ρ a a l R 1 or = =R× =R×K a ρ ρ l ∴ = R × K = 4364 × 2.166 ohm–1 cm–2.220 ENGINEERING CHEMISTRY Example 3.075 cm–1 a R 3050 ρ= = ohm. the observed resistance of the cell is 72. cm. K = cell constant × observed conductivity 1 = 1.PM5 220 . If the cell is now filled with 0. l 1 1 l 1 18 .02 N solution at that temperature is 0.075 = 252. l/ a 12.18 1000 λv(equivalent conductivity) = Kv × C 1000 = 0. The resistance of a decinormal solution of a salt occupying a volume between two Pt electrodes 1.02109 × 0.767 × 10–3 ohm–1 cm–1.010416 λv = = = 104. Sol. Calculate the equivalent and molar conductivities of the ZnSO4 solution.2 (N) KCl is 2. Sol. cm.767 × 10–3 cm–1 = 12.80 cm apart and 5.002768 ohm–1 cm–1. The specific conductivity of 0.002768 = 1.45 ohm–1 cm2 1000 K 1000 × 0.

Equivalent conductance of acetic acid at 25°C is 0. 3 Sol. The equivalent conductances at infinite dilution of various electrolytes are given: λ∞HCl = 426. Example 8.PM5 221 .0 – 126.1 + 91.05α .1 λ∞AcONa = 91. wt.6 Example 7.004 ohm–1 m2 eq–1 = 0.3 mho eq–1 cm2. 1 – α ≈ 1] = 0.1233.0388 λv 0.0018 ∴ Degree of dissolution = = = 0. Its equivalent conductance at infinite dilution is 390.5 = λ∞ AcOH = 390. C-8∴N-ENGCHE∴ECH9-1.05 = .004 ohm–1 m2eq–1. λv 48. Ag = 108.05α (0.0388 Example 9. Calculate the degree of dissociation of acetic acid.05α2 Ka 1.15 Sol. (Ka = 1.01898. α= = = 0. λ∞HCl + λ∞AcONa – λ∝NaCl = (λ H + + λ Cl – ) + (λ Na + + λ OAc – ) − (λ Na + + λ Cl – ) = λ H+ + λ OAc – = λ∝AcOH ∴ 426.15 ohm–1 cm–2 eq–1 at 298 K. Calculate the percentage ionisation of acetic acid. Example 10. Strength of CH3COOH solution = g equiv. The specific conductivity of saturated solution of AgCl is 1. Calculate the degree of dissolution of acetic acid.8 × 10–5).0348 ohm–1 m2 eq–1 and 0.046. The equivalent conductance of 1. respectively. Sol.05 0.6 Ohm–1 cm2.05 0. Cl = 35.05(1 – α) .05 0 0 Degree of ionisation = α At equilibrium = . what will be the concentration of acetate ion. λ∞ 0. If ionic conductance of H+ ions and CH3COO– ions at infinite dilution are 0. l–1 = 0.0348 + 0.ELECTROCHEMISTRY 221 Example 6.028 × 10–3 (N) acetic acid is 48.8 and 65.24 × 10–6 mho cm .0018 ohm–1m2 eq–1.05α × 0. Calculate λ∞(AcOH).05(N) 60 CH3COOH CH3COO– + H+ Initially = 0.0λ∞ NaCl = 126.05 (1 – α) 0.5).05 [α being negligible. The mobilities of Ag+ and Cl– ions are 53.8 × 10 −5 18 × 10 –6 ∴ α= = = = 18. If 3g of acetic acid is added to enough water to make one litre solution. λ∞(CH3COOH) = λ∞H+ + λ∞CH3COO– = 0.05α [CH3 COO – ] [H + ] 0. Calculate the solubility –1 of AgCl in gl–1 (At. λ v∞ 390.05) 2 α 2 Ka = = = [CH 3COOH] 0.5.6 ohm–1 cm–2 eq–1.9 × 10–3 0. Sol.

of Cu( x) wt.6236 g.88).1351 = = 63..478 = 0. A dilute solution of CuSO4 was electrolysed.0398 ∴ tSO4∞ = 1 – tCu +2 = 1 – 0. = = Speed of NO 3 – v 1.000 u 0. of Cu Eq.1351 g.PM5 222 . 3 Example 12.916 Sol. Wt. λα(AgCl) = λ(Ag+) + λ(Cu–) = 58.6350 g. The speed ratio of Ag+ and NO3– ions in a solution of AgNO3 electrolysed between Ag-electrodes is 0. ∴ Loss in wt.5) g l–1 = 0. of Ag x 0.1 mhos eq–1 cm2 λv = KvV λ ∞v 119.1 ∴ V= = = 9. Speed of Ag + u 0.6 107.24 × 10 –6 = 9.6350 – 0.6 × 102 l eq–1 1 ∴ Solubility = eq l–1 = 0.88 Loss at anode 0. tNO – = 1 – tAg + = 1 – 0. of Cu from anodic solution (anolyte) = (0.286 = 0. ∴ Amt. Find the transport number of Ag+ and NO3– ions. λα = λ+ + λ– i. Calculate the transport number of Cu+2 and SO4–2 ions. using Pt-electrodes. of Ag deposited in voltameter = 0. wt. and 0.88 2 0. Cu(63. placed in series. [At.6)] Sol.6236 g before and after electrolysis. The weight of Ag deposited in a silver coulometer.0114 g Wt.286 Total loss 0. was found to be 0.478 u + v 0. According to Kohlrausch’s law.6 × 10 2 = (0.114 ∴ tCu +2 = = = 0. C-8∴N-ENGCHE∴ECH9-2.916 ∴ tAg + = = = = 0. Example 11. respectively.3 = 119.6 × 105 cm3 eq–1 Kv 1.00104 eq l–1 9. = Ag(107.8 ∴ x= = 0. of Cu deposited equivalent to 0. Wt.0104 × 143. wt.916 Hence.e. of Cu in anodic solution after electrolysis is = 0.3 + 65.916.6236) g = 0. wt. wts. of Ag = = Eq. The amount of Cu in the anodic solution was found to be 0.1351 g.714.1495 g l–1.916 0.1351 g of Ag.1351 × 31.522.222 ENGINEERING CHEMISTRY Sol. of Cu in anodic solution before electrolysis = 0.0398 g 107.916 + 1 1.6350 g.

Q. Q.m. the products are halogens from metallic – – –  halides (Cl .ELECTROCHEMISTRY 223 SHORT QUESTIONS AND ANSWERS Q. Br. Mention some important uses of electrolysis process. (i) Extraction of Na. Q. Br . If the anode is graphite or platinum. (ii) Electrochemical cell reactions: Electrochemical cell reactions are mainly redox reactions. Al etc. Ans. Ions can only conduct electricity when they are free to move. the liberation at the anode depends on the type of electrode.PM5 223 . Electrochemical reactions are the reactions which involve the flow of current. What are the products of electrolysis of an aqueous solution of a salt? Ans. What is electrolysis? Ans. Q. Mention the types of electrochemical reactions. 1. Q. What are the products of electrolysis of molten salts? Ans. Metals are deposited at the cathode and the nonmetals are liberated at the anode. Electrochemistry is the study of interrelations of electrical energy and chemical energy and interconversions of the two energies. it gets deposited at the cathode viz. the product at the cathode is hydrogen. 6. If the metal is in lower position of electrochemical series.f. of a cell as well as electrolysis. What are electrochemical reactions? Ans. (i) Electrolysis: Electrolysis requires electrical energy from some external source to bring about a chemical change i. which is only possible in molten state or in solution. (ii) Electrolysis of brine to produce NaOH and Cl2 (iii) Electroplating (iv) Copper refining. 3. 7. Ans. I ) 2X– (aq) → X2(g) + 2e (X = Cl. electrical energy is consumed. Why are the molten compounds or solutions used as electrolytes? Ans. 4.e. the deposition at the cathode depends on the type of metal ion in the salt. I) C-8∴N-ENGCHE∴ECH9-2. Q. 8. What is electrochemistry? Ans.. 5. Q. Electrolysis is a process where electric current is used to decompose a molten ionic compound or a solution of ions into elements. This statement applies for both generation of e. 2. from hydrogen ions produced by the ionisation of water 2H+ (aq) + 2e H2(g) During the electrolysis of a salt solution. Cu+2 Cu+2(aq) + 2e Cu°(s) But if the metal is in higher position in electrochemical series. in this type of reaction. involved in the cell where electrical energy is produced due to a chemical change. During electrolysis of a solution of a salt in water.

Electrolytic cell. C-8∴N-ENGCHE∴ECH9-2. What mass of Na is formed in an hour at the steel cathode? Ans. If the anode is a metal (Cu. Quantity of electricity in an hour = 30000 C/S × 3600 s. What is the utility of electrolysis of brine? Ans.000 Mass of Na formed per hr.000. hydrogen and sodium hydroxide. while the solution turns to NaOH. = mol 96.000 C. Q. 108. Q. = × 23 = 25. Q.000. The concentration of a salt solution has an effect on the product of electrolysis at the anode.11.PM5 224 .000 A. 11.750 g 96. Brine is a solution of NaCl in water. During electrolysis chlorine is liberated at the anode. (b) The equation for liberation at the cathode is – Na+ + e → Na Time of electrolysis = 3600 sec. Electrolysis of brine is used to manufacture chlorine.000. In a commercial cell the current is 30.480 108. atoms of electrode turn into ions. = 108. 9.480 = 25.000 Amount of Na formed per hr. 9. Chlorine is liberated at the anode during electrolysis of a concentrated solution of NaCl. 10. In electrolysis of a dilute solution of NaCl increasing amounts of oxygen are liberated. (a) Draw a neat sketch of an electrolytic cell. (a) – + Cathode +ve Anode ions Negative ions lose Positive ions gain electrons at the electrons at the –ve anode (oxidation) cathode (reduction) ions and turn into atoms Electrolyte Fig.75 kg.224 ENGINEERING CHEMISTRY Otherwise oxygen is liberated from water. What is the effect of concentration of a salt solution during electrolysis? Ans. Electrolysis of brine is the basis of the alkali and chlorine industry—a well known electrochemical industry. or Ag). hydrogen is liberated at the cathode and bubbles off. Cu(s) → Cu2+ (aq) + 2e. (b) Sodium is extracted by the electrolysis of a mixture of a molten NaCl and CaCl2.

14. The conductance (C) is the reciprocal of R 1 C= R Unit of conductance = ohm–1 or mho It is a measure of ease with which current flows through a conductor. where l = length. otherwise they will react. l = 1 cm. What is conductance? Ans. What do you mean by resistance? Ans. 9.ELECTROCHEMISTRY 225 The cell to be used for electrolysis should be carefully designed so that chlorine can be kept apart from NaOH. R. a ∴ ρ= . l R∝ . Q. a = area of cross-section of the conductor a l or R=ρ a where. where a = 1 cm2. unit of R = ohms.PM5 225 . A membrane cell is shown in Fig. l Q. What do you mean by specific resistance or resistivity? Ans. Specific resistance or resistivity is the resistance offered by the conductor of 1 cm length and 1 cm2 area of cross-section. ρ= l ρ = R. Cl2(g) H2(g) Brine NaOH(aq) Porous membrane + – Ti-electrode Ni-electrode Fig. Thus it is resistance offered by a conductor of 1 cm3. R. 12.12. Two types of cell are in use: (a) mercury cell (b) membrane cell.12 Membrane cell. a From. unit of ρ = ohm-cm. The membrane permits the solution to pass and prevents mixing of NaOH and Cl2. C-8∴N-ENGCHE∴ECH9-2. ρ = proportionality constant and is known as specific resistance or resistivity. Resistance (R) of any conductor is the obstruction offered to the flow of current. The membrane has ion-exchange properties. 9. it allows positive ions to pass but not the negative ions. 13. Q.

at infinite dilution of an electrolyte. Q. 15. What are the applications of conductance measurement? Ans. molar conductivity λm = M where. Ans.. What is the effect of dilution on molar conductivity? Ans. 19. Q. Define Kohlrausch’s law. 20. carried by cations or anions. The specific conductance (K) is the reciprocal of specific resistance (ρ). What is specific conductance? Ans. Q. Q. 18. λm Q. Molar conductivity increases with dilution. 23.226 ENGINEERING CHEMISTRY Q. (iii) Conductometric titration. It is the conductivity of all the ions produced in a solution containing one gm mole 1000 K of the electrolyte. What do you mean by degree of dissociation of an electrolyte? Ans. is equal to the sum of ionic conductances of cations and anions. Unit of λeq = ohm–1 cm2 equiv–1. C-8∴N-ENGCHE∴ECH9-2.e. It is the conducting power of all the ions present in a solution of an electrolyte containing 1 g equiv.PM5 226 . The degree of dissociation (α) is the fraction of the electrolyte that dissociates into ions. Ans. i. Q. 16. (ii) Determination of solubility and solubility product. 21. For weak electrolytes it is related to λm and λm∞ as follows: λ α = m∞ . 17. What do you mean by equivalent conductivity of an electrolytic solution? Ans. Q. 22. FG IJ 1 1 l K= = H K ρ R a It is defined as the conductance of 1 cm3 of a conductor unit of K = ohm–1 cm–1 Q. b = constant c = concentration λm∞ = molar conductivity at infinite dilution λm = molar conductivity at a given dilution As c → 0 λm = λm∞. M = molarity of the solution K = specific conductance. The relation is λm = λm∞ – b c where. 1000 K Equivalent conductivity λeq = C C = normality of the solution. It is the fraction of total quantity of electricity. What is transport number? Ans. What do you mean by molar conductivity of an electrolyte? Ans. (i) Measurement of degree of dissociation. The molar conductance. Give the relationship of molar conductivity with concentration.

PM5 227 . c (Fig. Equivalent conductivity- -ohm –1 cm 0 eq–1 150 Sodium chloride 100 Sodium acetate 50 Acetic acid 0 –4 –8 C – (C in equivalent/liter) Fig. All conductance measurements are done with the help of A. we plot conductance vs. λ∞ can be determined by extrapolation of the curve λ vs.. the equivalent conductance at infinite dilution. Ans. D.13 Extrapolation of λ versus ?. 27. and c are related by the equation. 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. In all conductometric titrations. Q. but resistance R = H C K does not vary linearly with the volume of titre. Q. Conductance varies linearly with the volume of titre. Why equivalent conductivity at infinite dilution cannot be directly determined experimentally? Ans. 9. i. However λ are not so related in case for weak electrolytes. at high dilution λ∞.C. That is why equivalent conductivity of weak electrolyte increases with dilution. 24. Q. 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∞. FG 1IJ Ans. volume will not give straight line. so is the number of ions. 25. λ = λ∞ – K c So.C. Equivalent conductivity of a weak electrolyte increases with dilution— explain.ELECTROCHEMISTRY 227 Q. C-8∴N-ENGCHE∴ECH9-2.e. Ans.13) for strong electrolytes to zero concentration. 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. volume of titre and not resistance vs volume of titre—explain. so plot of resistance vs. 26. 9.—explain. That is why resistance cannot be plotted against volume of titre. degree of dissociation increases.

As a result. E1 E2 E (b) Prove that = = . (a) State the Faraday’s laws of electrolysis. (b) State and explain Kohlrausch’s law. EXERCISES 1. With the aid of a plot.C. (a) Define the terms (i) specific conductance and (ii) equivalent conductance. What is an electrolyte? Give examples. conductivity and conductance. But it outweighs the minor increase in conductance due to increase in degree of dissociation.E. Z1 Z2 Zn 4. while equivalent conductance increases on dilution—explain.. 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. C-8∴N-ENGCHE∴ECH9-2. explain the variation of equivalent conductance of KCl and CH3COOH on dilution. 6. Specific conductances decreases with dilution while the equivalent conductance increases—explain. (c) Write the shortcomings of the theory of electrolytic dissociation.E. 5. How would you account for the result? 7. Ans. (b) State Kohlrausch’s experimental equation. How will you determine transport number? (b) Specific conductance of an electrolyte decreases.. n = F. 3.. (b) Define specific conductance. and E. specific conductance decreases with dilution. (d) Define Faraday’s second law.E. (a) Write Kohlrausch’s empirical equation.PM5 228 .228 ENGINEERING CHEMISTRY Q. Mention its units. (b) Relate C. 11. (e) Give the applications of the theory of electrolytic dissociation.e. (a) Define the specific resistance of a solution. Explain a few applications of this law. (a) State the relationship between the cell constant. But equivalent conductance increases because the total number of ions per gram equivalent increases with dilution for the increased value of degree of dissociation. 9. degree of dissociation increases and also the total volume increases. (c) Define the absolute ionic mobility. What do you mean by electrolysis? 2. (b) Discuss the effect of change in concentration of the solution on specific conductance and equivalent conductance. (a) Explain the terms : (i) Faraday (ii) E. i. (a) Define the terms: (i) Specific conductance (ii) Equivalent conductance. 28. (a) Define transport number. 8. Discuss its significance and applications. 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. (b) State and explain Kohlrausch’s law of independent mobilities of ions. (c) State Kohlrausch’s law. 10. the number of ions per millilitre decreases.C.2. When an electrolyte is diluted.

Write short notes on : (i) Cell constant (ii) Absolute velocity of an ion (iii) Conductometric titration (iv) Kohlrausch’s extrapolation method of determining λv. The resistance of 0. [Ans.382 × 10–2 S m 2 eq–1] 22. 1.098 (N) KCl was found to be 214.878 cm–1. [Ans. A 2.00277 ohm–1 cm–1.1 N KCl solution and 0.84 × 10–4 and 133. tCu +2 = 0.02 N of an electrolytic solution in a conductivity cell were found to be 310 ohms and 2. 99. of Cu+2 ion. Discuss all types of conductometric titrations. Calculate the equivalent conductance (λv) of the solution at the same temperature. tCu +2 = 0. After electrolysis 51. 0. tSO = = 0.PM5 229 . 13.215] 24. loss of Cu in the anode compartment was 0. 1.30 ohm cm eq–1.84% CuSO4 solution was electrolysed using Pt cathode and Cu-anode. The equivalent conductance of 0. The cell was then washed out and filled with 0.02 M KCl solution at this temperature was 0.1 N KCl solution is 0. Calculate the transport number of Cu+2 and SO 4– – ions [At.88 cm–1). The resistance of a cell filled with 0. If the resistance of 50 cell containing this solution is 500 ohms.2 ohm–1 cm2] 21. The specific con- ductance of 0. Find the transport no. The ionic conductances –1 2 of H+ and CH3COO– ions at infinite dilution are 349 and 40 ohm –1 cm2 eq–1. tAg + = 0.1 M of CuSO4 .0 ohm–1 cm 2] 20.36 × 10–4 Sm2 eq–1 respectively. Specific conductivity of an KCl solution at 25°C is 0.9 ohm–1 cm2] 19. Calculate the equivalent and molar conductances of CuSO4 solution. if the cell constant is 0. current was passed for 2 mins. The equivalent conductance at infinite dilution of NH4Cl.ELECTROCHEMISTRY 229 12. The resistances of 0. S(32) and O(16)].7 g solution. [Ans.138 cm –1] 17. Calculate the equivalent conductance of AgCl at infinite dilution. [Ans.46] C-8∴N-ENGCHE∴ECH9-2. The resistance of a conductivity cell filled with 0.0 ohm–1 cm 2.420.000275 mhos cm–1. = Cu(63. the cathode solution contained 0.1 (N) solution of NaCl is 210 ohm at 18°C. 4.4 ohms at 298 K. [Ans.19%] 23.058 g of Cu was deposited.785] 4 25.74 × 10–4.215. NH4NO3 and AgNO3 are 149. Also explain the nature of the graph between conductance and volume of titrant used.0 g of the anode solution (anolyte) was found to contain 0. and its resistance was found to be 37. Why does the equivalent conductivity of a NaCl solution increase with dilution? How can the electrolytic conductance be measured? N 16. of Ag+ in AgNO3. 41. After electrolysis.409 g Cu in 54. In a voltameter connected in series. A one amp. 14. 42. 144.804 g.000 ohms respectively at 298 K. During the electrolysis of CuSO4 solution.519 g of AgNO3. wt. What is the percentage dissociation of acetic acid at this concentration? [Ans.5 ohms. [Ans. [Ans.80% AgNO3 solution was electrolysed using Ag-electrodes. [Ans. The specific conductance of 0. respectively. Calculate the equivalent conductance (λv) of the solution (cell constant = 0.01 N acetic acid is 16. 166. what is the cell constant? [Ans. A 0. Define Kohlrausch’s law and discuss its applications.18 ohm–1 cm –1] 18. The increase in the weight of cathode was 0.02 (N) KCl solution at 25°C is 225 ohms. Calculate the equivalent conductance of the given solution.0128 ohm –1 cm –1.6). What is the transport no. 15. 83.

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. of the cell. 10 Electrochemical Cells ELECTRODE POTENTIAL Oxidation is a process where electrons are lost by a substance and reduction is a process where electrons are gained by a substance. we get Sn+4 in the vessel B and Fe+2 in vessel A. +3 Fe + Sn +2 Fe+2 + Sn+4 +3 For 1 g. a cell is constructed of two electrodes and the e. atom of Fe+2.85 g. By 230 .f.. 10. 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.m.f. twice the Avogadro’s number of electrons is lost.e. 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. mA NaCl salt bridge HCl Pt Pt HCl FeCl3 SnCl2 A B Fig. If we make an arrangement as shown in Fig. 55. Reaction in vessel A : 2Fe+3 + 2e Fe+2 [reduction] Reaction in vessel B : Sn+2 – 2e Sn+4 [oxidation] 2Fe+3 + Sn+2 Fe+2 + Sn+4 [cell reaction] So.m. of the cell is obtained from the algebraic sum of the two electrode potentials. Avogadro’s number of electrons are gained to get reduced to 1 g. Nernst called this tendency as “solution pressure”. atom of Sn+2. 10.1 after sometime. atom of Fe . And for every g. And we get deflection in milliammeter. As for example in the reaction: 2FeCl3 + SnCl2 2FeCl2 + SnCl4 i.1 Construction of a cell.

E. osmotic pressure exceeds solution pressure and Cu rod Fig. as a result. gets positively charged. So.341 × 298 ∈ = ∈° + log10 aM + n n × 96500 0. To consider the electrodes separately. the solution pressure Zn Cu exceeds osmotic pressure. metal rod becomes negatively charged.M. At 25°C the equation comes to : 2. For example. On the contrary. This established potential is called electrode potential. of the cell is algebraic sum of the two electrode potentials. As for example. And so is the case with Cu/Cu+2. in the case of Zn/Zn+2. But when one exceeds the other the metals get either positively or negatively charged. 10.059 = ∈° + log10 aM + n n C-8∴N-ENGCHE∴ECH10-1. Zn rod sends Zn+2 ions into the solution and gets negatively charged and attracts + – – + – + + – + – – + positive charges towards the rod and.303 × 8. the metal rod accumulates electrons and as a result. the solution has a tendency to send M+n ions to the metal rod due to “osmotic pressure”. an electric cell is composed of two electrodes. And each electrode has a potential which is known as single electrode potential (∈∈). When “solution pressure” equalises “osmotic pressure” there is no net effect. 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. E = ∈1 + ∈2 Single Electrode Potential (∈ ∈) The electrode potential for an electrode reaction: M+n + ne M (metal) RT is given by Nernst equation ∈ = ∈° + ln aM + n where ∈° is a constant dependent upon the nF metal.F. n ⇒ Valency of metal R ⇒ Gas constant T ⇒ Absolute temperature F ⇒ Faraday constant a ⇒ Activity of M+n. an + – – + – + + – electrical double layer is set up and a potential is + – – + – + + – established between the metal rod (Zn) and its ions ZnSO4 CuSO4 (Zn+2).2 Electrode potential.PM5 231 . but in this case.ELECTROCHEMICAL CELLS 231 sending the ions. The electrode potential is also established in the case of every electrode where electrical double layer is set up by exchange of electrons. Here also a electrical double layer is set up and electrode potential is established. we call each of them as single electrode.

. oxidation takes place at anode and at the cathode Cu+2 is neutralised i..f. Determination of Standard Potential ∈° of a Metal Electrode The electrode potentials cannot be determined straight. aM + n = C M + n 0. (See page 227) Zn|ZnSO 4 (solution) H 2SO 4 (solution)|H 2 (Pt) (aZn+2 = 1) (aH + = 1) C-8∴N-ENGCHE∴ECH10-1. So reduction takes at the right hand electrode and oxidation takes place in the left hand electrode.e.PM5 232 . • Electrons flow through the external wire from the negative electrode to the positive electrode. a solution of acid with ([H+] = 1) and to which hydrogen gas is bubbled at one atmosphere and platinum foil is dipped. We have a zero potential for this electrode. of the cell E = ∈right – ∈left (when both are reduction potentials) E = ∈red + ∈ox. • The single vertical lines denote electrical contact. • E.e. then the expression is : ∈ = ∈° + log10 C + n [A form of Nernst equation] n M When a = 1.232 ENGINEERING CHEMISTRY For general purpose. • Oxidation potential may be taken as reduction potential with a minus sign. Total cell reaction is: Zn + Cu+2 Zn+2 + Cu. If we construct the following cell: Zn(–)| Zn+2 || Cu+2 |(+) Cu. For example. • A complete cell consists of two half cells.059 So.015 V For this cell Zn/Zn+2 is anode and Cu/Cu+2 is cathode and at anode. Zn is ionised to Zn+2 i.m. we take the ∈° value for hydrogen electrode to be ‘zero’ i. then ∈ = ∈° ∈° is known as Standard electrode potential of metal M. • 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. We are to assign a definite value of electrode potential for a definite electrode. Ecell = 1. Highlights: According to IUPAC convention. Now if we want to determine standard electrode potential of zinc (∈°Zn) we are to construct the following cell. reduction takes place at the cathode. The right hand half cell is regarded as the positive electrode and the left hand half cell is regarded as negative electrode..e. to determine the electrode potential.

Na+ Na+ + e = Na – 2.e.798 Pt. Cu++ Cu++ + 2e = Cu 0.715 Li.ELECTROCHEMICAL CELLS 233 Table. H+ 2 O2 + 2H+ + 2e = H2O 1.f. of the cell Zn ZnSO4 (solution) CuSO4 (sol n ) (aZn +2 = 1) Cu (aCu+ = 1) Sol.m. = 0.122 Reductants Sn.e. E° of the above constructed cell which is ∈°Zn. Hg2++ Hg2++ + 2e = 2Hg 0.799 Ag. electronegative 1 Pt.771 Cu. of a cell Liquid junction potential Daniel cell: Zn | ZnSO4(C1) || CuSO4(C2) | Cu Cell reaction is: Zn + Cu+2 Zn+2 + Cu E = ∈right – ∈left [when both are reduction potentials] ° RT [Cu +2 ] ∈right = ∈Cu + ln 2F [Cu] C-8∴N-ENGCHE∴ECH10-1.959 The e.344 + 0.106. Cl– Cl2 + e = Cl– 1.PM5 233 . H+ H+ + e= 1 H2 0. Fe++ Fe+++ + e = Fe++ 0.f of a cell is measured by potentiometer. electropositive Pb. = Standard reduction potential of Cu + std. Zn++ Zn++ + 2e = Zn – 0. and we get standard e. of the cell will be E° = ∈°H + ∈°Zn = ∈°Zn [Q ∈°Η = 0] The e.360 i. Sn++ Sn++ + 2e = Sn – 0.000 2 i. 762 Mg.344 Calomel electrode 1 Hg2Cl2 + e = Hg + Cl– 0.m.866 Na. This list with ∈° values are known as electrochemical series.136 Zn. 25°C Electrode Electrode reaction E°(Volts) (Reduction) F2. Cl2(g). Mg++ Mg++ + 2e = Mg – 1. Fe+++.f. Calculate the e. Pb++ Pb++ + 2e = Pb – 0. O2.268 2 (Pt) H2.m.1) Example 1.80 2 Pt. 10. the electrode potential of other metals are determined similarly and listed in table. Typical calculation of e.762 = 1.m..06 Hg.23 Oxidants Au. Likewise.1: Standard Electrode Potentials (Reduction).m. (Table 10. Ag+ Ag+ + e = Ag 0. Li+ Li+ + e = Li – 2.. F – 1 F2 + e = F– 2. oxidation potential of Zn. Au+++ Au+++ + 3e = Au 1.f.f.

234 ENGINEERING CHEMISTRY RT or = ∈°Cu + − ln [Cu +2 ] [Q [solid] = 1] 2F Likewise. For example – Zn(∈°Zn = – . Let Fe and Cu are used as electrodes.. 2.f. RT ∈left = ∈°Zn + ln [Zn +2 ] [Q [solid] = 1] 2F °45 RT 78 45 .m. possessing lower standard electrode potential (reduction) will displace the metal from the solution of its ions with a higher standard electrode potential (reduction) value. of the cell is obtained from the oxidation potential of anode and reduction potential of cathode. = 0. RT a 0. ln [Cu +2 ] − ∈°Zn + RT . Electrode potential (∈) is given by: Oxidant + ne Reductant Ox + ne Red. Any oxidised or reduced form of an element behaves so. C-8∴N-ENGCHE∴ECH10-1.785 volt. ln [Zn +2 ] 78 6 Ecell = ∈Cu + 2F 9 6 2F 9 ° ° RT [Cu +2 ] ∴ Ecell = (∈Cu − ∈Zn ) + ln . 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. the non-metals with the higher electronegativity displace the elements possessing lower electronegativity. The higher electropositive metal i. 3. If a cell is constructed with the two elements as the electrodes then the e.1) 1.344) Likewise.344 + 0.762) will displace Cu from its solution (∈°Cu = . of the cell.f. 2F [Zn +2 ] Interpretation of the Electrochemical Series (Table 10.059 [Ox] ∈ = ∈°Red–ox + ln Ox = ∈° log 10 nF aRed Red–ox + n [Red] (for general purpose) Here also ∈° values are determined against standard hydrogen electrode.e. Lower position in the table of an element indicates its higher tendency of ionisation. higher is the electronegativity of that element. These electrodes are known as redox electrodes. then e.PM5 234 .m. E = Reduction potential of Cu + Oxidation potential of Fe.441 = 0. The higher the standard electrode potential (reduction) of an element.

∈° = .25 (Pt) H+/ 21 H2 H+ + e 1 2 H2 0.69 Co+2/Co CO+2 + e CO+2 + 1.ELECTROCHEMICAL CELLS 235 Table 10. the different oxidation states are represented by the corresponding ∈° values as follows: Mn2+ + 2e + Mn. ∈° = – 1.26 V MnO4 + e MnO42– . 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.54 1 1 (Pt) I /I– 2 2 I 2 2 +e I– + 0.23 V C-8∴N-ENGCHE∴ECH10-1. ∈° = 2. We know that Mn exists in different oxidation states and in acidic medium preferably at zero pH.PM5 235 .36 MnO4–/Mn+2 MnO4– + 8H+ + 5e Mn+2 + 4H2O + 1. 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.18 V +3 Mn + e 2+ Mn .52 Ce+4/Ce+3 Ce+4+e Ce+2 + 1.16 (Pt) [Fe(CN)6]2–/[Fe(CN)4]4– Fe(CN)63– + e Fe(CN)64– + 0.41 (Pt) V + 2/V+2 V+3 + e V+2 – 0.77 (Pt) 1 Br2/Br– 1 Br2 + e Br– + 1. ∈° = + .82 S2O42–/2SO42– S2O42– + 2e 2SO42– + 2.01 1 F2/F– 1 F2 + e F– + 2.36 2 2 Cr2O7 2–/2Cr+3 Cr2O72– + 14 H+ + 6e 2Cr+3 + 7H 2O + 1.23 Tl+3/Tl+2 Tl+3 + 2e Tl+1 + 1. ∈° = 1.65 2 2 The pair which occupies lower position in the table can oxidise the pair which occupies a higher position in the table.56 V + MnO2 + 4H + 2e 2+ Mn + 2H2O.065 2 2 (Pt) IO2–/ 21 I2 IO3– + 6H+ + 5e 1I 2 2 + 3H2O + 1. ∈° = 1.15 (Pt) Cu+2/Cu+1 Cu+2 + e Cu+1 + 0.20 (Pt) MnO2/Mn+2 MnO2 + 4H+ 2e Mn+2 + 2H2O + 1.52 BrO2–/ 21 Br2 BrO3– + 6H+ + 5e 1 2 Br2 + 3H2O + 1.00 (Pt) Sn+4/Sn+2 Sn+4 + 2e Sn+2 + 0.25 1 Cl2/Cl– 1 Cl2 + e Cl– + 1.21 – 0.36 (Pt) MnO4–/MnO42– MnO4– + e MnO42– + 0.61 MnO4–/MnO2 MnO4– + 4H+ + 3e MnO2 + 2H 2O + 1.95 V MnO42– + 4H+ + 2e MnO2 + 2 H2O.535 (Pt) Fe+2/Fe+2 Fe+3 + e Fe+2 + 0.2: Normal potentials (∈°) of some redox system (Hydrogen scale) Electrode Electrode reaction Electrode potential ∈°(volts) (Pt) Cr+2/Cr+2 Cr2+ + e Cr2+ 0.52 V MnO2 + 4H+ + e Mn3+ + 2H2O.

The species H+. are called skip couples and the corresponding potentials are called skip-step potentials. ∆G° = – nF∈°.70) = 1.52 F Adding (a) and (b).PM5 236 .76 = – 3.236 ENGINEERING CHEMISTRY MnO4– + 4H+ + 3e MnO2 + 2H2O.70 volt 1. On the other hand. H2O etc.4 F (b) Reduction: H2O2 + 2H+ + 2e → 2H2O ∈°Red = 1. 0. 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. For example. the oxidation states of Mn decrease gradually from left to right. 0.51 V The whole information can be summarised in the compact manner in a collinear diagram as follows. are not included in the diagram. a species will undergo comproportionation if the potential on the left is higher than that of the right species in the diagram. C-8∴N-ENGCHE∴ECH10-1. we know that H2O2 disproportionates into H2O and O2 under acidic conditions.12 F Since the process is accompanied by decrease in Gibbs free energy. We know that ∆G° values corresponding to different steps can be added but the ∈° values cannot be so added. in this case the comproportionation reaction Ag2+ + Ag = 2Ag+ will take place.98 V 0. therefore dispro- 1.76 V ∴ ∆G°2 = – nF∈° = – 2F × 1. Again ∆G° is related to ∈° as follows. Since the nF factor cancels in this way. the Latimer diagram is also helpful in predicting whether a particular species will undergo disproportionation or comproportionation.76 volt O 2 → H 2 O 2 −1 → H 2 O −2 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) Oxidation: H2O2 → O2 + 2H+ + 2e ∈°Ox = – . ∈° = 1. 2H2O2 → 2H2O + O2 ∆G° = – 2. 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.18 V MnO4– → MnO42– → MnO2 → Mn3+ → Mn2+ → Mn In this diagram. A species will disproportionate into its neighbour species if the potential on the left is lower than that of the right species.52 V – 1. The couple such as MnO4–/MnO2 or MnO4–/Mn2+ or MnO2/Mn2+ etc. A Latimer diagram helps us to derive the standard potentials of such non-adjacent couples.70 V MnO4– + 8H+ + 5e Mn2+ + 4H2O. On the other hand. adding them together and converting the sum back to ∈° for the non-adjacent couple dividing by – nF for the overall electron transfer. Hence.26 V 0.95 V 1.56 V 2. ∈° = 1. we can write n1∈°1→ 2 + n2 ∈°2 → 3 ∈°1 → 3 = n1 + n2 Besides calculating the ∈° values of non-adjacent couples.70 V ∴ ∆G°1 = – nF∈° = – 2F × (– .80 V portionation will be spontaneous.

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.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. The reducing agent of the couple with less +ve slope will tend to undergo oxidation.3(a) and 10. 10. On the basis of this diagram. The oxidising agent of a redox couple will show tendency to reduction if the slope is more +ve. in NH4NO3. 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. 10.. 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 (a) Fig.3 (b) Frost diagram for nitrogen (N). This is due to the fact that. however.PM5 237 . 2+ Cu /Cu HNO3 6 + H /H N2O4 +2 5 Zn /Zn HNO2 4 n ° (V) NH2OH NO N ° 3 Most stable NH 3 2 N2H4 NH3OH N2O4 oxidation Increasing N2O NO stability state N2 1 – NO2 NO3 N2O 0 N2H5 N2 –1 NH4 –3 –2 –1 0 +1 +2 +3 +4 +5 Oxidation number Oxidation number Fig. NH4+ ion contains N in –3 oxidation state and in NO3– ion N is present in +5 oxidation state. 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+. however. Cu. Hence. we can make thermodynamic predictions about the reaction between any two couples by comparing the steps of the corresponding lines. not spontaneous as it is not kinetically favoured. on the C-8∴N-ENGCHE∴ECH10-1.g. it can be predicted whether the oxidant or the reductant will show greater tendency for a reaction. From the diagram it is seen that since NH2OH lies above the line joining NH3 and N2 it will undergo disproportionation. the potential of the corresponding couple is higher. The disproportionation is. Under such circumstances comproportionation will be thermodynamically favoured e. The Frost diagram for nitrogen in various oxidation states is as given in Fig.e. 10.. 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.3(b). When the line joining two points in the diagram is quite steep. the average free energy of the intermediate species is larger than the mean free energy of the two adjacent species. (at pH = 0). 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.

NO + NO2 + H2O → 2 HNO2 3HNO2 → HNO3 + 2NO2 + 2H2O 3NO2 + H2O → HNO3 + HNO2 A Frost diagram can be constructed from a Latimer diagram e. therefore. 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 undergoes comproportionation.238 ENGINEERING CHEMISTRY other hand N2O has an oxidation state of +1.76 volt. – 1 and – 2. NH4+ + NO3– → N2O + 2H2O.23 V The oxidation numbers of ‘O’ atom in O2. then no one species will be the exclusive product e.70 volt. Therefore. 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∈° = – . let us consider the Latimer diagram.. respectively. The change in oxidation number from H2O2 to H2O is –1. n = – 2.76 H2O2/H2O is equal to = + 1. When the line joining three adjacent species becomes approximately a straight line. This is due to the fact that NO. 10. When these values of n∈° are plotted against the corresponding oxidation numbers. The difference is. −1 +1 0 O2 n (V) H2O2 –1 Acidic –2 H2O –2 –1 0 Oxidation number Fig.70 = – .PM5 238 . HNO2 and HNO3 lie approximately on a straight line in the Frost diagram.70 volt and n∈° corresponding to oxidation number of – 2 is – 2.4 Frost diagram for the system O2 → O2–2 → 2O–2. 0. ∴ ∈° = – 1 × . 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.g. change in oxidation number = – 1. When ‘O’ changes from O2 to H2O2.46 volt. This is in accordance with the Latimer diagram. – 2. we get the required Frost diagram as follows. C-8∴N-ENGCHE∴ECH10-1. Therefore.23 = – 2.46 volt.46 – (– .. n∈° for the formation of H2O = – 2 × 1. oxidation number of ‘O’ changes from 0 to –1.70) = – 1.g. H2O2 and H2O are 0.76 volt.76 V O2 H2O2 H2O +1. when O changes to H2O its oxidation number changes from 0 to – 2 and in this case. the ∈° for the couple − 1. Hence.70 V 1.

Ag cannot displace H2 from HCl. Find whether Cu+ disproportionate in aqueous solution into Cu+2 and Cu° i.344] Adding Zn+2 + Cu Zn + Cu+2 [E°Cu = – 1.762] Cu – 2e Cu+2 [∈° = 0. Example. Example. Cu+ will disproportionate spontaneously in aqueous solution into Cu+2 and Cu°. E°cell = – ve.762 ∈°Cu +2 /Cu = 0.00 V] Adding 2Ag + 2H+ 2Ag+ + H2 [E°cell = – 0.37 V] Since E°cell is positive.15 V] Adding Cu+ + Cu+ Cu+2 + Cu° [E°cell = 0. ∈° Cu +2 /Cu + = + 0. 3.52 V] Cu+ –e Cu+2 [∈° = 0. given ∈° Ag+/Ag = 0. Ag will not displace hydrogen from HCl.798] 2H+ + 2e H2 [∈°H+/H = 0. So.52 V The two half cell reactions are: Cu+ + e Cu° [∈° = 0. Concentration Cell When a metal is dipped into two solutions of one of its salts of different concentrations. Given.798] Since.798. 2. Example.PM5 239 . Prediction of an oxidation-reduction reaction. the E°cell value is negative. Sol. Prediction regarding liberation of hydrogen by a metal from a hydracid.15 V ∈° Cu + / Cu ° = 0. cell reaction is 2Cu+ Cu+2 + Cu°.106] Since. Cell reaction: 2Ag + 2H+ → 2Ag+ + H2 The two half cell reactions are: 2Ag – 2e 2 Ag+ [∈° = – 0. Prediction of feasibility of a chemical reaction. Zn+2 + Cu Zn + Cu+2 ∈° Zn +2 / Zn = – 0.e.ELECTROCHEMICAL CELLS 239 Highlights: Uses of standard potential (reduction) values: 1. the reaction will not occur spontaneously. Predict whether the reaction will occur spontaneously or not.344 The two half cell reactions are: Zn+2 + 2e Zn [∈° = – 0. a very interesting situation arises: C-8∴N-ENGCHE∴ECH10-1..

C1 The stronger solution acts as positive electrode. So. [Concentrated] NH4NO3 or Ag | AgNO3(C1M) || AgNO3(C2M) | Ag (C2 > C1) Voltmeter – Electron e NH4NO3 flow Salt bridge – + Ag electrode Ag electrode + + Ag Ag + e – Ag + e– Ag + + C1M Ag ions C2 > C1 C2M Ag ions Fig. 10.138 × (298) C E = 2. of such cell depends on the relative concentration and not on the absolute values. e.m.f.m.303 × 8. E= log 2 [Q n = 1] 1 C1 Therefore. the cell reaction is Half cell reaction (left) oxidation Ag – e Ag + (C1) Half cell reaction (right) Ag+(C2) +e Ag° Total: Ag+ (C2) = Ag+ (C1) ∈°R = ∈°L and n = 1 RT C 2.059 C So.303 log 2 = log 2 nF C1 n × 96500 C1 0.240 ENGINEERING CHEMISTRY Ag | AgNO3(C1) || AgNO3(C2) | Ag Ag AgNO3(C1) Salt bridge AgNO3(C2) Ag (Dilute) of satd.PM5 240 . 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–.f. Imagine that current passes through the external wire as shown by the arrow. the observed e. is 59 mV. C-8∴N-ENGCHE∴ECH10-1.5 Concentration cell. C2 If = 10.

0.05M) | Ag. of the cell is 0.f. of the following cell. Saturated solution Ag | Ag NO3 (0.045 or = Antilog 13.05 × 0. of the cell is: E = 2F ln p .059 C E= log 2 n C1 Here n = 1. concentration of Ag+ in 0.f.m. Given e.m. 0.059 0. 2 Application of the Concentration Cells H2 Determination of solubility of sparingly-soluble salts. Calculate (i) Solubility product of AgI.33 C1 0.788 V at 25°C.01 g.f.138 × 1013 C-8∴N-ENGCHE∴ECH10-1.045 0.059 log C1 0. 0. C1 i. Cell: Ag/AgI/ in 0.045 or 0.9 = 0. one such cell is: Pt | H2 (p1) | H+ | H2 (p2) | pt p1 and p2 are unequal pressures of H2 The cell reaction is: Oxidation: H2 (p1) – 2e 2H+ Reduction: 2H+ + 2e H2 (p2) Overall: H2(p1) → H2(p2) RT p1 e.f. of the cell is given by.059 0.045 M The concentration of I– in KI is 0.059 0.05 (M) KI) | NH4NO3 | AgNO3(0.788 = 0.m.ELECTROCHEMICAL CELLS 241 This type of concentration cell is known as electrolyte concentration cell. Another type of concentration cell is electrode concentration cell.05 × 0.045 ∴ E= log 1 C1 0.PM5 241 .m.01N) of KNO 3 Saturated AgCl | Ag salt bridge e.045 M Let C1 be the concentration of Ag+ in AgI solution.33 C1 = 2.e.788 or log = = 13.. The activity coefficient (f) is 0. Ag+ in AgCl can be calculated.01 So.9 each. (ii) Solubility of AgI in water at 25°. The concentration of Ag+ in AgNO3 is 0. ion l–1 is (C2).01(N) AgNO3 solution is 0. Example 1. E= log 1 C1 So. we are to measure e. If we want to determine the solubility of AgCl.9 = 0.

242 ENGINEERING CHEMISTRY

0.045
∴ C1 = = 2.105 × 10–15 mol l–1.
2.138 × 10 13
∴ Ksp of AgI = [Ag+] [I–]
= 2.105 × 10–15 × 0.045
= 9.472 × 10–17
Solubility of AgI = K sp


= 9.472 × 10 17
= 9.732 × 10–9 mol l–1
= 9.732 × 10–9 × 143.5 g l–1
= 1.396 × 10–6 gl–1
Determination of valency
Hg || Hg2(NO3)2 0.5(N) || Hg2(NO3)2 (0.05) (N)/Hg
C2 C1
The e.m.f. of the above cell = 0.029 V
0.059 C 0.059 0.5
We have, E= log 2 = log where n is valency.
n C1 n 0.05
0.059 0.059
= log 10 =
n n
0.059 0.059
or 0.029 = ∴ n= ≈ 2.
n 0.029
INDICATOR ELECTRODES
Hydrogen Electrode
It consists of a small piece of platinum foil electroplated
with platinum black, over which hydrogen gas is passed. The
platinum black surface exhibits a strong absorption power
towards hydrogen gas, as a result, the metal surface remains
in continuous contact with the hydrogen gas. The electrode H2-Gas
will act as if it were an electrode of metallic hydrogen. When
in use, therefore, only a part of the foil is immersed in 1(N)
HCl; the remainder is surrounded by pure hydrogen gas at
1 atm. pressure. This is standard hydrogen electrode. The HCl
e.m.f. of this electrode has been arbitrarily assigned to be zero.
The pH of a solution can be determined with the
help of a hydrogen electrode in that case, the platinum
Fig. 10.6 Hydrogen Electrode.
electrode is dipped into the solution whose pH is to be
determined, instead of 1(N) HCl and H2 gas at 1 atm passed
over the platinum electrode.
The electrode reaction is
1
H+(aq) + e H 2 ( g)
2

C-8∴N-ENGCHE∴ECH10-1.PM5 242

ELECTROCHEMICAL CELLS 243

The electrode potential is given by,

RT [H 2 ]1/ 2
∈ = ∈° + log
F [H + ]
1
∈ = ∈° + 0.059 log (n = 1)
[H + ]
∈ = 0 – 0.059 log [H+]
= 0.059 pH at 25°C.
A full cell is constructed by coupling the above half cell with a standard hydrogen
electrode. The e.m.f. E of the cell is then determined potentiometrically. Since electrode potential
of standard hydrogen electrode is zero, the observed e.m.f. of the cell gives directly the electrode
potential (∈) of the half cell. So,
the cell is: (Pt) H2 | H+(a = 1) || H+ (a = unknown) | H2(Pt)
EObs = ∈ = 0.059 pH
E Obs
∴ pH =
0.059

– H2
+

Trap

H2

Sat.
KCl
HgCl
&
KCl

+
HgCl
paste
H2
Salt bridge Solution
Hydrogen
Calomel electrode
electrode

Fig. 10.7 Determination of pH by Hydrogen Electrode.

Reference Electrodes
For determination of standard electrode potentials (∈°), standard hydrogen electrode is
used as reference. But there are some difficulties with hydrogen electrode. Maintaining 1 atm.
pressure of hydrogen and to make aH+ = 1 is very difficult. To overcome this difficulty another
electrode which is known as secondary reference electrode is used for determining standard
electrode potential. One of such electrodes is calomel electrode. To determine pH of a solution
the cell constructed with the calomel electrode will be: (Pt) H2 | H+ (a) || Normal calomel
electrode (Fig. 10.7).

C-8∴N-ENGCHE∴ECH10-1.PM5 243

244 ENGINEERING CHEMISTRY

Calomel Electrode
This electrode possesses certain advantages. It can be prepared easily and can be used
for a long time. The standard electrode potential of this electrode is determined against standard
hydrogen electrode.

KCl

HgCl + Hg

Hg

Fig. 10.8 Calomel Electrode.
The bottom of the electrode is filled with mercury. Mercury layer is covered with a paste
of Hg2Cl2 (0.1N) and over it there is a saturated solution of KCl with some crystals of KCl. The
electrode reaction is:
1
Hg 2 Cl 2 (s) Hg + Cl– ( aCl − )
2
The electrode potential ∈ is given by
RT
∈ = ∈° + ln aCl − ( Q n = 1).
F
The standard electrode potential (reduction) of calomel electrode
For 1.0(N) KCl = + 0.28 V
Saturated KCl = + 0.2422 V
Any electrode whose standard potential is to be determined is connected to calomel
electrode by means of KCl salt bridge. The e.m.f. of the set-up cell is determined
potentiometrically from which the standard electrode potential of the electrode is calculated.
To determine pH of a solution, we have,
EObs = ∈ (calomel) – ∈ (H2 electrode)
= ∈ (calomel) – 0.059 log [H+]
= 0.28 + 0.059 pH
E Obs − 0.28
or pH =
0.059
Ag-AgCl Electrode
The use of this reference electrode is very common. The electrode consists of a silver
wire, coated electrolytically with silver chloride and is dipped into a solution KCl of definite
strength. The potential of this electrode

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ELECTROCHEMICAL CELLS 245

Ag/AgCl(s) Cl– ( aCl − = 1) || HCl (a = 1), H2 (1 atm)/Pt

∈° = – 0.2224 V at 25°
has been accurately determined against a standard hydrogen electrode.
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. The thick glass
membrane serves as a solid electrode whose potential changes with pH of the solution with
which it remains in contact. For good electrical contact the bulb contains a silver–silver chloride
electrode immersed in a standard HCl solution. A platinum wire may be used in place of the
Ag–AgCl electrode (Fig. 10.9).
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. The potential of the glass electrode varies
linearly with pH (Fig. 10.10).
RT
∈glass electrode = ∈° + ln [H + ]
F
2.303 RT
= ∈° – pH
F
= ∈° – 0.059 pH at 25°.

– +
Potentiometer

Saturated
Pt wire or calomel electrode
silver chloride
coated silver Glass
wire electrode

0.1 M HCl
Solution of
unknown pH

+
[H = ?]
Thin-walled
glass bulb

Fig. 10.9 Glass Electrode. Fig. 10.10 Determination of pH by Glass Electrode.

C-8∴N-ENGCHE∴ECH10-2.PM5 245

246 ENGINEERING CHEMISTRY

Highlights:
• e.m.f. of the cell comprising of glass electrode and calomel electrode gives the pH
of the solution from the equation, ∈ = ∈° – 0.059 pH
• Glass electrode is virtually hydrogen electrode.
• ∈° value is not zero in the case of a glass electrode.
• ∈° value of glass electrode can easily be determined by calibration using buffers of
known pH.
• Glass electrode is the most extensively used electrode for pH determination.

The advantages of glass electrode. (a) Its rapid response, (b) remains unaffected by
the presence of oxidising and reducing agents.
The disadvantages of glass electrode. (a) Its fragility and (b) its inability in the
presence of high concentrations of alkali.
Only lithium silica glasses enable pH measurements to be valid over practically
the entire pH range.
pH and millivolt meters
A linear relationship exists between the pH of a solution, at a given temperature, and
the e.m.f. of a cell (E) constructed of a reference electrode and an indicator electrode.
Since, E = K – 0.0592 pH
∆E
i.e., = – 0.0592
∆pH
Thus a calibration in mV can be converted into pH units when divided by 0.059. In
practice, however, pH meter scales are calibrated in pH units and in millivolts (mV)
and the appropriate scale and range is selected by a simple control.
Polarisation
When a simple cell drives a current, the following is the cell reaction:
At Copper plate:
Cu Cu+2 + 2e
2H+ + 2e H2↑
At Zinc plate:
Zn Zn+2 + 2e
+2
Zn + SO4 –2 ZnSO4
Total cell reaction:
Zn + H2SO4 = ZnSO4 + H2

– +
Cu
Zn

dil. H2SO4

Bubbles of H2
Fig. 10.11

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ELECTROCHEMICAL CELLS 247

When current flows from Cu-plate to Zn-plate, a layer of hydrogen bubbles is found to be
formed on the surface of the Cu-plate. 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.
(ii) The layer of H2 in contact with the acid solution is found to acquire a potential lower
than that of Zn. The Zn-plate, therefore, behaves as positive electrode and H2 accu-
mulated as negative electrode, so, an additional e.m.f. is generated, which is called
polarisation e.m.f. or back e.m.f. and which tends to drive a current opposite to
the direction of the main current flow; and hence this back e.m.f. opposes the main
e.m.f. As the hydrogen bubble is generated more and more, the polarisation e.m.f.
increases and ultimately it comptetely neutralises original e.m.f. and the current
stops totally. This phenomenon is known as polarisation.
Polarisation effect is also seen during electrolysis: when an electric current is passed
through dil. H2SO4 using Pt-electrodes, H2 and O2 are evolved.
H2SO4 2H+ + SO4–2
–2
SO4 + H2O H2SO4 + O–2
At anode: The reaction is,
2O–2 – 4e O2↑
At cathode: The reaction is,
2H+ + 2e H2↑
If, after some time, the battery is removed and a galvanometer is fitted in the outer
circuit, a current is seen to pass between the two electrodes, but in opposite direction to that
during electrolysis. Hydrogen and oxygen gases covering the two Pt-electrodes become the
source of this e.m.f. (back e.m.f.). This phenomenon of back e.m.f. developed by products
of electrolysis is known as polarisation (Fig. 10.12).
Galvanometer
e

Pt Pt + –
+ –

dil. H2SO4

O2 H2
(a) Polarisation during (b) Polarised cell
electrolysis
Fig. 10.12 Development of polarisation by the products of electrolysis.
Decomposition Potential
If we start electrolysis of dil. H2SO4 using Pt electrodes applying an e.m.f. of one volt, it
will soon come to an end due to back e.m.f. developed during electrolysis. So, to keep the
electrolysis going on, we are to apply an e.m.f. which can overcome the effect of back e.m.f. The
minimum voltage, which is just sufficient to overcome the back e.m.f. or polarisation
e.m.f. is called decomposition potential of the given electrolyte (Fig. 10.13).

C-8∴N-ENGCHE∴ECH10-2.PM5 247

248 ENGINEERING CHEMISTRY

Current density
Decomposition
voltage

Voltage
Fig. 10.13 Decomposition Potential.
At this stage, if the applied e.m.f. is gradually increased, electrolysis continues
uninterrupted. So, a minimum voltage must always be applied to start the electrolysis process.
Highlights:
• The decomposition potential is different for different electrolytes.
• The decomposition potential of CuSO4 is 1.5 V with Cu-electrodes and that of
ZnSO4 is 2.55 V with Zn-electrodes. When an e.m.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.

Overvoltage
Theoretical voltage required for the decomposition of an acid solution should be equal to
the e.m.f. of the reversible cell constructed with H2 (g) at 1 atm. But it is seen that the value of
applied e.m.f. is always higher than this theoretical value. Electrolysis of dil. H2SO4 with Pt-
electrodes requires 1.7 V in place of 1.23 V (theoretical value). This difference between the
theoretical voltage and actual applied voltage necessary for electrolysis is known as
overvoltage.
Battery
Cells are devices where electric current is generated at the cost of some physicochemical
processes going inside the cell. In order to apply exact thermodynamic principles to cell reaction
it is customary to distinguish between reversible and irresversible cells. Because the thermo-
dynamic principle is only applicable to reversible cells. It is well known that any chemical
reaction conducted reversibly can yield some external work and the useful work available
from the process, provided the process has been conducted reversibly at constant temperature
and under a given pressure is equal to (the decreasing Gibbs free energy – ∆G). Since electrical
work is equal to nFE, where F = faraday and E = e.m.f. of the cell
so, 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. Battery works on the above thermodynamic principle.
Battery

Primary Secondary Flow
[The cell reaction [The cell reaction [The reactants, products and
is not reversible] is not reversible] electrolytes pass through the battery
and during the passage electric current
is generated at the expense of chemical
reactions as in electrochemical cells]

C-8∴N-ENGCHE∴ECH10-2.PM5 248

ELECTROCHEMICAL CELLS 249

Primary Cells
(a) Leclanche cell. (Fig. 10.14) This type of cell was devised by Georges Leclanche. The
cell consists of a glass vessel B, which contains a saturated solution of NH4Cl as an active
liquid. The cathode is an amalgamated Zn-rod (Z) dipped partially in NH4Cl solution. The
anode is made of gas carbon (C) placed within a porous pot P which is also dipped partially in
NH4Cl solution. The space between the carbon rod and the pot is filled with a mixture of
powdered charcoal and MnO2 which serves as a depolariser. Since MnO2 is a very poor conductor,
charcoal is added to increase the conductivity. The top of the pot is sealed with pitch. The seal
has a hole to allow the escape of NH3 gas. The e.m.f. of the cell is 1.4 V.
Pitch
Hole C +

P –

Zn
Glass vessel
Porous pot

Carbon rod Zinc rod(–)

Carbon–
manganese NH4Cl (Sol)
dioxide mixture

B

Fig. 10.14 Leclanche cell.
Cell reaction: Zn + NH4Cl = ZnCl2 + 2 NH3 + H2
H2 is oxidised by MnO2 as H2 + 2 MnO2 = Mn2O3 + H2O.
When current is drawn from the cell, Zn Hole
rod is used up and the MnO2 is reduced. The
resulting Mn2O3 is slowly oxidised by air to MnO2.
Pitch
2Mn2O3 + O2 = 4 MnO2
(b) Dry cell. (Fig. 10.15) It is essentially a
Paper
Leclanche cell. Instead of NH4Cl solution, NH4Cl
paste is used here. The paste contains NH4Cl,
Zinc
MnO2 and C (graphite). The cell is not really dry.
A zinc vessel serves as negative electrode.
Carbon
A carbon rod is placed at the centre to act as a
positive electrode. It is filled at the top with a brass Paste
cap. The carbon rod is insulated at the bottom Mixture of carbon
from Zn-vessel with a cardboard washer. The and manganese
dioxide
inside of the Zn-vessel is lined up with a thin sheet
Fig. 10.15 Dry cell.

C-8∴N-ENGCHE∴ECH10-2.PM5 249

250 ENGINEERING CHEMISTRY

of blotting paper. To prevent drying of the paste, the top of the cell is sealed with pitch. A small
hole is at the seal. The e.m.f. of the cell is 1.45 V.
This type of cell is widely used in torches, transistors, signalling equipments, telephone
etc.
Alkaline Battery
It is a modification of dry cell where NH4Cl has been replaced by KOH and acts as an
electrolyte. In this type of battery, zinc is used in powder form and makes a gel with KOH. And
the graphite-rod is kept surrounded by a paste of MnO2. 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. The life of alkaline battery is longer than the dry cell because zinc does not
corrode.
Use. It is mainly used in camera, calculators, watches etc.
Nickel-Cadmium Battery
These battery is constructed of cadmium anode and a paste of NiO(OH)(s) cathode. The
cell reaction is
Anode: Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e–
Cathode: 2NiO . OH(s) + 2H2O(l) + 2e– → 2Ni(OH)2(s) + 2OH–(aq)

Net reaction: 2NiO.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. This type of battery is portable and reachargeable. The main advantage of this
battery is that, it undergoes no deterioration as no gases are produced during charging and
discharging.
Use: It is used in calculators, electronic flash units etc.
Mercury Battery
This type of battery is constructed of zinc-amalgam (a solution of Zn in mercury) as
anode and a paste of KOH, Zn(OH)2 and HgO as cathode. The anode and the cathode are
divided by a paper. The paper permits the migration of ions. The cell reaction is:
Anode: Zn-amalgam(s) + 2OH–(aq) → ZnO(s) + H2O(l) + 2e–
Cathode: HgO(s) + H2O(l) + 2e– → Hg(l) + 2OH–(aq)

Net reaction: Zn-amalgam(s) + HgO(s) → ZnO(s) + Hg(l)

The entire cell is covered in a stainless steel case. The size is small. It is expensive.
Use: It finds its use in pacemakers, hearing aids, digital watches etc.
Fuel Cells
In these cells combustion of the fuel is employed as chemical reaction to generate
electricity.
Fuel + O2 → Combustion products + electricity

C-8∴N-ENGCHE∴ECH10-2.PM5 250

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: 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: O2(g) + 2H2O(l) + 4e– → 4OH– (aq) (Reduction)

Net reaction is: 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 electrolyte is aqueous solution of NaCl (or NaOH).
It is expected that this type of battery will find its application in automobiles as source
of energy replacing fuels.
Storage Cells
A storage cell can operate both as a voltaic cell and as an electric cell. The common
example of storage cell is lead-acid storage cell.
It is constructed of electrodes made of lead and the other electrode in PbO2. The two
types of electrodes are separated by strips of wood or glass fibres. The electrodes are totally
immersed in 20% dilute H2SO4. The cell reaction is
At anode:
Pb → Pb2+ + 2e–
Pb2+ + SO42– → PbSO4↓
At cathode: 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.
The cell can be again charged when both the anode and the cathode get covered with
PbSO4. The cell loses its function as a voltaic cell. 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.
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.
Use: This type of battery is used in electrical vehicles, automobiles, power stations etc.
Solar Battery
In this type of battery, solar energy is utilised to generate electric current in a photovoltaic
cell. In this type of photovoltaic cell, p-type semiconductor is connected with n-type

C-8∴N-ENGCHE∴ECH10-2.PM5 251

252 ENGINEERING CHEMISTRY

semiconductor. Due to this contact, a limited number of electrons can flow and cross the junction
between the two types of semiconductors.

SOLVED EXAMPLES
Example 1. Calculate the standard potential of Cu+2/Cu if the electrode potential at 25°
is 0.296 V when [Cu+2] = 0.015 M.
0.0592
Sol. ∈ = ∈° + log [M + n ]
n
0.0592
= ∈° + log [Cu +2 ]
2
0.0592
∴ ∈° = ∈ – log 0.015
2
= [0.296 – 0.0296 × (– 1.8239)] V
= [0.296 + 0.05398] V
= 0.34998 V.
Example 2. Calculate the single electrode potential of copper metal in contact with
0.15 (M) Cu+2 solution. ∈° for copper = + 0.34 V (R = 8.314 J. K–1 mol–1, T = 298 K).
RT
Sol. ∈ = ∈° + ln [M + n ]
nF
2.303 × 8.314 × 298
= 0.34 + log [Cu +2 ]
2 × 96500
2.303 × 8.314 × 298
= 0.34 + log 0.15
2 × 96500
= 0.3156 V.
Example 3. Calculate the voltage at 25°C of a cell formed by dipping silver in silver
nitrate (0.1 M) and zinc in zinc sulphate (0.2 M) and connecting them without liquid junction
potential.
Sol. (–) (+)
The cell ⇒ Ag/AgNO3 (0.1 M) || ZnSO4 (0.2 M)/Zn
The cell reaction ⇒ Zn+2 + 2e Zn (Ecell = ∈R – ∈L = ∈+ – ∈–, R = Right hand
electrode and Reduction L = Left hand electrode undergoing oxidation)
2Ag – 2e 2Ag+
Zn+2 + 2Ag Zn + 2Ag+

FG RT IJ FG RT IJ
∴ H
Ecell = ∈°Zn +
2F K H
ln [Zn +2 ] − ∈° Ag +
2F
ln [ Ag + ]2
K
F
= GH ∈°
RT I F
]J − G ∈°
RT I
]J
Zn +
2F
ln [ Zn + 2
K H Ag +
F
ln [ Ag +
K
= (– 0.762 + 0.0296 log 0.2) – (0.798 + 0.059 log 0.1)
= – 1.522 V.

C-8∴N-ENGCHE∴ECH10-2.PM5 252

ELECTROCHEMICAL CELLS 253

Highlights:
• If after calculation of Ecell it comes negative, half cells are to be reversed to get
positive value of Ecell. 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.
• If we cannot make right choice during construction of a cell, Ecell would come out
negative, but the table of ∈° values and the above procedure will help to calculate
Ecell of any reversible cell.

Example 4. Calculate the e.m.f. of a Daniel cell at 25°C, when the concentrations of
ZnSO4 and CuSO4 are 0.001 M and 0.1 M, respectively. The standard potential of cell is 1.1 volts.
RT [Cu +2 ]
Sol. We can write Ecell = (∈°+ − ∈°− ) + ln
nF [Zn +2 ]
0.0592 0.1
= E°Cell + log [Q E°cell = ∈°+ – ∈°– ]
2 0.001
= 1.1 + 0.0296 log 100
= 1.1 + 0.0296 × 2
= 1.1592 V.
Example 5. Calculate the e.m.f. of the cell:
Ni | Ni+2 1(M) || Pb+2 1(M) | Pb
at 25°C. Write down its cell reaction. Given ∈°Ni = – 0.24 V and ∈°Pb = – 0.13 V at 25°C.
Sol. E°cell = ∈°right – ∈° left
= (– 0.13) – (– 0.24)
= 0.11 V.
Cell reaction:
At anode: Ni – 2e Ni+2 (Ox)
At cathode: +2
Pb + 2e Pb (Red)

Ni + Pb+2 Ni+2 + Pb
Example 6. Sketch the electrochemical cell and write down the cell reaction, if Zn and
Ag electrodes are dipped in respective solutions. Also find out the standard emf of the cell, given
that ∈° Zn/Zn +2 = 0.76 V and ∈° Ag/Ag + = 0.8 V at 25°C.

Sol. ∈°Ox = ∈° Zn / Zn +2 = 0.76 V i.e., ∈°Red = ∈Zn +2 / Zn = – 0.76 V
∈°Ox = ∈° Ag / Ag + = – 0.8 V i.e., ∈°Red = ∈° Ag + / Ag = 0.8 V.
So here S.R.P of Ag-electrode is higher than that of Zn-electrode. So, Ag-electrode will
form right hand half cell i.e., +ve electrode.
Cu = Zn/Zn+2 (a = 1)/Ag+ (a = 1)/Ag+
According to ‘2R’ convention reduction will take place at right hand electrode (cathode).
Cell reaction ⇒
At cathode: 2Ag+ + 2e 2Ag (Reduction)
At anode: Zn – 2e Zn+2 (Oxidation)

2Ag+ + Zn+2 2Ag + Zn+2

C-8∴N-ENGCHE∴ECH10-2.PM5 253

01 log 10 Example 8.0592 [Zn +2 ] 0.1 0. ∈° Zn / Zn +2 = 0.e. ∈°Cu +2 / Cu = 0. Cell = Cu/Cu+2 (0..102 V..∈° = 0.8 – (– 0.P.0592 [Zn +2 ]/[Zn] or 0.f. Example 7. Two copper rods are placed in copper sulphate solution of concentration 0.0296 Ecell = log = = 0.0296 log [Cu +2 ]/[Zn] C-8∴N-ENGCHE∴ECH10-2.0592 [Zn +2 ] 0. Calculate the equilibrium constant for Daniel cell at 25°C from the following data. (Ox) for Cu electrode = – 0.1 M)/Cu 0.337 V Zn – 2e Zn+2 ..01 M) || Cu+2 (0..102 = 0.316 J.01 M n C1 0.0592 [Cu +2 ] ∈° Cu +2 / Cu − ∈° Zn+2 / Zn = log − log 2 [Zn] 2 [Cu] 0. [Zn +2 ] [Cu] ∴ K= [Zn] [Cu +2 ] 0.E.∈° = 0.765) = log 2 [Cu +2 ]/[Cu] [Zn +2 ]/[Cu] 1.. Sol. 0. Write the scheme of the cell and calculate its e.. Therefore. = 0.PM5 254 ..1 M and C1 = 0.765 V i. 2 0.765 V Cell reaction: Zn + Cu+2 Zn+2 + Cu (E°cell = ∈°Red + ∈°OX) = 1.337 V Cell = Zn/Zn+2 || Cu+2 /Cu Half cell reactions Cu+2 + 2e Cu .0592 [Cu +2 ] ∈° Zn +2 / Zn + log = ∈° Cu +2 /Cu + log 2 [Zn] 2 [Cu] 0.0592 0.76) = 1.. here C2 = 0.337 – (– 0.01 M separately in the form of a cell.56 V.337 V i.E.765 V and ∈°Cu / Cu +2 = – 0.0592 C Ecell = log 2 .e. at 298 K. these two electrode potentials will be equal. (Ox) for Zn electrode.059 [Cu + ] ∈° Cu +2 / Cu = ∈°Cu +2 / Cu + log 2 [Cu] At equilibrium.m. F = 96. R = 8.1 M and 0.P.337 Sol.500 C..765 V and S. ∈° Zn +2 / Zn = – 0.0296 V.254 ENGINEERING CHEMISTRY E°cell = ∈°Right – ∈°Left = 0.. S.0592 [ Zn +2 ] ∈Zn +2 / Zn = ∈° Zn +2 / Zn + log 2 [ Zn ] 0.

Ksp (AgI) = 8.3 × 10–17 (M). ∈Q/H2Q = 0.0592 pH = 0. Calculate the pH of the solution.6990 – 0. 0.0296 K = Antilog 37.2297 = 1.2297 0.3345 0. of the combined cell was determined to be 0.3 × 10 −17 [Ag+] = = = 8. K sp 8.799 V.6990. Cell reaction Ag+ + e Ag ∈° = 0. ∈° Ag + / Ag = + 0. Sol.ELECTROCHEMICAL CELLS 255 = 0. which is coupled with standard calomel electrode.0592 pH) – 0.2415 – 0. Ecell = ∈°H – ∈H = 0 – (– 0.6990 = – 0.29 ∴ pH = = ≈ 4. Find out the pH of a solution in a quinhydrone half cell. 0.3345 or pH = = 5.m. E°cell = 0.0296 log K 1.65 .2223 ∈° Ag + /Ag = 0. I 1 Example 10.798 at 25°C. Example 9. Sol.102 ∴ log10 K = = 37.2223 Ag + Cl– AgCl(s).798 Ag + Cl– AgCl(s) + e ∈° = – 0. Sol. The e.3 × 10–17.0592 pH) = 0. – ∆G° = nFE° nFE° = – RT ln K C-8∴N-ENGCHE∴ECH10-2.29 V at 298 K as measured against normal hydrogen electrode.0592 Example 11. Sol.PM5 255 . Ecalomel = 0. Calculate Ksp of AgCl from the following data: ∈°Ag–AgCl(s) = 0.5757 We have.123 + 0. The potential of a hydrogen gas electrode in a solution of an acid of unknown strength is 0.0592 0.2415.0592 pH E cell 0.123 V at 25°C.123 = (0. Calculate the potential of an Ag-electrode in a solution that is saturated with AgI and has an iodide concentration of exactly unity.9.0592 Example 12. Ecell = ∈Q/ H 2Q − ∈calomel 0.2415 or – 0.f. Highlight: • The high value of K indicates the spontaneity of the reaction.697 × 1037.

6.5757 or log K = – =– = – 9. Q. e. It is a device used for converting electrical energy into chemical energy. It is an inverted U-tube containing an electrolyte (e. 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. Daniel cell. KNO3).303 RT 0. What is the E. Q. It is the electrode potential of a metal in contact with its ions when the concentration of ions is 1 M (1 molar). 10. What is an electrolytic cell? Ans. Q. 5.M. 4. SHORT QUESTIONS AND ANSWERS Q..16 In the above cell Zn-electrode is anode and Cu-electrode is cathode. e V Salt bridge e 2– SO4 Cu Zn ZnSO4 CuSO4 Zn → Zn+2 + 2e– (oxidation) Cu2+ + 2e → Cu (reduction) Fig.886 × 10–10 mol2 l–2. Q. It is defined as the potential difference between the two terminals of the cell when no current is drawn from it. Q.0592 or Here K = Ksp = Antilog 10.g. What do you mean by standard electrode potential (E°)? Ans. 3. C-8∴N-ENGCHE∴ECH10-2. What is a salt bridge? Ans. What is galvanic cell or voltaic cell? Ans. 2. Such a cell is also known as electrochemical cell. KCl.256 ENGINEERING CHEMISTRY nFE° 1 × 0. 7.2754 = 1. Q.g. of a cell? Ans. What do you mean by electrode potential (E)? Ans. It connects (acts as a bridge) the solutions of the two half cells. 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.7246 = – 10 + 0.F. What are reduction and oxidation potentials? Ans.PM5 256 . 1.2754 2.. It is a simple device of producing electrical energy by chemical reaction.

9.17 A cell constructed with standard hydrogen electrode.M. How is the E. of a cell measured? Ans. 10. A normal hydrogen electrode generally consists of a Pt-foil coated with platinum. it consists of a strong electrolyte (e. It can be represented as: Pt. How is electrode potential measured? Ans. 10.PM5 257 . dipped in solution having 1 M H+ ion concentration and hydrogen gas at 1 atmospheric pressure constantly bubbled over it. 10. A = Solution of H+ ions of unit activity B = Redox solution of unit activity. Ans. named potentiometer.g. 8. KCl). of a cell is measured by means of a device. Saline bridge has the function of bringing into physical contact the two solutions without mixing them. Apparatus for measuring the standard electrode potential of a redox system is given in Fig. C-8∴N-ENGCHE∴ECH10-2. Its electrode potential is taken as zero at all temperatures. H2 (1 atm) || H+ (1 M) 1 Reaction: H+(aq) + e– → H 2 ( g) 2 1 or H 2 ( g) → H+(aq) + e– 2 Q. 10. Saline bridge Inert H2 electrode (Pt) (1 atm) + H (a=1) Redox system Pt A B Fig..ELECTROCHEMICAL CELLS 257 Q. ∆∈ = ∈°Redox – ∈° H /H+ 2 ∴ ∈° H / H+ = 0 2 ∴ ∆∈ = ∈° Redox B A C D G Fig.F.18 Diagram for Potentiometer. It is a reference or standard reference electrode.F.17.M. Define normal hydrogen electrode. Q. E.

13. a ⇒ activity of the ion in relation to which the electrode is selective. 12.258 ENGINEERING CHEMISTRY Q.059 0. [Mn+] ⇒ conc. 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. (c) Redox = Electrodes which are inert in contact with a redox couple in solution. Ans. 0.059 + ∈ = ∈° M / M n+ + 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). (d) Membrane type = Selective electrodes specific to certain ions. [A–n] = Conc. ∈ = ∈° M / M n+ + log K sp − K sp [ A − n ] n n where Ksp = solubility product of the salt which is not readily soluble. 0. ∈ = ∈°Redox + log [Ox]/[Red] n Pt ⇒ Platinum [Ox] = Conc. (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.PM5 258 .f. of cation in moles dm–3 0. What are reference electrodes? Ans. Give the hemistry the different indicating electrodes. where.) between two half cells.059 And. 11.246 V) and the silver-silver chloride electrode (∈ = + 0. Potentiometry is an electrochemical method of analysis based on measuring the potential difference (e. the potential of which is given by Nernst equation. A–n where. The best known of this type is glass electrode. Q. Pt/Ox.222 V). What is an indicating electrode? Ans.m. one of which is an indicating electrode and the other is a reference electrode. ∈r ⇒ Constant potential linked to the choice of the reference electrode and the internal solution. C-8∴N-ENGCHE∴ECH10-2. of the oxidised form in moles dm–3 . The most widely used are saturated calomel electrodes (∈ = + 0. 14. Q.059 And.059 ∈ = ∈r + log a n where. Red 0. What do you mean by potentiometry? Ans. It is an electrode in balance with an redox couple. of the anion in moles dm–3 . M ⇒ Metal MA(s) ⇒ the salt which is not readily soluble. Q. 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. [Red] = Conc.

What is lead storage battery? Ans.PM5 259 . Reactions: Anode: Pb + SO42– → PbSO4 + 2e– Cathode: PbO2 + SO42– + 4H+ + 2e– → PbSO4 + 2H2O Net reaction: Pb + PbO2 + 4H+ + 2SO42– → 2PbSO4 + 2H2O. Q. T ⇒ absolute temperature. 18. R ⇒ molar gas constant.303 RT [Reduced form] ∈Red = ∈°Red – log nF [Oxidised form] where. When the standard reduction potentials of the electrodes are arranged in an increasing order. ∈Red = observed reduction electrode potential. 16. What is Nernst equation? Ans.ELECTROCHEMICAL CELLS 259 Highlight: The potential of reference electrodes is determined as referred to the standard hydrogen electrode. Q. What is the reaction in nickel-cadmium battery? Ans. 15. Q.059. F = Faraday (96500 Coulombs) At 25°C the value of the term 2. So at 25°C 0.059 [Reduced form] ∈ = ∈° – log n [Oxidised form] Highlight: The concentration of metal is taken as unity. the series so obtained is known as electrochemical series. Define the electrochemical series? Ans. ∈° = standard reduction electrode potential. Reaction during recharging the battery PbSO4(s) + 2H2O(l) ⇔ Pb(s) + PbO2(s) + 4H+ + 2SO42– Q. 17. n ⇒ number of electrons involved in the redox reaction. Nernst proposed the fundamental electrode relation between the formal (or observed) potential and the standard electrode potential for the redox reaction: 2.303 RT/F comes out as equal to 0. It consists of six voltaic cells connected in series. Anode: Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e– Cathode: NiO2 + 2H2O + 2e– → Ni(OH)2 + 2OH– (aq) C-8∴N-ENGCHE∴ECH10-2.

(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. The Fe+2 ions formed at anode are oxidised by O2 to Fe+3 ions which then combine with OH– ions to form hydrated ferric oxide. Q. (a) Barrier protection. 22. (c) Electrical protection. Q. Ans.PM5 260 . Q. (b) Sacrificial protection. e. 21. 20. Ans. (b) Electrochemical corrosion ⇒ it involves deterioration of metal due to flow of electric current from one point to another. +2 ∈° = 0. Ans. 19. Fuel cells are the devices that convert chemical energy of a fuel directly into electrical energy. State the electrochemical theory of rusting. (c) Dry corrosion ⇒ it refers to the corrosion of metals involving direct chemical action between metals and dry gases. Given (i) Fe+2 + 2e → Fe. (a) Chemical corrosion ⇒ it involves direct chemical action between metals and gases. 23. (d) Use of anti-rust solutions. What measures ought to be taken to prevent corrosion? Ans. ∈° = – 0.g. rusting of iron. What are fuel cells? Ans.3H2O (rust) Q. Q..260 ENGINEERING CHEMISTRY Q. What do you mean by corrosion? Ans. Anode: {H2(g) + 2OH–(aq) → 2H2O(l) + 2e–} × 2 Cathode: O2(g) + 2H2O(l) + 4e– → 4OH–(aq) Net reaction: 2H2(g) + O2(g) → 2H2O(l) Highlight: Such a cell is used to generate electrical power such as in Apollo space programme. 25. 24. i.44 V +3 (ii) Fe + e → Fe . It generally refers to the slow and continuous deterioration of metals and alloys by chemical or electrochemical actions of environments.77 V Represent the data in the form of Latimer diagram. 2Fe+2 + H2O + O → 2Fe+3 + OH– 2Fe+3 + 6OH– → 2Fe(OH)3 or Fe2O3. Q.e. Classify corrosion. C-8∴N-ENGCHE∴ECH10-2. rust. Reaction: Anode: Fe → Fe2+ + 2e– Cathode: 2H2O + O2 + 4e– → 4OH–.. Give the reaction in H2–O2 fuel cell.

Fe+3 + 3e → Fe ∆ G° + 0.30 – + 0. 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.44 Fe Fe Fe –0. We have ∆G°(i) = – nFE° = – 2F (– 0.36 – ClO4 .19 Latimer diagram for Fe species. In alkaline solution (pH = 14) the Latimer diagram for chlorine is – + 0.04 V −n F −3F The Latimer diagram of the above system is Fig.11 F So ∆G°(iii) is the value for the reaction.ELECTROCHEMICAL CELLS 261 Ans. 10.77) = – 0.88 F ∆G°(ii) = – nFE° = – F(0. ∆G°(iii) = ∆G°(i) + ∆G°(ii) = 0. +3 0.44) = 0.37 – + 0.77 +2 –0.11 F ∈° = = = – 0.88 + (– 0.77) F = + 0.19.04 Fig.68 – + 0. 26.42 + 1. 10.77 F Adding the above two equations.

ClO3 .

ClO2 .

ClO .

Cl2 .

∆G° = – nFE° ∆ G I + ∆ G II − 178 . ∆G°I = – (+ 0. ∈° = + 1.18 V. F ∈° (ClO–/Cl–) = = = 0. ∈ Mn+2) = 1. ∈º(Mn+2. Ans.36 V ∈°(Mn+3. Mn) = 0. +e 1 Ans.78 F From the relation. Use the following data to draw a Frost diagram.42 V.95 V 3∈°(Mn+3. Cl ? Calculate from the above diagram ∈° value for the reaction. 27.42) F = – 0.36 V.36 F 2 2 Adding total ∆G for the reaction = – 1.51 V. ClO– → Cl .10 V C-8∴N-ENGCHE∴ECH10-2. Mn) = – 0. 2∈ ∈° = – 2. Mn) = – 1.89 V − nF −2F Q.36) F = – 1.18 V ∈°(MnO2. ∈° = + 0.42 F 2 2 1 +e Cl → Cl–. Mn+3) = 0. ∈°(Mn+2. Mn) = – 1. ClO– → Cl–.85 V 4∈°(MnO2. ∆G°II = – (+ 1.PM5 261 .

23 Ans.20 Frost diagram for Mn in acidic pH.e. Construct a Frost diagram from the Latimer diagram for Tl.34 Tl Tl Tl +1. C-8∴N-ENGCHE∴ECH10-2. here n = 1.25 + –0. 10. + 1 and 0. 28. Highlights: • Plot of n∈° vs n for Mn (n = oxidation state) such diagram are called Ebsworth diagram or Frost diagram. the higher the potential of corresponding couple. ∈° = – 0. in the three species. • The point for Mn(VI) similarly suggests disproportionation to Mn(VII) and Mn(IV). n∈° = – 0. so. Most species that reduce MnO4– should also reduce MnO2.PM5 262 . • Mn+3 is likely to disproportionate to Mn+2 and MnO2. the process is likely to be rapid. Since both these products involve one electron transfer. +3 +1. The oxidation states of Tl are + 3. Q. • 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.34 V. For the change of oxidation number from + 1 to 0 i. • A state is unstable with respect to disproportionation if it lies above the line connecting two adjacent oxidation states. Tl+1 → Tl0. • MnO2 is also a strong oxidizing agent—its slope to Mn+2 is greater than the slopes to higher oxidation states. • The steeper the line joining two points..262 ENGINEERING CHEMISTRY 7+ Mn +6 6+ +5 Mn +4 5+ +3 Mn +2 n °(V) +1 Mn° 4+ 0 Mn –1 3+ Mn –2 2+ Mn –3 0 +1 +2 +3 +4 +5 +6 +7 Oxidation number Fig.34 V.

What is an electrochemical series? 13. 3. Write a note on decomposition potential. 4. What is standard electrode potential? 8. 2. 16. Why are standard potentials of Zn/Zn +2 and Cu/Cu+2 electrodes opposite in sign? 14. What are primary and secondary reference electrodes? 18. C-8∴N-ENGCHE∴ECH10-2. n∈° = 3 × 1. 7. for n = 3. What is a standard hydrogen electrode? What is its potential? 5. Define the electrode potential. Why is a voltmeter is not used for the measurement of e.21 Frost diagram for Tl species. Describe the construction and working of H2 – O2 fuel cell.m. What is overvoltage? What is the cause of overvoltage? 6. Give the cell rotation for a concentration cell.PM5 263 . Prove that ∈ox = – ∈red. Explain how the pH of a solution is determined using the glass electrode. What is a calomel electrode? Describe its construction: Why it is used as reference electrode in place of a standard hydrogen electrode? 12. Tl+1 is the most stable oxidation state of Tl as the species lies lowest in the Frost diagram. (ii) significance of standard electrode potential. EXERCISES 1. Describe the construction of a glass electrode. 9.69 V. 10. 4 +3 3 Tl 2 1 0 Tl° n °(V) +1 Tl –1 –2 –3 0 +1 +2 +3 Oxidation number Fig. What is a storage cell? Name some of its types. of a cell? 10. 17.f.ELECTROCHEMICAL CELLS 263 For the change of oxidation number from + 3 to 0 (Tl+3 → Tl0) ∈° value = + 1. 19. 11.23 V = + 3. State the peculiarity of a concentration cell. 15. Write notes on: (i) Weston standard cell.23 V So. Distinguish between electrolytic and electrochemical cells. Give the reason: the hydrogen overpotential falls with rising temperature.

Explain the construction and working of lead storage battery.763 V (0. (ii) AgCl(s). Describe the construction and working of Daniel cell. of a Daniel cell at 25°C.01 (M) ZnSO4 solution at 25°C. Calculate the e.m. What are reversible and irreversible cells? 25. (iv) 2H+/H2(g) Pt. The potential of the normal calomel electrode is 0.m. when the concentrations of ZnSO4 and CuSO4 are 0.m. Will a reaction take place if an Ag-bar is placed in a solution of FeSO4? Explain using the follow- ing data: ∈°Ag + / Ag = 0. 22.13 V). Derive an expression for electrode potential of an M/Mn+ electrode? 23. 30. 33. Describe the potentiometric methods for (i) Determination of pH of a solution. Calculate E° at 25°C for cell: (Pt) H2/HCl (aq)/Cl2 (Pt). Explain the construction of Ni-Cd cell.PM5 264 . Calculate the pH of the solution. 0.m. if E°cell = + 0.44 V (– 1. Give the single electrode potential of Zn- half cell.799 V. and ∈°Fe +2 / Fe = 0.212 V. Cl–/Ag. Distinguish: (i) a reversible cell from an irreversible cell (ii) a galvanic cell from a concentration cell.78 V). Write down the electrode reactions and overall cell reactions for the following cells. both at the same temperature.f.f. (ii) Calculation of solubility product of AgCl. (i) Zn | ZnSO4 || CuSO4/Cu (ii) (Pt) H 2 (1 atm) | HCl/AgCl(s).8192 V) 36. 21. of voltaic cell: Fe | Fe+2 (aq) || Cu+2(aq) | Cu. Calculate the e. [Ans.5] C-8∴N-ENGCHE∴ECH10-2. respectively. 39.239 V) 38. What is fuel cell? Give detail of one such cells.f of the following concentration cell: Ag/Ag+ (0. Give the equilibrium constant for the reaction. Also give the expression for their e. (iii) Fe+3/Fe+2 Pt. The reaction H2 + Cl2 + 2H2O 2H2O + 2Cl– has an equilibrium constant K = 1046 at 25°C. 34.f. The standard potential of the cell is 1.f. 2Cu+ Cu2+ + Cu 35. The e. 27.44 V. How is single electrode potential measured experimentally? 31. Zinc rod is dipped in 0.m.2812 V and E° for the quinhydrone electrode is 0. Give the cell reaction of the following: (i) Zn+2/Zn.1 M) || Ag+ (1M) | Ag [Ans. (0. respectively. Give the use of Ag-AgCl electrode. 37.001 M and 0. Calculate the e.337 and 0. 6.34 V and –0.0 N)| Quinhydrone | Pt is 0.530 V. 29. 24.1 V (1.0592 V] 40. of the cell at 25°C Hg(l) | Hg2Cl2(s). KCl(sol) (1. Ag 32. What is Nernst equation? State its utility.6996 V. 26.1 M respectively.264 ENGINEERING CHEMISTRY 20. 28. Given the electrode potentials of Cu and Fe are 0. The standard potentials of Cu/Cu +2 and Cu/Cu+ system are 0.

at 25°C in 0.5622 V. (ii) 3. Calculate the equilibrium constant of the reaction at 25°C.1 N HNO3 | HgNO3 (0.ELECTROCHEMICAL CELLS 265 41.5355 V.PM5 265 . which is constructed by connnecting H2-electrode to normal calomel electrode. [Ans.44 V. E.2. 2] 42.036 V ∈°I(s)/I – ⇒ 0. (i) 6.m. [Ans. value ⇒ 0.m. 2 Fe+3 + Sn+2 2 Fe+2 + Sn+4 from ∈° values given in the Table 10.001 N) in 0. to calculate ionic product of water. K = 166] 44. ∈°Fe +3 / Fe ⇒ 0.f.16 × 10–7] C-8∴N-ENGCHE∴ECH10-2. [Ans. of the cell. K = 1021] 43. [Ans. When calomel electrode is connected to H2-electrode at 18°C. 1 Fe+3 + I– Fe+2 + I(s) 2 from the ∈° (reduction) values ∈° Fe +2 / Fe ⇒ 0. Calculate the valency of mercurous ions with the help of the following cell: Hg | HgNO 3 (0. Suggest a cell. Calculate its (i) pH and (ii) H+ concentration. Find the equilibrium constant of the reaction at 25°C. 5. gives e. H 2-electrode || O2-electrode] 45.5.01) | Hg+ [Ans.4] 46. Calculate the pH of the solution.664 V. [Ans.f.

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

(e) In the system of sodium sulfate-water. hence the system is univariant. F=C–P+2 where C is the number of components. ( f ) In the equilibrium. However.PHASE RULE 267 (c) In the thermal decomposition of MgCO3. It is a one component. then the composition of any one phase can be represented as Phase: MgCO3 = MgCO3 + OMgO Phase: MgO = O MgCO3 + MgO Phase: CO2 = MgCO3 – MgO So it is a two-component system. 10H2O. the volume of the gas is known. (b) The system ice(s) Water(l) vapor(g) is one-component. pressure and concentration and not influenced by gravity. Hence the degree of freedom is two. such as temperature. The number of degrees of freedom of a system is the minimum number of the independent variables of a system. So this system will have no degree of freedom i. C-8∴N-ENGCHE∴ECH11-1. 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. so the system is univariant. pressure and concentration. magnetic or electric forces. Degrees of Freedom or Variance. Na2SO4. three-phase system and all these three phases can co-exist at the freezing point of water at a particular temperature and pressure. so the system is a two-component system.PM5 267 . Na2SO4. one-phase system. one of the phases will disappear and the three phases will not be in equilibrium. the system becomes a two-component system. surface action. The composition of each of the three phases can be expressed in terms of at least any two of the three constituents. HCl) is exactly the same as that of the undissociated substance (NH4Cl). (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. If the temperature and pressure are specified. provided that the only significant external factors acting are temperature. the number of component is one. NaCl(s) NaCl-Water(aq) H2O(g) the solubility at the saturation point is fixed by either temperature or pressure.. which can completely define the equilibrium of a system. solution and vapor. 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. The composition of each phase can be expressed in terms of Na2SO4 and H2O.e. MgCO3(s) MgO(s) + CO2(g). (d) For the simple system water (l) Water vapor (g) temperature or the pressure is required to define the system. Thus. ice. 7H2O. P the number of phases and F is the degree of freedom. it is a non- variant or invariant system. if NH3 or HCl is introduced in the system in excess. (c) For the system. various phases may exist like Na2SO4. (a) A system consisting of pure gas or gas mixture. 3. If temperature or pressure is altered.

hence if a trace amount of a phase is present and not taken into account. 2.PM5 268 . 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. they are one-component systems with two phases (C = 1. 3.1. 3. 11. Limitations of phase rule 1. P = 3. (a) Water(l) Vapor ( g) C = 1. The point B has a natural limit of – 273°C. also called the vaporisation curve. From Fig. Different systems behave in a similar fashion if they have same degrees of freedom. the rule is inapplica- ble. The OA curve terminates at A. 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. Hence F = 1 – 2 + 2 = 1. P = 2. P = 3. 5. It states that all the phases must be present under the identical conditions of tem- perature and pressure. The equilibrium system requires no information regarding its molecular nature or micro structure. beyond which the two phases merge. the properties like melting point. The Water System This system consists of three phases—ice. boiling point. water.268 ENGINEERING CHEMISTRY Examples 1. (b) For water at critical point Ice (s) Water (l) Vapor ( g) C = 1. 2. For both of these curves OA and OB. triple point can be found. C-8∴N-ENGCHE∴ECH11-1. so it is of no value for systems which may attain equilibrium very slowly. the critical temperature of +374°C above which distinction between liquid and vapor vanishes. Hence F = 1 – 3 + 2 = 0. we find that curve BO is the vapor pressure curve of ice which indicates that ice has a small but definite vapour pressure. Phase rule is applicable to both physical and chemical equilibria. The rule considers only the number of phases and not their amounts present. (c) For CaCO3 (s) CaO (s) + CO2 ( g) C = 2. The nature or quantities of the components do not have any role. From the phase diagram. P = 2). Hence F = 2 – 3 + 2 = 1. Advantages of phase rule 1. vapor and one-component H2O. This rule can be applied only to systems that have attained equilibrium. 4. OA is the vapour pressure curve of water.

579 mm pressure and at this point C = 1. if the temperature is fixed. This curve represents a metastable system.2).. all other properties are also fixed.0098°C under 4. P = 3. rhombic and monoclinic sulfur have same vapor pressure and co-exist with sulfur vapor. it is actually the melting point of ice i. Sulfur at low temperature is in the rhombic form and at high temperature in the monoclinic form. 11. The dotted portion OD. ice.1 The phase-diagram for water (not to scale). Hence F = 0 i.579 mm O Water D vapour B . The curve OC represents the change of melting point of ice with pressure. AB is the vapor pressure curve of rhombic sulfur which is stable upto 95°C (0.e. Sulfur System. C-8∴N-ENGCHE∴ECH11-1... In the phase diagram for sulfur (Fig. BC is the similar curve of monoclinic sulfur and the point B is the transition point between the two allotropes of sulfur.006 mm) at B. 0.0075 °C 100 °C 374 °C Temperature Fig.PHASE RULE 269 C 218 atm A X Water Y Pressure 1 atm Ice Z 4.e. BOC and AOB in which only one phase is present and so the system becomes bivariant and to locate any point in these areas.. ice-water-vapour are in equilibrium. At B. 11. The other two modifications are liquid sulfur and sulfur vapor. i.e. because the three phases. The inclination of OC towards the pressure axis shows that melting point of ice is decreased by increasing pressure. 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. temperature as well as pressure is to be known because the degree of freedom F = 1 – 1 + 2 = 2. The point of intersection of these two curves is point O..e. Sulfur system is another one-component system with a slight more complexity. at this point neither temperature nor pressure can be altered without the disappearance of one of the three phases.e. called the triple point. Since F = 1 there is only one degree of freedom i. The curves OA.PM5 269 . which is the continuation of the curve AO below 0°C is the vapor pressure curve of supercooled water below 0°C. OB and OC divides the whole region into three portions AOC.

0.. 0. 1..e. i. pressure and concentration. B is actually the triple point.” F=C–P+2 Phase (P): Phase is defined as any physically distinct portion of matter which is itself homogeneous and uniform in composition. BE. CE and EF two phases co-exist and F = C – P + 2 = 1 – 2 + 2 = 1. concentration.6 °C. These two lines meet at E (151°C. CD.e. zero variant and three phases coexist. 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. 1288 atm) which is again a triple point where rhombic. pressure. These metastable systems are represented by dotted curves. BC. which can completely define the equilibrium of a system.2 The sulphur system. Along the lines AB.288 mm) Pressure (not to scale – schematic) SL G(115 °C. C-8∴N-ENGCHE∴ECH11-1.04 mm) monoclinic sulfur melts and CD is the vapor pressure curve of liquid sulfur. At the triple point F = C – P + 2 = 1 – 3 + 2 = 0 i. Curve BG is the metastable vapor pressure curve of rhombic sulfur. the system is univariant and either temperature or specific volume determines the system completely. Hence. such as temperature. 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. with pressure. There are three stable and one unstable triple points and four phases co-exist nowhere in the curve in equilibrium. 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. mechanically separable from other parts by definite boundary surfaces.270 ENGINEERING CHEMISTRY F SR E(151 °C.006 mm) A Temperature (not to scale – schematic) Fig.PM5 270 . Again at C (120°C.04 mm) Sv B B(95. 0. monoclinic and liquid sulfur co-exist in equilibrium.03 mm) D C(120 °C. Degrees of freedom (F): It is the minimum number of independent variables of a system. The lines BE and CE represent changes in transition temperature and melting point. 11. 0. respectively.

11. the rate of cooling is altered and there is a break in the cooling curve.3 Cooling curves. a a Freezing point b Temperature Temperature c b c d Freezing Eutectic point temperature d e Time Time (a) (b) Fig. Eutectic Systems The cooling curve of a pure substance can be represented as Fig. If the mixture becomes eutectic the temperature falls until the eutectic point is reached.e. Phase Rule for Two-Component Alloy Systems For a two component system. Thus now the system is present at atmospheric pressure and it remains constant.3 (b). 11. 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. From the cooling curve of any mixture of definite composition freezing point and eutectic temperature both can be obtained.3 (a). The cooling curve of a mixture of solid is represented by Fig. the highest degree of freedom F = C – P + 2 = 2 – 1 + 2 = 3 i. F = C – P + 1 and the system is called condensed system. The temperature decreases continuously but at different rate than before freezing point.e. The variables reduce to temperature and composition and hence the diagrams are represented on temperature-composition equilibrium. The system becomes invariant. C-8∴N-ENGCHE∴ECH11-1. the behaviour of a system may be represented by a three-dimensional diagram of pressure. rhombic sulfur separates on cooling liquid sulfur along EG. which will reduce the degrees of freedom by one i. When a solid solution is cooled at freezing point.PM5 271 . temperature and composition which cannot be drawn on a paper.PHASE RULE 271 From the diagram it is also found that under ordinary pressure. Thus actual observation can be explained perfectly in terms of phase rule.. cooling of liquid sulfur leads to solid monoclinic variety along CE but under high pressure.. temperature remains constant until total solidification occurs (along cd) and again temperature falls uniformly along de. 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. The freezing point of a system varies with the composition but the eutectic point remains constant. a solid phase appears.

272 ENGINEERING CHEMISTRY If the composition of the mixture coincides with the eutectic composition. the system is univariant along AO and BO and at point O.e. solution of Ag + Pb and vapor. 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”. Lead-Silver-Sample (Eutectic System) It is a two-component system with four possible phases—solid Ag. Similarly. 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”. C-8∴N-ENGCHE∴ECH11-1. Curve AO represents the freezing point curve of Ag. The composition corresponding to a freezing point gives the composition of the alloy. A Liquid 961 °C P B Solid Ag + Temperature Liquid 327 °C P 303 °C O Solid Pb Eutectic + + Liquid Solid Ag Eutectic + Solid Pb 100% Ag 100% Pb 2. which is the eutectic temperature and a lead-silver mixture can never have a melting point below the eutectic temperature.. there is no double break but the curve mimicks that of pure component. By plotting freezing point against composition. 11.6 Ag 97. F = 3 – P = 3 – 3 = 0 i.PM5 272 . automobiles etc. This point O is the eutectic point (2. At constant atmospheric pressure. the vapour phase is absent and the condensed phase rule is applicable as F = C – P + 1. as Ag is added the melting point gradually falls till the lowest point O is reached with the above mentioned composition. another curve BO is obtained starting from the melting point of pure lead (327°C) at B.4 % Pb) and the whole mass at this point crystallizes out with the above fixed composition. invariant. 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. According to reduced phase rule equation. T-C curve is obtained for alloy system.4 Pb Composition Fig.4 T-C diagram of Pb-Ag system. solid Pb. A is the melting point (961°C) of Ag.6 % Ag and 97. It is also necessary to know the freezing points of the pure components. The eutectics are applied for constructing safety devices in boilers.

C—compound Mg2Sn.5. S are invariant and the areas in between the lines are univariant. the freezing point decreases along RS and reaches the second eutectic point S (565°C). Thus along QR from molten alloy only solid compound crystallizes out in equilibrium with the liquid. Q. 11. the melting point of Sn (232°C) lowers along PQ.67% weight of carbon. Tin-Magnesium System The equilibrium diagram of tin (Sn) and magnesium (Mg) is shown in Fig. Further addition of Mg raises the melting point along QR and the maximum is reached at R. a1 a2 a3 a4 a5 800° R 783° w 651° T C+L B+L 565° 500° U S Z C+L P 232° A+L B+C 210° X Q Y 100° A+C 0 50 100 Mg (mole percent) Fig. This temperature (783°C) is the congruent melting point of the compound. R. W. At O (210°C) a new solid phase of a compound of Sn and Mg begins to separate alongwith Sn. The compound formed is stable and has its melting point at the maximum. At the eutectic points the solid compound is in equilibrium with either solid tin or solid Mg. The hump in the diagram indicates the formation of a compound. Pure iron exists in three allotropic modifications α. At R the composition of the liquid and the solid phase is the same. C-8∴N-ENGCHE∴ECH11-1. The melting points and the eutectic points P. B—Mg crystals. The phase-diagram of iron-iron carbide system is used upto 6. L—liquid. which is Mg2Sn. Again on increasing the Mg the freezing point rises along SW.5 Phase diagram of the system Sn-Mg: A—Sn crystals. When Mg is added to Sn. Iron-Carbon Alloy System The equilibrium diagram of Fe-C is especially useful to understand the heat treatment of steel. Further increasing the magnesium. C atoms being small compared to iron atoms form only interstitial solid solutions and the solubility of C in these allotropes is quite different. So Q is the invariant eutectic point. γ and δ.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.PM5 273 . 11.

On further addition of C. 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. the mixture is austenite containing 2% C and liquid has eutectic composition. In the phase diagram.130°C) H 1100 C Temperature °C 1000 Austenite Austenite Cementite + te I Acm ni +Ledeburite + 900 Ferrite te s ite +Cementite Ledeburite A2 A3 Au + ent 800 m L K Ce (723 °C) M 700 Eutectic (Ledeburite) 0. austenite separates out from the liquid. But with faster cooling rates metastable phases like martensite and bainite are formed which are not shown in the phase diagram.e.6 Equilibrium diagram for Fe-C system.8 1. From the curve.4 0. the curve ABCD is the liquidus line and AEPGCH is the solidus line. For an iron-C alloy (cast iron) containing 3% C.e.PM5 274 .088% C is commercially pure iron. C-8∴N-ENGCHE∴ECH11-1. whereas 0.6 Hypoeutectoid Hypereutectoid Wrought iron Steels Cast iron x Weight %C Fig.008% 0 N 0.0 3. The phase diagram indicates that upto 0. then at 1130°C.3% C by weight.0 2.025% A1 Eutectoid (pearlite) 600 Ferrite Cementite Pearlite + 500 + Pearlite Pearlite Ferrite + +Transformed Cementite Ledeburite 0. when equilibrium is attained. a mixture of austenite and cementite. freezing point increases upto 6. which are formed when the cooling rate is slow i. The transformation of one solid phase into another takes place at the critical temperatures indicated on the diagram. freezing begins at 1270°C.3 5 6 6.67% C content and it is called cementite.274 ENGINEERING CHEMISTRY +L Liquid 1600 A x D 1539 B E y 1500 Aus P tenit e+ 1400 Liqu + id Austenite Liquid 1300 + Fe3C 1200 G (1. 11. The Fe-C phase diagram shows the phases.5 0. Hence further removal of heat leads to total solidification of the liquid to ledeburite. Area DCH represents cementite and liquid.. On further cooling. 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. 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. Pure iron changes from δ to α form at a temperature of 910°C. AEB area represents δ-iron and liquid. all the ledeburite is transformed into pearlite and cementite mixture. Area BCGP represents austenite and liquid and finally PGKI represents δ-iron (i.088% to 2% C content is steel and C content above 2% represents cast iron.0 4 4. austenite) only.

PHASE RULE 275

Highlights:
Condensed phase rule. For two-component alloy systems it is considered that
there is practically no gas phase and the effect of pressure is negligible. So the
system is considered to be under atmospheric pressure which reduces the degrees
of freedom by one and hence,

F=C–P+1

Triple point. It is the point of a system at which the gaseous, liquid and solid
phases of a substance can co-exist in equilibrium. At triple point the system is non-
variant.
Eutectic point. 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.
Congruent melting point. A compound possesses congruent melting point if it
melts to give a liquid having the composition same as the solid.

SOLVED PROBLEMS
Problem 1. An alloy of Cd and Bi contains 25% Cd. Find the mass of eutectic in 1 kg of
the alloy, if the eutectic system contains 40% Cd.
Sol. In the eutectic system, 40 % is Cd and hence 60 % is Bi.
In 1 kg alloy content of Cd is 25%, i.e., 250 gm.
250 × 60
∴ Corresponding to 250 gm Cd, the content of Bi in eutectic is gm = 375 gms.
40
∴ The mass of eutectic in 1 kg alloy is (250 + 375) gm = 625 gm. Ans.
Problem 2. An alloy AB contains 40% A in 1 kg. AB on cooling forms eutectic containing
60% A and 40% B and the rest of B. What is the amount of B formed during eutectic formation?
Sol. In 1 kg of AB, A = 40 % = 400 gm and B = 60% = 600 gm.
The eutectic mixture contains 60 % A and 40 % B.
400 × 40
∴ Corresponding to 400 gm A, the content of B = = 266.7 gm
60
∴ Amount of B separated out = (600 – 266.7) gm = 333.3 gm. Ans.

SHORT QUESTIONS AND ANSWERS

Q. 1. State Phase rule.
Ans. See page 267.
Q. 2. What is condensed phase rule?
Ans. See page 272.
Q. 3. Define the following terms:
(a) Phase (b) Component (c) Degrees of freedom.

C-8∴N-ENGCHE∴ECH11-1.PM5 275

276 ENGINEERING CHEMISTRY

Ans. (a) See page 266.
(b) See page 266.
(c) See page 267.
Q. 4. What is triple point?
Ans. See page 269.
Q. 5. What is an invariant system? Give an example.
Ans. A system in which the degree of freedom is zero is called an invariant system. This
signifies that no condition is required to define the system at that point.
Example: Triple point of water is where ice, water and water vapour are in equilibrium.
Q. 6. What is the significance of triple point?
Ans. A triple point for a system is invariant. It is constant for a substance at a set of
temperature and pressure conditions. If temperature or volume is altered, one phase of the
substance disappears and the system becomes univariant from invariant.
Q. 7. State two important merits of phase rule.
Ans. (i) Phase rule is applicable to both physical and chemical equilibria.
(ii) Phase rule helps to predict the behaviour of a system under different sets of conditions.
Q. 8. State limitations of phase rule.
Ans. (i) Phase rule can be applied only for a system which is in equilibrium.
(ii) Phase rule conditions that all phases of the system must be present simultaneously
under similar set of conditions.
Q. 9. What do you mean by eutectic? What is the eutectic composition of Pb-Ag
System? Give one application of eutectics.
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 → 97.4 % Pb, 26% Ag. By suitable choice, very low
melting alloys can be selected for preparing safety devices like fire sprinklers, plugs in
automobiles etc.
Q. 10. State (i) number of phases and (ii) number of components for
Fe(s) + H2O(g) FeO(s) + H2(g).
Ans. (i) There are two solid phases—Fe and FeO— and one gaseous phase of a mixture
of H2O(g) and H2(g). So there are three phases in equilibrium.
(ii) The minimum number of components required to express the composition of each
phase is three.
Q. 11. How many degrees of freedom are there for the following systems?
(i) Water(l) Water vapour(g)
(ii) Gaseous mixture of H2 and O2
Ans. (i) For Water(l) Water vapour(g) system either temperature or pressure is
to be specified to define the system completely. Hence degree of freedom is one.
(ii) For the gaseous mixture of H2 and O2 both the pressure and the temperature are to
be specified to define the system completely, so the system has two degrees of freedom.
Q. 12. For a two-component alloy system of Pb and Ag, state the degrees of
freedom (i) as per phase rule and (ii) as per condensed phase rule.

C-8∴N-ENGCHE∴ECH11-1.PM5 276

PHASE RULE 277

Ans. (i) For a two-component alloy system of Pb and Ag when P = 1, degree of freedom
according to phase has the highest value of F = C – P + 2 = 2 – 1 + 2 = 3.
(ii) As per condensed phase rule:
For solid-liquid equilibrium of alloy, practically no gas is present and hence at atmospheric
condition the pressure remaining constant, degrees of freedom reduces by one and F becomes
F = C – P + 1 = 2 – 1 + 1 = 2.

EXERCISES
1.State phase rule.
2.Define the following terms:
phase, component, degrees of freedom.
3. What is condensed phase rule?
4. What is triple point?
5. Write a brief note on: eutectic point, metastable state.
6. Write down the limitations of phase rule.
7. What is “phase diagram”? Explain (a) triple point and (b) eutectic point with reference to phase
diagram.
8. Draw and explain the phase diagram of ice-water-water vapor system and show the variation of
melting-point of ice with pressures.
9. What are the merits and the limitation of phase rule?
10. Discuss the application of phase rule to sulfur system with special reference to triple points and
metastable equilibrium.
11. What are meant by invariant and bivariant degrees of freedom?
12. Draw and explain the phase diagram of a binary alloy system with simple eutectic formation.
Objective Type Questions MCQ
1.Gibbs phase rule is:
(a) F + P = C + 2 (b) F – C = P + 2 (c) P + C = F + 2.
2. Condensed phase rule equation is:
(a) F = C – P + 2 (b) F = C – P + 1 (c) F = C + P – 2.
3. The maximum number of degrees of freedom for a two-component alloy system is
(a) 3 (b) 1 (c) 2.
4. The composition of the eutectic mixture of Pb-Ag system is
(a) 2.6% Pb, 97.4% Ag (b) 2.6% Ag, 97.4 % Pb (c) 26% Pb, 74% Ag.
5. In the thermal decomposition of CaCO3(s) CaO(s) + CO2(g) the system is a
(a) one component (b) two component (c) three component.
6. Heterogeneous mixture of CaCO3(s) CaO(s) + CO2(g) consists of
(a) one phase (b) two phases (c) three phases
7. In the water system at triple point, the system is
(a) univariant (b) trivariant (c) invariant.
8. Condensed phase rule has two variables, namely
(a) temperature and concentration.
(b) temperature and pressure
(c) pressure and concentration
9. Eutectic mixture has:
(a) highest melting point. (b) variable composition (c) lowest melting point.
10. Number of components of the system Fe(s) + H2O(g) FeO(s) + H2(g)
(a) two (b) three (c) four.

C-8∴N-ENGCHE∴ECH11-1.PM5 277

12
Colloids

INTRODUCTION
Thomas Graham (1861) while doing his classical researches on liquid diffusion observed
two classes of substances.
Solution of some substances could readily pass through animal and vegetable membranes.
To this class belonged almost all inorganic acids, bases and salts and many organic compounds
like urea, sugar etc. Graham called them crystalloid as most of them were crystalline.
The other class of substances are diffused very slowly in solution and the solution could
not pass through the membrane, they were called colloids (from the Greek word Kolla meaning
glue, which is a member of this class). Other members are starch, gelatin, albumin, proteins
and other amorphous substances.
Graham’s view has undergone changes since it has been seen that every substance can
exhibit colloidal properties under suitable conditions. 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. In a colloidal solution there exists a discontinuous phase called the dispersed phase
and the continuous dispersion medium, and also a stabilizing agent which does not allow the
dispersed phase to coalesce and settle.
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 12.1) of colloids are formed.
Table 12.1 Types of colloidal systems

Dispersion Dispersed Colloidal Examples
medium phase system
Gas Liquid Liquid aerosol Mist, Fog, Cloud, Insecticide spray,
Solid Solid aerosol Smoke, Fume
Liquid Gas Foam Foam, Froth, Whipped cream,
Lemonade
Liquid Emulsion Milk, Cream, Mayonnaise,
Solid Sol Glue, Paints, Starch paste, Milk
of Magnesia, Gold sol, As2O3, S,
FeO3 or AgCl sol in water
Solid Gas Solid foam Pumice stone, bread dough, Lava,
Styrene foam, Rubber.
Liquid G