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

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

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

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

Schrödinger wave equation is time independent.. p = mf is a starting point of classical mechanics. we can write. i. ψ = a + ib and its conjugate ψ* = a – ib and their product. 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) dx 2 h2 The equation (4) is known as the time-independent Schrödinger equation in one dimension. |ψ2|dx represents the probability of finding an electron within a range of x and x + dx.. This mathematical expression displays how the probability of finding an electron varies in space.. For three-dimensional motion of an electron.. But in three dimension system |ψ2|dV represents the probability of an electron within the volume range of V to (V + dV).. The corresponding wave function ψ which is generally complex is called characteristic or eigen function.. this equation becomes. As.dz.dy. This is known as the condition of normalisation and the corresponding wave function ψ is said to be normalised.PM5 4 . the Schrödinger wave equation is also governed by boundary conditions.(5) h2 This Schrödinger equation is a basic equation of wave mechanics. Generally its solutions are only attained for certain energy values called characteristic or eigen values.e. Schrödinger equation can be employed for determining the total energy of an electron. l According to the Heisenberg’s uncertainty principle. It is seen from equations (3) and (4) that 8 π 2m k2 = × (E − V) . which is real.ψ* = (a – ib) (a + ib) = a2 + b2. Like other differential equation. For a one dimension system. The total probability of finding an electron in space extending to infinity is expressed as follows: z +∞ ψ2d V = 1 −∞ where dV = dx. Because of the spherical symmetry of an atom the wave functions are most satisfactorily expressed in terms of C-8\N-ENGCHE\ECH1-1. So. ψ. 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.(6) h2 So. Significance of ψ and ψ2 l ψ denotes the amplitude of a three dimensional stationary electron wave.4 ENGINEERING CHEMISTRY Now. 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 .. de-Broglie wavelength is given by h h λ= = . mv 2m(E − V) Substituting this value in equation (1) and replacing y by ψ as is customary.

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

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

y.PM5 6 . we have.4 The potential energy V of the electron at the bottom of the box is constant. the solution of the above equation produces the electron distribution in space as well as the allowed energy state of the electron. ψ function must be zero for all values x > l. The solution of the above second order differential equation furnishes the values of E. Alternatively. the quantised or allowed or permitted energies of electrons and ψ is the wave function. A general solution of Schrödinger equation is: ψ(x) = a sin kx + b cos kx For boundary conditions.4. inside the box V = 0. So. h = Planck’s constant. may be taken as zero. 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. 1. Let the potential energy be infinite for x < 0 and x > l. it is found that the equation can be solved when E assumes certain values which are related by integers. z = co-ordinates of the electron. Application of Schrödinger Equation Particle in a box illustrating energy quantization (Like electrons in metals) Let us consider a particle of mass m which is free to move in a one dimensional box of length l as shown in Fig. the concept of quantised energy levels and quantum numbers are the consequences of the wave theory. When this equation is applied to hydrogen atom. 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.   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. Hence. Hence. 1. ψ function has to be zero at x = 0 and for all negative values of x.6 ENGINEERING CHEMISTRY V = potential energy of the electron. Alternatively. x. ψ = wave function or the eigen function of the electron representing the amplitude of the wave associated with the electron. Similarly. E = total energy of the electron.

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

e. how r.. In the presence of external magnetic field these vary in their energy content depending on the magnetic quantum number. shapes or boundary surfaces of orbitals gives the probability of finding an electron in a particular direction. 1. An s-electron has no preferred direction in space i. A p-level has an accommodation for six electrons distributed over three p-orbitals to each value of the principal quantum number.. 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. the distance from the nucleus does vary.e..6 below. The different shapes are shown in Fig.e. 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.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. y z + x Fig. there is an equal chance of finding it in any direction around the nucleus. In the absence of magnetic field these orbitals are equivalent in energy content and are said to be triply degenerate. in the case of py and pz orbitals the electron will be found along y and z axes. This is graphically shown in Fig. py and pz orbitals. 1.6 In this diagram..e.. 1.8 ENGINEERING CHEMISTRY These are namely (i) an angular probability distribution i. y y y z z z + + – + x x x – – px py pz (a) (b) (c) Fig. 1.e. C-8\N-ENGCHE\ECH1-1. (i) Angular probability distributions of orbitals i. how the angular position θ varies from nucleus with respect to a fixed axis and (ii) a radial probability distribution i.PM5 8 . y-z plane in this case is nodal plane with zero electron density.7 below. Similarly.

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

C-8\N-ENGCHE\ECH1-1. l The distributions vary according to the principal quantum number.PM5 10 . 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. 2s. 3s. 2p. 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. 1. 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. All these facts are based on the proper interpretation of Schrödinger wave equation.9 Radial probability distribution of 1s. This means the electron can never be at nucleus.10 ENGINEERING CHEMISTRY Highlights: l The probability of finding an electron at the origin is zero which is the nucleus. 3p and 3d orbitals.528Å).

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

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

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

.H .8 5 Rb Sr In Sn Sb Te I 0.O .6 1.8 2.2 1.7 1. The power of attracting electrons of one of the atoms in a covalent bond is known as its electronegativity.9 2.9 2.8 1. .0 2. H atom has less tendency of this sort. × H ×  (NH4) × × H H Ammonium ion + . F – × × .+.1 below.0 3.5 2.0 1. In comparison.B .5 4..1 2 Li Be B C N O F 1. Some examples of coordinate bond formation: + .0 2.B F . H + + × H ×  (H3O) × × H H Hydronium ion – .0 1. H .2 7 Fr Ra 0.0 3 Na Mg Al Si P S Cl 0. .8 1.1: Electronegativity values (L.9 C-8\N-ENGCHE\ECH2-1. 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. .0 2. .F . . F ..N . Comparative values of electronegativities of different elements taking the electronegativity value of H as 2.4 2.0 2.7 0. The phenomena can be represented as follows: A.5 3.7 0.0 1.1 is given in Table 2.. H .14 ENGINEERING CHEMISTRY accepts the pair of electrons is known as ‘acceptor’ atom.8 1.5 6 Cs Ba Ti Pb Bi Po At 0. × ×  (BF4) × × F F Electronegativity The attraction and repulsion powers of atoms of different elements are not same..1 2. Table 2.N .1 2. The donor atom should have a lone pair of electrons.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 ‘→’. As for example. – .0 4 K Ca Ga Ge As Se Br 0.O .PM5 14 . .8 2..F .9 1.5 1.8 1. .9 1.. F .. Pauling Scale) Group → I (1) II (2) III (13) IV (14) V (15) VI (16) VII (17) Period↓ 1 H 2. H + + × × H .. .H H . .5 3.

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

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

R = Resultant moment of the molecule.2 kcal NaCl(s) Na(s) + 2 2 Crystal 1 D = +28. and in those molecules centre of positive charge action and centre of negative charge action are at the same place. A ( g) + e − ( g) → A − ( g) + Energy released Neutral gaseous atom Anion (Electron affinity of atom A. d ⇒ 0. are non-polar molecules. Na(g) Cl(g) I = +118. 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. E A ) Electron affinity is represented by the ‘–ve’ sign as energy is liberated in this case. When energy is supplied it is represented by ‘+ve’ sign and called second electron affinity (E2). etc. • HCl.. • Cl2. CH4. H2.0 kcal 2 Determination of electron affinity of Na atom. CO2.. If R is zero. C6H6. its dipole moment is 1.9 kcal S = +26. ∴ µ ⇒ 0.8 D. NH3. i.e.0 kcal U0 . i.e.VALENCY AND CHEMICAL BONDING 17 Highlights: • The dipole moment of H2O molecule is 1. CH3OH are polar molecules i. H2O. the molecule becomes non-polar and if R has got a positive value the molecule becomes polar.8 × 10–18 esu-cm.. µ1 and µ2 = dipole moments of the different bonds of the molecule.e. 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. • 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. their centre of action of positive charges and centre of action of negative charges are not same and the molecule is not symmetrical. The molecules are symmetrical.

4 ∴ E = – 90.4 kcal 1 Q=S+ D + I + E + U0 2 – 98. Cl(g) → Cl–(g) C-8\N-ENGCHE\ECH2-1. Lattice energy of E = ? (+e) (– e) NaCl crystal. + – Na (a) Cl (g) U0 = –180.9 + 118 + E – 180.PM5 17 .2 = + 26 + 28.7 kcal/g atom of Cl Negative sign indicates that energy is released in the formation.

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

So some other concept becomes essential to explain the formation of NH3 molecule. In this case also the bond angle appears to be 90°. py pz py pz px + px F atom F atom F2 molecule Fig.5 Formation of H2O molecule. 2. C-8\N-ENGCHE\ECH2-1. (iv) Fluorine molecule : p-p overlapping to form a σ-bond. 2. This fact also leads to the idea of hybridization of orbitals.4 (b) Formation of NH3 molecule. But actually bond angle in NH3 is 106° 45′. 2.6 px-px overlapping along the axis to form F2 molecule. (iii) Water molecule x x 1s + + y y + + + + + 1s + z z – – – – H2O molecule Fig. Here the overlapping takes place between the three (2p) orbitals of nitrogen atom with 1s orbital of each hydrogen atom. That concept is the concept of hybridization. But the actual bond angle in water molecule is 104° 27′.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. then bond angle in NH3 should be 90°. If it were the case.

+ + + . 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. Hybridization: Carbon has electronic configuration: 1s2 2s2 2p2. the axes of hybrid orbitals are directed towards the vertices of a regular tetrahedron (Fig. This can be explained only by the Concept of hybridization. 2. C atoms form four identical bonds with H-atom with equal energy. 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. 2.8). (a) Overlapping of two px orbitals along the axes leads to the formation of a sigma bond. but in CH4.7 σ and π bonds in N2 molecule. (b) Lateral overlapping of two py and pz orbitals leads to the formation of two π bonds.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.

C-8\N-ENGCHE\ECH2-1. 2. + + + s px sp3 sp3 sp3 sp3 hybrid orbitals py pz 3 sp 109° 28 3 3 sp sp C 3 sp Fig.PM5 20 .8 sp3 hybridised C atom. 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.

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

Four unpaired C in the excited state .

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

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.PM5 21 . Three sp2 hybrid orbitals of each C-atom form three sigma bonds in ethylene molecule. 2.10 Ethylene molecule. 2. 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. Highlights: • Ethylene molecule contains five sigma bonds. 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. H H C C -bond H H -bond -bond Fig. • Four sigma bonds are formed due to overlapping of sp2-s orbitals and one out of sp2-sp2 overlapping. 2. Residual 2p orbitals of each sp2 hybridised C-atom overlap laterally to form a π-bond (Fig.10).10).

11).11 Formation of triangular planar BF3 molecule. (Another example of sp2 hybridization). 1s2 2s2 2p1. Boron atom has electronic configuration. sp-hybridization Electronic configuration of: 1s 2s 2p C in the ground state . 2. 2s and 2p hybridise electrons to produce three sp2 hybrid orbitals directed towards the vertices of an equilateral triangle. F sp2–p (–bond) B sp2–p (-bond) F sp2–p (-bond) F Fig. 2.22 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.

px py pz Four unpaired C in the excited state .

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

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

VALENCY AND CHEMICAL BONDING 23 In the excited state one of the 2s2 electrons jumps to 2p-orbital before forming any bond. Then these 2s and 2px orbitals mix to give two sp-hybridised orbitals. 2. the Be atom has the configuration ⇒ 1s2 2s1. Now. Electronic configuration of: 2s 2p Be in ground state . 2px1 2py0 2pz0. These two hybrid orbitals next overlap with p orbitals of two F-atoms along the axes making BeF2 a linear molecule (Fig.13).

Two unpaired Be in excited state .

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

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

3). the hybrid orbitals are not equivalent. 2. px s py pz 2 dz 3 dsp Fig.14). the shape of the molecule becomes square planar and the bond angle is 90° (see Table 2. But in this case.15). 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. The hybrid orbitals consist of one group of two equivalent oppositely directed orbitals and the second group of three equivalent orbitals. So. The shape of the molecule will be trigonal bipyramidal (Fig.14 sp3d hybridization. 2.24 ENGINEERING CHEMISTRY corners of a square. Example of sp3d hybridization: Electronic configuration of: 3s 3p 3d P-atom in ground state . 2.

P-atom in the excited state .

Five unpaired electrons sp3 d hybridization 3d .

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

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 .

F F F S F F F Fig. C2H4 4 sp3 Tetrahedral 109° 28′ CH4. C2H2 3 sp2 Trigonal planar 120° BF3.PM5 25 . bp) in the valence shell. the molecule then acquires a regular geometry.3 No. 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. 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. Table 2. (NH3)2 Cl22– 90° 5 dsp3 Trigonal bipyramidal 120° and 90° PCl5. 2.16 Octahedral structure of SF6 molecule. of electron pairs Hybrid Shape of Bond angles Example in outer shell orbital the molecule of the atom 2 sp Linear 180° BeF2. 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. SiF4 90° 4 dsp2 Square planar 90° 90° 90° [Ni (CN)4]2–.

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

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

Linear combination of 1s-atomic orbitals (σ-symmetry) of two H-atoms to give bonding and antibonding molecular orbitals (σ-symmetry).23 Linear combination of two 2px orbitals to form σ2p (bonding) and σ*2p (antibonding) molecular orbitals (σ-symmetry). 2. .21) + . Energy level diagram (Fig. A) +. 2.21 Bonding and antibonding orbitals. Molecular orbital Antibonding 1s Atomic Atomic Energy orbital 1s 1s orbital 1s Bonding Fig. 2. 2. (ii) Molecular orbitals from p atomic orbitals: (a) End-end overlap + – – + 2p (Antibonding) E – + + + – – + – 2p (Bonding) Fig. + .22 Representation of M.PM5 28 . + * is (Antibonding. + +.28 ENGINEERING CHEMISTRY φB = ψA(1s) + ψB(1s) φA = ψA(1s) – ψB(1s) (i) The two conditions can be represented pictorially (Fig. diagram.O.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. 2. C-8\N-ENGCHE\ECH2-2. E HA HB Atomic orbitals .  is (Bonding B) Fig.

of electrons in bonding molecular orbitals.PM5 29 . − N.B. 2. *2p *y2p. of electrons in antibonding molecular orbitals.24): + – 2* 2p – + + + A(Antibonding) E + – – + 2 2p Bonding – Fig.B.) of a molecule is calculated as follows: N. ⇒ no. B. *z2p 2p z z 2p z y y x *y2p.): Bond-order (B. Linear combination of two 2pz orbitals to form πz2p (bonding) and πz2p* (antibonding) molecular orbitals (π-symmetry).O.VALENCY AND CHEMICAL BONDING 29 (b) Side-by-side overlap (Fig. N. ⇒ 2 N.O. (Energy level diagram of molecular orbitals for a homonuclear diatomic molecule) So. 2.24 π-Bonding.).O. C-8\N-ENGCHE\ECH2-2. 2. y2p 2p *2s Energy 2s 2s 2s Fig.O.A. 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. ⇒ no. A.25 Order of energy of molecular orbitals (M.

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

O. *2p y*2p z*2p A. = 8 – 2 = 3 E 2 N2 molecule has triple bond (N N) *2s 2s 2s 2s Fig.28 M.VALENCY AND CHEMICAL BONDING 31 So.O.O. diagram for N2. • Energy level diagrams of other molecules: *2px (sp)2 *2py *2pz *2py *2pz . 2px 2py 2pz 2pz 2py 2px y2p z2p 2p B. the electronic configuration of N2 molecule will be KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) [KK denotes (σ1s2) (σ*1s2)] M. 2.O. A.O.

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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).30 Molecular orbital diagram of of B2 (without s-p interaction). C-8\N-ENGCHE\ECH2-2.29 Molecular orbital diagram Fig. 2.PM5 31 . 2s (sp)1 B B2 B B B2 B Fig. 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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O2 (with s-p interaction). 2. 2. • Electronic configuration of O2 molecule: KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) (π*y2p1) (πz*2p1) *2px *sp)2 .31 Molecular orbital diagram Fig.32 Molecular orbital diagram of of O2 (without s-p interaction). 2s (sp)1 O O2 O O O2 O Fig.

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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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PM5 32 . 2. 2s (sp)1 N NO O N NO O Fig. NO (with s-p interaction). 2.33 Molecular orbital diagram Fig. C-8\N-ENGCHE\ECH2-2.34 Molecular orbital diagram of of NO (without s-p interaction).

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

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. • Benzene is more stable than expected.. 2. benzene follow an entirely different path. This delocalisation energy is frequently used instead of resonance energy. which is substitution in which the benzene ring system is retained. (1. When overlapping is not restricted between two nuclei and it occurs between more than two nuclei. And there still remains six electrons in the six p-orbitals with two equal lobes.34 ENGINEERING CHEMISTRY Highlights: • The idea of resonance explains six identical bonds in benzene. If we fit the six sp2-hybridized carbon atoms. The 36 Kcal of resonance energy is responsible for a new set of properties. it is an intermediate in length. the phenomenon is known as delocalisation.6 Kcal mole–1 to be converted into cyclohexadiene. we get a regular hexagon with a bond angle 120°. The delocalisation in benzene molecule gives π-clouds above and below of the plane of the ring as shown in the Fig. • We see that addition will lead to a less stable product by destroying the resonance stabilized benzene ring system.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. Because the resonating Kekule’s structures have a resonance hybrid structure. which has 36 Kcal mole–1 extra stability. as its six carbon atoms are sp2 hybridised. with overlapping. known as aromatic properties.36). Orbital Picture of Benzene Benzene is a flat molecule. 2. a hybrid bond or benzene bond. hydrogenation of benzene requires 5.39Å) between a single and a double bond. C-8\N-ENGCHE\ECH2-2. • As a result of this resonance stabilisation. benzene possesses chemical properties that are not intermediate between compounds containing single or double bond.PM5 34 . (2.36 Delocalised π clouds in benzene.e. i. So. which is a new type of bond. one lying above the plane and the other lying below the plane of paper. Fig. As for example. -clouds Benzene ring -clouds Fig. 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.

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

Give examples of single.C . ××× × F ×× × F× Ca++ ×× Ca : + ××  + × ×– ×× F × . 6.37 (a) Forces of attraction during H2 molecule formation. 8) (2. Attraction Proton in + + nucleus Shared electrons Fig. .C. (b) . ×.× . Ans.: C×. 8. 7) Calcium ion two fluoride (2.PM5 36 .  H . H . How are the atoms held together in a covalent bond? Ans. : : : : : : : : (a) O: + :O  O ::O  O=O Double bond H H . 8.. (a) :Cl . 2) (2. Q. What is a covalent bond? Ans. 8) – Ans. 8. double and triple covalent bonds by dot and cross diagrams.Cl : : : : : : : : :  : Cl : Cl :  Cl—Cl Single bond H . + 4H ×  H ×.:N  N N Triple bond . 8. + 2H ×  H×. 8. C ::C× H  × + 4H H—C = C—H . ×× . 8. + . 8) ions (2.C. 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. (a) N.36 ENGINEERING CHEMISTRY Q. (iii) Triple covalent bond. (i) Single covalent bond. 5. (b) 2.×Cl ×× ×× – + × Cl ×× × ×  Na+ + ×× × × Sodium atom Chloride atom Sodium ion Chloride ion (2. Give dot and cross diagrams for NaCl and CaF2 molecule formation. 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.N : : : : : :  N:. 2. C-8\N-ENGCHE\ECH2-2. 7. 8) Q. 1) (2. H  H—C—H × H H (ii) Double covalent bond. . 8. × × (b) 2. + . Na.H  H—C C—H Q. 7) (2. H.. × × × ×F× ×× ×× Calcium atom (2. .C.C:. H ×.

190 nm. e. Fig. What is the special feature of a covalent bond? Ans.037 nm H2  0.e. This type of bond is formed by unequal sharing of electron pair... (a) Covalent bond holds together the atoms of nonmetals in a molecule and giant structures. between dissimilar atoms during bond formation viz. 2. (b) Molecules have a definite shape because covalent bonds have a definite length and direction. 12. 11. 2. Cl—Cl.37 (b) Forces of attraction during H2 molecule formation. 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.37 (c) Covalent and van der Waals radii for bromine. (ii) van der Waals bond. (iii) Hydrogen bond.g. The covalent radius of an element is half the bond length. 13. Q.114 nm van der Waals radius  0. Covalent radius = 0. A polar bond is formed when sharing takes place between the atoms of different electronegativities i. Covalent radius Covalent radius Bond length  0. (i) Metallic bond. Ans.VALENCY AND CHEMICAL BONDING 37 Q.e. The coordinate bond is indicated by an arrow to express this unequal sharing. Covalent radius of an atom is half of the distance between the nuclei of two like atoms bonded together by a single covalent bond. van der Waals radius is the effective radius of an atom when held in contact with another atom by weak intermolecular forces. 10. between similar atoms during bond formation.. H—H. H+δ → Cl–δ Q.PM5 37 .104 nm Cl2  0. Q. What is the special feature of a coordinate bond? Ans. Mention special types of bonds. Br—Br. 9. What are polar and non-polar covalent bonds? Ans. Q. What is covalent radius? Ans. O = O. When two atoms of the element (same or different) are joined by a single covalent bond. etc. C-8\N-ENGCHE\ECH2-2.. one of the participating atoms in the bond formation donates both the electrons for bond formation.141 nm sum of covalent radii HCl Fig. van der Waals radii determine the effective size of a molecule. A nonpolar bond is formed when sharing takes place between the atoms of same electronegativity i.

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

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

O. Calculate the bond orders of: (i) H2O. H− F − δ . (ii) sp2. Explain. (iii) He2+. H− F −δ . H− F −δ Due to hydrogen bonding. one is σ and the other is π-bond. Ans. (i) B. +δ +δ +δ +δ Ans. (iv) He2 and interpret the result. Mention the types of hybridisation. According to Hund’s rule two unpaired electrons fill the degenerate (orbitals of same energy) πy*2p and πz*2p orbitals (see Figs. N − Na 2−0 Ans. What do you mean by hybrid orbitals? Ans. 1− 0 1 (ii) B. = = 2 2 H2+ has a transient existence. 2−2 (iv) B..PM5 40 . Here the number of bonding electrons exceeds the number of electrons in antibonding orbital.. O2 molecule contains double bond (O = O). (vi) d2sp3. (v) sp3d.. = =0 2 Here the number of electrons in σ-orbital = the number of electrons in σ*-orbital. ⇒ ⇒ =2 2 2 So. the number of electrons in s-orbital is greater than the number of electrons in s*-orbital. Q. That is why. Hydrogen bond in HF inhibits release of H+ partially in aqueous solution. So He is monoatomic. HCl is gas and HF is less acidic than HCl. 27.40 ENGINEERING CHEMISTRY Q. Q. 28. (iv) dsp2.O.O. 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. = b = =1 2 2 H-atoms are held together by one covalent bond. What is hybridisation of atomic orbitals? Ans. Explain why HF is liquid.O. (i) sp3.31 and 2. = = 2 2 He2+ also has transient existence. 31. Q. 29. 2−1 1 (iii) B. 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. 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. Q. O2 molecule is paramagnetic. 32. O2 molecule is paramagnetic.. Ans.. C-8\N-ENGCHE\ECH2-2. 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. so it is less acidic. (iii) sp. The molecule does not exist. (ii) H2+. 30.. 2. Here.32). Q. H− F −δ .

So O H O a crystal of ice is not a single molecule but an associated molecule. So. this tetrahedral structure is H destroyed. Write a note on co-ordinate bond. 7.38 H-bonding in 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. (b) Give a concise account of delocalisation of benzene. 5. 3. In H2O molecule. 31 above. Q. And the water molecules are hydrogen bonded in a chain. The density of water is greater than that of ice. H H Ans. 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. O Ans. 2. bond angle and shape of the following molecules: (i) BeF2. 8. What is hybridisation? Give different types of hybridisations with examples. Q. H——O– – –H——O– – –H——O– – –H——O H H H H The reason is same as in Q no. ethyl alcohol is less volatile than dimethyl ether though both have the same mol. H H Explain. Due to loss of this void space. Explain H2O is a liquid and H2S is a gas. when ice melts its volume Fig. 33. Ans. 4. (a) Explain the structure of benzene. reduces and density increases. there is some void H O H space in ice. Explain the bond order of N2 molecule. Discuss hydrogen bonding and explain why density of ice is less than that of water. Write a short note on ionic bonding.VALENCY AND CHEMICAL BONDING 41 Q. 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. Explain. And each oxygen atom contains two lone pairs. every oxygen atom is connected Covalent bond to two hydrogen atoms as covalent bonds. EXERCISES 1. 35. Due to tetrahedral structure. These electrons can form H hydrogen bonds. But there is no H-bonding in dimethyl ether molecule as H here is not attached to O-atom. (iii) CH2 = CH2. (ii) BF3. there is no molecular association due to H-bonding in dimethyl ether. When ice melts. By X-ray crystallography. formula. C-8\N-ENGCHE\ECH2-2. (vi) H2O. 34. (iv) CH ≡ CH. (v) NH3. 6. sp2 and sp3 hybridisations with examples.PM5 41 . C2H6O. Explain sp. it has been Hydrogen O bond established that in a crystal of ice. 2. Give the state of hybridisation. so it is more volatile than ethyl alcohol.

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

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.

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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.

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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.

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

provided the ratio Pb206 to Pb207 is determined with the help of a mass spectrometer. After the death of the plant.693 a− x C 14 Here.303 t1/2 F Pb 206 I. Alternatively. the decay constant of U238 is known from the relation 0. a = ratio in the fresh plant C 12 C 14 (a – x) = ratio in dead plant.NUCLEAR CHEMISTRY 55 Hence.303 t GH log 1 + 238 U JK Since. 2.730 yrs) age of the wood (t) can be calculated.693 λ= t1/ 2 Thus. 2. C 12 C-8\N-ENGCHE\ECH3-1.PM5 55 . 2. U238. Pb206 represent their respective masses. values of Pb206 and U238 can be determined experimentally.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.303 U 238 + Pb 206 So. the age of a rock can be determined as follows. λ= log t U 238 F Pb 206 I. In radio-carbon dating ratio C14 to C12 is assumed constant in the plant.303 t1/ 2 a t= log . t= 0. by measuring C14 to C12 ratio and t1/2 of C14 (5. the age of the rock can be calculated.303 a λ= log t a− x a = amount of U238 originally present in the rock at the time it was formed. (a – x) = amount of U238 still left after the lapse of time (t). age of the rock (t) can be calculated. no more CO2 is assimilated so ratio C14 to C12 in the plant changes. The radioactive decay follows the first order rate law. 0. 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. U238 present in the rock at time t is: a = U238 + Pb206 and (a – x) = U238 where. λ = decay constant of U238. as the plant assimilates CO2 with C14O2 during photosynthesis. 2. λ= 2.

calculate how much of Madam Curie’s 200 mg of radium would be left in the year 8378 A.693 0. in all directions.8672 × 10–15 sec–1. Prove that N ≈ 0.56 ENGINEERING CHEMISTRY So.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. age of the wood (t) can be calculated.D. λ 1 − λ.D. We have.m. 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 = 12.478 × 106 years.PM5 56 .37 N0.37 N0. A radioactive source contains one microgram (µg) of Pu239. (t1/2 of radium is 1620 years).00387 a. This source is estimated to emit 2300 α-particles/sec. by measuring the ratio C14 to C12 in the fresh and dead plants. 6480 No.u. Total time = (8378 – 1898) = 6480 yrs.00387 × 1. Sol.646 × 10–24 g Mass of 2300 α-particles = 2300 × 6.8672 × 10 −15 = 1.66 × 10–24 g = 6. 2.368 N0 ≈ 0..693 Half-life (t1/2) of Pu239 = = sec. Estimate half-life of Pu239 from this data.8672 × 10–21 g dM As − = λM dt − d M/ dt − 14.5 mg. Mass of one α-particle = 4. N = N0e–λt 1 when t = . Sol. Sol. Example 3. Assuming that it were to remain undisturbed since 1898 A.867 × 10 −21 / 1 So λ= = = 14. then the above equation will take the form.464 × 10–24 g = 14. C-8\N-ENGCHE\ECH3-1. Example 1. N0 λ N = N0 e = N0e–1 = e N0 = 0. = 4. λ 14. Example 2. M 1 × 10 −6 0.

M= 1.173 ∴ M = M0e0. The half-life period of radium is 1620 years.69 × 105 disintegrations/sec. N = N0e–λt N0 or. M0 = Initial mass of 92U234 M = Mass at the end of 62. time during which one centigram of radium is lost due to disintegration be = t. 0. The mass of radium would be left behind at the end of time t = 1 – 0.99 g.189 M M0 or. Sol.01 C-8\N-ENGCHE\ECH3-1.364 mg.0 mg of 92U234. (a) Let.173 or. M0 = M . 1.88 × 10–14 × 62000 × 365 × 24 × 3600 = 0.173 = 1. e0. A radioactive sample initially contains 4.48 × 105 yrs. (a) How much of it will remain unchanged after 62.88 × 10–14 s–1).48 × 10 5 λt may also be calculated.693 λ= = = 4. Example 5..173 t1/2 2.4343 99 ∴ t = 23.28 × 10–4 year–1.000 years ? (b) What will be its activity at the end of that time? (t1/2 = 2. (a) We know. M = M0e–λt 0.189 (b) Activity of 234 92U is: 3.4343 N 100 or. N0 1 (b) Here = = 100 N 0.NUCLEAR CHEMISTRY 57 Example 4. log10 = 4. log10 = λt × 0.693 0.000 yrs. = eλt N N0 or. We have.189 234 4 ∴ Mass of 92U left unchanged = = 3.88 × 10–14 × 234 = 7.28 × 10–4 × t × 0.PM5 57 .01 = 0. Now.023 × 10 23 A = λN = 8.693 × 62000 and λt = ×t= = 0.693 0. t1/2 1620 Let. λ = 8.68 years. In how many years will one gram of pure element (a) lose one centigram (b) be reduced to one centigram? Sol.364 × 10 −3 × 6. as follows: λt = 8.

3 × 10–13 g.58 ENGINEERING CHEMISTRY ∴ log10 100 = 4.02 × 10 23 = 214 dN Now.1 × 10–8 g.7 × 1010 disintegrations/sec. The number of atoms of RaB contained in mass (m) m × 6.31 × 10–4 × 214 ∴ m = 3.5 × 109 years) is: m × 6. Highlights: • For one curie. Sol. s −1 dt m × 6. Calculate the mass for RaB for 1 rd activity.023 × 10 23 106 = 4. Example 6. = 10 6 dis.2 × 106 g.98.7 × 1010 = 4.s–1. Calculate the mass of RaB in gram which gives 3. For 1 rd activity.5. Example 8.7 × 1010 = 4.5 × 109 years) Sol. U238 = (U238 + Pb206) e–λt C-8\N-ENGCHE\ECH3-1.28 × 10–4t × 0. One Ci is defined as that quantity of a radioactive material which gives 3.5 × 109 × 365 × 24 × 3600 and 92 U t1/2 = 4. • Smaller units like millirad (mrd) and microrad (µrd) are also used.760 years. One rutherford is de- fined as that quantity of a radioactive substance which gives 106 dis. − = λN dt m × 6. The ratio of mass of Pb206 to the mass of U238 in a certain rock specimen is found to be 0. Highlights: • A new absolute unit of radioactivity is rutherford (rd).9 × 10–18 × 238 ∴ m = 80. (t1/2 for U is 4. Example 7.693/4.023 × 10 23 ∴ 106 = 4. The unit for measuring radioactivity is curie (Ci).31 × 10–4 × 214 ∴ m = 8. We know that. the mass of 238 (λ = 0. the mass of 238 92U is m × 6.4343 ∴ t = 10.02 × 10 23 ∴ 3.PM5 58 . • For one rutherford. estimate its age.023 × 10 23 3.9 × 10–18 × 238 ∴ m = 3.7 × 1010 dis/s. Assuming that the rock originally contained no lead. dN Sol.

We have. 1 = 1+GH U 238 JK e –λt or.303 × 5760 × 0.5 × 10 9 = log 2 = 4.05H K 2. 0. Sol. 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.3 Mole of Pb206 = = 0.525 yrs. (t1/2 of C = 5577 yrs).693 ∴ t = 0.303 × 5760 1 t= log 0. 0. Half-life period of C14 is 5760 years. t= 0.693 C-8\N-ENGCHE\ECH3-1. What is the age of the old piece of wood? Sol. The amount of 6C14 isotope in a piece of fresh wood is found to be 1/6th of the total carbon.303 × 5577 × 0.9 Sol.303 × log10 1.5 or.5 e–λt ∴ eλt = 1.9 g of U238 and 10. (t1/2 = 4.5 × 10 9 ∴ t = 2.170 yrs.3 g of Pb206. 0.5) e–λt = 1.693 Example 11. 1 = (1 + 0.63 × 109 years.303 t1/2 1 t= log 0.693 1/ 4 2.693 GH log 1 + 238 U JK 2. Example 9.05 206 2. 2.23 × 0.5 × 109 years.303 × 4.1761 0.693 1/ 6 2.3 × 0. Calculate the age of the ore.303 t1/2 FPb 206 I We have. λt = 2.693 log 1 + 0.5 × 109 years) 11. 2.303 × 4. Mole of U238 = = 0. A sample of U238 is found to contain 11.NUCLEAR CHEMISTRY 59 F Pb 206 I or.05 IJ = 0.693 2.5 = 2.6021 = = 11.5 × 10 9 FG 0.303 × 5577 = log 6 0.05 238 10.7782 = = 20. We have.1761 4.PM5 59 . Calculate the age of wood.693 Example 10.

(a) What is Q-value for a nuclear reaction? (b) Calculate the Q-value for the following nuclear reaction: 14 + 2 He4 → 8O17 + 1H1.m. C-8\N-ENGCHE\ECH3-2.u.60 ENGINEERING CHEMISTRY Example 12. if Q-value is negative.01140 Total = 18. The half-life of Ac222 is 6. Sol.00387 8O 17. 3 Example 13.693 1/ x 2.u.693 10 × 0. = – 1. there is decrease in mass in the reaction.) 4 17 2He 4.13 or 10 = log x 0.4696 = 2. Calculate the fraction of the sample of this substance present at the end of 10 hrs. there is gain of mass in the reaction.13 hrs.u.303 × 6.00124 a.4696 2. = 931MeV] = 1.m.15 MeV So.0045 14 1 7N 14.303 t1/2 1 t= log 0. there is increase in mass and absorption of energy. If Q-value is positive. (b) Interacting particles Mass (a.00814 Total = 18. 2.PM5 60 .u.m. there is absorption of energy.u.693 or log x = = 0. (a) The overall energy liberated or absorbed in a nuclear reaction is called nuclear reaction energy.00124 × 931 MeV [Q 1 a.m. 7N Sol. On the other hand.) Product particles Mass (a.01264 – 18. the reaction is accompanied by liberation of energy. and such reaction are called endothermic or endoergic.01140 = 0.948 x≈3 1 ∴ the fraction of the Sample = . such a reaction is exothermic or exoergic.15 MeV The Q-value for the reaction is negative.303 × 6.01264 Increase in mass = 18.m. the reaction is 4 + 7N14 = 8O17 + 1H1 + Q 2He ∴ Q-value of the reaction is = – 0.00124 a. 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. ∴ Q-value = 0.00753 1H 1.13 ∴ x = Antilog 0. so the reaction is endoergic.

m. Sol. Calculate the energy released from the fusion of 3 Li6 and 1D2 by the reaction.01862 × 931 = + 17. Mass defect ∆m for Ca-atom = (20 × 1. So the reaction is exothermic of exoergic. Example 18.u.01474 2 He = 4.0086) – 39. Example 15.353 a.00774 ∴ 7 + 1H1 = 2He4 + 2He4 + Q 3Li ∴ Q = Decrease in mass = (8.954 + 2 × 1.u. (energy released/fission of U 235 MeV = 200 MeV).124 + 1.m.m. Sol.m.258 MeV. Example 17.00387 Total = 8. 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 235.2151 × 931 MeV = 200.0099) – (94.u. The mass of proton is 1. the reaction is accompanied by liberation of energy (decrease in mass).m.m.00814 2He 4. Q value is positive.u. and the mass of neutron is 1.u.2151 a.00387 1 4 1H 1. From the above equation. 3 Li Sol.u.00774) = 0.03387) = 0.353 × 931 ∴ Binding energy per nucleon = MeV.m.03402 × 931 = 31. Calculate the energy released in the following fission reaction: 235 + 0n1 → 36 Kr95 + 57 Ba139 + 2 0n1.216 MeV.u. = 0. Here. C-8\N-ENGCHE\ECH3-2. 0. 40 = 8.m. ∴ Energy released = 0.u.945 + 138.0086 a. Q = (2. Example 16.PM5 61 .67 MeV. = 0.02636 – 8.m.0099) = 0.u. Calculate the limiting energy per nucleon 20Ca40.01702) – (2 × 4.0078 + 20 × 1.01822 2He 4.u.0078 a.u. 2 4 1D = 2.00387 a. which has atomic mass of 39.975 a. 3 Li6 = 6. = 0.u.m. 6 + 1D2 = 2 He4 + 2 He4 + Q 3 Li where isotopic masses are.01474 + 6.) Product particles Mass (a.NUCLEAR CHEMISTRY 61 Example 14.3 MeV. Interacting particles Mass (a. Show the following reaction is exoergic 7 + 1H1 = 2 He4 + 2 He4.01862 a.m.01702 a. The reaction is 92U235 + 0n1 = 36Kr95 + 57Ba139 + 2 0n1 + Q or Q = (235. 92 U Sol.03402 a.m.) 7 4 3Li 7.975 a.02636 Total = 8.

calculate the amount of fuel required for one day’s operation.5 × 1023 atoms of U235 are present in 235 × 13.2 × 10 −11 (ii) 1 kg atom of U235 = 235 kg = 6.6 × 10–13 J) Example 19. 1. Hence. Energy consumed in the city in a day = 100 × 106 × 24 × 3600 = 864 × 1010 J Since efficiency of the reactor is 20%.023 × 1026 atoms of U235 are present in 235 kg ∴ 13. etc. of U235 atoms to be fissioned 432 × 10 11 = = 13. ∴ No. disintegration.2 × 1013 J. If this is to be supplied by a nuclear reactor of efficiency 20%. (i) Energy released per fission of U235 nuclide = 200 MeV = 200 × 1. SHORT QUESTIONS AND ANSWERS Q. 235 = 8. C-8\N-ENGCHE\ECH3-2.1 × 1010 fissions sec–1.023 × 1026 atoms or nuclides. (Q 1 MeV = 1.62 ENGINEERING CHEMISTRY Sol.PM5 62 . its stability. Energy required to be produced in a day 864 × 10 10 = = 432 × 10 11 J 0. What do you mean by nuclear chemistry? Ans. Nuclear chemistry is concerned with changes of the nuclei i..6 × 10–13 J = 32 × 10–12 J. A city requires 100 MW of electrical power on an average. fission rate for generation of 1 watt 1 = = 3.53 kg.023 × 10 26 = MeV. Given that energy released per fission of U 235 is 200 MeV.2 Energy released/nuclide = 200 × 1.s. energy released per 1 kg of U235 200 × 6.5 × 10 23 = kg 6. 3. using U 235 as the nuclear fuel.5 × 1023 32 × 10 −12 6.025 × 10 26 = 530 × 10–3 kg = 0. Sol.e. So.2 × 10–11 J or W.6 × 10–13 J = 3.

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

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

.

PM5 64 . 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. C-8\N-ENGCHE\ECH3-2. and this reaction is the principle for atom bomb.

(iii) During fusion. they fuse to produce elements with even proton numbers. neutrons are emitted. how can you determine by simple experiments if the mineral is radioactive? C-8\N-ENGCHE\ECH3-2.NUCLEAR CHEMISTRY 65 Q. (iii) During fission. 14. Ans. Q. What is radioactivity? Give an account of the discovery of radioactivity? 2. If you are given a piece of mineral. 4 1H1 → 2He4 + 2 positrons + 109 kJ. combining of two lighter nucleus into lighter ones with release of nuclei into a heavy nucleus with release of large amount of energy. What do you mean by nuclear fusion? Ans. Fe. large amount of energy. 15. Q. Nuclear reactions are the changes affecting the nuclei of atoms. In the sun. It is also the process that accounts for the origin of all the elements. Ans. 238 β β 92 U + 0n1 → 92U239  → 93Np239  → 94Pu239 Nuclear reactions are used to give birth to radioactive isotopes to be used as tracers.13. EXERCISES 1. Q. positrons are emitted. When two light nuclei combine with release of a huge amount of energy. Why the elements with even proton numbers are more abundant than other elements? Ans. Fission Fusion (i) Fission involves breaking up of a heavy (i) Fusion involves. at a temperature of ten million degrees. (ii) Fusion takes place at very high temperature (106 K). the phenomenon is known as ‘nuclear fusion’. (v) Fusion does not give rise to chain reaction. Nuclear reactions are brought about by bombarding nuclei with high energy particles in particle accelerators or with beams of neutrons from nuclear reactors. (ii) Fission takes place at ordinary temperature. Apart from atom bombs and alternative energy sources. since 2He4 has even number of 2He nucleons. 2 + 1H2 → 2He4 + energy 1H 1 + 1H3 → 2He4 + energy. with higher proton numbers than uranium. How are nuclear reactions carried out? Mention the uses of nuclear reactions. nuclear reactions can be used to make elements that do not occur in nature. Compare fission and fusion reactions. the following fusion takes place. 1H Nuclear fusion is the source of energy of the sun and the other stars. Si. 16. How will you show that radioactivity is nothing but a nuclear property? 3. 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. (iv) Fission gives rise to chain reaction.PM5 65 .

2385 yrs.and γ-rays? Compare their ionising power. Calculate the amount of energy released during the bombardment of 10 n on 235 92 U . What is nuclear fission? Show how nuclear fission is a chain reaction. Give a brief account of the nuclear reactors. [Ans. 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. 20. 15.66 ENGINEERING CHEMISTRY 4. β. Write a short note on nuclear transmutation. 19.. Derive a relation between mass defect and nuclear binding energy. Calculate the time required for 10% disintegration of a sample of thorium.. 21. How long will it take for 1 g of the element to lose 0. 17. 6C Given: Mass of H-atom = 1. 11. 13. What is a nuclear reaction? Discuss some uses of nuclear reactions.. Write a short note on nuclear fusion.4 MeV.] 27. What is radioactive displacement law? 12. Explain the terms: (i) Disintegration constant (ii) Half-life period 6.. Where is the radioactive displacement law invalid? 23. State and explain the law of radioactive disintegration. 6.. Complete the following nuclear reactions: 9 4 Be + 42 He → 12 6C + . 10.04 1 amu = 931. 54. Actual mass of C-atom = 12.m.76 MeV] 28. 24 24 11 Na → 12 Mg + .u. 9.PM5 66 . range and velocity. Given the t1/2 of thorium = 1.. What are radio-isotopes? How are they prepared? Mention their uses. 26. Give a relation between half-life and the decay constant of a radioactive substance. What is nuclear binding energy? 16. + 11H 7 3 Li + 11H → . What are the causes of nuclear instability? Explain with suitable examples. Write notes on: (i) Radioactive equilibrium (ii) Atomic weight of lead in radioactive minerals (iii) Tracer technique. What are the units of radioactivity? 7.00866 a. Write a short note on radio-carbon dating. 8.u. 22... Explain artificial radioactivity with suitable examples. Why is natural radioactivity mostly limited among heavier elements? 14.. + 74 Be..4 × 1010 yrs.00782 a. 25. 10 5B + 42 He → . What informations are available from these curves? 18.1 g? [Ans. Give a comparative account of the nuclear binding energy curve and packing fraction curve. The half-life of radium is 1590 years. What are α-. Calculate the binding energy in MeV per nucleon of 12 .] C-8\N-ENGCHE\ECH3-2.93 × 10–5 yrs. [Ans. Mass of neutron = 1. 5.m. 238 239 92 U → 90Th + . 24.

u.114 MeV] 34. [Ans.01472 a.76 MeV] 37.862 years] 38. = 931 MeV. [Ans. Calculate the weight of 1 curie of 222Rn. 39.7 times that in a living plant.009 a. A fresh sample of wood shows 15. What is its half- life period? [Ans.u. Given: Mass of neutron = 1.5 × 10–6] 32. 1 a. 16. An old wooden article shows 2. Mass of 10 n = 1.6725 × 10–24 g.01605 a.u.003 a. Calculate the age of the wooden article.014 a. 2970 years] 30.m. A sample of uranium ore is found to contain 11. [Ans.PM5 67 . of 206Pb.33. A radioactive element disintegrates to 1/16th of its original mass in 160 days. Write short note on components of a nuclear power reactor and their functions. [Ans.9 g of 238U and 10. Mass of 2H = 2. Calculate the energy released in the nuclear fusion reaction: 2 1H + 31H → 42 He + 01n Given: Mass of 21 H = 2.5 × 109 yrs.2 counts min–1 g–1. 40 days] 33. 0.m.u.m. Given t1/2 of uranium = 4.6747 × 10–24 g. Half life of 222Rn in 3.13 yr–1] 36. 14 Given: t1/2 for 6C = 5.NUCLEAR CHEMISTRY 67 29. Mass of 1H = 1.73 MeV] 35. 4.m. Calculate the approximate life period when the plant died.760 yrs. Calculate the age of the rock. Mass of 42 He = 4. Mass of 11B = 11.5 × 109 years] 31.016 a. Mass of electron = 9 × 10–28 g.u. A neutron breaks into a proton and an electron. Given t1/2 = 5760 years. 9. Calculate the energy produced in MeV. Mass of 31 H = 3. Calculate the decay constant of 60Co.m.m. [Ans. Mass of proton = 1. Distinguish between nuclear fuel and a chemical fuel.3 years. A piece of wood was found to have 14C/12C ratio 0.82 days. [Ans.m.m. C-8\N-ENGCHE\ECH3-2. 16. Calculate the energy released in MeV from the reaction: 10 5B + 21H → 11 5B + 11H Given: Mass of 10B = 10.01286 a. [Ans.00812 a. Given the t1/2 of cobalt = 5. [Ans.u.u.u.0 counts min–1 g–1.m. 6. 0.u.

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

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

respectively. the algebraic sum of all the heat terms is equal to the algebraic sum of all the work terms. it may be used up by the system as partly increasing the internal energy of the system and partly in doing mechanical work. ∆E = 0. heat supplied to a system is q. 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. Mathematical formulation of the first law Let us suppose. from first law. Here the work. When the volume (V) is constant. exclusively. For an adiabatic change. and it may be stated as “the energy of an isolated system remains constant and whenever a quantity of some form of energy disappears. we arrive at a very important relation that for a cyclic process.70 ENGINEERING CHEMISTRY Cyclic process Fig. it completes a cyclic path and the overall change of energy (E) i. an exactly equivalent quantity of some other form of energy must make its appearance”.. So in an adiabatic process.e. ∴ W = – ∆E. Since heat energy cannot be lost. q = ∆E + W or ∆E = q – W If the above change is infinitesimally small. it suffers a fall in temperature”. Joule-Thomson effect Joule-Thomson effect states: “When a gas under high pressure is permitted to expand into a region of low pressure.. dV for very very small changes. 4. the work done becomes P dV and hence the mathematical expression of first law becomes.e. according to the first law Heat absorbed = Increase of internal energy + Work done by the system i. Thus. dq and dw represent small quantities of heat absorbed and external work done by the system. C-8\N-ENGCHE\ECH4-1. dV = 0.1 THE FIRST LAW OF THERMODYNAMICS The first law of thermodynamics is simply the law of conservation of energy.PM5 70 . is of pressure × volume type. 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). ∆E = q – W = 0 ∴ q = W. Hence. dE = dq – P. we can write dE = dq – dw where dE is the increase in internal energy. If the system is under a pressure P and volume increases by dV. Hence. work done by the system = decrease in internal energy of the system. q = 0.

P1V1 = P2V2 ∴ W = 0. H is a similar state function. if the process is carried out at constant volume change in enthalpy and change in internal energy are equal. the gas was allowed to do no work and there was no interchange of heat with the surroundings. Since E is a characteristic of the system (state function). 4.e. Suppose.e. ∆H will depend only on the initial and final states of the system. thus the gas while expanding does some work and hence the temperature falls. q = 0. Since the expansion is carried out adiabatically i. The gas expands is passing through porous plug (Fig. according to the first law.. from first law of thermodynamics. Porous plug V1 P1 P2 V2 Fig. Heat absorbed by the system is q. C-8\N-ENGCHE\ECH4-1. 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. But Joule-Thomson observed that most gases cooled down by such a pressure drop.. when q = 0. P2V2 – P1V1 = W. the energy of the gas falls i. Change in enthalpy = change in internal energy. i. The volume increase is from V1 to V2. 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. The quantity (E + PV) is universally represented as H and called the heat content or enthalpy of a system..PM5 71 .e. there should be no change in temperature. from the first law of thermodynamics q = (E2 – E1) + W = (E2 – E1) + (P2V2 – P1V1) = (E2 + P2V2) – (E1 + P1V1) = H2 – H1 = ∆H. for an ideal gas. Thus. Hence.. ∆E = q – W = q – 0 = q. i. Hence. ∆V = 0. Constancy of Enthalpy (isoenthalpic) in Joule-Thomson expansion Joule-Thomson experiment is carried out adiabatically.THERMODYNAMICS 71 Joule and Thomson performed an experiment where a gas was allowed to expand adiabatically through a porous plug against a constant pressure. For an ideal gas. Hence. So. Hence. Hence. ∆E = –ve. a system at constant pressure is undergoing a change from states 1 to 2.2) and the work done is P2V2 – P1V1. ∴ ∆H = ∆E + 0 = ∆E.e.2 Joule-Thomson expansion. when heat does not flow out of the system nor does it come into system from the surrounding. The work done is at the expense of the kinetic energy of the molecule while they are separated from each other. ∆H = ∆E + PV = ∆E + W = q (heat absorbed) and at constant volume. work done by the gas is. not on the path followed during the change. ∆H = (E2 + P2V2) – (E1 + P1V1) = (E2 – E1) + (P2V2 – P1V1) ∴ At constant pressure. 4.

3). µ becomes negative. Inversion temperature If the gas in above expansion suffers a fall in temperature by dT. Work done in a reversible isothermal expansion: Suppose n moles of a gas is enclosed in a cylinder by a frictionless piston (Fig. But. For van der Waals gas. = 2 in an isothermal expansion of a perfect gas. thermostat at T K. we can define Joule-Thomson coefficient (µ) by the relation. V1 P1 C-8\N-ENGCHE\ECH4-1.3 V2 V2 nRT Then. The gas has a volume V1 and the piston is at point A. W= PdV = dV [Q PV = nRT] V1 V1 V V2 ∴ W = nRT ln V 1 V2 P Since. for a lowering of pressure dP. At every step a minute distance (∆l) of the piston may be V1 T made so that work done (W) is.e.e. W = P × a × ∆l. For gases having positive µ value cools on expansion but for H2 gas µ is negative i. from first law. W = force × displacement = force × area × distance A = P × a × l. This temperature is called the “inversion temperature.. when neither heating nor cooling of the gases occurs on expansion after pasing through orifices. The cylinder is kept in a constant temperature bath i. The work of expansion (W) will be given by the product of opposing force and the displacement. change in enthalpy is equal to heat absorbed at constant pressure. E2 – E1 = – P2V2 + P1V1 ∴ E2 + P2V2 = E1 + P1V1 or H2 = H1. then instead of cooling the gases are heated. under adiabatic conditions.e.. 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. The gas is to be expanded from volume V1 to volume V2. ∆H = ∆E + P∆V = ∆E + P(V2 – V1) = ∆E + w = qP (heat absorbed at constant pressure) i.e. i. ∆E = q – W = 0 – (P2V2 – P1V1) i. 4... if the temperature is high. The cooling effect is seen when the temperature is low. isothermal condition is maintained. 4. a × ∆l is the volume swept by the piston. H2 warms up on expansion. i. FG δT IJ µ= H δP K H µ is zero for an ideal gas (PV = nRT). For every gas there is a temperature where µ = 0.72 ENGINEERING CHEMISTRY Hence.. it is dV z z Fig..e.PM5 72 .e. Ti” of the gas.

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

.

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

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

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

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

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

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

600 cal which is exothermic whereas for the formation of 2 moles of HI. the heat of reaction for the formation of 2 moles of HCl is 43. From first law we find that ∆HP and ∆EV will be independent of the path. to measure experimentally can be easily found out by addition. The heat of combustion is experimentally determined in a Fig. when molar quantities react and indicated by a balanced equation.e. (ii) Heat of combustion. so heat of combustion is always negative. subtraction. etc. Let us take the example of formation of CO2 in one step and two steps (a) and (b): C + O2 = CO2 ∆H = – 94.608 cals (exothermic) (b) H2 + I2 = 2 HI –12.05 Kcal.63) Kcal which illustrates the law = – 94. complete combustion means when these compounds are converted finally to CO2 and H2O. ∆H terms algebraically. In the case of organic compounds. Combustion reactions are always exothermic. Example: (a) H2 + Cl2 = 2 HCl +43. 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. (i) Heat of reaction. The experimentally determined values of heat of combustion are useful. • Enthalpy changes of reaction from enthalpy changes of formation. Heat of reaction (∆H) is the difference between the heat contents of the products and the reactants. The principal advantage of this law is that thermochemical equations can be treated as simple algebraic equations and the heat of formation. which are difficult Highlights: Hess’s law is used to calculate: • Enthalpy changes (∆H) of formation from enthalpy changes of combustion. • Lattice energies is the Born-Haber cycle. multiplication of the quantities i. heat changes in the two directions must be equal in magnitude but opposite in sign.THERMODYNAMICS 81 change is zero i.. Example: C2H5OH + 3O2 = 2CO2 + 3H2O ∆H = – 325 Kcal C-8\N-ENGCHE\ECH4-1.680 cal of heat is absorbed and the reaction is endothermic. 4.. 12.63 Kcal.. 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. 2 2 Summing up we get.5).42 – 69.05 Kcal 1 (a) C + O2 = CO ∆H1 = – 26.680 cals (endothermic) Thus. 4. “bomb calorimeter” which is a pressure vessel internally enamelled with platinum (Fig. Hess’s Law of Constant Heat Summation. ∆H1 + ∆H2 = (– 26.PM5 81 . B.42 Kcal 2 1 (b) CO + O = CO2 ∆H2 = – 67.e. heat of transition.5 Bomb calorimeter.

But when a weak acid or a weak base is neutralized. Example: HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O ∆H = – 13. they can be assumed to be completely dissociated. C-8\N-ENGCHE\ECH4-1. i. The heat of solution changes with concentration. The standard enthalpy of formation (∆Hfo) is just the negative of the heat of formation... (v) Heat of solution and heat of dilution. when the enthalpy of formation of a compound is negative. H+ + OH– = H2O. the enthalpy of any element at 1 atm and 298 K is assumed to be ‘zero’. all in their respective standard states and at a reference temperature. At high dilution.7 Kcal.7 kJ indicates the HF is much more stable than HI. The enthalpy of formation is related to the stability of compound. The heat change taking place when 1 gm mole of the solute is completely dissolved in a solvent is called the heat of solution.8 kJ. Whereas.7 Kcal HCl(aq) + KOH(aq) → KCl(aq) + H2O ∆H = – 13. The value of heat of solution obtained graphically by extrapolating ∆H to infinite dilution is the integral heat of solution at infinite dilution.PM5 82 .. C(graphite) + 2 H2 (g) → CH4(g) ∆Hf = – 74. it means the energy content of the compound is greater than the energy content of its constituent elements and hence the compound is unstable. the energy content of the corresponding compound is lower than its constituent elements and hence the compound is stable. i. the heat of neutralisation deviates considerably from 13. the more stable is the compound.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.7 Kcal. In order to measure the change in enthalpy.7 Kcal of heat. Example: KCl(s) + 50 H2O = KCl (50 H2O) – 4276 Cal. Heat of fusion is always positive. H+ + A– + B+ + OH– = B+ + A– + H2O i.e. It is the amount of heat liberated or absorbed when one mole of the compound is formed from its constituent elements. KCl(s) + 100 H2O = KCl (100 H2O) – 4391 Cal. If the enthalpy of formation of a compound is positive. one gm mole of KCl dissolved in 50 moles of water and in 200 moles of water will cause different heat changes. it is needed to assume some arbitrary value for substances at a given state.e. Therefore. (iv) Heat of formation. (vi) Heat of fusion. The lower the enthalpy of formation of a compound. Example: ∆Hf of HI is + 26. the stability of a compound is inversely proportional to the enthalpy of formation of a compound. the heat change becomes constant. 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. If the acid and base are both strong. Thus. and this is always the equivalent of 13.9 kJ and ∆Hf of HF is – 161. Conventionally. the heat of neutralisation is really the heat of formation of 1 gm mole of water from 1 gm ion of hydrogen and hydroxyl ion.e. Example: H2O(s) → H2O(l) ∆H = 6 kJ.

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

2.1 kJ/mol. (iii) Bond energy varies with the total environment of the molecule. (ii) Bond energy varies with the difference between the electronegativity of the two atoms. 1. respectively. (a) It is impossible to convert heat completely into an equivalent amount of work. to convey heat from a body at a low to one at a high temperature.84 ENGINEERING CHEMISTRY Variation of bond energy (i) Bond energy varies with the size of the atoms. Second law of thermodynamics guides the conditions under which heat and work are interconvertible. second law of thermodynamics can be stated in some different important forms. ∆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. = 670. (b) It is impossible for a self-acting machine unaided by any external agency. 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.PM5 84 . i.5) Kcal. convert a portion of it into work and give up the rest of heat to a body at lower temperature. (c) All spontaneous processes tend to equilibrium.3 + 6 × 98.5 and 43. Example: Heat of formation of ethane is. (d) The energy of the universe is constant..3 Kcal mol–1. The engine must take up heat at higher temperature. From the above experience. Bond energy decreases as H—F > H—H > C—C > N—N > F—F. For the conversion of heat into work two conditions must be fulfilled.e. Example: bond energy for H—F and H—Cl are 56. the total enthalpy change involved in these bond breaking and making gives the heat of reaction. 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. So. 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. Effect of temperature on free energy-(Gibbs-Helmholtz equation) We know. 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. SECOND LAW OF THERMODYNAMICS Heat is readily available and man is interested to convert this heat energy to useful work. but the entropy approaches a maximum.

(a) When a reaction is exothermic i. (c) If both ∆H and ∆S are positive and T∆S > ∆H. Imagine a very small change of a small amount of liquid vaporizing at C-8\N-ENGCHE\ECH4-2. can be studied thermo- dynamically.PM5 85 . we get dG = dE + PdV + VdP – TdS – SdT We know. which are in equilibrium at a temperature T..e. Application of thermodynamics to phase transition i. vaporization. (b) If both ∆H and ∆S are negative and ∆H > T∆S. 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. when the free energy of the reactants and the products are equal. 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. the reaction occurs if T∆S is positive and greater than ∆H. ∆H is positive. the process will be spontaneous only when ∆H is greater than T∆S.. (b) In endothermic process. Hence. ∆H is neagtive. etc. change of phase. We know G = H – TS ∴ ∆G = ∆H – T∆S FG ∂∆G IJ ∴ ∆G = ∆H – T H ∂T K p This is Gibbs-Helmholtz equation. Let G1 and G2 be the free energies of a liquid and its vapour. which relates free energy and ethalpy changes at constant pressure.THERMODYNAMICS 85 Differentiating. (c) When ∆H is negative and ∆S is also negative.e.e. and ∆S is positive. ∆G has negative value and the reaction becomes spontaneous.. We know that if ∆G is negative the reaction takes place spontaneously and when ∆G = 0 i. (Clapeyron- Clausius equation) Change of phase taking place during freezing. the reaction attains equilibrium. the criteria for spontaneous processes are: (a) If ∆H is negative and ∆S is positive – ∆G becomes negative.

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

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

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

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

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

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

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

158 – 0.3.PM5 93 .314 × 300 = 8. ∆H = ∆E + ∆nRT.836 = 3. ∆n = 1 – 2 = – 1. Zn + H2SO4 → ZnSO4 + H2↑ 1 mol. n2 = 1 ∴ ∆n = n2 – n1 = 0. n1 = 1 mols of gaseous product. Sol. hydrogen.332 kJ. 68. We know. We have. 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. 372.4942 kJ.8 Kcal mol–1 at a definite temperature. Sol. Here. Calculate the work done by the following reaction at 27°C. Sol. qp = qv (As n2 = n1) Example 5. Sol. 1000 = 2. C-8\N-ENGCHE\ECH4-2.2 Here q = 990 cals = kJ = 4. Example 6.36 × 109 ergs = kJ = 0.13 10 3 8. C(s) + O2(g) = CO2(g) Here qv = – 97000 cal. So.36 × 10 9 w = 8. w = P(V2 – V1) = PV2 [Q V1 = 0] = nRT = RT [Q n = 1] 8.314 × (273 + 27) = kJ. qp = qv + ∆nRT. Calculate the internal energy change of the system. Mg(s) + 2HCl(g) → MgCl2(s) + H2 (g) (Given ∆H = – 109 Kcal). mols of gaseous reactant. Example 3.THERMODYNAMICS 93 Example 2. Calculate the heat of reaction of C2H4(g) + H2(g) → C2H4(g) at that temperature. and ethane are 337. Calculate the heat of combustion at constant pressure of carbon. (Given qv at 200°C is 97000 cals).36 × 109 ergs. Example 4. We have. The amount of work of a system is 8.2. = – 97000 + 0 × RT = – 97000 cals. Calculate the value of ∆E for the reaction at 500 K. ∆E = q – w 990 × 4.836 kJ 10 7 × 10 3 ∴ ∆E = 4. of heat. Heats of combustion of ethylene. Here. after absorbing 990 cals.

7 Kcal) ∴ C2H4 + H2 → C2H6. Example 7. Example 8. ∆H = 68.. ∆H = 60 Kcal. C-8\N-ENGCHE\ECH4-2. 2 2 7 (iii) C2H6 + O → 2CO2 + 3H2O. ∆H = – 337.8 Kcal. 2 2 Adding the equations (i).7 Kcal. and for breaking of these two bonds energy requirement is 222 Kcal.(iii) 2 2 Sol. (i) C2H4 + 3O2 → 2CO2 + 2H2O. 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.PM5 94 . H2O(g) → 2H(g) + O(g). ∆H = – 58 Kcal . ∴ O—H bond energy is 111 Kcal. ∆H = + 372.. ∆H = – 32.3 Kcal. for dissociation of one O—H bond energy requirement is 222 ÷ 2 = 111 Kcal. H2O(g) → H2(g) + O (g) ∆H = 58 Kcal. ∆H = 120 Kcal .94 ENGINEERING CHEMISTRY Sol... (iv) 2CO2 + 3H2O → C2H6 + O. From equation (ii) 1 O (g) → O(g). Calculate the enthalpy of formation of propane (C3H8 ) at 298 K. 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.. H2(g) → 2H(g).. ∆H = 222 Kcal. ∆H = 104 Kcal . 1 7 C2H4 + 3O2 + H2 + O + 2CO2 + 3H2O → 2CO2 + 2H2O + H2O + C2H6 + O2 2 2 2 (∆H = – 32.e. We know that. ∆H = – 372. Calculate O—H bond energy from the following heats of reactions.8 Kcal 2 2 7 or. 1 (ii) H2 + O → H2O. there are two O—H bonds in a molecule of water. (ii) and (iv) we have. Given.2 Kcal.(ii) 1 H2(g) + O (g) → H2O(g)..(i) O2(g) → 2O(g). So. 2 2 1 From equation (iii).

The latent heat of evaporation of water at 100°C at constant pressure is 538 cal g–1.PM5 95 . We have. Sol. 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).THERMODYNAMICS 95 Sol. Example 10. ∆H100° = 538 8. = 3 × (– 393) + 4 × (– 286) kJ mol–1 = – 2323 kJ mol–1 ∆H3 = ∆H °C = – 2220 kJ mol–1 Hence. calculate the latent heat of water at 150°C. ∆H150° =?.55. If average Cp for water and steam are 1 cal g–1 and 8. 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.1 cal mol–1. ∆H2 – ∆H1 = ∆Cp(T2 – T1) ∆H150° – ∆H100° = – 0.1 Cp for water = 1. respectively for the interval. Calculate the enthalpy change of transition from yellow P to Red P from the given thermochemical cycle.45 – 1 = – 0. ∆H °f (C3H8) = (– 2323) – (– 2220) kJ mol–1 = – 103 kJ mol–1.55(50) C-8\N-ENGCHE\ECH4-2. Cp for steam = . Sol. Example 9. T2 – T1 = 423 – 373 = 50 K. 18 ∆Cp = 0. Basis = 1 g.

5 × 18 cal mol–1 = 9819 cal mol–1. From the integrated form of Clausius-Clapeyron equation.14 × 18 = = 1.55 × 50 = 510. dS = T 19. Sol.303 × 8.33 J mol–1. dS = T 12. Here. We know that ∆E = 0 V2 Therefore. (273 − 182.5 cal g–1. P2 = 1 atm = 760 mm of Hg.96 ENGINEERING CHEMISTRY ∆H150° = ∆H100° – 0.5 cal g–1 = 545.19 J g–1.26 J mol–1.66 × 103 J = 1.14 J g–1.55 × 50 = 538 – 0. qrev Sol.9) 90. R = 1.303R T1 T2 N Q C-8\N-ENGCHE\ECH4-2.19 × 32 12.19 × 32 = = = 4. Given L = 12.31 × 298 log 1 = 1. Sol. q = W = RT ln V1 qrev V2 dS = = R ln [Positive quantity] T V1 Example 15. 273 Example 13. T1 = ?. Calculate the change of molar entropy during melting of ice. T2 = 100°C = 373 K. P1 = 528 mm of Hg. qrev Sol.PM5 96 . Hv = 545.5 cal g –1. (– 182. Example 11.987 cal K–1 mol–1. Calculate the change of molar entropy during the conversion of liquid oxygen to oxygen gas at its b.66 kJ.p. Calculate change of entropy in isothermal reversible expansion of one mole of an ideal gas. At what temperature will water boil when the atmospheric pressure is 528 mm Hg? Given latent heat of vapourisation of water is 545. Example 12. Maximum work = 2.9°C). Calculate the maximum work done for the isothermal reversible expansion of one mole of an ideal gas at 25°C from 2 atm to 1 atm.303 RT ln P 2 2 = 2. we have P2 ∆H v 1 − 1 LM OP log P = 1 2.1 Example 14. P1 Sol. Given latent heat – 19.

The value of Kp (equilibrium constant) of the reaction regarding ammonia synthesis at 27°C is 3. Cp = Cv + R = (5 + 2) cal = 7 cal. Pressure is increased reversibly upto 7 atm and temperature is incremented to 90°C. 2 2 2 Consider the reaction to be independent of heat and temperature. atm = 24. C-8\N-ENGCHE\ECH4-2.5577 cal deg–1. T1 = 27°C = 300 K. heat energy. T2 = 90°C = 363 K.987 N T 373 Q 1 or. 300 7 Example 19. So. (i) Since operation is isothermal and the gas is ideal so. = 10 L atm × H 0.7 J = 1012.303 × 1.PM5 97 . But. ∆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. Work done in an irreversible process is given by W = P(V2 – V1) = 2(20 – 10) = 20 lit. Example 17. ∆E = 0 or q = W. Sol.7 J. P1 = 1 atm. Sol.25) cal [Q 1 lit.THERMODYNAMICS 97 760 9819 LM 1 − 1 OP ∴ log 528 = 0. (iv) ∆H = ∆E + P∆V = 0 + 1012.7 J. W. = (20 × 24. for a reversible process.314 J IJ = 1012. Calculate the entropy change for the process. From the 1st law of thermodynamics. work done by system. 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. The initial temperature and pressure for one mole of an ideal gas is (Cv = 5 cal) 27°C and 1 atm. (ii) Now.7 J. A gas during expansion from 10 litre to 20 litre under 2 atmospheric pressure absorbs 300 cal. internal energy will decrease by an amount of 185 cal. ∆E = q – W = (300 – 485) cal = – 185 cal.2 Kcal. q = ∆E + W or. T1 = 363 K. Example 16.atm. P2 = 7 atm. 363 1 ∴ ∆S = 7 ln + 2 × ln = – 2.25 cal] = 485 cal. from 1st law. Calculate q.1582 = 2. 1 3 N (g) + H2(g) NH3(g) + 11.0821 L atm K (iii) q = W = 1012. Find the change in internal energy. ∆E = 0. Thus find the value of Kp for the following reaction at 37°C. Example 18. W = P(V2 – V1) = 1 atm (20 – 10) dm3 = 10 atm dm3 = 10 atm L FG 8.49 × 10–2 atm–1.

K P2 = 1. Derive Gibbs-Helmholtz equation and mention its significance. What is enthalpy? Ans. Q. 3. Q. Q.98 ENGINEERING CHEMISTRY Sol. 8. it can be stated as the net energy of the universe remains constant. R = 1. C-8\N-ENGCHE\ECH4-2. Ans. T1 = 27°C = 300 K.2 Kcal = – 11200 cal. K P2 ∆H T2 − T1 LM OP ∴ log K P1 = 2. Since. so enthalpy is more useful than internal energy. 6. 5. in most of the reactions. From Van’t Hoff equation. State First law with mathematical expressions. respectively. 7.9038 × 10–2 atm–1.303 × 1.. Why is enthalpy more useful than internal energy? Ans. The entropy of a substance becomes zero when the substance is perfectly crystalline i. See text page 66. See text page 84. See text page 85. See text page 71. Why? Ans.987 300 × 310 Q or. Q. Derive Clapeyron-Clausius equation and mention its applications. K P2 = ? ∆H = – 11. 2. See text page 68. they occur at atmospheric pressure. 1. 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.PM5 98 .49 × 10 −2 = N 2. State intensive property of a system. K P1 = 3. Alternatively. Ans. ordered state and at the temperature of 0 K. Ans.303R T1T2 N Q K P2 − 11200 LM 310 − 300 OP log 3. T2 = 37°C = 310 K. we have K P2 LM ∆H T2 − T1 OP ln K P1 = R T1T2 N Q Here. 4. Internal energy and ethalpy of a system are measured by keeping the volume and the pressure constant. The molar heat of sublimation of a solid is always greater than the molar heat of vaporization of the corresponding liquid. Q. Q.e.49 × 10–2 atm–1. When does the entropy of a substance become zero? Ans.987 cal deg–1 mol–1. SHORT QUESTIONS AND ANSWERS Q. Q. Ans.

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

EXERCISES 1. Ans. What is inversion temperature? Ans. Ans. Q. Describe a relation be- tween the two. 24. 21. It means that if a mole of H2 and mole of O2 both at unit pressures at constant 2 temperature (25°C). Define work function and free energy. What do you mean by ∆G° for the reaction H2 + O = H2O is – 54. State relation between them. Q. Q. How can you measure a spontaneous system with the help of free energy? Ans. See page 73. What do you mean by a cyclic process? Ans. See page 71. See page 72. 17. 16. See page 81. C-8\N-ENGCHE\ECH4-2. 18. Q. See text page 79. Alternatively it can be stated as the net entropy of the universe tends to a maximum. 22. 26. (iii) Define the concepts of Helmholtz free energy and Gibb’s free energy. 1 Q. 82. Ans. the decrease in free energy is 54. Explain that Joule-Thomson experiment is isoenthalpic. Q. (c) heat of neutralisation. See page 80. Ans. Define Cp and Cv. 27. Ans. Q. (iv) What is the significance of entropy? What is the criteria for spontaneity? (v) Derive Kirchoff’s equation. See pages 78 and 79. 19. See page 89. State Maxwell’s relations. Ans.PM5 100 . (b) heat of combustion. State the law of Laplace and Lavoisier. 23. (ii) Derive Clapeyron-Clausius equation and state its applications. Q. Q.100 ENGINEERING CHEMISTRY Q. State the second law of thermodynamics.65 Kcal 2 2 at 25°C? 1 Ans. State with example the significance of Hess’s law. See page 70. It is based on which law? Explain.65 Kcal. See page 84. Q. Ans. Short Questions: (i) Derive an expression for the variation of heat of reaction with the temperature with the help of first law of thermodynamics. Define (a) heat of formation. Q. Ans. 25. See page 81. 20.

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

The volume of a 45 g nitrogen gas is expanded from 5 litre to 10 litre at 25°C isothermally and reversibly. [Ans. heat from the surrounding.8. Considering the gas to be an ideal find out the work obtained in this case. [Ans. 17.82 and of water of unity. 15. [Ans. (iii) Heat of neutralisation. (a) State Hess’s law. The density of ice is 0.4 Kcal. Derive Maxwell’s relation and state its usefulness.1 cals] 2 3. (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. [Ans. are heated inside a gas cylinder to 100°C 3 assuming it to behave ideally and having Cv = R. (iv) Heat of formation. 18.788 × 107 ergs] 5. (b) Give the significance of Gibbs-Helmholtz equation. 21. Entropy change for the mixture of gases can be represented by – ∆Smix = – nR Σ xi ln xi where xi = mole fraction of gas. 1440. – 4.1 cals. Calculate the heat of oxidation of ethyl alcohol to carbon dioxide.05 and – 68. When ice melts at 0°C.6 Kcal] C-8\N-ENGCHE\ECH4-2. (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. (v) Heat of solution. 22. Show that entropy change for an irreversible isothermal expansion of an ideal gas is positive.32 Kcal. What is the enthalpy change in the transformation of diamond to graphite? [Ans. 2. Find the internal energy change of the system. 223. ∆H.T. (a) Derive Gibbs-Helmholtz equation. Calculate ∆E. Consider the gas to behave like an ideal. cals. 790 cals] 4. (vi) Heat of fusion. 20. Calculate ∆E and ∆H if 10 litres of helium at N.102 ENGINEERING CHEMISTRY 11.8 cals] 6. 13. – 450 cal] 7.. A system performs 8. the latent heat of fusion is 80 cals. 326.PM5 102 .. (1440. 19. The heats of formation of CO2 from diamond and graphite are – 94500 and – 94050 cal.36 × 109 ergs work after absorbing 990 cals. How can you determine the bond energy and lattice energy with the help of Hess’s law? 16.01 × 106 ergs) 2. (b) Mention the applications of Hess’s law. (vii) Heat of vaporisation. Derive Clausius-Clapeyron equation. The heat of formation of ethyl alcohol is – 66. (viii) Heat of sublimation.P.. . respectively. 1381. Long Questions 1. 12. Calculate the work done in calories. (c) Explain the terms (i) Heat of reaction. 133. 1440 cals. During isothermal reversible expression of 4 g of helium gas at 27°C the pressure reduces from 10 atm to 1 atm. Derive Gibbs-Duhem relations. (ii) Heat of combustion. lL + mM + . when the heats of formation of carbon dioxide and liquid water are given as – 94. [Ans. g–1. What do you mean by Van’t Hoff reaction isotherm? Derive an expression for the reaction isotherm of the general reaction aA + bB + . q and w per mole.. Derive an expression for chemical potential at a temperature T in terms of P.

24 kJ mol–1.3 kJ mol–1. ∆G and ∆H for a particular reaction at 127°C are – 12 Kcal and 17.2 K and G = 101 cal g–1) [Ans.86 kJ] 13. [Ans. 760 mm Hg] C-8\N-ENGCHE\ECH4-2.p.42 × 1012 N20000 × 2000 Q = 5677 × 107 ergs. 153080 cals] 9. 94380 cals and 68380 cals. ∆G°298 = – 71.03 + 1.42 × 1012 dynes cm 4 mol–1 and b = 30 c. a = 3. Given.65 Kcal. (Ans. l) = – 68320 cal. Find the change in entropy when 1 kg of benzene at 10°C is mixed with 4.380 2 2 NaOH + water = NaOH (aq) + 13. L = 6500 cal mol–1. 0.5 Kcal. ∆A and ∆G for vaporisation of 2 moles of benzene (b. Evaluate the heat of formation of methyl alcohol. ∆S = 44.THERMODYNAMICS 103 8.43 Kcal/mol–1] 19. [Ans. – 70. Calculate the work done if a = 1. 21. Find out ∆S.5 kJ mol–1. Calculate the vapour pressure at 100°C. heat of benzene is 0. OP V1 − b N V2 V1 Q 20 − 0. – 17120 cals] 10. – 108. Calculate the heat of formation of benzene given that the heats of combustion of benzene.8 Kcal mol–1. Given. [Ans. H2 + Br2 → 2 HBr.4 Kcal] 15. g) = – 94050 cal. [Ans.5 Kcal.043 litre mol–1. Calculate the free energy change of g mole of SO2 at 25°C and 10 atm pressure.03 LM2000 − 20000 OP ergs W = 2.5 cal/°K. Calculate ∆Q. ∆W. boiling point = 35°C. From the following bond enthalpies calculate ∆H for the reaction. 70 g of nitrogen gas was initially at 50 atm and 25°C. Br—Br bond energy = 192.39. The sp. 2 ∆H f (CO2 . Isothermally at 27°C one mole of a van der Waal’s gas expands reversibly from 2 litres to 20 litres. ∆A = – 1.0 kg of benzene at 30°C. Bond energy H—H = 435. The average latent heat of vaporisation of water is 546 cal g –1 within the temperature range 90°C – 100°C.303 × 8. – 57040 cal] 14. ∆H. [Ans. = 353.9879 eV] 17. Calculate ∆S. 1. The heat of combustion of methyl alcohol is – 173.59 litre2 atm/mol–2 and b = 0. 2036 K] 16. Find heat of formation of caustic soda from the following data: 1 Na + H2O = NaOH (aq) + H + 98.] 11. H—Br bond energy = 368. respectively. [Ans. W = RT ln V2 − b +a LM1 − 1 .75 eV] 20. What is the inversion temperature of the gas? [Ans.PM5 103 . The van der Waal’s constant for CO2. Given.1 eV] 18. [Ans.c mol–1. Calculate the entropy change in vaporisation of ether. [Ans. 0.300.000 2 2 1 H2 + O = H2O + 68. It was allowed to expand isothermally against a constant external pressure of one atmosphere. ∆U. [Hint. carbon and hydrogen are 754300 cals. [Ans.31 × 107 × 300 log 2 − 0. ∆H(H O. – 13. 1. ∆G = 0. The vapour pressure of water at 90°C is 530 mm Hg. 0] 12.5 Kcal.

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

• The order of a reaction will be determined by the power terms of the concentrations of the rate equation. [HI]2 2 (ii) H2 + I2 = 2HI r = k . Therefore. for decomposition of H2O2. the powers of the concentration terms are added to get the order of a reaction. As for example. one molecule is needed and hence the molecularity is one. The experimentally determined rate equation for the decomposition of H2O2 is: r = k . Molecularity of a Reaction The minimum number of molecules. In the experimentally determined rate equation. Again for the reaction: 2H2O2 = 2H2O + O2 But the reaction can be written as H2O2 = H2O + O So. [A]a . we should take into account the ‘order’ and the ‘molecularity’ of a reaction. [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 order of a reaction may be zero or fraction. minimum two molecules of HI will be required.REACTION DYNAMICS/CHEMICAL KINETICS 105 To consider the rate of a reaction. So. As for example 2HI = H2 + I2 For this reaction.PM5 105 . the order of the reaction will be = (a + b). 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 H2O2.1 Reactions Experimentally determined Order rate (i) 2HI = H2 + I2 r = k . atoms or ions taking part in a chemical reaction is known as molecularity of the reaction. the molecularity is ‘two’. Table 5. So it is a first order reaction. for a reaction: aA + bB → Products rate of the reaction (r) = k . [B]b. C-8∴N-ENGCHE∴ECH5-1. So. Order of a Reaction The rate of reaction will definitely depend on the concentration of the reactants.

(a – x) x At time ‘t’. x = concentration of the product at time t. dc If c be the concentration. (a – x) dt dx or = k . [N2O5] So.5 and the molecularity is 2. the order of the reaction is four but the molecularity is twelve. x=0 Then. • For the reaction CO + Cl2 = COCl2 Rate = k . [NO]2 [O2] So. Let the reaction be A → Products. the order of the reaction is one and the molecularity is two. a− x Integrating we have. Therefore. – ln (a – x) = kt + z where z = integration constant when t = 0.106 ENGINEERING CHEMISTRY Highlights: • For the reaction 2N2O5 = 4NO2 + O2. the rate equation will be dx = k . then the rate of the reaction = – = kc. are called first order reactions. • For the reaction BrO3– + 5Br– + 6H+ = 3Br2 + 3H2O The observed rate = k . The observed rate = k . both the order and the molecularity of the reaction are three. [BrO3–] [Br–] [H+]2 So. the order of the reaction is 2. where the experimentally determined rate of the reaction is dependent on the first power of the concentration of the reactant. – ln (a – x) = kt – ln a a or ln = kt a– x C-8∴N-ENGCHE∴ECH5-1.PM5 106 . [CO] [Cl2]1. dt where k = rate constant. a = initial concentration of A.5 So. • 2NO + O2 = 2NO2 Rate = k . – ln a = z So. dt. Mathematical Formulation of First Order Reaction The reactions.

REACTION DYNAMICS/CHEMICAL KINETICS 107 1 a or k= . log10 2 = . ln 2 k 2. c • If we put a – x = c i. unit of k will be time–1. then the equation x = a(1 – e–kt) will be a = a(1 – e–kt) ∴ t = infinity. (iv) From the equation. 1 t = . the value of k will be same.. kt = ln 0 c ∴ c = c0 . dc dc / C fraction of reactants (iii) k=– C=– = dt dt time So.303t −k ∴ log c is plotted against ‘t’ we get a straight line with a negative slope = . we have. t a– x So. 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 0. k k (v) For complete reaction x = a. So. ln .693 = . concentration at any time ‘t’ and a = c0. ln a– a Nx= 2 Q 2 1 = . ln t a− x 2. 1 a (ii) k = .e. e–kt –k Therefore. log c = + log c0 2. it is purely a dimensionless number. log . • The above equation expresses a number of characteristics of a first order reaction— a (i) is a common ratio. k is change of fraction of reactants in unit time.PM5 107 . So. ln a/(a – x) k The half-life of a first order reaction can be calculated 1 a LM aOP t1/2 = k . e–kt or x = a(1 – e–kt). a first order reaction is never completed. 2. for any unit of a– x concentration.303 C-8∴N-ENGCHE∴ECH5-1.303 a = .

Let. identical or different. take part and the rate of the reaction is proportional to the concentration of each of them.PM5 108 . the reaction be represented by. 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.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. are called second order reaction. A + B → C + D Initial concentration of A = a Initial concentration of B = b C-8∴N-ENGCHE∴ECH5-1. 3-butadien.

a = b. then we can write.PM5 109 . dx dx = k(a – x)2 or = k(b – x)2 dt dt C-8∴N-ENGCHE∴ECH5-1.. 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. concentration of both the reactants are equal i.e.303 a(b – x) = log (b – a)t b(a – x) If.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.

mol–1 sec–1 [l = litre] dt c time conc 2 (iii) Physical significance dx k= = When c = 1 dt i. kt = – ∴ = kt + . x = 0. if we put a – x = c a–x a t a(a − x) 1 1 1 1 then. 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= . 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. 2 = × = conc–1 ..e. time–1 = l .e.PM5 110 .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. t1/2 = = = k a(a – x) k a(a – a / 2) ak i.. c a c a Characteristic of a Second Order Reaction (i) Time of half reaction 1 x 1 a/ 2 1 .

dx = k(a – x)3 dt C-8∴N-ENGCHE∴ECH5-1. Initial concentration of A = a Initial concentration of B = b Initial concentration of C = c no. c Unit of k sec–1 l mol–1 . t1/ 2 Independent of initial concentration. of moles of each reactant decomposed at time t = x. 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. Dependent on concentration.PM5 111 . sec–1 k Independent of concentration. When. 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. a=b=c the rate equation becomes.

the rate of the reaction is not dependent on the concentration of the reactant or. C-8∴N-ENGCHE∴ECH5-1. (ii) k is dependent on the unit of concentration. 1 2 H a . .. rate of the reaction is proportional to the zero power of the concentration of the reactant i. 2 1 FG 1 IJ 1 3 2 k= . in other words. the time required for the completion of the same fraction of the change is inversely proportional to the square of the initial concentration. x = 0 1 1 1 . 1 1 ..e. (iii) Unit of k is mole–1 sec–1. 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.PM5 112 .e. 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 . 2 = . Characteristics of a Third Order Reaction 1 (i) Where x = a. = kt + z (Integration constant) 2 (a – x) 2 When t = 0. 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 . Examples of Third Order Reaction (i) 2NO + O2 → 2NO2 (ii) 2NO + Cl2 → 2 NOCl (iii) SnCl2 + 2FeCl3 → SnCl4 + 2FeCl2 Zero Order Reactions There are certain reactions where rate of reaction does not diminish with time i. 2 t 2 a2 k 2 a 2 k a 1 ∴ t∝ 2 a So.

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

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

so the order can be determined.. 1/a2 gives a straight line. (iv) Graphical method If we plot ‘time’ vs ‘a function of concentration’. i. If t1/2 remains constant the reaction is of the first order. the rate equations for the two experiments will be dc R1 = – 1 = kc1n. (iii) Van’t Hoff’s differential method Let. If the plot t1/2 vs. A Amount decomposed (x) Rate of reaction (dx/dt) dx C .e. if t1/2 varies inversely as the initial concentration the reaction is of the second order.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. plot of t1/2 vs. the reaction is of third order. For the second experiment the initial concentration = c2.693/k (fixed) Second order = 1/(ak) Third order = 1/(a2k′) In separate sets of experiments if different concentrations are taken and t1/2 are measured the order can easily be determined. we can get the order of a reaction. If a plot of 1/c vs ‘t’ gives a straight line the reaction is of second order and if the plot of 1/c2 vs ‘t’ gives a straight line the reaction is of third order (Fig.1 (a) and (b)). For. By plotting log c vs t if a straight line is obtained the reaction is of first order. 5. 1/a will give a straight line. dt dc2 R2 = – = kc2n. So. the first experiment the initial concentration = c1. 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. the order of a reaction be = n.

Slop = tan .

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

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

the products obtained change to a third product. 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 . CH2 . COOH CH2 + H2O k2 (Hydroxy butaric acid) CH2CH2 (Lactone) Rate equation for the first reaction is: dx = k1(a – x)(b – x) – k2 x2. These types of reactions are known as consecutive reactions. 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. which can be measured and that determines the order of the reaction.REACTION DYNAMICS/CHEMICAL KINETICS 117 OCO k1 CH2OH . COOC2 H5 k1 CH 2 COOC2 H 5  + NaOH →  + C2 H 5 OH CH 2 . CH2 .PM5 117 . Period of induction Sometimes it is seen that even though the proper conditions for the reaction are maintained the reaction does not start. After some time the reaction starts and proceeds as usual with normal speed. This period of static state of reaction is known as period of induction. (c) Consecutive reaction: In many reactions. the first proceeds very slow. 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. As for example—period of induction is noted during the reaction of H2 and Cl2 in the presence C-8∴N-ENGCHE∴ECH5-1.

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

Highlights: • Temperature coefficient of a chemical reaction is defined as the ratio of two rate constants of the reaction at two temperatures differing by 10°.3 C-8∴N-ENGCHE∴ECH5-1. the molecules should be raised to a state of sufficient energy. − k = Ae a where.303R T1 T2 MN PQ So. which is known as energy of activation (Ea).PM5 119 .REACTION DYNAMICS/CHEMICAL KINETICS 119 or log k1 =– E 1 – 1 LM OP k2 2. which take part in a chemical reaction should get activated by gaining a minimum definite amount of energy. For every reaction. If E for a reaction is known. Energy of Activation (Ea) of a Reaction: its Significance The molecules of reactants. k25° Temperature co-efficient = (usually) k35° 1 • Plot of ln k vs. 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. 5. otherwise the reaction will not be Ea Potential energy A+B H C+D A+B C+D Progress of reaction Fig. Arrhenius equation describes how the rate constant for a reaction varies with temperature and makes it possible to determine the activation energy for the reaction. if we can determine the two rate constants k1 and k2 we can find out the value of E from the above equation. • The exponential form of the above equation is known as Arrhenius equation E /RT . k = Rate constant Ea = Energy of activation R = Gas constant T = Absolute temperature A = Another constant known as frequency factor. we can determine the value of k2 when k1 is known.

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

1 at t = 50.e.1 at t = 30. Decomposition of H2O2 Time 0 5 10 20 30 50 Time value (KMnO4 in cc) 46. k = ln = 0. ln t a– x Here.1 1 46. So.1 29.1 at t = 10.3 5.044 min–1.0427 min–1 20 19.1 k= ..8 1 46. 5. SOLVED EXAMPLES Example 1. a = 46. 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. For a Ist order reaction 1 a k= . k = ln = 0.1 Now. In an experiment. x.1 at t = 20. Determine from the following data the value of k and establish that the decomposition is of the Ist order.0 C-8∴N-ENGCHE∴ECH5-1.8 19.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. The titre values will give the change in concentration of H2O2 i. ln = 0. of properly oriented molecules per unit volume per unit time] × fraction of molecules equal to or greater than threshold energy. k = ln = 0.0436 min–1 10 29.0434 min–1 5 37. 250 cc of H2O2 solution of strength 2 (N) is taken. k = ln = 0.1 37.4 Rate of a reaction = [No. 50 5.044 min–1 30 12.0 Sol.6 1 46.PM5 121 .3 1 46. putting t=5 1 46.6 12.

14 k= log = 0. r0 – rα = 24.43 k= log = 0.74 Show that the reaction is of the Ist order.7 + 15 – 10. respectively. 27. 2 ml of aliquot (reaction mixture) was withdrawn at different intervals and titrated against a standard alkali.83 2.e.14 1 34.00316 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 7.09 + 10.83 k= log = 0.71 C-8∴N-ENGCHE∴ECH5-2. Sol.79 119 15.20 26.79 Time Vα – Vt k 2. rotation after time ‘t’ and rotation after infinite time where the reaction is assumed to be completed.18 32.74 k= log = 0.303 22.00395 min–1 75 17.05 25. Example 3.79 = 34.83 27.83 1 r – rα Time rt – rα.83 18 28.60 29.24 = 22.e.14 k= log = 0.00519 min–1 18 28.303 22.18 18 27. k = ln 0 t rt – rα 1 34.303 22. a = r0 – rα (a – x) = rt – rα where r0. of alkali used: 19.32 42.14 1 34.05 α Rotation (degrees) + 24. Example 2.03 From the above data show that the hydrolysis is of the Ist order.09 + 21.18 32.122 ENGINEERING CHEMISTRY Since the ‘k’ values are fairly constant by putting the data in the Ist order-rate equation the reaction i..71 k= log = 0. decomposition of H2O2 is of the Ist order.79 183 12.00485 min–1. 50 cc of this solution and 50 cc of (N) HCl is mixed at constant temperature.00321 min–1 119 15. the hydrolysis of methyl acetate is of the Ist order. The data are as follows: Time ( in minutes): 0 75 119 183 α Vol.05 25. A 20% sugar solution is taken.PM5 122 ..5(N) HCl kept at a temperature of 25°C.00486 min–1 7. rt and rα are initial rotation. after a time t and after an infinite time.79 75 17.24 24.03 – 19. Sol. The mixture is poured in a polarimeter tube. Vα – Vo = 42.43 2. Here a = Vα – Vo a – x = Vα – Vt where Vo.79 Since. Vt and Vα are the volumes of alkali initially. 1 cc methyl acetate was added to a flask containing 20 ml 0.83 7. The optical rotation of this solution is measured at regular intervals and the final reading is taken after 24 hrs. the k-values are fairly constant by putting the data in the Ist order rate equation i.4 + 17. Here.

000433 20 C-8∴N-ENGCHE∴ECH5-2. 0. Half-life for a first order reaction is 17 mins. Example 4. Calculate the time for 80% disintegration.e. k 25 0. A Ist order reaction is 25% completed in 30 mins. Time of 50% reaction.693 ∴ k= year–1 = 0. Calculate the rate constant and time for 75% completion of the reaction.303 100 2.303 a k= log t a–x Here a = 100 % (a – x) = 100 – 80 = 20 2.303 ∴ t= log = log 4 = 34 minutes . Sol. the hydrolysis of methylacetate is of the Ist order.693 ∴ 1600 = k 0. a = 100% a – x = (100 – 75)% = 25% 2. 0.303 a and k= .e. We know t1/2 = k Here.0095 min–1 30 75 0.693 ∴ t1/2 = = 72.693 Sol. The half-life for radium is 1600 years. 0.17 yrs.9 minutes. 0.000433 year–1 1600 2. Determine the time of 50% completion of the reaction.. Radioactive disintegration is of the Ist order 0.0407 Example 6. i.693 ∴ t1/2 = k 0.REACTION DYNAMICS/CHEMICAL KINETICS 123 Since the ‘k’ values are fairly constant by putting the data in the Ist order rate equation i.693 Sol. 0. t1/2 = 17 mins. t1/2 to be determined for Ist order reaction t1/2 is k 2.0407 min–1 17 Here.303 100 ∴ k= log t 25 2.. log t a– x Here.303 100 k= log = 0.303 100 t= log = 37. t = 30 min a = 100% a = (100 – 25)% = 75% 2.693 ∴ k= min–1 = 0.PM5 123 .0095 Example 5.

24 6. T a–x x k 1 5.c.41 12.32 3. the hydrolysis of ethylacetate by NaOH is of the 2nd order. Sol.0069 conc–1 sec–1 16 × 25 4.59 k= × = 0.41 Since the k values are fairly constant by putting in the 2nd order rate equation i.32 11.68 k= × = 0. So the concentration of A at time t is (a – x).e.32 1 12. t OP N (n – 1) ( a – x) n–1 a Q C-8∴N-ENGCHE∴ECH5-2.007 conc–1 sec–1 16 × 5 10.76 5 10.0067 conc–1 sec–1 16 × 15 6. The following is the data for the hydrolysis of ethyl acetate by NaOH solution.76 k= × = 0. Time (in minute) 0 5 15 25 35 Vol.PM5 124 .0066 conc–1 sec–1 16 × 35 3..13 1 11.87 15 6.24 5.59 35 3. An aliquot (25 cm) of the reaction mixture was titrated against a standard acid at regular time intervals. Sol.x=0 1 LM 1 1 − n− 1 = k .87 k= × = 0. The 2nd order rate equation is 1 x k= at (a – x) Here a = 16 c. – 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. Example 8.13 4.24 1 9.13 9.41 Show that the reaction is of the 2nd order. The rate equation is – d[ A ] = k . Deduce the rate constant and t1/ 2 for nth order reaction. of acid (a – x) 16 10. Let the reaction be nA → Products.68 25 4. [A]n dt Let a be the initial concentration and x be the concentration which has reacted in the time ‘t’.124 ENGINEERING CHEMISTRY Example 7.

5 to 1 mol l–1. the time of half completion for a reaction is found to change from 50 sec.2 × 10–3 mol–1 litre min–1. t1/2’s are related to initial concentrations as T1 a FG IJ n–1 T2 = 2 a1 H K Here. 60 × 5. Calculate the time taken for the concentration to be reduced to 20% of the initial value. where the initial concentration of the reactants is the same half of the reactants are consumed in 10 mins. In a 2nd order reaction. Example 9.PM5 125 . For a 2nd order reaction x k= at(a – x) Here. t = 60 mins. x = a/2 k = 5.2 × 10 –3 Example 10. a . to 25 sec. When the initial concentration is changed from 0.2 × 10–3 mol–1 litre min–1 a/2 1 ∴ 5.5 H K or 2 = 2n–1 ∴ n–1=1 or n=2 C-8∴N-ENGCHE∴ECH5-2. what is the initial concentration of the reactants? Sol. 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)–1.2 mol litre–1. If the specific reaction rate is 5. T2 = 25 sec. T1 = 50 sec. Sol.5 mol l–1 a2 = 1 mol l–1 50 1 FG IJ n– 1 ∴ 25 = 0.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 t1/2.2 × 10–3 = = 60 . a / 2 60a 1 a= = 3. a1 = 0.

half-life period. the initial concentration of reactants is 0.8 × 25 t= = = 200 sec.2 Example 11. For a unimolecular reaction 2.1 mol l–1 x = 0.1 = 0.04 l mol–1 sec–1 at1/2 0.625 Example 12.303 × 0.PM5 126 .303 a k= log 1 a–x Here. a = 100 a – x = (100 – 1) = 99 2.08 mol l–1 For the second order reaction. The reaction is found to be 20% complete in 40 minutes. Sol.0625 x′ = 0.303 160 k= log 60 a– x 2. 1 1 1 ∴ k= = = l mol–1 sec–1 = .1 mol l–1.2 × 0. a – x = (0. time required to complete 75% of the reaction.075 mol l–1.08 = 0. Here. ak(a – x′ ) 0. Calculate the rate constant.1 × 40 × 0.1 × 0. calculate how much would remain undecomposed at the completion of the first hour.2 a = 0. x 0.0625 × 0.01 = log 60 a–x C-8∴N-ENGCHE∴ECH5-2.126 ENGINEERING CHEMISTRY So.1 – 0.5 × 50 25 k 0. Sol.0625 mol–1.303 100 or 0.0625 l mol–1 min–1 1 k= at1/2 1 1 ∴ t1/2 = = = 160 mins.0044 min–1 = 0. In a 2nd order reaction.01 min–1 when t = 1 hr = 60 mins 2. the reaction is of the 2nd order. k = 0.1 × 0.303 100 ∴ k= log 1 99 = 2. ak 0.02 mol l–1 t = 40 min. a = 0. ak(a – x) 0.2)mol l–1 = 0.025 mol l–1 x′ 0.02 k= = at(a – x) 0.075 ∴ t′ = = = 480 mins.5 × 0.75a = 0. t = ? (a – x′) = 0. If one percent decomposes in the first minute in a unimolecular reaction.

2605 = 2 – 0. 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.25a = 2. At the end of one hour A is 75% reacted.7395 ∴ (a – x) = Antilog 1. the reaction will be. Example 13. Let.75a 0.303 a 1.2605 = 1. If k1 = k2 = k3 for three reactions being respectively of first.3865 × 2 a ∴ log = = 1. k3 = mole–2 l2 t–1 = mole–2 106 ml2 t–1 or 10–6 k3 = mole–2 ml2 t–1 So.303 a − x′ a 100 ∴ (a – x′) = = = 12.3865 = log [where x′ = amount reacted] 2 a – x′ a 1. A certain substance A is mixed with equal moles of a substance B. Example 14. second and third orders when concentration is expressed in mole l–1. For nth order reaction.REACTION DYNAMICS/CHEMICAL KINETICS 127 60 × 0.303 log 4 = 1.3865 hr–1. k1 = t–1 (k1 will remain same) For second order reaction.7395 = 54.PM5 127 .5% 16 16 C-8∴N-ENGCHE∴ECH5-2.303 a– x or log (a – x) = log 100 – 0.204 = 16 a – x′ 2.89.01 100 or = log = log 100 – log (a – x) 2.89 ∴ % undecomposed = 54. x = 0.303 a a (i) When first order in A=K= log = 2. 2. what will be the above relation if the concentration unit is mol m–1? Sol.75a 2. 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. k1 = 10–3 k2 = 10–6 k3. when time t′ = 2 hrs. (ii) first order in A and first order in B? Sol.204 ∴ = Antilog 1.303 log 1 a – 0. 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. initial concentration = [A] = [B] = a t = 1 hrs.

respectively for a first order reaction. mole–1 ∴ log 162 × 10 –5 = Ea 303 – 273LM OP 2.128 ENGINEERING CHEMISTRY So.t.. The specific reaction rates of a chemical reaction at 273 K and 303 K are respectively 2. 100 ≈ 14.PM5 128 . k2 = Ea T2 – T1LM OP log k1 2.r. The exponential form of Arrhenius equation is.303 × 1.e.25a At t′ = 2 hrs. Example 16.45 × 10–5 and 162 × 10–5. k = t1/ 2 Here. Calculate the activation energy of this reaction. 968 cal mole–1. T1 = 273 K T2 = 303 K k1 = 2. x 0. % of A and B left unreacted = a – H 7 a K 6 i. Calculate the temperature at which its half-life is 10 mins. The values of Arrhenius factor and activation energy are 4 × 1013 s–1 and 98.6 kJ mol–1. 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.45 × 10–5 k2 = 162 × 10–5 R = 1. − Ea / RT k = Ac where A is called the Arrhenius factor and Ea is the energy of activation.5% % of B left unreacted = 100% (Q order = 0 w.45 × 10 –5 2.987 273 × 303 N Q Ea 30 1. the over all order of the reaction is 2. 0. C-8∴N-ENGCHE∴ECH5-2.987 Cal K–1 .3. % of A left unreacted = 12. Sol. B) (ii) In the second case. 100 –.303 × 1. 7 Example 15.75a ∴ k= = = 3a–1 hr–1 (when t = 1 hr) at(a – x) a × 1 × 0. Rate constants at two temperatures are given by Arrhenius equation.303R T1T2 N Q Here.8203 = × 2.693 As the reaction is first order. t1/2 = 10 mins = 600 sec. Sol.987 273 × 303 ∴ Ea = 22.

155 × 10–3 sec–1 From Arrhenius equation we have. A = 4 × 1013 sec–1 k = 1.555 = 98600 = 373 K.316 × 16.316 × G –3 98600 = K 2.314 × 1073 × 1148 K2 ∴ = Antilog 0.39 × 5 × 10–3 l mol–1 s–1 = 7. What is the value of the rate constant at 875°C? Sol.115 × 10–3 sec–1. mol–1.5 × 10 4 (1148 – 1073) ∴ log = = 0.0 × 10–3 l mol–1 s–1. Example 17.303 × 8.316 J mol–1 K–1.303 × 8. 98600 ∴ T= F 4 × 10 I 3 K H 1.303 × 8. T1 = (800 + 273) = 1073 R = 8. R = 8. K1 = 5 × 10–3 l mol–1 s–1. then photons of frequency E 2 – E1 1→2= are spontaneously emitted as molecules drop from the state 2 to the state 1.600 J. the populations be n 2 and n1 and energies of the two states be E 2 and E 1.39 K1 ∴ K2 = 1. A second order reaction.115 × 10 JK 2. 2.693 ∴ k= 600 = 1. Let. whose rate constant at 800°C was found to be 5.303 log 10 (k/A) = – Ea/RT Ea or T= 2. When E2 > E1.5 × 104 J mol–1 T2 = (875 – 273) = 1148 K.303 RT1T2 Here.Ea = 98.314 J mol–1 K–1 K2 4. K2 E (T – T1 ) log = a 1 K 1 2. h C-8∴N-ENGCHE∴ECH5-2. The use of lasers has initiated new types of spectroscopic experiments and has improved the precision of spectroscopic experiments.303R log( A /K) Here. let us state we have a population inversion with n2 > n1.0 × 10–3 l mol–1 s–1 has an activation energy of 45 kJ mol–1.1431 = 1.PM5 129 . To achieve a laser action a Population inversion should be generated in the system.REACTION DYNAMICS/CHEMICAL KINETICS 129 0. We have. Lasers in Chemistry Laser means “light amplification by stimulated emission of radiation”.1431 K 1 2. Ea = 4.

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

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

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

15. Ans. What will be the time for the change from a/2 to a/4? C-8∴N-ENGCHE∴ECH5-2.REACTION DYNAMICS/CHEMICAL KINETICS 133 Q. Integrated form for a first order rate equation is: c = c0e–kt The plot of concentration vs. Q. x = a. For a second order reaction one hour is needed for a change of concentration a to a/2. Is a first order or a second order reaction completed? Ans. For a first order reaction one hour is needed for a change of concentration c to c/2. 0. What is the time for the change from c/2 to c/4? Ans. it is known as first order reaction. One hour. 12. concentration will be zero at infinite time. Rate of growth of bacterial culture. dt Q. t1/2 for a first order reaction = . a second order reaction is also an incomplete reaction. For a reaction: A + B → Products Rate = k . What is a second order reaction? Ans. 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. 14.693 Ans. [A] = rate equation for a first order reaction. ak So. Hence. half-life in this case is inversely proportional to the initial concentration. – dA ∴ Rate = = k . 10. For a second order reaction the integrated form of the rate equation is: 1 x k= t a(a – x) when. time will be asymptotic plot. A second order reaction is a reaction. Give examples of first order reaction. If the rate of a chemical reaction varies to the first power of concentration of the single reactant. Q. t = ∞ So. So. Q. k 1 t1/ 2 for a second order reaction = . 16.PM5 133 . 2. [A] [B] or Rate = k . it is a constant quantity. So the reaction is not completed. Q. [A]2 = Rate equation for second order reaction. 11. Comment on half-life of a first order and a second order reaction. Q. 1. A → Products. 13. What is a first order reaction? Ans. Radioactive disintegration process.

Activation energy of a reaction is defined as the extra energy over and above the average potential energy of the reactants. So. Q. It is denoted by ET. EA = ET – ER Q. When concentration changes from a to a/2. c = 0. 21. 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.PM5 134 . 5. 5. t1/′ 2 ak ak / 2 2 Q.134 ENGINEERING CHEMISTRY 1 Ans. 18. What is threshold energy? Ans. 20.6). What is the special characteristic of a zero order reaction? Ans. the rate is not at all dependent on the concentration of the reactants. What is activation energy? Ans. where c0 = initial concentration t c = concentration at time t. c0 when. It is denoted by EA. Q. t1/2 = . 17.6 C-8∴N-ENGCHE∴ECH5-2. t1/2 = a/ 2 . k t1/′ 2 1 1 1 ∴ = = or t 1/2 ′ = 2 . the reaction will be completed and for a zero order reaction. 19.1 = 2 hrs. which must be supplied to the reactants to enable them to cross-over the energy barrier between the reactants and products. What is transition state theory? Ans. t = ka which is a finite quantity. Q. ak 1 When concentration changes from a/2 to a/4. Chemical reactions occur through an intermediate stage known as transition state or activated complex (Fig. How are the activation and threshold energies related? Ans. t1/2 = 2. 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= .

Explain the terms ‘rate constant’. 13. Derive the rate constant for a 1st order reaction and show that it is an incomplete reaction. 9. 12.0173 min–1] 15. State the molecularity and order of the above reaction.PM5 135 . Describe an accurate method for determining order of a reaction with three reactants. 6. The hydrolysis of ethyl nitrobenzoate by aqueous NaOH was followed at 25 °C. From the given data.c. Distinguish between rate and specific reaction rate of a chemical reaction. 22. Calculate the rate constant and the time taken to complete 80% of the reaction. Briefly develop the concept of activation energy and temperature. Discuss the various factors affecting the rate of a reaction. Half-time change for a 1st order reaction is 40 mins.c. 3. During the hydrolysis of ethyl acetate by NaOH using equivalent concentration. Discuss any two methods of determination of order. The study of chemical kinetics helps to determine the mechanism of a chemical reaction. upon impact.REACTION DYNAMICS/CHEMICAL KINETICS 135 Particles in collision react only if. How does rate of a reaction vary with temperature? What is Arrhenius equation? 11. 10.85 mins] 16. The volumes of acid used by unchanged NaOH are given below: Time (minute) 0 5 15 25 35 Vol. Derive an expression for rate constant of zero order reaction and discuss about its (i) half-life.41 Show that the reaction is of the 2nd order.32 3. For. 5 Br– + BrO3– + 6H+ → 3Br2 + 3H 2O Rate = Constant × [Br–] [BrO–3] [H+]2. What is the rate constant of the reaction at the same temperature? [ 0. show that the reaction is of the 2nd order. 8. 5. C-8∴N-ENGCHE∴ECH5-2. of the reaction mixture was titrated at regular intervals against standard acid. 2. EXERCISES 1.13 4. The half-life period of a 1st order reaction is 15 mins. ‘order of a reaction’ and ‘molecularity of a reaction’. they attain the energy of the transition state. Classify the statement: “decomposition of H2O2 is of the 1st order”. What is the utility of the study of chemical kinetics? Ans. 4. of acid (c. What is meant by order of a reaction? Derive an expression for the velocity coefficient of a second order reaction. ∆H > 0 endothermic reaction (Curve I) ∆H < 0 exothermic reaction (Curve II) Q. (ii) completion time.) 16 10. 25 c. Indicate how the specific reaction rate of a first order reaction can be evaluated.24 6. the reactants A and B are at equal concentrations. by titration of the hydroxide against standard acid at different stages in reaction. [34. Explain the meaning of pseudo unimolecular reaction. 7. Derive the rate con- stant expression of a 2nd order reaction: k A + B → c. 14. 17. they attain impact.

22.c.41 Show that reaction is of 2nd order. 18. 050 Cal mol–1] 23. 3000 seconds] 21. [Ans. follow first order kinetics.) 16.25 × 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. is 20%.044 atm. calculate the rate of the reaction (ii) at 300 K. At the same temperature B decomposes twice as fast as A.4 kJ mol–1] C-8∴N-ENGCHE∴ECH5-2.0 10. (ii) B → Products. The decomposition of Cl2O7 at 400 K in the gas-phase to Cl2 and O2 is a 1st order reaction. using equal concentration of ester and NaOH: Time (minutes): 0 5 15 25 35 Vol. is completed in 500 seconds. A 2nd order reaction. When log K (velocity constant for a reaction) was plotted against 1/t. If the energy of activation for the reaction (ii) is half that of reaction (i).462 × 10–19] 25. Calculate the fraction of molecules of reactants having energy equal to or greater than activation energy.52 1. Calculate the activation energy of the reaction. The activation energy for the reaction 2HI (g) H2 (g) + I2 (g) is 209.5 × 10–4 sec–1 at 318 K. the slope of the line was found to be – 5400 K. (ii) Calculate the pressure of Cl2O7 after 100 sec. (i) After 55 seconds at 400 K the pressure of Cl2O7 falls from 0. Calculate the energy of activation for this reaction (R = 8. The half-life for this reaction at 310 K is 30 minutes. 0. Calculate the rate constant. 103. [Ans. How long will it take to go to 60% completion? [Ans.92 1 Find the reaction is of which order. The following data were obtained in the hydrolysis of ethyl acetate. A 1st order reaction has rate constant equal to 1.PM5 136 .5 kJ mol–1at 581 K.24 6.0332 atm] 20. 19. of HCl (c. [Ans.13 4.0327 min–1] 24. 3.314 JK–1 mol–1) [Ans.136 ENGINEERING CHEMISTRY 18.236 × 10–3 sec–1.062 to 0. The half-life periods for the decomposition of ammonia (catalytically) are as follows : Pressure in mm 50 100 200 Half-life period in hrs. 6.32 3. of decomposition at this temperature. [Ans. Two reactions: (i) A → Products. 1. 0. where a = b.

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. So the proper definition of a catalyst will be—a catalyst is a substance which alters the rate of a chemical reaction without involving itself in the reaction. (i) Positive catalysis or catalysis. Berzelius named the phenomenon of acceleration of the reaction as catalysis and the substance influencing the reaction. The catalyst which retards the rate of a reaction is called a negative catalyst and the phenomenon is negative catalysis. which was not at all related to the reactants. not related to the reactants. DEFINITION A catalyst is a substance. A catalyst which increases the rate of a reaction is called a positive catalyst or a catalyst and the phenomenon is catalysis. 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 . (ii) Negative catalysis. The phenomenon of influencing a reaction by a foreign substance is known as catalysis or ‘a catalyst is a substance which enhances the rate of reaction approaching equilibrium but without involving itself in the process’. a catalyst. it can be said that catalysts smoothen the passage towards equilibrium. influences the velocity of the reaction by not involving itself in the reaction. A catalyst may also retard a chemical reaction. Since all reactions tend to attain equilibrium.

so if a catalyst changes k1. (v) Catalytic action is universal.PM5 138 . the point of equilibrium is independent of the catalyst. So it has no influence on the standard free energy change ∆G° i. happen”. (iv) Catalyst has no influence on the point of equilibrium. it never increases the equilibrium yield. but does not happen. 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. Those catalysts are termed Enzymes or Low catalysts.e. • So “a catalyst is a substance that makes a chemical reaction that could happen.. it also accelerates the backward reaction. 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.e.138 ENGINEERING CHEMISTRY Characteristics of a Catalyst (i) A small amount is effective. (ii) Catalyst remains unaltered at the end of the reaction. Highlights: • Catalyst undergoes no chemical change in a reaction.. it will also change k2 in the same k2 proportion so that their ratio K remains unchanged. • This means if a catalyst accelerates the forward reaction. Homogeneous Catalysis In this type of catalytic reactions. k1 • Since K = . in one single phase. This type of catalytic reactions occur in gas or solution phase i. • So. the catalyst remains in the same phase with the reactants and is evenly distributed throughout the reaction phase. • Catalyst only helps to attain the equilibrium rapidly. • Catalyst merely lowers the energy barrier (Ea) of a reaction. on K. (iii) Catalyst hastens the attainment of equilibrium.

1 Progress of reaction. 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. The minimum amount of energy required to attain transition state is called energy of activation. usually a finely divided solid either as such or supported on an inert solid such as asbestos or gas (fluidised bed).PM5 139 . Important Applications of Catalysts Reactions Examples Catalyst used (i) Dehydration C2H5OH → C2H4 + H2O Alumina. Ea. Catalyst lowers the energy of activation (Ea) of a reaction. Pt.) C-8\N-ENGCHE\ECH6-1.CATALYST 139 Heterogeneous Catalysis In this type of catalytic reactions. 6. 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. This type of catalysis has a great technical importance. 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. This is usually termed contact catalysis. Pd (Contd. the catalyst forms a separate phase.

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

δ+ δ− RCl + AlCl3 → R . the C-8\N-ENGCHE\ECH6-1. (v) A catalyst cannot initiate a reaction. The following examples can be given in support of the above theory: (a) NO2 acts as an oxygen carrier in Lead Chamber process. Mechanism of Catalytic Reactions The following two theories have been widely accepted: (i) Intermediate compound formation theory (ii) Adsorption theory.. 6. (vii) Change of temperature can alter the rate of a catalytic reaction as for a non- catalytic reaction. (ii) Adsorption theory (Heterogeneous catalysis) This theory mainly explains the mechanism of a catalytic reaction between two gases catalysed by a solid.. 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.CATALYST 141 (iv) A catalyst is specific in its action. anhydrous AlCl3 forms an intermediate compound with RCl and finally generates R+ for the reaction.2 Effect of catalyst on time to attain equilibrium. (c) In Friedel–Craft reaction. (vi) A catalyst does not change the position of equilibrium but can only shorten the time required to attain the equilibrium. Here. Here. AlCl 4 R+ + AlCl4– .. The adsorption theory is compared to the intermediate compound formation theory. the catalyst works by adsorption of the gas molecule on its surface.PM5 141 . H2SO4 to ether. A+B Reaction: A + B C+D Catalytic reaction Rate of reaction Equilibrium Without use of a catalyst C+D Time Fig.. (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 .

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

substrate i. • Enzymes do not act in cold conditions. Mention the effect of a catalyst on activation energy (Ea) of a reaction. • Enzymes lose their activity at higher temperatures. What is the effect of a catalyst on free energy change of a reaction? Ans. Ans. A catalyst lowers the activation energy of a reaction. 1. What is the effect of a catalyst on the equilibrium constant of a reaction? Ans. C-8\N-ENGCHE\ECH6-1. A catalyst does not alter the equilibrium constant of a reaction. • Enzymatic reactions are generally dependent on the concentrations of enzymes.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.. Q. 5. 3. 2 2 Highlights: • Enzymatic reactions generally take place at 35°-45°C. Q. 2. it only shortens the time of attaining the equilibrium.. • Enzymatic activity is pH dependent. A catalyst cannot change the free energy change of a reaction. 4. Q. • For its full activity. A catalyst is a substance that speeds up chemical reactions without changing itself. Draw a distribution curve showing how the proportion of molecules able to react increases when a catalyst lowers the activation energy. enzyme needs help of another factor (compound) known as co-factor or co-enzyme.e. • Enzymatic reactions not at all depend on the concentration of the reactant i. SHORT QUESTIONS AND ANSWERS Q. enzymatic reactions are zero order reactions.PM5 143 . What is a catalyst? Ans.e. Q.

Q. 8. the rate of reaction increases. are used as antioxidants for prolonging the life of rubber. 6. What is autocatalysis? Ans.5 Give experimental evidence that different catalyst has no influence on the yield of a reaction.6 Ans. CH3COOH is formed acts as catalyst. It has been observed that at the same temperature the yield of SO3 is the same. etc. The rate is maximum when the reaction is complete (Fig. 6.PM5 144 . 9. Ans. Why is the hydrolysis of ethyl acetate autocatalytic? Ans. Q.144 ENGINEERING CHEMISTRY Activation energy with kinetic energy (E) with a catalyst Number of molecules Activation energy without a catalyst Kinetic energy (E) Fig. Widest technical use of negative catalyst is TEL as ‘antiknock’ compound in motor fuel. CH3COOC2H5 + H2O → CH 3COOH + C2H5OH catalyst C-8\N-ENGCHE\ECH6-1..6). Q. Fe2O3 or V2O5 . In autocatalysis reaction as the catalytic product is gradually formed. When one of the products of a reaction itself acts as a catalyst for that reaction the phenomenon is called autocatalysis. As traces of moisture initiate the reaction. 7. 6. Aromatic amines. 6. lentoxy anisole are added to retard the rancidity of oil. n-propyl gallate. whether the catalyst used be Pt. An important type of negative catalyst is termed anti-oxidants. Completion of reaction Rate of reaction Sigmoid curve Time Fig. Draw a graph for an autocatalytic reaction. Ans. thiourea. Q. Give important uses of negative catalysts of technical importance.

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

acts as a homogeneous catalyst for the hydrogenation of alkenes and alkynes. 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. mostly alkenes is an important industrial reaction. 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). Structure and bonding in organometallic complexes. The stage IV is very very significant in the overall hydrogenation process as in this stage. 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. Organometallic chemists made the process very popular. Homogeneous systems are used for pharmaceutical industries. so it can readily accept π electrons from the alkene to give (IV). let us cite the following examples: Compounds Central metal Electronic confi. The hydrogenations of alkenes and alkynes have been studied extensively. The 14-electron species (II) is formed by dissociation of phosphene ligand from (I). guration of the donated by electrons in tion number central metal of ligands (n – 1) d. the 16-and 18-electrons rule: The role of metals in catalytic cycles during some chemical reactions: • Hydrogenation using (Ph3P)3RhCl The hydrogenation of unsaturated organic compounds i.e. of electrons Total no. It is dissociated (only 5%) into 14 electron species in pure solvents. The structure (II) is seen to possess a vacant coordination site shown by a square. which is generally known as Willkinson’s catalyst.. (Ph3P)3 RhCl. which acts heterogeneously. (V) undergoes reductive elimination to release the alkane and regenerate the 14-electron species. though it is a very reactive compound. the substrates alkene. C-8\N-ENGCHE\ECH6-1. of atom with oxida. thus: (Ph3P)3 RhCl (Ph3P)2RhCl + PPh3 The species (Ph3P)2 RhCl is of low coordinating power. No. The action of the Willkinson’s catalyst is represented by the following cycle. Almost all large scale hydrogenation processes are carried out using Raney Ni as catalyst. hydrogen are now bonded to the same metal atom.146 ENGINEERING CHEMISTRY To illustrate. Next step is the rearrangement of the coordination site to give V.PM5 146 . The catalyst is not able to reduce other organic functional groups.

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

8 EXERCISES 1. although it shortens the time required to establish the equilibrium. 6. 8. Give a brief account of the various theories of the mechanism of catalysis. 9. 2. Write notes on: (i) Adsorption theory of catalysis.”—explain. (ii) positive catalysis. (ii) Enzyme catalysis.PM5 148 . What are catalyst poisons and promoters? 4. 5. C-8\N-ENGCHE\ECH6-1. Discuss a few important catalytic processes. What will be a more effective catalyst—platinum as a lump or finely divided platinum? Give reason. (iii) negative catalysis. Define with illustrations: (i) catalysis. “A catalyst doesn’t affect the final state of equilibrium.148 ENGINEERING CHEMISTRY The mechanism of hydroformylation using cobalt carbonyl as catalyst is shown in the scheme. 7. 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. How does a catalyst accelerate the speed of a reaction? Explain with proper energy profile dia- gram. 6.

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

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

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

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

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

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

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

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. Elimination reaction. C C X + C C H H A carbocation . 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).S. C C + KOH (alcoholic) C C + KBr + H2O H Elimination of a hydrogen halide from an alkyl halide produces alkene.156 ENGINEERING CHEMISTRY The mechanism of the substitution can be represented as follows: – – OH + C X HO C X HO C+X T. Br Example 1. (a) E1 reaction.

H OH H H    Conc. Fast Step 2. 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.PM5 156 . 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.

The Kekule structure is still the accepted structure for benzene. 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. 7. 2.2). 7. The difference in energy of any of the contributing structures and the hybrid structure is called the resonance energy (Fig. there is resonance.PM5 157 . Despite having three double bonds benzene undergoes substitution reactions more easily than addition reactions. All the C—C bond lengths in benzene is 1. That theory is the concept of resonance.MECHANISM OF ORGANIC REACTIONS 157 This is an example of acid catalysed elimination reaction. So the idea needs to be discussed here: According to Kekule the benzene molecule has following two structures (I) and (II). (c) Only π electrons and non-bonded electrons can be shifted.39 Å instead of 1. 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.34 Å for a C==C bond.54 Å for a single bond and 1. The resonance hybrid structure is more stable than any of the contributing structures. This acceptance is not for the discovery of new facts about benzene but is a result of modification of the structural theory. 1.2). C-8\N-ENGCHE\ECH7-1. Each of these drawn structures contributes to the resonance hybrid (Fig. (I) (II) The structures (I) and (II) cannot satisfactorily explain all the properties of benzene. Benzene is more stable than expected. (b) Position of σ-bonds cannot be changed. 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. 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. 3.

8 Kcal/mole.PM5 158 . the hyperconjugation may be represented as follows: . the odd electron and the bond pair of the C—H bond. two carbons and one hydrogen. C-8\N-ENGCHE\ECH7-1. Hyperconjugation (No bond resonance) The stabilities of tertiary. 6-tribromoaniline does not. In terms of resonance.. (iii) As a resonance hybrid benzene is more stable than either of the contributing resonat- ing structures 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. benzene is more stable by 36 Kcal/mole than expected which is resonance energy of benzene.2 Stability of benzene (Resonance energy).. 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. H H H H H H H H Each of the above no-bond resonance structures appears strange.8 Kcal Cyclohexene + H2 55.8 Kcal/mol but actually it is 49. This type of delocalisation involving σ-orbital is known as hyperconjugation. Victor Meyer attempted to explain these abnormalities by steric hindrance i. help to bind together the three nuclei i. o–groups in 2. For this overlapping. 4. Steric Hindrance Aniline reacts to form anil with benzaldehyde but 2.158 ENGINEERING CHEMISTRY Graphical representation of the idea of resonance from the heats of hydrogen- ation values. That is. 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. Explanation (i) We should expect from the graph that the heat of hydrogenation of cyclohexatriene i.e. Sign of resonance Cyclohexatriene + 3H2 Resonance energy (Resonating structures) 36 Kcal Benzene + 3H2 (Resonance hybrid structure) Potential energy Cyclohexadiene + 2H2 49.8 Kcal (obs) 85..e.e.e.2 Kcal (calc) (obs) (calc) 28. ←→ H • C — C ←→ H  C — C ←→ H  C — C         . (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. benzene to be 85. the three electrones i... H H H H H H H H        H  C  C. 4.e.4 Kcal 57.6 (obs) Cyclohexane Fig. Kekule structures. 7.

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

CH2 . CH3 . CCH2.

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

.

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

.

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

160 ENGINEERING CHEMISTRY Isomerism Different organic compounds having the same molecular formula are known as isomers. CH 2 .CH 2 . Cl (ii) CH3— CH —CH3 1-chloropropane  Cl 2-chloropropane (Contd.PM5 160 . 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. The phenomenon is known as isomerism. 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.CH2 . The isomerism is of two types: (i) Structural isomerism (ii) Stereoisomerism.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 .) C-8\N-ENGCHE\ECH7-1.

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

4(c)]. In the case of cyclohexane the following conformations are common [Fig. Conformations of Cyclohexane Factors influencing the stability of conformations: To go deep into the chemistry i. the —CH3-groups are 60° apart and they are less stable than the anti-form and more stable than the eclipsed form. the eclipsed conformation is least stable due to severe crowding.. And the result can be either destabilisation or stabilisation of the conformation.5°) are accompanied by angle strain.. From the potential energy diagram.e.e.1 Kcal 3. This non- bonded interaction can either be repulsive or attractive.162 ENGINEERING CHEMISTRY 4.4 (b) Potential energy changes during rotation about C2—C3 bond of n-butane. 7.. i. In two Gauche conformations. we see that the anti-conformation of n-butane is more stable (CH3-groups are as apart as possible. HA HA HA HB HB HB Chair Twist Boat Conformer Conformer Conformer Fig. 7. • Any two atoms or groups that are not bonded to each other can interact.PM5 162 . Any deviation from the staggered conformation is accompanied by torsional strain. ethane-like).5 Kcal Potential energy 0. • Any pair of tetrahedral carbon attached to each other tend to have their bonds staggered (i. sp3 hybridised carbon (bond angle 109.e. • Any deviations from the normal. we must take help of conformational analysis.4–6.4 (c) Conformers of cyclohexane. C-8\N-ENGCHE\ECH7-1. 180°). 7. the stability of the cyclic compound and its reactivity.9 Kcal CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 Anti Gauche Eclipsed Gauche Angle of rotation Fig.

7. So the chair cyclohexane is more stable conformer of the cyclohexanes. The half chair form is a most unstable form which lies at energy maximum (see Fig. 7.PM5 163 .4(d)]: Fig. 1.4 (d ) Cyclohexane (chair form) staggered form of ethane.5 Potential energy diagram (conformations of cyclohexane).4 (e) The boat conformation is less stable than the chair conformation at an energy maximum. C-8\N-ENGCHE\ECH7-1. 7. it is thus not a conformer but a transition state between two conformers. The twist form or skew boat form is a conformer lying at energy minimum.3 Kcal Potential energy 11 Kcal 5.5).MECHANISM OF ORGANIC REACTIONS 163 Newman projection formula of chair conformer [Fig. Between the chair form and twist form there are half chair forms with angle strain and torsional strain. 7. For boat cyclohexane the Newman projection formula is as Fig. Cyclohexane (boat form) Eclipsed ethane Fig. 7.4(e). 7. Here the three pairs of tetrahedral carbon of cyclohexane remain in staggered forms.6 Kcal Chair Half Twist Boat Twist form chair form form form Fig. Here the three pairs of tetrahedral carbon of cyclohexane remain in eclipsed forms.

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

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

etc. then the stereocentre is said to have ‘S’ configuration [Fig. There are certain methods of assigning R-S notations to any chiral centre of a molecule. If the path provides a clockwise motion. 4 or a.PM5 166 . • 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. 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.166 ENGINEERING CHEMISTRY Stereoisomers which are not pairs of enantiomers are known as diastereomers. • The four different groups (ligands) attached to each of the stereocentres are found out and given priority 1. When similar groups are attached or the opposite side of the C = C bond. If the path describes a counter clockwise or anticlockwise path. 7.8 (d) Optically inactive isomer (meso form). 7. c. Geometrical Isomerism This type of isomerism arises out of restricted rotation about C = C bond. This type of isomer is known as mesoform. The (R) or (S) designation is written in italics within the parentheses followed by a hyphen before the name of the compound. the configuration is known as trans isomers (E-isomers). The system is often termed as “absolute configuration” assignment as this type of specifying configuration is independent of any reference compound. based on ‘sequence rule’. These are as follows: • The number of stereocentres in the molecule are identified. 7. The geometrical isomerism is also a case of diastereoisomerism [Fig. 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. CH3 H Cl H Cl CH3 Fig. When similar groups are attached to the same side of the molecule. then the stereocentre is designated to have ‘R’ configuration.8 (e) R-S System of Nomenclature R-S system of nomenclature was developed by Cahn. C-8\N-ENGCHE\ECH7-1.9]. Ingold and Prelog to designate the configurations of stereoisomers having chiral centres. 7. the configuration is known as cis-isomers (Z-isomers). Another interesting phenomenon arises among the compounds containing similar chiral carbon atoms [Fig. d. 3. b. such that 1 → 2 → 3 → 4 or a → b → c → d.8(d)]. 2.8(e)]. 7.

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

let us consider the following examples: CHO H   H  C  OH —CHO is considered as  C O   CH 2 OH O Glyceraldehyde Here O.168 ENGINEERING CHEMISTRY • A double or triple-bonded atom X to C is considered to be equivalent to two or three X′s. H of —CHO attains the priority over the O. H. H of —CH2OH group. 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. The —C6H5 group is considered as C . The priority sequence of 1-amino-2-methyl- HC C CH 1-phenyl-propane is —NH2 → C6H5 → C3H7 → H. C-8\N-ENGCHE\ECH7-1.  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.PM5 168 . The complete priority sequence is then —OH → —CHO → —CH2OH → H. O.

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

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

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

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

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

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

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

C-8\N-ENGCHE\ECH7-2. HX X– ROH → R – OH+2 → [ X − δ . the order or reactivity of the alcohols follows the order 3° > 2° > 1°—explain. Developing ion pair gets solvated easily and helps the process ionisation. The solvolysis of (CH3)3 Br becomes 3 × 104 times faster in 50 % ethanol than in ethanol alone. 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. That is. Change of solvent may have marked effect on SN2 reaction.-R.-O + H2 ] → RX + H2O. In SN2 reaction: R R R – – – HO + C Br HO C Br HO C R R R R R R T. The alcohol is first protonated. For a given HX.. there is attack by X– to give RX. Ans. Q.. So. Ans. Because in CH3OH due to hydrogen bonding N–3 is solvated and its nucleophilic activity is reduced. only a slight decrease in reaction rate is observed. Q. the reaction is nucleophilic substitution and the leaving group is H2O. 24. The reaction rate becomes 4.176 ENGINEERING CHEMISTRY As the planar carbocation is formed in rate determining step and the process of formation is slow. Transfer from protic polar solvent to polar nonprotic solvent may change the reaction pathway from SN1 → SN2 by increasing the effectiveness of the nucleophilic. SN1 reaction becomes faster if the solvent polarity increases. Nucleophilicity of X– decreases in order: I– > Br– > Cl–.S. Increase in solvent polarity and ion solvating ability may change reaction pathway from SN2 → SN1. The change of solvent (I) affects the rate of the reaction (II) which may change the mechanistic pathway. Increase in solvent polarity has little effect in SN2 reaction. Discuss the effect of solvent on SN1 and SN2 reactions. 25. Explain. Hence the order of reactivity of HX is HI > HBr > HCl. Whereas in DMF the hydrogen loading is absent and N3– remains unsolvated and powerful nucleophile can attack.5 × 104 fold faster than the reaction CH3 I with N–3 if we change the solvent from CH3OH to HCON(CH3)2 (DMF). The order of reactivity of halogen acids towards an alcohol is— HI > HBr > HCl. always racemisation takes place during SN1 reaction. The back side attack by the nucleophile always leads to inversion of configuration in SN2 reaction. Q.PM5 176 . 23.

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

.

.

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

.

.

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

p-orienting. Justify the pKa values Acid pK a CH3COOH 4.90 ICH2COOH 3.76 FCH2COOH 2. Q. Acidity order with pKa values of the following acids is: Cl Cl Cl   CH COOH (pKa = 0. (ii) o.65) > CH COOH(pKa = 1.86 BrCH2COOH 2. 29. HCOOH is an acid as the anion has resonance stability.86 (CH3)3CCOOH 5. The electron withdrawing substituents with (–I) effect has got marked influence on the acidity of simple aliphatic acids.29) > Cl ← CH2COOH(pKa = 286) Cl Cl Justify. 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. acidity order will be. pKa value decreases. 32. Phenol is (i) acidic.66 ClCH2COOH 2. Justify the pKa values Acid pKa CH3COOH 4.178 ENGINEERING CHEMISTRY – O O + HCOOH + H2O H C H C + H3O O O So. 30. Explain. Ans. 31. As the number of electron withdrawing groups increases acidity increases. So pKa value gradually increases i. : : : : + : + : + : O H O H O H O H O H ! ! : : ! : C-8\N-ENGCHE\ECH7-2. Q.05 O  Ans..76 (CH3)2CHCOOH 4. Q. acidity decreases. The electronegativity order of halogens is: F > Cl > Br > I So.e. F ← CH2COOH > Cl ← CH2COOH > Br – CH2COOH > I-CH2COOH: pKa values are in accordance with the above acidity order.16 Ans.PM5 178 . Q.

*This property common to other groups. The pKa values are in accordance with the above fact. 33. NH3 is basic. 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. CH 3 NH 2 .. o. it is less basic than NH3. : OR . (ii) Due to resonance. Q. the basicity is increased. pKa values of NH3. NH 3 is a Lewis base. 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. CH3  : : : NH3 CH3 NH2 NH CH3  pKa = 9. (CH 3 ) 2 NH are 9.77 Q.62) becomes less basic than NH3. CH3NH2 and PhNH2 are 9.PM5 179 . Do you expect that p-nitroaniline is less basic than aniline? Ans. 35.64 pKa = 10. p-orienting*. 10. So phenol is o-. Justify.. helps electrophilic substitution and are o-. . . So bonding electrons of O—H bond will be pulled strongly towards O-atom making release of H+ easier. 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.. like NH2 .62 respectively. So aniline (pKa = 4. When this donation capacity is increased by any effect. So. This increased electron density activates the benzene ring towards electrophilic substitution SE2.25. the anion formed on the release of H+ by phenol molecule is resonance stabilised. Yes. . Ans. the electron density over ‘N’ atom becomes less than that over NH3. CH3NH2 is more basic. . Benzene having a delocalised π-cloud is susceptible to electrophilic substitution. Justify. 34.and p. The resonating structures of aniline is: + + + : : : NH2 NH2 NH2 NH2 NH2 ! : ! : ! : Example of resonance Due to resonance. The electrophiles can attack at those positions leading to electrophilic substitution.25.e. Q.positions. 10.64 and 4. pK a values for NH 3 . C-8\N-ENGCHE\ECH7-2.and p.positions of the benzene ring of phenol molecule become electron rich. p-orienting. Ans.77 respectively. due to the (+I) effect of the –CH3 group.MECHANISM OF ORGANIC REACTIONS 179 (i) The electronegative atom ‘O’ of phenol gets positively charged due to resonance.. Moreover.62 i.25 pKa = 10. phenol can behave as an acid.64 and 10. it can donate a pair of electrons. But we see that pKa of aniline is 4..

it is known as picric acid. 6-Trinitrophenol (picric acid) is a very strong acid—explain.9 pKa = 1. 6-trinitrophenol exercise pronounced (–I) effect making the phenol molecule total acidic. —NO2 group is m-orienting—explain. 4. Introduction of an —NO2 group in the phenol molecule increases its acidity due to (–I) effect of the —NO2 group. 2.02 Q. Ans. The three —NO2 groups in 2. 37.62 O O – O – O pKa = 0.180 ENGINEERING CHEMISTRY + : : Ph NH2 NH2 NH2  N N pKa = 4. The resonating structures of nitrobenzene are: – + : – + – – + – – + – – + : : : O. 4.98 Q. OH OH O2N NO2 NO2 pKa = 0. 36. That is why. Ans.

N O O .

N.

O O .

N.

O O .

N.

O O.

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

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

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

5-cyclohexatriene is 85. 24. Draw Fischer projection formula of D. Write a short note on nucleophilic addition reaction. What do you mean by 1.PM5 183 . Heat of hydrogenation value of 1. 26. What are the significances of the terms: (i) Resonance hybrid and (ii) Resonance energy. C-8\N-ENGCHE\ECH7-2. . 14. Explain with proper mechanism involved with examples. 25. What do you mean by dehydrohalogenation? Explain with proper mechanism and example. Draw all the Fischer projection formulae of: (i) glyceraldehyde (ii) lactic acid (iii) tartaric acid (iv) 2.and L-glycine (NH2CH 2COOH). Draw the resonance structures of: (i) phenate ion (ii) acetate ion (iii) chlorobenzene (iv) butadiene. 16.B → AB 12. Name them as per R—S nomenclature. 2-shift. Name them as per R. 23. Compare the basicity among the following: NH2 NMe2 NMe2 Me Me .8 kcal/mole—explain. Write a short note on hyperconjugation. Draw the energy profile of the following reaction: A + B → A --. 11. What does the term ‘isomerism’ refer to? Give different classifications of isomerism. What is resonance? State the important features of it. 21. 13. 18. 19. 22. Write notes on electrophilic addition and electrophilic substitution. 20. 17. What is elimination reaction? Describe different types of elimination reactions. 3. 15. 3-dibromopentane.8 kcal/mole while that of benzene is 49.MECHANISM OF ORGANIC REACTIONS 183 10. Electrophiles are in general Lewis acids–explain. What do you mean by SN1 and SN2 reactions. S-nomenclature.

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

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

CH3COONa → CH3COO– + Na+. As a result. HF (iii) Amphiprotic (Both proton seeking H2O. H2SO4. Highlights: • HClO4. CH3COOH. CCl4. acetic acid is weak. EtOH and generating) (iv) Aprotic (Independent of proton C6H6. CH3COO is a strong base as its conjugate acid. Therefore. 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. HCl and HNO3 are of same strengths in water. Classification of Solvents Solvent Example (i) Protophilic (Proton seeking) H2O.PM5 186 . NH3 (ii) Protogenic (Proton generating) H2O. H2O H+ + OH– – According to Bronsted. seeking and generating) C-8\N-ENGCHE\ECH8-1. • 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. the solution will get enriched with OH– ions and will behave alkaline.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. And water will remain undissociated being a weak electrolyte. 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. CH3COO– ions will readily accept protons from water molecules setting OH– ions free. Solvent behaves as a base towards acid and vice versa. HBr.

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

Highlight: Following such conventions we express Ka and Kb as follows: pKa = – log10 Ka. and pKb = – log10 Kb As for example: Ka for salicylic acid = 10–3.PM5 188 .ion l . the solution becomes alkaline.ion l–1. and all alkaline solutions will have pH greater than 7. 10–2 g. where [H+] = 10–7 ∴ – log10[H+] = – log10(10–7) ∴ pH = 7 Again in pure water.L. Again 0. And in the solution where the [H+] becomes less than that of [OH–]. Therefore. the solution becomes acidic. It is somewhat inconvenient to express the concentration of the solution in such a manner. so [OH–] of the solution will be 10–13 g. So. [OH–] = 10–7 – log10[OH–] = – log10(10–7) ∴ pOH = 7. S. [H+] = [OH–] = 10–7. C-8\N-ENGCHE\ECH8-1. 1 (N) solution of a strong acid contains an [H+] of 10–1 g. N Let us consider an acid solution of concentration . so its hydrogen ion concentration 6000 –4 –1 will be 1. Sorensen (1909) simply applied negative logarithm of hydrogen ion concentration to remove this sort of difficulty for expressing such concentrations. So in an aqueous solution when [H+] exceeds that of [OH–].01 (N) strong alkali solution contains [OH–]. in any aqueous solution pH + pOH = 7 + 7 = 14 Highlight: [H+] × [OH–] = Kw. Pure water is neutral because in pure water. A simple operation like this made an easy expression for hydrogen ion concentration of the solution. 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. – log10 [H+] + (– log10[OH–]) = – log10Kw ∴ pH + pOH = pKw = 14 where – log10Kw = pKw. ∴ pKa = 3. hydrogen ion concentration of the solution will be 10–12 g. all acidic solutions will have pH less than 7.ion l–1 which is completely dissociated in aqueous solution. Because [H+] × [OH–] is constant in aqueous medium and its value is 10–14.ion l–1.66 × 10 g.ion l–1. Therefore. or.P.188 ENGINEERING CHEMISTRY H+ ions though in small concentration. 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. In pure water [H+] = [OH–] = 10–7. As strong acid dissociates completely in aqueous solution.

IONIC EQUILIBRIUM 189 Example 1. The arrest of pH changes of these solutions is known as buffer action. Sol. 10 −14 [H+] = = 7.34 × 10–4 g-ion litre–1.76 ∴ pH = 14 – pOH = 14 – 2. Example 3.63 – log10 [H+] = 3.63. C-8\N-ENGCHE\ECH8-1. ratio of strengths should be CA: CB.2041 = 2. There are several other processes for comparing strengths of acids.69 = 3.37 = 2.9 × 10–4) ∴ pH = 4 – log10 4.7 × 10–12 g-ion litre–1. As the acid and base are strong. Given: α = 0. [OH–] and pH of a weak base [0. Relative Strengths of Acids and Bases Tendency of donating protons in any aqueous solution is a measure of acidity of the solution. [OH–] = 0. (a) [H+] = 4. Let.63 = – 3 – 0.76 = 11.1135. So.63 = 4 – 0. Example 2.1(N)]. So. pH = 3. S1 α 1C α1 K 1C K1 = = = S2 α2C α2 K 2C K2 So.7959 or 2.6 = 3 – 0.6 × 10–3) ∴ pOH = 3 – log10 1.37 [H+] = antilog 4. Calculate pH of the following solutions: (a) 4. Sol.6 × 10–3 g-ion l–1 – log10 [OH–] = – log10 (1. their strengths S1 and S2 are represented by.1 = 1. Calculate [H+].24.9 × 10–4 (N) acid. the ratio of dissociation constants of two acids compare their strengths.3 × 10–3 g-ion litre–1.31 (b) [OH–] = 1. One such method is by comparing dissociation constants of the acids.013 × 0.013. Buffer Solutions Some solutions do not change their pH on addition of little acid or alkali.8865 = 11.9 = 4 – 0. (b) 0.63 log10 [H+] = – 3.7 = 12 – 0. Such solutions are known as buffer solutions.34 × 10–4 ∴ [H+] = 2. degree of dissociation of acid A1 = α1 Degree of dissociation of acid A2 = α2 The concentrations of the acids were same (C).0016 (N) base. Both acid and base are strong.37 = 4. Sol.9 × 10–4 g-ion l–1 – log10[H+] = – log10(4. 1. the dissociation is complete. Calculate [H+] of a solution of pH 3.7 × 10–12) = 12 – log 7.PM5 189 . If concentrations of two acids A and B are CA and CB respectively.3 × 10 −3 pH = – log10 (7.

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

76 = 5.38 (iii) Acetic acid/Sodium acetate 3. • The buffer capacity of a solution is defined by db/dpH. (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 .6 (iv) NaH2PO4/ Na2HPO4 5.00 – 4.738 [Acid] C-8\N-ENGCHE\ECH8-1. when concentration of salt becomes 10 times the concentration of acid and vice versa. the addition of acid decreases the pH and is equivalent to a negative amount of base. pH depends upon the ratios of the concentration of salt and acid.2 (vi) NH4OH/NH4Cl 10 (vii) Na2HPO4/Na3PO4 11-12 Example 1.8-9.76 + log [Acid] [Salt] ∴ log = pH – 4. Prepare a buffer solution of pH 5.24. The buffer action is favourable in pH ranges pKa ± 1 i. [Given pKaCH3COOH at 25° is 4. pH = pKa + log [Acid] [Salt] = 4.2-3.7 (ii) Phthalic acid/Potassium hydrogen phthalate 2.8-8 (v) Boric acid/Borax 6.7-5. i.IONIC EQUILIBRIUM 191 The acidity or alkalinity of mixed solution. then pH = pKw – pKb.. [Salt] Sol. where dpH is the increase of pH resulting from the addition of db of base. 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. Different Buffer Solutions Component conjugate acid–base pair pH ranges (i) Glycine/Glycine hydrochloride 1.0-3.e.24) = 1.PM5 191 .76]. 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.. [Acid] [Salt] ∴ = antilog (0.76 = 0.

equiv..05 × 10–4)2 = 9.0305 gl–1 = 3. of CaCO3 = 100) Solubility S = 0.ion l–1. The constant Ksp is called the solubility product of the salt BA.PM5 192 . ion l–1 i. 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.l–1. Highlights: • When the solubility of Mg3(PO4)2 is C mol. [A ] = yS ∴ Ksp = [B+]x [A–]y = (xS)x (yS)y = xxyy.3 × 10–8. [B+] [A–] = constant = Ksp.mol. when 1. [B + ] [A − ] K= [BA( s)] or K[BA(s)] = [B+][A–] The concentration of solid salt [BA (s)] is constant.e. The solubility of CaF2 is 0. wt. the desired buffer solution of pH 5 is obtained. Example 1. Therefore. By convention it is unity. (mol.0002 mol l–1. CaF2 Ca+2 + 2F– C-8\N-ENGCHE\ECH8-1. So [BA (s)] = 1. 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. BA(s) BA (solution) B+ + A– Applying law of mass action. Calculate Ksp of CaF2 . But it can be successfully applied to the saturated solutions of sparingly soluble salts. then [B+] = S g.738 g-moles of CH3COONa is mixed with 1 g-mole of CH3COOH and the volume of the solution is made upto one litre. 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. 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.Sx+y It is a universally applicable equation. because a heterogeneous equilibrium is set up as follows. If S is the solubility of BA. per litre.0305 gl–1. Calculate its solubility product. The solubility of chalk is 0. • It is customary to express the concentrations of the ions in g. Solubility Product The law of mass action cannot be successfully applied to the process of electrolytic dissociation except to the cases of weak electrolytes.mol l–1 and [A–] = S g. ions of each type formed by dissociation of one molecular formula weight of the salt. formula weight per litre and not in g.192 ENGINEERING CHEMISTRY Therefore.05 × 10–4 mol l–1 Ksp = S2 = (3. • The solubility product of a sparingly soluble binary electrolyte is simply the square of its solubility in pure water expressed in mol l–1. Example 2. each concentration term being raised to a power representing the number of gm.

12 × 10 OP =M −11 1/2 = 1. 3. A litre of a solution contains 0.2 (b) [(NH4)2SO4] = = 0. Example 4. [F–] = 2 × 0.ion l–1.1 × 10–4 g. [Ba = 137] 0.1) = 10–10.1 g. As a result. For doing so. [NH +4 ] [OH − ] So. Calculate the solubility product of the salt.12 × 10–11 ∴ [OH–] L 1. we are to suppress the dissociation of NH4OH by adding common ion NH4+. Ksp = [B+] [A–] If we add to the solution a substance.0004)2 = 3. for a saturated solution of a sparingly soluble salt BA. [NH 4 OH] C-8\N-ENGCHE\ECH8-1.1 × 10–4 g. ∴ Ksp = S′ × (S′ + 0. Example.2 gl– at 25°C.00233 Sol. Therefore.33 gl–1. (a) At 25° the solubility of BaSO4 is 0.1 (M) 132 ∴ [SO4=] = 0. [SO4=] = 10–5 × 10–5 = 10–10. 4 2 Sol. Ksp = [Ca+2] [F–]2 = 0. • The presence of a neutral salt without a common ion often results in an increase of solubility of a sparingly soluble salt. Kb = = 1. (a) [Ba++] = [SO4=] = = 10–5 g. taking complete dissociation. ∴ S′ = 2.0002 × (0. the changed solubility of BaSO4 = S′. We know that Ksp = [Mg+2] [OH–]2 = 1.00233 gl–. What will be concentration of NH4+ ion from NH4Cl? Given K b NH OH = 1. 10 −10 ∴ S′ = [S′ is negligible compared to 0.ion Mg+2.PM5 193 . N 0.001 g.001 Q So.8 × 10–5. To arrest the precipitation of Mg(OH)2. l–1.1] 10 −1 = 10–9 mol. which has an ion common to the above salt then concentration of that ion will increase.0002 g ion l–1 .IONIC EQUILIBRIUM 193 [Ca+2] = 0.8 × 10–5 and K sp Mg(OH) = 1.ion l–1 to arrest the precipitation of Mg(OH)2.ion l–1 137 + 96 ∴ Ksp = [Ba++] . [OH–] should not exceed 1. 13.0002 g ion l–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. (b) Calculate the solubility of BaSO4 in a solution of (NH4)2SO4 containing 13. the concentration of other ion will decrease otherwise the constant Ksp will change. B+ and A– will combine to give the solid BA(s) and the solubility of BA will decrease.ion l–1.01 mole NH4OH and 0.2 × 10–11.12 × 10–11. Effect of Common Ion on Solubility We know that. Let.

Sn+2). Only PbCl2 has higher solubility product and for that reason it is not completely precipitated here. The precipitation of C-8\N-ENGCHE\ECH8-1. This effect is known as salt effect. Q activity (a) = Concentration (c) × activity coefficient (γ) ∴ a = cγ. which are sparingly soluble in water. To increase the ionisation of H 2S. Group I. Pb+2. HCl. Ag+) are insoluble. HCl. It may remain in saturated solution for sometime. So concentration of sulphide ion CS= remains low. so CS= should be high for them. So. 0. 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. The reagent is H2S in presence of dil. the value of solubility product of the salt should always be higher than its ionic product.ion l–1. Zn+2) sulphides have higher values of solubility products. IIIB metallic ion (Co+2.6 × 10–3 g. are soluble in salt solutions due to this salt effect. • The effect of common ion on solubility is utilised in qualitative inorganic analysis to separate the ions present in a solution. Cu+2. Group III A. get precipitated here i. [Ag+] .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. Again diluted acid medium precipitates colloidal As2S3 and SnS which creates difficulty in filtration. Bi+3. As a result Fe+3. Ni+2.. so their precipitation is arrested here. Al+3.e. As+3. CdS and PbS have comparatively higher values of solubility products. Cr+3 get precipitated as hydroxides because their solubility products are exceeded. Highlights: • Many proteins.PM5 194 . The chlorides of Group I metals (Hg2+2.1 × 10 −4 or = = 1. low acidity or higher pH is necessary. Pb+2. The common NH 4+ suppresses the dissociation of weak base NH4OH thereby COH– remains low.e. Here reagent is NH4Cl/NH 4OH. The common ion H+ suppresses the ionisation of H2S. ionic product (CM+ × CCl–) easily exceeds the solubility products and the cations are precipitated. 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. For a very dilute solution γ = 1 then a = c. [Cl–] increases in order to keep the true Ksp value constant. whose solubility product of sulphides are low. A salt may not get precipitated even when its ionic product exceeds its solubility product. on addition of dil. The metallic ions (Hg+2. despite low S= ion concentration. to reduce acidity of the medium water is added to dilute the medium. Mn+2. the ionic products (CM+2 × CS–2) of metal ions exceed the solubility products because of low value of solubility products.194 ENGINEERING CHEMISTRY [NH +4 ] × 1.. It is also precipitated in Group II. for precipitation in chemical analysis. [ Ag + ] . Group II.8 × 10–5 ∴ [NH4+] = 1. That is why. solubility of a sparingly soluble salt increases on addition of any salt without a common ion. If we add KNO3 to a saturated solution of AgCl the γ-term of the expression of Ksp decreases. true expression is Ksp = γ Ag + . γ Cl− [Cl − ] where γ = activity coefficient. Ksp = aAg + . Therefore. Sb+3. aCl − So.

[OH–] and pH of a solution prepared by diluting 20 ml of 0. or x2 + 10–8x – 10–14 = 0 − 10 −8 ± (10 −8 ) 2 + 4 .e. Sr+2 are precipitated as carbonates. So. Calculate [H+]. NH4OH.5 × 10–8) + = 10.3 [OH] = 10–11. Here reagents are NH4Cl. Group IV.0 × 10–8 + x) = (1.005 = 10–2 mol.5 = 6.7 = 11. the contribution of H+ ions is to be counted during calculation of pH.98. ∴ pH = 14 – 2 = 12.01 × 10–12 g. Ca+2. Sol. the [H+] of the solution = (1 × 10–8 + x) and [OH–] = x ∴ Kw = [H+] [OH–] = (1 × 10–8 + x) × x = 10–14.7 ∴ pOH = 14 – 2. 20 × 0.ion l–1. ∴ total [OH–] = (1 × 10–8 + x) So.002 = 2 × 10–3 mole l–1.IONIC EQUILIBRIUM 195 Zn+2.1 Sol. (a) When the [H+] is 10–6 or greater the ionisation of water is negligible due to common ion effect. 1 . Calculate the pH of 0. l–1.1 M HCl to 1 litre.0 × 10–8 + 9. (b) 1 × 10–8 (M) NaOH solution. Example 2.005M Ca(OH)2 solution assuming complete dissociation.PM5 195 .5 × 10–8) = 8 – log10 10. Calculate the pH of (a) 1. ∴ pOH = 2. Ba . But when it exceeds 10–6. [H+] = = 0. +2 SOLVED EXAMPLES Example 1. Group IV metals i. Mg+2 and Mn+2 as hydroxides are arrested as their solubility product values for hydroxides are comparatively higher. Let the contribution of [H+] from water = x.6990 ~ 2. [H+][OH–] = Kw = 10–14 ∴ (1 × 10–8 + x) × x = 10–14 C-8\N-ENGCHE\ECH8-1. and (NH 4)2CO 3.3010 = 2.0 × 10 – 8 (M) HCl solution.3 – log10 [OH] = 11. 10 −14 ∴ x= 2×1 –8 = 9.5 × 10–8 ∴ pH = – log10[H+] = – log10 (10. [OH–] = 2 × 0.5 × 10 (M) [H ] = (1.. 1000 ∴ pH = – log10 [H+] = – log10 [2 × 10 –3] = 3 – log 2 = 3 – 0. Sol. Example 3.3 = 5. (b) Here let the contribution of OH– ions from water be x.

45 × 10–11. Sol. Sol.5 × 10–8 g. The solubility product of CaF2 in water at 18°C is 3.5 × 10 −7 4.02.5 × 10 – 7.0004 × C = = C(1 − 0.02) 0.74).8 × 10 −5 × 0. [H + ] [HCO 3− ] ∴ Ka = [H 2 CO 3 ] [HCO3− ] Ka 4. = 4S3 C-8\N-ENGCHE\ECH8-1. Ksp = [Ca+2] [F–]2 = [S] × [2S]2 where.196 ENGINEERING CHEMISTRY ∴ x2 × 1.004 = 0. Given Ka of H2CO3 = 4. CH3COOH H+ + CH3COO– at equilibrium: C(1 – α) Cα Cα [H + ] [CH 3 COO − ] ∴ Ka = [CH 3 COOH] 0. A buffer solution contains 0.24 × 10–2. According to Henderson equation pH of a buffer solution [salt ] pH = pKa + log [acid] 0.98 × 10–8 g.1 Example 6. Sol.1 = 4. (a) Calculate the molar concentration of an CH3COOH solution.5 = 6. (pKa = 4.0 × 10–8x – 10–14 = 0 ∴ x = 9.98 ∴ pH = 14 – 6.4 ∴ – log10 [H+] = 7.98 ∴ c= molar 0. S = solubility. Calculate the ratio of HCO3– and H2CO3 . (Given Ka = 1.98 × 10 −8 11 pH = 7.02) (b) Calculate the degree of dissociation of 0.2C 0. H2CO3 H+ + HCO3–.5 × 10 −7 ∴ = = = _ ~ [H 2CO 3 ] [H + ] [H + ] 3.4 = 3.PM5 196 . Sol.ion l–1 Example 7.98 1. Example 4.74.8 × 10 −5 (b) α= = = 4.1 mole CH3COOH and 0. pH of blood is 7.01 Example 5.4 ∴ [H+] = 10–7.74 + log = 4.01 (M) AcOH.5 × 10–8 (M) ∴ [OH–] = 9.044 molar. C 0.4.02C × 0.8 × 10–5 . Ka 1.1 mole of CH3COONa per litre. α = 0.98 = 7. 0. Calculate the solubility of CaF2 in water. ion l–1 ∴ pOH = 8 – log 9. Calculate the pH of buffer solution.

2. 4.1 M NaF Solution = S mole (2S + 0.1M NaF solution. Ksp of SrF2 = 8 × 10–12.PM5 197 . C Q. Cl– is a conjugate base of – acid HCl.01S 8 × 10 −10 ∴ S= = 8 × 10–8 mol l–1. 3. α = degree of dissociation of a weak electrolyte. 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. 0. C = concentration of the weak electrolyte. An acid is a substance which in aqueous solution gives H+ ions. differing by a proton.01 SHORT QUESTIONS AND ANSWERS Q. 1. 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. What is the Lowry and Bronsted concept of acid and base? Ans. Thus. HSO4 is a conjugate base of H2SO4. ∴ Ksp = 8 × 10–10 = [Sr+2] × [F–]2 = S × (0. K= C(1 − α) where.45 × 10–11 3 3. What is the Arrhenius concept of acids and bases? Ans.IONIC EQUILIBRIUM 197 ∴ 4S3 = 3. Sol. Give an expression for the ionisation constant. HCl is an acid and NaOH is a base. So. K = ionisation constant. α is negligibly small. Given.1)2 = 0. α 2 C2 Ans. What are conjugate acid-base pairs? Ans.1) mol. – Again HCl is the conjugate acid of Cl– and H2SO4 is the conjugate acid of the base HSO4. For weak electrolytes. C-8\N-ENGCHE\ECH8-1.45 × 10 −11 S= mole l–1 4 = 2. Calculate the solubility SrF2 in 0. Q. Q. A base is a substance which in aqueous solution gives OH– ions. Example 8. mol l–1. SrF2 Sr+2 + 2F– S mole 2S mole Initially = in 0. 1–α≈1 K ∴ K = α2C ∴ α = . This sort of pairs are known as conjugate acid-base pairs. Every acid has a conjugate base and every base has a conjugate acid.05 × 10–4 mole l–1.

Ans. H . . As.. : → H •• acid base acid H base Cl H   Cl  B ← : N  H   Cl H acid base Q. HNO3/NO3–. 8. H H: N + . Show that ionic product of water (Kw) is 1 × 10–14. Show that solvent acts as a base or an acid according to Lowry Bronsted concept. 7.198 ENGINEERING CHEMISTRY Some conjugate acid-base pairs are: HSO4–/SO4=. 5. Ans. In pure water. 18 Kw = K [H2O] = [H+] [OH–] = 1. 6. C-8\N-ENGCHE\ECH8-1. what will be the [H+] or [OH–]? Ans. AcidI + BaseII AcidII + BaseI Q.e... given K for water = 1. Q. Ans. H2O/OH–.8 × 10–16 × 55.5555 = 100 × 10–16 = 1. 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.8 × 10–16. 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. If the acid is strong. [H+] [OH–] = 10–14 and in pure water. NH4+/NH3 and so on. [H+] = [OH–] ∴ [H+] = [OH–] = 10–7 g. its conjugate base will be weak and vice-versa. every acid–base reaction proceeds according to the equation i.00 × 10–14.ion l–1. Q. Give Lewis concept of acids and bases.PM5 198 . H3O+/H2O.. + – H ← : O . conjugate acids and bases are formed during the reaction.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.

Phenolphthalein pH 7 pH 7 Methyl orange 0 0 0 25 0 25 Alkali(c.3 or [H+] = 10–2. i. Q. In alkaline solutions. 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. [H+] range = 10–8 – 10–14 g . pH = 2.1 Neutralisation Curves. Ans. ion l–1.3 or log10 [H+] = – 2. Q. The pH scale is a logarithmic scale for measuring the concentration of hydrogen ions in aqueous solutions.PM5 199 . 12.3010 = 1.c.02 mol dm–3 HCl? Ans.) Strong acid–strong base Weak acid–strong base Fig. 13.37? Ans.7. pH = – log10 [H+] = – log10 [2 × 10–2] (as the acid is strong) = – log10 2 + 2 log10 10 = 2 – 0.. Explain the pH scale. 11.IONIC EQUILIBRIUM 199 Q. What is the pH of 0. It is negative logarithm of hydrogen ion concentration.699 ≈ 1. 8. 10.3 or – log10 [H+] = 2. ion l–1 In neutral solutions.c. ion l–1. Q. What is the hydrogen concentration of coca cola with pH 2. In acidic solutions. Ans. [H+] = [OH–] = 10–7 g . What is pH? Ans.3 = 5 × 10–3 mol dm–3.e. [H+] range = 100 – 10–6 g . 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. pH = – log10 [H+] or [H+] = 10–pH The acidity or alkalinity of a solution is generally expressed by pH. Explain the pH changes during acid–base titration. C-8\N-ENGCHE\ECH8-1. 9.) Alkali(c.

This experimental evidence supports the above view. 8. Q. strong or weak. the pH is not always neutral.PM5 200 . What is the pH of a 0. How can you use pK values for pH calculations? Ans. a salt is formed. We know that. 15. 17. H3O+ + OH– → 2H2O (l) Enthalpy change of neutralisation is same for all acid-base partners. – log10 Kw = pKw Taking logarithms produces a convenient small scale of values. hydrolysis of salts does not take place and the solutions remain neutral at the equivalence point (pH = 7). Weak acid/strong base end point is alkaline (pH > 7) Strong acid/weak base end point is acidic (pH < 7). 1 1 (iii) pH of a weak base = 14 – p K b + log c 2 2 where c = concentration of undissociated base. What is pK? Ans. When a salt formed at the equivalence point has either a ‘parent acid’ or a ‘parent base’ weak.02 mol. Ans.3. (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. dm–3 solution of NaOH? Ans. c = concentration of undissociated acid. useful for pH calculations.1). Kb = dissociation constant of weak base. Neutralisation reactions do not always produce neutral solutions—explain. The ‘strong parent’ in the partnership wins. it hydrolyses to give a solution that is not neutral.7 = 12. 16.200 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. – log10 Ka = pKa. when exactly equal amounts of acid and alkali have been added. Q. if acid and base both are strong. It is to be noted that. Q. Neutralisation is essentially a reaction between H+ and OH– ions in aqueous solution—explain.7 pH = 14 – pOH = 14 – 1. 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. at the equivalence point. C-8\N-ENGCHE\ECH8-1.02 mole dm–3 pOH = – log 0. NaOH is a strong base [OH–] = 0. Q. 18. 14. Q. At the equivalence point. Ans.02 = 1. pK is the logarithmic form of an equilibrium constant. – log10 Kb = pKb.

IONIC EQUILIBRIUM 201 Q. What is a buffer solution? Ans.PM5 201 . – Ans. 23. K a = 3 [HPO −42 ] Ka > K > Ka . K a = 1 [H 3 PO 4 ] [H + ] [H 2 PO4−2 ] (ii) H2PO4– H+ + HPO4–2. (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. Ans. Q. Relate Ka. 22. 19. The change in equilibrium position due to addition of an ionic compound that contains one of the ions involved in the equilibrium is known as common ion effect. ∴ Ka × Kb = Kw or – log Ka – log Kb = – log Kw ∴ pKa + pKb = pKw = 14. [H + ] [H 2 PO 4− ] (i) H3PO4 H+ + H2PO4–. There are three dissociations for H3PO4 and accordingly ka values. Mention the importance of pH. (iii) pH value helps to determine the condition of reactions in laboratory and in industry. Q. Q. (ii) The common ion effect influences the behaviour of buffer solution. 20. which help to keep pH of a solution more or less constant. C-8\N-ENGCHE\ECH8-1. (i) The common ion effect can change the ionisation of weak acids and weak bases. What is common ion effect? Ans. K a = 2 [H 3 PO4− ] [H + ] [PO 4−3 ] (iii) HPO4–2 H+ + PO4–3. H3PO4 has three Ka values–explain. Kb and Kw. 1 a 2 3 Q. 21. (ii) A small variation of pH of human blood (6. Ka × Kb = × = [H3O+] [OH–] [HA] [A − ] = Kw = 10–14. Ans.7) causes bodyache. (iii) The common ion effect alters the solubility of a sparingly soluble salt. (i) The pH value of soil helps to decide the type of fertiliser to be used in agriculture. Buffer solutions are mixtures of a weak acid and its salt or a weak base and its salt.

Give an expression for the solubility product of the salt Ax By.1 × 10–19 = 10–20 Ksp . 18. (MnS) = 1. 17.1 × 10–22 = = [Q S H 2S = 0. C-8\N-ENGCHE\ECH8-1. What do you mean by common-ion effect? How is it utilized in qualitative chemical analysis? 10.1M] [H 2 S] 0.01) [S −2 ] ∴ 1. 20.202 ENGINEERING CHEMISTRY Q.8 + 0. Tricovalent phosphorus compounds can serve as Lewis bases and also as Lewis acids–comment. pH = pKa + log 0. 4. Show that it is different from dissociation con- stant of water.4 mol dm–3 methanoic acid and 1. Give the Bronsted-Lowry concept of acids and bases. What is the basic equation for acid-base reaction of Bronsted theory? 14.4 = 4. 8. What is a buffer solution? Explain buffer action. What is the pH of a buffer solution containing 0. Derive an expression for pH of the buffer solutions: (a) Weak acid and its salt.01) 2 × [S −2 ] (0. 5. What do you mean by solubility product? What is true solubility product? 19. 24.8. 9.1 × 10–22 [H 2S] (0. 2. Explain the following–Aqueous solution of NaCl conducts electricity while chlorine water does not conduct electricity. K = = 1. 3. Discuss the effect of common ion on solubility product. H2S 2H+ + S–2. 15.0 mol dm–3 sodium methanoate? pKa(HCOOH) = 3. FG N IJ Mn FG N IJ H Q. Deduce the relation between solubility and solubility product of CaF2 at room temperature. Derive an expression for ionic product of water.40 = 3. 13. BI3. (b) hydrolysis. 12. Which are the strongest Lewis acids in the series? (a) BF3. Deduce the Hendersen equation and state its utility. 100 . EXERCISES 1. Explain the terms: (i) Buffer solution (ii) Buffer capacity and (iii) Buffer action. will not be obtained. 6. BCl3. Explain (a) neutralisation. (b) Lewis theory and (c) Solvent system concept. 16. (b) Weak base and its salt.PM5 202 . What is pH? Give its importance and usefulness.1 ∴ [S–2] = 10–19.2.4 × 10–15 So. (b) BeCl2. The reaction HCl (aq) + KOH (aq) → KCl (aq) + H2O is neutralisation according to: (a) Bronsted-Lowry concept. in the light of Bronsted theory. Elucidate. 7. Deduce Ostwald’s dilution law and state its limitations. Will H 10 K +2 containing H 100 K + be precipitated by passing H2S? [H + ] [S −2 ] Ans. Ans. 25. BCl3. ppt. What do you mean by autoprotolysis of water? 11. ∴ [Mn+2] [S–2] = 0.

000775 (N) acid (c) 0.6 × 10–8] 28. 10. [Ans. .00345 (N) acid (b) 0. Ksp(PbS) = 3.78] 25. [Ans. 1. [Ag+]in a solution is 4 × 10–3 g-in l–1. Given Kb = 2 × 10–5.54 (b) 3.5 g. What will be the pH of a solution obtained by mixing 5g.89 (c) 11. of CH3COONa. Given Ka(H2S) = 1.014] 24. of CH3COOH and 7.00886 (N) base [Ans. 13] 23. 12.IONIC EQUILIBRIUM 203 21. [Ans.05 (N) NaOH and 200 ml of 1N HCl? [Ans. 1. 5 × 10–8 g-in l–1] 30. Calculate the minimum concentration of Cl– to precipitate –10 AgCl.038 g-l–1. Calculate its solubility product.69 × 10–11 moles l–1] 26. Calculate the [H+]. Calculate its solubility product. 11. Find α for NH4OH in a solution of . making a volume equal to 500 ml? [Ans. (a) 2. [Ans. Calculate the pH and pOH of .PM5 203 .1 × 10–23.05] assuming complete dissociation. What will be the pH of a solution obtained by mixing 800 ml of 0.6 (M)] C-8\N-ENGCHE\ECH8-1. 2.3] 22.1N HCl. 27.001 (M) Pb(NO3)2. [Ans. Given Ksp of AgCl = 1. Calculate the pH and pOH of: (a) 0.46.95.4 × 10–28.8 × 10 . [Ans.1M.57. [Ans. 5. 4. 1. 2. Calculate the concentration of H2S required to arrest the precipitation of PbS from a solution of 0. Solubility of PbSO4 is 0. Solubility of Ag2CrO9 g-l–1.4 × 10–12} 29.11. pH of a solution is 10.

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

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

then.C.008 1 So. Combination of First and Second Laws of Faraday From first law.C. 1 ∴ F=Q= (for 1 gm. 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.C. equiv.E.C. This quantity of electricity is called one faraday (F). W ∝ E (where Q is constant) ∴ W = KQE (where E and Q vary) W or Q= (K = Constant) KE 1 When W = E.206 ENGINEERING CHEMISTRY That is to say. of any element during electrolysis. the quantity of electricity is fixed. Let. of hydrogen. of any element = Z E × ZH E × ZH ∴ Z= ≈ 1.5/2 g Cu will be liberated in cell (2) and 108 g Ag will be liberated in cell (3) (Fig. chemical equivalent of any element = E E. of hydrogen = ZH. E. Q = K Therefore. E. when 1 g of H2 is liberated in cell (1).E. If one of the elements is H. 9. to liberate 1 gm equiv. the quantity of electricity = Q coulomb the quantity of Cu deposited = W1 g the quantity of Ag deposited = W2 g Then. W = ZQ or E = ZQ (for 1 gm.PM5 206 . of any element = Chemical equivalent of the element × E. E Z E × ZH = or Z = EH Z H EH Chemical equivalent of hydrogen = EH. equiv.2). 63.E. W ∝ Q (where E is constant) From second law.E.) K QE ∴ W = KQE = F From first law.) = ZF E or F= Z C-8∴N-ENGCHE∴ECH9-1.

0003294 96494 96495 O 8. a A C A N T O H D O D E E b Fig. the total quantity of the current passed will remain same as above i. So. 100 units but the current carried by cations is 80 per cent and the current carried by anions is 20 per cent. If 100 cations cross the barrier from left to right..0 0.. C-8∴N-ENGCHE∴ECH9-1..0001118 96495 Cu 31.. So. 1 F = 96500 coulomb. then current is wholly carried by cation. 9.0000104 96496 Ag 107. Ions of an electrolyte i. 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.008 0. we can accept that.. the transport number of anions is hundred per cent and that of cations is zero per cent. so their transport numbers are unequal.78 0.e. Usually both cations and anions cross the barrier (ab) but in unequal numbers owing to their unequal speeds. It is to be noted that deposition at the electrodes in the above two cases will be same (Fig. The case may be totally reversed.e.2: Displaying the constancy of E/Z for different elements Element E Z F = E/Z (Coulomb) H 1.88 0. For example. Table 9..PM5 207 . So we can define transport number as the fraction of the current carried by an ni Z i ion. Transport number is proportional to speeds of the ions. cations and anions present in the solution conduct current.ELECTROCHEMISTRY 207 for one gm equivalent of different elements E 1 E2 E = = .3).3 Concept of transport number. in that case. ni = number of the ions and Zi = valency of the ions which cross the barrier. transport number (t) = Σ ni Z i where. 9. if 80 cations cross the barrier (ab) towards cathode compartment and 20 anions cross the barrier (ab) towards anode compartment.0000829 ≈ 96500 The concept of transport number. = n = F Z 1 Z2 Zn Therefore.. We can say that the cation transport number is hundred per cent and the anion transport number is zero per cent.

9. therefore.5). 9. 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. 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. The current I is flowing. If unit of the charge is ‘e’ (Fig. As every part of the electrolyte is electrically neutral. are kept inside an electrolyte and their potential difference is E. ions are always discharged in equivalent amounts but their speeds are different. The following model will make the idea clear (Fig. but it is not so. this phenomenon creates an idea that perhaps the ions move at the same rate during electrolysis. 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. t+ = = = = I n+ z+ eu + n+ z+ ev n+ z+ e(u + v) u+v I− n− z− ev n+ z+ ev v Similarly.208 ENGINEERING CHEMISTRY Transport number or transference number of an ion is dependent on the speed of the ions. and the valency of ions is z(±). n+z+ = n–z– I+ n+ z+ eu n+ z+ eu u So.4 Voltameter. Let the two electrodes. The total current carried by the positive and negative ions = I = I+ + I– = (n+u)z+e + (n–v)z–e. 9. The number of ions liberated at the positive and negative electrodes per unit area are given by n+ u and n– v. C-8∴N-ENGCHE∴ECH9-1. the solution contains n(±) number of ions per millilitre + – A B + – + – + v u Fig.PM5 208 .

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

02 amp. of silver deposited in the coulometer W – ( y – Z) × 108 tAg + = 170 × w ∴ tNO – = 1 – tAg + 3 C-8∴N-ENGCHE∴ECH9-1.210 ENGINEERING CHEMISTRY The total gm. is passed for a period of 2–3 hours through the AgNO 3 solution. y g . 9. No. The tubes are fitted with silver plates which act as X anode and cathode which are introduced into A and B. e Let. A current 0. The three tubes are fitted with Y R stopcocks. AgNO3 = (x – y) g AgNO3 present in (x – y) g of water before electrolysis = z g. After a definite time. The solution collected from anode (anolyte) = x g The amount of AgNO3 in x g anolyte =yg Fig. of equiv. The solution from the anode compartment is taken for analysis (Fig. Transference number The amount of water containing determination by Hittorf’s method. coulometer X are connected in series. The number of electrolytes lost from anode compartment So. A dilute M – + AgNO3 solution (N/20) is taken for electrolysis. the current is stopped. Weight of silver deposited on cathode in the coulometer = w g.6. of AgNO3 lost from anode compartment due to migration tAg + = No. loss due to migration. = (W + Z) – y = {W – (y – Z)}g. B are connected in the middle by a ‘U’ tube ‘e’. the total weight of AgNO3 should have been present (x – y) g of water in the anode compartment = (W + z) g. A milliammeter M.6). of equiv. The increase in weight of AgNO3 in anode compartment due to dissolution of silver from w × 170 the anode = = Wg. Actual weight of AgNO3 present = y g so.PM5 210 . Total number of equivalence of the electrolyte liberated on the electrode Determination of Transport Number (Hittorf’s Method) Two broad vertical glass tubes A. equivalence liberated from both the compartments is proportional to (u + v). t+ = Total number of equivalence of the electrolyte liberated on the electrode The number of electrolytes lost from cathode compartment t– = . 9. 108 If no migration would have taken place.01 A B to .

916 during electrolysis of a silver nitrate solution. would have been 0.521) = 0. After electrolysis the amt. surrounding anode = 0. Increase in wt.79 g.153 and Transport number of SO4– – = (1 – tCu + + ) = (1 – 0.12) g = 0. of Cu+2 in the liquid per unit vol.479. Example 1.442 0. Increase in wt.91 – 0. This is true for other complex compounds too. Calculate the transport number of Ag+ and NO3– ions when the speed ratio of the two ions is 0. Example 2. 0.153 g.33 ∴ Transport number of Cu++ ( tCu + + ) = = 0.10 0. This abnormal transport number does indicate the formation of complex ion. Calculate the transport number of the Cu++ and SO4– – ions.153 g and masses of Cu per unit volume of the anode liquid before and after electrolysis were 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’.153 – 0. Cd ion is moving towards both cathode and anode and towards anode due to above complex ion formation.20 0. Let.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 CdI2.916 Speed of NO 3 − v u 1– n 1 r= = (n = tNO 3 – ) or n = v n 1+ r 1 n = tNO 3 – = = 0. Concentration (N) 0. In an electrolysis of CuSO4 between copper electrodes the total mass of copper deposited at cathode was 0.785.003 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 .02 0.033 g.. CdI2 ionises as follows in a concentrated solution: 2CdI2 Cd+2 + [CdI4]–2 +2 i.91 g respectively. of Cu-cathode in the coulometer = 0.91 g.153 g.396 0.12 g.521 1 + 0. Speed of Ag + u = = ratio (r) = 0. Before electrolysis the amt.05 0.296 0.79) g = 0.916 tAg + = 1 – tNO – = 1 – n = (1 – 0. of Cu+2 in the liquid per unit vol.12 g.79 and 0.50 tCd + 2 0.215 0. If no Cu++ had migrated from the anode.PM5 211 . But actual increase = 0. surrounding anode = 0. increase of wt. Fall in concentration due to migration of Cu+2 ions = (0. It can only be explained by the formation of complex ions.444 0. due to dissolution of Cu anode during electrolysis = (0.01 0.215) = 0. C-8∴N-ENGCHE∴ECH9-1.e.127 0.

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

01 0.82 0.8 107.2 41. Experimental Determination of Specific Conductance (K) The arrangement of apparatus adopted for the determination is modified Wheatstone’s meterbridge arrangement (see Fig.0 0.05115 0.5 70.2 1.01119 0.0000129 0.00024 111.0000107 129.9 61.5 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∞.001 0.0 Classification of Electrolytes (i) Strong electrolytes: Strong acid HCl.0000752 0.00000768 0. Such electrolytes whose λv values increase with dilution are known as weak electrolytes (see Fig.4 2.0412 0.5 76. 9.001225 0.3 0.C.ELECTROCHEMISTRY 213 dilution more and more of the electrolyte ionises. is necessary to avoid this difficulty.30 0. 9.1 2.3 49.000702 0.PM5 213 . no increase of λv or λm with dilution. Such electrolytes are called strong electrolytes.e.3 Specific conductivity (Κ) Equivalent conductivity (λv) Normality KCl CH3COONa CH3COOH KCl CO3COONa CO3COOH 1. 9.6 75.0982 0.000143 122. After a certain dilution there remains no more electrolyte molecule to ionise and then there is no change i.1 0. strong alkali NaOH have high conductances even at low dilutions and there is no sharp increase in their equivalent conductances on dilution.00132 98.7 Change of equivalent conductivity with dilution. C-8∴N-ENGCHE∴ECH9-1..2 14.7).0 0. Table 9. The modification is necessary as the passage of current will electrolyse the electrolyte.000041 127.8). (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. Strong electrolyte Molar conductivity Weak electrolyte Concentration Fig. The products of electrolysis will accumulate on the electrodes which will change the effective resistance.2 41.0001 0.0001276 0.0247 0. The use of A.00611 0.001005 102.01 0.

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

C-8∴N-ENGCHE∴ECH9-1. Cation λc Mobility.00046 2 Na+ 50.1 0.1 0.00205 1 K+ 73. λc = Ionic conductance of cation.4 Ionic Conductance and Ionic Mobilities of some Ions at Infinite Dilution at 25°C. λ∞ = λc + λa where.PM5 215 .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. V cm2/sec.00076 Cl – 76.8 0.8 0. 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. The cell constant being known it is easy to obtain the specific conductance of any solution by using the above relation.00362 OH– 197. i. volt cm2/sec volt H+ 349.00064 1 Ca++ 59.ELECTROCHEMISTRY 215 FG N IJ KCl be l If the observed resistance with H 50 K 1 the cell constant (x) = ρ1 × 0..5 0.6 0.00076 SO4– 79.4 0. λ∞ = Ionic conductance of anion.5 0.4 0.00083 2 NH 4+ 73.00074 2 1 Mg++ 53.00042 It is evident from the table that each ion contributes a certain definite quantity towards λ∞ of the solution. the higher is the observed conductance and so for weak electrolytes a conductivity cell having a small cell constant should be used.00052 CH 3COO– 40.00055 HCO 3– 44. The lower the cell constant.002768.e.00079 Ag+ 61.9 0.5 0. 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. U Anion λa Mobility. 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.3 0. • According to equation: K = x × observed conductance.00062 NO 3– 71.

216 ENGINEERING CHEMISTRY Highlight: Kohlrausch’s law can be stated in another way: At infinite dilution.PM5 216 . Calculate λ∞ for CH3COOH. ( 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.11 ohm–1 Br– = 78. y and z. λm + + – – where r+ and r– are numbers of cations and anions and λ +∞ and λ ∞– are molar conductances of cations and anions respectively. the ionic conductances of cations and anions can be determined from their experimentally determined transport numbers from the above relations. Thus.44 ohm–1 Applications of Kohlrausch’s law (i) Determination of ionic conductances. We have (i) λ Na + + λ CH COO − = x 3 (ii) λ H + + λ Cl − = y (iii) λ Na + + λ Cl – = z. each ion makes a definite contribution towards the molar conductance of the electrolyte irrespective of its ∞ = r . It 1000 Ah = t+ .22 ohm –1 Cl– = 76. So.40 ohm–1 NO3– = 71. Its unit is ohm–1 cm–2 and is directly proportional to the speeds of the ions.4 ohm–1 + K = 53. But λ∞ for weak electrolytes can be calculated from Kohlrausch’s law. λ∞ + r . except at a infinite dilution. λ∞ association with other ions. 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. respectively. Example: The λ∞ values for CH3COONa. because they do not ionise to a sufficient extent in solu- tion. F C C-8∴N-ENGCHE∴ECH9-1. when the dissociation of an electrolyte is considered complete. Ionic conductance possesses a constant value at a definite temperature. (ii) Determination of λ∞ of weak electrolytes: λ∞ for weak electrolytes cannot be determined experimentally. HCl and NaCl are x.34 ohm–1 NH4+ = 73. 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. λc ∝ u or λc = ku λa ∝ v or λa = kv where k is a constant.

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

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 initial fall in conductance is due to the replacement of H+ ions (350) with Na+ ions (50) and the rise beyond equivalence point is due to excess OH– ions (199) [Fig. the sharper is the end point (Fig. 9. (a) Neutralisation Reactions In the titration of a strong acid with a strong base. For this reason.10(a)]. C-8∴N-ENGCHE∴ECH9-1. So. Beyond the equivalence point. • Measurements of conductance in the region of equivalence point are of little value due to hydrolysis. The nature of the titration curve is as in Fig. 9. there is always an initial decrease in conductance. The precipitate should be formed fairly rapidly and should not have strong adsorbent properties. so they (CH3COOH) (aq) with a strong conduct electricity very well. The titration of KCl solution vs AgNO3 solution satisfies the above conditions. 9. The conductance then rises beyond the equivalence point.10 (c). the graph shows a curvature rather than a clear intersection of the two straight lines [Fig. In water H+(aq) during titration of a weak acid and OH–(aq) ions are very mobile. base (NaOH) (aq). the increase in conductivity is due to excess of H+ ions with very high ionic molar conductivity (350). 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. In the titration of NaOH with HCl.10 (b) Changes in conductivity of NaOH(aq) with HCl(aq). 9. Highlight: The stronger the solution used for the titration.PM5 218 . 9.10 (a) Changes in conductivity during titration Fig. dissociation or solubility of the reaction products. the decrease in conductance is due to the replacement of OH– ions (molar ionic conductivity = 199) by Cl– ions (molar ionic conductivity = 76). 9.10). end point of the reaction can be determined easily. (b) Precipitation Reactions Conductometric titrations of this type may be performed if the reaction product is sparingly soluble salt. The point of intersection of the two curves is sharp.10(b)]. In the titration of HCl with NaOH.

The conductance increases as the concentration of the salt increases. The equivalence point is located by extrapolating the straight lines.4 × = 8. Cell constant = = = 8. apart. what is the cell constant? l l Sol. They are 10.10(b)).ELECTROCHEMISTRY 219 Conductance Volume of AgNO3 Fig.0002765 mhos cm–1.0002765 cm–1 a = 0. If the cell is filled with an electrolyte and offers a resistance of 1996 ohm.138 cm–1.10 (c) Titration curve of KCl solution by AgNO3 solution. 1996 Specific conductivity = Cell constant × observed conductivity. SOLVED EXAMPLES Example 1. N Example 2. In the region of the equivalence point. Titration of a very weak acid with strong base or a very weak base with strong acids results in a small initial conductance.PM5 219 .4 cm–1 a 1. 9. A conductivity cell contains two electrodes of area of cross-section 1.2 × 10–3 ohm–1 cm–1. C-8∴N-ENGCHE∴ECH9-1. Cell constant = and R=ρ a a l R 1 or = =R× =R×K a ρ ρ l ∴ = 500 × 0.25 1 Observed conductivity = ohm–1.25 cm2. calculate the cell constant and specific conductivity.5 Sol. Specific conductivity of an KCl solution at 25°C is 0. 50 If the resistance of cell containing this solution is 500 ohms. 1 1 = 8.5 cm. due to hydrolysis the titration curve shows a marked curvature (Fig.4 × 1996 1996 = 4. 9. l 10.

2 N ZnSO4 .9 ohm cm . l/ a 12.02109 ohm–1 cm–1 72.18 1000 λv(equivalent conductivity) = Kv × C 1000 = 0.02 N KCl solution offers a resistance of 550 ohm at a definite temperature.166 ohm–1 cm–2. Calculate specific resistance of the solution. Calculate the cell constant.4 K = 0. The specific conductivity of 0.58 ohm. the observed resistance of the cell is 72.5224 × = 0. Cell constant = R=ρ a a l R 1 or = =R× =R×K a ρ ρ l ∴ = R × K = 4364 × 2.2 (N) KCl is 2. Cell constant = R × K = 550 × 0. C 0.010416 λv = = = 104. l 1 1 l 1 18 .002768 = 1. Calculate the equivalent conductance (λv ) of the solution. Sol. cm. l l Sol.18 ohm. If the cell is filled with another solution the observed resistance is 3050 ohm.4 cm2 in area was found to be 32 ohms. R=ρ or = = × a ρ R a 32 5. A conductivity cell containing 0. Sol.1 C-8∴N-ENGCHE∴ECH9-1.010416 ohm–1 cm–2 1000 K 1000 × 0.075 cm–1 a R 3050 ρ= = ohm.1 –1 = 210. Specific conductivity of a conductivity cell containing 0.02109 × 0. The resistance of a decinormal solution of a salt occupying a volume between two Pt electrodes 1.220 ENGINEERING CHEMISTRY Example 3. the observed resistance of the cell is 4364 ohm.02109 λm(molar conductivity) = = M 0.02 N solution at that temperature is 0.075 = 252.5224 cm–1 Again. cm. If the cell is now filled with 0.002768 ohm–1 cm–1.767 × 10–3 cm–1 = 12.45 ohm–1 cm2 1000 K 1000 × 0. 2 Example 5. Calculate the equivalent and molar conductivities of the ZnSO4 solution.80 cm apart and 5.PM5 220 . K = cell constant × observed conductivity 1 = 1.767 × 10–3 ohm–1 cm–1. Example 4.2 = 105.

05 0 0 Degree of ionisation = α At equilibrium = .6 Example 7.05α .8 × 10–5). Sol. Ag = 108.05(1 – α) .0λ∞ NaCl = 126. λ∞ 0. l–1 = 0. The specific conductivity of saturated solution of AgCl is 1.8 and 65.05α [CH3 COO – ] [H + ] 0. Calculate the degree of dissolution of acetic acid.PM5 221 .1 λ∞AcONa = 91.ELECTROCHEMISTRY 221 Example 6.05 0. λ v∞ 390.0348 ohm–1 m2 eq–1 and 0. Example 8.3 mho eq–1 cm2.05 = .9 × 10–3 0. Sol.5).0018 ohm–1m2 eq–1.1 + 91.6 ohm–1 cm–2 eq–1. Calculate the degree of dissociation of acetic acid.8 × 10 −5 18 × 10 –6 ∴ α= = = = 18. Calculate the solubility –1 of AgCl in gl–1 (At. λv 48.05 [α being negligible. Equivalent conductance of acetic acid at 25°C is 0.0388 Example 9. λ∞HCl + λ∞AcONa – λ∝NaCl = (λ H + + λ Cl – ) + (λ Na + + λ OAc – ) − (λ Na + + λ Cl – ) = λ H+ + λ OAc – = λ∝AcOH ∴ 426.0388 λv 0.05(N) 60 CH3COOH CH3COO– + H+ Initially = 0. Calculate the percentage ionisation of acetic acid.028 × 10–3 (N) acetic acid is 48.1233.0 – 126.05 (1 – α) 0. 1 – α ≈ 1] = 0.5. The equivalent conductance of 1. C-8∴N-ENGCHE∴ECH9-1. (Ka = 1.15 ohm–1 cm–2 eq–1 at 298 K. what will be the concentration of acetate ion.24 × 10–6 mho cm . λ∞(CH3COOH) = λ∞H+ + λ∞CH3COO– = 0. The equivalent conductances at infinite dilution of various electrolytes are given: λ∞HCl = 426.046. 3 Sol.15 Sol. Its equivalent conductance at infinite dilution is 390.05α2 Ka 1. wt.05α (0.0018 ∴ Degree of dissolution = = = 0.5 = λ∞ AcOH = 390.004 ohm–1 m2eq–1. If 3g of acetic acid is added to enough water to make one litre solution.05α × 0.0348 + 0.05 0. The mobilities of Ag+ and Cl– ions are 53.05) 2 α 2 Ka = = = [CH 3COOH] 0.01898. If ionic conductance of H+ ions and CH3COO– ions at infinite dilution are 0.004 ohm–1 m2 eq–1 = 0. respectively.6 Ohm–1 cm2. Calculate λ∞(AcOH). Strength of CH3COOH solution = g equiv. Cl = 35. Example 10. α= = = 0.

tNO – = 1 – tAg + = 1 – 0. The amount of Cu in the anodic solution was found to be 0.1351 g of Ag. Cu(63.714. and 0.1351 = = 63.6236) g = 0.1351 g.6236 g. wt.916 ∴ tAg + = = = = 0.000 u 0. of Cu Eq. placed in series.1495 g l–1. 3 Example 12.6 × 10 2 = (0.1351 × 31. wts. wt. The weight of Ag deposited in a silver coulometer.916 0. A dilute solution of CuSO4 was electrolysed. C-8∴N-ENGCHE∴ECH9-2.916 + 1 1.. Wt. λα(AgCl) = λ(Ag+) + λ(Cu–) = 58.6)] Sol. of Cu in anodic solution after electrolysis is = 0. According to Kohlrausch’s law. The speed ratio of Ag+ and NO3– ions in a solution of AgNO3 electrolysed between Ag-electrodes is 0. wt. was found to be 0.6236 g before and after electrolysis. ∴ Loss in wt.6350 g.3 + 65.222 ENGINEERING CHEMISTRY Sol.3 = 119.0104 × 143.8 ∴ x= = 0. of Ag x 0.e. = = Speed of NO 3 – v 1.6350 – 0.24 × 10 –6 = 9.88 Loss at anode 0.916 Sol.6 × 105 cm3 eq–1 Kv 1.0398 g 107.6 × 102 l eq–1 1 ∴ Solubility = eq l–1 = 0.88 2 0.286 Total loss 0.0398 ∴ tSO4∞ = 1 – tCu +2 = 1 – 0. using Pt-electrodes.1 ∴ V= = = 9.6 107.286 = 0.916 Hence.00104 eq l–1 9.522. ∴ Amt.478 u + v 0. of Cu from anodic solution (anolyte) = (0. of Cu in anodic solution before electrolysis = 0.0114 g Wt. Example 11. Calculate the transport number of Cu+2 and SO4–2 ions. = Ag(107. of Cu deposited equivalent to 0. Find the transport number of Ag+ and NO3– ions.88). λα = λ+ + λ– i.6350 g. respectively. Speed of Ag + u 0. of Cu( x) wt.1351 g.114 ∴ tCu +2 = = = 0. of Ag = = Eq. of Ag deposited in voltameter = 0.5) g l–1 = 0.478 = 0.PM5 222 . Wt. [At.1 mhos eq–1 cm2 λv = KvV λ ∞v 119.916.

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

Quantity of electricity in an hour = 30000 C/S × 3600 s. 11. hydrogen and sodium hydroxide. Electrolytic cell. (b) Sodium is extracted by the electrolysis of a mixture of a molten NaCl and CaCl2.000 C.000 Mass of Na formed per hr. (a) Draw a neat sketch of an electrolytic cell. 9. while the solution turns to NaOH.480 = 25. Q. 9. = mol 96.11. = 108. During electrolysis chlorine is liberated at the anode. If the anode is a metal (Cu. = × 23 = 25.75 kg. or Ag).480 108.PM5 224 .750 g 96.000 A. 108. In a commercial cell the current is 30.000. Q. C-8∴N-ENGCHE∴ECH9-2. Q.000 Amount of Na formed per hr. Chlorine is liberated at the anode during electrolysis of a concentrated solution of NaCl. The concentration of a salt solution has an effect on the product of electrolysis at the anode. What is the effect of concentration of a salt solution during electrolysis? Ans. Brine is a solution of NaCl in water. 10. In electrolysis of a dilute solution of NaCl increasing amounts of oxygen are liberated.000. Cu(s) → Cu2+ (aq) + 2e. What is the utility of electrolysis of brine? Ans. (b) The equation for liberation at the cathode is – Na+ + e → Na Time of electrolysis = 3600 sec. What mass of Na is formed in an hour at the steel cathode? Ans. Electrolysis of brine is the basis of the alkali and chlorine industry—a well known electrochemical industry. hydrogen is liberated at the cathode and bubbles off. (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.224 ENGINEERING CHEMISTRY Otherwise oxygen is liberated from water. atoms of electrode turn into ions. Electrolysis of brine is used to manufacture chlorine.000.

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

20. λm Q. Q. What do you mean by equivalent conductivity of an electrolytic solution? Ans. Q. 18. What do you mean by molar conductivity of an electrolyte? Ans. 1000 K Equivalent conductivity λeq = C C = normality of the solution. i.226 ENGINEERING CHEMISTRY Q. Define Kohlrausch’s law. 16. Q. is equal to the sum of ionic conductances of cations and anions. C-8∴N-ENGCHE∴ECH9-2. 19. What are the applications of conductance measurement? Ans. Q.. Ans. b = constant c = concentration λm∞ = molar conductivity at infinite dilution λm = molar conductivity at a given dilution As c → 0 λm = λm∞. What is transport number? Ans. Q. molar conductivity λm = M where. It is the fraction of total quantity of electricity. It is the conductivity of all the ions produced in a solution containing one gm mole 1000 K of the electrolyte. (iii) Conductometric titration. The molar conductance. carried by cations or anions. (i) Measurement of degree of dissociation. 17. 15. The relation is λm = λm∞ – b c where.e. (ii) Determination of solubility and solubility product. Unit of λeq = ohm–1 cm2 equiv–1. Molar conductivity increases with dilution. What is specific conductance? Ans. The degree of dissociation (α) is the fraction of the electrolyte that dissociates into ions. Q. Ans. 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.PM5 226 . What is the effect of dilution on molar conductivity? Ans. The specific conductance (K) is the reciprocal of specific resistance (ρ). 23. It is the conducting power of all the ions present in a solution of an electrolyte containing 1 g equiv. Give the relationship of molar conductivity with concentration. 22. For weak electrolytes it is related to λm and λm∞ as follows: λ α = m∞ . What do you mean by degree of dissociation of an electrolyte? Ans. M = molarity of the solution K = specific conductance. at infinite dilution of an electrolyte. 21.

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

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. specific conductance decreases with dilution. (b) State and explain Kohlrausch’s law of independent mobilities of ions. 10.PM5 228 . the number of ions per millilitre decreases. and E. E1 E2 E (b) Prove that = = . 3. i. 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. As a result. (d) Define Faraday’s second law. But it outweighs the minor increase in conductance due to increase in degree of dissociation. (a) Define the specific resistance of a solution. (b) Relate C. (b) State and explain Kohlrausch’s law. What is an electrolyte? Give examples.E. 8. When an electrolyte is diluted. What do you mean by electrolysis? 2. (b) Discuss the effect of change in concentration of the solution on specific conductance and equivalent conductance. (b) Define specific conductance. (a) State the relationship between the cell constant. degree of dissociation increases and also the total volume increases. n = F. 11.E. (a) State the Faraday’s laws of electrolysis. (b) State Kohlrausch’s experimental equation. Mention its units.. (e) Give the applications of the theory of electrolytic dissociation. (c) Write the shortcomings of the theory of electrolytic dissociation. (c) State Kohlrausch’s law. conductivity and conductance.e. Ans. With the aid of a plot. 28. C-8∴N-ENGCHE∴ECH9-2. How will you determine transport number? (b) Specific conductance of an electrolyte decreases. But equivalent conductance increases because the total number of ions per gram equivalent increases with dilution for the increased value of degree of dissociation. How would you account for the result? 7.C. 9. Specific conductances decreases with dilution while the equivalent conductance increases—explain. (a) Define transport number. (a) Write Kohlrausch’s empirical equation. Discuss its significance and applications. (c) Define the absolute ionic mobility.E. (a) Define the terms (i) specific conductance and (ii) equivalent conductance.. Explain a few applications of this law. (a) Define the terms: (i) Specific conductance (ii) Equivalent conductance. (a) Explain the terms : (i) Faraday (ii) E.228 ENGINEERING CHEMISTRY Q. Z1 Z2 Zn 4. 6.2. EXERCISES 1. explain the variation of equivalent conductance of KCl and CH3COOH on dilution.. 5.

Calculate the equivalent conductance (λv) of the solution at the same temperature. The cell was then washed out and filled with 0. 166. During the electrolysis of CuSO4 solution. [Ans.420. [Ans. If the resistance of 50 cell containing this solution is 500 ohms. 1.000275 mhos cm–1.9 ohm–1 cm2] 19.46] C-8∴N-ENGCHE∴ECH9-2. 0. Specific conductivity of an KCl solution at 25°C is 0.36 × 10–4 Sm2 eq–1 respectively. current was passed for 2 mins.785] 4 25. 1.PM5 229 . After electrolysis 51. Write short notes on : (i) Cell constant (ii) Absolute velocity of an ion (iii) Conductometric titration (iv) Kohlrausch’s extrapolation method of determining λv. 4. respectively. Why does the equivalent conductivity of a NaCl solution increase with dilution? How can the electrolytic conductance be measured? N 16. tAg + = 0.2 ohm–1 cm2] 21. The resistances of 0.1 N KCl solution and 0.058 g of Cu was deposited. Calculate the transport number of Cu+2 and SO 4– – ions [At. and its resistance was found to be 37.80% AgNO3 solution was electrolysed using Ag-electrodes. [Ans.000 ohms respectively at 298 K.5 ohms. tSO = = 0.098 (N) KCl was found to be 214. if the cell constant is 0. [Ans.0 ohm–1 cm 2] 20. Calculate the equivalent conductance (λv) of the solution (cell constant = 0. Define Kohlrausch’s law and discuss its applications. What is the transport no.1 N KCl solution is 0.84 × 10–4 and 133. A 2.02 N of an electrolytic solution in a conductivity cell were found to be 310 ohms and 2. [Ans.84% CuSO4 solution was electrolysed using Pt cathode and Cu-anode. What is the percentage dissociation of acetic acid at this concentration? [Ans. After electrolysis. 42. tCu +2 = 0.878 cm–1.215. A one amp. Find the transport no.1 M of CuSO4 .00277 ohm–1 cm–1.30 ohm cm eq–1. [Ans. = Cu(63. of Cu+2 ion. The resistance of a conductivity cell filled with 0.18 ohm–1 cm –1] 18. The ionic conductances –1 2 of H+ and CH3COO– ions at infinite dilution are 349 and 40 ohm –1 cm2 eq–1. The resistance of a cell filled with 0. 14. The equivalent conductance at infinite dilution of NH4Cl. [Ans.0 g of the anode solution (anolyte) was found to contain 0. Calculate the equivalent conductance of the given solution. 13.382 × 10–2 S m 2 eq–1] 22.409 g Cu in 54. The resistance of 0. loss of Cu in the anode compartment was 0. The equivalent conductance of 0. the cathode solution contained 0.02 (N) KCl solution at 25°C is 225 ohms. In a voltameter connected in series. A 0. tCu +2 = 0. 15.138 cm –1] 17. Also explain the nature of the graph between conductance and volume of titrant used.0 ohm–1 cm 2.215] 24.4 ohms at 298 K.74 × 10–4.02 M KCl solution at this temperature was 0.ELECTROCHEMISTRY 229 12. The specific con- ductance of 0. NH4NO3 and AgNO3 are 149.6). Calculate the equivalent and molar conductances of CuSO4 solution. [Ans. 83. Discuss all types of conductometric titrations. The increase in the weight of cathode was 0.1 (N) solution of NaCl is 210 ohm at 18°C. what is the cell constant? [Ans.19%] 23. The specific conductance of 0. of Ag+ in AgNO3.88 cm–1).7 g solution.0128 ohm –1 cm –1. S(32) and O(16)].01 N acetic acid is 16. 99. Calculate the equivalent conductance of AgCl at infinite dilution. 41. 144.804 g.519 g of AgNO3. wt.

10.f. atom of Fe+2. +3 Fe + Sn +2 Fe+2 + Sn+4 +3 For 1 g. atom of Fe .85 g.1 Construction of a cell. 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. 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. And for every g. 55. As for example in the reaction: 2FeCl3 + SnCl2 2FeCl2 + SnCl4 i. twice the Avogadro’s number of electrons is lost. a cell is constructed of two electrodes and the e. of the cell. By 230 .f.m. Avogadro’s number of electrons are gained to get reduced to 1 g. we get Sn+4 in the vessel B and Fe+2 in vessel A. atom of Sn+2. And we get deflection in milliammeter.e.m.. Nernst called this tendency as “solution pressure”. 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. 10. 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. 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.1 after sometime. of the cell is obtained from the algebraic sum of the two electrode potentials. If we make an arrangement as shown in Fig.

This established potential is called electrode potential.341 × 298 ∈ = ∈° + log10 aM + n n × 96500 0. as a result. So. At 25°C the equation comes to : 2. but in this case. metal rod becomes negatively charged. But when one exceeds the other the metals get either positively or negatively charged. Zn rod sends Zn+2 ions into the solution and gets negatively charged and attracts + – – + – + + – + – – + positive charges towards the rod and.M. When “solution pressure” equalises “osmotic pressure” there is no net effect.ELECTROCHEMICAL CELLS 231 sending the ions.303 × 8. 10.PM5 231 . the solution pressure Zn Cu exceeds osmotic pressure. the system (Pt) Fe+2 (Pt) Fe+3 + e sets up an electrical double layer where an inert metal platinum is dipped into a mixture containing Fe+2 and Fe+3 and an electrode potential is established. As for example. of the cell is algebraic sum of the two electrode potentials. And each electrode has a potential which is known as single electrode potential (∈∈). n ⇒ Valency of metal R ⇒ Gas constant T ⇒ Absolute temperature F ⇒ Faraday constant a ⇒ Activity of M+n. the solution has a tendency to send M+n ions to the metal rod due to “osmotic pressure”. Here also a electrical double layer is set up and electrode potential is established. in the case of Zn/Zn+2. For example. On the contrary. E. we call each of them as single electrode. To consider the electrodes separately. And so is the case with Cu/Cu+2. The electrode potential is also established in the case of every electrode where electrical double layer is set up by exchange of electrons. an + – – + – + + – electrical double layer is set up and a potential is + – – + – + + – established between the metal rod (Zn) and its ions ZnSO4 CuSO4 (Zn+2). an electric cell is composed of two electrodes.2 Electrode potential. gets positively charged. osmotic pressure exceeds solution pressure and Cu rod Fig. the metal rod accumulates electrons and as a result. 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.059 = ∈° + log10 aM + n n C-8∴N-ENGCHE∴ECH10-1.F.

• E. (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. If we construct the following cell: Zn(–)| Zn+2 || Cu+2 |(+) Cu. Determination of Standard Potential ∈° of a Metal Electrode The electrode potentials cannot be determined straight.015 V For this cell Zn/Zn+2 is anode and Cu/Cu+2 is cathode and at anode. oxidation takes place at anode and at the cathode Cu+2 is neutralised i. to determine the electrode potential. of the cell E = ∈right – ∈left (when both are reduction potentials) E = ∈red + ∈ox. Highlights: According to IUPAC convention. Zn is ionised to Zn+2 i.e. aM + n = C M + n 0.059 So.f.. We have a zero potential for this electrode. we take the ∈° value for hydrogen electrode to be ‘zero’ i. Ecell = 1.e. • Electrons flow through the external wire from the negative electrode to the positive electrode. We are to assign a definite value of electrode potential for a definite electrode.. Now if we want to determine standard electrode potential of zinc (∈°Zn) we are to construct the following cell.232 ENGINEERING CHEMISTRY For general purpose. • 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.PM5 232 .. • The single vertical lines denote electrical contact. • A complete cell consists of two half cells. • Oxidation potential may be taken as reduction potential with a minus sign. For example. then ∈ = ∈° ∈° is known as Standard electrode potential of metal M. So reduction takes at the right hand electrode and oxidation takes place in the left hand electrode. then the expression is : ∈ = ∈° + log10 C + n [A form of Nernst equation] n M When a = 1.e. 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. Total cell reaction is: Zn + Cu+2 Zn+2 + Cu. a solution of acid with ([H+] = 1) and to which hydrogen gas is bubbled at one atmosphere and platinum foil is dipped.m.

the electrode potential of other metals are determined similarly and listed in table. 762 Mg.1: Standard Electrode Potentials (Reduction). Mg++ Mg++ + 2e = Mg – 1. Likewise.106. H+ H+ + e= 1 H2 0. = Standard reduction potential of Cu + std.f.000 2 i.f.1) Example 1.715 Li. 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. Li+ Li+ + e = Li – 2.f of a cell is measured by potentiometer.06 Hg.360 i. This list with ∈° values are known as electrochemical series. Fe+++. Hg2++ Hg2++ + 2e = 2Hg 0. Sn++ Sn++ + 2e = Sn – 0.m.771 Cu.866 Na. of the cell Zn ZnSO4 (solution) CuSO4 (sol n ) (aZn +2 = 1) Cu (aCu+ = 1) Sol. Na+ Na+ + e = Na – 2.ELECTROCHEMICAL CELLS 233 Table. 25°C Electrode Electrode reaction E°(Volts) (Reduction) F2.80 2 Pt.798 Pt. H+ 2 O2 + 2H+ + 2e = H2O 1.. Calculate the e.m. of the cell will be E° = ∈°H + ∈°Zn = ∈°Zn [Q ∈°Η = 0] The e. Cl– Cl2 + e = Cl– 1.e.f. Cl2(g). electropositive Pb.m..268 2 (Pt) H2.136 Zn.23 Oxidants Au. oxidation potential of Zn. Cu++ Cu++ + 2e = Cu 0.e. Fe++ Fe+++ + e = Fe++ 0.799 Ag. Typical calculation of e. electronegative 1 Pt.762 = 1.959 The e.m. Pb++ Pb++ + 2e = Pb – 0. F – 1 F2 + e = F– 2.122 Reductants Sn.344 Calomel electrode 1 Hg2Cl2 + e = Hg + Cl– 0. O2. Ag+ Ag+ + e = Ag 0.f. (Table 10.344 + 0.m. 10. and we get standard e.PM5 233 . Zn++ Zn++ + 2e = Zn – 0. E° of the above constructed cell which is ∈°Zn. Au+++ Au+++ + 3e = Au 1. = 0.

E = Reduction potential of Cu + Oxidation potential of Fe.e.1) 1. The higher electropositive metal i. possessing lower standard electrode potential (reduction) will displace the metal from the solution of its ions with a higher standard electrode potential (reduction) value. then e. These electrodes are known as redox electrodes.344) Likewise. RT a 0.f. higher is the electronegativity of that element. Electrode potential (∈) is given by: Oxidant + ne Reductant Ox + ne Red.m. 3. For example – Zn(∈°Zn = – . C-8∴N-ENGCHE∴ECH10-1. If a cell is constructed with the two elements as the electrodes then the e.234 ENGINEERING CHEMISTRY RT or = ∈°Cu + − ln [Cu +2 ] [Q [solid] = 1] 2F Likewise. 2. ln [Cu +2 ] − ∈°Zn + RT . Lower position in the table of an element indicates its higher tendency of ionisation. = 0.344 + 0.441 = 0. of the cell is obtained from the oxidation potential of anode and reduction potential of cathode. RT ∈left = ∈°Zn + ln [Zn +2 ] [Q [solid] = 1] 2F °45 RT 78 45 .785 volt.m. The higher the standard electrode potential (reduction) of an element. 2F [Zn +2 ] Interpretation of the Electrochemical Series (Table 10. ln [Zn +2 ] 78 6 Ecell = ∈Cu + 2F 9 6 2F 9 ° ° RT [Cu +2 ] ∴ Ecell = (∈Cu − ∈Zn ) + ln .PM5 234 .f.. Let Fe and Cu are used as electrodes. the non-metals with the higher electronegativity displace the elements possessing lower electronegativity. 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.762) will displace Cu from its solution (∈°Cu = . of the cell. Any oxidised or reduced form of an element behaves so.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.

54 1 1 (Pt) I /I– 2 2 I 2 2 +e I– + 0. ∈° = 1.535 (Pt) Fe+2/Fe+2 Fe+3 + e Fe+2 + 0.65 2 2 The pair which occupies lower position in the table can oxidise the pair which occupies a higher position in the table. 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. ∈° = 2.56 V + MnO2 + 4H + 2e 2+ Mn + 2H2O.PM5 235 . 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.2: Normal potentials (∈°) of some redox system (Hydrogen scale) Electrode Electrode reaction Electrode potential ∈°(volts) (Pt) Cr+2/Cr+2 Cr2+ + e Cr2+ 0.ELECTROCHEMICAL CELLS 235 Table 10. the different oxidation states are represented by the corresponding ∈° values as follows: Mn2+ + 2e + Mn.36 MnO4–/Mn+2 MnO4– + 8H+ + 5e Mn+2 + 4H2O + 1.52 Ce+4/Ce+3 Ce+4+e Ce+2 + 1.77 (Pt) 1 Br2/Br– 1 Br2 + e Br– + 1.25 1 Cl2/Cl– 1 Cl2 + e Cl– + 1.95 V MnO42– + 4H+ + 2e MnO2 + 2 H2O. ∈° = – 1.23 V C-8∴N-ENGCHE∴ECH10-1. ∈° = 1.36 2 2 Cr2O7 2–/2Cr+3 Cr2O72– + 14 H+ + 6e 2Cr+3 + 7H 2O + 1.69 Co+2/Co CO+2 + e CO+2 + 1.20 (Pt) MnO2/Mn+2 MnO2 + 4H+ 2e Mn+2 + 2H2O + 1.61 MnO4–/MnO2 MnO4– + 4H+ + 3e MnO2 + 2H 2O + 1.23 Tl+3/Tl+2 Tl+3 + 2e Tl+1 + 1. ∈° = .52 V MnO2 + 4H+ + e Mn3+ + 2H2O.16 (Pt) [Fe(CN)6]2–/[Fe(CN)4]4– Fe(CN)63– + e Fe(CN)64– + 0.065 2 2 (Pt) IO2–/ 21 I2 IO3– + 6H+ + 5e 1I 2 2 + 3H2O + 1. ∈° = + .82 S2O42–/2SO42– S2O42– + 2e 2SO42– + 2.26 V MnO4 + e MnO42– .18 V +3 Mn + e 2+ Mn .52 BrO2–/ 21 Br2 BrO3– + 6H+ + 5e 1 2 Br2 + 3H2O + 1.21 – 0.25 (Pt) H+/ 21 H2 H+ + e 1 2 H2 0.00 (Pt) Sn+4/Sn+2 Sn+4 + 2e Sn+2 + 0. We know that Mn exists in different oxidation states and in acidic medium preferably at zero pH.41 (Pt) V + 2/V+2 V+3 + e V+2 – 0.15 (Pt) Cu+2/Cu+1 Cu+2 + e Cu+1 + 0.01 1 F2/F– 1 F2 + e F– + 2.36 (Pt) MnO4–/MnO42– MnO4– + e MnO42– + 0.

the oxidation states of Mn decrease gradually from left to right. C-8∴N-ENGCHE∴ECH10-1. We know that ∆G° values corresponding to different steps can be added but the ∈° values cannot be so added.70 V MnO4– + 8H+ + 5e Mn2+ + 4H2O.18 V MnO4– → MnO42– → MnO2 → Mn3+ → Mn2+ → Mn In this diagram. 2H2O2 → 2H2O + O2 ∆G° = – 2. we know that H2O2 disproportionates into H2O and O2 under acidic conditions.95 V 1.236 ENGINEERING CHEMISTRY MnO4– + 4H+ + 3e MnO2 + 2H2O.12 F Since the process is accompanied by decrease in Gibbs free energy. ∆G° = – nF∈°. A Latimer diagram helps us to derive the standard potentials of such non-adjacent couples. a species will undergo comproportionation if the potential on the left is higher than that of the right species in the diagram. H2O etc. in this case the comproportionation reaction Ag2+ + Ag = 2Ag+ will take place. adding them together and converting the sum back to ∈° for the non-adjacent couple dividing by – nF for the overall electron transfer.PM5 236 .52 F Adding (a) and (b). On the other hand.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 = – .51 V The whole information can be summarised in the compact manner in a collinear diagram as follows. 0.4 F (b) Reduction: H2O2 + 2H+ + 2e → 2H2O ∈°Red = 1.56 V 2. ∈° = 1.98 V 0. 0. 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. 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.70 volt 1.52 V – 1. therefore dispro- 1. are called skip couples and the corresponding potentials are called skip-step potentials.76 = – 3. The couple such as MnO4–/MnO2 or MnO4–/Mn2+ or MnO2/Mn2+ etc. for the change Ag2+ → Ag+ → Ag it can be shown by similar calculation that disproportionation of Ag+ will not take place because it will be accompanied by increase in ∆G° value. On the other hand. A species will disproportionate into its neighbour species if the potential on the left is lower than that of the right species.76 V ∴ ∆G°2 = – nF∈° = – 2F × 1. The species H+. ∈° = 1. Hence.70) = 1.26 V 0.80 V portionation will be spontaneous. are not included in the diagram. we can write n1∈°1→ 2 + n2 ∈°2 → 3 ∈°1 → 3 = n1 + n2 Besides calculating the ∈° values of non-adjacent couples. Again ∆G° is related to ∈° as follows.70 V ∴ ∆G°1 = – nF∈° = – 2F × (– .

e. 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.. The oxidising agent of a redox couple will show tendency to reduction if the slope is more +ve.3 (a) Fig. 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. we can make thermodynamic predictions about the reaction between any two couples by comparing the steps of the corresponding lines. This is due to the fact that. however. The reducing agent of the couple with less +ve slope will tend to undergo oxidation. 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. The Frost diagram for nitrogen in various oxidation states is as given in Fig. it can be predicted whether the oxidant or the reductant will show greater tendency for a reaction. in NH4NO3.g. Hence.3(a) and 10. Cu. A substance that lies below the line connecting two adjacent neighbours in a Frost diagram is more stable than they are because its average free energy is lower.3 (b) Frost diagram for nitrogen (N).PM5 237 . When the line joining two points in the diagram is quite steep. on the C-8∴N-ENGCHE∴ECH10-1. 10. the average free energy of the intermediate species is larger than the mean free energy of the two adjacent species. 10. not spontaneous as it is not kinetically favoured.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. 10. the potential of the corresponding couple is higher..3(b). On the basis of this diagram. NH4+ ion contains N in –3 oxidation state and in NO3– ion N is present in +5 oxidation state. (at pH = 0). From the diagram it is seen that since NH2OH lies above the line joining NH3 and N2 it will undergo disproportionation. The disproportionation is. 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+. 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. 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. however. Under such circumstances comproportionation will be thermodynamically favoured e.

n∈° for the formation of H2O = – 2 × 1.238 ENGINEERING CHEMISTRY other hand N2O has an oxidation state of +1.46 volt.. we get the required Frost diagram as follows.76 volt.23 = – 2..46 – (– . 10. C-8∴N-ENGCHE∴ECH10-1. oxidation number of ‘O’ changes from 0 to –1. let us consider the Latimer diagram. Hence. change in oxidation number = – 1.46 volt. respectively. 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∈° = – . NH4+ + NO3– → N2O + 2H2O.76 volt. – 2. H2O2 and H2O are 0.4 Frost diagram for the system O2 → O2–2 → 2O–2. Therefore.g.70 = – .70) = – 1.PM5 238 . When ‘O’ changes from O2 to H2O2. Therefore. ∴ ∈° = – 1 × .70 volt. When these values of n∈° are plotted against the corresponding oxidation numbers. When the line joining three adjacent species becomes approximately a straight line. 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. 0. The change in oxidation number from H2O2 to H2O is –1. therefore. when O changes to H2O its oxidation number changes from 0 to – 2 and in this case. HNO2 and HNO3 lie approximately on a straight line in the Frost diagram. n = – 2. The difference is. This is in accordance with the Latimer diagram.23 V The oxidation numbers of ‘O’ atom in O2. NO + NO2 + H2O → 2 HNO2 3HNO2 → HNO3 + 2NO2 + 2H2O 3NO2 + H2O → HNO3 + HNO2 A Frost diagram can be constructed from a Latimer diagram e.76 H2O2/H2O is equal to = + 1. then no one species will be the exclusive product e. the ∈° for the couple − 1. −1 +1 0 O2 n (V) H2O2 –1 Acidic –2 H2O –2 –1 0 Oxidation number Fig.g.70 volt and n∈° corresponding to oxidation number of – 2 is – 2. – 1 and – 2.76 V O2 H2O2 H2O +1. This is due to the fact that NO. 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.70 V 1.

Concentration Cell When a metal is dipped into two solutions of one of its salts of different concentrations.15 V] Adding Cu+ + Cu+ Cu+2 + Cu° [E°cell = 0.106] Since. ∈° Cu +2 /Cu + = + 0.762 ∈°Cu +2 /Cu = 0.15 V ∈° Cu + / Cu ° = 0.798] Since.37 V] Since E°cell is positive. Given. 2. Predict whether the reaction will occur spontaneously or not. Cell reaction: 2Ag + 2H+ → 2Ag+ + H2 The two half cell reactions are: 2Ag – 2e 2 Ag+ [∈° = – 0.798] 2H+ + 2e H2 [∈°H+/H = 0. a very interesting situation arises: C-8∴N-ENGCHE∴ECH10-1.798. given ∈° Ag+/Ag = 0. Prediction regarding liberation of hydrogen by a metal from a hydracid. the E°cell value is negative. Prediction of an oxidation-reduction reaction. cell reaction is 2Cu+ Cu+2 + Cu°. E°cell = – ve. Sol. Find whether Cu+ disproportionate in aqueous solution into Cu+2 and Cu° i.52 V] Cu+ –e Cu+2 [∈° = 0.52 V The two half cell reactions are: Cu+ + e Cu° [∈° = 0. Example.. Example. Cu+ will disproportionate spontaneously in aqueous solution into Cu+2 and Cu°. Ag cannot displace H2 from HCl.00 V] Adding 2Ag + 2H+ 2Ag+ + H2 [E°cell = – 0.ELECTROCHEMICAL CELLS 239 Highlights: Uses of standard potential (reduction) values: 1.762] Cu – 2e Cu+2 [∈° = 0. the reaction will not occur spontaneously.344] Adding Zn+2 + Cu Zn + Cu+2 [E°Cu = – 1.e. So. Example. Prediction of feasibility of a chemical reaction.344 The two half cell reactions are: Zn+2 + 2e Zn [∈° = – 0. Ag will not displace hydrogen from HCl.PM5 239 . 3. Zn+2 + Cu Zn + Cu+2 ∈° Zn +2 / Zn = – 0.

C2 If = 10. C-8∴N-ENGCHE∴ECH10-1.m. [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.303 × 8. e. the observed e.303 log 2 = log 2 nF C1 n × 96500 C1 0. Imagine that current passes through the external wire as shown by the arrow. C1 The stronger solution acts as positive electrode. So. 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 2.138 × (298) C E = 2.f. 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–.5 Concentration cell.f. of such cell depends on the relative concentration and not on the absolute values.m. is 59 mV. E= log 2 [Q n = 1] 1 C1 Therefore.240 ENGINEERING CHEMISTRY Ag | AgNO3(C1) || AgNO3(C2) | Ag Ag AgNO3(C1) Salt bridge AgNO3(C2) Ag (Dilute) of satd.059 C So.PM5 240 . 10.

concentration of Ag+ in 0. of the following cell. Another type of concentration cell is electrode concentration cell. 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.045 M Let C1 be the concentration of Ag+ in AgI solution.059 0.01N) of KNO 3 Saturated AgCl | Ag salt bridge e. Example 1.9 = 0.m. of the cell is 0.9 each.PM5 241 .m. 2 Application of the Concentration Cells H2 Determination of solubility of sparingly-soluble salts.f. 0. Calculate (i) Solubility product of AgI.f. Given e. of the cell is given by.9 = 0.045 or 0. 0. 0.788 or log = = 13. (ii) Solubility of AgI in water at 25°.045 M The concentration of I– in KI is 0.01(N) AgNO3 solution is 0.f. If we want to determine the solubility of AgCl. Cell: Ag/AgI/ in 0.059 C E= log 2 n C1 Here n = 1.33 C1 = 2.138 × 1013 C-8∴N-ENGCHE∴ECH10-1.045 or = Antilog 13.m.059 0. Ag+ in AgCl can be calculated.05 × 0.05 (M) KI) | NH4NO3 | AgNO3(0. of the cell is: E = 2F ln p .m.788 = 0.05 × 0. C1 i.045 ∴ E= log 1 C1 0. ion l–1 is (C2).05M) | Ag. E= log 1 C1 So.059 0. Saturated solution Ag | Ag NO3 (0.ELECTROCHEMICAL CELLS 241 This type of concentration cell is known as electrolyte concentration cell.33 C1 0.f.. we are to measure e.045 0. The activity coefficient (f) is 0.788 V at 25°C.01 g. The concentration of Ag+ in AgNO3 is 0.01 So.e.059 log C1 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

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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]

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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

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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

. Write the scheme of the cell and calculate its e.0592 C Ecell = log 2 .1 M and C1 = 0.E.0592 [Zn +2 ] 0.e.1 M)/Cu 0.765 V Cell reaction: Zn + Cu+2 Zn+2 + Cu (E°cell = ∈°Red + ∈°OX) = 1. Cell = Cu/Cu+2 (0. (Ox) for Zn electrode.254 ENGINEERING CHEMISTRY E°cell = ∈°Right – ∈°Left = 0.∈° = 0.m.. F = 96.P..01 M) || Cu+2 (0. (Ox) for Cu electrode = – 0. ∈°Cu +2 / Cu = 0. Calculate the equilibrium constant for Daniel cell at 25°C from the following data... Therefore.765 V and S. at 298 K.1 M and 0.e.765 V and ∈°Cu / Cu +2 = – 0.337 V Cell = Zn/Zn+2 || Cu+2 /Cu Half cell reactions Cu+2 + 2e Cu .76) = 1. = 0.P.01 log 10 Example 8.f.01 M separately in the form of a cell. ∈° Zn / Zn +2 = 0..0592 [Zn +2 ] 0.. 0.PM5 254 . S. Example 7.01 M n C1 0.0592 [Cu +2 ] ∈° Cu +2 / Cu − ∈° Zn+2 / Zn = log − log 2 [Zn] 2 [Cu] 0.316 J.337 – (– 0..0592 [Zn +2 ]/[Zn] or 0.0592 [ Zn +2 ] ∈Zn +2 / Zn = ∈° Zn +2 / Zn + log 2 [ Zn ] 0. ∈° Zn +2 / Zn = – 0.337 V Zn – 2e Zn+2 . [Zn +2 ] [Cu] ∴ K= [Zn] [Cu +2 ] 0.102 = 0.102 V.059 [Cu + ] ∈° Cu +2 / Cu = ∈°Cu +2 / Cu + log 2 [Cu] At equilibrium.0592 0.. 2 0.765 V i.0296 Ecell = log = = 0.1 0. these two electrode potentials will be equal.0296 V..0592 [Cu +2 ] ∈° Zn +2 / Zn + log = ∈° Cu +2 /Cu + log 2 [Zn] 2 [Cu] 0.E. Sol. Two copper rods are placed in copper sulphate solution of concentration 0. R = 8.8 – (– 0.56 V.500 C. here C2 = 0.0296 log [Cu +2 ]/[Zn] C-8∴N-ENGCHE∴ECH10-2.337 V i.∈° = 0.765) = log 2 [Cu +2 ]/[Cu] [Zn +2 ]/[Cu] 1.337 Sol.

Cell reaction Ag+ + e Ag ∈° = 0. – ∆G° = nFE° nFE° = – RT ln K C-8∴N-ENGCHE∴ECH10-2. K sp 8.2415 – 0.3 × 10–17 (M). Calculate the potential of an Ag-electrode in a solution that is saturated with AgI and has an iodide concentration of exactly unity.102 ∴ log10 K = = 37.0296 log K 1.0592 pH) = 0. The potential of a hydrogen gas electrode in a solution of an acid of unknown strength is 0.0592 0.29 ∴ pH = = ≈ 4. Sol. Example 9. 0.0592 Example 11.2297 0.5757 We have.3 × 10–17.2297 = 1.6990 = – 0.123 V at 25°C. ∈Q/H2Q = 0.798 Ag + Cl– AgCl(s) + e ∈° = – 0.123 + 0. Calculate Ksp of AgCl from the following data: ∈°Ag–AgCl(s) = 0.3 × 10 −17 [Ag+] = = = 8. Highlight: • The high value of K indicates the spontaneity of the reaction.0296 K = Antilog 37.6990 – 0. Calculate the pH of the solution.123 = (0. Ecell = ∈°H – ∈H = 0 – (– 0. Find out the pH of a solution in a quinhydrone half cell.m.f.0592 pH) – 0. Sol.9.798 at 25°C. which is coupled with standard calomel electrode. Ksp (AgI) = 8.799 V.2415 or – 0. Ecell = ∈Q/ H 2Q − ∈calomel 0.697 × 1037.ELECTROCHEMICAL CELLS 255 = 0.PM5 255 . I 1 Example 10.0592 Example 12.3345 0. ∈° Ag + / Ag = + 0. of the combined cell was determined to be 0.3345 or pH = = 5.0592 pH E cell 0. 0.2223 Ag + Cl– AgCl(s). Sol. Ecalomel = 0.29 V at 298 K as measured against normal hydrogen electrode. E°cell = 0.0592 pH = 0.2223 ∈° Ag + /Ag = 0.65 . Sol.2415. The e.6990.

What is a salt bridge? Ans. e.0592 or Here K = Ksp = Antilog 10.303 RT 0. What is galvanic cell or voltaic cell? Ans. It is a device used for converting electrical energy into chemical energy. KCl. Q.256 ENGINEERING CHEMISTRY nFE° 1 × 0. 4. It is a simple device of producing electrical energy by chemical reaction. What is an electrolytic cell? Ans. Q. It connects (acts as a bridge) the solutions of the two half cells. What are reduction and oxidation potentials? Ans.5757 or log K = – =– = – 9.M. What is the E. What do you mean by standard electrode potential (E°)? Ans. Daniel cell. 3. Such a cell is also known as electrochemical cell..2754 2. It is defined as the potential difference between the two terminals of the cell when no current is drawn from it.PM5 256 . 5.. 10.F.7246 = – 10 + 0. 7. It is an inverted U-tube containing an electrolyte (e. 2.g. It is the electrode potential of a metal in contact with its ions when the concentration of ions is 1 M (1 molar).g. C-8∴N-ENGCHE∴ECH10-2. e V Salt bridge e 2– SO4 Cu Zn ZnSO4 CuSO4 Zn → Zn+2 + 2e– (oxidation) Cu2+ + 2e → Cu (reduction) Fig. Q. Q.2754 = 1.886 × 10–10 mol2 l–2. SHORT QUESTIONS AND ANSWERS Q. 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. Reduction potential is the tendency of an electrode in a half cell to gain electrons and oxidation potential is the tendency of an electrode in a half cell to lose electrons. Q. 6. Q. 1.16 In the above cell Zn-electrode is anode and Cu-electrode is cathode. What do you mean by electrode potential (E)? Ans. KNO3). of a cell? Ans.

Q.M.M.F.PM5 257 . 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. KCl). of a cell measured? Ans. 10. 10.. named potentiometer. C-8∴N-ENGCHE∴ECH10-2. dipped in solution having 1 M H+ ion concentration and hydrogen gas at 1 atmospheric pressure constantly bubbled over it. Saline bridge Inert H2 electrode (Pt) (1 atm) + H (a=1) Redox system Pt A B Fig. 9. it consists of a strong electrolyte (e. ∆∈ = ∈°Redox – ∈° H /H+ 2 ∴ ∈° H / H+ = 0 2 ∴ ∆∈ = ∈° Redox B A C D G Fig. 10. E. A normal hydrogen electrode generally consists of a Pt-foil coated with platinum.17 A cell constructed with standard hydrogen electrode. How is electrode potential measured? Ans. It can be represented as: Pt. Its electrode potential is taken as zero at all temperatures. Define normal hydrogen electrode. A = Solution of H+ ions of unit activity B = Redox solution of unit activity.18 Diagram for Potentiometer. Saline bridge has the function of bringing into physical contact the two solutions without mixing them.ELECTROCHEMICAL CELLS 257 Q.17. 8. Apparatus for measuring the standard electrode potential of a redox system is given in Fig. Ans.F.g. 10. How is the E. of a cell is measured by means of a device. It is a reference or standard reference electrode.

The most widely used are saturated calomel electrodes (∈ = + 0.059 And.059 0.222 V). C-8∴N-ENGCHE∴ECH10-2. What are reference electrodes? Ans. (d) Membrane type = Selective electrodes specific to certain ions. Q. 0. The best known of this type is glass electrode. 14.059 + ∈ = ∈° 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). Q. where. What is an indicating electrode? Ans.059 And. 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. Pt/Ox.246 V) and the silver-silver chloride electrode (∈ = + 0. of the oxidised form in moles dm–3 . 0. It is an electrode in balance with an redox couple. [Red] = Conc. Red 0. ∈r ⇒ Constant potential linked to the choice of the reference electrode and the internal solution. 13. These are the electrodes whose potential is constant and independent of the composition of the contacting solution. Q. of the reduced form in moles dm–3. 12. one of which is an indicating electrode and the other is a reference electrode. ∈ = ∈° M / M n+ + log K sp − K sp [ A − n ] n n where Ksp = solubility product of the salt which is not readily soluble. the potential of which is given by Nernst equation. of cation in moles dm–3 0. a ⇒ activity of the ion in relation to which the electrode is selective. [Mn+] ⇒ conc.PM5 258 . Ans. (a) First Class ⇒ Metallic electrodes in contact with a solution of their own ion (an electrode which is reversible in relation to the cation) Mn+ + ne– M.258 ENGINEERING CHEMISTRY Q. A–n where.059 ∈ = ∈r + log a n where. Potentiometry is an electrochemical method of analysis based on measuring the potential difference (e.f. of the anion in moles dm–3 . Give the hemistry the different indicating electrodes. (c) Redox = Electrodes which are inert in contact with a redox couple in solution.) between two half cells. M ⇒ Metal MA(s) ⇒ the salt which is not readily soluble. What do you mean by potentiometry? Ans. ∈ = ∈°Redox + log [Ox]/[Red] n Pt ⇒ Platinum [Ox] = Conc.m. [A–n] = Conc. 11.

303 RT/F comes out as equal to 0. What is Nernst equation? Ans.PM5 259 . 16. What is the reaction in nickel-cadmium battery? Ans.ELECTROCHEMICAL CELLS 259 Highlight: The potential of reference electrodes is determined as referred to the standard hydrogen electrode. When the standard reduction potentials of the electrodes are arranged in an increasing order.059 [Reduced form] ∈ = ∈° – log n [Oxidised form] Highlight: The concentration of metal is taken as unity. So at 25°C 0. the series so obtained is known as electrochemical series. T ⇒ absolute temperature. It consists of six voltaic cells connected in series. F = Faraday (96500 Coulombs) At 25°C the value of the term 2. 18.303 RT [Reduced form] ∈Red = ∈°Red – log nF [Oxidised form] where. Reaction during recharging the battery PbSO4(s) + 2H2O(l) ⇔ Pb(s) + PbO2(s) + 4H+ + 2SO42– Q.059. ∈° = standard reduction electrode potential. Q. Q. 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. ∈Red = observed reduction electrode potential. R ⇒ molar gas constant. Nernst proposed the fundamental electrode relation between the formal (or observed) potential and the standard electrode potential for the redox reaction: 2. Q. 17. n ⇒ number of electrons involved in the redox reaction. Define the electrochemical series? Ans. Reactions: Anode: Pb + SO42– → PbSO4 + 2e– Cathode: PbO2 + SO42– + 4H+ + 2e– → PbSO4 + 2H2O Net reaction: Pb + PbO2 + 4H+ + 2SO42– → 2PbSO4 + 2H2O. 15. What is lead storage battery? Ans.

(a) Chemical corrosion ⇒ it involves direct chemical action between metals and gases. 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. +2 ∈° = 0. C-8∴N-ENGCHE∴ECH10-2.g. It generally refers to the slow and continuous deterioration of metals and alloys by chemical or electrochemical actions of environments.PM5 260 . 22.77 V Represent the data in the form of Latimer diagram.e. Classify corrosion. rusting of iron. Give the reaction in H2–O2 fuel cell. What do you mean by corrosion? Ans. Q. 23. Ans.260 ENGINEERING CHEMISTRY Q. 19. 21. 24.. Given (i) Fe+2 + 2e → Fe.3H2O (rust) Q. Q. Q. 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. State the electrochemical theory of rusting. (b) Electrochemical corrosion ⇒ it involves deterioration of metal due to flow of electric current from one point to another. (c) Electrical protection. Q. Q. rust. 2Fe+2 + H2O + O → 2Fe+3 + OH– 2Fe+3 + 6OH– → 2Fe(OH)3 or Fe2O3. (d) Use of anti-rust solutions. Ans. (b) Sacrificial protection.44 V +3 (ii) Fe + e → Fe . 20. i. e. Ans. (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. (c) Dry corrosion ⇒ it refers to the corrosion of metals involving direct chemical action between metals and dry gases. Reaction: Anode: Fe → Fe2+ + 2e– Cathode: 2H2O + O2 + 4e– → 4OH–. What measures ought to be taken to prevent corrosion? Ans. (a) Barrier protection.. ∈° = – 0. Fuel cells are the devices that convert chemical energy of a fuel directly into electrical energy. What are fuel cells? Ans.

10.68 – + 0. Q.19 Latimer diagram for Fe species. ∆G°(iii) = ∆G°(i) + ∆G°(ii) = 0.77) F = + 0.30 – + 0.44 Fe Fe Fe –0.36 – ClO4 . We have ∆G°(i) = – nFE° = – 2F (– 0.77) = – 0.77 +2 –0.04 Fig. In alkaline solution (pH = 14) the Latimer diagram for chlorine is – + 0.77 F Adding the above two equations.44) = 0. +3 0.04 V −n F −3F The Latimer diagram of the above system is Fig. 10.42 + 1. Fe+3 + 3e → Fe ∆ G° + 0.37 – + 0.19.88 F ∆G°(ii) = – nFE° = – F(0.88 + (– 0. 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.11 F So ∆G°(iii) is the value for the reaction.11 F ∈° = = = – 0.ELECTROCHEMICAL CELLS 261 Ans. 26.

ClO3 .

ClO2 .

ClO .

Cl2 .

42 F 2 2 1 +e Cl → Cl–.18 V. ClO– → Cl–.42) F = – 0. 2∈ ∈° = – 2. Mn) = 0. Mn) = – 1. Ans. Use the following data to draw a Frost diagram. ∈° = + 1.89 V − nF −2F Q.PM5 261 .10 V C-8∴N-ENGCHE∴ECH10-2. Cl ? Calculate from the above diagram ∈° value for the reaction. Mn) = – 1. +e 1 Ans.36 F 2 2 Adding total ∆G for the reaction = – 1. ∆G°II = – (+ 1.51 V. ∈° = + 0.36 V. 27. ∈°(Mn+2.36 V ∈°(Mn+3. ∆G°I = – (+ 0. ∈ Mn+2) = 1. Mn) = – 0. ∈º(Mn+2. Mn+3) = 0. ∆G° = – nFE° ∆ G I + ∆ G II − 178 .78 F From the relation.18 V ∈°(MnO2.42 V. F ∈° (ClO–/Cl–) = = = 0.36) F = – 1. ClO– → Cl .85 V 4∈°(MnO2.95 V 3∈°(Mn+3.

Most species that reduce MnO4– should also reduce MnO2. the higher the potential of corresponding couple.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. in the three species. • The minimum at Mn+2 suggests this to be the common product of reduction of MnO4– [Mn(VII)] in acidic solution and it is the most stable oxidation state of Mn. • The point for Mn(VI) similarly suggests disproportionation to Mn(VII) and Mn(IV).23 Ans. ∈° = – 0. Since both these products involve one electron transfer. Highlights: • Plot of n∈° vs n for Mn (n = oxidation state) such diagram are called Ebsworth diagram or Frost diagram. Tl+1 → Tl0. C-8∴N-ENGCHE∴ECH10-2. so.. +3 +1. here n = 1. The oxidation states of Tl are + 3. For the change of oxidation number from + 1 to 0 i.25 + –0.34 Tl Tl Tl +1. Q. • The steeper the line joining two points.34 V. n∈° = – 0.34 V.20 Frost diagram for Mn in acidic pH. • MnO2 is also a strong oxidizing agent—its slope to Mn+2 is greater than the slopes to higher oxidation states. 28. Construct a Frost diagram from the Latimer diagram for Tl. • A state is unstable with respect to disproportionation if it lies above the line connecting two adjacent oxidation states. + 1 and 0. • Mn+3 is likely to disproportionate to Mn+2 and MnO2. 10.PM5 262 . the process is likely to be rapid.e.

9. 3. Write a note on decomposition potential. State the peculiarity of a concentration cell. Distinguish between electrolytic and electrochemical cells.f. 4 +3 3 Tl 2 1 0 Tl° n °(V) +1 Tl –1 –2 –3 0 +1 +2 +3 Oxidation number Fig. 16. Tl+1 is the most stable oxidation state of Tl as the species lies lowest in the Frost diagram. What is an electrochemical series? 13. Describe the construction of a glass electrode. Write notes on: (i) Weston standard cell. for n = 3. What are primary and secondary reference electrodes? 18.23 V So. 19.m. Describe the construction and working of H2 – O2 fuel cell. n∈° = 3 × 1. What is standard electrode potential? 8. Why are standard potentials of Zn/Zn +2 and Cu/Cu+2 electrodes opposite in sign? 14. What is a storage cell? Name some of its types. Give the reason: the hydrogen overpotential falls with rising temperature.ELECTROCHEMICAL CELLS 263 For the change of oxidation number from + 3 to 0 (Tl+3 → Tl0) ∈° value = + 1.23 V = + 3. 17. Prove that ∈ox = – ∈red. C-8∴N-ENGCHE∴ECH10-2. Explain how the pH of a solution is determined using the glass electrode. What is a standard hydrogen electrode? What is its potential? 5. 11. 7. 4. 15. What is overvoltage? What is the cause of overvoltage? 6. 2. EXERCISES 1. of a cell? 10. 10. Why is a voltmeter is not used for the measurement of e. (ii) significance of standard electrode potential. What is a calomel electrode? Describe its construction: Why it is used as reference electrode in place of a standard hydrogen electrode? 12.21 Frost diagram for Tl species.69 V. Give the cell rotation for a concentration cell. Define the electrode potential.PM5 263 .

m. Distinguish: (i) a reversible cell from an irreversible cell (ii) a galvanic cell from a concentration cell. respectively. (i) Zn | ZnSO4 || CuSO4/Cu (ii) (Pt) H 2 (1 atm) | HCl/AgCl(s). [Ans. What is Nernst equation? State its utility. Derive an expression for electrode potential of an M/Mn+ electrode? 23. (0. How is single electrode potential measured experimentally? 31. Calculate the pH of the solution. both at the same temperature.44 V (– 1.m. 37. when the concentrations of ZnSO4 and CuSO4 are 0.13 V). The reaction H2 + Cl2 + 2H2O 2H2O + 2Cl– has an equilibrium constant K = 1046 at 25°C. 28.239 V) 38. Cl–/Ag.f. Give the cell reaction of the following: (i) Zn+2/Zn. 27. (ii) Calculation of solubility product of AgCl.337 and 0.PM5 264 . 21. Calculate the e. Give the use of Ag-AgCl electrode.799 V. Calculate the e. 39. 0. The potential of the normal calomel electrode is 0. Calculate E° at 25°C for cell: (Pt) H2/HCl (aq)/Cl2 (Pt). and ∈°Fe +2 / Fe = 0. Give the equilibrium constant for the reaction.0 N)| Quinhydrone | Pt is 0.1 M respectively. 30. (iv) 2H+/H2(g) Pt. 6.f. Also give the expression for their e.m.2812 V and E° for the quinhydrone electrode is 0.8192 V) 36. 34.6996 V. (iii) Fe+3/Fe+2 Pt. 22.0592 V] 40. Describe the potentiometric methods for (i) Determination of pH of a solution.01 (M) ZnSO4 solution at 25°C.530 V.f.264 ENGINEERING CHEMISTRY 20. 33. Give the single electrode potential of Zn- half cell.763 V (0. Zinc rod is dipped in 0.f of the following concentration cell: Ag/Ag+ (0.44 V. if E°cell = + 0. Given the electrode potentials of Cu and Fe are 0. 26.f. of the cell at 25°C Hg(l) | Hg2Cl2(s). Explain the construction and working of lead storage battery. Ag 32.1 V (1. (ii) AgCl(s). The standard potential of the cell is 1. of voltaic cell: Fe | Fe+2 (aq) || Cu+2(aq) | Cu. Write down the electrode reactions and overall cell reactions for the following cells.m. Calculate the e. Will a reaction take place if an Ag-bar is placed in a solution of FeSO4? Explain using the follow- ing data: ∈°Ag + / Ag = 0.78 V). of a Daniel cell at 25°C.5] C-8∴N-ENGCHE∴ECH10-2.m. 29. The standard potentials of Cu/Cu +2 and Cu/Cu+ system are 0. What is fuel cell? Give detail of one such cells.212 V. 24.001 M and 0. Describe the construction and working of Daniel cell. KCl(sol) (1. 2Cu+ Cu2+ + Cu 35.1 M) || Ag+ (1M) | Ag [Ans.34 V and –0. What are reversible and irreversible cells? 25. respectively. Explain the construction of Ni-Cd cell. The e.

Calculate its (i) pH and (ii) H+ concentration.44 V. at 25°C in 0.16 × 10–7] C-8∴N-ENGCHE∴ECH10-2.664 V. Calculate the valency of mercurous ions with the help of the following cell: Hg | HgNO 3 (0. of the cell. value ⇒ 0.m.f. [Ans. Calculate the equilibrium constant of the reaction at 25°C. to calculate ionic product of water. 5. [Ans. When calomel electrode is connected to H2-electrode at 18°C. ∈°Fe +3 / Fe ⇒ 0.f.036 V ∈°I(s)/I – ⇒ 0.PM5 265 .5622 V. Calculate the pH of the solution. K = 166] 44. 2] 42.01) | Hg+ [Ans.001 N) in 0.5355 V. Find the equilibrium constant of the reaction at 25°C. [Ans. 2 Fe+3 + Sn+2 2 Fe+2 + Sn+4 from ∈° values given in the Table 10. Suggest a cell.5. gives e. (ii) 3.1 N HNO3 | HgNO3 (0. (i) 6. which is constructed by connnecting H2-electrode to normal calomel electrode. E.m.4] 46.ELECTROCHEMICAL CELLS 265 41.2. H 2-electrode || O2-electrode] 45. [Ans. 1 Fe+3 + I– Fe+2 + I(s) 2 from the ∈° (reduction) values ∈° Fe +2 / Fe ⇒ 0. K = 1021] 43. [Ans.

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

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

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 – 3 + 2 = 0. Hence F = 1 – 2 + 2 = 1. the properties like melting point. vapor and one-component H2O. The OA curve terminates at A. P = 3. The Water System This system consists of three phases—ice. hence if a trace amount of a phase is present and not taken into account.268 ENGINEERING CHEMISTRY Examples 1. C-8∴N-ENGCHE∴ECH11-1. For both of these curves OA and OB. 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. OA is the vapour pressure curve of water. Advantages of phase rule 1. also called the vaporisation curve. the critical temperature of +374°C above which distinction between liquid and vapor vanishes. The rule considers only the number of phases and not their amounts present. 2. 11. 3. It states that all the phases must be present under the identical conditions of tem- perature and pressure. (a) Water(l) Vapor ( g) C = 1. we find that curve BO is the vapor pressure curve of ice which indicates that ice has a small but definite vapour pressure. they are one-component systems with two phases (C = 1.1. P = 2. P = 3. 2. 3. The nature or quantities of the components do not have any role.PM5 268 . The point B has a natural limit of – 273°C. the rule is inapplica- ble. so it is of no value for systems which may attain equilibrium very slowly. Limitations of phase rule 1. Hence F = 2 – 3 + 2 = 1. Different systems behave in a similar fashion if they have same degrees of freedom. The equilibrium system requires no information regarding its molecular nature or micro structure. This rule can be applied only to systems that have attained equilibrium. 4. From Fig. beyond which the two phases merge. From the phase diagram. (c) For CaCO3 (s) CaO (s) + CO2 ( g) C = 2. 5. P = 2). triple point can be found. Phase rule is applicable to both physical and chemical equilibria. boiling point. (b) For water at critical point Ice (s) Water (l) Vapor ( g) C = 1. water.

temperature as well as pressure is to be known because the degree of freedom F = 1 – 1 + 2 = 2. i. The inclination of OC towards the pressure axis shows that melting point of ice is decreased by increasing pressure. This curve represents a metastable system. Since F = 1 there is only one degree of freedom i. 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.579 mm O Water D vapour B .. it is actually the melting point of ice i. P = 3.e. called the triple point. at this point neither temperature nor pressure can be altered without the disappearance of one of the three phases.PHASE RULE 269 C 218 atm A X Water Y Pressure 1 atm Ice Z 4.. 0.e. The other two modifications are liquid sulfur and sulfur vapor. all other properties are also fixed. rhombic and monoclinic sulfur have same vapor pressure and co-exist with sulfur vapor.0075 °C 100 °C 374 °C Temperature Fig.0098°C under 4. Sulfur at low temperature is in the rhombic form and at high temperature in the monoclinic form. if the temperature is fixed. AB is the vapor pressure curve of rhombic sulfur which is stable upto 95°C (0. Sulfur system is another one-component system with a slight more complexity. Hence F = 0 i. 11. ice. because the three phases.e.2). OB and OC divides the whole region into three portions AOC.579 mm pressure and at this point C = 1. which is the continuation of the curve AO below 0°C is the vapor pressure curve of supercooled water below 0°C. Sulfur System..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.PM5 269 . ice-water-vapour are in equilibrium. At B.. 11.e. BC is the similar curve of monoclinic sulfur and the point B is the transition point between the two allotropes of sulfur. The curve OC represents the change of melting point of ice with pressure. The point of intersection of these two curves is point O.1 The phase-diagram for water (not to scale). In the phase diagram for sulfur (Fig. The dotted portion OD. C-8∴N-ENGCHE∴ECH11-1..006 mm) at B. The curves OA.

. These two lines meet at E (151°C.04 mm) monoclinic sulfur melts and CD is the vapor pressure curve of liquid sulfur. monoclinic and liquid sulfur co-exist in equilibrium. which can completely define the equilibrium of a system. 0. At the triple point F = C – P + 2 = 1 – 3 + 2 = 0 i. B is actually the triple point. BE. These metastable systems are represented by dotted curves.288 mm) Pressure (not to scale – schematic) SL G(115 °C. 1. Again at C (120°C. Degrees of freedom (F): It is the minimum number of independent variables of a system. pressure and concentration. with pressure. i.” F=C–P+2 Phase (P): Phase is defined as any physically distinct portion of matter which is itself homogeneous and uniform in composition. 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. respectively. pressure. concentration. Along the lines AB.03 mm) D C(120 °C. The lines BE and CE represent changes in transition temperature and melting point. 1288 atm) which is again a triple point where rhombic. 11.. mechanically separable from other parts by definite boundary surfaces. 0. CD.006 mm) A Temperature (not to scale – schematic) Fig. 0. the system is univariant and either temperature or specific volume determines the system completely. CE and EF two phases co-exist and F = C – P + 2 = 1 – 2 + 2 = 1. such as temperature.PM5 270 .04 mm) Sv B B(95. Hence. Curve BG is the metastable vapor pressure curve of rhombic sulfur. zero variant and three phases coexist. 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. 0. BC. There are three stable and one unstable triple points and four phases co-exist nowhere in the curve in equilibrium.e.e. C-8∴N-ENGCHE∴ECH11-1.6 °C.270 ENGINEERING CHEMISTRY F SR E(151 °C. 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.2 The sulphur system.

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

Similarly. 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.PM5 272 . invariant. The composition corresponding to a freezing point gives the composition of the alloy.6 % Ag and 97.4 % Pb) and the whole mass at this point crystallizes out with the above fixed composition.272 ENGINEERING CHEMISTRY If the composition of the mixture coincides with the eutectic composition. F = 3 – P = 3 – 3 = 0 i.6 Ag 97. there is no double break but the curve mimicks that of pure component. as Ag is added the melting point gradually falls till the lowest point O is reached with the above mentioned composition.4 T-C diagram of Pb-Ag system. A is the melting point (961°C) of Ag. C-8∴N-ENGCHE∴ECH11-1. The eutectics are applied for constructing safety devices in boilers. solution of Ag + Pb and vapor. This point O is the eutectic point (2.4 Pb Composition Fig. According to reduced phase rule equation. At constant atmospheric pressure. the vapour phase is absent and the condensed phase rule is applicable as F = C – P + 1. solid Pb. 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”. T-C curve is obtained for alloy system. It is also necessary to know the freezing points of the pure components. 11. Curve AO represents the freezing point curve of Ag. another curve BO is obtained starting from the melting point of pure lead (327°C) at B. 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. the system is univariant along AO and BO and at point O. By plotting freezing point against composition.e. Lead-Silver-Sample (Eutectic System) It is a two-component system with four possible phases—solid Ag. automobiles etc. 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”. which is the eutectic temperature and a lead-silver mixture can never have a melting point below the eutectic temperature..

Again on increasing the Mg the freezing point rises along SW. So Q is the invariant eutectic point. C atoms being small compared to iron atoms form only interstitial solid solutions and the solubility of C in these allotropes is quite different. L—liquid. Further increasing the magnesium. 11. Pure iron exists in three allotropic modifications α. The hump in the diagram indicates the formation of a compound. B—Mg crystals. W. 11.5 Phase diagram of the system Sn-Mg: A—Sn crystals. Tin-Magnesium System The equilibrium diagram of tin (Sn) and magnesium (Mg) is shown in Fig. 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. At the eutectic points the solid compound is in equilibrium with either solid tin or solid Mg. The phase-diagram of iron-iron carbide system is used upto 6. Q. Thus along QR from molten alloy only solid compound crystallizes out in equilibrium with the liquid. At R the composition of the liquid and the solid phase is the same. the freezing point decreases along RS and reaches the second eutectic point S (565°C).67% weight of carbon. R. S are invariant and the areas in between the lines are univariant.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. The melting points and the eutectic points P. γ and δ. The compound formed is stable and has its melting point at the maximum.PM5 273 . This temperature (783°C) is the congruent melting point of the compound. At O (210°C) a new solid phase of a compound of Sn and Mg begins to separate alongwith Sn. Iron-Carbon Alloy System The equilibrium diagram of Fe-C is especially useful to understand the heat treatment of steel. C—compound Mg2Sn. C-8∴N-ENGCHE∴ECH11-1. the melting point of Sn (232°C) lowers along PQ.5. Further addition of Mg raises the melting point along QR and the maximum is reached at R. When Mg is added to Sn. which is Mg2Sn.

which are formed when the cooling rate is slow i. Pure iron changes from δ to α form at a temperature of 910°C.025% A1 Eutectoid (pearlite) 600 Ferrite Cementite Pearlite + 500 + Pearlite Pearlite Ferrite + +Transformed Cementite Ledeburite 0.0 2.e. Hence further removal of heat leads to total solidification of the liquid to ledeburite.6 Hypoeutectoid Hypereutectoid Wrought iron Steels Cast iron x Weight %C Fig. Area BCGP represents austenite and liquid and finally PGKI represents δ-iron (i.0 3. whereas 0. AEB area represents δ-iron and liquid. 11. 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.e.0 4 4.274 ENGINEERING CHEMISTRY +L