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

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

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

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

2

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

3

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

4

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

5

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

6

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

7

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

8

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

9

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

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

10

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

11

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

12

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

13

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

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14

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

15

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

16

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

17

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

18

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

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

19

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

20

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

21

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

22

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

23

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

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

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

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

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

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

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

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

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

e. in the case of py and pz orbitals the electron will be found along y and z axes.. y z + x Fig. py and pz orbitals. In the absence of magnetic field these orbitals are equivalent in energy content and are said to be triply degenerate.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 below. how r. An s-electron has no preferred direction in space i.6 below.e. . (i) Angular probability distributions of orbitals i. the distance from the nucleus does vary..8 ENGINEERING CHEMISTRY These are namely (i) an angular probability distribution i. how the angular position θ varies from nucleus with respect to a fixed axis and (ii) a radial probability distribution i. shapes or boundary surfaces of orbitals gives the probability of finding an electron in a particular direction.e.. there is an equal chance of finding it in any direction around the nucleus. 1. 1. y z + y z y z + x x – – + x – px (a) py (b) pz (c) Fig.. y-z plane in this case is nodal plane with zero electron density. The different shapes are shown in Fig. In the presence of external magnetic field these vary in their energy content depending on the magnetic quantum number.6 In this diagram. Similarly. A p-level has an accommodation for six electrons distributed over three p-orbitals to each value of the principal quantum number.. 1.7 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. 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. This is graphically shown in Fig. 1.e.

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

The distributions vary according to the principal quantum number. 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. 3p and 3d orbitals.528Å). 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. 1.9 Radial probability distribution of 1s.10 Highlights: l ENGINEERING CHEMISTRY The probability of finding an electron at the origin is zero which is the nucleus. . Probability 1s Probability 2s r0 1 Distance r (a) 2 Å 0 r1 2 r2 4 Distance r (b) 6 8 Å Probability Probability 3s 2p 0 2 4 6 Distance r (c) 8 Å 0 2 4 8 10 6 Distance r (d) 12 Å Probability 3p Probability 3d Distance r (e) Distance r (f) Fig. This means the electron can never be at nucleus. l l All these facts are based on the proper interpretation of Schrödinger wave equation. 3s. 2p.

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

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

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

O.9 K 0.5 S 2.F B × – × º (BF4) – × . ..1 As 2..1: Electronegativity values (L.1 Po 2. H .0 Sb 1.0 Ba 0.2 Ca 1.H N.0 O 3. H .. . ..0 Al 1.6 In 1.9 Bi 2..7 Be 1.4 Te 2. Table 2.9 Ra 0. F .1 Li 1. × + º (H3O) + × F F Electronegativity The attraction and repulsion powers of atoms of different elements are not same.H O.5 Si 1.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 ‘→’. Comparative values of electronegativities of different elements taking the electronegativity value of H as 2. Pauling Scale) Group → Period↓ 1 2 3 4 5 6 7 I (1) H 2.5 Ga 1. .8 Sn 1.0 Sr 1..0 Na 0. .2 II (2) III (13) IV (14) V (15) VI (16) VII (17) × .– . H .0 P 2. F . H atom has less tendency of this sort. The donor atom should have a lone pair of electrons.5 Mg 1.. N × × × H H Ammonium ion × H + H .5 At 2.14 ENGINEERING CHEMISTRY accepts the pair of electrons is known as ‘acceptor’ atom.5 Se 2.8 Ge 1.8 Pb 1.1 below. Some examples of coordinate bond formation: H . H . .8 C 2. × + × º (NH4) + .8 Rb 0. .0 Br 2.1 is given in Table 2. .+. B × × H + . The phenomena can be represented as follows: A.7 Fr 0. .9 N 3. F .0 F 4.0 Cl 3.. × × H H Hydronium ion F . The power of attracting electrons of one of the atoms in a covalent bond is known as its electronegativity. 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. In comparison.9 B 2.7 Ti 1.8 Cs 0. F .8 I 2. As for example. . . .

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

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

E A ) Energy released Electron affinity is represented by the ‘–ve’ sign as energy is liberated in this case. µ1 and µ2 = dipole moments of the different bonds of the molecule. When energy is supplied it is represented by ‘+ve’ sign and called second electron affinity (E2).2 = + 26 + 28. • Cl2. The molecules are symmetrical. Born-Haber cycle is represented diagrammatically with the formation of NaCl (s) from 1 Na (s) and Cl2 (g) by direct combination to determine electron affinity of ‘Cl’ atom: 2 Na(s) + 1 Cl (g) 2 2 Q = –98. and in those molecules centre of positive charge action and centre of negative charge action are at the same place.e..9 + 118 + E – 180. ∴ µ ⇒ 0. R = Resultant moment of the molecule.e. etc. CO2. If R is zero..0 kcal (– e) Na (a) + – 1 D = +28. U0 Þ Lattice energy of NaCl crystal. their centre of action of positive charges and centre of action of negative charges are not same and the molecule is not symmetrical.7 kcal/g atom of Cl Negative sign indicates that energy is released in the formation. • HCl.. d ⇒ 0. H2. Neutral gaseous atom A ( g) + e − ( g) → A − ( g) + Anion (Electron affinity of atom A.VALENCY AND CHEMICAL BONDING 17 Highlights: • The dipole moment of H2O molecule is 1. 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.8 D.4 ∴ E = – 90. S = +26.2 kcal NaCl(s) Crystal Determination of electron affinity of Na atom.0 kcal Na(g) I = +118. CH3OH are polar molecules i. H2O. are non-polar molecules. Cl(g) → Cl–(g) Q=S+ . i. NH3. CH4. i. its dipole moment is 1. C6H6. the molecule becomes non-polar and if R has got a positive value the molecule becomes polar. • 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.4 kcal 1 D + I + E + U0 2 – 98.8 × 10–18 esu-cm.9 kcal 2 Cl(g) E = ? (+e) Cl (g) U0 = –180.

that for KCl is –711 kJ mol–1 and that for AgCl is –905 kJ mol–1 calculated as per Born-Haber cycle. • The cycle is an application of Hess’s Law (see Chapter 4). (iv) Each covalent bond requires overlapping of a pair of orbitals. H H H : H Fig. Molecular orbital theory is gaining much importance. 2. (ii) When the overlapping takes place along the axes of the atomic orbitals maximum overlapping of atomic orbitals can occur. 2. Both the theories admit that — (i) A covalent bond is formed as a result of overlapping of the atomic orbitals. Molecular orbital theory. NH3. Valence-bond theory 2. (v) The overlapping orbitals must be valence orbitals and must contain an odd electron. In this connection.3 Formation of H2 molecule by the overlapping of two 1s atomic orbitals of two H atoms. • The lattice energy for NaCl is –780 kJ mol–1.18 Highlights: ENGINEERING CHEMISTRY • Born-Haber cycle is a thermochemical cycle that can be used to calculate the lattice energy for a compound of a metal with a nonmetal. (iii) Maximum overlapping gives a strong bond known as sigma (σ) bond. • A Born-Haber cycle can also help to determine whether the bonding in a compound is truly ionic. 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. Schematic representation of the formation of some simple molecules on the basis of valence bond theory: (i) s-s overlapping ⇒ H2 molecule (ii) s-p overlapping ⇒ the formation of HF. two main approaches are — 1. The application of wave mechanics gives a satisfactory explanation of some of these problems.4 (a) Formation of HFmolecule. 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. H2O molecules (i) HF molecule H + F H F Fig. . • We have utilised Born-Haber cycle in determining the electron affinity of ‘Cl’ atom.

6 px-px overlapping along the axis to form F2 molecule. This fact also leads to the idea of hybridization of orbitals.VALENCY AND CHEMICAL BONDING 19 (ii) NH3 molecule z 1s H y + + + 1s + + + N 2pz 2py 2px Here the overlapping takes place between the three (2p) orbitals of nitrogen atom with 1s orbital of each hydrogen atom. (iii) Water molecule x 1s + y + + z – – – – + + + + 1s z + y x In this case also the bond angle appears to be 90°. + + NH3 molecule H2O molecule px + px F atom F atom F2 molecule Fig. If it were the case.5 Formation of H2O molecule. 2. . Fig. So some other concept becomes essential to explain the formation of NH3 molecule. then bond angle in NH3 should be 90°. But actually bond angle in NH3 is 106° 45′. But the actual bond angle in water molecule is 104° 27′. 2.4 (b) Formation of NH3 molecule. (iv) Fluorine molecule : p-p overlapping to form a σ-bond. py pz py pz + + + + 1s z – – – z Fig. 2. That concept is the concept of hybridization.

8 sp3 hybridised C atom.8). 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. (a) Overlapping of two px orbitals along the axes leads to the formation of a sigma bond. Hybridization: Carbon has electronic configuration: 1s2 2s2 2p2. 2. 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. but in CH4. + + px py + Þ pz sp 3 + sp3 sp3 hybrid orbitals + sp3 + sp3 s 109° 28¢ sp 3 C sp 3 sp 3 Fig.7 σ and π bonds in N2 molecule.20 (v) N2 molecule: p-p overlapping to form σ and π bonds py pz px py pz py py pz ENGINEERING CHEMISTRY pz p-bond s-bond Fig. then bond angle and bond energies in CH4 molecule can satisfactorily be explained as follows: 1s C-atom C-atom (ground state) (excited state) ⇒ ⇒ 2s 2p Now this one s-orbital and three p-orbitals of a carbon atom mix to give four hybrid orbitals of equal energies. 2. 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. C atoms form four identical bonds with H-atom with equal energy. . (b) Lateral overlapping of two py and pz orbitals leads to the formation of two π bonds. 2.

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

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

the overlapped charged cloud is parallel to internuclear axis.10 225 dsp2-hybridization In this type of hybridisation one s-orbital. the Be atom has the configuration ⇒ 1s2 2s1. Now. 2.34 144 C≡C 1.VALENCY AND CHEMICAL BONDING 23 In the excited state one of the 2s2 electrons jumps to 2p-orbital before forming any bond. • π-bonds are comparatively weaker than σ-bonds.52 38 N≡N 1. Highlights: • When orbitals overlap along the axes.54 83 C=C 1. 2p sp hybridized Be atom Þ sp hybridized orbitals 180° F F Be F Be F Fig. axes of which are directed towards the . In this type of bonding. • In double bonds and triple bonds. Hence. 2. Table 2.13 Structure of BeF2 (example of sp hybridisation). charge cloud exists symmetrically.21 196 N—N 1. the π-bonds open easily and take part in the chemical reactions. • When the number of bonds between the atoms increase the bond energy increases and bond length decreases.2: Displaying bond lengths and bond energies Bond Bond length (Å) Bond energy (Kcal) C—C 1. 2px1 2py0 2pz0. as they form by lateral overlapping. These two hybrid orbitals next overlap with p orbitals of two F-atoms along the axes making BeF2 a linear molecule (Fig. Electronic configuration of: 2s Be in ground state Be in excited state Þ Þ 2p Two unpaired electrons sp hybridization with two unpaired electrons. Then these 2s and 2px orbitals mix to give two sp-hybridised orbitals. In this type of bonding. there is σ-bonding.13). two p-orbitals (px and py) and one d-orbital ( dx 2 − y2 ) mix to give four equivalent hybrid orbitals. there are lateral overlapping and due to this lateral overlapping the π-bonds are formed.

2.15 Trigonal bipyramidal structure of PCl5.24 ENGINEERING CHEMISTRY corners of a square. 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. 2. px s py pz dz 2 3 dsp Fig.15). the shape of the molecule becomes square planar and the bond angle is 90° (see Table 2. . The hybrid orbitals consist of one group of two equivalent oppositely directed orbitals and the second group of three equivalent orbitals. So. Cl Cl Cl P Cl Cl Fig.14 sp3d hybridization. The shape of the molecule will be trigonal bipyramidal (Fig.3). Example of sp3d hybridization: Electronic configuration of: 3s P-atom in ground state Þ P-atom in the excited state Þ 3p 3d Five unpaired electrons sp3 d hybridization 3d Þ These sp3d hybrid orbitals of one P-atom overlap with five p orbitals of five Cl atoms to form PCl5. 2. 2. 2. The shape of the molecule is trigonal bipyramidal (Fig.14).15). the hybrid orbitals are not equivalent. But in this case.

2. SiF4 BeF2.16 Octahedral structure of SF6 molecule. (NH3)2 Cl22– PCl5. C2H4 CH4. the molecule then acquires a regular geometry. 5 ` 6 dsp3 or sp3d d2sp3 or sp3d2 Trigonal bipyramidal Octahedral 120° and 90° 90° SF 6.VALENCY AND CHEMICAL BONDING 25 d2sp3 or sp3d2 hybridization Electronic configuration of: 3s S-atom in ground state Þ S-atom in excited state Þ 3p 3d Six unpaired electrons sp d hybridization Þ These sp3d2 hybrid orbitals of one S-atom overlap with p-orbitals of six F-atoms to form SF6. When the central atom contains one or more lone pairs (lp) of electrons in the valence shell with bond pairs (bp) the . F F S F F F F 3 2 Fig. C2H2 Square planar 90° 90° [Ni (CN)4]2–. Co(NH 3)6 Fe(CO)5 VSEPR Theory and Molecular Model It is interesting to note that if the central atom in a molecule is surrounded only by overlapped bonding orbital or orbitals containing shared pairs of electrons (Bond pairs. of electron pairs in outer shell of the atom 2 3 4 4 Hybrid orbital sp sp2 sp3 dsp2 Linear Trigonal planar Tetrahedral 90° Shape of the molecule Bond angles Example 180° 120° 109° 28′ 90° 90° BF3. Table 2.3 No. bp) in the valence shell.

Example: BeF2. Here lp-bp repulsion is greater than the bp-bp repulsion. 2. there is sp3 hybridization .17 0.19 V-shaped water molecule. the orbitals containing lone pairs as well as the bond pairs are so arranged that there is maximum repulsion between them. Central atom surrounded by four bond pairs: Example methane.p.26 ENGINEERING CHEMISTRY shape of the molecule becomes distorted for minimum energy and for maximum stability. In all the above cases there were only bond pairs in the molecules and the molecules have a regular geometry. 2. the shape of the molecule becomes pyramidal (Fig.p..18 sp3 hybridized ‘O’ atom. and one hybrid orbital contains lone pair of electrons. So the bond angle is reduced (107°) and if we overlook the fourth corner of tetrahedron occupying an orbital containing an unshared pair of electrons. The central atom surrounded by three bond pairs: They remain as apart as possible and the bond angle is 120°. 2. 2. Molecule containing lone pair and bond pair: Example ammonia molecule: The geometry of the molecule is distorted tetrahedron. Fig. H Å 105 O ° O b. we can write lp-lp repulsion > lp-bp repulsion > bp-bp. It is again greater than the bond pair-bond pair repulsion i. Case I. The bond angle becomes more reduced (Fig.20).19).96 b. the shape of the molecule and bond angle may be predicted. if the distribution of the orbitals about the central atom of the molecule can be predicted. 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. Here the bond angle is 105°. Now. 2. Case III. The bond angle is 180°. N But the bond angle here is 107°. Here there are four bond pairs and the shape of the molecule is tetrahedral. Central atom surrounded by two bonding pairs: The two bonding pairs remain as apart as possible. 107° H H H Here O-atom is sp 3 hybridized and only two H-atoms occupy the two corners of a tetrahedron. In NH3. The other two corners of the tetrahedron is occupied by the two sp3 hybrid orbitals containing unshared pairs of electrons. repulsion. 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.. This is the basis of Valence Shell Electron Pair Repulsion (VSEPR) theory.p l.17). H H H Fig. l. Case IV. 2. Case II.e. H2O molecule: Fig. Overlooking those two corners of the tetrahedron the H2O molecule becomes ‘V’ shaped (Fig. .p.

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

2.21 Bonding and antibonding orbitals. . + .28 φB = ψA(1s) + ψB(1s) φA = ψA(1s) – ψB(1s) (i) The two conditions can be represented pictorially (Fig.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.21) + ENGINEERING CHEMISTRY . s is (Bonding fB) Fig. 2. Molecular orbital Antibonding s1s Energy Atomic orbital 1s 1s Atomic orbital s1s Bonding Fig.23 Linear combination of two 2px orbitals to form σ2p (bonding) and σ*2p (antibonding) molecular orbitals (σ-symmetry). Energy level diagram (Fig.22 Representation of M. 2. HB Atomic orbitals . 2. E HA + + . Linear combination of 1s-atomic orbitals (σ-symmetry) of two H-atoms to give bonding and antibonding molecular orbitals (σ-symmetry). fA) + . 2. diagram. + s* is (Antibonding. (ii) Molecular orbitals from p atomic orbitals: (a) End-end overlap + – – + s*2p (Antibonding) E – + + + – – + (Bonding) – s2p Fig.O. .

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

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

O. 2pz 2py 2px 2s 2s s2s Fig. Fig. 2. = 8 – 2 = 3 2 N2 molecule has triple bond (N º N) pz2p py*2p pz*2p A.O. .30 Molecular orbital diagram of B2 (with s-p interaction). O.29 Molecular orbital diagram of B2 (without s-p interaction).O. diagram for N2. s*2p A. the electronic configuration of N2 molecule will be KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) [KK denotes (σ1s2) (σ*1s2)] M.O.28 M. • Energy level diagrams of other molecules: s*2px p*2py p*2pz ­ 2px 2py 2pz p2py p2pz ­¯ s2px ­¯ s*2s ­¯ 2s ­¯ s2s B B2 B B ­¯ 2s ­¯ 2s ­¯ s(sp)1 B2 B ­ 2pz 2py 2px ­ 2px 2py 2pz s(sp)2 ­ ­ 2py 2pz ­¯ s*(sp)1 ­¯ 2s s(sp)2 p*2py p*2pz ­ 2py 2px 2pz Fig. 2. 2px 2py 2pz py2p s2p E s*2s B.VALENCY AND CHEMICAL BONDING 31 So. 2.

.32 Molecular orbital diagram of O2 (with s-p interaction). 2. 2. Fig.31 Molecular orbital diagram of O2 (without s-p interaction). Fig.33 Molecular orbital diagram of NO (without s-p interaction).32 • Electronic configuration of B2 molecule: KK(σ2s2) (σ*2s2) (σ2p2) s*2px ­ ­ p*2py p*2pz ­ ­ ­¯ 2pz 2py 2px ­¯ ­¯ p2py p2pz ­¯ s2px ­¯ s*2s ­¯ 2s ­¯ O s2s O2 O O ­¯ 2s ­¯ 2s ­¯ ­ ­ ­¯ 2pz 2py 2px ­ ­ ­¯ 2pz 2py 2px ­¯ ENGINEERING CHEMISTRY s*sp)2 ­ ­ p*2py p*2pz ­ 2pz s(sp)2 ­ ­ p2py p2pz ­¯ s*(sp)1 ­¯ 2s ­ ­¯ 2py 2px s(sp)1 O2 O Fig. 2. • Electronic configuration of O2 molecule: s*2px ­ ­ p*2py p*2pz ­ ­ ­¯ 2pz 2py 2px ­¯ ­¯ p2py p2pz ­¯ s2px ­¯ s*2s ­¯ 2s ­¯ N s2s NO O ­¯ 2s ­ ­ ­¯ 2pz 2py 2px KK(σ2s2) (σ*2s2) (σ2p2) (πy2p2) (πz2p2) (π*2p1) (πz*2p1) y s*sp)2 ­ ­ p*2py p*2pz ­ ­ ­¯ 2pz 2py 2px ­¯ s(sp)2 ­ ­ p2py p2pz ­¯ s*(sp)1 ­¯ 2s ­¯ N s(sp)1 NO O ­¯ 2s ­ 2pz ­ ­¯ 2py 2px Fig.34 Molecular orbital diagram of NO (with s-p interaction). 2.

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

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

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

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

(ii) van der Waals bond. e. A polar bond is formed when sharing takes place between the atoms of different electronegativities i. Q. (b) Molecules have a definite shape because covalent bonds have a definite length and direction. A nonpolar bond is formed when sharing takes place between the atoms of same electronegativity i. The covalent radius of an element is half the bond length. 13.. van der Waals radii determine the effective size of a molecule. Cl—Cl. 2. etc. What is the special feature of a coordinate bond? Ans. (i) Metallic bond. What is covalent radius? Ans. 11.e.g.190 nm. Q. (a) Covalent bond holds together the atoms of nonmetals in a molecule and giant structures. O = O. . (iii) Hydrogen bond. What are polar and non-polar covalent bonds? Ans. Ans. one of the participating atoms in the bond formation donates both the electrons for bond formation.. 9. 12.37 (c) Covalent and van der Waals radii for bromine. Br—Br.114 nm van der Waals radius » 0. 2. When two atoms of the element (same or different) are joined by a single covalent bond. Covalent radius Þ 0.e. This type of bond is formed by unequal sharing of electron pair.141 nm sum of covalent radii HCl Fig. Q. H+δ → Cl–δ Q. 10. between similar atoms during bond formation. What is the special feature of a covalent bond? Ans. Mention special types of bonds. Covalent radius = 0.. The coordinate bond is indicated by an arrow to express this unequal sharing.37 (b) Forces of attraction during H2 molecule formation. Fig. between dissimilar atoms during bond formation viz. 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.104 nm Cl2 Bond length Þ 0.037 nm H2 Covalent radius Þ 0.. 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.VALENCY AND CHEMICAL BONDING 37 Q. H—H.

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

Ans.O.134nm B C≡C .e.) overlap along the internuclear axis (see Figs. E(C—H) ⇒ C–C 0. Bond length is the distance between the nuclei of atoms bonded by one or more covalent bonds. What do you mean by electronegativity? Ans. by the overlapping of + – regions of the atomic orbitals (see Figs.5 Kcal mole–1. 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. Ans. the more polar the bond. 26. What do you mean by bond length? Ans. 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. are shorter than single bonds. When does a bonding in a covalent compound become fully ionic? Ans. 21.O.O. But in this case. 24. H ¾Cl ¯ +d –d polar bond. the higher its electronegativity.21 and 2.O. B.e. Ans.e. The bigger the difference in the electronegativity of the elements forming a bond. Nb .. 0. 25. This happens in compounds like NaCl. Interpret the idea of bond order.157nm B C=C 0. 2. In a simplified form. 23. 398 = 99.O. stabler is the molecule. M. For the same two atoms triple bonds are shorter than double bonds which. (φB) is obtained when ++ regions of both the atomic orbitals (A.23). Q.120nm B Q. = where. Q.. Q. Q. Bond order zero and negative indicates that molecule does not form or exist. Nb − N a 2 ⇒ number of bonding electrons. Higher the bond order. φA results from subtraction of the two atomic orbitals (φA = ψA – ψB) i. in turn. is produced by addition of two atomic orbitals (φB = ψA + ψB). 22.. 4 Q. 2. Na ⇒ number of antibonding electrons.21 and 2. The bonding molecular orbital is a region in space where the probability of finding the bonding electrons is maximum. Molecular orbitals are the solutions to the Schrödinger wave equation like atomic orbitals. The stronger the pulling power of an atom. MgO. Bond order (B. CaF2 etc. Give the concept for antibonding molecular orbitals.23) i.) is given by the expression. Bonding M.O. Give the conception of a bonding molecular orbital. it may be stated that molecular orbitals (M. Antibonding orbitals (φA) are also solutions to the Schrödinger wave equation like the bonding molecular orbitals.) are obtained by the overlapping of atomic orbitals of the atoms linked by a covalent bond.VALENCY AND CHEMICAL BONDING 39 C—H bond energy in CH4 is mean value of D values i.

So He is monoatomic. 30. (iv) dsp2.. = 2−1 1 = 2 2 He2+ also has transient existence. the number of electrons in s-orbital is greater than the number of electrons in s*-orbital. Q. 31.O. = Nb − N a 8−4 ⇒ =2 2 2 So. (ii) sp2. Q. 29..32). (ii) H2+. B. Calculate the bond orders of: (i) H2O. (iv) He2 and interpret the result. 32.O. ⇒ Ans. (i) B. According to Hund’s rule two unpaired electrons fill the degenerate (orbitals of same energy) πy*2p and πz*2p orbitals (see Figs. Q.31 and 2. 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. (vi) d2sp3. Explain why HF is liquid. H− F −δ .O. 2. (v) sp3d. O2 molecule is paramagnetic. 1− 0 1 = 2 2 H2+ has a transient existence. H− F −δ . The intermixing the atomic orbitals of slightly different energies so as to redistribute their energies and to give a new set of orbitals (known as hybrid orbitals) of equivalent energies and shape is known as hybridisation. Here the number of bonding electrons exceeds the number of electrons in antibonding orbital. O2 molecule contains double bond (O = O). 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. +δ +δ +δ +δ . so it is less acidic.O.40 Q. Mention the types of hybridisation. Hydrogen bond in HF inhibits release of H+ partially in aqueous solution. Explain. Here. The electronic configuration of: O-atom ⇒ 1s2 2s2 2p4 The electronic configuration of: O2-molecule ⇒ KK(σ2s2)(σ*2s2)(σ2p2)(πy2p2)(πz2p2)(πy*2p1)(πz*2p1) (iv) B. H− F − δ . Ans.. HCl is gas and HF is less acidic than HCl. Q. O2 molecule is paramagnetic. = 2−2 =0 2 Here the number of electrons in σ-orbital = the number of electrons in σ*-orbital. = b = =1 2 2 H-atoms are held together by one covalent bond. one is σ and the other is π-bond. The molecule does not exist. (i) sp3. 27. (iii) B. Q. What is hybridisation of atomic orbitals? ENGINEERING CHEMISTRY Ans. (ii) B...O. 28. What do you mean by hybrid orbitals? Ans. That is why.. (iii) sp. N − Na 2−0 Ans. (iii) He2+. Ans. H− F −δ Due to hydrogen bonding.

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

10. (d) Hund’s rule. (c) Resonance. combine to form a compound. (b) Molecular orbital theory. 15. Give the molecular orbital diagrams of H2 and O2 molecules. Explain inter and intramolecular hydrogen bonding with examples. What is dipole moment? How is dipole moment of a molecule calculated? 13. Give its name also. (c) Explain sp3hybridisation. Two elements having the atomic numbers 11 and 17. What is VSEPR theory of molecular model? Explain with suitable examples. (f) Aromaticity. 12. 16. (b) Give the characteristics of covalent bond. (e) Delocalization. 14. respectively. Write short notes on: (a) Intermolecular forces.42 ENGINEERING CHEMISTRY 9. State the nature and formula of the compound so formed. 11. Discuss Born Haber cycle with an example. . (a) Explain hydrogen bonding.

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

2. 3. Z 70 90 Fig. or γ-rays to give daughter elements.u.000 km per sec.83 × 108 m/sec. (v) Nearly 1/10 the speed of light or 20. Nuclei with 84 or more protons are radioactive. (iii) No mass (0) (iv) Charge (iv) Possess positive charge of 2 units = 9.44 (iii) Mass (iii) 4 a. These nuclei are unstable and emit spontaneously α. β. These numbers are magic numbers.000 to 30.6 × 10–10 e. A 120 80 40 0 10 30 50 Atomic number.2 × 10–19 coulomb. (vi) Maximum (vi) Penetrating power It has been observed that heavier elements in which neutron-proton ratio (N/p) exceed 1.u. 8. (v) 2. Nuclear Stability 1.36 × 108 to 2. ENGINEERING CHEMISTRY (iii) 1 of hydrogen 1836 atoms or 0. 50.5 show radioactivity. Nuclei with even numbers of protons and neutrons are more stable than that with odd numbers.000548 a. 3. Nuclei containing 2.s.8 × 10–10 e. 82 and 126 protons or neutrons are more stable than other nuclei containing different number of protons and neutrons.m.1 . or 3. (vi) Medium (iv) No charge (0) (v) Velocity (v) Nearly same as light 3 × 108 m/sec. 240 200 160 Mass number.6 × 10–19 coulomb.s.u.m. (vi) Low (iv) Possess negative charge of 1 unit = 4. 20. or 1.u.

i.. Fraction present t=T t = 2T t = 3T Time t Fig.1) is a plot of proton number (Z) vs mass number (A). At any instant of time. light elements possess equal number of protons and neutrons and the nucleus is stable. 3.e. As the difference of Z and A increases the nucleus becomes totally unstable.NUCLEAR CHEMISTRY 45 The graph (Fig. when t = 0 N = N0. Integrating we have.e–λt When M0 = original mass and M = mass at time t. When the value of Z is less.2). . − So. The graph is more or less linear. the rate of disintegration is proportional to the number of atoms (N) present. then ∴ or ∴ dN = − λdt N loge N = – λt + C loge N0 = C loge N = – λt + loge N0 loge N = – λt N0 [C = integration constant] If ‘N0’ be the number of atoms present initially. 3. the equation is M = M0...e.e–λt Hence. 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. Radioactive Decay The radioactive decay follows an exponential law. So it can be said that radioactivity is a phenomenon to stabilize the nucleus by decreasing the ratio A/Z of the nucleus.e.2 Decay curve of radioactive substances. the decay curve is exponential in nature (Fig. The ‘negative sign’ indicates that with passage of time ‘t’ the number of atoms decreases. 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. then the ratio A/Z for a nucleus is 2 i. 3. i.

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

u.m. Nuclear Fission In 1939. 1 × 12 C 1 a.u. Mass–Energy Equivalence In 1905. . 1 This phenomenon is known as Artificial Radioactivity. it is converted to a radioactive atom.6 × 10 −6 ≈ 931 MeV.66 × 10–24 g. The year 2005 has been declared as year of physics to observe the centenary of this famous equation. e.6 × 9 × 10 20 1. 1 a.6 × 10–12 ergs.m. German scientists Hahn and Strasman bombarded uranium atom with neutrons and obtained two elements with atomic numbers 56 and 36. c = velocity of light.m. Mass-Energy conversion factor We know that.u. = 1. 1 eV = 1. we get radioactive 13 phosphorus which is ultimately converted to silicon. = 1.023 × 1023 1 a. Einstein established from theoretical standpoint that mass and energy are mutually convertible. Atomic Mass Unit Masses of atoms are usually expressed in atomic mass units (a. 27 13 Al + 4 He → 2 30 15 P 30 15 P 30 19 Si 1 + 0n → + 0e .). = 1 6.66 × 10 −24 g.m. 1 g of matter is equivalent to 9 × 1013 J of energy. 1 MeV = 1.u.u.u.g. The famous equation in this regard is E = mc2 where E = energy . So. So. if we bombard 27 Al with an alpha (α) particle.6 × 10–6 ergs and 1 a. Highlight: E = mc2 = 1 × (3 × 1010)2 g cm2 sec–2 = 9 × 1020 g cm2 sec–2 = 9 × 1020 ergs = 9 × 1013 joules.m. = N 12 N where N (Avogadro number) = 6.m. = 6 12 1 12 1 g= g × So.NUCLEAR CHEMISTRY 47 Artificial Radioactivity If an atom of a non-radioactive element is bombarded by a powerful particle.023 × 10 23 = 1. ∴ 1 a.

141 56 Ba 92 36 Kr 1 30 n Final masses ⇒ 140. 1 0n (Secondary neutrons) Neutrons Fission Fragments 235 92U Fig.m.0261 a.0439 a. and this amount of energy will be generated within 10–6 second. the generation of huge amount of energy leads to an explosion with a temperature of one crore degree.0087 a.3) and as a result it can generate a huge amount of energy.u.u. This nuclear fission reaction is the principle of an atom bomb.u. .48 235 92 U ENGINEERING CHEMISTRY 1 1 + 0 n → 266 U → 141 Ba + 92 Kr + 3 0 n. 3. 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.u.8373 a. So.m. ⇒ ⇒ 91. 236. ⇒ 1. A small fraction of mass is lost and is converted to energy according to the equation: E = mc2.9139 a.m.u. 3. 1 g of U-235 will generate 2 × 107 kcal.u. This process of repeated fission is known as chain reaction (Fig. 235 1 141 92 1 92 U + 0 n → 56 Ba + 36 Kr + 3 0 n.u.m. 235.m. 92 56 36 This phenomenon of splitting a nucleus into two approximately equal fragments is called nuclear fission or simply fission. For the reaction. 235 92 U 1 0n Initial masses ⇒ 235. 3.m.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.8973 a.0526 a.m.

2153 a.2 megawatt continuously for one year.u. the atomic weights are calculated from number of protons. (in 3 So.m.0601058 a. For a 7 Li atom. Besides that. we are to control the chain reaction to get the heat energy according to necessity.02863 a.m. (Energy released due to above fusion) The difficulty is to attain the high temperature for such fusion process. the atomic weight will be 3 3 × 0. But due to the presence of isotopes in unequal amounts.m.u. But actual atomic weight of 7 Li is 7. mass defect (∆) = 7. which is sufficient to supply energy at the rate of 2.u. the mass lost is 0.0162 → 4.NUCLEAR CHEMISTRY 49 So.01818 a. that means such a fusion process would also lead to liberation of huge amount of energy which causes explosion.u. i. But it is believed that such condition is attained for preparing thermonuclear bombs such as hydrogen bomb. two nuclei combine to give a new atom. Atomic Fusion At a very high temperature.0601058 – 7.u. 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. the energy released would be 8. Highlight: It can be shown that when 1 kg of uranium is completely fissioned. in an atomic reactor. which is equivalent to an energy of 0. The calculated mass (M) and actual weight (A) is determined considering the contribution for the presence of isotopes.u. Aston examined the atomic weights of various elements and concluded that the atomic weights of all the elements would be a whole number. And during this fusion reaction some mass is destroyed. the atomic weights become fractions.00893 = 7.01818 = 0. 1 1 2 Mass Defect and Binding Energy After the discovery of isotopes. The transformations for fusion reactions are: 2 1H (i) 3 H + 2 H → 4 He + 1 n + 17 MeV 1 1 2 0 (ii) 3 H + 1H → 4 He + 20 MeV etc. the motion of neutrons are retarded by graphite or heavy water to control the chain reaction.02863 × 931 MeV = 26. To utilise the energy released during the fission.0005486 + 3 × 1.00758 + 4 × 1. electrons and neutrons. Now-a-days.2 × 1013 J. This phenomenon is known as atomic fusion. which is equivalent to 0.e.2153 × 931 ≈ 200 MeV.m. + 2 H → 4 He + Energy 1 2 2 × 2.m. 16O scale) .. So.6545 MeV.0419258 a.00389 ∴ ∆m = 0. the atomic weights of the different elements depend upon another factor: in a.m. The difference of these two quantities is called mass defect (∆) or ∆m ∴ ∆ = M – A. two nuclei combine to give a comparatively heavy nucleus..

03 MeV.” In other words it is a device where controlled nuclear fission of 235U. 10 Binding energy/Nucleon (MeV) 9 8 7 6 5 4 3 2 1 0 20 40 60 80 100 120 140 160 180 200 220 240 Mass number (A) Fig. neutrons and radio-isotopes. When mass defect is divided by mass number. . 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. So.81 Therefore. Nuclear reactors are of various types depending on their neutron spectrum. construction. the nuclear binding energy will be 0.4).50 ENGINEERING CHEMISTRY When protons and neutrons unite a small fraction of mass is converted to nuclear binding energy. 233U etc. heat.0419258 × 931 = 39. The reactors are differentiated by the following features. packing fraction is average mass defect for any particle. The mechanism for heat generation: In the nuclear reactors due to the fission fragments which move at high speed because they take bath in a dense mass of metal. The value of packing fraction is very small.0419258 m−A × 10 4 = × 10 4 f= A 4 = 104. they are rapidly slowed down and brought to rest due to collison with other atom of the metal. composition and the purpose for which they are used. In doing so energy is converted to heat. Nuclear reactors may be looked upon as a nuclear furnace where fuel is 235U. so it has been expressed by multiplying 104. • Neutron energies: (a) High energy—as in fast reactors (b) Intermediate energy (c) Low energy—as in thermal reactors. 3. 233U or 239Pu and also chain reaction takes place and produces. 3. a fraction is obtained which is known as packing fraction (f) 0. 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. and this is the reason for mass defect.4 The graph is a plot of binding energy/nucleon vs.

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

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

plant absorbs elemental P both from the soil and from the added fertilizer. The element which is ‘labelled’ or ‘tagged’ is called a ‘tracer element’.6 neutrons. 2.9 neutrons and it is noteworthy to mention is a manmade nuclear fuel. per nuclear fission. The application of isotopes depends on the fact that the chemical properties of the isotope of a given element are essentially identical. (b) Biological Shield: It is a layer of concrete of few decimeter thick surrounding the thermal shield.5 neutrons remain in the reactor and 0. 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 the breeder reactor. In this case. (iv) 60Co (γ-radiations) is used in cancer therapy. which are then converted into sugar and starches.9. In general type of reactors the conversion factor is 0. At the same time.5 neutrons escape out of the reactor. it is a thick steel or iron covering. . A reactor with the conversion factor above unity is known as breeder reactor. The detection of a radioisotope is made on the basis of its radioactivity and a stable isotope by means of a mass spectrometer. particularly brain tumours. Among which one neutron is used to maintain the steady chain reaction. How much of the P is consumed from the fertilizer by the plant can only be determined by tracer technique. that 239Pu 235 U produces 239Pu by capturing those 0. It is used to absorb γ-rays and the neutrons leaking through the inner thermal shield.NUCLEAR CHEMISTRY 53 6. physics. Uses of Radioisotopes Radioisotopes provide a powerful tool for the solutions of enormous problem in chemistry. Shielding: It is an important consideration for a reactor installation.9 neutrons (ii) Moderator. kidney. they can take up CO2 and water. In high power reactors. 6CO2* + 10H2O → C6H12O6* + 6H2O* + 6O2 6CO2 + 12H2O* → C6H12O6 + 6H2O + 6O2* (b) Agriculture: During growth. The O2 produced may come from CO2 or H2O molecules or from both. it was found that O2 came only from water. A few example of the use of radioactive tracers are given below: (a) Photosynthesis in plants: When plants come in contact with sunlight. (a) Thermal Shield: It is kept very close to the reactor core. etc. 235U is fissioned by the slow moving neutrons. (ii) 59Fe is used to diagnose the blood disorder. 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 residual 1. industry. (c) Medicine and diagnosis: (i) Radioisotopes are used to locate the presence of tumours.5 neutrons is used up as follows: (i) 238U captures 0. 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”. biology and physiology. two shields are used. coolant absorbs 0. By performing experiments with labelled oxygen in CO2 or H2O. (iii) 131I is used to diagnose malfunctioning of liver. O2 is liberated.

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

as the plant assimilates CO2 with C14O2 during photosynthesis.303 log a− x t a = amount of U238 originally present in the rock at the time it was formed. . no more CO2 is assimilated so ratio C14 to C12 in the plant changes. 0. JK (h) Radio-carbon dating technique: The age of a piece of wood or animal fossil can be determined by radio-carbon dating technique. U238 λ = decay constant of U238. 14 7N + 0n1 (from cosmic rays) → 6C14 + 1H1 In radio-carbon dating ratio C14 to C12 is assumed constant in the plant. values of Pb206 and U238 can be determined experimentally.730 yrs) age of the wood (t) can be calculated.NUCLEAR CHEMISTRY 55 Hence.303 t1/2 Pb 206 log 1 + 238 0. t= Here. the decay constant of is known from the relation λ= 0. The radioactive decay follows the first order rate law. t= 2.693 t1/ 2 Thus. U238. Alternatively. a = (a – x) = C 14 C 12 C 14 C 12 2. C14 is formed in the atmosphere as follows : This is present in atmosphere as C14O2 with C12O2. Pb206 So.303 Pb 206 log 1 + 238 t U F GH I. by measuring C14 to C12 ratio and t1/2 of C14 (5. the age of the rock can be calculated. λ= a 2. present in the rock at time t is: a = U238 + Pb206 and (a – x) = U238 represent their respective masses.303 U 238 + Pb 206 log t U 238 where. (a – x) = amount of U238 still left after the lapse of time (t). λ= 2. the age of a rock can be determined as follows. age of the rock (t) can be calculated. provided the ratio Pb206 to Pb207 is determined with the help of a mass spectrometer.693 U F GH I. After the death of the plant. λ= 2.303 t1/ 2 a log . JK U238 Since.693 a− x ratio in the fresh plant ratio in dead plant.

= 4. Mass of one α-particle = 4. Estimate half-life of Pu239 from this data. then the above equation will take the form. 2. calculate how much of Madam Curie’s 200 mg of radium would be left in the year 8378 A.478 × 106 years.00387 a.464 × 10–24 g = 14.8672 × 10–15 sec–1.56 ENGINEERING CHEMISTRY So.D.867 × 10 −21 / 1 = 14. Example 1. of half-lives (t1/2) = Example 2.66 × 10–24 g = 6.693 sec. Sol.693 0.5 mg. Total time = (8378 – 1898) = 6480 yrs.8672 × 10 −15 = 1. Sol. This source is estimated to emit 2300 α-particles/sec. Assuming that it were to remain undisturbed since 1898 A.37 N0.37 N0. No. in all directions. = M 1 × 10 −6 0. − dM = λM dt λ= = − d M/ dt − 14. N = N0e–λt 1 . when t = Example 3. λ N = N0 e − λ. We have. Prove that N ≈ 0.718 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.D. by measuring the ratio C14 to C12 in the fresh and dead plants.m. (t1/2 of radium is 1620 years).u..00387 × 1.646 × 10–24 g Mass of 2300 α-particles = 2300 × 6. 1 λ = N0e–1 = N0 e N0 = 0. .368 N0 ≈ 0.8672 × 10–21 g As So Half-life (t1/2) of Pu239 F 1I Mass of radium left = M G J H 2K F 1I = 200 G J H 2K 0 6480 =4 1620 n 4 = 12. Sol. age of the wood (t) can be calculated. = λ 14. A radioactive source contains one microgram (µg) of Pu239.

and 0. M0 = Initial mass of 92U234 M = Mass at the end of 62.4343 99 t = 23. The mass of radium would be left behind at the end of time t = 1 – 0. (a) We know.01 .88 × 10–14 s–1). or.693 0. The half-life period of radium is 1620 years.69 × 105 disintegrations/sec.173 left unchanged = is: 4 = 3.88 × 10–14 × = 7.364 × 10 −3 × 6.364 mg. ∴ Mass of 92U 234 M0 = M .189 M M= M0 1.48 × 105 yrs. (a) Let. Now. ∴ (b) Here log10 log10 N = N0e–λt N0 = eλt N N0 = λt × 0.173 t1/2 2.28 × 10–4 year–1.693 × 62000 ×t= = 0.693 0. = t1/2 1620 Let.023 × 10 23 234 (b) Activity of 92U 234 A = λN = 8. N0 1 = = 100 N 0.28 × 10–4 × t × 0.68 years. Sol.173 M = M0e0.000 yrs.99 g.. (a) How much of it will remain unchanged after 62.000 years ? (b) What will be its activity at the end of that time? (t1/2 = 2.0 mg of 92U234. Example 5.4343 N 100 = 4. 1. In how many years will one gram of pure element (a) lose one centigram (b) be reduced to one centigram? Sol. or. M = M0e–λt λt = We have.01 = 0.189 = 0.173 = 1. λ= 0. e0. or.48 × 10 5 λt may also be calculated. time during which one centigram of radium is lost due to disintegration be = t. λ = 8.88 × 10–14 × 62000 × 365 × 24 × 3600 ∴ or.NUCLEAR CHEMISTRY 57 Example 4.693 = 4.189 3. or. as follows: λt = 8. A radioactive sample initially contains 4.

The number of atoms of RaB contained in mass (m) = Now. ∴ ∴ − dN = λN dt m × 6. Assuming that the rock originally contained no lead.s–1.023 × 10 23 214 Highlights: • For one curie. Calculate the mass for RaB for 1 rd activity.7 × 1010 dis/s. U238 = (U238 + Pb206) e–λt . The ratio of mass of Pb206 to the mass of U238 in a certain rock specimen is found to be 0. m × 6. estimate its age. m × 6.2 × 106 g.693/4.760 years. One rutherford is defined as that quantity of a radioactive substance which gives 106 dis.023 × 10 23 238 Example 8.9 × 10–18 × ∴ m = 3.31 × 10–4 × m = 3. the mass of t1/2 = 4.3 × 10–13 g.98. For 1 rd activity. The unit for measuring radioactivity is curie (Ci).58 ∴ ∴ log10 100 = 4.7 × 1010 = 4. One Ci is defined as that quantity of a radioactive material which gives 3. • Smaller units like millirad (mrd) and microrad (µrd) are also used. Calculate the mass of RaB in gram which gives 3.5 × 109 × 365 × 24 × 3600 and m × 6.4343 t = 10.7 × 1010 disintegrations/sec.02 × 10 23 214 3.5 × 109 years) Sol. We know that. (t1/2 for U is 4. ∴ ∴ Highlights: • A new absolute unit of radioactivity is rutherford (rd). ENGINEERING CHEMISTRY Example 6. 238 92 U m × 6. s −1 dt 106 = 4.1 × 10–8 g. 92U 238 • For one rutherford. Sol.31 × 10–4 × m = 8. the mass of is 106 = 4.7 × 1010 = 4.5 × 109 years) is: (λ = 0.02 × 10 23 214 dN = 10 6 dis. Example 7.023 × 10 23 238 3.28 × 10–4t × 0.5. Sol.9 × 10–18 × ∴ m = 80.

5 × 109 years.3 = 0.05 log 1 + = 0.693 4.9 = 0. Calculate the age of wood. 0. t= 11. or.05 206 2. Mole of U238 = Mole of Pb206 = We have. We have.5 × 10 9 1 = 1+ F GH Pb 206 U 238 I JK e –λt 1 = (1 + 0. We have.303 × 4. Sol.693 Example 11. 0.693 0.170 yrs.525 yrs.1761 t = 2.23 × 0.05 = FG H I JK IJ K 2.693 2.303 t1/2 Pb 206 log 1 + 238 0.5 λt = 2.63 × 109 years.303 × 4.3 g of Pb206.9 g of U238 and 10.693 Example 10. (t1/2 = 4.303 × 5577 log 6 0.6021 = 11.05 238 10.5 e–λt eλt = 1. (t1/2 of C = 5577 yrs).693 U F GH 2. ∴ or. 0.1761 t = 0.7782 = = 20. t= = 2. Calculate the age of the ore. The amount of 6C14 isotope in a piece of fresh wood is found to be 1/6th of the total carbon.303 × log10 1.693 . Half-life period of C14 is 5760 years. ∴ ∴ 0. A sample of U238 is found to contain 11.5 × 10 9 log 2 = 4.303 × 5760 × 0.5) e–λt = 1. t= = 2.693 1/ 6 2.693 1/ 4 2. 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 × 0.5 = 2. What is the age of the old piece of wood? Sol.303 × 5577 × 0.NUCLEAR CHEMISTRY 59 or.303 t1/2 1 log 0.5 × 109 years) Sol.303 × 5760 1 log 0.5 × 10 9 0. Example 9.

the reaction is accompanied by liberation of energy. (b) Interacting particles 2He 7N 4 Mass (a.01264 – 18.01140 = 0. = 0.4696 2. the reaction is = 18. there is absorption of energy.693 = 0.60 ENGINEERING CHEMISTRY Example 12. (a) The overall energy liberated or absorbed in a nuclear reaction is called nuclear reaction energy.00814 Total = 18.303 × 6.15 MeV The Q-value for the reaction is negative. there is gain of mass in the reaction. = – 1.u.13 hrs.0045 1. and such reaction are called endothermic or endoergic.00753 Total = 18.) 4.13 log x 0. (a) What is Q-value for a nuclear reaction? (b) Calculate the Q-value for the following nuclear reaction: 14 7N + 2 He4 → 8O17 + 1H1.m. 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. so the reaction is endoergic.) 17. there is increase in mass and absorption of energy. 3 Example 13.693 10 × 0.00124 × 931 MeV = 1. .m. Sol.303 × 6. Calculate the fraction of the sample of this substance present at the end of 10 hrs.01140 Product particles 17 8O 1 1H Mass (a.m. = 931MeV] + 7N14 = 8O17 + 1H1 + Q ∴ Q-value of the reaction is = – 0. such a reaction is exothermic or exoergic.693 1/ x 2. if Q-value is negative. t= or or ∴ 10 = 2.303 t1/2 1 log 0.13 log x = x = Antilog 0. Sol.u.15 MeV 2He 4 [Q 1 a. The half-life of Ac222 is 6.u.u.4696 = 2.m.01264 14 Increase in mass ∴ Q-value So. there is decrease in mass in the reaction. On the other hand.00387 14. If Q-value is positive.m.00124 a.948 x≈3 ∴ the fraction of the Sample = 1 .u.00124 a.

u.m.m.67 MeV.u.u.258 MeV.2151 a.03402 × 931 = 31.0078 a.01822 1.353 × 931 MeV.) 4. Mass defect ∆m for Ca-atom = (20 × 1.02636 Product particles 2He 4 4 2He Sol.00774) = 0.954 + 2 × 1. Sol. Show the following reaction is exoergic 3 Li 7 + 1H1 = 2 He4 + 2 He4.03387) = 0.00387 a.m. which has atomic mass of 39. 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. The mass of proton is 1. Here. Example 16. the reaction is accompanied by liberation of energy (decrease in mass). The reaction is 92U235 + 0n1 = 36Kr95 + 57Ba139 + 2 0n1 + Q 235 92 U or Q = (235.353 a.u. Calculate the limiting energy per nucleon 20Ca40. = 0.m. = 0.m.01702 a.NUCLEAR CHEMISTRY 61 Example 14.u. (energy released/fission of U 235 MeV = 200 MeV).m.0099) – (94. ∴ Binding energy per nucleon = 40 = 8.02636 – 8.01862 a.0086 a.0078 + 20 × 1. + 1D2 = 2 He4 + 2 He4 + Q where isotopic masses are.3 MeV. 3 Li6 = 6.01474 2 He = 4.u.0099) = 0.945 + 138. 6 4 = 2.975 a. = 0.01474 + 6. From the above equation. Example 18. = 0.u.975 a.2151 × 931 MeV = 200. So the reaction is exothermic of exoergic.m. 3 Li 2 1D Example 15.u. 0. Interacting particles 7 3Li 1 1H Mass (a. and the mass of neutron is 1.00387 Total = 8.03402 a. Sol. Sol.00774 ∴ ∴ 3Li 7 + 1H1 = 2He4 + 2He4 + Q Q = Decrease in mass = (8.m.00387 4.u.216 MeV.00814 Total = 8.01702) – (2 × 4.m.01862 × 931 = + 17.m.u.0086) – 39.u.u. . Calculate the energy released in the following fission reaction: + 0n1 → 36 Kr95 + 57 Ba139 + 2 0n1. ∴ Energy released Example 17.m. Q = (2. Q value is positive. Calculate the energy released from the fusion of 3 Li6 and 1D2 by the reaction.124 + 1.m. Mass (a.) 7.

.023 × 10 26 MeV. 3.53 kg.023 × 1026 atoms or nuclides.5 × 10 23 kg = 6.2 Energy released/nuclide = 200 × 1.62 Sol. energy released per 1 kg of U235 = 200 × 6.5 × 1023 32 × 10 −12 6.2 × 10–11 J or W. A city requires 100 MW of electrical power on an average.s.2 × 10 −11 (ii) 1 kg atom of U235 = 235 kg = 6. Energy required to be produced in a day 864 × 10 10 = 432 × 10 11 J 0. 1. (Q 1 MeV = 1. (i) Energy released per fission of U235 nuclide ENGINEERING CHEMISTRY = 200 MeV = 200 × 1. etc.1 × 1010 fissions sec–1.025 × 10 26 = 530 × 10–3 kg = 0.5 × 1023 atoms of U235 are present in 235 × 13. ∴ No.2 × 1013 J. Hence. SHORT QUESTIONS AND ANSWERS Q. Sol. So. disintegration. of U235 atoms to be fissioned = = 432 × 10 11 = 13. Nuclear chemistry is concerned with changes of the nuclei i. its stability. . What do you mean by nuclear chemistry? Ans.023 × 1026 atoms of U235 are present in 235 kg ∴ 13. Energy consumed in the city in a day = 100 × 106 × 24 × 3600 = 864 × 1010 J Since efficiency of the reactor is 20%. calculate the amount of fuel required for one day’s operation. using U 235 as the nuclear fuel. 235 = 8.6 × 10–13 J = 3.6 × 10–13 J) Example 19. Given that energy released per fission of U 235 is 200 MeV.6 × 10–13 J = 32 × 10–12 J.e. If this is to be supplied by a nuclear reactor of efficiency 20%. fission rate for generation of 1 watt 1 = = 3.

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

(iii) Radioactive change is always exothermic. Such type of radioactivity is known as “artificial or induced radioactivity”. (ii) Chemical change is mostly reversible. Compare radioactive change and chemical change. 10. Radioactive change (i) Radioactive change does not depend upon external conditions like temperature. and this reaction is the principle for atom bomb. Ans. Q. Q. 8. − or dN = λN dt λ= − d N/ dt N So. 11.64 ENGINEERING CHEMISTRY Q. (iv) Radioactive change is a nuclear phenomenon. (iii) Chemical change may be exothermic or endothermic. etc. Whereas modern techniques of artificial transmutation of elements have made it possible to produce radioactivity in many other lighter elements. What do you mean by radioactive decay constant? Ans. This chain of successive disintegrations is termed ‘radioactive series’. Chemical change (i) Chemical change depends upon external conditions like pressure. Natural radioactivity is exhibited by heavier elements found in nature. As for example: 56Ba 92U 235 140 + 36Kr + 38Sr 93 + 3 0n + 2 0n 1 + 0n ¾¾® 1 92U 236 54Xe 55Cs 144 90 1 144 + 37Rb 90 + 2 0n 1 A huge amount of energy is released during nuclear fission according to famous Einstein’s equation E = mc2. temperature. Q. Q. etc. pressure. 9. What do you mean by radioactive series? Ans. The division of a nucleus into two approximately equal parts is termed ‘nuclear fission’. Alternatively. (ii) Radioactive change is irreversible. the daughter element is also radioactive then it decays further and the process continues till a stable isotope is reached. the radioactive decay constant (λ) may be defined as the ratio of the amount of the substance. If. which disintegrates in a unit time to the amount of the substance present. it may be defined as the rate of disintegration when the number of radioactive nucleus present is one. What do you mean by nuclear fission? Ans. The radioactive decay equation is. during radioactive disintegration. No change takes place of the nucleus of the atom. (iv) Chemical change involves only outermost electrons of the atoms. 12. . What do you mean by natural radioactivity and artificial radioactivity? Ans.

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

. Give a relation between half-life and the decay constant of a radioactive substance. 10. 21. 17. + 7 Be. 9. range and velocity. How long will it take for 1 g of the element to lose 0. 6.00782 a. Write notes on: (i) Radioactive equilibrium (ii) Atomic weight of lead in radioactive minerals (iii) Tracer technique. [Ans.] . Derive a relation between mass defect and nuclear binding energy.04 1 amu = 931.. 92 0 24.1 g? [Ans.4 × 1010 yrs.66 4. What is nuclear fission? Show how nuclear fission is a chain reaction. 13. Give a brief account of the nuclear reactors. Explain artificial radioactivity with suitable examples.. 20. Given the t1/2 of thorium = 1. 22. 8.m. + . What is radioactive displacement law? 12. 54. What are the causes of nuclear instability? Explain with suitable examples.00866 a. The half-life of radium is 1590 years. Mass of neutron = 1. Why is natural radioactivity mostly limited among heavier elements? 14. 5. 25. Write a short note on nuclear fusion. Write a short note on radio-carbon dating. 1 4 7 3 Li 26.. 15. β. What are radio-isotopes? How are they prepared? Mention their uses..] 27. What informations are available from these curves? 18. → → 24 12 Mg 239 90Th 10 5B + 4 He → . Calculate the amount of energy released during the bombardment of 1 n on 235 U . Give a comparative account of the nuclear binding energy curve and packing fraction curve.and γ-rays? Compare their ionising power. Write a short note on nuclear transmutation. Calculate the binding energy in MeV per nucleon of 12 . Calculate the time required for 10% disintegration of a sample of thorium.93 × 10–5 yrs.4 MeV.76 MeV] 28.u. What is a nuclear reaction? Discuss some uses of nuclear reactions. ENGINEERING CHEMISTRY What are α-.m. What are the units of radioactivity? 7. Where is the radioactive displacement law invalid? 23. 6C Given: Mass of H-atom = 1. Explain the terms: (i) Disintegration constant (ii) Half-life period 6. [Ans.. What is nuclear binding energy? 16.. + 1H 2 1 + 1H → .u. 2385 yrs. Actual mass of C-atom = 12. + . Complete the following nuclear reactions: 9 4 Be + 4 He → 2 24 11 Na 238 92 U 12 6C + . 11. State and explain the law of radioactive disintegration.. 19. 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...

5 × 109 yrs.73 MeV] 35.009 a. Mass of proton = 1.m. 0. 16.2 counts 37.u. Given the t1/2 of cobalt = 5.m. Distinguish between nuclear fuel and a chemical fuel.u. [Ans. [Ans. 39.5 × 10–6] 32.01605 a. Write short note on components of a nuclear power reactor and their functions.m. Calculate the approximate life period when the plant died.u. Mass of 11B = 11. Calculate the age of the wooden article.0 counts min–1 g–1. [Ans. = 931 MeV. A piece of wood was found to have 14C/12C ratio 0.u. [Ans. 9.33.u. 2970 years] 30. Given t1/2 of uranium = 4. Calculate the energy released in the nuclear fusion reaction: 2 1H 1 + 3 H → 4 He + 0 n 1 2 Given: Mass of 2 H = 2. Mass of 1H = 1. 16.01472 a. A sample of uranium ore is found to contain 11. An old wooden article shows 2. 1 a. Mass of electron = 9 × 10–28 g.01286 a. Mass of 2H = 2. .76 MeV] A fresh sample of wood shows 15. Calculate the weight of 1 curie of 222Rn. 1 Mass of 4 He = 4.u. Calculate the energy released in MeV from the reaction: 10 5B + 2 H → 1 11 5B + 1H 1 Given: Mass of 10B = 10.00812 a. What is its halflife period? [Ans. Half life of 222Rn in 3. Calculate the age of the rock. Given t1/2 = 5760 years.6747 × 10–24 g.9 g of 238U and 10. [Ans.m. 2 Mass of 1 n = 1.760 yrs.NUCLEAR CHEMISTRY 67 29. 6.6725 × 10–24 g. [Ans.13 yr–1] 36.m. Calculate the energy produced in MeV. [Ans. 40 days] 33.016 a. A neutron breaks into a proton and an electron.m.m.m. Given: Mass of neutron = 1.114 MeV] 34. of 206Pb.u.u.7 times that in a living plant.82 days.014 a.5 × 109 years] 31.862 years] 38.3 years. Calculate the decay constant of 60Co. [Ans. 0 min–1 g–1. 1 Mass of 3 H = 3. A radioactive element disintegrates to 1/16th of its original mass in 160 days. 4.m. Given: t1/2 for 14 6C = 5. 0.003 a.u.

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

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

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

when heat does not flow out of the system nor does it come into system from the surrounding. Hence. The work done is at the expense of the kinetic energy of the molecule while they are separated from each other.e. if the process is carried out at constant volume change in enthalpy and change in internal energy are equal. ∆H = ∆E + PV = ∆E + W = q (heat absorbed) and at constant volume. ∆H = (E2 + P2V2) – (E1 + P1V1) = (E2 – E1) + (P2V2 – P1V1) ∴ At constant pressure. Heat absorbed by the system is q. For an ideal gas. q = 0. H is a similar state function. ∆V = 0. Hence. Change in enthalpy = change in internal energy. But Joule-Thomson observed that most gases cooled down by such a pressure drop.. 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. thus the gas while expanding does some work and hence the temperature falls. ∆E = –ve. Constancy of Enthalpy (isoenthalpic) in Joule-Thomson expansion Joule-Thomson experiment is carried out adiabatically.e. ∆H will depend only on the initial and final states of the system.2) and the work done is P2V2 – P1V1. a system at constant pressure is undergoing a change from states 1 to 2. 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.e. Thus.. . Since the expansion is carried out adiabatically i. 4.. the energy of the gas falls i.THERMODYNAMICS 71 Joule and Thomson performed an experiment where a gas was allowed to expand adiabatically through a porous plug against a constant pressure. the gas was allowed to do no work and there was no interchange of heat with the surroundings. i. Hence. ∴ ∆H = ∆E + 0 = ∆E. The volume increase is from V1 to V2. The gas expands is passing through porous plug (Fig. P2V2 – P1V1 = W. So. The quantity (E + PV) is universally represented as H and called the heat content or enthalpy of a system. work done by the gas is. when q = 0.2 Joule-Thomson expansion. i.e. 4. Suppose.. P1V1 = P2V2 ∴ W = 0. not on the path followed during the change. for an ideal gas. there should be no change in temperature. Hence. Since E is a characteristic of the system (state function). ∆E = q – W = q – 0 = q. from the first law of thermodynamics q = (E2 – E1) + W = (E2 – E1) + (P2V2 – P1V1) = (E2 + P2V2) – (E1 + P1V1) = H2 – H1 = ∆H. according to the first law. Porous plug V1 P1 P2 V2 Fig. Hence. from first law of thermodynamics.

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

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

.

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

∆S = S2 – S1 = z 2 1 q T1 q The decrease in entropy of state 2 = T2 T − T2 q q − = q. the change of entropy (∆S) is given by: dqr . for an ideal gas at constant temperature. The vessels are kept in a thermostat of the temperature T. T1 V1 P V2 = 1 P2 V1 z V2 V1 dV V Since. T1 Entropy change in irreversible process Entropy is a state function. T2 ∆Sp = Cp ln T 1 ∆Sv = Cv ln T2 .4). q = ∆E + W . for isothermal expansion. P2 V1 At constant pressure P. ∴ ∆S = Cv ln P1 T2 + R ln . So. and small quantity of heat q flows from T1 to T2. P1 V ∆ST = R ln 2 = R ln . The vessel is connected to a vessel of volume V2 by a tube containing stop cock. ∆S = Cv ln T2 V + R ln 2 . we have. 1 ∴ Net change of entropy = T2 T1 T1T2 The difference is a positive quantity. 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. for a change from states 1 to 2 we have.e. T When the flow of heat is irreversible. ENGINEERING CHEMISTRY z S2 S1 dS = Cv z T2 T1 dT +R T or. hence. The decrease in entropy of state 1 = Irreversible isothermal expansion of an ideal gas Let n moles of an ideal gas is enclosed in a vessel of volume V1. the irreversible heat flow leads to increase in entropy. which is evacuated (Fig. P2 T1 At constant temperature i. At constant volume V. From the first law of thermodynamics. 4.76 Thus.. let a heat reservoir at T1 (state 1) is brought in contact with a second reservoir at T2 (state 2) where T1 > T2.

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

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

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

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

Example: C2H5OH + 3O2 = 2CO2 + 3H2O ∆H = – 325 Kcal . From first law we find that ∆HP and ∆EV will be independent of the path. 4. ∆H terms algebraically. The heat of combustion is experimentally determined in a Fig.608 cals (exothermic) (b) H2 + I2 = 2 HI –12. the heat of reaction for the formation of 2 moles of HCl is 43.42 – 69. which are difficult Highlights: Hess’s law is used to calculate: • Enthalpy changes (∆H) of formation from enthalpy changes of combustion.e. 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. 4.. etc. The experimentally determined values of heat of combustion are useful.05 Kcal.63 Kcal. heat of transition. • Lattice energies is the Born-Haber cycle. Combustion reactions are always exothermic. (i) Heat of reaction. heat changes in the two directions must be equal in magnitude but opposite in sign. “bomb calorimeter” which is a pressure vessel internally enamelled with platinum (Fig. • Enthalpy changes of reaction from enthalpy changes of formation. Let us take the example of formation of CO2 in one step and two steps (a) and (b): C + O2 = CO2 ∆H = – 94. (ii) Heat of combustion. multiplication of the quantities i. B. when molar quantities react and indicated by a balanced equation. In the case of organic compounds. The principal advantage of this law is that thermochemical equations can be treated as simple algebraic equations and the heat of formation.5). 2 2 Summing up we get. 12.e..5 Bomb calorimeter..05 Kcal 1 (a) C + O2 = CO ∆H1 = – 26. Example: (a) H2 + Cl2 = 2 HCl +43. Heat of reaction (∆H) is the difference between the heat contents of the products and the reactants.42 Kcal 2 1 (b) CO + O = CO2 ∆H2 = – 67.600 cal which is exothermic whereas for the formation of 2 moles of HI.680 cal of heat is absorbed and the reaction is endothermic. 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.THERMODYNAMICS 81 change is zero i. complete combustion means when these compounds are converted finally to CO2 and H2O. to measure experimentally can be easily found out by addition. subtraction.680 cals (endothermic) Thus.63) Kcal which illustrates the law = – 94. Hess’s Law of Constant Heat Summation. ∆H1 + ∆H2 = (– 26. so heat of combustion is always negative.

the heat of neutralisation deviates considerably from 13. (v) Heat of solution and heat of dilution. the stability of a compound is inversely proportional to the enthalpy of formation of a compound. The standard enthalpy of formation (∆Hfo) is just the negative of the heat of formation. it is needed to assume some arbitrary value for substances at a given state. If the enthalpy of formation of a compound is positive. KCl(s) + 100 H2O = KCl (100 H2O) – 4391 Cal. Example: H2O(s) → H2O(l) ∆H = 6 kJ. Thus. Therefore. one gm mole of KCl dissolved in 50 moles of water and in 200 moles of water will cause different heat changes. Heat of fusion is always positive. Conventionally. Example: ∆Hf of HI is + 26. In order to measure the change in enthalpy.e. If the acid and base are both strong. 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.. they can be assumed to be completely dissociated. the energy content of the corresponding compound is lower than its constituent elements and hence the compound is stable. and this is always the equivalent of 13. But when a weak acid or a weak base is neutralized.e. The heat of solution changes with concentration.7 kJ indicates the HF is much more stable than HI..7 Kcal.9 kJ and ∆Hf of HF is – 161. H+ + OH– = H2O. . i.7 Kcal of heat.8 kJ..7 Kcal HCl(aq) + KOH(aq) → KCl(aq) + H2O ∆H = – 13. the more stable is the compound. At high dilution. (vi) Heat of fusion. when the enthalpy of formation of a compound is negative. The value of heat of solution obtained graphically by extrapolating ∆H to infinite dilution is the integral heat of solution at infinite dilution. the enthalpy of any element at 1 atm and 298 K is assumed to be ‘zero’. Whereas. all in their respective standard states and at a reference temperature. the heat change becomes constant.e. Example: HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O ∆H = – 13. The lower the enthalpy of formation of a compound. It is the amount of heat liberated or absorbed when one mole of the compound is formed from its constituent elements. 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. (iv) Heat of formation. H+ + A– + B+ + OH– = B+ + A– + H2O i.7 Kcal. C(graphite) + 2 H2 (g) → CH4(g) ∆Hf = – 74.82 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. Example: KCl(s) + 50 H2O = KCl (50 H2O) – 4276 Cal. 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 heat of neutralisation is really the heat of formation of 1 gm mole of water from 1 gm ion of hydrogen and hydroxyl ion. i.

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

The engine must take up heat at higher temperature. ∆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. 2. to convey heat from a body at a low to one at a high temperature. convert a portion of it into work and give up the rest of heat to a body at lower temperature. (a) It is impossible to convert heat completely into an equivalent amount of work. Second law of thermodynamics guides the conditions under which heat and work are interconvertible.3 + 6 × 98.3 Kcal mol–1. the total enthalpy change involved in these bond breaking and making gives the heat of reaction. (c) All spontaneous processes tend to equilibrium. without producing some other effects in the system. i.1 kJ/mol. SECOND LAW OF THERMODYNAMICS Heat is readily available and man is interested to convert this heat energy to useful work. respectively. 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. but the entropy approaches a maximum. For the conversion of heat into work two conditions must be fulfilled. So.84 Variation of bond energy ENGINEERING CHEMISTRY (i) Bond energy varies with the size of the atoms. H = E + PV and G = H – TS = E + PV – TS . second law of thermodynamics can be stated in some different important forms.. 2C(g) + 6H(g) → H H   H— C — C —H(g)   H H ∆Hf for ethane is = 1 × (bond energy for C—C) + 6 × (bond energy for C—H) = (1 × 79. 1.5) Kcal. (b) It is impossible for a self-acting machine unaided by any external agency. Example: Heat of formation of ethane is. Example: bond energy for H—F and H—Cl are 56. = 670. (d) The energy of the universe is constant. 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. (ii) Bond energy varies with the difference between the electronegativity of the two atoms.e. (iii) Bond energy varies with the total environment of the molecule. Bond energy decreases as H—F > H—H > C—C > N—N > F—F.5 and 43. From the above experience.

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

S − S1 ∆S ∆P = 2 = V2 − V1 V2 − V1 ∆T ∆S = q T ∆S q dP = = T(V2 − V1 ) V2 − V1 dT q dP = . LM N OP Q or.e. the volume V1 of the liquid can be neglected as it is very small compared to the volume of vapor V2. We know q dP = .. log OP Q P2 L 1 1 = − P1 2. 2. for ideal gas ∴ or. 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. T(V2 − V1 ) dT When two phases of liquid (Vol. RT 2 P Assuming. ∴ Now. This equation is the famous Clapeyron-Clausius equation. V1) and vapor (Vol. The drop in free energy of the liquid is –∆G1 and corresponding gain in free energy of the vapour is +∆G2. 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.86 ENGINEERING CHEMISTRY equilibrium. as net or. Since the system is in equilibrium. Determination of latent heat. P2 L 1 1 ln P = R T − T 1 1 2 LM N or. Since. latent heat is constant and on integrating. or. L q dP = = T V2 T V2 dT (q = L = latent heat of vaporization) PV = RT. Thus. 2. V2) are in equilibrium. Effect of pressure on boiling point. P2 T2 − T1 L log P = .303R T1 T2 LM N OP Q . Application of Clapeyron-Clausius equation 1.303R T1T2 1 Thus. T(V2 − V1 ) dT where q is molar heat of transition from one phase to another. i. V = LP dP = RT 2 dT RT P dT dP =L. ∴ ∆G = 0 ∴ ∆G1 = ∆G2 V1∆P – S1∆T = V2∆P – S2∆T.

THERMODYNAMICS 87 3. These Cp values are plotted against T and can be extrapolated to T = 0. Absolute value of entropy can be measured by determining the heat capacities (Cp) of a substance at different temperature. so when in the . there is no disorder and hence the entropy of all pure substances at absolute zero is zero. Many reactions occur in nature which have ∆G = positive only when they are coupled with another reaction whose ∆G is much larger negative. At absolute zero temperature. ∴ ST = ST = z T z T Cp 1 0 dT = z T 0 C p d ln T 0 2.6 Graphical determination of entropy. ATP is a high energy molecule. Hence. • Entropy and the third law—Third law can be used to determine the entropy of a substance. 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. 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. ∴ (I) z T Cp T 0 dT S0 = 0. Coupling of non-spontaneous reactions Those chemical/biological reactions only take place spontaneously for which ∆G = negative. we have ST – S0 = From 3rd law. THIRD LAW OF THERMODYNAMICS In 1912. Planck enunciated the third law of thermodynamics as “the entropy of a solid or a liquid is zero at the absolute zero of temperature”. Example. kinetic energy of a substance is zero and it is present in a perfectly arranged crystalline state. the energy required for the first reaction to occur is supplied by the second reaction which is coupled to it. Mathematically. 4. So. 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).303 C p d log T (II) Cp Cp T 1 log T 2 O 10 T 20 30 Fig.

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

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

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

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

GC and GD from (ii) and (iii). • The above relation shows that equilibrium constant (Keq) can be calculated from a table of standard free energy values.92 ENGINEERING CHEMISTRY Substituting the values of GA. • The above expression gives free energy change for a reaction. One gm of water requires 536 calories of heat for conversion to steam at 100°C. q = 536 × 18 cal mol–1 ∆E = q – w = 9648 – 746 = 8902 cal mol–1 = 8. GB.(v) Combining (iv) and (v).. It is of great importance as it gives a quantitative relation for free energy change accompanying a chemical reaction. we have ∆G = – RT ln Keq + RT ln or. According to first law of thermodynamics q = ∆E – w Here or. P = 1).. – ∆G is called the Affinity of the reaction. Example 1.902 Kcal mol–1.(vi) This expression (vi) is called Van’t Hoff reaction isotherm. ∆G = 0 So. Highlights: • ∆G° = – RT ln Keq when pressures of reactants and products are one (i.e. ∆G = + RT ln (PA ) a (PB ) b (PC ) c (PD ) d . we have ∆G = (cGC0 + cRT ln PC + dGD0 + dRT ln PD) – (aGA0 + aRT ln PA + bGB0 + bRT ln PB) = (cGC0 ∆G0 + dGD – 0 aGA0 – bGB0) + RT ln (PA ) a (PB ) b (PC ) c (PD ) d So. = – RT ln Keq ∴ ∆G0 = – RT ln Keq (PC ) c (PD ) d LM (P ) (P ) OP NM (P ) (P ) QP C A c a D d B b eq ∆G° is a constant as G is a state function LMwhere K MN eq = (PC ) c (PD ) d (PA ) (PB ) a b O P P Q . Calculate the increase in internal energy per mol of water assuming water vapour to behave as an ideal gas. Sol.. w = PV = RT = 2 × 373 cals = 746 cals. – ∆G = RT ln Keq – RT ln (PA ) a (PB ) b (PA ) a (PB ) b (PC ) c (PD ) d .(iv) Now.. at equilibrium. . ∆G0 = – RT ln ∆G° is the difference in free energy between the products and the reactants...

836 = 3. 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. Calculate the work done by the following reaction at 27°C.3.8 Kcal mol–1 at a definite temperature. Sol. Here ∆E = q – w q = 990 cals = 990 × 4. Calculate the value of ∆E for the reaction at 500 K. We know. n2 = 1 ∴ We have.36 × 10 9 kJ = 0.314 × (273 + 27) = = 2. mols of gaseous reactant. ∴ ∆H = ∆E + ∆nRT.4942 kJ. Heats of combustion of ethylene. 372. n1 = 1 mols of gaseous product.36 × 109 ergs. of heat. qp = qv + ∆nRT.314 × 300 kJ. Here. after absorbing 990 cals. ∆n = n2 – n1 = 0.13 w = 8. We have.158 – 0. ∆n = 1 – 2 = – 1. 68. 1 mol.2 10 3 kJ = 4. Here C(s) + O2(g) = CO2(g) qv = – 97000 cal. and ethane are 337. 1000 Example 4.2.836 kJ 10 7 × 10 3 ∆E = 4. Calculate the heat of combustion at constant pressure of carbon. [Q V1 = 0] [Q n = 1] Example 3. Sol.THERMODYNAMICS 93 Example 2. hydrogen. = – 97000 + 0 × RT = – 97000 cals. Here. Sol. So. 8. (Given qv at 200°C is 97000 cals). Sol.36 × 109 ergs = ∴ 8. The amount of work of a system is 8. qp = qv (As n2 = n1) Example 5. Calculate the heat of reaction of C2H4(g) + H2(g) → C2H4(g) at that temperature. Mg(s) + 2HCl(g) → MgCl2(s) + H2 (g) (Given ∆H = – 109 Kcal). Zn + H2SO4 → ZnSO4 + H2↑ w = P(V2 – V1) = PV2 = nRT = RT = 8. . Example 6. Calculate the internal energy change of the system.332 kJ.

We know that. 2 2 7 O. 1 O (g) → H2O(g). and for breaking of these two bonds energy requirement is 222 Kcal. ∴ O—H bond energy is 111 Kcal. C . ENGINEERING CHEMISTRY 1 O → H2O. ∆H = 104 Kcal ∆H = 120 Kcal ∆H = – 58 Kcal . Given the standard enthalpies of combustion: ∆H° (C3H8) = – 2220 kJ mol–1 C ∆H ° (C) = – 393 kJ mol–1 C ∆H° (H2) = – 286 kJ mol–1. 2 2 (iii) C2H6 + or. Example 8. Calculate the enthalpy of formation of propane (C3H8 ) at 298 K..8 Kcal ∆H = + 372. (ii) H2 + ∆H = – 337.2 Kcal. 1 1 O2(g) + H2O(g) → 2H(g) + O(g) + H2(g) + O2(g) 2 2 ∆H = 222 Kcal..94 Sol. there are two O—H bonds in a molecule of water. 2 2 7 O → 2CO2 + 3H2O.3 Kcal. Example 7. (iv) 2CO2 + 3H2O → C2H6 + Adding the equations (i).(i) . So.. ∆H = 60 Kcal. Calculate O—H bond energy from the following heats of reactions.7 Kcal) ∆H = – 32..7 Kcal.(ii) .8 Kcal..e. H2O(g) → 2H(g) + O(g). Given. for dissociation of one O—H bond energy requirement is 222 ÷ 2 = 111 Kcal. C2H4 + 3O2 + H2 + ∴ 1 7 O + 2CO2 + 3H2O → 2CO2 + 2H2O + H2O + C2H6 + O2 2 2 2 (∆H = – 32.. H2O(g) → H2(g) + (i) + (ii) – (iii) gives = H2(g) + i. ∆H = – 372. H2(g) → 2H(g). From equation (ii) H2(g) + 1 O (g) → O(g).(iii) C2H4 + H2 → C2H6. (i) C2H4 + 3O2 → 2CO2 + 2H2O. O2(g) → 2O(g). 1 O (g) 2 2 ∆H = 58 Kcal. ∆H = 68.. 2 2 Sol. 2 2 From equation (iii). (ii) and (iv) we have.

55(50) 21 8. The latent heat of evaporation of water at 100°C at constant pressure is 538 cal g–1. Sol. ∆H100° = 538 Cp for water = 1. ∆H150° – ∆H100° = – 0. calculate the latent heat of water at 150°C. Example 10.1 cal mol–1. respectively for the interval. Cp for steam = T2 – T1 = 423 – 373 = 50 K. ∆H150° =?. 18 13 DH 86 ca ls . A thermodynamic cycle is drawn: 3C(s) + 4H2(g) + 5O2(g) 2 DH DH1 C3H8(g) + 5O2(g) DH 3 3CO2(g) + 4H2O(l ) According to Hess’s law – ∆H1 = ∆H2 – ∆H3 ∆H1 = ∆H °f (C3H8) ∆H2 = 3 ∆H ° (C) + 4 × ∆H ° (H2). If average Cp for water and steam are 1 cal g–1 and 8. Calculate the enthalpy change of transition from yellow P to Red P from the given thermochemical cycle.55.1 . Sol.45 – 1 = – 0. C C = 3 × (– 393) + 4 × (– 286) kJ mol–1 = – 2323 kJ mol–1 ∆H3 = ∆H ° = – 2220 kJ mol–1 C Hence. ∆H ° (C3H8) = (– 2323) – (– 2220) kJ mol–1 f = – 103 kJ mol–1. Basis = 1 g. ∆H2 – ∆H1 = ∆Cp(T2 – T1) ∆Cp = 0. Example 9.THERMODYNAMICS 95 Sol. Thermochemical cycle: Yellow P 23 DH 2 DHT (DH1) 3 Red P ca ls H3PO4 According to Hess’s law – ∆HT = ∆H2 – ∆H3 = 2386 – 2113 cals = 273 cals. We have.

9°C).55 × 50 = 510. Sol. Given L = 12. Calculate change of entropy in isothermal reversible expansion of one mole of an ideal gas.987 cal K–1 mol–1. Maximum work P1 = 2. Example 11. Hv = 545.9) 90. P1 = 528 mm of Hg. we have P2 ∆H v 1 1 − log P = 2. R = 1.14 J g–1. Given latent heat – 19.33 J mol–1. Sol. T2 = 100°C = 373 K.19 × 32 12. (– 182.5 cal g–1. Here. (273 − 182. T1 = ?.55 × 50 ENGINEERING CHEMISTRY = 538 – 0.5 cal g–1 = 545.66 kJ.19 J g–1. dS = = qrev T 19.31 × 298 log = 1. 2 1 Example 12.96 ∆H150° = ∆H100° – 0.303R T1 T2 1 LM N OP Q . P2 = 1 atm = 760 mm of Hg. Sol.303 × 8. From the integrated form of Clausius-Clapeyron equation.19 × 32 = = 4.5 cal g –1. Calculate the change of molar entropy during melting of ice.1 Example 14. 273 Example 13. ∆E = 0 q = W = RT ln dS = V2 V1 [Positive quantity] V2 qrev = R ln V1 T Example 15. We know that Therefore. Sol. At what temperature will water boil when the atmospheric pressure is 528 mm Hg? Given latent heat of vapourisation of water is 545.303 RT ln P 2 = 2.p. dS = = qrev T 12.14 × 18 = 1.66 × 103 J = 1. Sol. Calculate the change of molar entropy during the conversion of liquid oxygen to oxygen gas at its b. 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.26 J mol–1.5 × 18 cal mol–1 = 9819 cal mol–1.

H 0. 2 2 2 Consider the reaction to be independent of heat and temperature. From the 1st law of thermodynamics. Example 17. heat energy. Calculate the entropy change for the process. from 1st law. Find the change in internal energy. 300 7 Example 19. So.25) cal [Q 1 lit.atm. work done by system. ∆H = ∆E + P∆V = 0 + 1012. Pressure is increased reversibly upto 7 atm and temperature is incremented to 90°C.314 J IJ = 1012.5577 cal deg–1. = (20 × 24.7 J = 1012. Calculate q. But. q = ∆E + W or.7 J. 363 1 + 2 × ln = – 2. (ii) Now. log 9819 760 = 0. W = P(V2 – V1) = 1 atm (20 – 10) dm3 = 10 atm dm3 = 10 atm L = 10 L atm × (iii) (iv) FG 8.303 × 1. Cp = Cv + R = (5 + 2) cal = 7 cal. A gas during expansion from 10 litre to 20 litre under 2 atmospheric pressure absorbs 300 cal.7 J. The initial temperature and pressure for one mole of an ideal gas is (Cv = 5 cal) 27°C and 1 atm. ∆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. Example 18. 1 3 N (g) + H2(g) NH3(g) + 11.1582 = 2. Thus find the value of Kp for the following reaction at 37°C.7 J.2 Kcal. (i) Since operation is isothermal and the gas is ideal so. Work done in an irreversible process is given by W = P(V2 – V1) = 2(20 – 10) = 20 lit. internal energy will decrease by an amount of 185 cal.49 × 10–2 atm–1. P1 = 1 atm.987 528 T1 = 363 K.25 cal] = 485 cal. ∴ ∆S = 7 ln . T1 = 27°C = 300 K. For one mole of an ideal gas the entropy change in a reversible process is ∆S = Cp ln T2 P + R ln 1 T1 P2 Here. for a reversible process. The value of Kp (equilibrium constant) of the reaction regarding ammonia synthesis at 27°C is 3. W. ∆E = 0 or q = W.THERMODYNAMICS 97 ∴ or. Sol. LM 1 − 1 OP N T 373 Q 1 Example 16. atm = 24. P2 = 7 atm. ∆E = 0. T2 = 90°C = 363 K. ∆E = q – W = (300 – 485) cal = – 185 cal.0821 L atm K q = W = 1012. Sol.

K P1 = 3. ordered state and at the temperature of 0 K. we have K P2 ∆H T2 − T1 ln K = R T1T2 P1 ENGINEERING CHEMISTRY LM N OP Q Here. in most of the reactions. State intensive property of a system. K P2 = ? ∆H = – 11. Ans.49 × 10–2 atm–1. See text page 68.303 × 1. See text page 71. The entropy of a substance becomes zero when the substance is perfectly crystalline i. See text page 66. so enthalpy is more useful than internal energy. What is enthalpy? Ans. it can be stated as the net energy of the universe remains constant.98 Sol. Why is enthalpy more useful than internal energy? Ans. Q. 1. R = 1. Ans. Derive Clapeyron-Clausius equation and mention its applications.303R T1T2 P1 LM N log or. SHORT QUESTIONS AND ANSWERS Q. See text page 84. 2..2 Kcal = – 11200 cal. From Van’t Hoff equation. When does the entropy of a substance become zero? Ans.987 cal deg–1 mol–1. Since. Q. Derive Gibbs-Helmholtz equation and mention its significance. 7. 5. . See text page 85. 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.e. State First law with mathematical expressions. respectively. Q. Why? Ans.9038 × 10–2 atm–1. T1 = 27°C = 300 K. T2 = 37°C = 310 K. The molar heat of sublimation of a solid is always greater than the molar heat of vaporization of the corresponding liquid. 4. they occur at atmospheric pressure.987 300 × 310 LM N OP Q OP Q K P2 = 1. ∴ K P2 T2 − T1 ∆H log K = 2. Q. Internal energy and ethalpy of a system are measured by keeping the volume and the pressure constant. Q. 8. Ans. Alternatively. 3.49 × 10 −2 K P2 = 310 − 300 − 11200 2. Ans. 3. Q. 6. Q.

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

See text page 79. State Maxwell’s relations. Define (a) heat of formation. 82. See page 89. ENGINEERING CHEMISTRY Q. See page 80. 16. 20. Ans. 19. Ans. 18. See page 84. See pages 78 and 79. 24. Q.100 Q. What do you mean by a cyclic process? Ans. . Ans. See page 81. Alternatively it can be stated as the net entropy of the universe tends to a maximum. Q. What is inversion temperature? Ans. Ans. See page 71. (iii) Define the concepts of Helmholtz free energy and Gibb’s free energy. State with example the significance of Hess’s law. Q. (iv) What is the significance of entropy? What is the criteria for spontaneity? (v) Derive Kirchoff’s equation. 25. See page 73. Define work function and free energy. Ans. 23. See page 70. Q. See page 81. Q. State the law of Laplace and Lavoisier. (b) heat of combustion. Ans. 21. Ans. Q. State the second law of thermodynamics. See page 72. Q. Q. (ii) Derive Clapeyron-Clausius equation and state its applications. It means that if a mole of H2 and 1 O = H2O is – 54. Short Questions: (i) Derive an expression for the variation of heat of reaction with the temperature with the help of first law of thermodynamics. Q. EXERCISES 1. State relation between them. Define Cp and Cv. What do you mean by ∆G° for the reaction H2 + at 25°C? Ans.65 Kcal. 26. 22. (c) heat of neutralisation. Explain that Joule-Thomson experiment is isoenthalpic. It is based on which law? Explain. Q. the decrease in free energy is 54.65 Kcal 2 2 1 mole of O2 both at unit pressures at constant 2 temperature (25°C). 27. Ans. Describe a relation between the two. How can you measure a spontaneous system with the help of free energy? Ans. 17.

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

Consider the gas to behave like an ideal.1 cals. Entropy change for the mixture of gases can be represented by – ∆Smix = – nR Σ xi ln xi 13. 326. ∆H. When ice melts at 0°C. (v) Heat of solution. (a) State Hess’s law. when the heats of formation of carbon dioxide and liquid water are given as – 94. 3 R. (viii) Heat of sublimation. Derive Maxwell’s relation and state its usefulness. . The heat of formation of ethyl alcohol is – 66. respectively. 21. 1440 cals. (b) Mention the applications of Hess’s law. where xi = mole fraction of gas.T. 17. g–1. 1440. (vii) Heat of vaporisation. (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. [Ans. Long Questions 1. (b) Give the significance of Gibbs-Helmholtz equation.102 ENGINEERING CHEMISTRY 11. cals. 15.6 Kcal] 5. [Ans. heat from the surrounding. 790 cals] The volume of a 45 g nitrogen gas is expanded from 5 litre to 10 litre at 25°C isothermally and reversibly. (1440. q and w per mole. 19. 18. the latent heat of fusion is 80 cals.82 and of water of unity. 133..1 cals] A system performs 8.8. What is the enthalpy change in the transformation of diamond to graphite? [Ans. 12.788 × 107 ergs] During isothermal reversible expression of 4 g of helium gas at 27°C the pressure reduces from 10 atm to 1 atm.36 × 109 ergs work after absorbing 990 cals.05 and – 68. (iii) Heat of neutralisation.8 cals] The heats of formation of CO2 from diamond and graphite are – 94500 and – 94050 cal. . 4. 1381.. Calculate ∆E.. What do you mean by Van’t Hoff reaction isotherm? Derive an expression for the reaction isotherm lL + mM + . [Ans. Show that entropy change for an irreversible isothermal expansion of an ideal gas is positive. (vi) Heat of fusion. (c) Explain the terms (i) Heat of reaction. of the general reaction aA + bB + . Derive an expression for chemical potential at a temperature T in terms of P.P.4 Kcal. Considering the gas to be an ideal find out the work obtained in this case. (a) Derive Gibbs-Helmholtz equation. 2 [Ans. 6. – 450 cal] Calculate the heat of oxidation of ethyl alcohol to carbon dioxide. Derive Clausius-Clapeyron equation. (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? 14.32 Kcal. 2. (ii) Heat of combustion. are heated inside a gas cylinder to 100°C assuming it to behave ideally and having Cv = 3.. Calculate ∆E and ∆H if 10 litres of helium at N. – 4. Find the internal energy change of the system. Calculate the work done in calories. Derive Gibbs-Duhem relations. The density of ice is 0. 7. [Ans. 223.01 × 106 ergs) 2. (iv) Heat of formation. 20. 22. How can you determine the bond energy and lattice energy with the help of Hess’s law? 16.

– 70. [Ans. ∆A = – 1. The heat of combustion of methyl alcohol is – 173. = 353. ∆G = 0. ∆G and ∆H for a particular reaction at 127°C are – 12 Kcal and 17. 0. – 13. heat of benzene is 0. [Ans. Calculate the free energy change of g mole of SO2 at 25°C and 10 atm pressure. 0. a = 3. carbon and hydrogen are 754300 cals.c mol–1. l) = – 68320 cal. 94380 cals and 68380 cals. 0] 12.p.0 kg of benzene at 30°C.303 × 8. boiling point = 35°C.59 litre2 atm/mol–2 and b = 0. 760 mm Hg] . ∆W. Calculate the heat of formation of benzene given that the heats of combustion of benzene. – 108. The van der Waal’s constant for CO2. Isothermally at 27°C one mole of a van der Waal’s gas expands reversibly from 2 litres to 20 litres.75 eV] 20. Given. Given. Given. 2036 K] 16. What is the inversion temperature of the gas? [Ans. From the following bond enthalpies calculate ∆H for the reaction.5 Kcal. 153080 cals] 9. [Ans.9879 eV] 17. ∆A and ∆G for vaporisation of 2 moles of benzene (b. Calculate ∆S.42 × 1012 dynes cm 4 mol–1 and b = 30 c. g) = – 94050 cal.5 Kcal.000 2 2 1 O = H2O + 68. [Ans.39. 1.2 K and G = 101 cal g–1) [Ans.5 Kcal. H—Br bond energy = [Ans.42 × 1012 2 − 0. +a − V1 − b V2 V1 LM N O P Q W = 2. respectively. Br—Br bond energy = 192. 2 L M N O P Q ∆H f (CO2 .] 11. The average latent heat of vaporisation of water is 546 cal g –1 within the temperature range 90°C – 100°C. 21. – 17120 cals] 10. [Ans. 1. [Ans. The sp. Find heat of formation of caustic soda from the following data: Na + H2O = NaOH (aq) + H2 + 1 H + 98.THERMODYNAMICS 103 8. [Ans.65 Kcal. L = 6500 cal mol–1. ∆U. It was allowed to expand isothermally against a constant external pressure of one atmosphere.43 Kcal/mol–1] 19. Find out ∆S.86 kJ] 368. ∆S = 44.24 kJ mol–1.5 cal/°K. [Hint. Calculate the entropy change in vaporisation of ether. Calculate the work done if a = 1. ∆G°298 = – 71.1 eV] 18. ∆H.5 kJ mol–1.03 2000 − 20000 ergs + 1. The vapour pressure of water at 90°C is 530 mm Hg. (Ans.4 Kcal] 15. Calculate ∆Q.31 × 107 × 300 log 20 − 0. 13. Calculate the vapour pressure at 100°C. ∆H(H O.3 kJ mol–1.03 20000 × 2000 = 5677 × 107 ergs.380 2 2 NaOH + water = NaOH (aq) + 13. W = RT ln V2 − b 1 1 . – 57040 cal] 14.300.8 Kcal mol–1.043 litre mol–1. [Ans. 70 g of nitrogen gas was initially at 50 atm and 25°C. Bond energy H—H = 435. H2 + Br2 → 2 HBr. Evaluate the heat of formation of methyl alcohol. Find the change in entropy when 1 kg of benzene at 10°C is mixed with 4.

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

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

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

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

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

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

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

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

in other words. kc2(c – x) ENGINEERING CHEMISTRY [when a – x = c] [when a = b ≠ c and (a – x) = c] dx = k(a – x)3 dt dx = k dt ( a – x) 3 (Integration constant) 1 1 . = or t = . FG H FG IJ H K IJ K Examples of Third Order Reaction (i) 2NO + O2 → 2NO2 (ii) 2NO + Cl2 → 2 NOCl (iii) SnCl2 + 2FeCl3 → SnCl4 + 2FeCl2 Zero Order Reactions There are certain reactions where rate of reaction does not diminish with time i. 2 1 1 1 3 2 a . 2a – a a 2 – a2 a 1 2 1 1 4 2 4 = = k= . . x = 0 1 1 . L M N 1 L k= M 1 2t N ( a – x) 1 1 1 – 2 2 2 (a – x) a 2 OP Q 1 O 1 x (2a – x) – P = t 2 a ( a – x) a Q 2 2 2 . (ii) k is dependent on the unit of concentration.e. . =Z ∴ 2 a2 1 1 1 – = kt 2 ( a – x) 2 2a 2 Z= 1 2a2 or ∴ ∴ kt = Characteristics of a Third Order Reaction 1 (i) Where x = a. (iii) Unit of k is mole–1 sec–1. = kt + z 2 (a – x) 2 When t = 0.112 = kc3 = Again or Integrating. 2 1 4 t t t 1 a4 1 a 2a 2 . a 2 2 2 13 1 3 1 1 3 1 .e. . 2 = t 2 a2 2k a2 k 2 a 1 ∴ t∝ 2 a So.. the rate of the reaction is not dependent on the concentration of the reactant or.. rate of the reaction is proportional to the zero power of the concentration of the reactant i. the time required for the completion of the same fraction of the change is inversely proportional to the square of the initial concentration.

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

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

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

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

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

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

k = Ae a where. the molecules should be raised to a state of sufficient energy. − Energy of Activation (Ea) of a Reaction: its Significance The molecules of reactants. Highlights: • Temperature coefficient of a chemical reaction is defined as the ratio of two rate constants of the reaction at two temperatures differing by 10°. If E for a reaction is known.REACTION DYNAMICS/CHEMICAL KINETICS 119 or log k1 E 1 1 – =– k2 2.303R T1 T2 So. k25° (usually) k35° LM MN OP PQ 1 gives a straight line so the equation of the straight line is: T ln k = a – b T where k is the specific reaction rate and T is the absolute temperature. if 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. otherwise the reaction will not be Potential energy Ea A+B DH C+D C+D A+B Progress of reaction Fig.3 . which take part in a chemical reaction should get activated by gaining a minimum definite amount of energy. For every reaction. 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. which is known as energy of activation (Ea). 5. we can determine the value of k2 when k1 is known. Temperature co-efficient = • Plot of ln k vs.

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

6 30 12. ln t a– x a = 46. k = 46. 250 cc of H2O2 solution of strength 2 (N) is taken. ln = 0..8 20 19.1 ln = 0.044 min–1 12.1 ln = 0.1 ln = 0.3 46.1 = 0. 5.0434 min–1 5 37. SOLVED EXAMPLES Example 1. The titre values will give the change in concentration of H2O2 i.044 min–1. Now. 5. For a Ist order reaction k= Here.1 .3 50 5.0 a 1 . of properly oriented molecules per unit volume per unit time] × fraction of molecules equal to or greater than threshold energy. k = 50 t = 10.0436 min–1 29.8 46.1 Sol. x. Determine from the following data the value of k and establish that the decomposition is of the Ist order. In an experiment. k = 20 1 t = 30. Decomposition of H2O2 Time 0 Time value (KMnO4 in cc) 46.6 46. putting 5 37.0427 min–1 19.0 ln . k = 30 1 t = 50. So.REACTION DYNAMICS/CHEMICAL KINETICS 121 + H2 I2 Collision Reaction + Product HI + HI Collision Collision Transition state (effective collision) molecules react when they collide in a preferential direction Ineffective Ineffective Fig. 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.4 Rate of a reaction = [No.1 10 29.1 at at at at 1 10 1 t = 20.1 t=5 k= 1 46.e.

The data is given below: The optical rotation of sucrose in 1(N) HCl at various times is given in the following table: Time (in minute) 0 7. the hydrolysis of methyl acetate is of the Ist order.18 18 27. 27. respectively. The mixture is poured in a polarimeter tube.79 75 17.83 k= log = 0..05 α Rotation (degrees) + 24.05 25. The data are as follows: Time ( in minutes): 0 75 119 183 α Vol.303 22.00519 min–1 18 28. 2 ml of aliquot (reaction mixture) was withdrawn at different intervals and titrated against a standard alkali.79 = 34. 50 cc of this solution and 50 cc of (N) HCl is mixed at constant temperature.00321 min–1 119 15.e.00316 min–1 183 12.60 29.14 k= = 0.14 k= r – rα 1 ln 0 t rt – rα 1 34.00486 min–1 7.7 + 15 – 10.18 32.83 Time 7. Sol.03 – 19. r0 – rα = 24.4 + 17..79 Since. k = 32. Vα – Vo = 42. The optical rotation of this solution is measured at regular intervals and the final reading is taken after 24 hrs.18 rt – rα.03 From the above data show that the hydrolysis is of the Ist order.00485 min–1.14 1 34. rotation after time ‘t’ and rotation after infinite time where the reaction is assumed to be completed.83 log 27. after a time t and after an infinite time.5(N) HCl kept at a temperature of 25°C. Vt and Vα are the volumes of alkali initially.71 k= = 0.43 k= = 0.83 log = 0.24 24.79 log 119 15.05 25. the k-values are fairly constant by putting the data in the Ist order rate equation i.303 22.43 2.74 k= = 0.e.09 + 10.74 Show that the reaction is of the Ist order.00395 min–1 75 17.122 ENGINEERING CHEMISTRY Since the ‘k’ values are fairly constant by putting the data in the Ist order-rate equation the reaction i. Here.83 2.79 Time Vα – Vt k 2. decomposition of H2O2 is of the Ist order.09 + 21. Sol. A 20% sugar solution is taken. 1 cc methyl acetate was added to a flask containing 20 ml 0.24 = 22.83 log 18 28. rt and rα are initial rotation. Example 3. of alkali used: 19.79 log 183 12.71 .20 26. Example 2. Here a = Vα – Vo a – x = Vα – Vt where Vo. a = r0 – rα (a – x) = rt – rα where r0.14 1 34.303 22.32 42.

000433 20 . Sol. Sol. ∴ Sol.303 2.693 k 0. Time of 50% reaction. log t a– x t = 30 min a = 100% a = (100 – 25)% = 75% 2. the hydrolysis of methylacetate is of the Ist order.. ∴ Here.693 = 72.303 . The half-life for radium is 1600 years. k= a 2. A Ist order reaction is 25% completed in 30 mins. Calculate the rate constant and time for 75% completion of the reaction. Radioactive disintegration is of the Ist order ∴ ∴ ∴ Here 0. Half-life for a first order reaction is 17 mins.e.303 100 log 4 = 34 minutes .. t1/2 to be determined for Ist order reaction t1/2 is and Here.17 yrs.693 k k= ∴ t1/2 = 0.REACTION DYNAMICS/CHEMICAL KINETICS 123 Since the ‘k’ values are fairly constant by putting the data in the Ist order rate equation i. We know Here.693 k = 17 mins.693 min–1 = 0. t1/2 = t1/2 0. Calculate the time for 80% disintegration.693 1600 = k 0.303 100 log = 0. 0.303 log k= t a–x a = 100 % (a – x) = 100 – 80 = 20 t1/2 = t= 2.693 k= year–1 = 0. i.9 minutes. 0. log ∴ t= = 0.0095 Example 5.0407 k 25 Example 6.0407 min–1 17 a = 100% a – x = (100 – 75)% = 25% k= k= 2. Determine the time of 50% completion of the reaction. Example 4.303 100 log = 37. 0.e.0095 min–1 30 75 0.303 100 log t 25 2.000433 year–1 1600 a 2.

32 3.59 × = 0. Example 8. So the concentration of A at time t is (a – x).13 25 4.76 9. The following is the data for the hydrolysis of ethyl acetate by NaOH solution. Sol.41 Since the k values are fairly constant by putting in the 2nd order rate equation i. t n–1 (n – 1) ( a – x) a OP Q . The rate equation is – d[ A ] = k .007 conc–1 sec–1 16 × 5 10.13 1 11. a–x 10. Sol.24 6. of acid (a – x) 0 16 5 10. ∴ ∴ – d[ A ] – d(a – x) dx = = = k(a – x)n dt dt dt dx Q z L M N ( a – x) n x = k dt =k dx (a – x) n 0 t=0.124 ENGINEERING CHEMISTRY Example 7.76 × = 0. the hydrolysis of ethylacetate by NaOH is of the 2nd order.41 1 5.59 k= k= k= k= k a = 16 c.c. The 2nd order rate equation is k= Here T 5 15 25 35 x 1 at (a – x) x 5.24 1 9.41 Show that the reaction is of the 2nd order. An aliquot (25 cm) of the reaction mixture was titrated against a standard acid at regular time intervals. Let the reaction be nA → Products.0069 conc–1 sec–1 16 × 25 4.x=0 z t 0 dt 1 1 1 − n− 1 = k .87 11.13 4.24 15 6.32 35 3. Deduce the rate constant and t1/ 2 for nth order reaction.68 12.68 × = 0.87 × = 0.e..0067 conc–1 sec–1 16 × 15 6. Time (in minute) Vol. [A]n dt Let a be the initial concentration and x be the concentration which has reacted in the time ‘t’.32 1 12.0066 conc–1 sec–1 16 × 35 3.

T1 = 50 sec. If the specific reaction rate is 5.2 × 10–3 = a= ∴ a/2 1 = 60 .2 mol litre–1. Calculate the time taken for the concentration to be reduced to 20% of the initial value. a / 2 60a 1 = 3.2 × 10 –3 Example 10. to 25 sec. the time of half completion for a reaction is found to change from 50 sec. For a 2nd order reaction k= Here. x = a/2 ∴ LM N LM 1 1 t= k(n – 1) N ( a – x) LM N LM 2 1 = k(n – 1) N a 1 1 1 – n–1 n–1 t (n – 1) ( a – x) a n–1 – 1 a n–1 OP Q OP Q OP Q t1/2 = t1/2 1 1 1 – n– 1 k(n – 1) ( a / 2) (a) n– 1 n− 1 ∴ −1 n− 1 unit of k is (conc)–(n–1) (time)–1. what is the initial concentration of the reactants? Sol.5 to 1 mol l–1. a .2 × 10–3 mol–1 litre min–1. In a 2nd order reaction.5 mol l–1 50 1 = 0. t1/2’s are related to initial concentrations as a T1 = 2 a1 T2 a2 = 1 mol l–1 ∴ or ∴ or FG IJ H K n–1 Here.5 25 2 = 2n–1 n–1=1 n=2 FG IJ H K n– 1 . where the initial concentration of the reactants is the same half of the reactants are consumed in 10 mins. x = a/2 k = 5.REACTION DYNAMICS/CHEMICAL KINETICS 125 ∴ k= For t1/2. x at(a – x) t = 60 mins. OP Q Example 9. 60 × 5. a1 = 0. Sol. When the initial concentration is changed from 0.2 × 10–3 mol–1 litre min–1 5. T2 = 25 sec.

075 mol l–1. ∴ 2.1 = 0.126 So. k= x 0.075 = = 480 mins.303 100 log 1 99 = 2. the initial concentration of reactants is 0. half-life period.02 = at(a – x) 0.303 × 0. t = ? (a – x′) = 0. Sol. Here.303 100 log 0. the reaction is of the 2nd order. For a unimolecular reaction k= Here.08 1 at1/2 = 0.0625 × 0.025 mol l–1 ∴ t′ = x′ 0.01 = 60 a–x k= . a – x = (0. time required to complete 75% of the reaction. In a 2nd order reaction.75a = 0.0625 x′ = 0. Calculate the rate constant.2 Example 11. a = 0. ak(a – x) 0. If one percent decomposes in the first minute in a unimolecular reaction.5 × 0.2 a = 0. ∴ k= t= ENGINEERING CHEMISTRY 1 1 1 = = l mol–1 sec–1 = .1 mol l–1.5 × 50 25 k 0.8 × 25 = = 200 sec.1 × 0. The reaction is found to be 20% complete in 40 minutes.0625 l mol–1 min–1 k= ∴ t1/2 = 1 1 = = 160 mins.303 160 log 60 a– x 2.1 mol l–1 x = 0.1 × 40 × 0.0044 min–1 = 0.04 l mol–1 sec–1 at1/2 0.1 × 0. k = 0.0625 mol–1.02 mol l–1 t = 40 min.08 mol l–1 For the second order reaction.1 – 0. ak 0. Sol.01 min–1 when t = 1 hr = 60 mins or 2.625 Example 12. ak(a – x′ ) 0.2)mol l–1 = 0.303 a log 1 a–x a – x = (100 – 1) = 99 a = 100 k= 2.2 × 0. calculate how much would remain undecomposed at the completion of the first hour.

303 log 4 = 1.7395 (a – x) = Antilog 1. 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. (ii) first order in A and first order in B? Sol.3865 = ∴ ∴ log A=K= 2.REACTION DYNAMICS/CHEMICAL KINETICS 127 or or ∴ ∴ 100 60 × 0.75a (i) When first order in when time t′ = 2 hrs. Let. the reaction will be. k3 = mole–2 l2 t–1 = mole–2 106 ml2 t–1 or 10–6 k3 = mole–2 ml2 t–1 So.7395 = 54. For nth order reaction. 1.303 a 100 = = 12. At the end of one hour A is 75% reacted.25a = 2. k1 = 10–3 k2 = 10–6 k3.303 log (a – x) = log 100 – 0. 2. and unit of k = mole1–n ln–1t–1 when c = mol l–1 mole1–n ln–1 t–1 = mole1–n 103(n–1) mln–1 t–1 when c = mol ml–1 For first order reaction.3865 hr–1.01 = log = log 100 – log (a – x) a– x 2. Example 14. second and third orders when concentration is expressed in mole l–1.303 a a log = 2. k1 = t–1 (k1 will remain same) For second order reaction. Example 13. 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.3865 × 2 = = 1. initial concentration = [A] = [B] = a t = 1 hrs. A certain substance A is mixed with equal moles of a substance B.89.89 % undecomposed = 54.303 a log 2 a – x′ [where x′ = amount reacted] a 1.204 = 16 a − x′ (a – x′) = . what will be the above relation if the concentration unit is mol m–1? Sol.2605 = 2 – 0. If k1 = k2 = k3 for three reactions being respectively of first.303 log 1 a – 0.5% 16 16 a = Antilog 1.2605 = 1. x = 0.75a 0.204 ∴ a – x′ 2.

987 273 × 303 2. log Here.8203 = LM N OP Q Ea 30 × 2. % of A left unreacted = 12.987 Cal K–1 . Rate constants at two temperatures are given by Arrhenius equation. % of A and B left unreacted = a – i. the over all order of the reaction is 2.3.e. k= 3a–1 = x′ when x′ = amount of reactants A and B reacted at(a – x′ ) x′ a × 2 × (a – x′ ) 6a 7 or 6 = x′ a – x′ ∴ x′ = So. The exponential form of Arrhenius equation is. Calculate the activation energy of this reaction.303R T1T2 T1 = 273 K LM N OP Q T2 = 303 K k1 = 2.6 kJ mol–1.r.45 × 10–5 and 162 × 10–5. 968 cal mole–1.. ∴ At k= ENGINEERING CHEMISTRY x 0. The specific reaction rates of a chemical reaction at 273 K and 303 K are respectively 2. k2 Ea T2 – T1 = k1 2. Calculate the temperature at which its half-life is 10 mins.75a = = 3a–1 hr–1 at(a – x) a × 1 × 0. .987 273 × 303 ∴ Ea = 22. 7 Example 15. respectively for a first order reaction.693 t1/ 2 t1/2 = 10 mins = 600 sec.45 × 10–5 R = 1. Sol. As the reaction is first order.128 So. mole–1 k2 = 162 × 10–5 ∴ log Ea 162 × 10 –5 303 – 273 = –5 2. B) (ii) In the second case. k = Ac − Ea / RT where A is called the Arrhenius factor and Ea is the energy of activation.45 × 10 1.t. Sol. 0.303 × 1.25a (when t = 1 hr) t′ = 2 hrs. 100 ≈ 14. k = Here.5% % of B left unreacted = 100% (Q order = 0 w. Example 16.303 × 1. 100 – FG H 6 a 7 IJ K 6 . The values of Arrhenius factor and activation energy are 4 × 1013 s–1 and 98.

39 K1 K2 = 1. T= ∴ T= F 4 × 10 I 2.5 × 10 4 (1148 – 1073) = 0. Ea = 4. whose rate constant at 800°C was found to be 5. The use of lasers has initiated new types of spectroscopic experiments and has improved the precision of spectroscopic experiments.316 × 16. mol–1. h .303 RT1T2 K1 = 5 × 10–3 l mol–1 s–1.115 × 10–3 sec–1.Ea = 98. then photons of frequency 1→2= E 2 – E1 are spontaneously emitted as molecules drop from the state 2 to the state 1.5 × 104 J mol–1 T2 = (875 – 273) = 1148 K. A = 4 × 1013 sec–1 k = 1. T1 = (800 + 273) = 1073 R = 8.316 J mol–1 K–1. 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. the populations be n 2 and n1 and energies of the two states be E 2 and E 1.303 × 8. We have. = log Here. To achieve a laser action a Population inversion should be generated in the system. A second order reaction. R = 8.314 × 1073 × 1148 K2 = Antilog 0.303 log 10 (k/A) = – Ea/RT ∴ k= or Ea 2.39 × 5 × 10–3 l mol–1 s–1 = 7.REACTION DYNAMICS/CHEMICAL KINETICS 129 0.303 × 8. When E2 > E1.115 × 10 JK 3 –3 98600 K 98600 K 2.0 × 10–3 l mol–1 s–1.693 600 = 1. K2 E (T – T1 ) = a 1 K 1 2. Lasers in Chemistry Laser means “light amplification by stimulated emission of radiation”. 2. Example 17.155 × 10–3 sec–1 From Arrhenius equation we have.314 J mol–1 K–1 log ∴ ∴ ∴ K2 4.1431 = 1.600 J.303R log( A /K) Here.555 = 98600 = 373 K.303 × 8.316 × G H 1.1431 = K 1 2. What is the value of the rate constant at 875°C? Sol. Let.

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

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

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

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

What is activation energy? Ans. It is denoted by EA. k or t 1/2 = 2 . 19. Chemical reactions occur through an intermediate stage known as transition state or activated complex (Fig. t1/2 = When concentration changes from a/2 to a/4. c = 0. when. Q. t1/2 = ∴ t1/ 2 ′ 1 = ′ t1/ 2 ak 1 1 = ak / 2 2 ENGINEERING CHEMISTRY 1 . So. Q. It is the minimum amount of energy from zero level of the reactant molecule which must possess in order to react. Activation energy of a reaction is defined as the extra energy over and above the average potential energy of the reactants. The integrated form of zero order reaction is K= c0 – c . 18. t = H¾H + I¾I Initial state H¾H Transition state Final state 2HI I¾I Activated state I Ea Energy Final state DH > 0 Initial state DH < 0 II Final state Reaction co-ordinate Fig. 5. ak 1 a/ 2 . 20. 21. Q. What is transition state theory? Ans. ′ Q. t1/2 = 2. It is denoted by ET.6 .6).134 Ans. When concentration changes from a to a/2.1 = 2 hrs. 17. which must be supplied to the reactants to enable them to cross-over the energy barrier between the reactants and products. What is threshold energy? Ans. c0 ka which is a finite quantity. 5. EA = ET – ER Q. the reaction will be completed and for a zero order reaction. where c0 = initial concentration t c = concentration at time t. How are the activation and threshold energies related? Ans. What is the special characteristic of a zero order reaction? Ans. the rate is not at all dependent on the concentration of the reactants.

85 mins] 16.) 0 16 5 10.REACTION DYNAMICS/CHEMICAL KINETICS 135 Particles in collision react only if. During the hydrolysis of ethyl acetate by NaOH using equivalent concentration. The volumes of acid used by unchanged NaOH are given below: Time (minute) Vol. ‘order of a reaction’ and ‘molecularity of a reaction’. Discuss the various factors affecting the rate of a reaction. Discuss any two methods of determination of order.c. State the molecularity and order of the above reaction. ∆H > 0 endothermic reaction (Curve I) ∆H < 0 exothermic reaction (Curve II) Q. 14. EXERCISES 1. 13. 4. What is meant by order of a reaction? Derive an expression for the velocity coefficient of a second order reaction. For. 6. Derive the rate constant for a 1st order reaction and show that it is an incomplete reaction. they attain the energy of the transition state. [34. of the reaction mixture was titrated at regular intervals against standard acid. Distinguish between rate and specific reaction rate of a chemical reaction. of acid (c. Explain the terms ‘rate constant’. From the given data.41 Show that the reaction is of the 2nd order. . they attain impact. 22. Explain the meaning of pseudo unimolecular reaction. 9. 8. 2. Derive an expression for rate constant of zero order reaction and discuss about its (i) half-life. The study of chemical kinetics helps to determine the mechanism of a chemical reaction.24 15 6.32 35 3. Derive the rate constant expression of a 2nd order reaction: A + B → c. 17.c. 7. Describe an accurate method for determining order of a reaction with three reactants. 5. 25 c. 3. 5 Br– + BrO3– + 6H+ → 3Br2 + 3H 2O k Rate = Constant × [Br–] [BrO–3] [H+]2. What is the utility of the study of chemical kinetics? Ans. Calculate the rate constant and the time taken to complete 80% of the reaction. The hydrolysis of ethyl nitrobenzoate by aqueous NaOH was followed at 25 °C.0173 min–1] 15. Classify the statement: “decomposition of H2O2 is of the 1st order”. 12. (ii) completion time. The half-life period of a 1st order reaction is 15 mins. What is the rate constant of the reaction at the same temperature? [ 0. Indicate how the specific reaction rate of a first order reaction can be evaluated.13 25 4. by titration of the hydroxide against standard acid at different stages in reaction. How does rate of a reaction vary with temperature? What is Arrhenius equation? 11. show that the reaction is of the 2nd order. Briefly develop the concept of activation energy and temperature. Half-time change for a 1st order reaction is 40 mins. upon impact. the reactants A and B are at equal concentrations. 10.

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

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

6

DEFINITION

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

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

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

2SO2 + O2 → 2SO3 N2 + 3H2 → 2NH3

Catalyst H2SO4 CO

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

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

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

Types of Catalysis
Catalysis

Homogeneous

Heterogeneous

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

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

–

2H2O2 → 2H2O + O2

CATALYST

139

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

(Pt-Catalyst) (Fe-Catalyst)

Activation energy and Catalysis reaction

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

Reactant molecules

Transition state

Product molecules
Uncatalysed reaction

Potential energy

Ea Ea ¢ Reactants

Catalysed reaction

Products Progress of reaction

Fig. 6.1 Progress of reaction.

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

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

(iv) Hydrogenation

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

ENGINEERING CHEMISTRY

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

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

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

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

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

CATALYST

141

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

Catalytic reaction

Rate of reaction

Equilibrium

Without use of a catalyst C+D Time

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

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

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

R+ + AlCl4– .

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

142

ENGINEERING CHEMISTRY

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

Ni

Ni

Ni

Ni

Ni

Ni

Ni

Ni

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

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

+

Ni

Ni

(c) Formation of activated complex with ethene.

(d) The product ethane released from catalyst surface.

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

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

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

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

CATALYST

143

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

fructose

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

1 Peroxidase H2O2 → H2O + O. 2 2

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

144

ENGINEERING CHEMISTRY

Number of molecules with kinetic energy (E)

Activation energy with a catalyst Activation energy without a catalyst

Kinetic energy (E)

Fig. 6.5

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

Completion of reaction

Rate of reaction

Sigmoid curve

Time

Fig. 6.6

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

CATALYST

145

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

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

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

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

ENGINEERING CHEMISTRY

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

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

(i) Ni (CO)4

(ii) Fe(CO)5

Fe(0)

3d8

2 × 5 (five CO groups) = 10

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

CATALYST

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

L

H Rh

H

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

L

C—C

Fig. 6.7 Catalytic applications of organometallics.

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

2. Define with illustrations: (i) catalysis. Give a brief account of the various theories of the mechanism of catalysis. 5. 7. How does a catalyst accelerate the speed of a reaction? Explain with proper energy profile diagram. 6. (ii) Enzyme catalysis. although it shortens the time required to establish the equilibrium. (ii) positive catalysis. 9. Write notes on: (i) Adsorption theory of catalysis.148 ENGINEERING CHEMISTRY The mechanism of hydroformylation using cobalt carbonyl as catalyst is shown in the scheme. 3. 1 Co2(CO)8 2 – 1 H2 + 1 H2 2 2 HCo(CO)4 RCH2CH2CHO + CO – CO RCH = CH2 Insertion of alkene into Co—H HCo(CO)3 Hydrogenolysis of Co-acyl RCH2CH2Co(CO)3 CO RCH2CH2CCo(CO)3 O RCH2CH2Co(CO)4 O Insertion of —C into Co-alkyl Fig. What do you mean by (i) homogeneous and (ii) heterogeneous catalytic reactions? What are catalyst poisons and promoters? Discuss a few important catalytic processes.8 EXERCISES 1. 6.”—explain. (iii) negative catalysis. “A catalyst doesn’t affect the final state of equilibrium. What will be a more effective catalyst—platinum as a lump or finely divided platinum? Give reason. . 8. 4.

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

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

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

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

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

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

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

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

Then all the structures so drawn are the structures of the molecule concerned and none of these structures can staisfactorily explain all the properties of the molecule but a hybrid of all these structures which cannot be represented by any one of them is the actual structure of the molecule.39 Å instead of 1. That theory is the concept of resonance. Whenever a molecule can be represented by two or more structures that differ only in the arrangement of electrons the different structures arrived at have the same arrangement of atomic nuclei. Despite having three double bonds benzene undergoes substitution reactions more easily than addition reactions. All the C—C bond lengths in benzene is 1. (I) (II) The structures (I) and (II) cannot satisfactorily explain all the properties of benzene. The difference in energy of any of the contributing structures and the hybrid structure is called the resonance energy (Fig. (b) Position of σ-bonds cannot be changed.2).34 Å for a C==C bond. Each of these drawn structures contributes to the resonance hybrid (Fig. . This acceptance is not for the discovery of new facts about benzene but is a result of modification of the structural theory. The Kekule structure is still the accepted structure for benzene. 7. there is resonance.2).MECHANISM OF ORGANIC REACTIONS 157 This is an example of acid catalysed elimination reaction. 3. 2. 7. Thus H H C H OH H C H C H H ¾¾¾® H+ H H C H + H OH H C C H H ¾¾¾® – H2 O H H C H C + H C H H H H H ¾¾¾® H C H C H C H H Resonance The idea of resonance has a major role in understanding the mechanisms of reactions. The resonance hybrid structure is more stable than any of the contributing structures. 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. (c) Only π electrons and non-bonded electrons can be shifted. 1.54 Å for a single bond and 1. Benzene is more stable than expected. So the idea needs to be discussed here: According to Kekule the benzene molecule has following two structures (I) and (II).

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

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

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

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

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

So the chair cyclohexane is more stable conformer of the cyclohexanes. 7.5 Potential energy diagram (conformations of cyclohexane). The half chair form is a most unstable form which lies at energy maximum (see Fig. For boat cyclohexane the Newman projection formula is as Fig.4(e). 7. it is thus not a conformer but a transition state between two conformers.4 (d ) Cyclohexane (chair form) staggered form of ethane. The twist form or skew boat form is a conformer lying at energy minimum.4(d)]: Fig.6 Kcal Chair form Half chair Twist form Boat form Twist form Fig.3 Kcal Potential energy 11 Kcal 5.5). Between the chair form and twist form there are half chair forms with angle strain and torsional strain. 7. Here the three pairs of tetrahedral carbon of cyclohexane remain in staggered forms. 1. .4 (e) The boat conformation is less stable than the chair conformation at an energy maximum. 7. Cyclohexane (boat form) Eclipsed ethane Fig.MECHANISM OF ORGANIC REACTIONS 163 Newman projection formula of chair conformer [Fig. Here the three pairs of tetrahedral carbon of cyclohexane remain in eclipsed forms. 7. 7.

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

• A mixture of equal parts of enantiomers is called racemic modification. Highlights: • Number of possible stereoisomers = 2n. 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. 7. 3-Dichloropentane. 7. .MECHANISM OF ORGANIC REACTIONS 165 H C H C HO2C OH CH3 H3C HO CO2H Mirror Fig. 7.6) either right or left. Asymmetric Molecules If we translate the three-dimensional molecule to a two-dimensional figure.8 (b) Then the test of chirality is very simple. The two configurations of lactic acid rotate plane of polarised light in the same degrees but in the opposite directions. (I) and (III). For compound containing two different chiral carbon atoms. CH3 H Cl C2H5 (I) Cl H Cl H C2H5 (II) CH3 H Cl H H C2H5 (III) CH3 Cl Cl Cl Cl C2H5 (IV) CH3 H H Fig. (III) and (IV) are pairs of enantiomers. (II) and (IV) are diastereomers.8 (c) Stereoisomers of 2. the stereoisomers (I) and (II). COOH COOH H OH HO H CH3 D(–)-Lactic acid mirror CH3 L(+)-Lactic acid Fig. we get Fischer projection formula of the molecule. The prefix (±) is used to designate the racemic mixture.8 (a) The mirror image forms of lactic acid. These two forms of stereoisomers (configurations) are known as enantiomers. where n = number of chiral carbon atoms in the molecule. 7. They can be separated by various physical and chemical methods. These types of molecules rotate plane of polarised light (see Fig.

based on ‘sequence rule’. The system is often termed as “absolute configuration” assignment as this type of specifying configuration is independent of any reference compound. This type of isomer is known as mesoform. . then the stereocentre is designated to have ‘R’ configuration. CH3 H H CH3 Cl Cl 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.8 (e) R-S System of Nomenclature R-S system of nomenclature was developed by Cahn. The (R) or (S) designation is written in italics within the parentheses followed by a hyphen before the name of the compound. d. 4 or a.8(e)]. etc. the configuration is known as cis-isomers (Z-isomers). 2. c. then the stereocentre is said to have ‘S’ configuration [Fig.9]. 7. H3C C H cis-2-butene (Z-2-butene) CH3 C H H C CH3 C CH3 H Trans-2-butene (E-2-butene) Fig. such that 1 → 2 → 3 → 4 or a → b → c → d. 7. 7. If the path provides a clockwise motion. 7. Geometrical Isomerism This type of isomerism arises out of restricted rotation about C = C bond. 3.8(d)]. The geometrical isomerism is also a case of diastereoisomerism [Fig. These are as follows: • The number of stereocentres in the molecule are identified. When similar groups are attached to the same side of the molecule.8 (d) Optically inactive isomer (meso form). There are certain methods of assigning R-S notations to any chiral centre of a molecule. Ingold and Prelog to designate the configurations of stereoisomers having chiral centres. b. 7. If the path describes a counter clockwise or anticlockwise path. Another interesting phenomenon arises among the compounds containing similar chiral carbon atoms [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. the configuration is known as trans isomers (E-isomers). • Then the molecule is viewed from the position far from the lowest priority group and a hypothetical path is drawn moving from 1 → 2 → 3 or a → b → c.

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

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

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

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

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

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

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

So. 16. Vinyl chloride does not undergo nucleophilic substitution—explain. + CH2 = CH – Cl CH2 – CH = Cl: Ans.e. C N : : N – – : : C (Resonance) So the products of the reaction are: C2H5 Br + Ag CN → C2H5 NC + C2H5CN + Ag Br major minor Q. Find out the nucleophile from the following: + . R—X + KNO2 → A + B + C : : : : O – N = O is an ambident nucleophile. Ans. Ans. Benzyl chloride undergoes SN1 reaction—explain. Q. CH2 + + CH2 + Q. : : : O–N=O – : : O=N=O R—X + KNO2 → RONO + RNO2 + KX Q. CN–. CH3Br. C6H5 CH 2 is resonance stabilised. Indentify the products of the following reaction: Ans. CN– . So. 14. vinyl chloride does not undergo nucleophilic substitution. as it has lone pairs C ≡ N . CH3Cl : : : – : : : : – : : minor (B) (C) : : : CH2 – CH = CH2 + CH2 + CH2 . CH3 I. CN– is an ambident nucleophile i. Allyl carbocation is resonance stabilised major (A) ! : : : CH2 = CH – CH2 + and behaves as if the chlorine atom is ionic. Q. Give the products of the reaction of ethyl bromide and AgCN. Arrange the reactivity of the following towards nucleophilic reagent: CH3F. CH2 = CH – CH 2 + OH– → CH2 = CH–CH2OH (SN1) + + Q. 15. Due to resonance C—Cl bond attains a partial double bond character and C—Cl bond energy increases and no carbocation is formed. it can attack from both the sides of the species. Q. C H 3 . so ionisation of benzyl chloride takes place and path is followed. SN1 Ans. N O2. Allyl Bromide undergoes nucleophilic substitution readily—explain. 13.174 ENGINEERING CHEMISTRY Ans. 12.. 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. 11.. 17. CCl4. Ans.

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

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

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

90 3. (ii) o. As the number of electron withdrawing groups increases acidity increases.76 2. Ans. The electron withdrawing substituents with (–I) effect has got marked influence on the acidity of simple aliphatic acids. : O H ! O H O H : + O + H ! : ! : + : O H ¬ : ¬ : : : : .e. The electronegativity order of halogens is: F > Cl > Br > I So. acidity order will be. 30.76 4. Justify the pKa values Acid CH3COOH FCH2COOH ClCH2COOH BrCH2COOH ICH2COOH pKa 4. 32. acidity decreases.178 O HCOOH + H2O H C O H C O O – ENGINEERING CHEMISTRY + H3O + So.16 Ans. 31. Q. Q. HCOOH is an acid as the anion has resonance stability.. Q. CH3 → C → O → H Acidity in CH3COOH is somewhat reduced due to (+I)-effect of the CH3 group and that effect is more pronounced in (CH3)2CHCOOH and still more pronounced in (CH3)3CCOOH. Phenol is (i) acidic.66 2. Justify the pKa values Acid CH3COOH (CH3)2CHCOOH (CH3)3CCOOH pK a 4.86 2.29) > Cl ← CH2COOH(pKa = 286) Cl ¬ CHCOOH (pKa = 0. Explain. So pKa value gradually increases i. Acidity order with pKa values of the following acids is: Cl¬ Cl¬ CH COOH(pKa = 1.86 5.05 O   Ans. 29. F ← CH2COOH > Cl ← CH2COOH > Br – CH2COOH > I-CH2COOH: pKa values are in accordance with the above acidity order.65) > Cl Cl Justify. p-orienting. pKa value decreases. Q.

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

The m-position of the benzene ring is comparatively electron-rich. On the contrary. The eletrophile SO3 is generated as follows: 2H2SO4 – SO3 + H3O+ + HSO4 : : – + – + – – + – – + – – + : : . So.positions of benzene ring of nitrobenzene become electron deficient. 37.9 NO2 pKa = 1. 4. —NO2 group in nitrobenzene deactivates the benzene ring by withdrawing electrons from the benzene ring and making o.02 Q. Ans. For electrophilic attack. Q.and p. Show that sulphonation of benzene is an elctrophilic substitution. electron-rich centre is necessary. SO3 dissolved in conc.98 – N O Å O – Q. Introduction of an —NO2 group in the phenol molecule increases its acidity due to (–I) effect of the —NO2 group. Ans.180 Ph NH2 NH2 + ENGINEERING CHEMISTRY : : NH2 N pKa = 4. That is why. 4. In phenol —OH group activates the benzene ring towards further electrophilic substitution by enriching the electron density at o. Nitration is an electrophilic substitution and takes place easily in the case of phenol. The three —NO2 groups in 2. Nitration of phenol is easier than that of nitrobenzene—explain. So. The resonating structures of nitrobenzene are: O¾N O O ¾ N¾O O ¾ N¾O O ¾ N¾O O¾N O Å Å Å Due to resonance. Ans. —NO2 group is m-orienting—explain. 39. 36.and p. o. So. 38. that is why electrophile attacks there and msubstitution takes place. OH O2N OH NO2 pKa = 0.e. 6-trinitrophenol exercise pronounced (–I) effect making the phenol molecule total acidic. Ans. —NO2 group is m-orienting.positions positively charged. it is known as picric acid.62 O O pKa = 0. The sulphonating agent is Oleum i. nitration of nitrobenzene molecule becomes difficult. 6-Trinitrophenol (picric acid) is a very strong acid—explain.positions due to resonance. H2SO4.and p. 2.. further electrophilic attack at nitrobenzene molecule becomes difficult. Q.

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

here the electrophile is NO+ HONO + HCl NOCl + H2O + : N (II) – CH3 CH3 CH3 NO + Cl + OH + OH OH + NO NO H +H + NO EXERCISES 1. CH. 6-Dimethyl –N. —N(Me)2 group goes out of plane of the benzene ring by free rotation about the single bond. N-dimethylaniline (II). Classify the different organic reactions. 42. What do you mean by steric inhibition of resonance? Ans. 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+. Yes. What is polymerisation reaction? Give an example of such type of reaction with plausible mechanism.Cl2COOH. 9. Mention the mechanism. 5. When Phenol is treated with NaNO2 and HCl at 0–5°C. 8. What do you mean by polarisation? What is the reason behind it? What do you mean by inductive effect? How does it play an important role in organic reactions? Compare the acidity among CH3COOH. Due to crowding in (I). So lone pair over —N(Me)2 group in (I) is available to be accepted by a proton (H+). 43. 3. So primary condition of resonance. p-nitrosophenol is obtained.182 ENGINEERING CHEMISTRY Q. 2. 4. N-dimethyl aniline (I) is more basic than N. 7.COOH. State the products obtained during the chlorination of CH4 in diffused sunlight. 6. is affected and resonance is inhibited. This is an example of steric inhibition of resonance. CCl 3COOH. What is electromeric effect? Is it permanent? State the origin of a carbocation. What do you mean by electrophiles and nucleophiles? . the planarity. 2. CH2Cl. H3 C H3 C : N CH3 (I) Q. carbonium ion and free radical.

Draw Fischer projection formula of D. What do you mean by SN1 and SN2 reactions. What do you mean by 1. Write a short note on hyperconjugation. S-nomenclature. Heat of hydrogenation value of 1. 26. 25. 17. Draw all the Fischer projection formulae of: (i) glyceraldehyde (ii) lactic acid (iii) tartaric acid (iv) 2. What is elimination reaction? Describe different types of elimination reactions. 13. Draw the energy profile of the following reaction: A + B → A --. Write a short note on nucleophilic addition reaction. Electrophiles are in general Lewis acids–explain. 18. Explain with proper mechanism involved with examples. 23. What do you mean by dehydrohalogenation? Explain with proper mechanism and example. What are the significances of the terms: (i) Resonance hybrid and (ii) Resonance energy. 15.8 kcal/mole—explain. 3. . Name them as per R.B → AB 12. 16. 2-shift.8 kcal/mole while that of benzene is 49. What is resonance? State the important features of it. 20. 21.MECHANISM OF ORGANIC REACTIONS 183 10. 3-dibromopentane. . Compare the basicity among the following: NH2 NMe2 Me . NMe2 Me 22. 14. What does the term ‘isomerism’ refer to? Give different classifications of isomerism. Name them as per R—S nomenclature. Write notes on electrophilic addition and electrophilic substitution. 19. 11. 5-cyclohexatriene is 85.and L-glycine (NH2CH 2COOH). 24. Draw the resonance structures of: (i) phenate ion (ii) acetate ion (iii) chlorobenzene (iv) butadiene.

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

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

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

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

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

63. [OH–] = 0.6 × 10–3 g-ion l–1 – log10 [OH–] = – log10 (1.63 = – 3 – 0. One such method is by comparing dissociation constants of the acids. Both acid and base are strong. Example 2. Sol. the ratio of dissociation constants of two acids compare their strengths. ratio of strengths should be CA: CB.1(N)]. Buffer Solutions Some solutions do not change their pH on addition of little acid or alkali.24. Such solutions are known as buffer solutions. Relative Strengths of Acids and Bases Tendency of donating protons in any aqueous solution is a measure of acidity of the solution.69 = 3.IONIC EQUILIBRIUM 189 Example 1. [OH–] and pH of a weak base [0. degree of dissociation of acid A1 = α1 Degree of dissociation of acid A2 = α2 The concentrations of the acids were same (C). S2 S1 = α2C α 1C = α2 α1 = K 1C K 2C K2 K1 So. (b) 0. Let.7 = 12 – 0.8865 = 11.1 = 1. Sol. Calculate [H+].7 × 10–12 g-ion litre–1.34 × 10–4 g-ion litre–1. (a) [H+] = 4.9 × 10–4 (N) acid.9 × 10–4) ∴ pH = 4 – log10 4.3 × 10–3 g-ion litre–1.63 – log10 [H+] = 3.76 ∴ pH = 14 – pOH = 14 – 2.37 = 2. 1.34 × 10–4 ∴ [H+] = 2.37 [H+] = antilog 4.013. the dissociation is complete.76 = 11.6 × 10–3) ∴ pOH = 3 – log10 1.63 = 4 – 0.2041 = 2. pH = 3. As the acid and base are strong.6 = 3 – 0. The arrest of pH changes of these solutions is known as buffer action.7 × 10–12) = 12 – log 7.9 = 4 – 0.0016 (N) base. Calculate [H+] of a solution of pH 3. So.31 (b) [OH–] = 1.1135.013 × 0.9 × 10–4 g-ion l–1 – log10[H+] = – log10(4. Given: α = 0. There are several other processes for comparing strengths of acids. . So.37 = 4. If concentrations of two acids A and B are CA and CB respectively.3 × 10 −3 pH = – log10 (7.63 log10 [H+] = – 3. their strengths S1 and S2 are represented by. [H+] = 10 −14 = 7. Calculate pH of the following solutions: (a) 4. Example 3.7959 or 2. Sol.

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

then pH = pKw – pKb.6 5. Different Buffer Solutions Component conjugate acid–base pair (i) Glycine/Glycine hydrochloride (ii) Phthalic acid/Potassium hydrogen phthalate (iii) Acetic acid/Sodium acetate (iv) NaH2PO4/ Na2HPO4 (v) Boric acid/Borax (vi) NH4OH/NH4Cl (vii) Na2HPO4/Na3PO4 pH ranges 1.7 2.24) = 1.76]. (ii) Buffer solution (prepared from a weak base and its salt) In this case: BOH Kb = B+ + OH– (weak) Kw [B + ] [OH − ] [B + ] = × [BOH] [BOH] [H + ] K [B + ] [H+] = w . [Given pKaCH3COOH at 25° is 4. Prepare a buffer solution of pH 5..7-5. i. [Acid] [Salt] = antilog (0.8-8 6.2 10 11-12 Example 1.738 [Acid] .76 + log [Acid] ∴ ∴ log [Salt] = pH – 4. pH = pKa + log [Salt] [Acid] [Salt] = 4.8-9. • The buffer capacity of a solution is defined by db/dpH. The buffer action is favourable in pH ranges pKa ± 1 i.e..76 = 0.e.IONIC EQUILIBRIUM 191 The acidity or alkalinity of mixed solution. when concentration of salt becomes 10 times the concentration of acid and vice versa.38 3. Sol. where dpH is the increase of pH resulting from the addition of db of base. 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. the addition of acid decreases the pH and is equivalent to a negative amount of base.2-3. pH depends upon the ratios of the concentration of salt and acid.00 – 4.24.76 = 5.0-3. K b [BOH] LMQ N [OH − ] = [H + ] Kw O P Q ∴ As entire B+ ions in the solution is due to complete ionisation of BA and BOH is weak ∴ pH = pKw – pKb – log [B + ] [Salt] = pKw – pKb – log [BOH] [Base] where [Salt] = [Base].

ion l–1.l–1. [A–] = yS If the solubility is S mol l ∴ Ksp = [B+]x [A–]y = (xS)x (yS)y = xxyy.738 g-moles of CH3COONa is mixed with 1 g-mole of CH3COOH and the volume of the solution is made upto one litre. wt. [B+] [A–] = constant = Ksp. Calculate its solubility product. 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. then [B+] = S g. K= Highlights: • When the solubility of Mg3(PO4)2 is C mol. By convention it is unity.3 × 10–8.0305 gl–1. formula weight per litre and not in g. Example 1.e.192 ENGINEERING CHEMISTRY Therefore. because a heterogeneous equilibrium is set up as follows. equiv.0305 gl–1 = 3. each concentration term being raised to a power representing the number of gm. Calculate Ksp of CaF2 . CaF2 Ca+2 + 2F– . 3Mg+2 + 2PO4–3 its Ksp is = × = 108 • The solubility product of a sparingly soluble binary electrolyte is simply the square of its solubility in pure water expressed in mol l–1. BA(s) BA (solution) B+ + A– Applying law of mass action. The solubility of chalk is 0. So [BA (s)] = 1. ions of each type formed by dissociation of one molecular formula weight of the salt.mol l–1 and [A–] = S g. ion l–1 i. l–1 Mg3(PO4)2(s) Mg3(PO4)2 (Solution) [Mg+2]3 [PO4–3]2 (3C)3 (2C)2 C5. 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 of CaF2 is 0.. If S is the solubility of BA. when 1. The constant Ksp is called the solubility product of the salt BA. But it can be successfully applied to the saturated solutions of sparingly soluble salts.0002 mol l–1.05 × 10–4 mol l–1 Ksp = S2 = (3.05 × 10–4)2 = 9. of CaCO3 = 100) Solubility S = 0. 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. Ksp = [B+] [A–] = S2 For a salt like BxAy: BxAy(s) BxAy (Solution) xB+ + yA– –1 then [B+] = xS.mol. Example 2. • It is customary to express the concentrations of the ions in g. [B + ] [A − ] [BA( s)] or K[BA(s)] = [B+][A–] The concentration of solid salt [BA (s)] is constant. the desired buffer solution of pH 5 is obtained. per litre. Therefore.

∴ S′ = 2.IONIC EQUILIBRIUM 193 [Ca+2] = 0.1 (M) 132 ∴ [SO4=] = 0. [F–] = 2 × 0.1 g. [OH–] should not exceed 1.33 gl–1.8 × 10–5 and K sp Mg(OH) = 1.1 × 10–4 g. Calculate the solubility product of the salt. Ksp = [B+] [A–] If we add to the solution a substance.8 × 10–5. 3. Effect of Common Ion on Solubility We know that.2 gl– at 25°C. ∴ Ksp = S′ × (S′ + 0.1 × 10–4 g.0002 × (0. For doing so.001 g. So.00233 = 10–5 g. • The presence of a neutral salt without a common ion often results in an increase of solubility of a sparingly soluble salt. Therefore.1) = 10–10. A litre of a solution contains 0.ion l–1 to arrest the precipitation of Mg(OH)2. (a) ∴ (b) [Ba++] = [SO4=] = 13.001 Q −11 1/2 = 1.0002 g ion l–1 . the changed solubility of BaSO4 = S′. To arrest the precipitation of Mg(OH)2.0004)2 = 3.12 × 10–11. [NH + ] [OH − ] 4 = 1.2 = 0. the concentration of other ion will decrease otherwise the constant Ksp will change.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.01 mole NH4OH and 0. for a saturated solution of a sparingly soluble salt BA. B+ and A– will combine to give the solid BA(s) and the solubility of BA will decrease. [(NH4)2SO4] = ∴ S′ = 10 −10 0. Kb = L 1. [S′ is negligible compared to 0. We know that Ksp = [Mg+2] [OH–]2 = 1. 4 2 Sol. l–1. Example 4. [Ba = 137] Sol.12 × 10 OP =M N 0.0002 g ion l–1.12 × 10–11 ∴ [OH–] So. Let. (b) Calculate the solubility of BaSO4 in a solution of (NH4)2SO4 containing 13.1] 10 −1 = 10–9 mol.ion l–1. As a result. we are to suppress the dissociation of NH4OH by adding common ion NH4+. taking complete dissociation. What will be concentration of NH4+ ion from NH4Cl? Given K b NH OH = 1. [NH 4 OH] . Example. Ksp = [Ca+2] [F–]2 = 0.ion l–1 137 + 96 Ksp = [Ba++] . which has an ion common to the above salt then concentration of that ion will increase.ion Mg+2.00233 gl–. [SO4=] = 10–5 × 10–5 = 10–10.2 × 10–11. (a) At 25° the solubility of BaSO4 is 0.

194 or = ENGINEERING CHEMISTRY Effect of a Salt without a Common Ion on Solubility For the correct expression for solubility product we should use activity (a) in place of concentration: i. This effect is known as salt effect. Cr+3 get precipitated as hydroxides because their solubility products are exceeded. So. So concentration of sulphide ion CS= remains low. 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. CdS and PbS have comparatively higher values of solubility products. [Cl–] increases in order to keep the true Ksp value constant. As+3. the ionic products (CM+2 × CS–2) of metal ions exceed the solubility products because of low value of solubility products. The chlorides of Group I metals (Hg2+2. Sn+2). [ Ag + ] . ionic product (CM+ × CCl–) easily exceeds the solubility products and the cations are precipitated. low acidity or higher pH is necessary. HCl.e. solubility of a sparingly soluble salt increases on addition of any salt without a common ion. The metallic ions (Hg+2.01 ∴ [NH4+] = 1.ion l–1. Pb+2. The common ion H+ suppresses the ionisation of H2S.1 × 10 −4 4 = 1. Again diluted acid medium precipitates colloidal As2S3 and SnS which creates difficulty in filtration. Pb+2. true expression is Ksp = γ Ag + . Q activity (a) = Concentration (c) × activity coefficient (γ) ∴ a = cγ. Here reagent is NH4Cl/NH 4OH. Ni+2. to reduce acidity of the medium water is added to dilute the medium. That is why. It is also precipitated in Group II... for precipitation in chemical analysis. Mn+2. The precipitation of .8 × 10–5 0. As a result Fe+3. Sb+3. Bi+3. [NH + ] × 1. so CS= should be high for them.e. If we add KNO3 to a saturated solution of AgCl the γ-term of the expression of Ksp decreases. despite low S= ion concentration. Ag+) are insoluble. HCl. γ Cl− [Cl − ] where γ = activity coefficient. aCl − So. [Ag+] . which are sparingly soluble in water. For a very dilute solution γ = 1 then a = c. on addition of dil. Only PbCl2 has higher solubility product and for that reason it is not completely precipitated here. A salt may not get precipitated even when its ionic product exceeds its solubility product. • The effect of common ion on solubility is utilised in qualitative inorganic analysis to separate the ions present in a solution. whose solubility product of sulphides are low. Al+3. Group II. Therefore. To increase the ionisation of H 2S. Group I. 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. Highlights: • Many proteins. The common NH 4+ suppresses the dissociation of weak base NH4OH thereby COH– remains low. IIIB metallic ion (Co+2. Cu+2.6 × 10–3 g. Group III A. so their precipitation is arrested here. are soluble in salt solutions due to this salt effect. get precipitated here i. Ksp = aAg + . It may remain in saturated solution for sometime. The reagent is H2S in presence of dil. the value of solubility product of the salt should always be higher than its ionic product. Zn+2) sulphides have higher values of solubility products.

Ba SOLVED EXAMPLES Example 1. Here reagents are NH4Cl. 10 −14 2×1 –8 (M) = 9.5 × 10–8) ∴ = 8 – log10 10.1 M HCl to 1 litre.5 × 10–8 pH = – log10[H+] = – log10 (10. Group IV. Ca+2. [OH–] and pH of a solution prepared by diluting 20 ml of 0. Sr+2 are precipitated as carbonates.. So. NH4OH.005M Ca(OH)2 solution assuming complete dissociation. Sol. [H+] = ∴ − 10 −8 ± (10 −8 ) 2 + 4 . pH = 14 – 2 = 12.0 × 10–8 + x) = (1.5 × 10–8) [H x= = 10.0 × 10 – 8 (M) HCl solution. But when it exceeds 10–6. the [H+] of the solution = (1 × 10–8 + x) and [OH–] = x ∴ Kw = [H+] [OH–] = (1 × 10–8 + x) × x = 10–14. (b) Here let the contribution of OH– ions from water be x.7 ∴ pOH = 14 – 2.5 × 10 +] = (1. [OH–] = 2 × 0.98.002 = 2 × 10–3 mole l–1.5 = 6. Example 2. 20 × 0.1 = 0.6990 ~ 2.3010 = 2. Sol.3 – log10 [OH] = 11.3 [OH] = 10–11.ion l–1.e. or x2 + 10–8x – 10–14 = 0 Sol.01 × 10–12 g. 1 . Let the contribution of [H+] from water = x. Calculate the pH of (a) 1.0 × 10–8 + 9. Group IV metals i. 1000 ∴ pH = – log10 [H+] = – log10 [2 × 10 –3] = 3 – log 2 = 3 – 0. and (NH 4)2CO 3. l–1. Calculate the pH of 0. ∴ So.7 = 11.IONIC EQUILIBRIUM 195 Zn+2. ∴ total [OH–] = (1 × 10–8 + x) [H+][OH–] = Kw = 10–14 (1 × 10–8 + x) × x = 10–14 . Calculate [H+].005 = 10–2 mol. ∴ ∴ pOH = 2.3 = 5. +2. (a) When the [H+] is 10–6 or greater the ionisation of water is negligible due to common ion effect. the contribution of H+ ions is to be counted during calculation of pH. Mg+2 and Mn+2 as hydroxides are arrested as their solubility product values for hydroxides are comparatively higher. Example 3. (b) 1 × 10–8 (M) NaOH solution.

74 + log [salt ] [acid] 0.004 = 0.5 × 10 −7 = _ ~ [H + ] 3. Ka = 1. Calculate the pH of buffer solution.98 × 10–8 g.24 × 10–2. A buffer solution contains 0. Ksp = [Ca+2] [F–]2 = [S] × [2S]2 where.98 molar 0. Sol. C 0.02) 0.5 × 10 −7 4. 0.4 ∴ – log10 [H+] = 7.8 × 10 −5 = 4.98 × 10 −8 11 .1 mole CH3COOH and 0. α = 0.98 = 7. – Sol.1 – Example 6. Calculate the ratio of HCO3 and H2CO3 .ion l–1 Example 7.4 ∴ [H+] = 10–7. Sol.8 × 10 −5 × 0.5 × 10 – 7.98 1. The solubility product of CaF2 in water at 18°C is 3.1 = 4. S = solubility. Given Ka of H2CO3 = 4.5 × 10–8 (M) [OH–] = 9. ion l–1 pOH = 8 – log 9. (a) Calculate the molar concentration of an CH3COOH solution.0 × 10–8x – 10–14 = 0 x = 9. H2CO3 H+ + HCO3 .196 ∴ ∴ ∴ ∴ ∴ x2 × 1. ∴ ∴ Ka = − [H + ] [HCO 3 ] [H 2 CO 3 ] pH = 7. ENGINEERING CHEMISTRY Example 4. According to Henderson equation pH of a buffer solution (b) α= pH = pKa + log = 4.4 = 3. (Given Ka = 1.01 Example 5.4.98 pH = 14 – 6.2C 0.5 = 6. (pKa = 4.01 (M) AcOH.0004 × C = C(1 − 0.02.02) (b) Calculate the degree of dissociation of 0.8 × 10–5 .74). Sol. at equilibrium: ∴ CH3COOH C(1 – α) Ka = = ∴ c= H+ + CH3COO– Cα Cα [H + ] [CH 3 COO − ] [CH 3 COOH] 0. pH of blood is 7.1 mole of CH3COONa per litre.044 molar.02C × 0.45 × 10–11.5 × 10–8 g.74. = 4S3 [H 2CO 3 ] − [HCO3 ] = [H + ] Ka = 4. Calculate the solubility of CaF2 in water.

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

given K for water = 1.. Q. AcidI + BaseII AcidII + BaseI Q.. Ans. An acid is a species which can accept a pair of electrons and a base is a species which can donate a pair of electrons. every acid–base reaction proceeds according to the equation i. 8. Ans.8 × 10–16 × 55.00 × 10–14. Q. H + acid . base H . As. its conjugate base will be weak and vice-versa. Show that solvent acts as a base or an acid according to Lowry Bronsted concept. [H+] = [OH–] [H+] = [OH–] = 10–7 g.. H3O+/H2O. 7.. H2O + H2O or H2O H+ + OH– K= [H2O] = [H3 O + ] [OH − ] [H 2 O] or [H + ] [OH − ] [H 2 O] 1000 = 55. H : N : → H + . ∴ [H+] [OH–] = 10–14 and in pure water.5555 moles l–1.e.8 × 10–16.5555 = 100 × 10–16 = 1. Show that ionic product of water (Kw) is 1 × 10–14.198 Some conjugate acid-base pairs are: ENGINEERING CHEMISTRY If the acid is strong. HNO3/NO3–. So. Give Lewis concept of acids and bases. . H2O/OH–. acid H base H Cl   Cl  B ← : N  H   H Cl acid base Q. According to Lowry Bronsted concept acid–base reaction always follows the equation: + BaseII AcidII + BaseI AcidI CH3COOH + HF H2 O + H2O H2O H3O+ H3O+ + CH3COO– F– OH– + + CH3COOH CH3COOH2+ + HSO4–/SO4=. In pure water. conjugate acids and bases are formed during the reaction.ion l–1. 18 Kw = K [H2O] = [H+] [OH–] = 1.. NH4+/NH3 and so on. 5. what will be the [H+] or [OH–]? Ans. H3O+ + OH– Ans. 6. ← : O • • H – .

1 Neutralisation Curves. Ans. What is the pH of 0. ion l–1.e. The pH scale is a logarithmic scale for measuring the concentration of hydrogen ions in aqueous solutions. ion l–1 In acidic solutions.IONIC EQUILIBRIUM 199 Q.c. Phenolphthalein pH 7 Methyl orange 0 0 25 Alkali(c. = 100 – 10–6 g .3 or log10 [H+] = – 2. [H+] = [OH–] = 10–7 g . 9. 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.3 = 5 × 10–3 mol dm–3. [H+] range In neutral solutions. In alkaline solutions. Ans.) Weak acid–strong base pH 7 Fig. Q. It is negative logarithm of hydrogen ion concentration. 8.699 ≈ 1. 12.02 mol dm–3 HCl? Ans. Explain the pH changes during acid–base titration. . 11. What is the hydrogen concentration of coca cola with pH 2. Explain the pH scale. 13. [H+] range = 10–8 – 10–14 g . 10. pH = – log10 [H+] or [H+] = 10–pH The acidity or alkalinity of a solution is generally expressed by pH.37? Ans.3 or [H+] = 10–2.7. pH = 2. pH = – log10 [H+] = – log10 [2 × 10–2] (as the acid is strong) = – log10 2 + 2 log10 10 = 2 – 0. What is pH? Ans.. Q. pH = – log10 [H+] pH = [H+] = 0 10 0 1 10 –1 2 10 –2 3 10 –3 4 10 –4 5 10 –5 6 10 –6 7 10 –7 8 10–8 9 10 –9 10 11 12 13 14 10–10 10 –11 10 –12 10–13 10 –14 acidic ← neutral → alkaline Q.) Strong acid–strong base 0 0 25 Alkali(c. i.3010 = 1.c.3 or – log10 [H+] = 2. ion l–1. Q.

Q. What is pK? Ans. Q. . (iii) pH of a weak base = 14 – Kb = dissociation constant of weak base. at the equivalence point. pK is the logarithmic form of an equilibrium constant. 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. it hydrolyses to give a solution that is not neutral.7 pH = 14 – pOH = 14 – 1. Weak acid/strong base end point is alkaline (pH > 7) Strong acid/weak base end point is acidic (pH < 7). Q. Ans. Neutralisation reactions do not always produce neutral solutions—explain. It is to be noted that.200 ENGINEERING CHEMISTRY The graphs show the pH range for the colour change of an acid/base indicator for detecting the end point of the titration.7 = 12. a salt is formed. Q. H3O+ + OH– → 2H2O (l) Enthalpy change of neutralisation is same for all acid-base partners. (i) ∴ pKw = pH + pOH = 14 pH = 14 – pOH 1 1 pK a − log c 2 2 when Ka = ionisation constant of weak acid.1). hydrolysis of salts does not take place and the solutions remain neutral at the equivalence point (pH = 7). – log10 Kb = pKb. 1 1 p K b + log c 2 2 where c = concentration of undissociated base. – log10 Kw = pKw Taking logarithms produces a convenient small scale of values. the pH is not always neutral. if acid and base both are strong. When a salt formed at the equivalence point has either a ‘parent acid’ or a ‘parent base’ weak. 17.3. 14. 8. useful for pH calculations. when exactly equal amounts of acid and alkali have been added. 16. 18. The ‘strong parent’ in the partnership wins. dm–3 solution of NaOH? Ans. Q. – log10 Ka = pKa. NaOH is a strong base [OH–] = 0.02 mole dm–3 pOH = – log 0. (ii) pH of a weak acid = pH = c = concentration of undissociated acid. This experimental evidence supports the above view. Neutralisation is essentially a reaction between H+ and OH– ions in aqueous solution—explain.02 = 1. How can you use pK values for pH calculations? Ans. At the equivalence point. What is the pH of a 0.02 mol. strong or weak. 15. Ans. We know that.

19. Ans.IONIC EQUILIBRIUM 201 Q. (iii) The common ion effect alters the solubility of a sparingly soluble salt. . K a = 2 − [H + ] [PO 43 ] H+ + PO4–3.7) causes bodyache. (i) The pH value of soil helps to decide the type of fertiliser to be used in agriculture. (i) H3PO4 (ii) H2PO4– (iii) HPO4–2 H+ + H2PO4–. Ka × Kb = [HA] [OH − ] [A − ] [H 3 O + ] [A − ] [HA] [OH − ] × = [H3O+] [OH–] [HA] [A − ] = Kw = 10–14. (ii) The common ion effect influences the behaviour of buffer solution. (iii) pH value helps to determine the condition of reactions in laboratory and in industry. (ii) A small variation of pH of human blood (6. There are three dissociations for H3PO4 and accordingly ka values. a 1 2 3 Q. 20. 22. Kb and Kw. 21. Q. Ans. What is a buffer solution? Ans. 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. Ans. K a = 1 − [H + ] [H 2 PO 4 ] [H 3 PO 4 ] − [H + ] [H 2 PO42 ] − [H 3 PO4 ] H+ + HPO4–2. What is common ion effect? Ans. Q. Mention the importance of pH. which help to keep pH of a solution more or less constant. Q. Relate Ka. H3PO4 has three Ka values–explain. K a = −2 3 [HPO 4 ] Ka > K > Ka . Buffer solutions are mixtures of a weak acid and its salt or a weak base and its salt. 23. ∴ or ∴ Ka × Kb = Kw – log Ka – log Kb = – log Kw pKa + pKb = pKw = 14. (i) The common ion effect can change the ionisation of weak acids and weak bases. (i) HA + H2O acid H3O + A – Conjugate pair base Ka = (ii) A + H2O – [H 3 O + ] [A − ] [HA] – HA + OH Conjugate pair Kb = Now.

1 × 10–22 [H 2S] [Q S H 2S = 0. Show that it is different from dissociation constant of water. What is the pH of a buffer solution containing 0. Deduce the relation between solubility and solubility product of CaF2 at room temperature. BI3. ppt. ∴ [Mn+2] [S–2] = 0. What is the basic equation for acid-base reaction of Bronsted theory? Explain (a) neutralisation. 25. Deduce Ostwald’s dilution law and state its limitations. 11. What is pH? Give its importance and usefulness. 20. Ans. 9. Will Ans.1 [S–2] = 10–19.01) [S −2 ] = [H 2 S] 0. What do you mean by common-ion effect? How is it utilized in qualitative chemical analysis? What do you mean by autoprotolysis of water? Derive an expression for ionic product of water. Derive an expression for pH of the buffer solutions: (a) Weak acid and its salt. ∴ ∴ FG N IJ Mn H 10 K 100 . +2 containing FG N IJ H H 100 K + be precipitated by passing H2S? H2S 1. K = [H + ] [S −2 ] = 1. Give the Bronsted-Lowry concept of acids and bases. pH = pKa + log Q. in the light of Bronsted theory.8 + 0. 19.1 × 10–19 = 10–20 Ksp . (b) Weak base and its salt. 12. 15. will not be obtained.1 × 10–22 = 2H+ + S–2. 8.40 = 3. BCl3.8. (b) BeCl2. 24.0 mol dm–3 sodium methanoate? pKa(HCOOH) = 3. (MnS) = 1. Explain the terms: (i) Buffer solution (ii) Buffer capacity and (iii) Buffer action. Discuss the effect of common ion on solubility product. . 2. BCl3. 6. 17. Explain the following–Aqueous solution of NaCl conducts electricity while chlorine water does not conduct electricity. 16.01) 2 × [S −2 ] (0. 5. 4.4 mol dm–3 methanoic acid and 1.2. (b) hydrolysis. What is a buffer solution? Explain buffer action.4 = 4. 7. EXERCISES 1. 10. 18.4 × 10–15 So. Deduce the Hendersen equation and state its utility. Which are the strongest Lewis acids in the series? (a) BF3. 3. 14.1M] (0. 13. Elucidate. 0. The reaction HCl (aq) + KOH (aq) → KCl (aq) + H2O is neutralisation according to: (a) Bronsted-Lowry concept. Tricovalent phosphorus compounds can serve as Lewis bases and also as Lewis acids–comment. (b) Lewis theory and (c) Solvent system concept.202 ENGINEERING CHEMISTRY Q. What do you mean by solubility product? What is true solubility product? Give an expression for the solubility product of the salt Ax By.

11. Calculate its solubility product. making a volume equal to 500 ml? [Ans. pH of a solution is 10.1N HCl.1M. Calculate its solubility product. 4. Calculate the [H+].54 (b) 3.95.89 (c) 11. 28.57.6 × 10–8] [Ans. l–1. Ksp(PbS) = 3. 13] [Ans. 10. 27. 1. 12.4 × 10–12} (b) 0. [Ag+] g-l–1.5 g. 2. What will be the pH of a solution obtained by mixing 800 ml of 0. Calculate the pH and pOH of .000775 (N) acid [Ans. 10–3 [Ans.038 g-l–1. Solubility of PbSO4 is 0.69 × 10–11 moles l–1] in a solution is 4 × g-in Calculate the minimum concentration of Cl– to precipitate –10.014] 24. Solubility of Ag2CrO9 29.IONIC EQUILIBRIUM 203 21. of CH3COOH and 7. Find α for NH4OH in a solution of . 11. [Ans. of CH3COONa. 23. 5 × 10–8 g-in l–1] AgCl. Calculate the concentration of H2S required to arrest the precipitation of PbS from a solution of [Ans.001 (M) Pb(NO3)2.00345 (N) acid (c) 0.6 (M)] 0. 1.05 (N) NaOH and 200 ml of 1N HCl? [Ans. What will be the pH of a solution obtained by mixing 5g.4 × 10–28.3] 22.1 × 10–23.8 × 10 30. 2. [Ans. Calculate the pH and pOH of: (a) 0.78] 25. Given Ksp of AgCl = 1. . . 1.00886 (N) base assuming complete dissociation.46.05] [Ans. 26. Given Ka(H2S) = 1. (a) 2. 5. Given Kb = 2 × 10–5.

e. 204 . asbestos etc. • It involves no chemical change during conduction of current. An arrangement for electrolysis is shown in Fig. Substances which conduct electricity are conductors.1. whereas when non-electrolytes conduct electricity there is no such chemical change. • Chemical change takes place i. acids.. 9. Some conduct it and some do not.Electrochemistry INTRODUCTION Substances behave differently towards electric current. Non-metallic conductors (electrolytes) • Flow of ions takes place during the passage of electricity through them. Salts.1 Set-up for electrolysis. 9 Electrolysis Dissociation of a compound by passing electric current through a compound in solution or in fused state is known as electrolysis. bases etc. and which do not conduct electricity are nonconductors as for example. The current is always passed into and out of the electrolyte by means of metal foils or plates Battery + – Anode + Cathode – Voltameter Electrolyte Fig. alkalies are examples of such electrolytes. as for example. Substances which conduct electricity and get dissociated in solution or in the fused states were termed electrolytes by Faraday. Table 9.1: Comparison Metallic conductors • Flow of electrons takes place during the passage of electricity through them.e. Electrolytes dissociate when they conduct electricity i. a chemical change occurs then.. But some physical changes may occur. acids. metals. Again conductors can be divided into two subdivisions: (i) electrolytes and (ii) nonelectrolytes. new products are obtained during conduction of current. wood. 9.

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

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

. t+ ∝ u and t– ∝ v and (t+ + t–) ∝ (u + v) But t+ + t– = 1 v u ∴ t+ = and t– = u+ v u+ v where u and v are the speeds of cations and anions respectively.. 9. cations and anions present in the solution conduct current. Ions of an electrolyte i.e. the total quantity of the current passed will remain same as above i. . in that case. Table 9. It is to be noted that deposition at the electrodes in the above two cases will be same (Fig. Usually both cations and anions cross the barrier (ab) but in unequal numbers owing to their unequal speeds.78 8. the transport number of anions is hundred per cent and that of cations is zero per cent... ni = number of the ions and Zi = valency of the ions which cross the barrier.3 Concept of transport number.0000104 0. 1 F = 96500 coulomb. The case may be totally reversed. = n = F Z 1 Z2 Zn Therefore. If 100 cations cross the barrier from left to right. if 80 cations cross the barrier (ab) towards cathode compartment and 20 anions cross the barrier (ab) towards anode compartment.0001118 0. So.008 107.ELECTROCHEMISTRY 207 for one gm equivalent of different elements E E 1 E2 = = . Transport number is proportional to speeds of the ions. then current is wholly carried by cation. We can say that the cation transport number is hundred per cent and the anion transport number is zero per cent..0003294 0. 9. we can accept that. So.0000829 F = E/Z (Coulomb) 96496 96495 96494 96495 ≈ 96500 The concept of transport number..88 31. For example. a A N O D E b C A T H O D E Fig.. transport number (t) = ni Z i Σ ni Z i where. 100 units but the current carried by cations is 80 per cent and the current carried by anions is 20 per cent.0 Z 0. So we can define transport number as the fraction of the current carried by an ion.e.3).2: Displaying the constancy of E/Z for different elements Element H Ag Cu O E 1. so their transport numbers are unequal.

but it is not so. Similarly. The current I is flowing. The number of ions liberated at the positive and negative electrodes per unit area are given by n+ u and n– v. 9. . 9. the solution contains n(±) number of ions per millilitre + A – B – – v + + + u Fig. ions are always discharged in equivalent amounts but their speeds are different. 9.4 Voltameter. are kept inside an electrolyte and their potential difference is E. As every part of the electrolyte is electrically neutral. therefore. The total current carried by the positive and negative ions = I = I+ + I– = (n+u)z+e + (n–v)z–e. If unit of the charge is ‘e’ (Fig. and the valency of ions is z(±). Let the two electrodes. n+z+ = n–z– So. ∴ t+ = t– = t+ = I+ I = n+ z+ eu + n+ z+ ev n+ z+ eu = n+ z+ e(u + v) n+ z+ eu = u u+v n− z− ev n+ z+ ev I− v = = = n+ z+ eu + n+ z+ ev n+ z+ e(u + v) u + v I u u+ v and t– = v u+ v It is obvious that.4) Current carried by the positive ions = I+ = (n+u)z+e Current carried by the negative ions = I– = (n–v)z–e.208 ENGINEERING CHEMISTRY Transport number or transference number of an ion is dependent on the speed of the ions. A and B. The following model will make the idea clear (Fig. 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. this phenomenon creates an idea that perhaps the ions move at the same rate during electrolysis.5).

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

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

479.442 0.. of Cu+2 in the liquid per unit vol. Before electrolysis the amt. CdI2 ionises as follows in a concentrated solution: Cd+2 + [CdI4]–2 2CdI2 +2 ion is moving towards both cathode and anode and towards anode due to i.91 g. It can only be explained by the 0. .916 during electrolysis of a silver nitrate solution.916 − v Speed of NO 3 r= 1 u 1– n = (n = tNO 3 – ) or n = 1+ r v n 1 = 0. would have been 0.153 – 0.444 0. increase of wt. After electrolysis the amt.153 – and Transport number of SO4 – = (1 – tCu + + ) = (1 – 0.296 0.ELECTROCHEMISTRY 211 Highlight: • Abnormal transport number: the transport number of Cd+ ion is normal in CdI2 solution but it decreases abnormally with increase in concentration of CdI2.127 0. This is true for other complex compounds too.12 g.153 g and masses of Cu per unit volume of the anode liquid before and after electrolysis were 0. of Cu+2 in the liquid per unit vol.01 0. But actual increase = 0.e. Increase in wt.33 = 0.91 g respectively.20 0. Calculate the transport number – of the Cu++ and SO4 – ions. of Cu-cathode in the coulometer = 0. If no Cu++ had migrated from the anode. Cd above complex ion formation.79 g. u Speed of Ag + = = ratio (r) = 0. Let.79) g = 0.02 0.215) = 0. Example 2.91 – 0.396 0.916 n = tNO 3 – = tAg + = 1 – tNO – = 1 – n = (1 – 0.003 formation of complex ions.153 g.153 g.785.521) = 0. This abnormal transport number does indicate the formation of complex ion.521 1 + 0.033 g. In an electrolysis of CuSO4 between copper electrodes the total mass of copper deposited at cathode was 0.05 0.79 and 0. due to dissolution of Cu anode during electrolysis = (0. Increase in wt. Concentration (N) tCd + 2 0. ∴ Transport number of Cu++ ( tCu + + ) = It is obvious that Cd+2 is moving towards anode in larger amounts than the cathode and that is the cause of decrease of tCd+ 2 . surrounding anode = 0.50 0. surrounding anode = 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’.215 0.10 0. Example 1.12) g = 0.12 g. Fall in concentration due to migration of Cu+2 ions = (0. Calculate the transport number of Ag+ and NO3– ions when the speed ratio of the two ions is 0.

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

9.000143 0.2 49.01119 0. The use of A.2 76.0001 Specific conductivity (Κ) KCl 0. (ii) Weak electrolytes: Weak acid like acetic acid has a low value of λv at higher concentration and there is rapid increase of λv with dilution.001225 0. After a certain dilution there remains no more electrolyte molecule to ionise and then there is no change i.0000752 0.ELECTROCHEMISTRY 213 dilution more and more of the electrolyte ionises. 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∞. The modification is necessary as the passage of current will electrolyse the electrolyte.1 70.0982 0. no increase of λv or λm with dilution.4 61. Table 9.00132 0. Such electrolytes are called strong electrolytes.0000129 CH3COONa 0.8 CO3COOH 1.3 41. strong alkali NaOH have high conductances even at low dilutions and there is no sharp increase in their equivalent conductances on dilution.000041 0.2 75. Experimental Determination of Specific Conductance (K) The arrangement of apparatus adopted for the determination is modified Wheatstone’s meterbridge arrangement (see Fig.5 0.0412 0. 9.5 127. is necessary to avoid this difficulty.0 Classification of Electrolytes (i) Strong electrolytes: Strong acid HCl. m¥ Molar conductivity Strong electrolyte Weak electrolyte Concentration Fig.3 Normality 1.001 0.01 0.00611 0.2 102.8).7 Change of equivalent conductivity with dilution.001005 0.0001276 0.0247 0.05115 0. .9 122. The products of electrolysis will accumulate on the electrodes which will change the effective resistance.00024 0.01 2.82 2.1 0..3 111.C.e.0 0.30 14.0000107 KCl 98.0 107.6 129.7).5 Equivalent conductivity (λv) CO3COONa 41. 9.00000768 CH3COOH 0. Such electrolytes whose λv values increase with dilution are known as weak electrolytes (see Fig.000702 0.

But the procedure is to calculate a factor for each cell known as cell constant (x). (c) the electrolyte is taken in a cell containing platinised Pt electrodes (Fig. Calculation of Specific Conductance (K) If necessary ρ is calculated from the observed resistance. specific resistance ρ is given by the following equation: ρ a = R b Since the conductivity of a solution rapidly increases with temperature. =x× FG N IJ KCl solution.9). 9. Different cells are in use. the common form is shown in Fig. The solution whose conductance is to be measured is put into the conductivity cell (see Fig.. the area of cross-section of the electrode. 9.C. 9.9. cm–1 at 25°C.C.9 Conductivity cell. Source Fig. When the sound in the telephone is minimum or zero reading on the appropriate meter.214 ENGINEERING CHEMISTRY C R T A a X R S b B Platinum electrodes A.9). 9. Specific conductance K = x × Observed conductance. The modifications are: (a) the use of A. if the area of the electrodes and the distance between them are accurately known. Fig. The H 50 K 1 b 1 =x× × ρ a R .002768 ohm–1 . the cell should be placed in a thermostat. l =ρ×x s The cell constant is known by determining the conductance of K value of the solution has been accurately determined by Kohlrausch to be 0.8 Determination of conductivity of solutions. (b) the use of telephone detector or magic eye indicator. Conductivity water (double distilled water) should be used throughout. the resistance R of liquid enclosed between the electrodes is: R=ρ× where l/s = x is cell constant. 9. Specific conductance = Observed conductance × Cell constant When l is the distance between the electrodes and s. Connections are made by Pt wires. C is a compensating condenser (adjustable).

00076 0.9 0. • According to equation: K = x × observed conductance.5 53. λ∞ = Ionic conductance of anion. The l where l is the distance between the s electrodes and s is the mean area of the electrodes.e.00052 NO 3– HCO 3– CH 3COO– 71.00062 0.002768. 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. Cation H+ K+ NH 4+ Ag+ λc 349.4 44.8 76.1 50.00076 0. This regularity was first observed by Kohlrausch and was put in the form of a law which is known as Kohlrausch’s law. 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 9.00205 0.00362 0.00042 Anion OH– λa 197. The lower the cell constant.5 73. λ∞ = λc + λa where.9 59. volt 0.8 73. λc = Ionic conductance of cation. U cm2/sec.1 Mobility.5 40.3 Mobility.4 Ionic Conductance and Ionic Mobilities of some Ions at Infinite Dilution at 25°C. Highlights: • It should be noted that cell constant (x) = FG N IJ KCl be l H 50 K 1 the cell constant (x) = ρ1 × 0.00079 1 SO4– 2 Cl – 1 Ca++ 2 1 Mg++ 2 Na+ It is evident from the table that each ion contributes a certain definite quantity towards λ∞ of the solution. V cm2/sec volt 0.00083 0.ELECTROCHEMISTRY 215 If the observed resistance with cell constant being known it is easy to obtain the specific conductance of any solution by using the above relation. the higher is the observed conductance and so for weak electrolytes a conductivity cell having a small cell constant should be used.00046 0.4 61.00064 0.6 79..00055 0. . i.00074 0.

except at a infinite dilution.11 ohm–1 + = 53.216 ENGINEERING CHEMISTRY Highlight: Kohlrausch’s law can be stated in another way: At infinite dilution. Ah = t+ F C (ii) λ H + + λ Cl − = y 3 . ( λ + + λ + λ H + + λ Cl − ) – ( λ Na + + λ Cl – ) = (x + y – z) = (λ CH 3COO − + λ H + ) Na CH 3COO – λ∞(CH3COOH) (iii) Ionic mobility (Absolute velocity of ions) We have.22 ohm –1 K Cl– = 76. λm = r+ . Ionic conductance possesses a constant value at a definite temperature. λc ∝ u or λc = ku λa ∝ v or λa = kv where k is a constant.40 ohm–1 NO3– = 71. Its unit is ohm–1 cm–2 and is directly proportional to the speeds of the ions. We have (i) λ Na + + λ CH COO − = x And λa = (iii) λ Na + + λ Cl – = z. each ion makes a definite contribution towards the molar conductance of the electrolyte irrespective of its ∞ association with other ions. respectively. Examples are: λm (KCl) = λK ∞ ∞ ∞ ∞ + λ Cl – and λm (K3PO4) = 3λ K + + λ ′ PO 4 −3 Ionic Conductance of Some ions at 25°C Br– = 78. the ionic conductances of cations and anions can be determined from their experimentally determined transport numbers from the above relations. because they do not ionise to a sufficient extent in solution. (ii) Determination of λ∞ of weak electrolytes: λ∞ for weak electrolytes cannot be determined experimentally. Calculate λ∞ for CH3COOH.44 ohm–1 Applications of Kohlrausch’s law (i) Determination of ionic conductances. when the dissociation of an electrolyte is considered complete.34 ohm–1 NH4+ = 73. Example: The λ∞ values for CH3COONa. So. It 1000 . But λ∞ for weak electrolytes can be calculated from Kohlrausch’s law. y and z. HCl and NaCl are x. And λ∞ = λc + λa = ku + kv = k(u + v) λc u kv ∴ = = = t+ u+ v λ ∞ k(u + v) kv v = = t– = (1 – t+) λ ∞ k(u + v) u + v So.4 ohm–1 Na+ = 50. λ∞ + –  ∞  where r+ and r– are numbers of cations and anions and λ + and λ ∞ are molar – ∞ ∞ conductances of cations and anions respectively. Thus. λ∞ + r– .

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

Beyond the equivalence point. the sharper is the end point (Fig.10(a)]. 9.10(b)]. the increase in conductivity is due to excess of H+ ions with very high ionic molar conductivity (350). (b) Precipitation Reactions Conductometric titrations of this type may be performed if the reaction product is sparingly soluble salt. 9.218 ENGINEERING CHEMISTRY Highlights: • The change in volume throughout the course of titration must be kept small by using a titrant which is at least 100 times more concentrated than the solution being titrated. Highlight: The stronger the solution used for the titration. The precipitate should be formed fairly rapidly and should not have strong adsorbent properties. In water H+(aq) and OH–(aq) ions are very mobile. 9. dissociation or solubility of the reaction products. In the titration of NaOH with HCl. The point of intersection of the two curves is sharp. For this reason.10 (c). the graph shows a curvature rather than a clear intersection of the two straight lines [Fig. there is always an initial decrease in conductance. • Measurements of conductance in the region of equivalence point are of little value due to hydrolysis. so they conduct electricity very well. So. (a) Neutralisation Reactions In the titration of a strong acid with a strong base. The conductance then rises beyond the equivalence point. the decrease in conductance is due to the replacement of OH– ions (molar ionic conductivity = 199) by Cl– ions (molar ionic conductivity = 76). The titration of KCl solution vs AgNO3 solution satisfies the above conditions.10).10 (a) Changes in conductivity during titration of NaOH(aq) with HCl(aq). Conductivity falls as OH– (aq) ions are neutralized Conductivity Conductivity of Na+Cl– (aq) End point Volume of HCl (aq) added Conductance Conductivity rises due to excess H+ (aq) ions added Volume of alkali Fig. end point of the reaction can be determined easily. 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. Fig.10 (b) Changes in conductivity during titration of a weak acid (CH3COOH) (aq) with a strong base (NaOH) (aq). The nature of the titration curve is as in Fig. . 9. In the titration of HCl with NaOH. 9. 9.

what is the cell constant? Example 2. SOLVED EXAMPLES Example 1. The equivalence point is located by extrapolating the straight lines.ELECTROCHEMISTRY 219 Conductance Volume of AgNO3 Fig. Specific conductivity of an Sol.2 × 10–3 ohm–1 cm–1.10 (c) Titration curve of KCl solution by AgNO3 solution.4 cm–1 a 1.4 × N KCl solution at 25°C is 0. 9.5 cm. Titration of a very weak acid with strong base or a very weak base with strong acids results in a small initial conductance. or ∴ Cell constant = l a and R=ρ l a 1 R l = =R× =R×K ρ ρ a l = 500 × 0. 1 1 = 8.0002765 mhos cm–1. The conductance increases as the concentration of the salt increases. calculate the cell constant and specific conductivity. If the cell is filled with an electrolyte and offers a resistance of 1996 ohm.0002765 cm–1 a = 0. apart. due to hydrolysis the titration curve shows a marked curvature (Fig.25 cm2.5 = = 8. = 8.4 × 1996 1996 = 4. They are 10. A conductivity cell contains two electrodes of area of cross-section 1. In the region of the equivalence point. Cell constant = l 10.138 cm–1. Sol. 1996 = Cell constant × observed conductivity.25 Observed conductivity = Specific conductivity 1 ohm–1. 9. .10(b)). 50 If the resistance of cell containing this solution is 500 ohms.

the observed resistance of the cell is 4364 ohm.767 × 10–3 ohm–1 cm–1. The specific conductivity of 0.4 ρ K = 0. × = = R a 32 5. If the cell is now filled with 0. 12.5224 × 1 = 0.02109 ohm–1 cm–1 72.2 (N) KCl is 2. = 210.1 –1 cm2. cm.02109 × 1000 0.45 ohm–1 cm2 λm(molar conductivity) 1000 K 1000 × 0.767 × 10–3 cm–1 = 12.58 ohm. Sol.80 cm apart and 5. Calculate the equivalent and molar conductivities of the ZnSO4 solution. Example 4. or ∴ Cell constant = l l R=ρ a a R 1 l = =R× =R×K a ρ ρ l = R × K = 4364 × 2.166 ohm–1 cm–2. R=ρ l a or 1 1 l 1 18 . Cell constant = R × K = 550 × 0. A conductivity cell containing 0.2 = 105.002768 = 1.18 ohm.02109 = M 0.010416 ohm–1 cm–2 λv = 1000 K 1000 × 0. C 0.075 l/ a = 252.2 N ZnSO4 .002768 ohm–1 cm–1.220 ENGINEERING CHEMISTRY Example 3. K = cell constant × observed conductivity = 1.4 cm2 in area was found to be 32 ohms.075 cm–1 a ρ= 3050 R = ohm. Specific conductivity of a conductivity cell containing 0. Sol.010416 = = 104. the observed resistance of the cell is 72.18 1000 C λv(equivalent conductivity) = Kv × = 0. If the cell is filled with another solution the observed resistance is 3050 ohm.9 ohm = Example 5. The resistance of a decinormal solution of a salt occupying a volume between two Pt electrodes 1.02 N solution at that temperature is 0. Calculate specific resistance of the solution.5224 cm–1 Again.1 . Calculate the cell constant. Calculate the equivalent conductance (λv ) of the solution. Sol. cm.02 N KCl solution offers a resistance of 550 ohm at a definite temperature.

8 × 10 −5 = 0.05 (1 – α) [CH 3COOH] 0. The equivalent conductances at infinite dilution of various electrolytes are λ∞HCl = 426. λ∞HCl + λ∞AcONa – λ∝NaCl = (λ H + + λ Cl – ) + (λ Na + + λ OAc – ) − (λ Na + + λ Cl – ) = λ H+ + λ OAc – = λ∝AcOH ∴ 426.05α 0.05α2 ∴ α= Ka = 0. l–1 = 0.5 = λ∞ AcOH = 390.05α [CH3 COO – ] [H + ] (0. .0348 + 0. Ag = 108. Sol.0λ∞ NaCl = 126.0388 Example 9. wt. Its equivalent conductance at infinite dilution is 390.05 [α being negligible. 0.01898.3 mho eq–1 cm2. Example 8. respectively.1 λ∞AcONa = 91.0348 ohm–1 m2 eq–1 and 0. (Ka = 1.004 ohm–1 m2 eq–1 = 0. Strength of CH3COOH solution = Initially Degree of ionisation At equilibrium CH3COOH = 0. Calculate the degree of dissolution of acetic acid.0018 = 0.6 Ohm–1 cm2.8 × 10–5). Calculate the percentage ionisation of acetic acid. Calculate the degree of dissociation of acetic acid. The equivalent conductance of 1. what will be the concentration of acetate ion.9 × 10–3 0.24 × 10–6 mho –1 .05 = .1233. cm–2 Sol. 1 – α ≈ 1] = 0.05 = = . Cl = 35. If 3g of acetic acid is added to enough water to make one litre solution.05 1.5. Sol.05α .05(1 – α) Ka = 3 g equiv.05) 2 α 2 = = 0. 390.046.0388 ∴ Degree of dissolution = λ∞ λv = 0.0 – 126.004 ohm–1 m2eq–1. If ionic conductance of H+ ions and CH3COO– ions at infinite dilution are 0. Calculate the solubility cm of AgCl in gl–1 (At.05 18 × 10 –6 = 18. Sol.6 given: Example 7.6 ohm–1 cm–2 eq–1.8 and 65. α= ∞ λv λv = 48. Equivalent conductance of acetic acid at 25°C is 0.15 ohm–1 eq–1 at 298 K.05(N) 60 CH3COO– + H+ 0 0 α .1 + 91. Example 10.ELECTROCHEMISTRY 221 Example 6.05α × 0. The mobilities of Ag+ and Cl– ions are 53.5). The specific conductivity of saturated solution of AgCl is 1.15 = 0.028 × 10–3 (N) acetic acid is 48. λ∞(CH3COOH) = λ∞H+ + λ∞CH3COO– = 0. Calculate λ∞(AcOH).0018 ohm–1m2 eq–1.

placed in series.6236 g before and after electrolysis. Wt.286 = 0. .000 tAg + = tNO 3 – u 0. respectively. ∴ Amt.e. of Cu Eq. and 0. wt.0104 × 143.00104 eq l–1 9.24 × 10 –6 = 9.916 0.8 = 0.. = Ag(107.88). wt.522. Calculate the transport number of Cu+2 and SO4–2 ions.6350 g.1 λ ∞v = = 9. ∴ Hence. of Ag = Eq.1351 g.5) g l–1 = 0. of Ag deposited in voltameter = 0.6 × 10 2 = (0.916 = 1 – tAg + = 1 – 0. of Cu( x) wt.478 = 0. Cu(63.916 + 1 1.1351 g of Ag.1351 x = 63. Example 12.916 = v 1. A dilute solution of CuSO4 was electrolysed.6 107. of Cu from anodic solution (anolyte) [At.114 = = 0.6236) g = 0. using Pt-electrodes.286 Total loss 0.478 u + v 0. = 0.916 = = = 0. of Cu in anodic solution before electrolysis ∴ Loss in wt.1495 g l–1. Find the transport number of Ag+ and NO3– ions. The weight of Ag deposited in a silver coulometer. of Cu deposited equivalent to 0.3 = 119. of Ag 0. wts. Example 11.1351 × 31.6350 – 0.88 2 ∴ ∴ ∴ x= 0.3 + 65. i.6 × 102 l eq–1 ∴ ∴ Solubility = 1 eq l–1 = 0.6350 g. The speed ratio of Ag+ and NO3– ions in a solution of AgNO3 electrolysed between Ag-electrodes is 0. Speed of Ag + Speed of NO 3 – = u 0. According to Kohlrausch’s law.1 mhos eq–1 cm2 λv = KvV V= 119. was found to be 0.714. Sol.88 Loss at anode 0.6)] = 0. of Cu in anodic solution after electrolysis is Wt.1351 g. λα = λ+ + λ– λα(AgCl) = λ(Ag+) + λ(Cu–) ENGINEERING CHEMISTRY = 58.0398 tCu +2 = ∞ tSO4 = 1 – tCu +2 = 1 – 0. = = wt.6 × 105 cm3 eq–1 Kv 1.916. The amount of Cu in the anodic solution was found to be 0.0398 g 107. = (0.222 Sol.0114 g Wt.6236 g. Sol.

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

000 × 23 = 25. Q. Electrolysis of brine is the basis of the alkali and chlorine industry—a well known electrochemical industry. Quantity of electricity in an hour = 30000 C/S × 3600 s. What mass of Na is formed in an hour at the steel cathode? Ans. hydrogen is liberated at the cathode and bubbles off. (b) The equation for liberation at the cathode is – Na+ + e → Na Time of electrolysis = 3600 sec.000. During electrolysis chlorine is liberated at the anode. Brine is a solution of NaCl in water.480 = 25. Q.000. What is the effect of concentration of a salt solution during electrolysis? Ans. hydrogen and sodium hydroxide. The concentration of a salt solution has an effect on the product of electrolysis at the anode. atoms of electrode turn into ions. If the anode is a metal (Cu. Q.11.000 C.000. = 108. 9. or Ag). In a commercial cell the current is 30.75 kg. (b) Sodium is extracted by the electrolysis of a mixture of a molten NaCl and CaCl2. Mass of Na formed per hr. Cu(s) → Cu2+ (aq) + 2e. while the solution turns to NaOH. Electrolytic cell.480 108. (a) – + Cathode +ve ions Anode Positive ions gain electrons at the cathode (reduction) and turn into atoms –ve ions Negative ions lose electrons at the anode (oxidation) Electrolyte Fig.750 g 96. 9. Electrolysis of brine is used to manufacture chlorine.000 A. = = 108. What is the utility of electrolysis of brine? Ans.000 mol 96.224 ENGINEERING CHEMISTRY Otherwise oxygen is liberated from water. . In electrolysis of a dilute solution of NaCl increasing amounts of oxygen are liberated. 10. 11. (a) Draw a neat sketch of an electrolytic cell. Amount of Na formed per hr. Chlorine is liberated at the anode during electrolysis of a concentrated solution of NaCl.

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

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

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

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

420. [Ans.ELECTROCHEMISTRY 229 12. and its resistance was found to be 37.02 N of an electrolytic solution in a conductivity cell were found to be 310 ohms and 2. S(32) and O(16)].0 g of the anode solution (anolyte) was found to contain 0. the cathode solution contained 0.000275 mhos cm–1. Calculate the equivalent conductance of AgCl at infinite dilution.88 cm–1).519 g of AgNO3.9 ohm–1 cm2] The resistance of a cell filled with 0. current was passed for [Ans. [Ans. 41. Why does the equivalent conductivity of a NaCl solution increase with dilution? How can the electrolytic conductance be measured? 16. What is the percentage dissociation of acetic acid at this concentration? [Ans. Calculate the equivalent conductance (λv) of the solution at the same temperature. NH4NO3 and AgNO3 are 149. 15. 18.1 N KCl solution is 0. tAg + = 0. of Ag+ in AgNO3. Calculate the equivalent conductance of the given solution. respectively. 1. [Ans.4 ohms at 298 K. Calculate the equivalent and molar conductances of CuSO4 solution.18 ohm–1 cm –1] The resistance of a conductivity cell filled with 0. tCu +2 = 0.80% AgNO3 solution was electrolysed using Ag-electrodes. Discuss all types of conductometric titrations. In a voltameter connected in series.2 ohm–1 cm2] The equivalent conductance at infinite dilution of NH4Cl. The ionic conductances The equivalent conductance of 0. The cell was then washed out and filled with 0.382 × 10–2 S m 2 eq–1] –1 cm2 eq–1 . 42.1 (N) solution of NaCl is 210 ohm at 18°C. wt. The increase in the weight of cathode – was 0. Write short notes on : (i) Cell constant (ii) Absolute velocity of an ion (iii) Conductometric titration (iv) Kohlrausch’s extrapolation method of determining λv.6). 14. 1. A 2. [Ans. 83. 20. 144. The specific conductance of 0. A 0.000 ohms respectively at 298 K. Calculate the transport number of Cu+2 and SO 4 – ions [At.19%] During the electrolysis of CuSO4 solution.409 g Cu in 54.785] 4 25.5 ohms. tSO = = 0. 21.1 N KCl solution and 0. Calculate the equivalent conductance (λv) of the solution (cell constant = 0. tCu +2 = 0. 23. 13. = Cu(63. loss of Cu in the anode compartment was 0.74 × 10–4.0128 ohm –1 cm –1. what is the cell constant? [Ans.46] 2 mins.7 g solution.01 N acetic acid is 16.0 ohm–1 cm 2.02 M KCl solution at this temperature was 0. Specific conductivity of an 17. if the cell constant is 0.84 × 10–4 and 133. If the resistance of 50 cell containing this solution is 500 ohms. [Ans. [Ans.215] 24.215.098 (N) KCl was found to be 214. Find the transport no. 22. .0 ohm–1 cm 2] The resistances of 0. N KCl solution at 25°C is 0. After electrolysis 51.02 (N) KCl solution at 25°C is 225 ohms.058 g of Cu was deposited.878 cm–1. 99.138 cm –1] The resistance of 0. Define Kohlrausch’s law and discuss its applications. What is the transport no. 19. [Ans. of Cu+2 ion.84% CuSO4 solution was electrolysed using Pt cathode and Cu-anode.36 × 10–4 Sm2 eq–1 respectively. 4. 166.00277 ohm–1 cm–1.1 M of CuSO4 . A one amp. Also explain the nature of the graph between conductance and volume of titrant used.804 g. The specific conductance of 0. 0.30 ohm of H+ and CH3COO– ions at infinite dilution are 349 and 40 ohm –1 cm2 eq–1. After electrolysis.

And we get deflection in milliammeter. twice the Avogadro’s number of electrons is lost. Nernst called this tendency as “solution pressure”. atom of Fe+2. atom of Fe to 1 g. of the cell is obtained from the algebraic sum of the two electrode potentials.f.1 after sometime. atom of Sn+2. And for every g. mA NaCl salt bridge HCl Pt FeCl3 A Pt SnCl2 B HCl Fig. a cell is constructed of two electrodes and the e. 10. we get Sn+4 in the vessel B and Fe+2 in vessel A. By 230 .. If we make an arrangement as shown in Fig.1 Construction of a cell. Fe Fe+2 + Sn+4 +3. 55. of the cell. 10.e.85 g. Avogadro’s number of electrons are gained to get reduced For 1 g.f.Electrochemical Cells ELECTRODE POTENTIAL 10 Oxidation is a process where electrons are lost by a substance and reduction is a process where electrons are gained by a substance.m. As for example in the reaction: 2FeCl3 + SnCl2 2FeCl2 + SnCl4 +3 + Sn+2 i.m. 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. Reaction in vessel A : Reaction in vessel B : 2Fe+3 + 2e Sn+2 – 2e Fe+2 [reduction] Sn+4 [oxidation] 2Fe+3 + Sn+2 Fe+2 + Sn+4 [cell reaction] So. 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. 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.

metal rod becomes negatively charged. an electric cell is composed of two electrodes. But when one exceeds the other the metals get either positively or negatively charged. For example.2 Electrode potential. the metal rod accumulates electrons and as a result. So. On the contrary. in the case of Zn/Zn+2. And each electrode has a potential which is known as single electrode potential (∈). When “solution pressure” equalises “osmotic pressure” there is no net effect. At 25°C the equation comes to : ∈ = ∈° + = ∈° + 2. E = ∈1 + ∈2 Single Electrode Potential (∈) ∈ The electrode potential for an electrode reaction: M+n + ne M (metal) is given by Nernst equation ∈ = ∈° + metal. As for example. of the cell is algebraic sum of the ∈ two electrode potentials. the solution has a tendency to send M+n ions to the metal rod due to “osmotic pressure”. but in this case. 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. we call each of them as single electrode. Fig. the solution pressure Zn Cu exceeds osmotic pressure. Here also a electrical double layer is set up and electrode potential is established. R ⇒ Gas constant RT ln aM + n where ∈° is a constant dependent upon the nF n ⇒ Valency of metal T ⇒ Absolute temperature F ⇒ Faraday constant a ⇒ Activity of M+n. osmotic pressure exceeds solution pressure and Cu rod gets positively charged. Zn rod sends Zn+2 ions into + – – + the solution and gets negatively charged and attracts – + + – + – – + – + + – positive charges towards the rod and.341 × 298 log10 aM + n n × 96500 0. 10.F. And so is the case with Cu/Cu+2.303 × 8. an + – – + – + + – + – – + electrical double layer is set up and a potential is CuSO4 ZnSO4 established between the metal rod (Zn) and its ions (Zn+2).059 log10 aM + n n . E. The electrode potential is also established in the case of every electrode where electrical double layer is set up by exchange of electrons.ELECTROCHEMICAL CELLS 231 sending the ions. This established potential is called electrode potential.M. To consider the electrodes separately. as a result.

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

000 – – – – – – 0. 25°C Electrode F2. Au+++ Hg. electropositive H+ Pb++ Sn++ Zn++ Mg++ Na+ Li+ The e.798 0.799 0. Sn. of a cell CuSO4 (sol n ) Cu + (aCu = 1) = Standard reduction potential of Cu + std.m. the electrode potential of other metals are determined similarly and listed in table. Typical calculation of e. Zn++ Mg. = 0.1: Standard Electrode Potentials (Reduction).771 0.06 0.959 Pt.715 2. Fe++ Cu. Likewise. Sn++ Zn.f. F – Oxidants i.f.1) Example 1. Calculate the e.e.360 1.f. of the cell will be E° = ∈°H + ∈°Zn = ∈°Zn [Q ∈°Η = 0] The e. Ag+ Pt. electronegative 1 2 1 2 Electrode reaction (Reduction) F2 + e = F– + e = Cl– + + + + + 3e = Au 2e = 2Hg e = Ag e = Fe++ 2e = Cu 1 2 E°(Volts) 2.762 = 1.122 0.136 0. 10. H+ Cl– Cl2 Au+++ Hg2++ Ag+ Fe+++ Cu++ 1 2 O2 + 2H+ + 2e = H2O Au.268 0..m.e. (Table 10. oxidation potential of Zn.106.ELECTROCHEMICAL CELLS 233 Table. Liquid junction potential Daniel cell: Cell reaction is: Zn | ZnSO4(C1) || CuSO4(C2) | Cu Zn + Cu+2 E = ∈right – ∈left ° ∈right = ∈Cu + Zn+2 + Cu [when both are reduction potentials] RT [Cu +2 ] ln 2F [Cu] . Cu++ Calomel electrode (Pt) H2. Hg2++ Ag. and we get standard e.m. Fe+++. Na+ Li. This list with ∈° values are known as electrochemical series. O2. Pt. E° of the above constructed cell which is ∈°Zn.f of a cell is measured by potentiometer. of the cell Zn ZnSO4 (solution) (aZn +2 = 1) Sol.80 1. Li+ Pb++ Hg2Cl2 + e = Hg + Cl– + e= + + + + + + H2 2e = Pb 2e = Sn 2e = Zn 2e = Mg e = Na e = Li Reductants i. Cl2(g).344 0. 762 1. H+ Pb. Mg++ Na..344 + 0.m.f.23 1.m.866 2.

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. ln [Zn +2 ] 2F 2F RT [Cu +2 ] ln . .762) will displace Cu from its solution (∈°Cu = .785 volt.. These electrodes are known as redox electrodes. of the cell is obtained from the oxidation potential of anode and reduction potential of cathode.f. then e. 2.344) Likewise. 2F [Zn +2 ] 7 4 8 5 9 6 7 8 9 ∴ ° ° Ecell = (∈Cu − ∈Zn ) + Interpretation of the Electrochemical Series (Table 10. The higher electropositive metal i. 3. ln [Cu +2 ] − ∈°Zn + . The higher the standard electrode potential (reduction) of an element. Lower position in the table of an element indicates its higher tendency of ionisation. of the cell. For example – Zn(∈°Zn = – .234 or Likewise. the non-metals with the higher electronegativity displace the elements possessing lower electronegativity. E = Reduction potential of Cu + Oxidation potential of Fe. Any oxidised or reduced form of an element behaves so. a RT 0.059 [Ox] ln Ox = ∈° log 10 (for general purpose) Red–ox + nF aRed [Red] n Here also ∈° values are determined against standard hydrogen electrode. ∈left = ∈°Zn + = ∈°Cu + ENGINEERING CHEMISTRY RT − ln [Cu +2 ] 2F RT ln [Zn +2 ] 2F [Q [solid] = 1] [Q [solid] = 1] ° Ecell = ∈Cu + 4 5 6 RT RT . If a cell is constructed with the two elements as the electrodes then the e. higher is the electronegativity of that element.m.344 + 0.441 = 0.1) 1.m.e. = 0.f. possessing lower standard electrode potential (reduction) will displace the metal from the solution of its ions with a higher standard electrode potential (reduction) value. Let Fe and Cu are used as electrodes. Electrode potential (∈) is given by: Oxidant + ne Ox + ne ∈ = ∈°Red–ox + Reductant Red.

20 + 1. A Latimer diagram in a compact form explains a great deal of information and shows the relationships between the various species in a simple and lucid form.36 0.36 + 7H 2O Mn+2 + 4H2O 1 2 (Pt) Fe+2/Fe+2 Br2/Br– 1 (Pt) IO2–/ 2 I2 Br2 + e (Pt) MnO2/Mn+2 Tl+3/Tl+2 1 2 IO3– + 6H+ + 5e MnO2 + 4H+ 2e Tl+3 + 2e Tl+1 Cr2O72– + 14 H+ + MnO4– + 8H+ + 5e BrO3– + 6H+ + 5e Ce+4 1 2 Cl2/Cl– 2–/2Cr+3 Cl2 + e Cl– 6e 2Cr+3 Cr2O7 MnO4–/Mn+2 1 BrO2–/ 2 Br2 + 1.82 2.23 V 2 .52 + + + + 1. ∈° = + .15 0.69 1.52 V MnO2 + 4H+ + e Mn3+ + 2H2O.56 V MnO4 + e + + 2e 2+ + 2H O.ELECTROCHEMICAL CELLS 235 Table 10. Mn Mn ∈° = 1.25 + 1.54 Cr2+ V+2 1 2 H2 Sn+2 Cu+1 Fe(CN)64– MnO42– Fe+2 Br– Mn+2 + 2H2O 1I 2 2 Sn+4/Sn+2 Cu+2/Cu+1 [Fe(CN)6]2–/[Fe(CN)4]4– MnO4–/MnO42– 1 I /I– 2 2 1 2 +e I– + 0.77 + 1.00 + + + + 0.2: Normal potentials (∈°) of some redox system (Hydrogen scale) Electrode (Pt) Cr+2/Cr+2 (Pt) V + 2/V+2 (Pt) (Pt) (Pt) (Pt) (Pt) (Pt) 1 (Pt) H+/ 2 H2 Electrode reaction Cr2+ + e V+3 + e H+ + e Sn+4 + 2e Cu+2 + e Fe(CN)63– + e MnO4– + e Fe+3 + e 1 2 1 I 2 2 Electrode potential ∈°(volts) 0. We know that Mn exists in different oxidation states and in acidic medium preferably at zero pH. 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. ∈° = – 1.21 – 0.18 V +3 + e 2+.61 1.065 + 3H2O + 1. the different oxidation states are represented by the corresponding ∈° values as follows: Mn2+ + 2e + Mn. ∈° = 2.41 – 0.01 MnO4–/MnO2 Co+2/Co S2O42–/2SO42– 1 2 Ce+4/Ce+3 +e MnO4– + 4H+ + 3e MnO2 + 2H 2O CO+2 + e CO+2 S2O42– + 2e 2SO42– 1 2 Ce+2 Br2 + 3H2O F2/F– F2 + e F– + 2.95 V MnO42– + 4H+ + 2e MnO2 + 2 H2O.16 0.26 V MnO42– .65 The pair which occupies lower position in the table can oxidise the pair which occupies a higher position in the table.36 + 1.25 0.52 + 1.23 + 1. ∈° = .535 + 0. MnO2 + 4H Mn ∈° = 1.

70) = 1. a species will undergo comproportionation if the potential on the left is higher than that of the right species in the diagram. 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 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. A Latimer diagram helps us to derive the standard potentials of such non-adjacent couples.98 V portionation will be spontaneous. 2H2O2 → 2H2O + O2 ∆G° = – 2.70 V MnO4– + 8H+ + 5e Mn2+ + 4H2O.70 V ∆G°1 = – nF∈° = – 2F × (– . ∈° = 1. On the other hand.80 V .52 V – 1. in this case the comproportionation reaction Ag2+ + Ag = 2Ag+ will take place. On the other hand. ∈° = 1.76 = – 3.70 volt 1. adding them together and converting the sum back to ∈° for the non-adjacent couple dividing by – nF for the overall electron transfer.236 ENGINEERING CHEMISTRY MnO4– + 4H+ + 3e MnO2 + 2H2O. We know that ∆G° values corresponding to different steps can be added but the ∈° values cannot be so added. H2O etc. The couple such as MnO4–/MnO2 or MnO4–/Mn2+ or MnO2/Mn2+ etc. we can write n1∈°1→ 2 + n2 ∈°2 → 3 ∈°1 → 3 = n1 + n2 Besides calculating the ∈° values of non-adjacent couples. we know that H2O2 disproportionates into H2O and O2 under acidic conditions. are called skip couples and the corresponding potentials are called skip-step potentials.26 V 0.56 V 2. For example.76 V ∆G°2 = – nF∈° = – 2F × 1. MnO4– → MnO42– → MnO2 → Mn3+ → Mn2+ → Mn In this diagram. The species H+. A species will disproportionate into its neighbour species if the potential on the left is lower than that of the right species. are not included in the diagram. O 2 → H 2 O 2 −1 → H 2 O −2 0. H2O2 + 2H+ + 2e → 2H2O ∈°Red = 1. the oxidation states of Mn decrease gradually from left to right.95 V 1. Hence.52 F 0.12 F Since the process is accompanied by decrease in Gibbs free energy. Again ∆G° is related to ∈° as follows.18 V The feasibility of disproportionation of H2O2 can be predicted by considering the change in the ∈° values for the following reactions: Overall reaction: 2H2O2 → 2H2O + O2 (a) ∴ (b) ∴ Reduction: Oxidation: H2O2 → O2 + 2H+ + 2e ∈°Ox = – .76 volt 0. the Latimer diagram is also helpful in predicting whether a particular species will undergo disproportionation or comproportionation. ∆G° = – nF∈°.51 V The whole information can be summarised in the compact manner in a collinear diagram as follows. therefore dispro1.4 F Adding (a) and (b). Since the nF factor cancels in this way.

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

n∈° for the formation of H2O = – 2 × 1.23 = – 2. oxidation number of ‘O’ changes from 0 to –1. This is due to the fact that NO. HNO2 and HNO3 lie approximately on a straight line in the Frost diagram. the ∈° for the couple H2O2/H2O is equal to − 1. H2O2 and H2O are 0.76 volt. we get the required Frost diagram as follows.46 volt. – 1 and – 2. change in oxidation number = – 1.76 volt. 10.g. then no one species will be the exclusive product e.. NH4 3 2 2 adjacent species becomes approximately a straight line. Hence. This is in accordance with the Latimer diagram. 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 HNO2.23 V H2O 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.70 volt and n∈° corresponding to oxidation number of – 2 is – 2. when O changes to H2O its oxidation number changes from 0 to – 2 and in this case.46 – (– .. Therefore. ∴ ∈° = – 1 × .70 = – . respectively. The difference is.70) = – 1.76 V O2 H2O2 +1.g. When ‘O’ changes from O2 to H2O2. which is intermediate between – 3 and + 5 and its – position in the Frost diagram is lower than that of NO3 ion and NH4+ ion and so NH4NO3 + + NO – → N O + 2H O.46 volt. −1 +1 0 nΰ (V) O2 H2O2 Acidic –1 –2 H2O –2 –1 Oxidation number 0 Fig. When these values of n∈° are plotted against the corresponding oxidation numbers. let us consider the Latimer diagram.238 ENGINEERING CHEMISTRY other hand N2O has an oxidation state of +1.70 volt. . When the line joining three undergoes comproportionation. 0. Therefore. The change in oxidation number from H2O2 to H2O is –1. n = – 2.4 Frost diagram for the system O2 → O2–2 → 2O–2. therefore.70 V 1. The potential corresponding to reduction of H2O2 to H2O can be calculated as follows from the examination of the line it is obvious that at the point corresponding to – 1 oxidation number n∈° = – .76 = + 1. – 2.

Example.344 Zn [∈° = – 0.52 V] Cu+2 [∈° = 0. Find whether Cu+ disproportionate in aqueous solution into Cu+2 and Cu° i. E°cell = – ve. Sol. the reaction will not occur spontaneously.344] Zn + Cu+2 [E°Cu = – 1. Example.52 V The two half cell reactions are: Cu+ + e Cu+ Adding Cu+2 –e Cu+ + Cu+ Cu° [∈° = 0. Prediction of feasibility of a chemical reaction. Example.798] The two half cell reactions are: Since.762] Cu+2 [∈° = 0. 3.37 V] Since E°cell is positive. ∈° Cu +2 /Cu + = + 0. Prediction of an oxidation-reduction reaction. Prediction regarding liberation of hydrogen by a metal from a hydracid. Ag cannot displace H2 from HCl.15 V] Cu+2 + Cu° [E°cell = 0. Cu+ will disproportionate spontaneously in aqueous solution into and Cu°.ELECTROCHEMICAL CELLS 239 Highlights: Uses of standard potential (reduction) values: 1. a very interesting situation arises: . cell reaction is 2Cu+ Cu+2 + Cu°.15 V ∈° Cu + / Cu ° = 0.762 The two half cell reactions are: Zn+2 + 2e Cu – 2e Adding Zn+2 + Cu Since.798] H2 [∈°H+/H = 0. Zn+2 + Cu Zn + Cu+2 ∈° Zn +2 / Zn = – 0.106] So.. ∈°Cu +2 /Cu = 0.e. Predict whether the reaction will occur spontaneously or not. Ag will not displace hydrogen from HCl. Concentration Cell When a metal is dipped into two solutions of one of its salts of different concentrations. the E°cell value is negative.00 V] 2Ag+ + H2 [E°cell = – 0. given ∈° Ag+/Ag = 0. Cell reaction: 2Ag + 2H+ → 2Ag+ + H2 2Ag – 2e 2H+ + 2e Adding 2Ag + 2H+ 2 Ag+ [∈° = – 0.798. Given. 2.

So.059 C log 2 1 C1 [Q n = 1] Therefore. of such cell depends on the relative concentration and not on the absolute values. the observed e. e.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–. NH4NO3 ENGINEERING CHEMISTRY AgNO3(C2) [Concentrated] (C2 > C1) Ag or Ag | AgNO3(C1M) || AgNO3(C2M) | Ag Voltmeter e – NH4NO3 Salt bridge – + Electron flow Ag electrode Ag electrode Ag ® Ag + e – + Ag + e–® Ag + C1M Ag ions + C2 > C1 C2M Ag ions + Fig.f. the cell reaction is Half cell reaction (left) oxidation Half cell reaction (right) Total: Ag+ (C2) = Ag+ (C1) ∈°R = ∈°L and n = 1 E = 2.5 Concentration cell.240 Ag | AgNO3(C1) || AgNO3(C2) | Ag Ag AgNO3(C1) (Dilute) Salt bridge of satd. C1 The stronger solution acts as positive electrode.303 × 8. 10.m.303 So. E= 2. Imagine that current passes through the external wire as shown by the arrow.m. is 59 mV.138 × (298) RT C C log 2 = log 2 C1 C1 nF n × 96500 Ag – e +e Ag+(C2) Ag + (C1) Ag° 0. . If C2 = 10.

01 log 1 C1 So.9 = 0.01N) Saturated AgCl | Ag salt bridge e.788 = = 13. Another type of concentration cell is electrode concentration cell. of the cell is given by.05M) | Ag.788 = 0.f. If we want to determine the solubility of AgCl.33 C1 0.138 × 1013 .059 0..f. So. E= ∴ or or or log 0.m.788 V at 25°C.33 C1 = 2.9 = 0. The concentration of Ag+ in AgNO3 is 0.01 g.e.m.059 log 2 C1 n Here n = 1.059 0.059 log 0. of the cell is 0. Ag+ in AgCl can be calculated.045 log 1 C1 0. (ii) Solubility of AgI in water at 25°. Given e.05 × 0. The activity coefficient (f) is 0.m.059 0.m. Cell: Ag/AgI/ in 0. ion l–1 is (C2).045 = Antilog 13. 2 2H+ H2 (p2) Application of the Concentration Cells H2 cell.045 M The concentration of I– in KI is 0.045 0. Determination of solubility of sparingly-soluble salts. concentration of Ag+ in 0.f.05 (M) KI) | NH4NO3 | AgNO3(0. of the cell is: H2 (p1) – 2e 2H+ + 2e H2(p1) → H2(p2) RT p1 E = 2F ln p .f.05 × 0.01(N) AgNO3 solution is 0. Calculate (i) Solubility product of AgI. one such cell is: Pt | H2 (p1) | H+ | H2 (p2) | pt p1 and p2 are unequal pressures of H2 The cell reaction is: Oxidation: Reduction: Overall: e.ELECTROCHEMICAL CELLS 241 This type of concentration cell is known as electrolyte concentration cell. C1 i.045 C1 0.045 M Let C1 be the concentration of Ag+ in AgI solution. E= C 0. E= 0. of the following Saturated solution of KNO 3 Ag | Ag NO3 (0. Example 1. we are to measure e.9 each.

The pH of a solution can be determined with the help of a hydrogen electrode in that case.f. The platinum black surface exhibits a strong absorption power towards hydrogen gas.5 g l–1 = 1. When in use.732 × 10–9 mol l–1 = 9.5(N) || Hg2(NO3)2 (0.f. This is standard hydrogen electrode.059 0.059 log 10 = = n n 0.732 × 10–9 × 143. instead of 1(N) HCl and H2 gas at 1 atm passed over the platinum electrode.472 × 10 17 = 9.05) (N)/Hg or The e.059 0. 10. n 0. pressure. the metal surface remains in continuous contact with the hydrogen gas.138 × 10 13 of AgI = [Ag+] [I–] = 2. the platinum electrode is dipped into the solution whose pH is to be determined.105 × 10–15 mol l–1.059 0. as a result.059 0.m.029 = ∴ n= ≈ 2. E= where n is valency. only a part of the foil is immersed in 1(N) HCl. of this electrode has been arbitrarily assigned to be zero.029 C2 C1 INDICATOR ELECTRODES Hydrogen Electrode It consists of a small piece of platinum foil electroplated with platinum black.059 0.m. n C1 n 0.472 × 10–17 C1 = K sp 0. 1 H 2 ( g) 2 . The electrode will act as if it were an electrode of metallic hydrogen. of the above cell = 0.6 Hydrogen Electrode.396 × 10–6 gl–1 Determination of valency Hg || Hg2(NO3)2 0.045 ENGINEERING CHEMISTRY Solubility of AgI = − = 9. 2.5 log 2 = log We have.242 ∴ ∴ Ksp = 2. therefore.05 0. The e. over which hydrogen gas is passed.029 V C 0.105 × 10–15 × 0. The electrode reaction is H+(aq) + e H2-Gas HCl Fig. the remainder is surrounded by pure hydrogen gas at 1 atm.045 = 9.

059 – + H2 Trap H2 Sat.7 Determination of pH by Hydrogen Electrode. 10. ∈ = ∈° + RT [H 2 ]1/ 2 log F [H + ] (n = 1) 1 [H + ] ∈ = 0 – 0. To overcome this difficulty another electrode which is known as secondary reference electrode is used for determining standard electrode potential.ELECTROCHEMICAL CELLS 243 The electrode potential is given by.m.f. To determine pH of a solution the cell constructed with the calomel electrode will be: (Pt) H2 | H+ (a) || Normal calomel electrode (Fig.7). standard hydrogen electrode is used as reference. 10.059 log [H+] = 0. But there are some difficulties with hydrogen electrode. pressure of hydrogen and to make aH+ = 1 is very difficult. Maintaining 1 atm.f. the cell is: (Pt) H2 | H+(a = 1) || H+ (a = unknown) | H2(Pt) EObs = ∈ = 0.m. Reference Electrodes For determination of standard electrode potentials (∈°). KCl HgCl & KCl HgCl paste + H2 Salt bridge Hydrogen electrode Solution Calomel electrode Fig. . ∈ = ∈° + 0. Since electrode potential of standard hydrogen electrode is zero. The e. E of the cell is then determined potentiometrically. So. of the cell gives directly the electrode potential (∈) of the half cell.059 log A full cell is constructed by coupling the above half cell with a standard hydrogen electrode. the observed e. One of such electrodes is calomel electrode.059 pH ∴ pH = E Obs 0.059 pH at 25°C.

we have.1N) and over it there is a saturated solution of KCl with some crystals of KCl.8 Calomel Electrode.28 0. F The standard electrode potential (reduction) of calomel electrode For 1. The electrode reaction is: 1 Hg + Cl– ( aCl − ) Hg 2 Cl 2 (s) 2 The electrode potential ∈ is given by RT ln aCl − ( Q n = 1).059 Ag-AgCl Electrode The use of this reference electrode is very common.059 pH ∈ = ∈° + or pH = E Obs − 0. To determine pH of a solution. The potential of this electrode .28 + 0. The e. EObs = ∈ (calomel) – ∈ (H2 electrode) = ∈ (calomel) – 0.m. The bottom of the electrode is filled with mercury.f. The electrode consists of a silver wire.2422 V Any electrode whose standard potential is to be determined is connected to calomel electrode by means of KCl salt bridge. Mercury layer is covered with a paste of Hg2Cl2 (0.0(N) KCl = + 0.28 V Saturated KCl = + 0. KCl HgCl + Hg Hg Fig.244 ENGINEERING CHEMISTRY Calomel Electrode This electrode possesses certain advantages. The standard electrode potential of this electrode is determined against standard hydrogen electrode.059 log [H+] = 0. 10. coated electrolytically with silver chloride and is dipped into a solution KCl of definite strength. It can be prepared easily and can be used for a long time. of the set-up cell is determined potentiometrically from which the standard electrode potential of the electrode is calculated.

9).9 Glass Electrode. A platinum wire may be used in place of the Ag–AgCl electrode (Fig. ∈glass electrode = ∈° + = ∈° – RT ln [H + ] F 2.2224 V at 25° has been accurately determined against a standard hydrogen electrode. 10. 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.ELECTROCHEMICAL CELLS 245 Ag/AgCl(s) Cl– ( aCl − = 1) || HCl (a = 1). – Potentiometer + Pt wire or silver chloride coated silver wire Saturated calomel electrode Glass electrode 0. 10. The thick glass membrane serves as a solid electrode whose potential changes with pH of the solution with which it remains in contact. 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.10). 10. For good electrical contact the bulb contains a silver–silver chloride electrode immersed in a standard HCl solution. 10. Fig.10 Determination of pH by Glass Electrode.303 RT pH F = ∈° – 0.1 M HCl Solution of unknown pH [H = ?] Thin-walled glass bulb + Fig.059 pH at 25°. . The potential of the glass electrode varies linearly with pH (Fig. H2 (1 atm)/Pt ∈° = – 0.

the following is the cell reaction: At Copper plate: Cu+2 + 2e Cu 2H+ + 2e H2↑ At Zinc plate: Zn Zn+2 + 2e +2 + SO –2 ZnSO4 Zn 4 Total cell reaction: Zn + H2SO4 = ZnSO4 + H2 – Zn + Cu dil. E = K – 0.0592 pH ∆E i. pH and millivolt meters A linear relationship exists between the pH of a solution. • ∈° value of glass electrode can easily be determined by calibration using buffers of known pH.e.f.. H2SO4 Bubbles of H2 Fig. (a) Its rapid response.f. 10. • Glass electrode is the most extensively used electrode for pH determination. pH meter scales are calibrated in pH units and in millivolts (mV) and the appropriate scale and range is selected by a simple control. The advantages of glass electrode.m. The disadvantages of glass electrode.246 Highlights: ENGINEERING CHEMISTRY • e. • ∈° value is not zero in the case of a glass electrode.0592 ∆pH Thus a calibration in mV can be converted into pH units when divided by 0. however.059. (b) remains unaffected by the presence of oxidising and reducing agents. and the e. Since. ∈ = ∈° – 0. = – 0.059 pH • Glass electrode is virtually hydrogen electrode. at a given temperature. Polarisation When a simple cell drives a current.11 . In practice. of a cell (E) constructed of a reference electrode and an indicator electrode.m. of the cell comprising of glass electrode and calomel electrode gives the pH of the solution from the equation. Only lithium silica glasses enable pH measurements to be valid over practically the entire pH range. (a) Its fragility and (b) its inability in the presence of high concentrations of alkali.

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

we have – ∆G = nFE or ∆G = – nFE A battery is an electrochemical cell which is used as the source of direct current of a constant voltage. Battery Cells are devices where electric current is generated at the cost of some physicochemical processes going inside the cell. • The decomposition potential of CuSO4 is 1. So. Electrolysis of dil. Overvoltage Theoretical voltage required for the decomposition of an acid solution should be equal to the e.m. This difference between the theoretical voltage and actual applied voltage necessary for electrolysis is known as overvoltage. Battery Primary [The cell reaction is not reversible] Secondary [The cell reaction is not reversible] Flow [The reactants. is gradually increased. Highlights: • The decomposition potential is different for different electrolytes. H2SO4 with Ptelectrodes requires 1.m. products and electrolytes pass through the battery and during the passage electric current is generated at the expense of chemical reactions as in electrochemical cells] . where F = faraday and E = e.m. provided the process has been conducted reversibly at constant temperature and under a given pressure is equal to (the decreasing Gibbs free energy – ∆G). It is well known that any chemical reaction conducted reversibly can yield some external work and the useful work available from the process.7 V in place of 1.55 V with Zn-electrodes.m. if the applied e.5 V with Cu-electrodes and that of ZnSO4 is 2. But it is seen that the value of applied e.m. Because the thermodynamic principle is only applicable to reversible cells.f. Since electrical work is equal to nFE.23 V (theoretical value). is always higher than this theoretical value. At this stage.13 Decomposition Potential.f. 10. 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. electrolysis continues uninterrupted.f. When an e. In order to apply exact thermodynamic principles to cell reaction it is customary to distinguish between reversible and irresversible cells.248 ENGINEERING CHEMISTRY Current density Decomposition voltage Voltage Fig.f. Battery works on the above thermodynamic principle. of the cell so. of the reversible cell constructed with H2 (g) at 1 atm. a minimum voltage must always be applied to start the electrolysis process.f.

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

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

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

(–) (+) The cell ⇒ Ag/AgNO3 (0.0592 log [M + n ] n 0. ∈° for copper = + 0. .15 (M) Cu+2 solution.296 V when [Cu+2] = 0. ∈ = ∈° + = ∈° + ∴ ∈° = ∈ – 0.059 log 0. T = 298 K). a limited number of electrons can flow and cross the junction between the two types of semiconductors.0296 × (– 1. R = Right hand electrode and Reduction L = Left hand electrode undergoing oxidation) 2Ag – 2e 2Ag+ Zn+2 + 2Ag ∴ Ecell = ∈°Zn + Zn Zn + 2Ag+ FG H F = G ∈° H RT RT ln [Zn +2 ] − ∈° Ag + ln [ Ag + ]2 2F 2F RT ln [ Zn + 2 2F Ag + IJ FG K H I F ]J − G ∈° K H + RT ln [ Ag + F IJ K I ]J K = (– 0. SOLVED EXAMPLES Example 1. Calculate the standard potential of Cu+2/Cu if the electrode potential at 25° is 0.0592 log 0.3156 V.05398] V = 0.34998 V. Example 2. Calculate the voltage at 25°C of a cell formed by dipping silver in silver nitrate (0.798 + 0. K–1 mol–1. Sol.34 + 2.1 M) and zinc in zinc sulphate (0.2 M) and connecting them without liquid junction potential.15 2 × 96500 = 0. Due to this contact.303 × 8.0592 log [Cu +2 ] 2 0.303 × 8. Calculate the single electrode potential of copper metal in contact with 0.314 J.1) = – 1. Sol.34 V (R = 8.2) – (0.252 ENGINEERING CHEMISTRY semiconductor. Sol.522 V. ∈ = ∈° + RT ln [M + n ] nF 2.0296 log 0.314 × 298 log [Cu +2 ] 2 × 96500 = 0.8239)] V = [0. Example 3.015 2 = [0.762 + 0.296 – 0.2 M)/Zn The cell reaction ⇒ Zn+2 + 2e Zn (Ecell = ∈R – ∈L = ∈+ – ∈–.015 M.314 × 298 log 0.1 M) || ZnSO4 (0.34 + = 0.296 + 0.

given that ∈° Zn/Zn +2 = 0. Calculate the e.0296 × 2 = 1. Ecell would come out negative.8 V at 25°C.8 V.13 V at 25°C. respectively.8 V Ox i. of a Daniel cell at 25°C. ∈° = ∈° Zn / Zn +2 = 0. E°cell = ∈°right – ∈° left = (– 0.1 + 0. Example 4.P of Ag-electrode is higher than that of Zn-electrode. Here if Ag-electrode is made positive electrode (one half cell) and Zn-electrode is made (negative electrode) (the other half cell) then Ecell would become positive.1 volts.11 V.76 V Ox ∈° = ∈° Ag / Ag + = – 0.0592 0.001 = 1.24 V and ∈°Pb = – 0.R.e. So here S. Ag-electrode will form right hand half cell i.76 V and ∈° Ag/Ag + = 0.0296 log 100 = 1.1592 V. Sol. Write down its cell reaction. Calculate the e.e.1 + 0.ELECTROCHEMICAL CELLS 253 Highlights: • If after calculation of Ecell it comes negative. if Zn and Ag electrodes are dipped in respective solutions. Sketch the electrochemical cell and write down the cell reaction.76 V i. half cells are to be reversed to get positive value of Ecell. Example 5.e. ∈°Red = ∈° Ag + / Ag = 0. Cu = Zn/Zn+2 (a = 1)/Ag+ (a = 1)/Ag+ According to ‘2R’ convention reduction will take place at right hand electrode (cathode).m. ∈°Red = ∈Zn +2 / Zn = – 0...1 log [Q E° = ∈° – ∈° ] cell + – 2 0.m. Cell reaction: At anode: Ni – 2e Ni+2 (Ox) +2 + 2e At cathode: Pb Pb (Red) Ni + Pb+2 Ni+2 + Pb Example 6. • If we cannot make right choice during construction of a cell. Also find out the standard emf of the cell.f. when the concentrations of ZnSO4 and CuSO4 are 0.001 M and 0.13) – (– 0.24) = 0. The standard potential of cell is 1. We can write Ecell = (∈° − ∈° ) + + − = E°Cell + RT [Cu +2 ] ln nF [Zn +2 ] 0.1 M. So.. of the cell: Ni | Ni+2 1(M) || Pb+2 1(M) | Pb at 25°C. Cell reaction ⇒ At cathode: 2Ag+ + 2e At anode: Zn – 2e 2Ag+ + Zn+2 2Ag (Reduction) Zn+2 (Oxidation) 2Ag + Zn+2 . +ve electrode.f. Sol. but the table of ∈° values and the above procedure will help to calculate Ecell of any reversible cell. Given ∈°Ni = – 0. Sol.

765 V and S.f.0296 log = = 0. i. ∈° Zn +2 / Zn = – 0. Therefore.254 E°cell = ∈°Right – ∈°Left ENGINEERING CHEMISTRY = 0.e. at 298 K.76) = 1.0592 [Cu +2 ] log log − 2 [Zn] 2 [Cu] ∈° Cu +2 / Cu − ∈° Zn+2 / Zn = or 0...0592 [Zn +2 ] 0.∈° = 0. (Ox) for Zn electrode...0296 log . [Zn +2 ] [Cu] [Zn] [Cu +2 ] 0.0592 0.0296 V. S.0592 [Zn +2 ]/[Zn] log 2 [Cu +2 ]/[Cu] [Zn +2 ]/[Cu] [Cu +2 ]/[Zn] 1.337 V Half cell reactions Cell reaction: ∴ ∈°Cu +2 / Cu = 0. Two copper rods are placed in copper sulphate solution of concentration 0.102 = 0...P.∈° = 0. = 0.500 C.01 M separately in the form of a cell.316 J.765 V and ∈°Cu / Cu +2 = – 0... 2 0.8 – (– 0.0592 [Cu +2 ] = ∈° Cu +2 /Cu + log log 2 [Zn] 2 [Cu] 0. C 0.765 V F = 96..56 V.337 i. Example 7. Cell = Cu/Cu+2 (0.01 M) || Cu+2 (0.059 [Cu + ] log 2 [Cu] ∈Zn +2 / Zn = ∈° Zn +2 / Zn + ∈° Cu +2 / Cu = ∈°Cu +2 / Cu + At equilibrium.337 V Cell = Zn/Zn+2 || Cu+2 /Cu Cu+2 + 2e Cu . these two electrode potentials will be equal.1 M)/Cu Ecell = Ecell = data.337 – (– 0.E. here C2 = 0.01 log 10 Example 8.P.765) = 0.337 V Zn – 2e Zn + Cu+2 K= Zn+2 . Sol.1 0.E.1 M and 0. Calculate the equilibrium constant for Daniel cell at 25°C from the following R = 8.m.0592 [Zn +2 ] 0.765 V Zn+2 + Cu (E°cell = ∈°Red + ∈°OX) = 1. Write the scheme of the cell and calculate its e. ∈° Zn / Zn +2 = 0. ∈° Zn +2 / Zn + 0.1 M and C1 = 0.102 V. Sol. (Ox) for Cu electrode = – 0.01 M C1 n 0.0592 log 2 .e.0592 [ Zn +2 ] log 2 [ Zn ] 0..

∴ pH = Ecell = ∈Q/ H 2Q − ∈calomel or or 0.9.799 V.29 V at 298 K as measured against normal hydrogen electrode.3345 = 5.3 × 10 −17 = 8. Ecell = ∈°H – ∈H = 0 – (– 0.3 × 10–17.0592 pH = 0.697 × 1037. ∈Q/H2Q = 0.2415.6990 – 0. Ecalomel = 0. [Ag+] = = E cell 0.123 V at 25°C.0592 pH) = 0.2415 – 0.0592 pH) – 0.102 = 37.5757 Ag + Cl– AgCl(s).123 = (0.0296 log K ∴ log10 K = 1. of the combined cell was determined to be 0. = 0. Cell reaction Ag+ + e Ag + Cl– We have.798 ∈° = – 0.2223 E°cell = 0. Calculate the potential of an Ag-electrode in a solution that is saturated with AgI and has an iodide concentration of exactly unity.29 ≈ 4.3345 0.0592 Example 12. Example 9.2297 0. 8. ∈° Ag + /Ag = 0.123 + 0. The potential of a hydrogen gas electrode in a solution of an acid of unknown strength is 0.0592 0.2415 – 0. Ag AgCl(s) + e ∈° = 0.0592 pH K sp ∈° Ag + / Ag = + 0. Calculate Ksp of AgCl from the following data: pH = ∈°Ag–AgCl(s) = 0. Highlight: • The high value of K indicates the spontaneity of the reaction.f. 0.m. I 1 Example 10. which is coupled with standard calomel electrode. Sol.65 . Sol. – ∆G° = nFE° nFE° = – RT ln K .6990 = – 0.2223 Sol. The e.0592 Example 11. Sol. Calculate the pH of the solution.3 × 10–17 (M).6990.ELECTROCHEMICAL CELLS 255 = 0.0296 K = Antilog 37. Find out the pH of a solution in a quinhydrone half cell.798 at 25°C.2297 = 1. Ksp (AgI) = 8.

SHORT QUESTIONS AND ANSWERS Q. of a cell? Ans.0592 Here K = Ksp = Antilog 10.886 × 10–10 mol2 l–2.7246 = – 10 + 0. 2. What is a salt bridge? Ans.F. Q. e V Salt bridge 2– e SO4 Zn Cu ZnSO4 CuSO4 Zn → Zn+2 + 2e– Cu2+ + 2e → Cu Fig. What do you mean by electrode potential (E)? Ans. What are reduction and oxidation potentials? Ans. Q.2754 = 1. What is galvanic cell or voltaic cell? Ans. It connects (acts as a bridge) the solutions of the two half cells. It is a simple device of producing electrical energy by chemical reaction. Q. What do you mean by standard electrode potential (E°)? Ans. 5. . 6. 3.. 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.256 or or log K = – ENGINEERING CHEMISTRY nFE° 1 × 0.5757 =– = – 9. What is the E. It is a device used for converting electrical energy into chemical energy. Q. Q.g. 1. It is the electrode potential of a metal in contact with its ions when the concentration of ions is 1 M (1 molar). KNO3). 7. 10.. Such a cell is also known as electrochemical cell.g.M.16 (oxidation) (reduction) In the above cell Zn-electrode is anode and Cu-electrode is cathode.2754 2. 4. It is defined as the potential difference between the two terminals of the cell when no current is drawn from it. What is an electrolytic cell? Ans. Q. e. It is an inverted U-tube containing an electrolyte (e.303 RT 0. Daniel cell. KCl.

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

∈ = ∈°Redox + 0. What are reference electrodes? Ans.059 log [M n ] n (b) Second class ⇒ Metallic electrodes in contact with one of their not readily soluble salts and with the anion of this salt: M | MA(s).258 Q. a ⇒ activity of the ion in relation to which the electrode is selective. Ans. The best known of this type is glass electrode. What do you mean by potentiometry? ENGINEERING CHEMISTRY Ans. where. Q. Q. [A–n] = Conc. What is an indicating electrode? Ans. ∈ = ∈° M / M n+ + (c) Redox = Electrodes which are inert in contact with a redox couple in solution. A–n where. It is an electrode in balance with an redox couple. 13. Potentiometry is an electrochemical method of analysis based on measuring the potential difference (e.222 V).059 log a n where. the potential of which is given by Nernst equation.059 0. of cation in moles dm–3 + 0. 11.f. of the reduced form in moles dm–3. Red 0. ∈r ⇒ Constant potential linked to the choice of the reference electrode and the internal solution. And. one of which is an indicating electrode and the other is a reference electrode. Pt/Ox. 12. 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. Q.059 log [Ox]/[Red] n Pt ⇒ Platinum [Ox] = Conc.m. 0. 14. ∈ = ∈r + . The most widely used are saturated calomel electrodes (∈ = + 0. (d) Membrane type = Selective electrodes specific to certain ions.246 V) and the silver-silver chloride electrode (∈ = + 0. [Mn+] ⇒ conc. Give the hemistry the different indicating electrodes. of the oxidised form in moles dm–3 . These are the electrodes whose potential is constant and independent of the composition of the contacting solution. (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. ∈ = ∈° M / M n+ + n n where Ksp = solubility product of the salt which is not readily soluble. [Red] = Conc.) between two half cells.059 log K sp − K sp [ A − n ] And. of the anion in moles dm–3 . M ⇒ Metal MA(s) ⇒ the salt which is not readily soluble.

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

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

37 – + 0.ELECTROCHEMICAL CELLS 261 ∆G°(i) = – nFE° = – 2F (– 0. = 0.36) F = – 1. ∆G°I = – (+ 0. 26.19.42 F ∆G°II = – (+ 1. Mn) = – 0. 2 2 ∈° = + 0.30 – + 0. Mn) = – 1. ∆G°(iii) = ∆G°(i) + ∆G°(ii) = 0. ClO– → Cl–.77 Fe +2 –0.77 F Ans.42) F = – 0.19 Latimer diagram for Fe species. Ans.68 – + 0. 27. Mn) = 0. ∈° = + 1. Mn+2) = 1.11 F So ∆G°(iii) is the value for the reaction.95 V 3∈°(Mn+3.18 V. 10. ∆G° = – nFE° ∈° (ClO–/Cl–) = 1 Cl .51 V. 10. We have Adding the above two equations.44 Fe –0. ∈°(Mn+3.36 V ∈ Q.77) F = + 0. ClO– → +e – + 0. In alkaline solution (pH = 14) the Latimer diagram for chlorine is ClO4 ¾¾® ClO3 ¾¾® ClO2 ¾¾® ClO ¾¾® Cl2 ¾¾® Cl ? Calculate from the above diagram ∈° value for the reaction.04 V −n F −3F The Latimer diagram of the above system is Fig.88 F ∆G°(ii) = – nFE° = – F(0. 2 2 Adding total ∆G for the reaction = – 1.18 V ∈°(MnO2. Q.04 Fig.42 + 1.36 F ∆ G I + ∆ G II − 178 F .44) = 0. Fe+3 + 3e → Fe ∈° = ∆ G° + 0. Mn+3) = 0.89 V = − nF −2F 2∈° = – 2. Use the following data to draw a Frost diagram.85 V 4∈°(MnO2.11 F = = – 0. Fe +3 0.88 + (– 0. ∈º(Mn+2.36 – 1 +e Cl → Cl–. Mn) = – 1. 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.36 V.77) = – 0. ∈°(Mn+2.42 V. ∈ Ans.10 V .78 F From the relation.

Highlights: • Plot of n∈° vs n for Mn (n = oxidation state) such diagram are called Ebsworth diagram or Frost diagram. • A state is unstable with respect to disproportionation if it lies above the line connecting two adjacent oxidation states. • The steeper the line joining two points. ∈° = – 0. 28. Q.23 Ans. 10. Construct a Frost diagram from the Latimer diagram for Tl. so.34 V. • MnO2 is also a strong oxidizing agent—its slope to Mn+2 is greater than the slopes to higher oxidation states. the process is likely to be rapid. . Most species that reduce MnO4– should also reduce MnO2. here n = 1. • Mn+3 is likely to disproportionate to Mn+2 and MnO2.20 Frost diagram for Mn in acidic pH.. Tl +3 +1. • The point for Mn(VI) similarly suggests disproportionation to Mn(VII) and Mn(IV). Tl+1 → Tl0.e. • 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. Since both these products involve one electron transfer.34 V. the higher the potential of corresponding couple. in the three species. n∈° = – 0.25 Tl + –0.34 Tl +1.262 +6 +5 +4 +3 +2 nΰ(V) ENGINEERING CHEMISTRY Mn 6+ 7+ Mn Mn 5+ +1 0 –1 Mn –2 –3 Mn 2+ Mn° Mn 3+ 4+ 0 +1 +2 +3 +4 +5 Oxidation number +6 +7 Fig. The oxidation states of Tl are + 3. + 1 and 0. For the change of oxidation number from + 1 to 0 i.

6. (ii) significance of standard electrode potential. of a cell? What is a storage cell? Name some of its types. 15. 17. Describe the construction of a glass electrode. What is standard electrode potential? State the peculiarity of a concentration cell. What is a standard hydrogen electrode? What is its potential? What is overvoltage? What is the cause of overvoltage? Give the reason: the hydrogen overpotential falls with rising temperature. Tl+1 is the most stable oxidation state of Tl as the species lies lowest in the Frost diagram. 3. n∈° = 3 × 1. 2. 19.f. 10. . What are primary and secondary reference electrodes? Write a note on decomposition potential. Define the electrode potential. 7. Distinguish between electrolytic and electrochemical cells. Prove that ∈ox = – ∈red. 8. 18.ELECTROCHEMICAL CELLS 263 For the change of oxidation number from + 3 to 0 (Tl+3 → Tl0) ∈° value = + 1.m.23 V = + 3. Write notes on: (i) Weston standard cell. 5. 4. 12. Why is a voltmeter is not used for the measurement of e. Explain how the pH of a solution is determined using the glass electrode.23 V So. 13. 9.69 V. 11. 14. EXERCISES 1. What is a calomel electrode? Describe its construction: Why it is used as reference electrode in place of a standard hydrogen electrode? What is an electrochemical series? Why are standard potentials of Zn/Zn +2 and Cu/Cu+2 electrodes opposite in sign? Describe the construction and working of H2 – O2 fuel cell. for n = 3. 4 3 2 1 0 Tl +3 nΰ(V) Tl° –1 –2 –3 Tl +1 0 +1 Oxidation number +2 +3 Fig. 16.21 Frost diagram for Tl species. 10. Give the cell rotation for a concentration cell.

26. The e. The standard potential of the cell is 1.m.2812 V and E° for the quinhydrone electrode is 0.f. respectively.34 V and –0. The potential of the normal calomel electrode is 0.13 V).f of the following concentration cell: Ag/Ag+ (0. KCl(sol) (1. of voltaic cell: Fe | Fe+2 (aq) || Cu+2(aq) | Cu. 22. Also give the expression for their e. both at the same temperature.763 V (0. Explain the construction of Ni-Cd cell. 37. Describe the construction and working of Daniel cell. 28.0592 V] .337 and 0. 34. Give the single electrode potential of Znhalf cell. Derive an expression for electrode potential of an M/Mn+ electrode? 23. of the cell at 25°C Hg(l) | Hg2Cl2(s).1 V (1. Write down the electrode reactions and overall cell reactions for the following cells. (ii) AgCl(s). Calculate the e. 33. 24.264 20.m. Explain the construction and working of lead storage battery.44 V (– 1. Give the equilibrium constant for the reaction.f. Give the use of Ag-AgCl electrode. 2Cu+ Cu2+ + Cu 35.239 V) 38. 27. 30.44 V. Calculate E° at 25°C for cell: (Pt) H2/HCl (aq)/Cl2 (Pt). Ag 32. (iii) Fe+3/Fe+2 Pt. when the concentrations of ZnSO4 and CuSO4 are 0. (ii) Calculation of solubility product of AgCl. 21. What is fuel cell? Give detail of one such cells.001 M and 0. How is single electrode potential measured experimentally? ENGINEERING CHEMISTRY 31. Will a reaction take place if an Ag-bar is placed in a solution of FeSO4? Explain using the following data: ∈°Ag + / Ag = 0. Cl–/Ag.m.m. 6.799 V. 0. Calculate the pH of the solution. Zinc rod is dipped in 0. (iv) 2H+/H2(g) Pt. 39.212 V.f.6996 V. 29.m.530 V. Distinguish: (i) a reversible cell from an irreversible cell (ii) a galvanic cell from a concentration cell. if E°cell = + 0. of a Daniel cell at 25°C.1 M respectively. [Ans.5] [Ans.01 (M) ZnSO4 solution at 25°C. (0. What are reversible and irreversible cells? 25. The reaction H2 + Cl2 + 2H2O 2H2O + 2Cl– has an equilibrium constant K = 1046 at 25°C. Give the cell reaction of the following: (i) Zn+2/Zn. respectively.1 M) || Ag+ (1M) | Ag 40.8192 V) 36. (i) Zn | ZnSO4 || CuSO4/Cu (ii) (Pt) H 2 (1 atm) | HCl/AgCl(s). Describe the potentiometric methods for (i) Determination of pH of a solution.f. Given the electrode potentials of Cu and Fe are 0.78 V). Calculate the e. Calculate the e. What is Nernst equation? State its utility. The standard potentials of Cu/Cu +2 and Cu/Cu+ system are 0.0 N)| Quinhydrone | Pt is 0. and ∈°Fe +2 / Fe = 0.

5. When calomel electrode is connected to H2-electrode at 18°C. K = 1021] 1 I(s) 2 ∈° Fe +2 / Fe ⇒ 0. of the cell. Calculate the equilibrium constant of the reaction at 25°C.1 N HNO3 | HgNO3 (0.4] 46.m.f. H 2-electrode || O2-electrode] 45.16 × 10–7] . 43. 2 Fe+3 + Sn+2 2 Fe+2 + Sn+4 from ∈° values given in the Table 10. (i) 6.2. Calculate the pH of the solution. Calculate its (i) pH and (ii) H+ concentration. 5. (ii) 3.ELECTROCHEMICAL CELLS 265 41. Suggest a cell. ∈°Fe +3 / Fe ⇒ 0.f.5622 V. gives e. Fe+3 + I– from the ∈° (reduction) values Fe+2 + [Ans. E. [Ans. at 25°C in 0. [Ans.m. K = 166] 44. [Ans.5355 V. which is constructed by connnecting H2-electrode to normal calomel electrode.664 V.01) | Hg+ 42. [Ans.036 V ∈°I(s)/I – ⇒ 0. to calculate ionic product of water.44 V. Find the equilibrium constant of the reaction at 25°C. value ⇒ 0. 2] [Ans. Calculate the valency of mercurous ions with the help of the following cell: Hg | HgNO 3 (0.001 N) in 0.

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

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

Different systems behave in a similar fashion if they have same degrees of freedom. 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. 5. The Water System This system consists of three phases—ice. they are one-component systems with two phases (C = 1. It states that all the phases must be present under the identical conditions of temperature and pressure. From the phase diagram. 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. CaO (s) + CO2 ( g) Hence F = 2 – 3 + 2 = 1. 3. vapor and one-component H2O. the properties like melting point. the rule is inapplicable. The equilibrium system requires no information regarding its molecular nature or micro structure. we find that curve BO is the vapor pressure curve of ice which indicates that ice has a small but definite vapour pressure. P = 2. The rule considers only the number of phases and not their amounts present.268 Examples 1. the critical temperature of +374°C above which distinction between liquid and vapor vanishes. The nature or quantities of the components do not have any role. so it is of no value for systems which may attain equilibrium very slowly. OA is the vapour pressure curve of water. Phase rule is applicable to both physical and chemical equilibria. P = 2). Limitations of phase rule 1. 2. For both of these curves OA and OB. This rule can be applied only to systems that have attained equilibrium. P = 3. . P = 3. triple point can be found. Ice (s) C = 1. 3. Water (l) Vapor ( g) C = 1. also called the vaporisation curve. (c) For CaCO3 (s) C = 2.1. (a) Water(l) Vapor ( g) Hence F = 1 – 2 + 2 = 1. Advantages of phase rule ENGINEERING CHEMISTRY (b) For water at critical point Hence F = 1 – 3 + 2 = 0. The OA curve terminates at A. water. The point B has a natural limit of – 273°C. From Fig. 1. 11. 4. boiling point. hence if a trace amount of a phase is present and not taken into account. beyond which the two phases merge. 2.

OB and OC divides the whole region into three portions AOC. temperature as well as pressure is to be known because the degree of freedom F = 1 – 1 + 2 = 2..579 mm pressure and at this point C = 1.. because the three phases. In the phase diagram for sulfur (Fig. ice-water-vapour are in equilibrium. . BC is the similar curve of monoclinic sulfur and the point B is the transition point between the two allotropes of sulfur.0075 °C Temperature Fig. it is actually the melting point of ice i. if the temperature is fixed. The inclination of OC towards the pressure axis shows that melting point of ice is decreased by increasing pressure. P = 3. Sulfur system is another one-component system with a slight more complexity. 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. called the triple point. ice. BOC and AOB in which only one phase is present and so the system becomes bivariant and to locate any point in these areas. Hence F = 0 i. 11.e.e. The point of intersection of these two curves is point O.e..006 mm) at B. The curves OA. The dotted portion OD.. rhombic and monoclinic sulfur have same vapor pressure and co-exist with sulfur vapor. at this point neither temperature nor pressure can be altered without the disappearance of one of the three phases. AB is the vapor pressure curve of rhombic sulfur which is stable upto 95°C (0..PHASE RULE 269 C 218 atm A X Water Pressure Y 1 atm Ice 4. Sulfur System. Sulfur at low temperature is in the rhombic form and at high temperature in the monoclinic form. 0. At B. i.e. 11.1 The phase-diagram for water (not to scale).0098°C under 4. all other properties are also fixed. The curve OC represents the change of melting point of ice with pressure.e.2). The other two modifications are liquid sulfur and sulfur vapor. which is the continuation of the curve AO below 0°C is the vapor pressure curve of supercooled water below 0°C. This curve represents a metastable system. Since F = 1 there is only one degree of freedom i.579 mm D B O Water vapour 100 °C 374 °C Z .

CE and EF two phases co-exist and F = C – P + 2 = 1 – 2 + 2 = 1. pressure. Component (C): Component is defined as the smallest number of independently variable constituents in terms of which the composition of each phase can be expressed in the form of a chemical equation. 1288 atm) which is again a triple point where rhombic. These two lines meet at E (151°C.288 mm) SL G(115 °C. 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. CD. 0.” F=C–P+2 Phase (P): Phase is defined as any physically distinct portion of matter which is itself homogeneous and uniform in composition.270 F SR Pressure (not to scale – schematic) ENGINEERING CHEMISTRY E(151 °C. Hence. zero variant and three phases coexist. monoclinic and liquid sulfur co-exist in equilibrium. 11. BE. There are three stable and one unstable triple points and four phases co-exist nowhere in the curve in equilibrium. respectively. such as temperature. Degrees of freedom (F): It is the minimum number of independent variables of a system. concentration. the system is univariant and either temperature or specific volume determines the system completely. 0. B is actually the triple point. with pressure.04 mm) monoclinic sulfur melts and CD is the vapor pressure curve of liquid sulfur.03 mm) D C(120 °C. pressure and concentration. The lines BE and CE represent changes in transition temperature and melting point. 0.6 °C. . These metastable systems are represented by dotted curves.006 mm) B¢ A Temperature (not to scale – schematic) Fig.04 mm) Sv B(95.. BC.e. 1.e. At the triple point F = C – P + 2 = 1 – 3 + 2 = 0 i. i. 0.2 The sulphur system. 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. mechanically separable from other parts by definite boundary surfaces. Along the lines AB. Curve BG is the metastable vapor pressure curve of rhombic sulfur.. Again at C (120°C. which can completely define the equilibrium of a system.

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

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

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

then at 1130°C.274 A E P d+g Austenite d+L x B Aus tenit ENGINEERING CHEMISTRY Liquid D y e+ Liqu id 1600 1539 1500 1400 1300 1200 Temperature °C Liquid + Fe3C G (1.130°C) C H 1100 1000 900 800 700 600 500 I A2 L 0. On further addition of C. Cooling further leads to the decomposition of the eutectic mixture of cementite and finally at 723°C the residual austenite transforms to pearlite and at temperature below 723°C. Area BCGP represents austenite and liquid and finally PGKI represents δ-iron (i. For an iron-C alloy (cast iron) containing 3% C.088% to 2% C content is steel and C content above 2% represents cast iron. The Fe-C phase diagram shows the phases. The phase diagram indicates that upto 0.3% C by weight. freezing begins at 1270°C. a mixture of austenite and cementite. the mixture is austenite containing 2% C and liquid has eutectic composition. whereas 0. The transformation of one solid phase into another takes place at the critical temperatures indicated on the diagram. On further cooling.088% C is commercially pure iron. all the ledeburite is transformed into pearlite and cementite mixture.6 Equilibrium diagram for Fe-C system. AEB area represents δ-iron and liquid.4 0.0 Hypoeutectoid Hypereutectoid Cast iron Steels x Weight %C 6 6. Pure iron changes from δ to α form at a temperature of 910°C.3 5 0. Area DCH represents cementite and liquid.6 Fig.e.. 11.e.8 1. austenite) only. freezing point increases upto 6. Hence further removal of heat leads to total solidification of the liquid to ledeburite. . But with faster cooling rates metastable phases like martensite and bainite are formed which are not shown in the phase diagram. which are formed when the cooling rate is slow i. Above the liquidus there is only liquid phase whereas below the solidus there is only solid phase and between the two lines both phases are present.67% C content and it is called cementite. when equilibrium is attained. In the phase diagram.5 0. From the curve.0 4 4. austenite separates out from the liquid.0 2. 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 4.008% 0 Austenite + Ferrite A3 K Eutectoid (pearlite) Acm ite en st + tite Au en m Ce Austenite +Ledeburite +Cementite (723 °C) Cementite + Ledeburite M Eutectic (Ledeburite) A1 Pearlite + Cementite Cementite + Pearlite +Transformed Ledeburite Wrought iron N 3. the curve ABCD is the liquidus line and AEPGCH is the solidus line.025% Ferrite Pearlite + Ferrite 0.

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

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

(b) temperature and pressure (c) pressure and concentration 9. Define the following terms: phase. 3.4% Ag (b) 2. 2. EXERCISES State phase rule. degrees of freedom. 11. 1. 8. In the thermal decomposition of CaCO3(s) CaO(s) + CO2(g) the system is a (a) one component (b) two component (c) three component. Draw and explain the phase diagram of a binary alloy system with simple eutectic formation. component. 1. Draw and explain the phase diagram of ice-water-water vapor system and show the variation of melting-point of ice with pressures. Eutectic mixture has: (a) highest melting point. 6. the system is (a) univariant (b) trivariant (c) invariant. 74% Ag. What is triple point? 5. The composition of the eutectic mixture of Pb-Ag system is (a) 2. Condensed phase rule has two variables. What is “phase diagram”? Explain (a) triple point and (b) eutectic point with reference to phase diagram. Discuss the application of phase rule to sulfur system with special reference to triple points and metastable equilibrium.6% Pb. (i) For a two-component alloy system of Pb and Ag when P = 1. What are the merits and the limitation of phase rule? 10. 5.4 % Pb (c) 26% Pb.PHASE RULE 277 Ans. 9.6% Ag. (ii) As per condensed phase rule: For solid-liquid equilibrium of alloy. Write a brief note on: eutectic point. 2. 4. Condensed phase rule equation is: (a) F = C – P + 2 (b) F = C – P + 1 (c) F = C + P – 2. The maximum number of degrees of freedom for a two-component alloy system is (a) 3 (b) 1 (c) 2. What are meant by invariant and bivariant degrees of freedom? 12. (b) variable composition (c) lowest melting point. 7. Write down the limitations of phase rule. namely (a) temperature and concentration. . 97. 8. In the water system at triple point. degree of freedom according to phase has the highest value of F = C – P + 2 = 2 – 1 + 2 = 3. Heterogeneous mixture of CaCO3(s) CaO(s) + CO2(g) consists of (a) one phase (b) two phases (c) three phases 7. Number of components of the system Fe(s) + H2O(g) FeO(s) + H2(g) (a) two (b) three (c) four. Objective Type Questions MCQ Gibbs phase rule is: (a) F + P = C + 2 (b) F – C = P + 2 (c) P + C = F + 2. degrees of freedom reduces by one and F becomes F = C – P + 1 = 2 – 1 + 1 = 2. 97. 10. metastable state. 6. What is condensed phase rule? 4. practically no gas is present and hence at atmospheric condition the pressure remaining constant. 3.

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

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

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

12. Metal rods Arc A little KOH containing solvent (water) Cooling mixture (ice) A High voltage Rheostat Fig. The coarse particles which come in between the two rotating discs get teared to smaller colloidal particles. Pt etc. The trace of alkali stabilizes the colloidal solution and finally the solution is cooled by cooling mixture.2 Colloidal mill. Ag. Pb. Suspension Metallic disc Colloidal solution (discharge) Driving belt Fig. 12. which constitutes the dispersion phase.COLLOIDS 281 (ii) Bredig’s arc method or electro dispersion: (Figure 12.1) Colloidal solution of metals like Au. This coarse suspension is then passed through colloid-mill which mechanically grinds the coarse particles. (iii) Mechanical dispersion method: (Fig. The colloid-mill consists of two discs made of metal. The heat of the spark converts the ends of the metal rods to form vapours of metal which immediately condense to give metal colloids. Cu.2) this technique consists of finely pulverising the substances to be dispersed in the medium. when an electric arc is produced between the tips of two closely placed electrodes of these metals. An electric current is passed through water containing traces of alkali. 12. are obtained by this method. which are finally stabilized by addition of a suitable protective colloid.1 Bredig’s arc method. The clearance between the discs is very small that apparently determines the size of the colloidal particle. which rotates in opposite direction at a very high speed. .

The sol to be purified is taken in a parchment or cellophane bag. The following methods are commonly used for purification. So. but it is common that the peptizing agent which are most effective contains a common ion with the precipitate forming colloid. they become unstable. Fe(OH)3(s) Precipitate + Fe3+ → Fe(OH)3 .282 ENGINEERING CHEMISTRY (iv) Peptization: A freshly prepared precipitate such as AgCl. In certain sols such as Al2O3 hydrosol. the disperse phase is too small to be retained by cellophane and hence the system needs controlled heating whereby the particles grow bigger in size. can be converted into colloidal state by the addition of small amount of a foreign electrolyte solution. Al(OH)3 etc. Dispersion is also sometimes carried out by the use of an atomiser e. which is partly immersed in water or the dispersion medium. of AgNO3 AgCl(s) Precipitate + + Ag+ H+ → → AgCl . Thus. it is essential to purify these colloidal sols. animal membrane have pore sizes which allow the free passage of only the dissolved molecules or ions of a true solution but retains the bigger colloidal particles. The semipermeable membranes like cellophane parchment paper. Purification of Colloidal Solutions The colloidal solutions prepared by the above methods contain several impurities of electrolytes and other soluble substances. water Sol stand Fig. The solvent is renewed from time to time. The process is allowed to continue until most of the ions are eventually removed and the retained colloid gets stabilized. The foreign electrolyte is known as the peptizing agent and the process is called peptization. Fe(OH)3. would give rise to ferric oxide sol. 12.3 Dialysis. The crystalloids from the sol move out through the cellophane while some amount of water or solvent from outside may enter the bag. the process of separation of crystalloids from colloids by diffusion through the animal or vegetable membrane is called Dialysis.g. if shaken with a dilute solution of FeCl3. Ag+ (Sol/Colloid) Peptizing agent Peptizing agent (c) Al(OH)3 Precipitate Al(OH)3 . H+ (Colloid) Though there is no rule. Fe3+ (Colloid/Sol) Peptizing agent (b) Freshly precipitated AgCl can be peptized by shaking with a dilute aq sol. (a) Thus freshly precipitated Fe(OH)3. in the dispersion of a liquid in a gas. (i) Dialysis. Hence. ..

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

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

Proteins are least soluble in isoelectric point and hence coagulate at isoelectric point. organic sols move towards cathode. basic dyes etc. the particles approach each other to form aggregates and settle down. The precipitation of colloidal solution is called ‘coagulation’ or flocculation. the phenomenon is called cataphoresis. they lose their charge and coagulate there. pH of the medium will dictate the Endosmosis migration of the colloidal particle to any electrode. The colloidal sols of protein are either positively or negatively charged in acidic or alkaline solution and hence when electrolysed in a medium.COLLOIDS 285 – Microscope + Powerful beam of light Path is invisible Colloidal solution Path is visible True solution Electrophoresis Fig. 12.7). Fig. In a U-tube.7 Hence the pH of the dispersion medium at which the dispersed particles are neutral and hence they do not migrate when subjected to an electric field is called isoelectric point.6 Electrophoresis. (b) Electro-osmosis. As2S3 metallic sols. 12. when a potential gradient is applied the colloidal particles move towards oppositely charged electrode. When the negatively charged particles like CdS. (v) Electrical properties (a) Electrophoresis. . Positively charged particles are Fe(OH)3. When electric current is passed through a colloidal solution such that the dispersed + – phase is prevented from movement. 12. Fig. the dispersion medium begins to move in the electric field. This can be achieved by (i) Adding oppositely charged: Two oppositely charged colloidal solutions when mixed. Coagulation of Colloids Colloid particles are electrically charged. After reaching the electrode. The isoelectric point of protein depends on pH and ionic strength in the medium. Lyophilic and lyophobic colloid particles are either positively or negatively charged. This Diaphragm phenomenon is called electro-osmosis (Fig. so they repel each other and become stable. The speed of the colloidal particle under the potential gradient of 1 volt/cm is called electrophoretic mobility.5 Tyndall effect exhibited by a colloidal solution. When the charge is neutralised. mutual coagulation of the two sols takes place. (c) Isoelectric Point. 12. The movement of the colloidal particles in an electric field is called electrophoresis. containing a colloidal solution. Al(OH)3. (ii) Electrophoresis: In electrophoresis the electrically charged colloidal particles migrate towards the oppositely charged electrode and finally coagulate.

02 0. Lyophilic colloids are much more stable than the lyophobic colloids—since the former are extensively solvated.e.003 to 0. 4 4 Generally.0058 % gold) containing also 1 ml of 10 % NaCl solution to just prevent its coagulation. It is defined as “the minimum weight in mg of a protective colloid. greater is the coagulating power—this is known as Schulze-Hardy law.0053 to 0.1 to 0. The higher the valency of the ion.01 to 0. the solvent layer forms a protective envelope.1 to 0.005 to 0. Thus. the coagulating power of trivalent ion is 500–1000 times greater than bivalent ion which is 100-500 times greater than monovalent ion.015 0. Thus. which when added to one ml of standard gold sol (containing 0. These sols are very stable.. The smaller the gold number the greater is the protective power of lyophilic colloid. When a lyophilic colloid is added to a lyophobic colloid.07 . This protection is due to the formation of a protective thin layer surrounding the particles of the lyophobic colloid. The process by which lyophilic colloid protects the lyophobic sol is called protection and the lyophilic colloid is called the protective colloid. (ii) Solvation. by adding electrolytes the charges of the colloidal particles are neutralised and precipitated.40 0. (iii) Protective agents. Coagulating power of an ion increases with the increasing valency of the coagulating ion. Protective agents are added to some colloidal systems. if a little albumin (lyophilic colloid) is added to a gold sol (lyophobic sol). the coagulating power increases in the series Na+ < Ba+2 < Al3+ or Cl– < SO 2− < PO 3− . All the colloidal particles of a colloidal solution bear similar charges and hence they repel each other. (iv) Protective colloids. Protection of Colloid The stability of colloids can be achieved by any of the following: (i) Electrical charge. the former acts as protective colloid and prevents coagulation of the latter even against addition of high concentration of an electrolyte. the latter becomes more stable even to the action of electrolytes. Colloidal particles are surrounded by a layer of solvent molecules which resists the dispersed phases from forming large aggregates and coagulate. Thus. Table 12. which get adsorbed on the surface of the colloidal particles and by coating them prevents coagulation. through which the oppositely charged ion of the electrolyte cannot penetrate to neutralize the charge for coagulation.2 0.286 ENGINEERING CHEMISTRY (iii) Adding electrolytes: By addition of oppositely charged ion i.2 10 to 15 0. like NaCl. This mutual repulsion prevents them from coalescing and coagulating. Zsigmondy introduced the term ‘gold number’ to measure the protective power of lyophilic colloids. This is indicated by the change of colour from red to blue.3 Gold numbers Protective colloid Gelatin Casein Albumin Gum Starch Sodium oleate Haemoglobin Gold number 0.

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

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

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

6. 4. (d) Protective colloids. 15. (b) 10–4 to 10–7 cm . Ans. Since Al3+ possess highest positive valency. Q. The pH of the medium at which the dispersed colloidal particles are neutral and hence do not migrate when an electric field is applied to the colloidal solution. (b) Absorbed completely Light passing through a colloidal solution is (a) Reflected (c) Scattered. What are the different ways of protecting a colloidal solution from coagulation? State Schulze-Hardy rule and explain with an example. EXERCISES 1. Ca2+. and Al3+.290 ENGINEERING CHEMISTRY Ans. Smoke coming out from the chimneys of different factories is led to charged metallic plate—explain. 9. 10. the positive ions obtained are K+. State Schulze-Hardy law. See page 288. What are lyophilic and lyophobic sols? Explain the following: (a) Tyndall effect. Ans. Q. What do you mean by isoelectric point? Ans. See page 286. From the above three electrolytes. (b) Brownian movement. Q. Explain: Electrophoresis and Electro-osmosis. as per Schulze-Hardy rule. Ans. the colloidal particles will pass through the pores of the filter paper since the pore-size of ordinary filter paper is larger than the size of the colloidal particles. Q. 12. Explain how deltas are formed where rivers meet the sea. (c) Gold number 3. Mention some important applications of colloid chemistry to industries. Q. The sizes of the colloidal particles fall in the range (a) 10–2 to 10–4 cm (c) 2. See page 288. Ans. 14. See page 288. 8. See page 288. See page 279. As2S3 sol is a negatively-charged sol and it can be precipitated by positively charged ions of the added electrolyte. 13. OBJECTIVE QUESTIONS 1. 2. Ans. Why is alum used to remove impurities from water? Ans. Write a note on application of colloid chemistry in (i) pollution control and (ii) industries. 11. What happens when a sol is filtered through a filter paper? Ans. 5. Q. 10–7 to 10–9 cm. Q. Differentiate between lyophilic and lyophobic solutions. Q. If a sol is filtered through an ordinary filter paper. AlCl3 will be the most efficient electrolyte to ppt As2S3 sol.

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

Many transition metal salts are paramagnetic because of the presence of unpaired electrons in the partially-filled inner d-energy levels. All form a variety of complex ions. iron (Fe) and copper (Cu) provide many examples of the above-mentioned features. as metals or as compounds. In the d-block series from scandium (1s2 2s2 2p6 3s2 3p6 3d1 4s2) to zinc (1s2 2s2 2p6 3s2 3p6 3d10 4s2). 13.1 Main oxidation states of the elements Sc to Zn (first transition series). It is to be noted that Sc and Zn form ions in one oxidation state i. 292 Oxidation states . All form coloured compounds. +7 +6 +5 +4 +3 +3 +4 +3 +3 +2 +4 +3 +2 +3 +2 +2 +2 +1 Sc Ti V Cr Mn Fe Co Ni Cu Zn +2 13 • • • • • Fig. respectively. All act as catalysts. manganese (Mn). Scandium is excluded because it only produces compounds in the +3 state and it loses all its three outer electrons when it forms Sc+3 cation. They are stated below: All are metals with useful mechanical properties with high melting points. Zn on losing two electrons produces Zn+2 cation with an electron configuration (1s2 2s2 2p6 3s2 3p6 3d10) in which all the d-energy levels are full. the definition holds good for all the element excepting scandium and zinc. Zinc is excluded because all its compounds are in the +2 state.Transition Metal Chemistry TRANSITION METALS Transition metals are d-block elements having partially filled d-energy levels in one or more oxidation states. Transition metals have a number of common features. The chemistry of titanium (Ti). All form compounds in more than one oxidation states. + 3 and + 2.e. chromium (Cr). vanadium (V).. cobalt (Co).

it can be said. but responds to a test for a new ion [Fe(CN)6]–4 (ferrocyanide ion). like ferrocyanide ion. Cr+3. the lower the value of Kins. K+. viz. Fe+3 etc. The double salt is characterised by complete dissociation in solution and gives the reactions of all the ions formed by the salts in solutions. The postulates of his theory may be summarised as follows: • Metals possess two types of valencies: (i) Primary or principal or ionisable valencies (ii) Secondary or subsidiary or non-ionisable valencies. Another important double salt is Mohr’s salt. follows the law of mass action. Na+. The dissociation constant is called instability constant (Kins) and is a measure of stability of a complex.6H2O.    Kins = Complex ions [Ag(NH3)2]+ [Ag(CN)2]– [Cu(CN)4]–3 [Cd(CN)4]–2 Ag+ + 2NH3 Ag+ + 2CN– Cu+ + 4CN– Cd+2 + 4CN– [M + ] [L− ] [ML] Instability constant 6.0 × 10–28 1. K2SO4. A complex salt is different from a double salt in respect of its distinctive character even in solution.FeSO4. FeSO4 + 2KCN = Fe(CN)2 + K2SO4 Fe(CN)2 + 4KCN = K4[Fe(CN)6] The solution of K4[Fe(CN)6] does not respond to the tests for Fe+2 or CN– ions. . are quite stable in the solid state as well as in solution.TRANSITION METAL CHEMISTRY 293 Double Salts and Complex Salts A double salt is formed generally when molar proportions of a monovalent cation sulphate solution in water is mixed with trivalent cation sulphate solution in water and evaporated to remove excess water.Al2(SO4)3. The theory is known also as co-ordination theory. This ion remains intact even in solution K4 [Fe(CN)6] 4K+ + [Fe(CN)6]–4 and gives its distinctive reactions. Examples of complex salts [Ag(NH3)2]Cl      [Cu(NH3)4]SO4   K[Ag(CN)2] [Ag(NH3)2]++ + Cl– [Cu(NH3)4]++ + SO4 K+ + [Ag(CN)2]– Instability Constants of Complex Salts The dissociation of a complex ion. A complex salt K4[Fe(CN)6] is prepared by adding KCN solution of FeSO4 solution and boiling. Al+3 and SO4–2 ions.24H2O in solution gives the reactions of K+. So. where ‘X’ is monovalent cation. and the salt crystallises as X2SO4Y2(SO4)3. like NH4+. (NH4)2 SO4. like ionisation of weak electrolyte.0 × 10–21 5.24H2O which is the general formula of a common alum. the higher is the stability of the complex and vice versa. and ‘Y’ is trivalent cation as Al+3. A complex salt does not give all the ions of its constituents in solution.4 × 10–17 Werner’s Theory for Formation of Complex Compounds Werner put forward a theory for the formation of complex compounds. it loses its entity in solution. A double salt exists as a distinct entity only in the solid crystalline state. the complexions.8 × 10–8 1.

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

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

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

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

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

6H2O are [Cr(H2O)6]Cl3. Thus for [Co(NH3)4(NO2)2]NO3 two types of geometrical isomerisms may develop (Fig. [Cr(H2O)4.Cl. Cl Pt Cl (a) cis-form NH3 Cl Pt NH3 NH3 H3N (b) trans-form Cl Fig. Hydrate isomers are generated due to variation in number of water molecules in the co-ordination sphere. [Cr(H2O)5.2H2O Geometrical Isomerism Geometrical isomerism originates due to the different arrangements of the co-ordinated groups in space around the central atom in a definite geometrical pattern. propane-1.4 Diamine dichloro platinum [Pt(NH2)Cl2] exists in two isomeric forms (Fig. In six co-ordinated complexes the six groups are arranged about the central metal ion in a regular hexagonal pattern or at the six corners of an octahedron. Ligand Isomerism Some ligands themselves may exist as isomers and are so co-ordinated in the complexes. Cisform is known as cisplatin and is an anticancer drug.3-diamine (tn) also called trimethylene diamine have the structures: They form isomeric complexes as [Co(pn)2Cl2]Cl and [Co(tn)2Cl2]Cl Hydrate Isomerism Water molecule is a very effective co-ordinating agent and may replace NH3. and thus enters into the co-ordination sphere of a metal ion. Cl2 etc. 13. The number of possible isomers is different for these two spatial arrangements. 13.Cl].TRANSITION METAL CHEMISTRY 299 For example: (i) [Cr(NH3)6]3+ [Cr(SCN)6]3– and [Cr(NH3)4 (SCN)2]+ [Cr(NH3)2 (SCN)4]– are co-ordination isomers.Cl2].2-diamine (pn) and propane-1.H2O. Thus.4). 13. NH3 H3N Co H3N NH3 (a) cis-form NO2 H3N NH3 (b) trans-form NO2 O2 N Co NO2 NH3 NH3 Fig.Cl2. 13. (ii) [Co(en)3]3+ [Cr(C2O4)3]–3 and [Co(en)2(C2O4)]+ [Cr(en)(C2O4)2]– are co-ordination isomers. forming aquo-complex. For example: three isomers of CrCl3.5 .5).

. Valence Bond Theory This theory was developed by Pauling and deals with hybridisation of the complex. .7 Optically active arsenic compound with co-ordination number 4.6 – (–) H3C As H5C2 (a) C6H4COO S OOCH4C6 As S (b) CH3 C2H5 Mirror plane Fig.6 and 13. (iii) Molecular orbital theory and (iv) Ligand field theory. Ag+ + 2 N H3 → [Ag(NH3)2]+ • An orbital of the ligand containing an unshared electron pair overlaps the hybridised orbitals of the metal ion and this is regarded either as partial donation of the ligand electrons to the metal ion or a sharing of that pair of electrons between the metal ion and the ligand. (ii) Crystal field theory. 13.and 4-co-ordination complex compounds is shown in Fig. Theories of Bonding in Co-ordination Compounds There are four distinct approaches to the theoretical treatment of bonding in co-ordination compounds. the first two theories have been discussed. • Ligands are groups which can donate electron pairs to metal ions which appear as electron pair acceptors. The complex [Cr(en)2Cl2] with co-ordination number 6 exhibits optical isomerism.300 ENGINEERING CHEMISTRY Optical or Mirror Image Isomerism Optical isomerism of 6. 13. . Mirror plane en Cl Cr Cl en (a) Cl Cl en Cr en (b) Fig. • The empty orbitals of the metal ion hybridise to give an equal number of equivalent hybrid orbitals.7. These are: (i) Valence bond theory. In this context. 13. It depends on the following assumptions: • The central metal atom provides a number of empty orbitals that are equal to its coordination number for forming the covalent bonds with ligand orbitals. This overlapping results in a σ-bond or possibly a π-bond.

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

8 Tetrahedral shape of [Ni(NH3)4]2+ ion resulted from sp3 hybridisation. The formation of the complex is shown below: .. NH3 Ni H3N 2+ NH3 NH3 Fig. Example is [Ni(CN)4]–2. 13.302 ENGINEERING CHEMISTRY Tetrahedral Complex As is implied the tetrahedral complexes are sp3 hybridised. it is paramagnetic in nature and the tetrahedral structure is shown below in Fig. So four lone pairs are donated of four ammonia molecules. The co-ordination of nickel is four. 3d 4s ) (b) Electronic configuration of Ni in ground state 2+ 8 2 4s 4p sp3 (c) Electronic configuration of Ni in sp hybridised state (d) Electronic configuration of Ni in [Ni(NH3)4] 2+ 2+ 3 2+ ×× ×× ×× ×× NH3 NH3 NH3 NH3 sp hybridised orbitals are filled with paired electrons donated by four NH3 ligands 3 complex The shape of the molecule is tetrahedral. The formation of such complexes can be illustrated by the formation of tetramine nickel (II) sulphate complex. 13.8.. On the basis of VBT [Ni(NH3)4]2+ is formed as follows: 3d (a) Electronic configuration of Ni in ground state (. Atomic number of Ni is 26. [Ni(Co)4]0 are also the examples of tetrahedral complexes. [Zn(NH3)4]2+. Square Planar Complexes These are formed by dsp2 hybridisation. Complex cation is produced from Ni2+ ion.

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

e.4 Do dz2 dx2–y2 dxy dyz dzx (a) (b) (c) dxy dyz dzx Fig. under the influence of the approaching ligands the orbitals dx 2 − y2 and dz2 exist in the higher energy levels compared to dxy. there splitting power is weak. The energy difference between eg and t2g sets of orbitals is denoted by ∆o or 10Dq where ‘o’ indicates an octahedral arrangement of ligands around the central metal ion. there splitting power is high whereas the weak ligands can split the set of orbitals weakly i. This repulsion force raises the degenerate d-orbitals of the metal to a higher energy state as shown in Fig. Strong and Weak Ligands Strong ligands can split the five d-orbitals into t2g and eg sets strongly i. d y and dzx orbital called as t2g set of orbitals which are directed in space 2 along x. The separation of five dorbitals in the t2g and eg sets of different energy states is known as crystal field splitting. Hence. (a) The five degenerate d-orbitals in the isolated central metal ion. In the free metal ion all the five d-orbitals are degenerate (orbitals of same energy) as shown in Fig.10.6∆o as shown in Fig. dyz and dzx. so the resultant .. The following is the arrangement of ligands with the splitting power of increasing order. the electrons in these orbitals experience a greater force of repulsion exerted by the electrons of the ligands than that by the electrons of the dxy. ∆o is called crystal field stabilisation energy (CFSE). Strong ligands confer higher value of ∆o and weak ligands confer lower values to ∆o.. It can be shown that when an octahedral complex is formed the energy of the t2g set is decreased 0. C-donor > N-donor > O-donor > X-donor Examples of C-donor = CN– N-donor = NO2–.e. the d-electrons are repelled by lone pair of electrons of the ligands. y and z axes. 13.e. 13.e. 13. (b) Hypothetical degenerate d-orbitals at a higher energy level if all the ligands approach the metal ion at an equal distance from each of the d-orbitals. This order is known as spectrochemical series. When the six ligands approach the central metal atom along the axes they exert an electrostatic force of repulsion on the d-electrons of outermost shell i.. Since the lobes of dz2 and dx 2 − y2 orbitals called as eg set of orbitals fall directly at the path of the approaching ligands.10 (a).6 Do – 0. NH3 O-donor = H2O.10 (b) which is considered as a hypothetical state. ∆o when high.4∆o while that of eg set is increased by 0. • The strong ligands i. OH– X-donor = F– > Cl– > Br– > I– Distribution of d-electrons in t2g and eg sets of orbitals—low spin and high spin complexes.304 dz2 dx2–y2 Energy Increasing ENGINEERING CHEMISTRY eg Do or 10 Dq t2g + 0.. 13. (c) Crystal field splitting of d-orbitals into t2g and eg sets by electrostatic field of the six approaching ligands. force the electrons to form a pair in the lower t2g set of orbitals and thus the number of unpaired electrons is reduced.10 Crystal Field Splitting in an octahedral complex.

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

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

10. 5. 7. 7.87. Give an expression for Kins and state its significance. What are chelate compounds? Give examples. 17.93 Bµ respectively] EXERCISES 1. 3. 6.83. [Ans. 26. 20. 21. 6 and 7 unpaired electrons. 4.93 and 7. 8. Show the hybridisation of an octahedral complex.TRANSITION METAL CHEMISTRY 307 5. 18. Give one example of each type. Give IUPAC nomenclature of the following: (a) CoCl2. 11.92. 4.6NH3. 5. Draw the structures of the following: (a) Tetraaquo dihydro aluminium ion. 14. 1. 2. . (b) Pt(NH3)2Cl2.732 Bµ] Calculate the magnetic moment µ for 2. 16. Mention the types of isomerism found in complex compounds. State the postulates of crystal field theory. Cite some fields of application of ligands in our daily lives. 2. ( f ) [Cr(H2O)5 Cl]2+ ( g ) [Cr(H2O)4 Cl2]+ (h) [Cr(H2O)6]Cl3 (i) [Pt(NH3)4Cl2]Br2 ( j ) [Pt(NH3)4 Br2]Cl2 (k) [Co(NH 3)4Cl2]NO2 8. 19. 6. Give main postulates of Werner’s theory. Explain geometrical and optical isomerisms of octahedral complexes. 25. Calculate the magnetic moment µ for one unpaired electron. Give the state of hybridisation of a square planar complex. State the postulates of Werner’s co-ordination theory and discuss the structure of K4Fe(CN)6 on the basis of this theory. 3. 5. 24. [Ans. On the basis of this theory predict whether the complexes [CoF6]–3 and [Co(NH3)6]+3 are paramagnetic or diamagnetic.9. 6. 9. Discuss the geometrical as well as optical isomerism in complexes with co-ordination number 4 and 6. Give an example of bridging ligand complex. 3. (c) [Co(en)2Cl2]+ (d) (en)2Co II NH2 O2 Co (en)2 IV (e) [Fe(CN)6]–3. (b) Ammonium diamine tetrathiocyano chromate (III) (c) Triamine aquo dichloro cobalt (III) chloride (d) Sodium hexa nitrito cobaltate (III). 4. 13. Explain with example the valence bond theory regarding complex molecules. 22. 12. What is the main postulate of CFT? What do you mean by crystal field splitting of d-orbitals? What is CFSE? What is spectrochemical series? What are low spin and high spin complexes? What is the main outcome of CFT? Give some uses of ligands. What is a ligand? What is co-ordination number? Mention main drawback of co-ordination theory. 23. 15. What are inner metallic complexes? What do you mean by ambident ligands? Give examples of each: (a) Cationic complex (b) Anionic complex.

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

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

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

3).7H2O) Kisserite (MgSO4. The process of extraction though costly may not be impossible from these minerals. As for example. 14. which are described below.. Particularly. Metallurgy The process by which the metals are extracted from their respective ores is known as metallurgy. There are several processes of the concentration of ores. . As a matter of fact. This is effected in grinding and pulverising mills (Figs. Concentration of the ore 3. Concentration of the Ore Almost all ores are associated with gangue or matrix. the ore is enriched with the desired metallic compound. Jaw crusher. Sometimes. Before the proper extraction of the metal the ore is freed from gangue or matrix to get it in the concentrated form.6SiO2) Ores Generally all minerals cannot be considered important for extraction of metal from them. Calcination/Roasting 4. Chloropative Carnallite KCl. Gyratory crusher etc. bauxite is the ore for aluminium etc. AlF3 ) Willemite (ZnSiO2) Felspar (K2O. Purification Crushing and Grinding. An ore is naturally occurring substance or mineral from which the metal can be extracted economically. the minerals from which metals can be extracted easily and cheaply are known as ores. The main steps for the extraction of metals are generally as follows: 1. MgCl2 6H2O Halides (iv) Calcium (v) Magnesium (vi) Aluminium (i) Sodium (ii) Potassium Silicates (iii) Zinc (iv) Aluminium Cryolite (3NaF. This process of removal of gangue is known as the concentration of the ore. the concentration and further treatment of some ores demand their reduction of size into a very fine state of division.METALLURGY 311 (v) Magnesium (i) Sodium (ii) Potassium (iii) Silver IB (Conductive metal) Epsomite (MgSO4. This process of concentration of ore makes the extraction of the metal easier and cheaper. haematite is the ore of iron.2 and 14.H2O) Rocksalt (NaCl) Sylvine (KCl) Horn silver (AgCl) Fluoropalite (3CaF2 (3COCl2. Reduction 5. Crushing and grinding 2.Ca3(PO4)2 ) Ca3(PO4)2). The step provides breaking of big masses of rocks containing the ore into small lumps by conventional crushing and grinding with machines viz.Al2O3.Al2O3.6SiO2) Sodium silicate (Na2SiO3 ) Felspar (K2O. This is one of the crucial steps of concentration process.

(iii) Oil floatation process. Oils form a film over the sulphide ore. This process includes all methods of concentrations in which water in motion is used. Froth Stirrer Concentrated ore Air Fig. But the sand and soil are settled down. A foam is produced and floats along with the sulphide ore over the surface of water. 14. 14.4). Generally some xanthates are used with pine oils. as a rule. Therefore. The concentrated ore is collected from foam (Fig. Concentration of the Ore (i) Washing. Fig. they are attracted by sulphide ores. From the pulverised ore in stream of water the lighter particles float away with water and thus some gangues are removed. sulphide ores will float on the surface while silica and other materials will sink.312 Lumps (ore) ENGINEERING CHEMISTRY Crushed ore Stamp Crushed ore Pulverised ore Fig. The pulverised sulphide ore is taken in a tank and some pine oil and water are used. Here concentration of the pulverised ore is effected by taking the advantage of the difference in its behaviour towards oil or water. do not get wet as do silica and most oxides when treated with water. Sulphide ores. 14. Oils have just the opposite effect. (ii) Floatation. Air is made to bubble through a perforated pipe from the underneath of the tank. . 14.3 Pulverisation.4 Concentration of ore by oil floatation.2 Crushing.

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

then an acid flux like sand (SiO2) must be employed. 14. If the gangue is basic in character. Furnaces • Reverberatory furnace. Charge (Hopper) Chimney Hearth Ore Air Flame fuel Fig. basic flux is to be used viz. MgO) • Neutral (fluorspar) Fuels Almost all industries require a fuel.7 Muffle furnace. made of refractory materials. Large scale industries. 14. open hearth furnace (for steel manufacture) and electric furnace (for Phosphorus extraction). like metal extraction. need economy of fuel consumption. but by the hot gases produced in the fire place (Fig.6). . Fig. There are three kinds of fluxes: • Acidic (SiO2) • Basic (CaO. • The other furnaces are blast furnace (for iron extraction).314 ENGINEERING CHEMISTRY Selection of Flux The nature of flux to be used depends on the nature of gangue. It is a type of furnace consisting of an enclosed chamber. • Muffle furnace. magnesia etc. lime. 14. In this furnace.6 Reverberatory furnace.7). This is a special type of furnace much used in metallurgy. the material is heated not directly over fire. If it is acidic. 14. from which the fuel and its products of combustion cannot come in contact with the materials heated in it (Fig.

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

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

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

a mixture of aluminium powder and iron oxide in the ratio 3:1 by weight. . (a) Electrowinning at low temperature in solution in water (for example.318 ENGINEERING CHEMISTRY (i) Pyrometallurgy: It means reactions at high temperature often above 1000°C. when a violent reaction takes place producing molten iron at 2500°C. chromium and titanium extraction). electropositive metal (for example. Goldschmidt Thermit process is nowadays mostly used for welding rails and machine parts (Fig. Thermite. Al).. lead) MO + C → M + CO (c) Chemical reduction by a more reactive i. reactions at low temperature in solution in water. MnO2 or Cr2O3 and for the separation of molten metals. 14. Fig. Cr2O3 + 2Al → Al2O3 + 2Cr (Goldschmidt Thermit process) (ii) Hydrometallurgy: It means. (a) Electrolytic reduction at high temperatures of the fused salts especially halides (for example Na. using iron to displace copper from a solution of CuSO4) CuSO4 + Fe = Cu + FeSO4 ∆ ∆ Goldschmidt Thermit Process The metallic aluminium has a strong affinity for oxygen at 1000°C. is ignited in a crucible by a ribbon of magnesium. 2Al + Fe2O3 = Al2O3 + 2Fe + 199 kcal The liquid iron is dropped on the two pieces directly to the joint to be welded. 14.g.10 Goldschmidt Thermit process. which is utilised in Goldschmidt Thermit process or Aluminothermic process for the reduction of metallic oxides e.10). The combination of oxygen with aluminium at that temperature evolves much heat. Zn extraction for ZnSO4 solution). (b) Cementation using a displacement reaction (for example.e. iron. (b) Chemical reduction by coke at high temperatures (for example..

p. The impure metal is melted and a stream of air is purged through the bottom. The purification processes are: 1. The distillate i.p. When zinc together with cadmium distils over leaving behind lead (b. which is known as spelter.e. Impure metal Impurities Furnaces Fig. arsenic as impurities.9% of zinc is left in the retort. 14. as a result the metal melts and the molten metal flows down the sloping hearth leaving behind the infusible impurities on the top. 767°C) distils out and 99. At last the molten zone containing all the impurities Sl op ing he ar th Pure molten metal . Electro-refining 1.11). The volatile oxides escape and a non-volatile oxide forms a scum over the molten metal. molten mixture of zinc and cadmium is redistilled in another retort at a temperature slightly above 767°C when more volatile cadmium (b. The advantage is taken out of the fact that the impurities are more soluble in the molten metal than the solid metal and the molten metal on resolidification crystallises out as a pure metal.11 Refining of metal by Liquation. 1620°C) and iron (b. • Fractional distillation. • Liquation. which is removed with the help of a laddle. Thermal refining and 2. contains about 2% of lead and traces of iron.. The impurities are to be removed to get the pure form of metal. 14. 2800°C). • Zone refining (Fig. The impure metal containing infusible impurities is heated on the sloping hearth of a special type of furnace (Fig. The spelter is at first heated in a retort at a temperature slightly above the boiling point of zinc (920°C). This process of purification is employed effectively in some special cases. This small molten zone is gradually and slowly shifted to the other end of the rod by gradual shifting of the source of heat. 14.12). The actual process is: a narrow rod of impure metal is taken and a small portion of it at one end is almost melted by application of heat. The crude zinc. cadmium. An easily fusible metal such as tin or lead can be refined by this process.METALLURGY 319 Purification of the Metals Extracted Almost all metals obtained by reduction processes contain some impurities. Easily volatile metals can be removed with the help of fractional distillation. as a result of which the easily oxidisable impurities are converted to oxides. Thermal refining • Oxidation of impurities by air poling.p.

The impurities either remain in solution or are deposited down the anode. POWDER METALLURGY Powder metallurgy (Fig.320 ENGINEERING CHEMISTRY reach the other end. In this technique. The electrolyte used is an aqueous solution of a suitable salt. Molten zone Resolidified portion Source of heat Most impure zone to be cut out Fig. 2.13) is a technique or operation or process to produce metallic or alloy articles. 14.13 Electrolytic refining of copper. the metal powders or alloy constituents are compacted in a die with melting or no melting followed by sintering. During electrolysis. This deposit is known as anode mud. Sometimes some valuable metals are recovered from anode mud. and (v) Sintering (vi) Finishing operation.12 Zone refining. pure metal from the electrolyte gets deposited on the cathode and the equivalent amount of metal from the anode passes into the solution. A typical example of electrolytic refining is of copper (Fig. The simultaneous method of compacting and sintering is called pressure sintering. 14. Usually an electrolytic cell is set up using thin sheets of pure metal as the cathode and comparatively thick impure metal slag as anode. Electro-refining. The rod is allowed to cool and the impure zone is cut off and removed. . 14. 14. 15% CuSO4 solution in dil. This method is widely used. The article is made into the desired shape by powder metallurgy in the following steps: (i) Pulverisation of metallic powders (ii) Mixing and blending (iii) Compacting (iv) Pre-sintering.13). H2SO4 as electrolyte Impure Cu anode Pure Cu cathode Fig. The remaining portion of the rod consists of the pure metal.

∆ WO2 + 2H2 → W + 2H2O 2.14 Technique of powder metallurgy adopted in a die. Zn. (v) Sintering. Compacted pieces are heated to a temperature below and very close to the melting point of the metal in a furnace. (b) Atomisation: This method involves forcing molten metal through a nozzle or spinnerette in a stream of water or compressed air. and Pb. Zn. High pressure Guide pins ∆ Top moulding part (Male joint) Bottom moulding part (Female joint) Alloy ingredients Extraction pin Fig. By decomposition. Pb. This operation is required when a combination of metallic powders are used. It involves heating the green compact to a temperature below the sintering temperature. preferably in an atmosphere of hydrogen. This method is commonly employed for metals like Mg. Ni(CO)4 → Ni + 4CO↑ The metals are obtained in a state of fine powders in both cases. For pulverisation ball mills can be employed. (vi) Finshing operations. The solid in this stage is known as ‘green compact’. This method requires control of pressure and temperature and the oxidation of metal into an atmosphere of inert gas. (c) Chemical: 1. Lubricants may be added if necessary. (iv) Pre-Sintering. plating etc. Time and temperature of sintering depend upon the nature of the metal. The metal powder in right proportions is then taken in a die into the cavity (female joint) of accurate dimensions and then compressed (100–1000 N/m2) by the male joint of the die. to get accurate shape of the work pieces. Sn etc. By reduction. The sintered articles require operations like machinery. This step is essential for tungsten. Al. (ii) Mixing and blending. This step increases the strength of green compact as well as removes the lubricant if used. For pulverisation of metals techniques adopted are: (a) Mechanical: This method may be adopted in the case of Mg. Cd. whereby metal particles sinter to a coherent mass.METALLURGY 321 (i) Pulverisation of metallic powders. 14. when fine powder of metals are obtained. (iii) Compacting. They are uniformly mixed in right proportions.. .

322 ENGINEERING CHEMISTRY Uses In making: (i) Porous bearings . It melts at a very high temperature of 1675 °C. (v) 100% raw material is consumed with no loss. Advantages (i) Articles of any intricate shape can be produced with desired accuracy and smooth finish. the titanium (IV) chloride condenses as a liquid that can be purified by fractional distillation. But as the extraction process is difficult and expensive. The metal is being protected like aluminium by a thin oxide layer formed on the surface of the metal. (iii) Metals and non-metals can be mixed to give the desired property to the article as for example W and C can be mixed to produce W2C (tungsten carbide) for cutting tools. (i) Dies of desired precision are required which are very much expensive.. it is not widely used. (v) Clutches. . TiO2 + C + 2Cl2 → TiCl4 + CO2 In Kroll process. (ii) Clean and smooth operations. 3d2. Among the most abundant metals in the earth’s crust Titanium achieves the fourth place. The chloride of the metal is then allowed to react with molten sodium or magnesium at 800 K in an inert argon atmosphere. Titanium is an element of d-block in the periodic table and its electronic configuration is [Ar] . but only +4 oxidation state is common. (iii) Sewing machines (iv) Gears . breaks etc. Disadvantages SOME SPECIFIC EXAMPLES OF EXTRACTION OF METALS Titanium (Ti) Titanium is a very strong metal and has a density much less than that of steel. Titanium (IV) chloride is a colourless liquid produced as an intermediate in titanium extraction and is used in the manufacture of titanium (IV) oxide.. +3 and +4. it is heated with carbon in a steam of chlorine gas at about 1100 K. (ii) Tungsten filaments for electric bulbs . Extraction The ores of titanium used for extracting metal are rutile (TiO2) and ilmenite (FeTiO3). which limits the production of very very intricate articles. It can exhibit three oxidation states +2.4s2. After the purification of the ore. (ii) Ejection of the articles from the die is necessary. Smoke grenades produce dense clouds of titanium (IV) oxide due to rapid hydrolysis of titanium (IV) chloride. (iv) Articles with impregnated lubricants can be produced which would be self-lubricating for ever. the reaction is exothermic and so temperature rises.

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

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

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

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

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

Indicate its position in the periodic table. (c) Give some uses of titanium.328 ENGINEERING CHEMISTRY 22. Write notes on: (i) Nickel (ii) Manganese (iii) Cobalt 25. 23. Give an account of zirconium with special reference to its important ores and one method of extraction. (c) State some uses of uranium. (a) State the electronic configuration of titanium. (a) Write down some of the ores of uranium with chemical formula. (a) How is chromium extracted from Cr2O3? (b) Give some uses of chromium. (b) With a net flow chart represent the process of uranium metal extraction. 24. 26. (b) Describe the extraction procedure of titanium from its ore. .

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

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

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

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

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

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

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

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

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

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

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

CO2.8°C) it is suited for loading in containers. This product is stored as pressed cylindrical rods. It is very safe to handle under ordinary condition. and (d) non-reactive towards metals to form unstable compounds. Nitrocellulose or smokeless powder: It is prepared by treating purified cellulose with mixed acid. which in turn is made by condensation of formaldehyde with acetaldehyde. because of its objectionable character as it reacts with metals to form picrates which are dangerously sensitive. Consist of only one chemical compound such as: (i) Ammonium nitrate: It is a powerful explosive compound when once initiated by an external detonation impulse of sufficient magnitude and in sufficient amount. the nitrocellulose and the spent acid are centrifuged. It is used to prepare binary explosives. (c) violent-disruptive explosive. (b) nonhygroscopic. It is used for blasting of coal. TNT is widely used as shell-firing explosive and under-water explosions. water vapour and no smoke. igniters and primer assemblies for propellants etc. It is largely replaced by TNT. in the aspects like (a) being safe explosive for manufacture. 1. storage and transportation. It produces CO. N2. CH2OH CH2OH C CH2OH CH2OH CH2ONO2 CH2ONO2 C CH2ONO2 CH2ONO2 + 4HNO3 ¾¾® + 4H2O This explosive compound has become important since the First World War as powerful military explosive. Trinitrotoluene (TNT): This high explosive is prepared by nitration of toluene. It is a high explosive and used as self-filling explosives. Its comparative excellence has made it useful for military consumption. 22% HNO3 and 15% H2O. (iv) 2. . 4. So. The raw material toluene is derived from coal tar or synthetically from petroleum products. Single compound explosives. Other uses include blasting in shells. having an approximate composition of 63% H2SO4. (ii) Picric acid: Chemically picric acid is trinitrophenol. two universally available cheap raw materials. The acid is sent to mixing tanks for fortification and subsequent re-utilisation. 2. When nitration is complete. It is stabilized by adding a stabilizer like diphenyl amine which can react with the liberated acid. It is also used as an explosive salt to replace a portion of the nitroglycerine used previously. stable and cheap. It is readily prepared by the neutralisation of HNO3 with NH 3. (C) High explosives: This group consists of six types of compounds. Because of its low melting point (80.340 ENGINEERING CHEMISTRY This excess carbon and sulphur undergo slower reduction leading to more gaseous products 4K2CO3 +7S → K2SO4 + 2K2S2 + 4CO2↑ 4K2SO4 +7C → 2K2CO3 + 2K2S2 + 5CO2↑ This large volume of gaseous products is responsible for its explosive action. (iii) Pentaerythritol tetranitrate (PETN): It is obtained by the nitration of the irregular tetrahydric alcohol pentareythritol. 6. It cannot be stored near inflammable materials and contact with alloys of copper is to be avoided as it detonates. it is known as smokeless powder. The nitrocellulose so formed is dissolved in alcohol and ether and the solvent evaporated when it forms a jelly-like mass.

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

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

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

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

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

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

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

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

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

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

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

000 grains 7 × 10 4 ENGINEERING CHEMISTRY 1 grain 1 grain 1 = = 1 USA gallon 58. Due to the presence of hardness producing salts in hard water. • For sugar industry. The stains of iron salts also are undesirable on fabrics. the salts responsible for hardness create difficulties in sugar refining and crystallization of sugar and the sugar becomes deliquescent. For textile industry and dyeing industry. do not cook in hard water. Drinking of hard water is also problematic since it affects the digestive system and at the same time the possibility of deposition of calcium oxalate crystals in the urinary tract is alarming. hard water causes wastage of costly soap and also interferes with the coloration due to the staining of iron salts.43° Fr = 10 ppm = 0. Relation between various units of hardness 1 ppm = 1 mg/l = 0. When .000 grains 5. Taste of tea.3 mg/l = 0.07° Cl = 0. Hard water also hampers the economy by wastage of soap as it does not form good lather. It also creates sticky precipitates that deposit on bath tub. For washing and bathing. hard water creates difficulties. For cooking hard water creates similar difficulties by producing scum on the bottom of the vessels.07° Cl = 14. • Hard water is not suitable for preparing drug solutions in pharmaceutical industry. the salts present in the hard water gets saturated and are finally deposited in the areas where the flow is slow. • For steam generation in boilers. body. Pulses etc. since it does not form lather freely with soap. Sludge and Scale Formation in Boilers When hard water is used for boilers.6 × 10 4 = 0. hard water creates many problems like (i) scale formation.352 1 Fr. • The hydration of cement and final hardening of cement are affected by use of hard water in concrete making.3 ppm = 10 mg/l Disadvantages of Hard Water (a) In domestic uses. coffee becomes unpleasant. (b) In industrial uses.83 × 10 4 1 German degree of hardness = 1 grain 1 grain 1 = = 1 German grain 56.7° Cl.300 grains 5. until all the Ca/Mg salts get precipitated. (ii) corrosion. on continuous evaporation. Thus a lot of soap get wasted also. • Calcium and magnesium salts also interfere with the smooth and glossy finish of the papers in the paper industry. degree of hardness = 1 Clark = 1 USA degree of hardness = 1 part of hardness 10 5 parts of water 1 grain of hardness 1 = 1 gallon or 70. (iii) priming and foaming and (iv) caustic embrittlement. clothes etc. • In laundry. boiling point gets elevated and during cooking a lot of fuel is wasted. hard water causes the usual problem of deposition of insoluble salts that interfere with the proper dyeing and printing of the fabrics. Iron salts interfere with the colour of the paper.1° Fr = 14.1° Fr 1 mg/l 1° Cl 1° Fr = 1 ppm = 1.

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

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

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

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

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

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

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

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

WATER TREATMENT 361 Injector Cation exchanger gravel Pump Anion exchanger gravel Injector Waste Acid regenerator liquor Waste liquor Alkaline regenerator Fig. . 17. W ate r HO–H H–N–C H HOH – – C C–N–H C H–OH H C–N–H C OH C C H + SO4 –– H–N–C H H H H C O O C Na O O C ++ O Ca O C O + H–OH OH H C–N–H Cl – H–N–C C SO4 –– –– H C SO4 H C–N–H H–N–C –– C H H H SO4 H C C–N–H C H–Cl –1 H–N–C H C – SO4 Hard water Cation exchange reaction: 2R H + Ca – + +2 –– H + Anion exchange reaction: CaR2 + 2H + + RNH2 + H2O – – RNH3OH + – + – – RNH3OH + Cl RNH3Cl + OH Fig. 17.M .5 Demineralisation of water showing the ion exchanges. H + H Cation exchange + H C C C C Filter bed C C C C C C C C ONa+ Cl – + Anion exchange O C OH O C O Ca O C O O C O H HO C O HO + C C C C C C C C C C C Cl H + C Cl – H D.4 Demineralisation of water.

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

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

364

ENGINEERING CHEMISTRY

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

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

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

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

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365
Sea water – Sea water Sea water + Anode

Cathode

Negative ions Positive ions

Membrane

Membrane

Concentrated brine

Pure water

Concentrated brine

Fig. 17.6 Line diagram of electrodialysis.

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

Cation selective membrane

C

A

C

A

C

A

Anion selective membrane

Cathode

Anode

C Pure water outlet Concentrated sea water outlet

A

C

A

C

A

Fig. 17.7 Electrodialysis cell.

366

ENGINEERING CHEMISTRY

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

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

V × 35.5 × 10 6 ppm. 2500 × 1000

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

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367

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

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

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

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

(50 − V) × 10 6 ppm. 50 × 1000

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

OOC · CH2 OOC · CH2

CH2COO N¾CH2¾CH2¾N CH2COO

368

ENGINEERING CHEMISTRY

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

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

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

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

insoluble precipitate

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

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

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

Sol. Temporary hardness = 7.5 ×

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

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

136 × 200 ppm 100

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

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

ENGINEERING CHEMISTRY

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

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

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

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

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

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

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

100 = 171.4 ppm CaCO3 84

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

WATER TREATMENT

371

∴ Lime required = =

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

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

20 × 100 = 50 ppm CaCO3 40

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

HCO3– = 150 ppm = ∴ Lime requirement = =

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

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

Soda requirement

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

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

100 CaCO3 117 = 1.932 × 104 g CaCO3

Vol. of water =

Problem 8. 10 ml of 0.85

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

FG M IJ H 100 K

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

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

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

ENGINEERING CHEMISTRY

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

FG IJ H K

3

= 0.019 g CaCO3.

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

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

Calculate the temporary and permanent hardness in degree French.

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

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

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

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

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

374 Q. 11. Differentiate between sludge and scale.

ENGINEERING CHEMISTRY

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

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

FG M IJ MgSO H 1000 K

4

solution.

FG M IJ MgSO H 1000 K

solution contains =

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

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

WATER TREATMENT

375

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

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

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

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

5. Calgon is the trade name of (a) Sodium hexametaphosphate (b) Sodium zeolite (c) Calcium silicate. Temporary hardness of water can be removed by (a) Filtration (b) Boiling (c) Coagulation Permanent hardness of water is caused by (a) Calcium chloride (b) Magnesium sulfate (c) Both. 12. 8. How can the factors can be eliminated? Describe the process of water softening by permutit process. What do you mean by caustic embrittlement? What measures can be taken to control the caustic embrittlement? What factors are responsible for boiler corrosion. Pure water can be obtained by (a) Lime-soda process (b) Boiling (c) Demineralization. 20. 18. A sample of water containing NaCl is (a) Hard water (b) Soft water (c) Pure water. 3. 6. 17. Write a short note with a proper sketch diagram on “reverse osmosis” process for desalination of brackish water. 14.376 ENGINEERING CHEMISTRY OBJECTIVE TYPE QUESTIONS 1. 19. Correlate the various units of the hardness. 21. 13. . 4. 10. 9. Write down the disadvantages associated with using of hard water. 7. The most ideal disinfectant in water works is (a) Chlorine (b) Bleaching powder (c) Chloramine. Why treatment of water is essential? Write down the possible sources of water? Give reasons for why water becomes hard. 16. 15. 11. (a) MgSiO3 A semipermeable membrane allows the flow of (a) Solute molecules (ii) Solvent molecules (b) Both solute and solvent molecules. (a) What are scales? What are the ill-effects of scales? (b) How can scale formation be prevented by (i) Phosphate conditioning and (ii) Calgon conditioning? Distinguish between: (a) Purification and softening of water (b) Boiler scales and sludges (c) Internal and external treatment of water. 2. Brackish water can be purified by (a) Reverse osmosis method (b) Lime-soda process (c) Calgon treatment. The chemical that gets dissolved in high pressure boilers (b) CaCO3 (c) CaSO4. Hard water can be softened by passing through (a) Calgon (b) Sodium silicate (c) Ion exchange resin.

Write different methods of sterilization.7° Clark and 51° French] 3.4 grain. Express its hardness in °Clark and °French. 62. 6. [Ans.10 ppm] A sample of hard water has a hardness of 510 ppm. 25. [Ans. the following results are obtained: Volume of sample water = 100 cc. The bed on exhaustion required 500 litres of NaCl solution containing 15 g l–1 of NaCl on regeneration. 27. 35.75 ppm] . [Hints → 1 ppm = 0. 5. 128. In an experiment for the determination of hardness of a sample of water. Write short notes on break point chlorination. 15. 23. Calculate the hardness in ppm. What is desalination? Name the different methods involved in desalination? Describe any one in detail. H 50 K FG N IJ H SO required the back titre the unreacted Na CO H 50 K 2 4 2 3 = 10 cc.07 ppm. 1 g = 15. (c) Write short notes on aeration. 30.1° French] [Ans. [Ans. 24. [Ans. From these data calculate the hardness of water in grains per gallon. Calculate the hardness of the sample water. FG N IJ Na CO solution is added to it = 20 cc. 28. Express the content of calcium in ppm. What are the methods involved for determination of temporary and permanent hardness of water? PROBLEMS 1. Briefly discuss the process of softening of water by means of ion-exchange process.99 grain of CaCO3] CaSO4 = 28 mg l–1. How free chlorine in water can be estimated? Write down the method for determination of alkalinity of water. The hardness of 1. 26.07° Clark = 0. 29. Briefly describe the different steps involved in the treatment of water for domestic purpose. (a) What do you mean by carbonate and non-carbonate hardness of water? (b) State harmful effects of silica present in water.H2O) was obtained from a 250 ml of water sample. 200 ml of a sample of water required 5 ml of (N/20) sodium carbonate solution for complete precipitation of calcium ion (Ca2+) and calcium carbonate.00. Given.5 ppm] 4. Find the temporary and permanent hardness of the water sample. 120 ppm] Analysis of a sample of water revealed the content of dissolved salts in the following data: Mg(HCO3)2 = 22 mg l–1 MgCl2 = 30 mg l–1 CaCl2 = 85 mg l–1 [Ans. 31.110 of calcium oxalate (CaC2O4. A precipitate of 0. 2 3 2. 6. 64. Write down the requirements for drinking water.000 litres of a sample of hard water was completely removed by passing through a zeolite softener.WATER TREATMENT 377 22.

000 litres of water sample having calcium hardness = 450 mg l–1 as CaCO3. The cost of lime of 80% purity is Rs. .000 per metric ton. CaCl2 = 111 mg l–1.000 litres of water contain the following: ENGINEERING CHEMISTRY HCl = 7. Calculate the cost of lime and soda required for softening 1 million litres of a water sample containing.5 g of calcium carbonate per litre required 30 ml of EDTA solution. Lime = 3. Calculate the hardness of water.3 kg] 8.000 litres of water was completely removed by a zeolite softener.6 kg] mg l–1 as CaCO3. 9. 20 ml of calcium chloride solution. magnesium = 150 mg l–1 as CaCO3 and total alkalinity = 400 [lime = 1. containing 15 g l–1 of NaCl for regeneration. Calculate the amounts of lime and soda to be required for softening the water. The zeolite softener required 30 litres of NaCl solution. The total hardness of 1.11 kg soda = 10. MgCl2 = 9. CaSO4 = 68 mg l–1. [Ans. Mg(HCO3)2 = 73 mg l–1.25 mg l–1. 384.2 mg l–1. whose strength is equivalent of 1. Al2(SO4)3 = 34.00. [Ans.6 ppm] Calculate the lime and soda required to soften 10. NaCl = 29.3 mg l–1. 10. MgSO4 = 120 mg l–1.7 kg. Calculate the hardness of a water sample. whose 10 ml required 20 ml of EDTA. 200 per metric ton and that of soda of 90% purity is Rs.378 7. 12. Soda = 5. [200 ppm] 11. 1.5 mg l–1.

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

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

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

09 H + 587) kcal/kg [Q H = % of hydrogen] = (8490.8 H) kcal/kg.9 × 0.8 × 4. Example 2.3) Sol.7% H. 18. HCV = 1 3 + 2240 × 0. or 292.575% ∴ HCV = (8490.638 cal/g. 8080 × 90 + 34500 H − 100 8 = 7754.09 H + 587) kcal/kg = (8490. In the apparatus (Fig.9 H × L) cal/g = (12.8 + 345 H = 8490. LM N FG H IJ K OP Q Exhaust gases Rubber tubing Inner Cu coil Outer Cu coil Air Air Condensed steam Meter Water inlet Insulated container Gaseous or liquid fuel Fig. 18. calculate HCV and NCV.5 kcal/kg. On burning 0.2) known volume of gas is burnt at a uniform rate by a burner. (W + w) (t2 − t1 ) (385 + 3500) (29. Separate thermometers measure the incoming and outgoing water temperatures (t1 and t2) . . 18.8 H.8 kcal/kg.8 + 345 H = kcal/kg.5 + 0.5°C to 29.382 Sol.5 + 52.83 g of a solid fuel in a bomb calorimeter.5 + 52.8 + 345 H = 8490.2 H = 1335% ∴ H = 4.638 – 0.83 m = 12. ∴ 7754. respectively. ENGINEERING CHEMISTRY HCV = net calorific value + (0. It is used for measuring the calorific value of gaseous and liquid fuels (Fig.2 − 26.2°C. HCV = = 0.2).5 + 52. = 7754.7 × 587) cal/g = 12.8 H. Around the burner there is a chimney containing coils wherein water at a constant rate is passed. Boy’s Gas Calorimeter. If the fuel contains 0.601 cal/g. the temperature of 3500 g of water was increased from 26.575) = 8731.2 Boy’s gas calorimeter. water equivalent of calorimeter and latent heat of steam are 385 and 587 cal/g. NCV = (HCV – 0.5 + 52.

N2 = 1% and the remaining being CO2.46 × = 0.FUELS AND COMBUSTION 383 Let V = volume of gas burning. W = mass of cooling water used in time t. Wood contains lignocellulose—wood pulp mainly consists of α cellulose and a very small amount of β cellulose.2 m3 2 Volume of O2 required = 0. Wood is largely used as domestic fuel.1 × 2 = 0.23 m3 2 CH4 + 2O2 = CO2 + 2H2O Volume of O2 required = 0. C2 H2 = 2%. H = 6%. t1 and t2 = Incoming and outgoing water temperatures m = mass of steam condensed in time t.68 × 100 3 m = 3. resins and proteins. 21 SOLID FUELS Wood Wood is derived from trunks and branches of trees. its use as engineering fuel is restricted.23 + 0. W(t2 − t1) V Mass of H2O condensed per m3 of gas = m/v kg. . It contains about 15% moisture after airdrying. Calorific value varies from 4000 to 6400 Btu/lb.05 2 Total O2 required = (0. Calculate the volume of air required for complete combustion of 1 m3 of a gaseous fuel having the composition: CO = 46%.05) m3 = 0.2 × = 0. CH4 = 10%.4 × C2H2 + 2 1 O = 2CO2 + H2O 2 2 5 Volume of O2 required = 0.2 + 0. L = HCV. Let the gaseous fuel be 1 m3 CO + LM N m × 587 kcal V m × 587 kcal/m3. Sol. O = 43% and ash = 1%. Latent heat of steam per m3 of gas We get L = = ∴ NCV = L − Example 3.238 m3.68 m3 ∴ Volume of air required = 0.2 m3 H2 + 1 O 2 = H2O 2 1 = 0. V OP Q 1 O = CO2 2 2 1 Volume of O2 required = 0.2 + 0. H2 = 40%. The average composition of wood on moisturefree basis is C = 55%.

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

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

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

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

C.C.T. . Heat radiated from the roof to the coal bed Coal 0. one at the top for charging the coals and the other on one side for the entry of air and also for removal of coke. the coke is quenched by water and raked out through the side door. There are two main types of oven for the manufacturing of coke: (a) Beehive oven: It is a batch process and now obsolete.T.C.T. tar. • Yield of tar ⇒ The yield of L.5 m Door for air supply for coke discharging Fig. Heat is supplied by the burning of the volatile matter and hence no byproducts are recovered.2 show the amount and nature of various products. 18. on the other hand the quantity of gaseous products is greater in the case of H.T. • Nature of other products ⇒ The amount of ammonia formed greatly increases with the rise of temperature showing that nitrogenous complexes are broken at higher temperature. The yield of coke is 80% of the coal charged (Fig.T.C.) and low temperature carbonisation (L. The firebrick chambers are of 2 m height and 3. tars are darker in colour and more viscous than that of L.T.T. as the working temperature is less. The Tables 18.C.C. Coal forms a layer of 60–90 cm depth. = 400–600°C H.1 and 18. The expenditure due to fuel is also less in the case of L.5 m diameter and form the shape of a beehive. leaving the oven hot enough to start the next batch. Carbonisation proceeds from the top to bottom and completes in 2–3 days.T.T.C.C. indicates that the process of aromatisation is greater in the case of H.T. • Physical characteristics of tar ⇒ H.6 m 4m Coal charging door Refractory lining Zone of combustion 2.C.C.C. less costly steel retorts are used whereas in the case of H.C.T.T. The formation of lower amount of paraffin and alicycilc compounds and higher amounts of aromatic compounds in the case of H. tar per ton of coal is much greater than that of H.C. At the end of carbonisation.T.) at a glance: • Temperature ⇒ L. than that of H. 18.388 ENGINEERING CHEMISTRY Distinction between high temperature carbonisation (H. The hot exhaust gases are utilised to run waste heat boilers to increase the heat efficiency.. There are two openings. • Nature of tar ⇒ The liquid volatile products are larger in quantity in the case of L. tars.C.3).C.T. retorts made of fire bricks are used.3 Beehive coke oven.T.T. = 1000–1400°C • Economy ⇒ In L.C.

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

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

the crude oil is separated into fractions by distillation and the fractions obtained are subjected to simple purification procedures or complex treatments to yield different petroleum products.3). These are separated in a fractionating column consisting of a tall tower where the higher boiling fractions condense first. Coltrell’s process.6 Petroleum distillation. This distillation is a continuous process and the following fractions are obtained (Fig.5 Mining of crude oil and use of air-lift pump. 2.6) (Table 18. Petroleum distillation. Sulfur compounds have objectionable properties of pollution so they are removed prior to distillation as copper sulfide by treatment with copper oxide. 18. All these steps are under petroleum refining which include: 1. The water is separated from the oil by passing the emulsion through Coltrell’s electrostatic precipitator. water and natural gas. . 18. Condenser Refinery Straight run gasoline Crude tower Bubble tower Strippers Gasoline storage Refinery Cracked gasoline Crude petroleum Reforming Condenser furnace Cooler Refinery Solvent naphtha Gas oil reduced crude Refinery Kerosine oil Fig. Crude oil is intimately mixed with water forming an emulsion.FUELS AND COMBUSTION 391 Compressed air Oil Natural gas Natural gas Brine Fig. Removal of objectionable compounds. Refining: After removal of dirt. The crude oil is subjected to distillation to about 400°C temperature in an iron retort whereby all volatile components except the solid residue are distilled out. 3. 18.

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

The catalyst powder is retained and sent back. 40% of the charge is converted to gasoline and 2–4% carbon is formed. The gasoline is stripped off dissolved gases and purified. CH3 CH3   CH3—CH2— C — C = CH 2  CH 3 2CH3CH2CH = CH2 This cracking taking place at 475°C–530°C temperature leads to liquid phase thermal cracking. The use of catalyst during cracking accelerates the reactions and at the same time modifies the yield and the nature of product. The bottom liquid is reboiled and recycled to the fractionating column and ultimately gas oil is obtained having high octane value. zeolites in the form of beads or pellets. At the top of the tower a cyclone separator is active to separate the cracked oil vapour and passes it to the fractionating column. The preheated heavy oil is forced through tower along with the fluidised catalyst. 2. . which is reactivated by burning away the deposits with compressed air in a regenerator (Fig.FUELS AND COMBUSTION 393 CH3(CH2)8CH2 → CH3(CH2)4CH3 + CH3CH2CH = CH2 n-decane n-hexane butene-1 The olefins formed isomerizes and polymerizes. There are two main types of catalytic cracking: (a) Fixed-bed catalytic cracking: The catalysts are fixed in towers. When the cracking oil is vaporized and then cracked at 600°C–750°C at a low pressure. This carbon deposits on the catalyst beds. through which the hot oil (500°C) flows from the top and passes down. The products are separated by fractional distillation. it is called vapour phase thermal cracking. Cracked vapour Cooler Stabilizer Gases Catalyst Vapour Gasoline Heavy oil charge Heavy oil Heater Pre-heater (425°C – 450°C) Catalyst chamber (425°C – 450°C) Fractionating column Gasoline + some dissolved gases Fig. The products have better anti-knock properties. The carbon deposits on the catalysts are burnt by compressed air in one chamber for reactivation while the other catalyst chambers are active (Fig. The catalyst becomes deactivated by a deposition.7 Fixed-bed catalytic cracking. 18.7). 18. (b) Moving bed or fluidized bed catalytic cracking: The finely powdered catalyst behaves as a fluid when suspended in gas or oil vapour. Catalyst used are synthetic composition of silica and alumina. Catalytic Cracking. 18.8).

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

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

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

The crude oil is fractionated to get (i) gasoline (ii) middle oil and (iii) heavy oil which is recycled. which react with any hydrocarbon peroxide molecules formed in the engine cylinder thereby solving down the chain oxidation reaction and preventing knocking. ditertiary butyl peroxide and metal organic compounds.FUELS AND COMBUSTION 397 Knocking Octane Number. The paste is preheated and treated with H2 at 250–350 atm. it is assigned a cetane number 40. TEL functions by being converted to a cloud of finely divided lead oxide particles. tertiary butyl acetate. Hydrogen combines with coal to form saturated hydrocarbons. diethyl telluride. the rate of oxidation sometimes becomes so great that the unburnt fuel may burn rapidly with the formation of explosive violence. This is known as knocking. Maximum power is derived from gasoline when it burns silently and uniformly in an internal combustion engine. pressure and 450°C–500°C temperature. too much fuel accumulates in the cylinder and burn very rapidly and causes “diesel knock”.4-trimethyl pentane) in a mixture of n-heptane and iso-octane having the same knocking tendency compared to the sample of gasoline being tested. tin or molybdenum compound. Cetane Number There is a delay period between the injection of diesel fuel and its ignition.2.0–1. The unreacted coal is filtered-off and the liquid product distilled. 1.5 ml of TEL is added per litre of petrol. Due to presence of certain constituents in the gasoline. This delay period is connected to the type of hydrocarbons present in the diesel. The cetane number of diesel can be improved by adding amyl/butyl nitrate. The order is the reverse for gasoline anti-knock quality. Middle oil is hydrogenated in vapour phase with catalyst to yield more gasoline. The hydrocarbons present influence the knocking properties of gasoline which vary according to the series: straight chain paraffin > branched chain paraffin > olefin > cycloparaffin > aromatics. carbamates. Knocking results in loss of efficiency of the engine and also leads to its short life. 1. Yield of gasoline is 60% of the coal dust. The most effective antiknock agent added is tetraethyl lead (TEL) along with ethylene dibromide which prevents the deposition of lead by forming volatile lead halides. This delay period if becomes large. iso-octane has the best antiknocking properties and assigned an octane number of 100 whereas n-heptane has poor antiknocking property and assigned an octane number of zero. . Increasing delay period occurs in the series: n-paraffins < olefins < naphthenes < isoparaffins < aromatics. n-hexadecane is given cetane number 100 and α-methyl naphthalene given cetane number zero. but it is not yet competitive with petroleum refining. If a given fuel matches in quality with the blend having 40/60 blend of cetane and α-methyl naphthalene. Liquid Fuel from Coal and Coal Tar The conversion of coal into oil is essentially raising the H:C ratio. Other antiknocking agents are tetramethyl lead (TML). The anti-knock quality of a fuel is expressed as its octane number. Bergius-Pier Process: Destructive hydrogenation of coal in presence of a catalyst yields oil. Octane number is equal to the percentage by volume of iso-octane (2. Coal is ground and made into a paste with a heavy recycle oil and a catalyst like iron. The fuel which has same knocking tendency with the mixture having 80% iso-octance has octane number 80. which decompose at high temperature yielding low-boiling hydrocarbons.

so needs reforming before use (Fig. The purified gas is compressed to 5 to 25 atm.11). The process is based on the catalytic hydrogenation of carbon monoxide leading to the following reaction: nCO + (2n + 1)H2 → CnH2n+2 + H2O Paraffin nCO + 2nH2 → CnH2n → CnH2n + nH2O Olefin Water gas (CO + H2). 18.11 Fisher-Tropsch method. The gasoline contains straight chain hydrocarbons and hence have low octane number.398 Powdered coal Heavy oil Catalyst (Sn or Ni oleate) Paste H2 Gases Condenser ENGINEERING CHEMISTRY Gases Gasoline Middle oil H2 Gasoline Heavy oil Converter at 450°C and 200 – 250 atm Crude oil Fractionating column Fig. then passing over a mixture of Fe2O3. 8 parts magnesium and 200 parts keiselguhr. Catalyst (Co + Th + MgO + Keiselguhr) Fe 2 O 3 Fe 2 O 3 + Na 2 CO 3 Cooler Gasoline Cracking Water gas (CO + H 2 ) H2 Purification of gas Compressor (5–25 atm) Heavy Gasooil line Fractionating column Fig. . Fischer-Tropsch Process.10 Bergius process of hydrogenation of coal to gasoline. The gas is purified by passing over Fe2O3 to remove H2S. The exothermic reaction leads to the formation of straight-chain saturated and unsaturated hydrocarbons. 5 parts thorium. at 200°C–300°C passed through a converter containing catalyst which is a mixture of 100 parts cobalt. 18. 2. 18. which are cracked to yield more gasoline.Na2CO3 to remove organic sulfur compounds. The crude oil on fractionation yields (i) gasoline and (ii) heavy oil. produced by passing steam over heated coke is mixed with hydrogen.

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

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

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

402

ENGINEERING CHEMISTRY

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

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

Blast of air

Tar separator Cooler Purifier

Fig. 18.14 Manufacture of carburetted water gas.

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

FUELS AND COMBUSTION

403

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

Excess feed stock

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

Fig. 18.15

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

404

ENGINEERING CHEMISTRY

Filter

Stop cock

Water reservoir

Gases tube

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

Graduated Burette

Fused CaCl 2

Rubber tube

Fig. 18.16

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

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

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

FUELS AND COMBUSTION

405

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

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

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

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

Fixed carbon % Fixed carbon

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

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

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

406

ENGINEERING CHEMISTRY

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

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

FG N IJ H SO H 10 K
2

4

acid solution. To neutralise the

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

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

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

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

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

1 O2 = 2CO2 + 3H2O 2

7 = 0.385 2

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

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

1 O = CO2 2 2

1 = 0.03 2
m3

Total = 1.42 m3 Less = 0.02

Net need = 1.4 m3 (O2)

FUELS AND COMBUSTION

407

Volume of air required (when 40% excess)

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

...(i)

Composition of product of combustion on dry basis. CO2 =

L M N

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

3

= 8.782 m3

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

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

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

1 = 0.20 2 5 0.02 × = 0.05 2

Total O2 = 0.68 m3 required

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

FG H

100 m 3 = 3.238 m3. 21

IJ K

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

408 Q. 2. What is a fluidised bed?

ENGINEERING CHEMISTRY

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

FUELS AND COMBUSTION

409

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

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

Isooctane

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

¾C ¾ C ¾ C ¾
Branched chain

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

( ii )

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

D cat

CH 3

+ 4H 2

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

410 Q. 17. What is oil gas?

ENGINEERING CHEMISTRY

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

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

C8H18 → C6H6

HDA

FUELS AND COMBUSTION

411

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

412
Coal

ENGINEERING CHEMISTRY

Distillation zone Pyrolysis zone

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

Gas 120°

Gas 600°

Gasification zone

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

Combustion zone

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

Air and steam blast

Fig. 18.17 Showing gasification reactions involved in a gasifier.

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

FUELS AND COMBUSTION

413

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

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

Anthracite is a coal of (a) Highest calorific value (b) Lowest rank (c) High volatile matter. (c) Knocking properties. N. 9. 10. 7. S (c) C and H. 6. (c) Water gas. 12. (c) More than 100. Bomb calorimeter is used to measure (a) Calorific value (b) Carbon content ENGINEERING CHEMISTRY (c) Boy’s gas calorimeter. 13. H2O. Analysis of flue gases is done by: (a) Bomb calorimeter (b) Orsat’s apparatus Alcohol-blended petrol possesses (a) Better calorific value (b) Reduced antiknock properties (c) Better antiknock properties. . ash and volatile matter (b) C. Fuel gas used as a source of hydrogen is (a) Natural gas (b) Producer gas Isooctane has an octane rating of (a) Zero (b) 100 Better diesel fuel is determined by (a) Octane rating (b) Cetane number Producer gas is a mixture of (a) CO + H2 (b) CH4 + H2 Fuel for jet plane is (a) Aviation gasoline (b) Kerosene Natural gas is composed of: (a) n-butane (b) Methane Proximate analysis of fuel determines the percentage of (a) C. H. 15. (c) CO + N2 (c) Diesel. 8. 14. (c) C content. 11.414 5. (c) Isooctane.

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

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

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

Portland cement is made by mixing calcareous (lime-stone) and argilaceous materials in the proper ratios and heating to the point of incipient fusion in a kiln and grinding the resulting clinker.65 Fe2O3) should not be more than 1.65 Fe 2O 3 The Portland cement is a mixture of the following compounds: Compounds (i) Tricalcium aluminate (ii) Tricalcium silicate (iii) Dicalcium silicate (iv) Tetracalcium alumino ferrate Formula 3 CaO . This was the start of the Portland cement industry as we know it today.418 ENGINEERING CHEMISTRY These types of superconductors are used in superfast magnetically leviated (maglev) train i. Al2O3 . mortar and cement products. SiO2 or (CaO)3 . In 1824. Of these. A cement is a substance.02 and not less than 0. The tremendous application of these products is due to their: • Convenience • Cheapness • Adaptability • Strength • Durability Man had early discovered certain natural rocks.e. Cement was first used by the Egyptians in constructing the pyramids.8 SiO 2 + 1. The present day civilization very much depends upon lime.. He called this ‘Portland’ as concrete made from it resembled a famous building stone obtained from the Portland island near England. Portland cement is now manufactured on a large scale. tunnels.2 Al2O3 + 0. Joseph Aspdin. The Greek and Romans used volcanic tuff for cement and a number of these structures are still standing. superfast floating train. Al2O3 3 CaO .8 SiO2 + 1. The hard clinkers (Brick type) resulting from the burning of argilaceous limestone is known by the term Portland cement to distinguish it from natural or Pozzuolana and other cements. This is an example of application ceramic superconductor like YBa2Cu3O7–y. dams and roads etc.e. viz.02 0.66 ≤ 2. Al2O3 or (CaO)3 . The cement will set under water and therefore it is known by the name of Hydraulic cement. SiO2 (CaO2) . • Roman cement • Portland cement. patented an artificial cement made by the calcination of an argillaceous lime stone (argil-clay).. The rocks on calcination gave a product that hardened on the addition of water. The raw materials should be so proportioned as to produce a cement in which the ratio of the amount of CaO to the amount of (2. which sets to a hard mass in presence of water. reinforced-concrete walls and girders (a chief beam). an Englishman. SiO2 or 2CaO .2 Al 2 O 3 + 0. Fe2O3 Abbreviation C3A C3S C2S C4AF CEMENT . CaO ≤ 1. Two types of cements are in use. SiO2 (CaO)4Al2O3 . Fe2O3 or 4CaO .66 i.

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

Heat is provided by burning oil.04 lb per ton of rock suspended in 4 tons of water has given good results. the choice of refractory linning is difficult. But the wet process is now being adopted largely for new plants for more accurate control and mixing of the raw mixture. Dry process kilns may be as short as 150 ft. For a time it was gradually displaced by the dry process. Reactions at various temperatures in the kiln Temperature 100°C > 500°C > 900°C 900°C to 1200°C Reactions Evaporation of water (H2O↑) Al2O3 . 3Al2O3 2CaO + SiO2 → 2CaO . In this process. SiO2 2CaO + Al2O3 → 2CaO . The kilns are rotated at from 1/2 to 2 r. gas or pulverised coal. For this reason. sized and more finely ground in tube mills. depending on size.m. SiO2 3CaO + SiO2 → 2CaO . Frothing aids in separation of desired materials from the undesired ones.p. Al2O3 3CaO + Al2O3 → 3CaO . 80-160 lbs of fuel are necessary per barrel (376 lbs) of cement. This slurry is filtered in a continuous rotary filter and fed into the kiln. Manufacturing Procedure Two methods of manufacture are used: • Wet process • Dry process The wet process was the original one. Waste heat boilers are used to conserve heat.. In order to obtain greater heat economy. Al2O3 Heat change Endothermic Endothermic Endothermic U | V | W Exothermic (Contd.) . but in the wet process. The internal diameter is usually 8 to 15 ft. although Portland cement clinker itself is satisfactory for the purpose. 300-500 ft kilns are not uncommon. In the wet process. This dry powdered material (moisture content 2%) is fed directly to the kiln. taking from 2-3 hrs (Fig. The dry process is especially applicable to natural cement rock and to the mixtures of limestone and shale or slate.6). xH2O → Al2O3. The moisture content of the feed is 40%. the solid material after dry crushing is reduced to a fine state of division in wet tube or ball mills and passes as a slurry through the bowl classifiers or screens. unit operations are used for removing the part of the water from slurry by slurry filters. then dried. 19.420 ENGINEERING CHEMISTRY may be employed as the collector.. A concentration of 0. the materials are roughly crushed in jaw crushers followed by gyratory mills. The kilns are slightly inclined so that materials fed in at the upper end and travel slowly to the lower end. high alumina bricks and high magnesia bricks are widely used for the lining of the kiln. SiO2 .. using preheated air from cooling the clinker.SiO2 + xH2O CaCO3 → CaO + CO2↑ *5CaO + 3 Al2O3 → 5 CaO . The slurry is pumped to correcting tanks where rotating arms make the mixture homogeneous and allow the final adjustment in composition of raw materials to be made. The tendency in recent years has been to lengthen the rotary kiln in order to increase its thermal efficiency. Because the lining of kiln has to withstand severe abrasion and chemical attack at the high temperatures in the clinkering zone.

The clinker falls through openings in the stationary firing ring of the kiln into rotating coolers. called clinker.6 Wet process for cement manufacture. bagging Fig. Lime produced combines with main constituents of clay viz. 19. • Retarders such as gypsum • Plaster or calcium lignosulphate • Air entraining agents • Dispersing agents and • Waterproofing agents .92%. The analysis of typical samples of cement gives the following composition: Lime ⇒ 55.06%. Unchanged clay and sand ⇒ 2. Potash ⇒ 1.46%. During fine grinding the following materials are added to the finished cement. SiO2 ⇒ 22. Al2O3 and SiO2. which simultaneously preheat the combustion air.7%.75%. Endothermic Endothermic 1250°C – 1280°C > 1280°C Oversize Crushed shale limestone Mills Water Filtrate Filter Screen Correcting tank Slurry mixers Kiln Fuel Hot air Gypsum Air Clinker storage C o o le r Shale – 500 lbs Limestone – 2400 lbs Gypsum – 70 lbs Mills Per ton of cement Water – 750 gal Coal – 600 lb Power – 90 kwh Labour – 2.27%. CaSO4 ⇒ 1. MgO ⇒ 0. Pulverising followed by the fine grinding in tube ball mills and packaging complete the steps to the finished cement. The final product formed consists of hard grannular masses from 1/8 to 3/4 inches in size.SILICATE TECHNOLOGY 421 Commencement of liquid formation Further formation of liquid and compounds *Main reactions between lime and clay.1 man hr Storage. Al2O3 ⇒ 8% Fe2O3 ⇒ 5.13% Soda ⇒ 1.77%.

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

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

Opal. • Colour is produced by microscopic or larger practicles. 2. Properties of glass • Physical: (a) Transparent (usually) amorphous solid. 6.424 ENGINEERING CHEMISTRY • Colour is produced by colloidal particles precipitated within an originally colourless glass by heat treatment. 5. 3% B2O3 and the rest Al2O3. acids. Safety or laminated glass Two layers of glass with an interleaf of plastic. On long standing or very slow cooling during annealing some of metallic silicates crystallise out. Na2O . Sight glasses for the handling of uranium hexafluoride in separation of uranium isotopes are made of phosphate glass. Only attacked by HF readily. Selenium rods (SeO2) used in traffic lights. Fibre glass • Glass wool is impregnated with various binders and used for insulation. SiO2 + 6HF → 2NaF + SiF4 + 3H2O CaO . 4. translucent or ground glass (ghosa kanch) Soft glass made translucent by rubbing the surface with emery powder and turpentine. oxidising agents. Glass is then said to devitrify. wholly or partially displacing SiO2. Phosphate glass It contains P2O5 as a major ingredient. (b) Fe2O3: Inability to transmit UV is due to the presence of FeO or Fe2O3 in glass. It can resist HF. water. Functions of different constituents of glass (a) K2O: increases the softening point. Using iron free raw materials. (b) Vitrifies easily. (c) Hard and brittle (d) No fixed melting point (e) Bad conductor of heat and electricity ( f ) Can incorporate colour maintaining transparency • Chemical: (a) Not attacked by air. which attacks more slowly than others. • It can be spun into yarn. This glass has high chemical durability and is extremely stable to all acids except HF. glass capable of transmitting UV light could be manufactured. 3. Example is the precipitation of gold (colloidal) producing gold ruby glass. but devitrifies by formation of crystals under suitable conditions. When the glass is broken the fragments are held in place by inter layer. or sand and water. using HF. . High silica glass 96% SiO2. SiO2 + 6HF → CaF2 + SiF4 + 3H2O (b) Ordinary glass attacked by alkali solutions.

BaO. Certain colour producing oxides are used for producing coloured glass. Na2CO3..Al2O3 serves to lower the melting point of the glass and to retard devitrification. e.(R2O) and SiO2. • BaO as such or as precipitated BaCO3. potash. Chemical reactions of the formation of glass in a furnace Na2CO3 + a SiO2 → Na2O . Substances of basic character. (d) B2O3: increases the hardness or refractory characters of glass and lowers expansion coefficient. • Silica is used in the form of sand. Devitrification means slow crystallisation. • For decolourisation. PbO etc. 3. • H3PO4 is used as an opacifying agent.5SiO2. (CaO) are limestone and burnt lime from dolomite.g. The green colour due to ferrous silicate being changed to yellow colour due to ferric silicate.Al2O3. ZnO.1. • Boric acid as such or as B2O3. Other sources are salt cake and NaNO3. SnO2 etc. c SiO2 + SO2 + CO. • Soda. Cr2O3. • Cullet is crushed glass from imperfect articles. It facilitates melting and utilises waste. • In window glass molecular ratios are approximately 2Na2O. MnO2 is added to the charges which oxidises Fe+2 to Fe+3.CaO. 2.6SiO2. CuO for blue colour. • PbO in the form of Pb3O4.045%. lime.8SiO2. Substances of an acid character. Feldspars supply Na2O or K2O. The latter is useful in oxidising iron and accelerating the melting. b SiO2 + CO2 Na2SO4 + c SiO2 + C → Na2O . It may be as low as 10% of the charge or as high as 80% of the charge. Na2O is principally supplied by soda ash. Fe3O4 for green colour. Various decolourising and opacifying agents like MnO2. Cu2O for ruby or red colour. • ZnO is sometimes used to replace lime. CaCO3. It is almost pure quartz (white sand) of which iron content should not exceed 0. • Feldspars having the general formula R2O. • It should be noted that the ratios Na2O/SiO2 and CaO/SiO2 need not be 1:1 molecular ratios. . MgO. like SiO2. a SiO2 + CO2 CaCO3 + b SiO2 → CaO . B2O3. • Potash is always used in the form of K2CO3. Raw materials The raw materials employed in the manufacture of glass can be classified under three heads: 1. MgCO3. nitre. • The compounds may be of the type Na2O. Pb3O4. Zn-compounds. • The important sources for lime. MnO2 for violet colour etc. The latter introducing MgO into the batch.SILICATE TECHNOLOGY 425 (c) PbO: increases the refractive index of glass. like soda.

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

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

Flint (Pure SiO2 + CaCO3) 4. Porcelain. It is used for sewer pipes. SiO2. (2) feldspar. tiles etc. (3) sand. Feldspar. Raw materials. CaCO3. the unglazed product is to be made. cryolite. Quartz (SiO2). Common fluxing agents. It is used for making jars suitable for storing acids. fluorspar. K2O = 6%. The raw materials for unglazed product 1. and heated at higher temperature for longer time. ZnO2. It is glazed with salt. Stoneware.. Marble (CaCO3) 6. CaO. It is not always white because the ingredients contain Fe2O3.2SiO 2 . Ball clay 3. It is a sort of glass. borax etc. It is made from Borax. crucibles. TiO2. The three main raw materials are: (1) clay (kaolinite). The thin coating melts and forms a glaze on the surface of the body. Cornish stone (Potash feldspar.2SiO 2 ¬¾¾¾ g -3Al 2 O 3 Mullite 1400°C 1000°C ®¾¾ + 900°C Silicate Crystal line formation (amorphous) 6SiO 2 Porcelain is used for making– (i) dinner and tea sets. The glazed product is obtained by applying glaze on the unglazed body. Raw materials for glaze Frit. Al2O3 = 18%. Quartz etc. boric acid. The reactions of porcelain formation are: 3Al 2 O 3 .428 Pottery: (articles made of clay) Pottery ENGINEERING CHEMISTRY Non-porous (1) China and Porcelain (2) Earthenware (3) Stoneware Porous (4) Unglazed pottery (3) Terracotta. (iii) electrical insulators. . are: In all cases. CaO = 1%. Common refractory materials. K2CO3. For glazing the shaped material is covered with a coating of mixture of powdered feldspar. Chemical stoneware. Na2CO3. iron oxides. bricks. This is a kind of porcelain. China clay 2. Borax. SiO2 = 75%) 5.2H 2 O ¾¾® 6H 2 O ­ + 3Al 2 O 3 China clay 600°C (amorphous) + 6SiO 2 (amorphous) (Crystal) SiO 2 ¬¾¾ 4SiO 2 + 3Al 2 O 3 . floor and wall tiles. therefore is looked upon as partly glass and partly stoneware. (iv) high class sanitary goods. Both glazed and unglazed clay products are manufactured. (ii) basin.

This improves the plasticity of the clay mixture because of uniform hydration and gelation. But in most cases. Ageing: The slip is filter-pressed. 19. The firing is done in a tunnel furnace.SILICATE TECHNOLOGY 429 Process: It consists of the following steps: 1. . Usual maximum temperature is 1400°C. In few cases glaze is put on the blanks before firing. Deairing: The aged cakes are deaired in a pug mill by slicing with knives and putting under vacuum. 2. Storage Water Vac Cutter Brick Clay Screen Crusher (a) Clay Vac Screen flint water Feldspar Jigger Extruder Mag. Glazing: The dried articles known as blanks are glazed. 3.7 Flow diagram: (a) Brick manufacture (b) Dinner plate manufacture. 6. blanks are fired to produce biscuits. 5. The residual cake contains 10-30% water. separator Cutter Slurry Agitation Slurry Blunger Dinner plate Drager Filter press Press (b) Fig. Shaping. Slurry preparation: The mixture of weighed ingredients is taken in a blunger and stirred well with water to form a creamy liquid known as clay slip. Trimming and drying: The shaped articles after airdrying are trimmed and then dried in hot air. The cakes are dumped for some days. 4.

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

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

3. copper convertors • In reverberatory furnaces for smelting lead. Magnesite bricks: Magnesite is naturally occurring magnesium carbonate (MgCO3) and is the raw material for the magnesite refractories.5 kg/cm2 • They possess good crushing strength. The bricks are then slowly heated to 1500°C and kept for about eight hours at this temperature and cooled then slowly. • Cheaper than silica bricks. Other binding materials used .e.. High alumina bricks: Composition—50% or more alumina. copper • In refining furnaces for gold. Uses • For linings for Portland cement rotary kilns • Furnace hearths and walls • In reverberatory furnaces • In combustion zones of oil-fired furnaces. Properties • Low coefficient of expansion • High porosity • Little tendency to spall • Excellent wear resistance and stability. silver and platinum etc. ENGINEERING CHEMISTRY 4.. Dolomite bricks: They are made by mixing calcined dolomite (i. Uses • In blast furnaces • In kilns • Charging doors etc. Properties • They are generally grey or brown in colour • They can be used upto 1500°C under a load of 3. Uses • For the lining of basic converters and open hearth furnaces in steel industry • They are used in hot mixer linings. The prepared powder is pressed into bricks in hydraulic presses. mixture CaO + MgO) in equimolar proportion with silica as binding material.e. MgO is powdered to a proper size and then mixed with caustic magnesia or iron oxide as binding material and then ground. Calcined magnesite (at 1600°C) i. good resistance to basic slags and very little shrinkage • Their resistance to abrasion is poor. 5.432 Properties • Light yellow-reddish brown in colour • Low porosity and lower refractoriness than silica bricks • Fusion temperature 1350°C • Crushing strength 200 kg/cm2 • Better resistance to thermal spalling than silica bricks.

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

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

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

Q. (iv) High alumina (70-80% Al2O3). Ans. rigid supercooled liquid of infinitely high viscosity. • Glass has almost 100% elastic recovery. The cement sets under water. 7. (vi) Mullite (Clay sand). 6. (v) Magnesite (MgO). What is vitrification? Ans. The greatest uses of advanced ceramic products are in • Aerospace industry due to their lighter weights compared to metal alloys • Heat shields for space vehicles • As bio materials like false teeth. The primary uses of refractories are for lining (i) Steel furnaces (ii) Coke ovens (iii) Glass wares. Q. 11. Q. Mention some important refractories. that is why the term hydraulic came. (ii) Silica. . Refractories are earthy ceramic materials of low thermal conductivity capable of withstanding extremely high temperature without any change. • Chemically as a mixture of a number of metallic silicates. bone replacement. The process of not forming crystals during cooling of glass is called vitrification. Give general composition of cement. 8. Q. Ans. Clay materials are known as ceramics. Q. Tungsten and tantalum (W and Ta) are refractory metals capable to withstanding high temperatures. 12. 10. (iii) Silicon carbide. What is a hydraulic cement? ENGINEERING CHEMISTRY Ans. What are ceramics? Ans. artificial hip joints etc. one of which is an alkali metal. 5. laboratory wares are made of ceramics. 9. Mention some refractory metals. transparent or translucent. kitchen wares. 13. roads. What are primary uses of refractories? Ans. Ans. See text page 418. Q. Even at the present time ceramics remain important in many spheres of life. 14. Q. (vii) Zirconia (ZrO2). furnaces. What are refractories? Ans. (i) Fire clay (aluminium silicates). Q. What is devitrification of glass? Ans. Building. Glass-wares left unused for a long time gradually loose their transparency and become opaque due to the crystallisation of some of metallic silicates of glass. What is glass? Ans. Glass may be defined • Physically as an amorphous.436 Q. That phenomenon is known as devitrification of glass. Q.

10. Discuss the effect of heat on clay. • Magnesia • Chromite • Forsterite. Al 2 O 3 . Describe the rotary kiln used in cement manufacture. How is portland cement prepared by wet process? Explain the setting and hardening of cement. Ans. Mention classification of refractories. Discuss the composition of Portland cement. 9. At the early stages of heating. . C. 4. Q. What do you mean by silicate technology? What do you mean by superconductive ceramics? Mention its uses. 7. 13. the overall fundamental reaction of heating of clay is 3(Al2O3. Pure zirconia undergoes (i) a change from monoclinic crystal to tetragonal form at 980°C and (ii) also volume change on inversion by adding certain oxides like MgO. 18.2SiO2. a crystalline form at 940°C. Describe the setting of mortar and lime. How are cements classified? Give the various physico-chemical reactions responsible for the setting and hardening of Portland cement. (a) Acidic (silica. At 1000°C.SILICATE TECHNOLOGY 437 Q. Clay is the common ingredient of all ceramic products. 3. 17. more SiO2 is converted to cristobalite. SiC).2H2O) Kaolinite → ∆ 3Al2O3. CaO. Distinguish between (a) Pozzuolanic cement and (b) Portland cement.2SiO 2 . So. Q. Discuss the structural pattern of silicates. What is the importance of zirconia as refractory? Ans. dolomite) (c) Amphoteric (Al2O3. 5. Q. 11. 6. a common example is Kaolinite.2SiO2 + 4SiO2 + 6H2O Mullite Cristobalite EXERCISES 1. 12. Mention some basic refractories. Describe various types of cement. 8. 16. 15. Ans. What are silicates? Define clay and soil. This type of zirconia possesses a working temperature of 2600°C. Al2O3 and SiO2 combine to form mullite (3Al2O3 .2H 2 O ¾¾® Al 2 O 3 + 2SiO 2 + 2H 2 O ­ amorphous mixture 600°C ¯ The amorphous form of alumina changes to γ-alumina. As the temperature increases. clay undergoes elimination of water of hydration at 600°C. Ans. 2. 2SiO2). fire clay) (b) Basic (magnesite.

36. Give reactions involved. Write notes on (i) Carborundum (ii) Silica refractories. What are basic refractories? Explain magnesite refractory in detail. 26. What are refractory materials? Write a brief note on chromite bricks. Write notes on (i) Clay and common clay (ii) China clay (iii) Fire clay (iv) Uses of clay (v) Pottery. State composition. Briefly describe its manufacture. 20. 27. Describe the manufacture of: (i) Fire clay bricks (ii) Silica bricks (iii) Magnesite bricks. 28. Give the reaction involved in porcelain formation. 32. What is glass? Discuss the physical and chemical properties of glass. 18. 31. 29. 25. Describe the process of manufacturing of porcelain. Explain the significance of the following properties of refractory materials (i) Porosity (ii) Dimensional stability. 22. What are refractories? How are they classified? Give examples. Classify glasses with composition and illustrations. 15. 34. 38. What is cement? Describe the composition of any cement. What are refractories? Give an account of any four characteristics of a good refractory material. Write short note on soda lime glass. Describe the manufacture of glass by pot furnace process. 19. 23. properties and uses of fire clay bricks. What are fire clay bricks? Describe the manufacture. Explain the theory underlying the manufacture of refractory products. 30. 16.438 14. Discuss the manufacture of ordinary glass with the help of flow diagram. . 21. What is glass? Write the raw materials used in the manufacture of glass. 17. 37. 33. 35. ENGINEERING CHEMISTRY What are the criteria of the Portland cement raw materials? What do you mean by wet and dry processes in cement manufacture? How is Portland cement manufactured? Describe with the help of a neat diagram of rotary kiln for the manufacture of Portland cement by wet process. Write notes on (i) Coloured glass (ii) Plate glass (iii) Shaping of glass (iv) Safety glass (v) Chemical action in glass making (vi) Fibre glass (vii) Annealing of glass (viii) Glass laminates (ix) Phosphate glass 24. properties and applications of the following materials: (i) Magnesite (ii) Fire clay (iii) Zirconia (iv) Silica.

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

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

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

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

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

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

Compounding Plastics for manufacturing of finished articles are always mixed with 4-10% of other materials. which impart some durable properties to the moulded material. which actually form crosslinking during the moulding process in presence of catalyst. PLASTICS (RESINS) Plastics are a class of high polymers which can be moulded into any desired form by heat and pressure. which binds all the additives together. Amorphous polymer becomes rubbery and then gummy and on further heating it liquefies. 2. hence repeated heating and cooling also does not alter its nature. Strength of a polymer is estimated from typical stress-strain curves for different polymers as shown in Fig.2 Four types of stress-strain curves illustrating how polymers of different types behave (the lines end where the sample breaks). Amorphous polymers. . The strength of the polymer is controlled by the length of the polymer chains and its cross-linking. 1. The process of mixing these additives to virgin plastics is called Compounding. hence the setting is permanent and irreversible. 20. This hardened material cannot be softened again. Resins are actually the binders used for plastics and these two terms are used synonymously. On increasing strain continuously ultimately the polymer chains are uncoiled and fully stretched called necking and after this point the polymer reaches its break point and yields. the glass transition temperature is reached (Tg) after which they soften. which do not have melting point have softening points. There are two classes of plastics or resins.POLYMERS 445 Stress Hard. Effect of heat Behaviour of polymer is controlled by the temperature. But the crystalline polymer on heating above Tg shows thermoplastic behaviour and finally liquefies. 20.2. Thermosetting resins are those which are heated during moulding and heating is continued until is set and hardened. These materials are known as additives which not only impart some properties to plastics but also make the processing easy. brittle polymers Rigid and high impact thermoplastics Polymer fibres Rubbery polymers Strain Fig. At very low temperature both the crystalline and amorphous polymers behave like glass and on heating. Thermoplastic resins soften on heating and harden on cooling and this change is not chemical but physical in nature. Thermosetting resins are added as linear low molecular weight polymers. Additives and their functions are discussed below: (i) Resin is the binding constituent.

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

Plastic powder is fed into a hot cylinder and then injected by a piston plunger into a tightlylocked mould with the help of a screw arrangement. furniture parts are made by this process. 20. 20.4 Compressing moulding of plastics. This method is applicable for both thermosetting and thermoplastic materials.3 A schematic representation of the film casting machine.. which are moved relative to each other. The mould consists of two halves.POLYMERS Polymer solution Wind-up roll 447 Polymer solution spreads as a film Control valve Solvent evaporates Continuous polymer film Endless metallic belt Fig. This process is applicable for thermoplastics only. telephone parts etc. Buckets. The whole process is automatic. The mould is cooled for curing and finally the half of the mould is opened for the ejection of the article. (iv) Compression moulding. (v) Injection moulding. . Heat and pressure applied. The cavities get filled with fluid plastic. Pressure Guide pins Top moulding part (male die) Bottom moulding part (female die) Moulding plastic ingredients in cavity Extraction pin Fig. Furniture handles. The compounding material in definite proportion fills the gap between the two pieces of mould. two halves are closed slowly. are made by this process. Finally curing is done by heating (for thermosetting) and cooling (for thermoplastic). bowls.

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

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

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

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

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

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

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

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

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

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

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

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

In releasing the stress the chains revert back to their original coiled state.[M] RUBBER Rubbers are high polymers. DP = K . which on stretching gets aligned causing crystallization.460 ENGINEERING CHEMISTRY At a certain stage of polymerization it is found that the number of active centres for polymerization is equal to the number of chain terminators. Rubber coagulates as soft white mass which is washed and further processed. The coagulum is allowed to drain and the absorbed serum is squeezed out through steel rollers upon which water is sprayed. The degree of polymerization influences the tensile strength of the polymer. Polyvinyl chloride. The latex is collected from the mature Havea tree by making deep cuts on the bark. • Thermosetting plastics are permanent setting resins which harden on heating during moulding and they cannot be softened again. • Cellulose derivatives • Polythene. Polystyrene. Natural rubber. The coagulum is converted to a sheet with uneven rough surface resembling crepe paper and called crepe rubber. Highlights: Classification of plastics • Thermoplastic resins soften on heating and harden on cooling reversibly. (iii) Terylene (Polyester) are condensation products of dicarboxylic acids with dihydroxy alcohols (iv) Epoxy resins (araldite) (v) Silicone resins. Natural rubber is polymerized isoprene. Coagulation is then effected by adding acetic acid (1 to 2% on weight basis). Latex is diluted to contain between 15-20% of rubber. Polytetrafluoro ethylene (Teflon) • Polyamides (nylon) • ABS polymers. Examples of this class include (i) Bakelite obtained by polymerization of phenolic derivatives with aldehydes. The molecular weight of raw rubber is about 100.000 and is made from the latex of different plants like Havea brasillians and gangule found in tropical and subtropical countries. Polypropylene. which occurs in the latex of various trees. Tapping is done at intervals of about 6 months. and by allowing the latex stream to collect in a pot attached below the cuts. . which have elastic properties and can be stretched upto about 300 percent. The unstretched rubber is amorphous and the polymer chains are in a coiled state. (ii) Melamine obtained by condensing melamine with formaldehyde. Natural rubber came into market first in early 19th century. Coagulation of the latex. filtered to make it free from dirt.000-150. At this stage the average degree of polymerization is [ c]1/ 2 This equation relates average degree of polymerization with monomer concentration as well as initiator concentration.

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

It also swells in organic solvents. But unfortunately it is easily attacked by oxidising agents. It is also used as soles and other components of shoes. It can be vulcanized as natural rubber. Tackiness 10. 3. 8. It possesses high resilience and good and tough mechanical properties. it returns to its original shape and size. 6. for insulating wires and cables. SBR is similar to natural rubber in processing character and also as finished product. Some important examples are: (i) GR-S or Buna-S. Uses. (ii) GRA or Buna-N. Raw rubber very high 200 kg/cm2 10°C-60°C very poor high good ” Low marked less inherent Vulcanized rubber low. as adhesives and lining for vessels. Elasticity Tensile strength Useful temperature range Chemical resistance Water absorption tendency Resilience Insulation property Resistance to organic solvents 9. It is a copolymer of butadiene and acrylonitrile xCH2 = CH—CH = CH2 + nCH2 = CHCN → Copolymerization  CH 2  CH = CHCH 2  CH 2  CHCN  x n LM N OP LM QN OP Q . depending on percentage of sulphur 2000 kg/cm2 40°C to 100°C higher low much better ” much higher but swells low better can be controlled by vulcanization Synthetic Rubbers Synthetic rubber is artificially produced rubber-like polymers which can be stretched to at least twice its length and on releasing the stress. 4. It is mainly used for the manufacture of tyres. 5. 7.462 ENGINEERING CHEMISTRY Comparative study between natural and vulcanized rubber Property 1. Properties. This variety is the most important synthetic rubber and it is obtained by copolymerization of butadiene and styrene. Quality 2. Durability 11. mainly ozone.

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

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

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

poor chemical resistance. Why is PVC soft and flexible but bakelite is hard and brittle? Ans. 10. Q. Why is teflon highly chemical resistant? Ans. What changes take place with polymers near glass transition temperature? Ans. HDPE is completely a linear polymer and hence packing of the chains is efficient and hence its density is high. 18. Natural rubber is long-coiled chains of polycisisoprene and gutta-percha is horny and tough form of polytransisoprene. which cannot be broken on heating. 13.g. Vulcanization. Why is natural rubber compounded? Ans. packing efficiency is low and hence density is low. 16.466 ENGINEERING CHEMISTRY Condensation polymerization takes place through different functional groups of monomers with elimination of small molecules like H2O etc. butadiene and styrene to yield GR-S rubber. thus. In PVC the molecular chains are bonded to each other by Van der Waal’s forces and hence these long chains are flexible and can slip or twist on applying force but in the case of bakelite the thermosetting polymer chains are crosslinked by covalent bonds. 11. the monomers are bound to each other by strong covalent bonds.e. Q. antioxidants. 17. Q. so. In thermosetting plastics. improves all the above properties. What is copolymerization? Ans. tackiness. adding some sulfur at 100°C-140°C causes saturation of the double bonds by S and hence stiffening of the polymer takes place. Polydispersity index (PDI) of a polymer is a measure of the molecular mass distribution of a polymer. Q. Natural rubber possesses many undesirable properties and so to improve its properties it is usually compounded with different ingredients like plasticizers. Why is natural rubber vulcanized? Ans. Q. Any rubber-like elastic polymer.. Raw rubber has high elasticity. poor strength. Q. filler. Polymers are different from other small sized molecules as they are mixtures of molecules having different molecular masses. In teflon the most electronegative element F contributes to the strong attractive force within the chains and hence is non-reactive towards other chemicals. colorant etc. But for LDPE. Q. they would deform but not break. Below the glass transition temperature. large water absorption capacity etc. 12. 8. the polymer is brittle and above it. 14. Q. What is an elastomer? Ans. which can be stretched to thrice its size and after removal of the stretching force it returns to its original shape is called an elastomer. What is natural rubber and what is gutta-percha? Ans. Copolymerization is the point polymerization of two or more monomers. Thus by heating it cannot be softened to reshape and reuse. Q. What is polydispersity index of a polymer? Ans. Q. 9. Q. it is hard and no deformation can take place on applying force. When the force becomes too large the covalent bonds are broken and it becomes brittle. 15. due to its branched structure. . Why thermosetting plastics cannot be reused? Ans. e.. Vulcanization i. Why is the density of HDPE different from LDPE? Ans.

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

and also for making binoculars. Explain with example: (i) addition polymerization. Discuss briefly the application of plastic in engineering and industry. 23. (a) Write short notes on (i) addition polymerization (iii) thermoplastic and thermosetting plastics (ii) condensation polymerization (iv) number average and molecular weight. (v) Nylon 66. (d) What are the functions of fillers and plasticizers in plastic industry? 9. It is used as an adhesive. Biodegradation is a process by which refuse mixes with environment by microorganisms. Write short notes on (i) free radical polymerization (ii) cationic polymerization (iii) silicone resin. Development of biodegradable polymer ‘biopol’ is now a challenge to scientists. (a) Discuss the effect of structure of polymers on their physical properties in detail. (ii) PP. EXERCISES 1. It is a component of emulsion paint. (b) Write the structures. 4. (ii) co-polymerization. (b) Give the preparation and properties of (i) Nylon 6. with their respective monomers. . Polyhydroxybutyrate is a ‘biopol’ which degrades within a few months in soil but it is too costly to be used very soon. rods etc. 3. Q. (c) Discuss the preparation of bakelite and PVC plastic. (b) Define the term functionality of monomers. 5.468 Polymer is: ENGINEERING CHEMISTRY Properties and uses It is a glass-like plastic. (iii) vulcanization of rubber. What do you mean by biodegradation of polymers? Ans. (iv) PTFE. (ii) Neoprene rubber (iii) SBR (iv) Silicone rubber. It is used for making transparent sheets. Q. 22. What is polyvinyl (Trade name: Fevicol) alcohol? Ans. 6. Explain its significance with suitable examples. 8. 7. Write the structures of five addition polymers and five condensation polymers. Monomer is: CH2=CHOH (Vinyl alcohol) Polymer is: — CH2—CH(OH)—CH2CH(OH)—CH2 ]n [ — It is a water soluble polymer which is soft and gummy. camera lenses. two properties and uses of: (i) PE. This biodegradation process is completely absent in the case of high polymers. (iii) PVC. Write short notes on: (i) Rayon (ii) Synthetic rubber (iii) Types of plastics. Discuss various methods of plastic processing. 2. (a) What is a heterochain polymer? Give one example. table lamp shades.

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

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

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

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

Naphtha and other petroleum fractions. naphthenates. Tints and Thinners Resins Feed Tank Oils Weight Tank Pigments Mixer Tinting & Thinning tank Labelling machine Filling machine Belt conveyer Grinding mill Hopper Carton Packaging Shipping Platform scale Fig. Driers (accelerate the drying of film) Additives in case of emulsion paints are antibacterial. Manufacturing of paints The manufacture of paints involves only (i) mixing of the ingredients (ii) proper grinding and lastly (iii) packing. white ZnO. Tung oil. mica. Zn. White extender pigments BaCO3 . Acrylics. Butyl acetate. Co. talc. Mn. Xylol. Methyl ethyl ketone (MEK). (ii) Volatile i. Types and Functions Oils and/or Resins (Film forming materials protect the surface from weathering). Pb.. BaSO4.1 A flow diagram of mixing of a paint.e. TiO2. 21. Fish oils.2: General formulations of paint are shown in the table Constituents Vehicle Class (i) Nonvolatile solvent based. Lithopone. etc. methylated naphthalene White lead. . chromegreen. casein. Dehydrated castor oil. stabilising surfactants and pH adjusters Ketones Esters Aliphatics Aromatics Example Linseed oil. zinc yellow. China clay. low boiling solvent based (thinners) Pigments Inorganic or Organic (i) Opaque (ii) Transparent (iii) Special purpose Extenders or Inerts Diatomaceous earth etc. Ethyl acetate.PAINTS 473 Table 21. Amyl acetate.

• They can be applied simply with a brush.474 ENGINEERING CHEMISTRY Common pigments and their colours White Red Blue Green Yellow 1. • They are free from fire risks. • More durable and more impermeable to dust and dirt. Chrommarine oxide 1. Lamp blues green chromate black 3. Rouge 2.: • Water and • The vehicle of film forming material (a synthetic resin or latex). Zinc oxide 3. Carbon black Orange Brown Metallic 1. Zine 3. Lead 2. Basic 1. . Chrome 2. Emulsifying agent or surface active agents. Copper chromate plumber powder 2. driers. Emulsion paint is an emulsion of two phases viz. White lead 1. Aluminium powder 2. Kerosene Manufacture of an emulsion paint Manufacture of emulsion paints involves following three steps: • Protein dispersion • Pigment dispersion • Paint formation and addition of other ingredients. The latex is dispersed in water by means of dispersing agent which acts as a binder. Cadmium orange 2. Red nium lead dioxide 2. Furnace chromate black Emulsion paints Emulsion paints are those paints in which water is used in place of organic solvents as thinner. stabilisers. Tita1. Ultra 1. Iron blues 3. Advantages of an emulsion paint • Emulsion paints can be applied on the surface of metal or wood very easily. Lithopone 4. • The surface on which the emulsion paint is applied can be easily washed with water. Litherge Black 1. Burnt 1. Cobalt 2. antifoaming agents and preservatives are also added. Zinc powder 3. • Emulsion paints dry quickly. Pigments and extenders are dispersed in such an emulsion. Constituents of emulsion paints Resin Polyvinyl acetate Polystyrene Alkyd Stabiliser Methyl cellulose Dextrin Casein Starch alginates Preservative Thymol Chlorothymol Mercuric chloride Antifoaming agent Pine oil.

For the oleoresinous varnishes the formation of the film is due to the polymerisation of the oil and in case of spirit varnishes the film formation is due to only solvent evaporation. The distempers have: (i) Good covering power (ii) Ease of application (iii) Durability Disadvantage of distemper is that it is not moisture-proof. Cement paints Cement paint contains: (i) White cement. But only difference is that varnishes do not contain colouring substances. extenders.8 1. generally methanol and ethanol. Varnishes Varnishes are organic compounds used as protective coating similar to paints.8 16.2 466 Distempers Distempers are water paints comprising pigments.PAINTS 475 A typical composition of an emulsion paint Constituents Titanium dioxide Clay Tetrasodium pyrophosphate Deionised water Casein solution Sodium penta chlorophenate solution Pine oil Tributyl phosphate Copolymer latex Parts by weight 270 76.4 4.. While the spirit varnishes are solutions of resins in volatile solvents only. Oleoresinous varnishes are also classified as: (i) ‘long oil’ varnishes have high proportions of drying oil (ii) ‘short oil’ type contains a lower proportion of drying oil . Before applying cement paint a primer coat of a dilute solution of sodium silicate and zinc sulphate is necessary. i. Oleoresinous varnishes are the solutions of one or more than one natural or synthetic resins in a drying oil and a volatile solvent. binders. In case of metal surface the dispersion medium is boiled linseed oil.e. Cement paint has marked water-proofing capacity and gives a stable and decorative film. pigments. Varnishes are classified under two heads: • Oleoresinous varnishes and • Spirit varnishes. and water as a dispersing medium. (ii) Colouring or pigments.2 13.5 764 17. The dispersion medium is water or an oil. and (iv) Fine sands as inert filler. (iii) Hydrated limes. In case of brick structure the dispersion medium is water.

aliphatic and aromatic naphthas. alcohols. harder and more brittle film — More weather resistant pliable films Field of application Floor and furniture General purposes Sparvarnishes Properties of varnishes vary greatly depending on the three following factors: • Cooking procedure • Type of drying oil used • Type of resin used Manufacture The manufacturing procedure depends on the type of oil and resin used. Zn resinates. when the resin is insoluble in oil.e. octotes etc. The sequences are as follows: • In case of natural resin. saya oil etc. Solvents and thinners. i. Anti-skinning agents i. The preheated drying oil is then mixed and heated to obtain the desired viscosity.476 ENGINEERING CHEMISTRY (iii) ‘medium oil’ containing the proportion of drying oil intermediate between the two. kerosene. Kauri. • A solution of shellac in methanol or ethanol is produced by stirring followed by heating to produce spirit varnishes. four main ingredients of a varnish): Film forming materials. i. ingredient 4 Guaiacol. Copal etc. the resin is depolymerised first by heating it upto 350°C till foaming ceases.. The mixture is cooled to 200°C and thinner and drier are added.. The table below provides the type. (ii) Natural resins: Shellac.e. silicones and vinyl resins. ingredient 1 (i) Oil: Linseed oil. Rosin.e. i.. field of application and properties of such varnishes: Type (i) Short (ii) Medium (iii) Long Drying oil per 100 lb resins 6-15 gallon 20-30 gallon 35-60 gallon Properties Faster drying. • In the case of synthetic resins preheating is not required and the procedure is likewise as above. coumarine-indene. ester gum. In either case filtration is necessary. . The classification is based on the use of drying oil in gallons per 100 lb of resin.e. ingredient 3 Co. (iii) Synthetic resins: Alkyd.. cotton seed oil. Pb. coconut oil. ingredient 2 Turpentine.e. chlorinated rubber. The table given below furnishes the constituents of a varnish (i. Mn. tung oil. acrylates.. xylol. tertiary amyl phenol. Driers.

Pigments (Not added in clear lacquers) 3. The purpose of using of a lacquer is for protective and decorative aspects. adhesion and water resistance (i) Esters: (i) Ethyl acetate (ii) Butyl acetate (iii) Amyl acetate (ii) Ketones: (i) Methyl ethyl ketone (MEK) (ii) Cyclohexanone (iii) Alcohols: (i) Ethyl alcohol (ii) Butanol (iii) Amyl alcohol To dissolve film forming materials 4. Diluents (i) Coal tar products: (i) Toluene (ii) Benzene (iii) Solvent naphtha To reduce viscosity and cost 5. Film forming Materials (i) Cellulose derivative: (i) Nitro cellulose (ii) Cellulose acetate (ii) Resins and gums: (i) Ester gum (ii) Copal (iii) Synthetic resins: (i) Phenol aldehyde (ii) Alkyd 2.. resins and plasticizers in solvents and or diluents.PAINTS 477 Lacquers Lacquers are dispersion or solution of a film forming material (like-nitrocellulose). To improve retention of glass. The table given below displays the constituents of lacquers: Class 1.e. The deep black Japans are based on boiled linseed oil and are made by cooking linseed oil with . i. Solvents — For pleasing colours Functions For waterproofness and durability. Enamels are brushed or sprayed on the surface and finally hardened by baking. Plasticizers (i) Castor oil (ii) Dibutyl phthalate (iii) Tricresyl phosphate To reduce film brittleness and to improve adherence Enamels and Japans Pigmented varnishes or lacquers are known as enamels. Carbon black is added in deep black Japans. solvents. The lacquer dries from the surface on which it is applied by simple evaporation of the volatile constituents. Japans are closely related to enamels.

varnishes. This lead oil is mixed with kerosene (thinner) and asphaltum. The functions are (i) To protect the film by reflecting back the destructive UV light (ii) To strengthen the film (iii) To impart an aesthetic appeal Q. (i) Synthetic resins (ii) Drying oil (iii) Volatile solvents Q. 3. Q. The main function of the drying oil in a paint formulation is to form a protective film by complex chemical reactions. A drying oil is generally glyceride of unsaturated fatty acids. The product is called lead oil.. 4. Otherwise. 5. Used for protective and decorative aspect 3. 1. An oil is a glyceride i. The paint films are formed by drying an unsaturated oil. What is ‘drying’ of an oil? Ans. . i. These Japans are applied and baked at 200°C for a few hours. How are the paint films formed? Ans. Ans. lacquers and enamels is given below: Paint 1. drying is a chemical change of an oil accompanied by oxidation and polymerisation due to the presence of unsaturation in the fatty acid portion of the formula of drying oil to form a protective film over the surface.e. What is a tonner? Ans. Drying is done by oxidative polymerisation Same Drying by oxidative polymerisation Drying by simple evaporation Drying by either oxidative polymerisation or evaporation or by baking as per composition SHORT QUESTIONS AND ANSWERS Q. Q. A paint is a mixture of opaque solids dispersed in a liquid medium Varnish A varnish is a colloidal dispersion or solution of syn-thetic or natural resins in oils or thinners Same Lacquer A lacquer is a colloi-dal dispersion or solution of film forming compound. Name the main constituents of an oil varnish. A comparative study of paints. 2. ester of glycerol and fatty acids. resin in a vol-atile solvent Same Enamel Enamels are pigmented varnishes or lacquers 2.e. What are the functions of pigments in a paint? Ans. Tonner is an insoluble inorganic dye used in paints.478 ENGINEERING CHEMISTRY litharge at 230°C for 5 hrs.

PAINTS 479 Q. Cite an example of a common spirit varnish. By what means is a paint applied? Ans. Ans. 6. What is a vehicle? Ans. naphtha etc. What is enamel? Ans. What do you mean by driers? Ans. Q. This is an emulsion paint.. (i) China Clay (ii) Gypsum (iii) Mica (iv) Silica (v) Talc. (i) By brushing (ii) By dipping (iii) By spraying Q. which is a naturally occurring resin. What are the characteristics of an emulsion paint? Ans. turpentine. fillers and extenders (ii) A resin dispersion (iii) Surface-active agents (iv) Protective colloids. Driers are generally heavy metal soaps. They can be employed on both interior or exterior surfaces. pigments and extenders are kept suspended in a vechicle. . 8. Emulsion paints have the following characteristics: (i) Ease of application (ii) Absence of disagreeable odour (iii) Non-inflammbility. 15. Q. Q. Q. Name some common extenders used is paints. Enamel is a pigmented varnish. In paints. What is an acrylic emulsion paint? Ans. 13. Q. 7. for example. in methylated spirit. Why are plasticisers added to a paint? Ans. It is a solution of shellac. 12. State the composition of an emulsion paint. Q. The monomer is generally ester of acrylic or methacrylic acid. Plasticisers help to reduce cracking in paints. used as diluents or a thinner during the application of paint. 10. soluble in oil and pretreated with oil (1-2% by weight) to hasten the process of drying by carrying oxygen to the position of unsaturation in oil. 14. An acrylic acid derivative monomer is polymerised and emulsified and to it other ingredients of the paints are added. Q. 11. 9. An emulsion paint consists of the following: (i) Dry powders of pigments. The vehicles may be film forming oil and other liquids. Ans. Ans. Q.

Baking improves adhesion. 3. to paints. In emulsion paints. 5. resistance to corrosion etc. What is the main difference of film forming of an emulsion paint from that of an ordinary paint? Ans. Ans. Write a short note on spirit varnish. The small articles are taken in a barrel with a required quantity of paint and the barrel is rotated while the articles get painted.480 Reactions are as follows: (a) CH ≡ CH + CO + ROH → CH 2 = CHCOOR HCl acrylic ester Ni(CO) 4 ENGINEERING CHEMISTRY (b) (CH3)2CO → (CH3)2CH(OH). What do you mean by baking? HCN Conc. 8. 16. 17. the film-forming materials are various latexes whereas in ordinary paints. 4. Q. EXERCISES 1. What are lacquers? What are enamels and Japans? . 6. 18. In the case of emulsion paints. Q. In the case of small articles. State the specific requirements in paint application. Write a short note on emulsion paint.CN → CH2 = C  CONH 2  CH 3 CH2 = C  COOR  CH3 Q. What is a paint? Mention the constituents of a paint and explain their functions. H2SO4 → ROH methylacrylate Ans. paint is applied by tumbling technique. This heating is known as baking. the film-forming materials are drying oils. 7. Give the characteristics of a good paint. hardness. The requirements are as follows: (i) Hiding (ii) Colour (iii) Weather resistance (iv) Washability (v) Gloss etc.. the painted articles are then heated at 400 °F. 2. forming of film takes place by coalescence of resin particles used as a base to form a strong continuous film. Distinguish between paint and varnish.

arranged symmetrically. Solids are generally classified under two heads. In a crystalline solid. 22 CRYSTAL The term crystal originates from the Greek word ‘‘Krystallos’’ that means clear ice. and was first applied to transparent quartz stone with a wrong assumption that these stones were formed from water by extreme cold. The rigidity arises due to the absence of the translatory movement of the structural units (like atoms. On the other hand the amorphous solids have no definite geometrical shape. A crystal grows from melt or a solution or from gaseous state by the deposition of atoms or ions onto its surfaces by which crystals are bounded. Thus the first notable feature of the regularity of the crystal structure is the periodicity of their patterns and a crystal is therefore a periodic array of atoms and molecules in space. The crystals often have a plane fracture and they also have sharp melting points. the constituent atoms are arranged in a definite pattern constantly repeated and in consequence giving rise to a definite geometrical configuration of crystalline solids. There is a basic unit in any real crystal and when the basic unit is systematically repeated.Solid State Chemistry Solids are mainly characterised by their definite shapes and considerable mechanical strength and rigidity. The amorphous solids melt slowly over a temperature range. In a more specific way a crystal may be defined as a solid substance having a definite geometrical shape with flat faces and sharp edges. reproduces the whole structure. 481 . The forces of attraction between these units are large enough. ions etc. namely crystalline and amorphous. The angle between the normals to the two intersecting faces is called the interfacial angle.) of the solid. In a crystal the atoms or ions are arranged like soldiers on a parade ground in well defined columns and rows and this regularity of atomic arrangements in a crystal is the basic feature of crystals. The various modes of arrangement of atoms of molecules in space to satisfy the need of periodicity are governed by some specific rules and principles which lead to the development of the subject of crystallography. In the 17th century the name crystal was extended to other solids possessing manifestations of solids that bore the relation to the original rock crystals of being bounded by many flat. shiny faces. These units remain fixed to a mean position about which they may undergo vibration. The surfaces are referred to as faces and an edge is formed where two surfaces intersect.

According to this law. In such cases the use of Weiss indices are rather awkward and have consequently been replaced by Miller indices. 3 and 4 are simple integral whole numbers and the standard intercepts are a. These intercepts are in the ratio of 2a : 3b : 4c. Law of rational indices In 1784 Haüy proposed the law of rational indices or rational intercepts. This can be understood in the following way. 22. In Fig. But a the angle of intersection of the two corresponding faces will a be same for any crystal of the same substance. This plane has intercepts OA. 22.1 Interfacial angle. Fig. where OL = a. and • Law of symmetry. all faces cut a given axis at distances from the origin. The crystals of substances are bounded by plane surfaces which are called faces. 22. The shapes are different but having the same interfacial angle. Law of constancy of interfacial angle or Steno’s law The law states that the angles between the corresponding faces on various crystals of the same substance are constant. called interfacial angle. then it will cut it at infinity. where 2.1. Weiss indices . The coefficients are known as Weiss indices of the plane given.e. b and c. These ratios characterise and represent any plane of the crystal. leading to various shapes of the crystals. For describing the geometry of a crystal usually three non-co-planar co-ordinate axes are selected arbitrarily. the ratio between intercepts on crystallographic axes for the different faces of a crystal can always be represented by rational numbers. OB and OC along X. 3b and 4c respectively. which bear a simple ratio to one another. OM = b and ON = c are the unit distances chosen along the three co-ordinates. • Law of constancy of interfacial angle • Law of rational indices. NaCl crystallises as cubes from aqueous solution and as octahedral from urea solution but interfacial angles of all crystals of NaCl are found to be 90°. The ratio of the intercepts in terms of the standard is 2 : 3 : 4. For example.. Y and Z axes at distances 2a. two crystals are represented two-dimensionally. In other words. b.482 ENGINEERING CHEMISTRY Fundamental laws of crystallography Geometrical crystallography is concerned with the outward spatial arrangement of crystal planes and the geometrical shapes of the crystals and thus crystallography is dependent upon the three following fundamental laws. If any plane is parallel to one axis. let us consider a plane ABC in the crystal as shown below: Z C N c a L O b M B Y X A Fig. and c i. Interfacial angle has a characteristic value for a given crystalline solid.2 Intercepts of crystallographic planes. It is often seen that the crystal faces are unequally developed. These faces always intersect at an angle. The Miller indices of a plane are obtained by taking the reciprocals of the coefficients of a. To illustrate. These are crystallographic axes.

. if a face of a crystal makes intercepts OA. For various cubic lattices. 22. Thus. the 1 1 Miller indices of the plane (2a : b : 2c) will be : 1 : i.3 Miller indices in the case of cubic lattices. 1) plane (1. b/OB and c/OC. 1. the Miller indices for the plane would be (1 1 0). b/OB = k and c/OC = l where h.. OB and OC on the three axes. b and c are unit distances along three axes. . 22. Now. the bar above one indicates the intersection of the plane on the negative side of the axis. l are the Miller indices of the plane.. and these reciprocal intercepts are whole number or integers i. The reciprocals of these lengths will be a/OA. 1. these interplanar spacings are given by the formula: a dhkl = 2 h + k2 + l 2 where ‘a’ is the length of the side of the cube and h. (100) plane. If a plane produces an intercept on the negative side. 1) plane Fig.e. OB/b and OC/c where. Thus. 0) plane (0. for a plane perpendicular to one axis and parallel to the other two.e. Some of the Miller indices in the case of cubic lattices are shown in Fig. X O Z Y (0. 1. having intercepts – a : ∞ b : ∞ c will have indices.SOLID STATE CHEMISTRY 483 and is multiplied throughout by the least common multiple to obtain integral values. 0. l are Miller indices of the face or plane of the crystal and the face is defined as (h k l) face. a/OA = h.3 below. k. 1 : 2 : 1 and this plane or face is 2 2 indicated as (1 2 1) face of the crystal. as: Weiss indices – 1 : ∞ : ∞ and Miller indices – 1 : 0 : 0 i. The distance between the parallel planes in a crystal is designated as dhkl. then the lengths of the intercepts may be expressed as OA/a. k. 1) plane (0. say – a : – b : ∞ c. The symbol 1 denotes minus unity. a.e.

Centre of symmetry A crystal is said to possess a centre of symmetry.. The line is called the axis of symmetry.4 Some elements of symmetry in crystals. If similar view appears two. 22. A crystal can have only one centre of symmetry. a line or a point. three. three. (b) axes of symmetry. (c) centres of symmetry. and • centre of symmetry. The law of symmetry states that: all crystals of the same substance possess the same elements of symmetry. There are three types of symmetry elements associated with a crystal.e. A Three B fold axis A B A Four fold axis Two fold axis B (b) (a) (c) Fig. the crystal is said to possess two. four or six times during one complete revolution of 360°. Symmetry in crystals may be with respect to : a plane. if every face has another identical face at an equal distance from the centre. altogether twenty-three elements of symmetry. namely: • plane of symmetry • line of symmetry. These planes. Plane of symmetry A crystal is said to have a plane of symmetry when it is divided by an imaginary plane into two halves in such a manner that one half is the mirror image of the other. Line of symmetry A crystal is said to possess a line of symmetry if it is possible to draw an imaginary line through the centre of the crystal and then to revolve the crystal about this line through 360° in such a way that the crystal appears unchanged more than once. lines and centre of symmetry of a crystal are called its elements of symmetry. (a) planes of symmetry. The cube has the greatest symmetry elements: (i) Nine plane of symmetries (ii) Thirteen axes of symmetries (iii) One centre of symmetry i. . four or six fold axes of symmetry.484 ENGINEERING CHEMISTRY The law of symmetry Another important property of crystals is their symmetry.

formed by its constituent atoms or molecules or ions. the three dimensional lattice or space lattice is obtained. A set of points that are repeated at a distance ‘a’ along a line form a one-dimensional lattice. a (a) b b a (b) a (c) (d) Fig. On the basis of the arrangement of structural units in their crystal lattices. c) two dimensional. 22. crystalline substances are classified as in Table 22.SOLID STATE CHEMISTRY 485 Crystal lattice The idea of lattice developed from the internal regularity suggested from the external appearance of the crystal. (d) three dimensional or space lattice. it constitutes a two dimensional lattice. When a set of points occur regularly in a plane. Thus a lattice may be defined as an infinite set of points repeated regularly through space. (b. A crystal lattice is a highly ordered three dimensional structure.5 Lattice arrangement: (a) one dimensional. . When the set of points are repeated regularly in three dimensions.1.

Thus the unit cell is the essential feature of the crystal structure. Sb. K2SO4. 5H2O. PbI2 Al2O3. Monoclinic 5. 10 H2O. HgS. BN. monoclinic sulphur CuSO 4 . .6 The seven crystal systems or crystalline forms. AgBr NaHCO3. Cubic 2. Tetragonal 3. This classification is based on the magnitude of the unit cell length and the angle of inclination between them. 22. BaSO4. SnO2 KNO3. All the crystal systems are made up of 14 types of crystal lattice and these crystal lattices are known as Bravais lattices. CaCO3.7. NaNO3 90° 90° a 90° 90° a Cubic a a Tetragonal 90° 90° c 90° c 90° a a 90° a Orthorhombic 90° 120° 90° a° a° a Rhombohedral a a Hexagonal a c a a 90° b Monoclinic a° c g° b° a° b Triclinic a c Fig. KCl. graphite. Trigonal or Rhombohedral Axial characteristics a=b=c a=b≠c a≠b≠c a≠b≠c a≠b≠c a=b≠c a=b=c Angles α = β = γ = 90° α = β = γ = 90° α = β = γ = 90° α = γ = 90° β ≠ 90° α ≠ β ≠ γ ≠ 90° α = β = 90° γ = 120° α = β = γ ≠ 90° No. which when repeated over and over again in three dimensions. of space lattices 3 2 4 2 1 1 1 ENGINEERING CHEMISTRY Examples NaCl. H3PO3 SiO2.1 Crystal systems and their characteristics System 1. Na2SO4 .486 Table 22. 22. CsCl. The unit cell is the smallest building unit in the space of a crystal. shown in Fig. forms a space lattice of the crystalline substance. Triclinic 6. K2Cr2O7. Orthorhombic 4. ZnS TiO2. Hexagonal 7.

A cubic crystal can be any of the following three types: (i) Simple crystal lattice (SC) (ii) Body centered crystal lattice (BCC) (iii) Face centered crystal lattice (FCC) .7 The 14 Bravais lattices. the intercepts on the three axes are equal and all the angles are equal to 90°.SOLID STATE CHEMISTRY 487 Cubic (P) Cubic (l) Cubic (F) Tetragonal (P) Tetragonal (I) Orthorhombic (P) Orthorhombic (C) Orthorhombic (I) Orthorhombic (F) Monoclinic (P) Monoclinic (C) Triclinic (C) Trigonal (R) Trigonal & Hexagonal (C) Fig. 22. CUBIC CRYSTALS In a cubic crystal.

8 Bravais lattices of a cubic system. the total number of atoms per unit cell = 1 (at the centre) + 8 × 1/8 (at the 8 corners) = 1 + 1 = 2 atoms/unit cell of BCC 1/8 atom 1 atom Fig. 22. 22. In a simple cubic structure. In simple crystal lattice. while each of the eight atoms situated at the corners is shared by a total of eight unit cells. 8 (a) Simple lattice (b) Body centered lattice (c) Face centered lattice Fig.488 ENGINEERING CHEMISTRY (i) Simple Crystal Lattice. there are lattice points at the eight corners of the unit cell. 22. is shared by a total of eight unit cells. So the total contribution of all the eight corner atoms to each cell = 1 × 8 = 1 atom/unit cell of SC.9 Unit cell of simple cubic crystal. each unit cell has 1/8 shares of every corner atom. The atom at the centre is independent of other cells.10 Unit cell of body centered cubic. there are lattice points at the eight corners and at the centre of the unit cell. an atom situated at any corner of each unit. thus. (ii) Body Centered Crystal Lattice. Thus. 1/8 atom Fig. . A BC cell has one additional atom at the centre besides having one atom each its right corners. In body centered crystal lattice.

An FCC has one atom at the centre of the each face besides having one atom at each corner. dhkl = where a = side of the cube. every atom situated at the centre of a face of a unit cell is shared by two adjoining unit cells. a h + k2 + l 2 2 Atomic radius of a cubic lattice Atomic radius of a unit cell may be defined as ‘‘half the distance between the centres of two immediate neighbours in a unit cell’’ and is denoted by ‘r’. Since there are six faces of a cube. In face-centered crystal lattice. Thus. Thus. so that total number of atoms per unit cell. and for body centered cell (BCC) (4r)2 = (a2 + a2) + a2 = 3a2 r= 3a / 4 . The perpendicular distance between the adjacent planes is known as the interplanar spacing and is denoted by dhkl. 22. in addition to those at the eight corners of the unit cell.SOLID STATE CHEMISTRY 489 (iii) Face Centered Crystal Lattice. for a simple cubic (SC) cell atomic radius r = a/2 as we know that a = 2r 2r 2r a 1/8 atom Fig. The distance between the centres of two corner atoms of the cube is called length of the cube edge and denoted by ‘a’.12 Simple cubic cell. there are lattice points at the centre of all faces.11 Unit cell of face centered cubic. = 1/2 × 6 (at the centre of six faces) + 8 × 1/8 (at 8 corners) =3+1 = 4 atoms/ unit cell of FCC 1/8 atom 1/2 atom Fig.22.

In case of most ionic crystals. the crystals have vacancies. . The important imperfections or defects are of the following types: • Stoichiometric defects: (i) Schottky defects and (ii) Frenkel defects. But this idea of crystal is non-existent. Radius ratio Radius ratio is the ratio of the cation radius to that of the anion in an ionic solid.e.490 ENGINEERING CHEMISTRY a 4r a a Fig. 22. 22.13 Body centered cubic cell. There are certain crystals is which some of the lattice points remain unoccupied i..14 Face centered cubic cell. Radius of anion (r− ) Solid defects Crystals are formed depending on perfectly regular arrangement of structural units. On account of electrical neutrality. • Non-stoichiometric defects or impurity defects. radius ratio = Radius of cation (r+ ) . While for face centered cubic cell (FCC) or Thus (4r2) = a2 + a2 16r2 = 2a2 r = a/2 2 r = a/ 8 4r a a Fig. Thus. Stoichiometric defects (i) Schottky Defects. the ions are not arranged in a perfect order and these crystals are said to have defects or in other words this deviation may be regarded as crystal imperfections.

For example. The insertion of Ca2+ ions for Na+ ions leads to create lattice vacancies and such vacancies permit the migration of ions as a result of which the conductivity of impure crystal increases. For example: when NaCl is treated with sodium vapour. Metal deficiency may also occur as follows: A positive ion may be missing from its lattice position and a doubly charged cation maintains the charge balance. In the mixed crystal Ca2+ ions occupy the positions of Na+ in crystal lattice and the position of Cl– ion in the lattice remains unchanged. This phenomenon occurs when ZnO is subjected to heating and its colour changes from white to yellow. ZnO exhibits this type of defect when its composition becomes Zn1+xO. if a very small amount of CaCl2 (less than 0. 22. There is an excess of either metal or non-metal atoms in non-stoichiometric compounds. . crystal defects may also arise as a result of the presence of small amount of impurities. (ii) Frenkel Defects. 22. the conductivity of NaCl increases by 10000 times. FeS and NiO are the examples of such defect. in AgBr crystal some Ag+ ions are missing from their regular positions and are found to be squeezed between other ions. Thus two cases generate (i) Metal excess and (ii) Metal deficiency. FeO. In compounds having non-stoichiometric defects. (b) an extra metal atom may be present in an interstitial lattice site and an electron being present in some other interstitial position balances the charge. One of the most common examples for impurity defect is semiconductors.15 Defects in crystals.15 below. For example. the ratio of positive and negative ions differs from that indicated in their respective chemical formula and the balance of the positive and negative charges is maintained by extra electron or positive ions as per necessity.SOLID STATE CHEMISTRY 491 equal number of cationic and anionic vacancies would exist in the crystal lattice as shown in Fig. Frenkel defects arise with those crystals in which an ion leaves its normal lattice site and occupies an interstitial site in the same crystal. + – + – + – – + – + – + + – + – + – – + – + – + + – + – + – – + – + – + + – + – + – – + – + – + – + – + – + – + – + + – + – + – – + – + – + + – + – + – – + – + – + – + – + – + – + – + – + + – + – + – – + – + – + Ideal Crystal Schottky defect Frenkel defect Fig. such a yellow non-stoichiometric variety is obtained. These impurities in crystalline substance drastically change their properties.1%) is added to NaCl. The free electron present is responsible for excitation to higher energy level by absorption of radiation of particular wavelengths. This type of crystal defect is known as Schottky defect. Impurity defects are introduced under controlled conditions in germanium and silicon in the production of semiconductors. Such defect is found in crystals of NaCl. Non-stoichiometric defects Besides structural imperfections. Metal excess may occur in the following ways: (a) an anion may be missing from its lattice site and an electron be present there for maintaining charge balance.

With rise in temperature the conductivity of semiconductors increase because at high temperature the excess electrons or holes become more free to move and so the conductivity increases. In other cases.16(a) and (b) show a grown P-N-P junction triode transistor and an N-P-N junction transistor respecttively Emitter Base Collector (Input) E P N P C (Output) (Input) E N P N C (Output) B (Base) (a) A PNP transistor B (Base) (b) An NPN transistor Fig. is introduced in place of Ge or Si. Both in Si and Ge. Semiconductors that exhibit conductivity due to excess electrons are called n-type semiconductors where n stands for negative hole.and p-type) are electrically neutral. there are some semiconductors in which electrical conductivity is imposed due to presence of positive holes. if a group III element like B. 22. A triod transistor contains two P-N junction diodes placed back to back. This hole instead of remaining confined to the impurity atom. Al etc. Si and Ge in pure state are very poor conductors of electricity. each atom is covalently bonded to four neighbours such that all four outer electrons of each are involved in bonding. impurity doped Si and Ge exhibit semiconductivity. Transistors (semiconductor triodes) The word transistor is derived from two words—transfer and resistor. However. Junction transistors are of two types: • Grown junction type and • Alloy junction type. Sb or Bi is introduced in place of Ge. or Si atoms. 22. Semiconductors are defined as inorganic crystals responding to electronegativity when excited by heat or electromagnetic radiation. Highlight: It may be noted that both type of semiconductors (n. discussed later on. they are known as p-type semiconductors. an electron vacancy in covalently bonded structure will be generated and such type of electron vacancy is known as ‘hole’.492 ENGINEERING CHEMISTRY Role of Silicon (Si) and Germenium (Ge) in the field of semiconductors Semiconductors are the materials that exhibit conductivities considerably lower than those of the metals. Doping of small amounts of group IV or V elements improves their electrical conductivity appreciably.16 Transistors. . migrates throughout the structure when filled by an electron. So. The following Fig. electrons are able to move in a crystal having such electron vacancies or hole and thus the crystal exhibits electrical conductivity. Similarly. Let us suppose an atom of group V element like P. then the four electrons of this atom will be utilized in the formation of covalent bonds and the remaining one will be free to move and thus induces an enhanced conductivity. As.

• High melting and boiling points in most cases. the conductance decreases with increase in temperature. Band theory Band theory provides the most satisfactory explanation of the characteristics of the metallic properties in a very natural manner. Separate bonding schemes have been proposed for the metals to give an accurate explanation of the characteristics of metal. • Metallic lustre • Constancy • Emission of electrons by some metals under the action of heat and light. at the same time. • The collector current is always less than the emitter current i. All these above properties of metal cannot be explained either by covalency or by an ionic model. and a collector is to collect these carriers through the base. 22. 22. the combination of two atomic orbitals gives rise to two molecular orbitals and these are two new energy levels for the electrons in the two joint fields of the nuclei.) treatment for a large number of atoms. Amplification by a transistor (current amplification or gain) • Conduction within a PNP transistor is by hole movement from the emitter to the collector. • Hardness and.e. If this idea is extended to an . these are: • High thermal and electrical conductances.SOLID STATE CHEMISTRY 493 Function of the emitter is to inject majority charge carriers into the base.17 The alloy junction transistor consists of two beads of indium metal alloyed on opposite sides of a thin slice of an N-type Ge. In an NPN transistor electron moves. The alloy junction transistor is shown in the following figure (Fig. Ic = Ie – Ib: • The current amplification or gain (α) of a transistor is. N-type germanium E C Indium B Fig. For homonuclear diatomic species. But the bond theory is the most satisfactory among all the proposed theories.17).O. The theory is an extention of molecular orbital (M. Elements of band theory Metals in general are characterised by certain distinct features. Collector is larger in size than the emitter. ′ collector current Ic = (α < 1) α= emitter current Ie for both PNP and NPN transistors. ductility and malleability.

The electronic configuration of a Li atom is 1s2. each offering one orbital for the combination with others. two molecular orbitals are formed by two 2s atomic orbitals from two Li atoms.18 An Mg atom has the electronic configuration 1s2.2s2.O. Similarly three or four Li atoms would give rise to formation of three or four energy levels by combination of their 2s-atomic orbitals.2p6. 22. When the electrons gain thermal energy or are placed in an electric field. Now extending this idea for ‘n’-atoms.3s2.s).19 Merger of the 3s and 3p bands in Mg. so there will be a total of n new energy levels similar to ‘n’ number of molecular orbitals (M. So. These large number of energy levels form an energy band by spacing closely one upon another. all 2s-atomic orbitals will combine to give a 2s-energy band with n-energy levels. 3p band 3s band Fig. One finds that the 3p band (formed by unoccupied 3p atomic orbitals of the Mg atoms) overlaps the 3s band in Mg and there is no energy gap between the highest occupied and lowest vacant electronic energy levels and Mg is an excellent conductor.494 ENGINEERING CHEMISTRY aggregate of a large number of atoms (n). The electrons are raised to higher unfilled energy levels. The 3s band in Mg is exactly filled by the 2n electrons of the ‘n’-Mg atoms. 2p band – – E + + Combination of 4-atomic orbitals 2s band Combination of n Li atoms Fig. Let us illustrate the following cases: Let us consider Li as an example. This phenomenon explains the high thermal and electrical conductivities of metals. Similar combination of the p-atomic orbitals will form a 2p energy band containing 3n-energy levels. . 2s1. The valence electrons from all the atoms will enter every level and a metal thus consists of energy bands formed by merging of individual atomic orbitals. 22. Each Li atom has only one valence electron and the total n-electrons from n-atoms will occupy doubly the lower n/2 energy levels in the 2s-band.

The gap between these two bands. . a few of the electrons may be promoted to energy levels higher than the actual occupied region in bands. 22. This conclusion is in harmony with the Dulong’s and Petit’s law. however. it jumps across the forbidden energy gap and enters the conduction band.. So when an electron is raised from the valence band. 22. These electrons are much less in number than the valence electrons and these are responsible to the heat capacity of the metal and hence the contribution of electrons to the specific heat of metals is thus small. It may be filled by electrons completely or partially. which involves the breaking an existing covalent bond and then re-establishing a covalent bond by filling up the hole. 0 Conduction band Empty or partially filled Band Energy (eV) –1 Valence band Fully or partially filled –8 –12 Completely filled inner bands –16 Fig. if the conduction electron radiates too much energy. The energy distribution of these electrons follows roughly the Maxwell–Boltzmann law. it will suddenly reappear in the valence band again. It may be noted that the covalent forces of the crystal lattice have their source in the valence band. It has to be kept in mind that holes are filled by electrons which move from adjacent atoms without passing through the forbidden energy gap. An electron in the conduction band can jump more readily to an adjacent conduction band than it can jump back to its original position. namely valence band and conduction band. The next higher permitted energy band is called the empty band or conduction band. electrons can move freely and therefore are known as conduction electrons. But. is known as forbidden energy gap. it may be defined as the lowest unfilled energy band.20 Now if a valence electron absorbs enough energy. It is these electrons which are mostly affected when a number of atoms are brought very close together as during the formation of a solid. Valence and conduction bands The outermost electrons of an atom i. electrons residing in the outermost shell of an atom are called valence electrons having the highest energy. In conduction band. This hole can travel to an adjacent atom by taking an electron from that atom. This is shown in Fig.SOLID STATE CHEMISTRY 495 At temperatures above the absolute zero. a covalent bond is broken and positively charged hole is formed. The band of energy occupied by the valence electrons is called the valence band and is the highest occupied band.21 below.e. In fact.

0 E Conduction band Overlap Valence band 16 Fig.21 In another way it may be concluded that the conditions in the conduction band have nothing to do with the hole flow. It denotes a very important distinction between the hole current and electron current. they experience more opposition than electron flow in the conduction band. semiconductors and insulators The band theory of metals may be extended to other non-metallic solids as well. to summarise: • Conduction electrons are found in conduction band and move freely in the conduction band. In terms of energy bands it means that electrical conductors are those which have overlapping valence and conduction bands. play no part in the process of conduction. The electrons lying in the lower energy bands. 22.496 O Conduction band E ENGINEERING CHEMISTRY Valence band 5 4 3 2 1 Fig. In fact there is no physical distinction between these two bands. Conductors Conducting materials are those in which there is the availability of plenty of free electrons for electric conduction. So. which are normally filled. Conductors. Although holes flow with ease. • Conduction electrons move almost twice as fast as the holes.22 Another point to be mentioned is that here the forbidden gap is not present for good conductors. hence the availability of a plenty number of conduction electrons. The total current is simply a flow of electrons. • Holes exist in and move in the valence band. The electrical conduction properties of different elements and compounds can be explained in terms of electrons having energies in the valence and conduction bands. . 22.

In terms of energy bands. there are no electrons in the condition band and the valence band is filled completely. Fig. 22.. This is the main difference between semiconductors and good conductors. so that some of the electrons are liberated into the conduction band. but their electrical properties lie in between. Ge Covalent bond E Fig. For example – germanium (Ge) and silicon (Si). the electrical conductivity of semiconductors increases with rise in temperature and in this regard they differ from the metals whose electrical conductivity decreases with rise in temperature.SOLID STATE CHEMISTRY 497 Semiconductors A semiconductor is a material whose electrical properties lie in between those of good conductors and insulators.23 At 0 K.23 (a) Intrinsic Ge. So. . Ge A F D C Ge Ge . The resistivity of the semiconductors ranges from 105 to 10–3 ohm-cm and decreases with increase in temperature according to an exponential law.. The energy gap is of the order of 1 eV. Semiconductors are of two types: Ge atom Ge G B . As temperature increases.. 22. the width of the forbidden gap decreases. . .. 0 E Conduction band Small energy gap Valence band 16 Fig.23 (b) Hole formation in semiconductors (conduction of current). 22. The semiconductors which conduct even in chemically pure state are called intrinsic semiconductors. semiconductors are the materials which have almost an empty conduction band and almost filled valence band with a very narrow energy gap separating the two. Semiconductors are neither good conductors nor good insulators.

Example.e.23). In such semiconductors the energy gap between the valence band and conduction band is very small (Fig.23 (c) N-type semiconductor.498 ENGINEERING CHEMISTRY (i) Pure or intrinsic semiconductors.. Depending on the type of doping agent. extrinsic semiconductors are divided into two classes: (i) N-type semiconductors (ii) P-type semiconductors. i. and so on. is called acceptor atom as it accepts one electron from Ge atom. on the other hand. The electrons jump across the gap and hence they behave as insulators at absolute zero. . . P) or trivalent atoms (Ga. 22... Ge Ge . . Sb. Thus a negative charge moves from G to A. But their electrical conductivity is raised with increase in temperature to break the covalent bonds (Fig. An intrinsic semiconductor may be defined as one in which the number of conduction electrons is equal to the number of holes. B Ge Ge Ge Ge .23(b)] and the electron has moved leaving behind a hole at A where an electron jumps from B creating a hole there. 22. Let covalent bond is broken at A with increase in temperature [Fig. Sb . (ii) Impure or extrinsic semiconductors.. P. The trivalent atom.. a positive charge from A to G alternately. Ge .23(a)) to get conducting electrons (Fig. Pentavalent doping atom is known as donor atom as it donates one electron to the conduction band of pure Ge. Hole Fig. In. . Usually doping agents are: l l pentavalent atoms (As..23 (d) P-type