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# TflYSICAL CMSTR7

Bruno Under

World Scientific

ELEMENTARY

PHYSICAL CHEMISTRY

ELEMENTARY

PHYSICAL CHEMISTRY

Bruno Linder

Florida State University, USA

World Scientific

NEW JERSEY

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LONDON

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SINGAPORE

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BEIJING

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SHANGHAI

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HONG KONG

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TA I P E I

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CHENNAI

5 Toh Tuck Link. In this case permission to photocopy is not required from the publisher. This book. ISBN-13 978-981-4299-66-4 Typeset by Stallion Press Email: enquiries@stallionpress. NJ 07601 UK office: 57 Shelton Street. or parts thereof. Pte. MA 01923. Singapore 596224 USA office: 27 Warren Street. Suite 401-402. Hackensack. Pte. Ltd.. USA. ELEMENTARY PHYSICAL CHEMISTRY Copyright © 2011 by World Scientific Publishing Co. recording or any information storage and retrieval system now known or to be invented. including photocopying. . For photocopying of material in this volume. may not be reproduced in any form or by any means. London WC2H 9HE British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. 222 Rosewood Drive. electronic or mechanical. without written permission from the Publisher. Ltd. Covent Garden.com Printed in Singapore. Danvers. All rights reserved. Inc.Published by World Scientific Publishing Co. please pay a copying fee through the Copyright Clearance Center.

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To Cecelia . and Carolyn v . Nancy. Richard. . and to William. Diane. .

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and Steve Leukanech for doing the drawings. These problems were graded and discussed by the assigned teaching assistant in the recitation session. reﬂecting more or less the topic contents. elements of atomic and molecular structure. consisted of three lectures weekly and one recitation hour meeting weekly.Preface This book is based on a set of lecture notes for a one-semester course in general physical chemistry (CHM 3400 at Florida State University) taught by me in the Spring of 2009. This course was designed specially for students working towards a Baccalaureate degree in Chemical Science. there are subtleties and conceptual diﬃculties. and intermolecular forces. especially thermodynamics and quantum mechanics. chemical kinetics. which tend to obscure the logical consistency of the subject. phase and chemical equilibria. conceptual diﬃculties are not “swept under the rug”. In the ﬁeld of physical chemistry. While the emphasis in this course is not on mathematical rigor. cell potentials. The course. but brought to the fore. The course consisted of an elementary exposition of general physical chemistry and included topics in thermodynamics. It is a pleasure to thank Jared Kinyon for reading the proofs and checking the problems. often ignored in even more advanced treatments. elements of spectroscopy. Bruno Linder August 2010 vii . An essential feature of the course is weekly assignment of homework problems. introductory quantum mechanics. entitled General Physical Chemistry.

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. . . . . . .9. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Properties of Gases 1. . . . .8. . 2. . . . . The Kinetic Theory of Gases . . Internal Energy . . . . . .1. 2. . . Ideal or Perfect Gas Law . . . . . . . . 2. . . . .2. . . . . . Work and Heat . . . . . . . .9. . 11 12 12 13 14 14 15 16 17 18 2. .10. . . . . .2. . . . . . . Relation of ∆U to qV (q at constant volume) Heat Capacity . . . . 1. . . . 2. . . . . . . . .8.1. . . .6. .Contents Preface 1. .3. . . . ix . .11. . . Graham’s Law . . . . . . 1.4. . . . . . .10. . . . . . . . . . . . . . . . . . .7. . . . . . . . . . . . . . . . . . . .4. . .6. . . . Description of Some States of Matter Units . . . . . . 1. . . Classiﬁcation . . . . . . . 1. . . . . . . . . . . . . Measurement of Work . . . . . 2. . . . . . . . . . Reversible Process . . Mixtures of Gases . . . 1. 2. . . . .5. 1. . . Diﬀusion of Gases. . . . . . . . . . . . . . Measurement of Heat . State of Matter. . . . . . . State of Matter . . . . . System and Surrounding . . . . . . . . . . . . . . . . . . . The First Law of Thermodynamics 2. . . . . 1. . . . . . . . . . . . . . . . . . . . . 2. . . . .5. . . . . . . 1. . Molecular Collisions . . . . . . . Evaluation of the Gas Constant. . . . . . . . . . R . . . . . . Molecular Basis of Graham’s Law . . . . . . . .3. . . vii 1 1 2 2 3 3 4 5 7 8 9 10 11 . . . . . . Exact and Inexact Diﬀerentials . . . . . 1. 1. . . . . 2. .7. . . . . . . . . . . Real Gases . . . . 2. . . . . .

. . . . . . . . . 3. . . . . .4. . . . . .6. . . 3. . . . K Variation of K with T . . . . . . . . .2. . . . . . . . . . . . . . . . . 3. . . . . . Variation of Enthalpy with Temperature . . . . . . . . . . . . . . . . Free Energy Changes in Chemical Reactions . . . . . Molecular Interpretation of Entropy The Surroundings . Entropy change in Phase Transitions (solid–liquid. . . . . .11. . . . . . Activity . . Isolated Systems . Determination of Entropy . . . .3. . . . . . Irreversible Process . . 5. . . . . 30 30 31 32 33 5. The Phase Rule . .x Elementary Physical Chemistry 2. .1. . . . . Statements of the Second Law . . . The Free Energy Functions 5. . . . . Standard Enthalpy . . 3. . . . 2. . . . liquid–vapor.12. . . .8. .3. . . . . . The Second Law of Thermodynamics 3. . 5. 18 18 19 20 21 22 22 24 25 26 27 27 27 28 29 3. . . . . . . 5. . . . . The Chemical Potential .2. . . . . General Changes in Entropy .2. . . . . . . . . . . . . . The Gibbs Free Energy .3. . .4. . . . . .4. . . .3. . . . . . . Engine Eﬃciency . . . . . . . .2. . . . . . . .1. . . . Variation of G with T and P . . . . 5. . . . . . . . . . 6. . Molal Quantities . Phase Equilibrium . . . . . .1. . . .4. . 4. . 6. Standard Entropy . . . . . . . . . .1.4. . . . . . . .13.3. .5. Carnot Cycle . . Enthalpy Changes in Chemical Reactions . . . . . . . . . 2. . . . The Entropy of the Surroundings . . .1. Reversible Process . . . . . . . . . . . . . . . Entropy change in (Ideal) Gas Expansion . . .1. . 4. . . . . . . . . . . . . . . . . The Third Law of Thermodynamics 4. Phase and Chemical Equilibria 6. .1. . . . . . . . . Relation of ∆Go ¯ to the Equilibrium Constant. .3. . 3. 5. .1. . . . . . The Clapeyron Equation . . . 5. . . . . . .3. . . .7. . . . . .2.1. Partial Molar. . . 3. . . . . . . . 3. . . . 4. 3. . 3. . . . . . . . .3. . . . . . . .4. . 4. . . . . . solid–vapor) . .2. . . . Generalization of the Free Energy. . . . 33 35 37 37 38 39 40 41 43 43 43 44 6. . . . . . . . . . . 5. .

k . . . . . . . . . . . . . .2. . . . . . . . 6. . . Activated Complex Theory . . . . . . . The Rate-Determining Step (or Equilibrium) Approximation . . . . .2. 6. . . . . . . . . . . . .8.2. 6. Elevation of Boiling Point. . . Concentration of Products . . . .6. . . . .2.4. . . .2. .1. . . . . . . . Units of the Reaction Rate Constant. . . . .10. 7. . 7. . . . . . . . . .6. . . . . . . . . . . . . . . . . . . Elements of Electrochemistry. . . . Osmotic Pressure . . . .4. . . . . 7. . . . . . . .5. . . . . . . . . . .2. . . . . . . . . . Ideal Solutions. . . Half-Lives . . . . . . . . .4. . . . Temperature-Dependent Reaction Rates. . . . . . . . . . . . . .3. . . . . .1. . .10. Reaction Rate Theories . . . . Chemical Equilibrium. . .4. 7. . . . 7. . . . . . 7.7. . . . .1. . . . . . . . . 6. . Order of Reaction . . . . Electrochemical Cells . . 7. . . . . Redox Reactions . 7. . . . . . . . . .7. Half-Reactions. . . . 7. . Chemical Kinetics 7. . . . . . First-Order Reaction . . . . . Isolation Method . . . . . . . . . . . 7. . . . . . . . Determination of the Rate Law . .13. . . Zero-Order Reactions . . . .2. . . . . . . . 7.11. . . . . .3. . . . . Cells at Equilibrium . . . . Collision Theory . . . Ideal Dilute Solutions. . . 6. . . . . . . . . . . 7. . . . . Chemical Reaction Equilibria . . . Depression of Freezing Point . . .12. . . . .5. . . . . . The Rates of Reactions . . . Third-Order Reactions . . . . . The Steady State Approximation . . . Integrated Rate Law . . . . . . . . . . Mixtures .7. . . 7. . .1. .10. . . . 7. . . . . . . . . . . Other Reaction Orders . . .9. . . . The Arrhenius Equation . . . . . .2. 7. Henry’s Law .Contents xi 6. 6. . . . . Raoult’s Law . . .9. . . . .2. . . .2. . . . . . .2. 6. 7. 6. . . . . .2. . . 7. . . . . . . . . . . . . . .1. . . .8. . . . . . . . . . . Initial Rate Method . . .5. . . . . Colligative Properties . . . . . .2. . . . Rate Law Mechanisms . . . 6.7. . 46 46 47 49 49 52 54 56 57 58 60 60 61 62 63 63 63 64 64 66 67 67 67 68 69 70 71 72 73 74 76 7. .2.1. . . . . . 7. .2. . . . . . . . . . . . 7. . . . . . . . .

. . .5. . . . 8. . . Introduction to Quantum Theory 8. . . The Rutherford Atom . . . . . . . . . Many-Electron Atoms . . . . . . . . . . . . . . . . . . . . 8. . 7. . . . . . . Failure of Classical Theories . . . . . . . . . . . . Chain Reactions . . . .15. . . . . 9. . . . . . . .10. . . . . . . .3. . Selection Rules for Spectroscopic Transitions . . .14. . . . . . .1. . . . . . Valence Bond Theory . . . . 9. Molecular Orbital Theory Bonding and Anti-bonding . 9. . . . . . . . . . Electron Spin . . . . .2. 105 107 108 109 . . . . . . . . 8. . 9. . . . . Transitions and Selection Rules . Shells and Subshells . . Hydrogenic Atoms (H. . . 8.3. . .2. . .3. . . . . Orbitals . . . Ionization Energy . . . . . . . . . 9. . . . . . . . . . . . . . . . . . 77 77 79 82 82 83 83 84 85 86 86 88 89 92 93 94 97 8. .1. . . . 9. . . . . . . . . . . . . . . . . . . .1. Li2+ .4. . . . . Applications of Quantum Theory 9. . . . . . . . . . . . . . . . . .2. . 8. . . The Schr¨ odinger Equation . . Shapes of Orbitals . . . . Pauli Exclusion Principle . . . . . Unimolecular Reactions . Schr¨ odinger’s Cat .4. . .1. . . . 8. .2.14. . Quantum Theory. . . .2. . One-Electron Wave-Functions . . . . . . 9. 10.7. . . .4. Particle-in-a-Box . . . .4. . . . . . 8. . . . Historical Development . . . . . .3. . . . . . 97 98 99 99 99 100 101 102 102 102 103 104 10. 9. . . . . . . . .6. . .9. . . . . . . . . The Chemical Bond 10. . . . .1. . . . . . . . . . . .8. . 10. . . . . 8. . . . . . . . . . . The Bohr Theory of the Hydrogen Atom Louis de Broglie . . . . . . . 9. . . . . . . . . . . . .2. . . . . . 8. . . . . . . . . . . . . The Lindemann Mechanism . . . . 8. . . . . . . . . . . . . . . . . . . . .xii Elementary Physical Chemistry 7. . . .8. . 7. . . . . .2. Heat Capacity of Solids . . . . . Photo-Electric Eﬀect . . . . . . 9.11. . . . 9. 10. . . . . . . Structure. . . . . . Black-Body Radiation . . . . . .6. . He+ . . Wave or Particle? . . . . . 8. . . . . . . . . Translational Motion.2. . . . . . . . etc. Polyatomic Molecules . . . . . . . . Summary and Conclusions . . . . .5. . . . . . .7. . .) .

. . . . . . . . . . . .3. . . . . 111 112 113 113 113 115 11. . 5 . . IV. . . . 11. .5. . . . 11. . . . . Chapter 7 . . . . . . . . Elements of Intermolecular Forces 12. . . . Polar Covalent Molecules . . Pure Rotational Spectra . . V. . . . . . . . . 11. 12. . . . . . . Classiﬁcation of Solids by Types of Intermolecular Forces . . . . . . . . . . . . . 9 . . . . . Chapter 6 . . . . . . . . . . . . . . . . Properties of Liquids . . . . . . . . . . . . . . . . . . Chapters 3. . . . . . . . . . . III. . VI. .2. . . 10.5.9. . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . Bond Order . . . . 12. . . .5. . . . . . . . . . . . . . 120 120 121 122 123 124 125 127 127 128 129 130 132 134 135 137 139 141 . . . . . . .4. . . . . . 11. . . . .7. . Elements of Molecular Spectroscopy 11. . .2. . . .6. . . . . Electrostatic Forces . . . . . . . . 12. . . . . Vibration–Rotation Spectra . . . II. . . . . 12. . . . . . Problem Problem Problem Problem Problem Problem Problem Appendix B: Thermodynamic Data Appendix C: Standard Reduction Potentials Index . . . . . . 11. . . . .8. . . . . . . Further Requirements . . . 4. . . Types of Intermolecular Forces . . . . . . . . . . . 115 115 116 116 117 117 120 12. . . . . . . . . 12. . . . 12 . . . Appendix A: Homework Problem Sets Set Set Set Set Set Set Set I. . . . . . . . 10. VII. . . . . . Structure of Polyatomic Molecules Normalization.1. . . . Intermolecular Forces and Liquid Properties . . . . .4. . . 10. . . . . .6. . Normal Constants . . . .2. . . . . . . . 10. . Vibration–Rotation Spectra of Diatomic Molecules Rotational Selection Rules . . Normalization Molecules (MO) . . . . . Chapters 10. . Chapter 2 . . . . . . .Contents xiii 10. 11. . . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . . .1. Hydrogen Bonding . . . Chapters 8. . van der Waals Forces . . Vibrational Selection Rules . .1.1. . . . . . Chapter 1 . . . . . 12.

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Chapter 1

State of Matter. Properties of Gases

Chemistry deals with the properties of matter, the changes matter undergoes and the energy that accompanies the changes. Physical Chemistry is concerned with the principles that underlie chemical behavior, the structure of matter, forms of energy and their interrelations and interpretation of macroscopic (bulk) properties of matter in terms of their microscopic (molecular) constituents. Broad classiﬁcation of Matter: A gas ﬁlls the container and takes on the shape of the container. A liquid has a well-deﬁned surface and a ﬁxed volume but no deﬁnite shape. A solid has a deﬁnite shape, a ﬁxed volume, and is independent of constraints. The foregoing classiﬁcation is a macroscopic classiﬁcation. From a microscopic (molecular) point of view — a gas consists of particles that interact with each other weakly; a liquid consists of particles that are in contact with each other but are able to move past each other; and a solid consists of particles that are in contact with each other but are unable to move past each other. For short, in a gas, particles have essentially no restriction on motion; in a solid, particles are locked together, mostly with ﬁxed orientation; and in liquid, particles behave in a manner between gas and solid. 1.1. State of Matter The above classiﬁcation is often referred to as a classiﬁcation into states of aggregation. In physical chemistry, the word state generally refers to another concept. A substance is described by its properties (pressure, volume, temperature, amount, composition, etc.). If all the properties

1

2

Elementary Physical Chemistry

of a substance are speciﬁed, the state of the system is said to be speciﬁed. Actually, there is no need to specify all properties, because, as a rule, the properties are interdependent. For example, if you know the pressure, the volume and the number of moles n of an ideal gas, you can ﬁgure out the temperature from the equation of state: [P V = nRT ]. 1.2. Description of Some States of Matter • Volume, V : a measure of occupied space. • Pressure: force per unit area. • Temperature: hard to deﬁne rigorously,∗ but in simple language it is a measure of the degree of hotness or coolness for which all of us have an intuitive feeling. • Amount of substance: a measure of the amount of matter.

∗

Comment: When two objects (bodies) are brought in contact with each other, the hotter body will cool, the colder body will heat up. This is interpreted that heat (a form of energy) is ﬂowing from the hotter body to the colder one. This process will continue until no more heat is transferred. When that happens the two bodies are said to be in thermal equilibrium — and the temperatures of the two bodies will be the same.

1.3. Units The recommended units are SI (Systeme Internationale) units: Length l Mass m Time t Electric current I Temperature T Amount n meter, m kilogram, kg second, s ampere, A Kelvin, K mole, mol

All other physical quantities that we use can be derived from these. For example, volume is length cube or m3 . Some derived quantities have special names. For example, • • • Force in SI units is kg m s−2 or Newton, N. Pressure in SI units is kg m−1 s−2 or pascal, Pa. Energy in SI units is kg m2 s−2 or joule, J.

414 L at STP (273.08206 atm L K−1 mol−1 b) If V is in cm3 . all having the dimension of energy per degree per mol.5) (1.3) Charles’ Law (1. Evaluation of the Gas Constant. R = (1 atm)(22. volume. 1) Holding constant n and T gives P V = const or P1 V1 = P2 V2 2) Holding constant P and n gives V /T = const or V1 /T1 = V2 /T2 3) Holding constant P and T gives V /n = const or V1 /n1 = V2 /n2 1. a) R is most easily calculated from the fact that the hypothetical volume of an ideal gas is 22. 1.06 atm cm3 K−1 mol−1 (1. Properties of Gases 3 Other (non-SI) units frequently used are: • Pressure: mmHg or Torr (1 Torr = 133. R The gas constant can be expressed in various units.1) . R = (1 atm)(22.4) Avogadro’s Law (1.1 K and 1 atm).414 L mol−1 )/(273.16 K ) = 0.3 Pa) or atm (1 atm = 760 mmHg) or 101. temperature and quantity of substance.325 kPa bar (1 bar = 105 Pa) • Energy: electron volt.5.2) Boyle’s Law (1. 414 cm3 mol−1 )/(273. Ideal or Perfect Gas Law P V = nRT This Law comprises three diﬀerent Laws that preceded it. Accordingly.State of Matter.4.16 K) = 82.602 × 10−19 J) Equation of state is an algebraic relation between pressure. eV (1 eV = 1.

6) e) In cgs units (V in cm3 .16 K Also 1 erg = 107 J.0 g mol−1 ) × (0.25 × 101.414 × 10−3 m3 mol−1 /273.314 × 107 erg K−1 mol−1 f) In cal K−1 mol−1 (1 cal = 4.013 × 106 dyne cm−2 ).314 J K−1 mol−1 [1 Pa = 1 kg m−1 s−2 ] (1.0826 atm L K−1 mol−1 × 298.325 kPa/atm = 5.01325 × 105 Pa × 22. 50.184 J). 414 cm3 mol−1 )/273.9) (1. R = 1.7) (1.314 kg m2 s−2 = 8. R = 1. R = (1.0 g/28.314 Pa m3 K−1 mol−1 = 8.1. R = 8.0 g of N2 (M = 28. Mixtures of Gases The partial pressure of a gas in a mixture is deﬁned as the pressure the gas would exert if it alone occupied the whole volume of the mixture at the same temperature.15 K.90 × 103 kP 1.01325 × 105 Pa.6. Solution P = nRT /V = (50.25 atm = 58. Assuming the gas behaves ideally.314 k Pa L K−1 mol−1 d) In J K−1 mol−1 . P in dyne/cm2 .16 K = 8.0 g) occupies a volume of 750 mL at 298. 1 atm = 1. Dalton’s Law states that the total pressure is equal to .8) Example 1.750 L = 58.4 Elementary Physical Chemistry c) In Pascal L K−1 mol−1 [1 atm = 1.15 K)/0. 1 L= 10−3 m3 ].987 cal K−1 mol−1 (1. R = 8.013 × 106 dyne cm−2 ) × (22. calculate the pressure of the gas in kPa.

The Kinetic Theory of Gases The theory is based on the following assumptions: 1.1) of the cubic box. each of weight m. Accordingly. it is reﬂected in the opposite direction. Depicts a particle in a cubic box of sides L colliding with the shaded . 1. If the distance between the shaded wall and Fig. = Σi ni RT /V = RT Σi ni /V = nRT /V where n = Σi ni is the total number of moles.] 1. the velocity of molecule in the X-direction is ux . 4. Pi /P = ni /n = xi or Pi = xi P (1. 2. There are N molecules. Molecules are in constant motion. Consider one molecule in a cubic box colliding with a shaded wall parallel to the YZ direction.10b) (1. P = Σi Pi. Before collision.10a) [This relation is strictly valid for ideal gases.State of Matter. When the molecule collides with the shaded wall (see Fig. 3. They collide with each other and with the walls of the container. 1. Properties of Gases 5 the sum of the partial pressures.7. The volume of molecules is negligible compared to the volume of container. having a velocity of −ux and a change of velocity of 2ux . That is.1 wall. molecules do not interact with each other. In ideal gases.

The molecule will make ux /2L collisions per unit time with the shaded wall.6 Elementary Physical Chemistry the opposite wall is L. the change in momentum per unit time will be N m u2 stands for average. Example 1. where M is the molar mass.12b) Equating this to the ideal gas law gives. This oversimpliﬁed analysis shows how a macroscopic (thermodynamic) property. can be related to the microscopic (mechanical) property.12a) If NA is Avogadro’s number.e. the molecule is reﬂected in the opposite direction. What is the mean square speed of a N2 molecule (treated as an ideal gas) at a temperature of 25◦ C and a pressure of 1 bar (105 Pa)? Using R = 8. the root-mean-square velocity: crms = c = c2 = (3RT /M ) (1. Pressure is force per unit area. Thus.2. and so P = N m u2 x /V . and a change of velocity of 2ux. we can write 1 2 2 ux = 3 c .e. Accordingly. having a velocity of −ux . For N molecules. yielding P = 1 1 N m c2 /L3 = N m c2 /V 3 3 (1. then N m = nNA m = nM . molecular velocity.314 Pa m3 K−1 mol−1 and observing that 1 Pa = 1 kg m−1 s−2 and that the molar mass of N2 is M = 28. i. where V is the volume V = A × L. c2 = u2 x + uy + uz .11) 2 2 If c denotes the speed in 3-dimensions. 3 P = f /A2 = N m u2 x /L (1. pressure. x /L where In classical mechanics.12c) Conclusion: The root-mean square speed of a molecule in an ideal gas is proportional to the square-root of the temperature and inversely proportional to its mass. PV = 1 nM c2 3 (1. i. the change in momentum per molecule per unit time at the shaded wall will be (2mux ) × (ux /2L) = mu2 x /L. Thus. the momentum change on an area represents the force exerted on that area.0 g/mol or . P = f /A. for n = 1. Denoting the force as f we can write f = N m u2 x /L as the force exerted on the shaded wall.

Comment 2: So far we have dealt only with average speeds. ε = 3 RT /NA 2 (1. λ. speed up afterwards. but with the average kinetic energy of a large number of molecules. P V = RT = 2 NA ε 3 (1. is the average distance (of molecules) between collisions. etc. Molecular Collisions The mean free path.38 × 10−16 erg K−1 molcule−1 ) gives ε = 3 kT 2 (1. Finally. An expression of the distribution of speeds was derived by Maxwell . The collision frequency. c. Molecules slow down as they collide with one another.2 ms−1 We now have a relation between the macroscopic quantity T and the microscopic property. 1. the speeds of molecules vary enormously.13c) Deﬁning R/NA as Boltzmann’s constant (k = 1.14) Comment 1: Temperature is not associated with the kinetic energy of a single molecule.0 × 10−3 kg/mol gives crms = (3 × 8.3145 × kg m2 s−2 K−1 mol−1 × 298 K/28 × 10−3 kg mol−1 )1/2 = 515. Actually. Since the average energy of molecule is ε = 1 m c2 we immediately obain 2 PV = and for one mole.13a) where NA is Avogadro’s number.13b) 2 N ε 3 (1.2. 1.8. z . Properties of Gases 7 28. A schematic diagram of the variation of speed with temperature is depicted in Fig.State of Matter. is the rate at which single molecule . It is a statistical concept.

The kinetic theory developed so far cannot be used to derive λ.8 Elementary Physical Chemistry Fig. It is obvious that the root-mean-square speed is c = λz . If D1 and D2 represent the rate of diﬀusion of Gas 1 and of Gas 2. The result (not derived here) is √ (1.2 Variation of the number of molecules with speed. σ = πd2 . collides with other molecules (i. 2) When P increases.9. 3) Gases with larger σ have smaller λ and greater z . Graham’s Law suggests that the rate of diﬀusion is inversely . and d the diameter. Graham’s Law states that the rate of diﬀusion is inversely proportional to the square root of the density. number of collisions/second). Eﬀusion is escape of a gas through a small hole. The rate at which gases diﬀuse depends on the density. 1.15) λ = RT /( 2NA σP ) √ z = 2NA σcP/(RT ) (1. λ increases and z increases. 1. Note: 1) λz = c.e. Diﬀusion of Gases.16) where σ is the area. We must take into account the ﬁnite size of the particles. Graham’s Law Diﬀusion is the tendency of a substance to spread uniformly through space available to it.

21a) It follows also that for the same gas at diﬀerent temperatures.19) (1. we can write P = (m/V )(RT /M ) = (ρ/M )RT It follows that for two gases at a given P and T . Example 1. root-mean-square velocity.State of Matter.21b) and for diﬀerent gases at the same P and T . D1 /D2 = (T1 /T2 ) (1. ρ2 /ρ1 = M2 /M1 and thus D1 /D2 = (M2 /M1 ) (1.4 m s−1 . Taking R in Joule (1 J = kg m2 s−2 ) and M in kg mol−1 . that is. we get c= (3 × 8. Properties of Gases 9 proportional to the square root of the density.3145 kg m2 s−2 × 298.20) (1. D1 /D2 = c1 /c2 = { (3RT /M1 )/ = M2 /M1 (3RT /M2)} (1.028 kg mol−1 ) = 515. a) Calculate the root-mean-square speed (in ms−1 ) of a H2 molecule at T = 298.18) 1.21c) in accordance with the kinetic theory of gases. The root-mean-square speed is c = (3RT /M ).3. D1 /D2 = (M2 /M1 ) (1. ρ.15 K/0.17) Since for an ideal gas P V = (m/M )RT . D is proportional to Accordingly.10. That is D1 /D2 = (ρ2 /ρ1 ) (1. Molecular Basis of Graham’s Law It is natural to suppose that the rate of diﬀusion is proportional to the c2 or to c.15 K. where m is the total mass of the gas and M its molecular weight.

11. etc. This is obviously unrealistic. The energy comes from the gas — the gas cools! .0) = 0.0 g mol−1 ) The ratio is proportional to the ratio of the speeds of the molecules.95 [M (N2 )/M (O2 )] = (1.10 Elementary Physical Chemistry b) Calculate the ratio of the rate of diﬀusion of O2 (M = 32. the gas cools.0 g mol−1 ) to N2 (M = 28. An equation of state that takes into account these interactions is the a) van der Waals equation of state (P + an2 /V 2 )(V − nb) = n RT where a and b are constants.22) (1. It takes energy to do that. C the third virial coeﬃcient. there are shortrange repulsive forces and long-range attractive forces. Why? In the compressed state the molecules are close to each other. ideal gases consist of molecules that do not attract or repel each other. when the gas expands the attractive van der Waals bonds are broken. or electrical charges). etc. the molecules are farther apart. there is great attraction. Therefore.23) where Vm is the molar volume of the gas. (D of O2 /D of N2 ) = c (O2 )/c(N2 ) = = 1. When a compressed gas in a container is forced through a porous plug into another where it is less compressed (the Joule–Thomson Experiment).0/32. Attractive forces are needed to account for liquefaction of gases. From a molecular point of view. Real Gases So far attention was focused on ideal gases. In a real gas (even if the molecules have no dipoles. which invalidates the ideal equation of state. In the dilute state. B the second virial coeﬃcient. quadrupoles. and if P and T are the same for both molecules. Another equation of state is the b) Virial equation of state 2 + ···] P Vm = RT [1 + B/Vm + C/Vm [3RT /M (O2 )]/[3RT /M (N2 )] (28.

Classiﬁcation If NA is Avogadro’s number. Free Energy. PV = 1 nM c2 3 Equating this to the ideal gas law gives. then N m = nNA m = nM . all having the dimension (in SI units) of kg m2 s−2 .1. to be introduced later. There are various classiﬁcations of energy. etc. such as Enthalpy. Kinetic energy is the energy an object possesses by virtue of its motion. and related forms. Heat. In Thermodynamics the most useful forms of energy are Work. c2 = 3RT /M A. Kinetic and Potential Energy. Thus. Potential energy is the energy an object possesses by virtue of its position or composition. 11 . This classiﬁcation is not very useful in Thermodynamics. for n = 1. The term energy is diﬃcult to deﬁne rigorously. 2. where M is the molar mass. Internal Energy.Chapter 2 The First Law of Thermodynamics Thermodynamics is concerned with the laws that govern the transformation of one kind of energy into another during a physical or chemical change. An intuitive way is to say that energy is the capacity to do work. B.

which is part of the universe in which one is interested. It is convenient to characterize a system as either • • • Open. 2. Heat is energy transfer that involves chaotic motion of the surrounding molecules. electrical work. Work and Heat Work and Heat are always associated with transfer of energy between systems and surrounding. gravitational and other types of work. Energy is a property of the system. Comment: There are various types of work: work associated with expansion or compression (we will call that PV work). but it will not be pursued in this course. which is a system that cannot exchange energy or matter with the surrounding. work is a form of energy transfer that utilizes uniform motion of the molecules in the surrounding. Work is the energy transfer that can be used to move boundaries of a system.2. There is a rigorous approach. which is a system that cannot exchange matter with surrounding. the axiomatic approach . or ˙ lift weight. From a molecular (as opposed to thermodynamic) point of view. Temperature obviously plays an important role in thermodynamics. More explicitly. . or Isolated. namely • • system . which is a system that can exchange energy and matter with the surrounding. We will denote the pressure– volume work as wPV and all types of work as wother .3. System and Surrounding We now introduce concepts which are essential to the application of thermodynamics. Heat is the energy transfer due to temperature diﬀerence between the system and surrounding. For the most part. The deﬁnition used here — thinking of temperature as a measure of degrees of hotness or coolness — is obviously not rigorous. or Closed. the rest of the universe or what is not the system. we will be concerned in this course with PV work.12 Elementary Physical Chemistry 2. and surrounding.

acted on by the external force fext .1) is compressed.4.1) b) When a gas in a cylinder (see Fig.e. m × g . fext .3) (2. the maximum work is obtained when the internal gas pressure is inﬁnitesimally less than the external. the piston. Fig.1 Compression of a gas by piston. compression cannot occur. a force must be applied in the direction away from the earth. The change in the volume of the system is dV = −Adx. the work done by the surrounding on the system is dwPV = (fext /A)Adx = −Pext dV For constant Pext the integrated value is wPV = −Pext ∆V (2. Force is mass times acceleration. The piston is displaced a distance dx in the direction of the force. which is equal to the mass times the gravitational acceleration. If greater.2) where ∆V = Vf − Vi . 2. (The negative sign is introduced because the ﬁnal volume Vf is smaller than the initial volume Vi . Measurement of Work Work is distance times force. 2. Obviously. moves a distance dx in the direction of fext . The following are examples of work: a) When lifting an object.The First Law of Thermodynamics 13 2. i.) Accordingly. the work done by the surrounding on the system is w = h × mg (2. If the object moves a distance h. . The external pressure on the piston of area A is Pext = fext /A.

A reversible process is a process which proceeds through a succession of equilibrium states . that is dTA /dTB = −CA /CB (2. for an ideal gas. then Pext = P and.5) . If the equilibrium temperature is T . Reversible Process When the internal pressure P is equal to the external one Pext . Measurement of Heat The traditional way to discuss the concepts of temperature and heat is to deﬁne one of these and deduce the other from it.6.4) Note again that the work is positive in a compression (Vf < Vi ) and negative in an expansion (Vf > Vi ). are sometimes used in deﬁning heat. Using such descriptions of heat to deﬁne temperature is obviously not very satisfactory and will be avoided here. Statements such as radiant energy. Therefore. the system is said to be in a state of equilibrium. whose initial temperature is TB . small changes in temperature of the two systems can be written as dTA = T − TA and dTB = T − TB . Attempts to deﬁne temperature in terms of heat are bound to cause diﬃculties since normally heat is not observed directly but inferred from changes in temperature. B.5. Consider a system. Comment: The concept of heat is most conveniently described in terms of the heat capacity. 2. P = nRT /V . initially at a temperature TA in equilibrium with a system. thermal heat ﬂow. An inﬁnitesimal increase in Pext will result in an increase in compression and an inﬁnitesimal decrease in Pext will result in an increase in expansion. A.14 Elementary Physical Chemistry 2. we introduce the concept by focusing directly on temperature changes of two systems in thermal equilibrium. The ratio of these quantities deﬁnes the ratio of the heat capacities . If an ideal gas is in equilibrium with its surroundings. the work (done by the surrounding on the system) in a reversible change is wPV = − ∫ (nRT /V )dV = −nRT ln Vf /Vi (2. Here. which is the heat divided by the temperature change (Section 10).

Once heat capacity is deﬁned.7) dq = C dT (2.] (2. Convention about signs In this course. Internal Energy When the surrounding does work on or supplies heat to the system. [Engineers often use the convention that work is positive when done by the system on the surrounding. q = ∫ C dT and.] Conservation of energy in Thermodynamics is eﬀectively the First Law of Thermodynamics. and a more accurate statement would be: Energy–matter must be conserved. 2.7. q = C ∆T .6b) .) If a particular value is assigned to one of the heat capacities. energy and matter can be interconverted.8) (2.6a) or For macroscopic systems. heat transferred can be expressed by the relation. (and used in most scientiﬁc but not engineering treatments. because one of the dT ’s has to be negative and we require the C ’s to be positive. [Note: since the advent of relativity. if the heat capacity is constant. It can be expressed as ∆U = q + w where. the other is automatically established. the surrounding loses energy. which tells us that w is positive in a compression and negative in an expansion. The energy lost by the surrounding is gained by the system in the form of internal energy.) w represents the work done by the surrounding on the system and q is the heat supplied by the surrounding to the system. Comment: Consistent with this convention is the formula dwPV = −Pext dV . w stands for total work: w = wPV + wother . and their First Law reads ∆U = q − w.The First Law of Thermodynamics 15 (The minus sign is introduced. in general. as indicated previously. But energy cannot be lost or gained — energy must be conserved. q/∆T = C (2.

But the sum of these two is independent of the path. Their integrated values depend on the path of integration. Obviously. This shows that individual integrals may be path-dependent. dU is an exact diﬀerential — its integral depends only on the initial and ﬁnal states of the system and not on the path of integration. but their sum could be path-independent (see Fig. 2. Exact and Inexact Diﬀerentials The First Law is frequently expressed in diﬀerential form: dU = dq + dw (2.9) There is a diﬀerence between the diﬀerentials dU on the one hand and dq and dw on the other hand. There are other state functions. which are denoted by small letters. The diﬀerentials dq and dw are generally not exact. . Fig. the value depends on the path of integration. All will be denoted by capital letters in contrast to the concepts of work and heat. 2.2). consider the integration of y dx (the horizontally shaded area) between the limits A and B.16 Elementary Physical Chemistry Note: U is a state function. As an illustration of the meaning of exact and inexact diﬀerentials. to be introduced later.8.2 Graphical representation of the sum of the integrals ∫ y dx + ∫ xdy . 2. meaning it is independent of the previous history of the system but depends only on the current state and not on the way the state was formed. The quantities q and w are not state functions. The same is true for the integral xdy .

with Pext = P . Question: Is there a state function which can be simply related to qP . then at constant pressure.11) These are useful relations.13) (2. chemists as a rule do not work with constant volumes. However. If there is other work. ∆U = q − Pext ∆V dU = dq − Pext dV If the volume is constant.The First Law of Thermodynamics 17 2. There is only PV work. ∆U = qP + wPV = qP − P ∆V and ∆H = qP dH = dqP (2. because U is and so are P and V . ∆H = ∆U + P ∆V If there is only PV work. wother .12) (2. Then.14) It is important to keep in mind that the above relation is valid only if there is no work other than PV work.15) (2. the change in H at constant temperature will be ∆H = qP + wother (2.17b) (2.17a) (2. ∆U = qV dU = dqV (2. the heat at constant pressure? There is! That function is the enthalpy .10) (2.18) .) Consider a change at constant pressure P .16) (2. H . because they allow the internal energy change to be obtained from measurements of qV . Relation of ∆U to qV (q at constant volume) Consider an expansion against a constant external pressure Pext . say in a bomb calorimeter.9. deﬁned as H = U + PV (H is a state function.

one can obtain the result from the following reactions.19) which is diﬃcult to produce. and speciﬁc heat capacity (heat capacity per gram). ∆H = +67. CO2 → CO + ∆H = −94.22) 1 O2 . Standard Enthalpy Standard enthalpy. the use of molar heat capacity is standard. It is pointed out that dqP = dU + P dV [Eq. at constant volume.1 kcal mol−1 (2. Standard enthalpy .10.20) with ∆H = −26.16)].m − CV. if one wants to know the enthalpy change for C+ 1 O2 → CO 2 (2. cg .12. Enthalpy Changes in Chemical Reactions What makes the enthalpy particularly useful is that the integral is independent of the path of integration.11. dqv /dT = (∂U/∂T )V = CV and at constant pressure. The heat capacity depends on the amount of material. Obviously. is the heat absorbed divided by the change in temperature. For one mole of an ideal gas. Most often used are the molar heat capacity (heat capacity per mole). In scientiﬁc work. For example. and molar heat capacity at constant pressure. dU = dq − P dV and dH = dU + P dV + V dP = dq + V dP .18 Elementary Physical Chemistry 2.21) (2. P V = RT . (2. 2. is the enthalpy of a system at one bar pressure and a speciﬁed temperature (usually 25◦ C). as noted earlier. CP. CV.6 kcal mol−1 2 Adding the two reactions gives Eq. in diﬀerential form. C = q/∆T or. In the absence of work other than PV work.m = dqP /dT − dqv /dT = P (∂V /∂T )P = P R/P = R 2.m . In addition to characterizing the heat capacity by the amount of material. Cmol . Heat Capacity The heat capacity. The heat capacities most often used are molar heat capacity at constant volume. (2. denoted as H o ¯ .5 kcal mol−1 .m . dqP /dT = (∂H/∂T )P = CP . which are easy to measure C + O2 → CO2 . it is also necessary to specify the condition under which the change takes place. and so CP. C = dq/dT .20) (2.

23) we can write for CP (∂H/∂I )P = CP and dH = CP dT (2. ∆r CP = Σi ni CP. C = q/∆T .ni (reactants) o o ∆ r H = Σn i H i ¯ (prod) − Σni Hi ¯ (react) o o ∆r H ¯ (T ) = ∆H ¯ (T ) + ∆CP ∆T (2.28) (2. Variation of Enthalpy with Temperature Returning to the concept of heat capacity.26) (2. The standard enthalpy of formation of an element is taken to be zero. 2.13. or more precisely C = lim (q/∆T ) = dq/dT ∆T →0 (2. changes to T and CP is constant H (T ) = H (T ) + CP (T − T ) For a chemical reaction.ni (products) − Σi ni CP.27) (2.The First Law of Thermodynamics 19 of formation is the standard enthalpy of reaction of the formation of a substance formed from its elements in their standard states.24) If the temperature.25) . originally at T .

20 . 5) Some solvents (for example. It was once thought that if ∆U is negative (energy is lowered).5 kcal mol−1 ). Such and many other experimental facts are not covered by the First Law.28 kcal mol−1 ) but occurs spontaneously. For example. the reaction H2 O (s. ∆H for the reaction Ag(s) + 1/2Hg2 Cl2 (s) → AgCl(s) + Hg(l) is positive (+1. For example. For example. others do not.Chapter 3 The Second Law of Thermodynamics The First Law enables one to determine energy changes that accompany given processes. benzene and toluene) mix completely although heat has to be supplied and the enthalpy change is positive. 2) Expansion of a gas into a vacuum occurs spontaneously. The First Law does not say whether such processes occur (spontaneously!) or do not occur. 4) It was once thought also that a negative ∆H is the proper criterion for spontaneity. There would be no violation of the First Law if heat would ﬂow from the colder to the hotter body as long as there is no net gain or loss of energy. This is frequently true but not always. but the reverse does not occur. 10◦ C) → H2 O (l. 3) Some chemical reactions occur spontaneously. 1) When two bodies in thermal contact are brought together. This is generally the case but not always. heat will ﬂow from the hotter to the colder body. the change will occur spontaneously. The reverse process (heat ﬂowing from the colder to the hotter body) does not even occur. 10◦ C) occurs spontaneously although ∆U is positive (∼ +1.

5) (3. behaves in a characteristic manner.1. experiences an increase in entropy. S = qrev /T (3. which as a consequence of the second Law. the First Law does not account for a large number of observations. if isolated. a new concept (the entropy) is introduced. In more fancy language. Rather. The entropy functions have the following characteristics: 1) S is a state function. the system. i. which are based on the observation that heat cannot spontaneously ﬂow from a colder to a hotter body.1) It is important to keep in mind that the simple relation between S and q is valid only under reversible conditions.3) (3. the entropy .The Second Law of Thermodynamics 21 Apparently. the integral dS is independent of path. S .2) (3. 3) For a non-isolated system at constant temperature. entropy does not exist but rather that under those circumstances entropy is not simply related to q. depending on whether the change is reversible or irreversible. 2) In an isolated system. Actually. any transformation will result in ∆S > 0 if change is irreversible or spontaneous ∆S = 0 if change is reversible or in equilibrium (3. ∆S = qrev /T ∆S > qirr /T if the process proceeds reversibly if the process proceeds irreversibly (3. Statements of the Second Law There are several ways to express the Second Law (Laws are often called Principles). This means that the integral of dqrev /T is also independent of path in spite of the fact that dqrev is path-dependent. This does not mean that when the process is not reversible. is deﬁned as dS = dqrev /T or if T is constant. the Second Law is not directly concerned with questions of spontaneity.e.4) Since all naturally occurring phenomena are irreversible changes. . This new function. Evidently another Law is needed and that other Law is the Second Law of Thermodynamics.6) 3.

1 and 3.e. followed by an adiabatic (no heat transfer) expansion of the gas from V2 to V2 . T2 . thereby generating work.22 Elementary Physical Chemistry the statement is usually expressed in the form of two equivalent Principles: Claussius Principle : It is not possible to construct an engine which has the sole eﬀect of transferring heat from a lower temperature reservoir to a higher one. The system (gas) is connected to an engine. It can be shown that either statement leads to the conclusion that dqrev /T is path-independent and this statement is used to deﬁne entropy. Carnot Cycle The standard way of proving the foregoing statements is by means of a Carnot cycle. [Note: q2 and q1 are symbolic representations: q2 is positive.2).] 3.3)–(3. extracted from the high temperature reservoir T2 is used to run the Carnot cycle. It can be shown also rigorously that statements (3. The heat. and returning the remaining heat q1 to the reservoir at the lower temperature T1 . and q1 is negative. i. and the other at the lower temperature.6) are valid. and thus the work done by the system must be −w. Engine Eﬃciency The eﬃciency. is deﬁned as the work done by the system in a complete cycle divided by the heat absorbed at the higher temperature. 3. Work done on the surrounding has a negative sign because we use the convention that w represents the work done by the surrounding on the system. 3. Kelvin–Planck Principle : It is not possible to construct an engine which has the sole eﬀect of converting heat entirely into work. q2 .7) . T1 (see Figs. ξ . or. ξ = −w/q2 (3. This is a reversible cycle consisting of an isothermal expansion of a gas from a volume V1 to a volume V2 at a temperature T2 . and ﬁnally followed by an adiabatic compression from V1 to V1 .2.3. consisting of two heat reservoirs. −w. one at the higher temperature. then followed by an isothermal compression from V2 to V1 at a temperature T1 .

The curves represent two isotherms and two adiabats. 3. it follows that q + w = 0. The upper isotherm is the higher temperature. transferring heat from the high temperature reservoir to the lower. ∆U = 0 (why?) and since ∆U = q + w (q = q2 + q1 ).8) . Thus. Note that in the complete Carnot cycle.The Second Law of Thermodynamics 23 Fig. 3.1 Carnot cycle. ξ = (q2 + q1 )/q2 = 1 + q1 /q2 (3. Fig.2 Carnot cycle running in a clockwise direction. The work done by the system on the surrounding must be represented by −w because by our convention w represents the work done on the system.

10a) Recalling that CP − CV = R for an ideal gas. we can write for the high temperature isothermal transition dU = 0 = dq2 − P dV = dq2 − RT2 dV /V (3. Accordingly.11b) (3.9) keeping in mind that an ideal gas varies only with temperature. gives CV dT /T + RdV /V = 0 (3. dT /T + [R/CV ]dV /V = dT /T + [(CP − CV )/CV ]dV /V = dT /T + (γ − 1)dV /V Integration along the adiabat from the high isotherm (T2 . dU = CV dT. Integrating from V1 to V2 at constant T2 gives (see Fig. 3.1) gives ln(T1 /T2 ) + (γ − 1) ln(V2 /V2 ) = 0 (3.1. 3.10b) (3. the low temperature transition at T1 gives q1 = RT1 ln V1 /V2 Adiabatic changes of ideal gases obviously obey the rule dq = dU − RT dV /V = 0 Recall that at constant volume ∆U = qV and so (dU/dT )V = dqV /dT = CV and therefore. V2 ) to the low isotherm (T1 . Reversible Process Using an ideal gas as the work producing system.11a) as dq = CV dT + Dividing by T . we get. we can express (3. upon dividing by CV . and introducing the symbol γ = CP /CV .24 Elementary Physical Chemistry 3.12a) .11c) RT dV = 0 V (3. V2 ) (see Fig.3.11a) (3.1) q2 = RT2 ln V2 /V1 Similarly.

for simplicity.3. q2 < q2 . 3. we must have ∗ −w∗ /q2 > −w/q2 (3.12c) shows that V2 /V2 = V1 /V1 or V2 /V1 = V2 /V1 .10a) yields ξ = 1 − T1 /T2 (3. q1 > q1 .The Second Law of Thermodynamics 25 Similarly. V1 ) to the higher isotherm (T2 .2.13) Note that since ξ = −w/q2 = (q1 + q2 )/q2 = 1 + q1 /q2 it follws that q1 /q2 = −T1 /T2 and thus.3). Dividing both sides of (3. coupled together (Fig.14) by −w∗ . (3. Replacing this by the diﬀerential form dqrev /T (emphasizing the reversible nature of the process) yields. and since ξ ∗ > ξ . upon integration along a closed contour. adjust the engines so ∗ < 1/q2 that −w∗ = −w. there is no prohibition! Since ξ = 1 − T1 /T2 for .14) Consider now two Carnot cycles. (3. Denoting the irreversible eﬃciency as ξ ∗ and the reversible as ξ . Let us.10b).8) and using (3. q1 /T1 + q2 /T2 = 0.12c) (3. the starred and the non-starred one. shows that q1 = −RT1 ln V2 /V1 (3. Irreversible Process What is the eﬃciency when the process is irreversible? Let us ﬁrst assume that the eﬃciency is greater for the irreversible than for the reversible case.12a) with (3. for the adiabatic transition from the lower (T1 . Can the eﬃciency of an irreversible change be less than that of a reversible change? Yes. Substituting this result in Eq. in violation of the Clausius Principle. 1/q2 ∗ ∗ and therefore.12b) Obviously. substituting this expression in Eq. dqrev /T = 0. is transferred from the lower means that heat. which is another indication that dqrev /T is an exact diﬀerential. since the w’s are the same. in the amount of q1 temperature reservoir to the higher temperature one.12d) Finally. Hence. So the eﬃciency of an irreversible change cannot be greater than that of a reversible change. 3. V1 ) we obtain ln(T2 /T1 ) + (γ − 1) ln(V1 /V1 ) = 0 which is equivalent to ln(T1 /T2 ) + (γ − 1) ln(V1 /V1 ) = 0 (3. comparing (3. This ∗ − q1 .

3. ∆S = SB − SA ≥ B A dq/T (3. dqirr /T < 0 3. ξ ∗ must be less than 1 − T1 /T2 for an irreversible case. and retuning from B to A (by another path) reversibly.16) Changing the second integration from A to B (which requires changing sign) gives B A dqrev /T > B A dqirr /T (3.18) where the sign > refers to an irreversible change.3 Two coupled Carnot cycles. General Changes in Entropy Consider a system undergoing a change from A to B irreversibly. . we can say that in general. for the irreversible case. In diﬀerential form this becomes. Since part of the transformation is irreversible. Hence. and the = sign refers to a reversible change. (1 + q1 /q2 )irr < (1 − T1 /T2 ) which gives q1 /T1 + q2 /T2 < 0.17) Since the integral over the reversible heat represents the entropy change. a reversible change. 3.15) dqirr /T + A B dqrev /T < 0 (3. Accordingly. The one on the left runs in the forward direction.3. after integration along a closed contour. the overall change is irreversible. the one on the right runs in the reverse direction.26 Elementary Physical Chemistry Fig. B A (3.

18) takes the form ∆Sisolated ≥ 0 (3. we have it for all.4. Thus. 3. H2 O (s.3. and most often one calculates entropy changes of isolated systems. (3. 0◦ C) = H2 O (l. 0◦ C) ∆H = 6.21) ii) At constant T and P .20) (3. Determination of Entropy Note: We consider in this section only reversible changes. where dq = 0. was derived for a particular system — an ideal gas. qP = ∆H and ∆S = ∆H/T Example 3. Entropy change in Phase Transitions (solid–liquid. Isolated Systems Variation of heats is diﬃcult to determine.4. if we derive the entropy for one system.4.1.15 K = 21.The Second Law of Thermodynamics 27 3. which relates entropy to heat change divided by temperature.01 kJ mol−1 ∆S = 6010J mol−1 /273. for an isolated system.99J K−1 mol−1 .1. Thus. Eq. 3. solid–vapor) i) At constant T ∆S = dq/T = q/T (3. liquid–vapor. What assurance do we have that the eﬃciency criterion applies to other systems? It does! There is a theorem (not to be developed here) that proves that all systems operating reversibly between the same temperatures have the same eﬃciency.19) Comment: The results obtained so far.

we know that the initial and ﬁnal volumes and temperatures are the same as in Part (a). Thus the value of ∆S is the same as in Part (a).4.79 L to a ﬁnal volume of 49. Calculate ∆S .22) (3. which are known from Part (b).2.25) (3. Calculate the change in entropy. ∆S = dq/T = we have at constant pressure.76J K−1 mol−1 b) One mole of an ideal gas expands at T = 298 K into a vacuum from an initial volume of 24. The entropy.23) (3. dT /T = Cp ln Tf /Ti dV /V = nRT ln Vf /Vi ∆S = nR ln Vf /Vi ii) For variable T. dT /T = CV ln Tf /Ti (3. w = 0 (since Pext = 0) and so q = 0.3145 J K−1 mol−1 × ln 2 = 5.26) a) One mole of an ideal gas expands at T = 298 K from 24. q = −wPV = − = nRT (−PextdV ) = P dV (3. . being a state function depends only on the initial and ﬁnal states. However. One cannot use dS = dq/T because q is not qrev .58 L in a reversible process.79 L to 49. Solution ∆S = R ln Vf /Vi = 8. Solution Here.2. ∆U = 0.28 Elementary Physical Chemistry 3. ∆S = CP and at constant volume ∆S = CV Example 3.24) C dT /T and if C is independent of T . Hence.58 L. Entropy change in (Ideal ) Gas Expansion i) At constant T.

e. ∆E . There are many systems which are not perfect: CO. Similar arguments have been presented for the other exceptions. which assumes perfect thermodynamic equilibrium. there are some “frozen-in” structures. Perfect means that the system is in perfect thermodynamic equilibrium. we can describe the concept in absolute values. The one we are using here is The entropy of a perfect crystalline solid at absolute zero is zero. But that does not happen. ∆H . There are several statements of the Third Law. If the entropies of the calorimetric measurements and the statistical values agree. All cases. the solid is imperfect. For example. CO has a very small dipole moment. can be explained or rationalized. N2 O. As the solid cools. on the other hand. observed so far. E . but not absolute values of H or E . The low temperature crystalline solid is then not in “perfect” thermodynamic equilibrium. What can be done is to measure the heat capacity over a temperature range around 0 K and compare the results with the statistical entropy calculated by statistical mechanics. At absolute zero the dipoles should all point in the same direction. H2 O are examples.Chapter 4 The Third Law of Thermodynamics Up to now we could describe only diﬀerences in H . i. Comments: Note the restriction perfect. with dipole moments pointing in opposite directions. the crystalline solid is “perfect”. In the case of entropy. 29 . What makes this possible is the Third Law of Thermodynamics. But how can you tell whether this is so experimentally at these very low temperatures? You can’t. Otherwise.

Also. distributed among the energy levels shown in Fig. Example 4. there is a standard entropy.1. But most chemists accept the law.1. The total . Since S (0) is assumed to be zero. Standard Entropy Just as with standard enthalpy. the increase in entropy seems to be accompanied from a microscopic (molecular) point of view by an increase in disorder. one obtains ∆S (T ) = S (T ) = T 0 (CP /T )dT (4.1 Variation of S with T . greater randomness in the distribution of the molecules. We have also seen that in an irreversible isothermal change. in all these cases.30 Elementary Physical Chemistry Fig. S o . 4. Suppose one wants to determine the entropy change ∆S = S (T ) − S (0). 4. and more chaotic motion.2. when there is an increase in temperature. Suppose you are dealing with a system consisting of particles. 4. Still. there is an increase in entropy. deﬁned as the entropy of one mole of a substance at 1 bar and a speciﬁed temperature. from a solid to a liquid or from a liquid to a gas.1) A schematic representation of the variation of S with T is shown in Fig. normally 25◦ C. as in the expansion into a vacuum of a gas at constant temperature. 4. some individuals are reluctant to call the Third Law a Law on par with the First and Second Laws. the entropy increases. and use it as the basis for absolute entropies. because there are exceptions. the entropy increases. Molecular Interpretation of Entropy We have seen that when a system changes from a solid to a gas.1.2. 4. Evidently. H o .

ΩD2 = 6. is greater than the entropy change in a reversible process. which is irreversible. Hence. ΩD3 = 1. Type 1 can be realized in three ways. ΩD1 = 3.2 Schematic diagram of the distribution of 3 particles among equally spaced energy levels. in fact explosively. S (0) = 0. all molecules are in their ground state and there is only one way to realize this. A spontaneous process is a process in which the molecules can distribute themselves more randomly. type D2 .e. either in terms of their energy distribution or their position. and suggested that the entropy is related to the number of microstates by the formula S = k ln ΩD∗ (4. Let us denote the number of microstates of this distribution as ΩD∗ . ΩD∗ = 0. therefore. 4. for all practical purposes. Boltzmann thought that the more ways you can distribute the particles. type D1 . associated with this distribution. there are six microstates. 4. How is that possible? . once initiated. energy of the three particles is 6 units.The Third Law of Thermodynamics 31 Fig. Yet. there are 3 microstates. this would be the only distribution. the entropy change in a spontaneous process.3. the higher the entropy would be. In a crystalline solid at 0 K. ∆S is negative (−327 J K−1 mol−1 ).2) where k is a constant (called Boltzmann’s constant). Type 2 can be realized in six ways. i. and type D3. There are three diﬀerent types of distributions. the most probable distribution would be so much more probable than all other distributions that. In type 3 there is one microstate. Had we used billions of particles instead of three. The Surroundings The reaction 2H2 (g) + O2 (g) → 2H2 O (l) proceeds spontaneously.

To get around this diﬃculty. as it should be. On the other hand. 205. as noted before. As stated. ∆Ssurr = −∆Hsys /T (4. 70. Had we calculated ∆S from q/T . [The rationale is that the surrounding. it is common practice to assume that the surrounding changes reversibly even though the system may change irreversibly. since S is a state function.2 − 2 × 130. at constant T . ∆S can only be equated to q/T if q is reversible. The Entropy of the Surroundings In treating the surrounding entropy.] Example 4.4) (4.92 kJ K−1 = 1920 J K−1 .6 kJ.32 Elementary Physical Chemistry The standard entropies of H2 (g). the system entropy.7.7) kJ = −326. Why?] The rule that ∆S has to be positive in an irreversible change applies to an isolated system.0 − 205. being so enormous. Let us return to the water reaction. would change quasi-statically. In general. O2 (g) and H2 O (l) at 25◦ C are respectively 130. the result would have been wrong.2. regardless of whether q is reversible or irreversible. It is found that at 25◦ C and one atmosphere the heat released is −572 kJ mol−1 . the standard procedure is to consider also the entropy of the surroundings (the rest of the universe). ∆Ssurr = qsurr /T = −qsys /T and if P is also constant. [This is the correct way to calculate ∆S . is ∆Ssys = −327 J K−1 and so ∆Stot equals (−327 + 1920) J K−1 = 1539 J K−1 and is positive. and if there is no work other than pV work.2. . Thus. In the above example. and regard the system and surroundings as an isolated system. the system is not isolated. The heat absorbed by the surrounding is qP = +572 kJ and thus ∆Ssurr = 572 kJ/298 K = 1.3) Comment: ∆H can always be related to q . the heat released by the system is assumed to be absorbed by the surrounding reversibly even though the system looses heat irreversibly. giving ∆S = (2 × 70.0 kJ mol−1 . ∆Stotal = ∆Ssystem + ∆Ssurroundings 4.4.

only the Gibbs function will be used. This can be accomplished by using free energy functions.2a) (5. = 0 if process is reversible.2b) (5.2d) (5.2c) (5.4) (∆Ssurr = −∆Hsys /T ) yields ∆Stot = ∆Ssys + ∆Ssurr = ∆Ssys − ∆H/T This requires that ∆Stot > 0 if process is spontaneous. If the system is not isolated.1. for short.1) There is a way to get around the problem of having to use an isolated system or a system plus surrounding. ∆Stot ≥ 0 (5. the system and surroundings have to be combined. of which there are two kinds: the Helmholtz free energy and the Gibbs free energy (also called Gibbs energy). The Gibbs Free Energy The Gibbs free energy is a property of the system only (surroundings not included). The Gibbs energy is deﬁned as G = H − TS 33 (5.Chapter 5 The Free Energy Functions There is a drawback in working with entropy except for isolated systems. rather than focusing on the system only. 5. and at constant T and P .3) . Or. < 0 if process is impossible. (4. using Eq. In this course.

The Gibbs energy discussed so far. ∆GT.P /T < 0 if process is spontaneous. ∆GT. ∆GT. using Eq. meaning that the integral.7b) (5. if there is only P V work. Or for short. because B H and S are state functions. (4.P /T = 0 if process is reversible.4) Thus. and write ∆GT.4). It is based on the assumption that only P V work is present.8a) (5. depends only on the initial and ﬁnal states A and B. then at constant P and T . ∆H = ∆U + P ∆V = qP − P ∆V + wother + P ∆V = qP + wother (5.P = 0 for a reversible change (system in equilibrium) and negative for an irreversible change.8b) (5. if the pressure is also constant. although more convenient to work with than entropy.P ≤ 0. we can write. At constant temperature. ∆GT.5) (5. (5. ∆G= A dG= G(B) − G(A).8c) When the system exchanges heat with the surroundings. is still not the most general. ∆G = ∆H − T ∆S or −∆G/T = ∆S − ∆H/T and. instead of using entropy of the system and surroundings.7a) (5.6) (5.34 Elementary Physical Chemistry Comment: It should be emphasized that G is a state function. the heat lost (gained) by the system is equal to the heat gained (lost) by the . If wother is also present. This is a powerful criterion for spontaneity. which refers to the system only.7d) (5. we can use the Gibbs free energy. −∆G/T = ∆Ssys + ∆Ssurr = ∆Stot (5.7c) Thus.P /T > 0 if process is impossible.

10) (5. in a typical handbook. ∆Hf . The reason. it will not be pursued here. The relation between ∆GP. for the change to proceed reversibly (in equilibrium). (5.9) is less than or equal to wother and ∆GT. and. etc. i.e.P = ∆H − T ∆Ssys = −T ∆Ssurr − T ∆Ssys + wother = −T ∆Stot + wother (5.9) Since ∆Stot ≥ 0. as it enables us to obtain ∆G from work measurements. The process is treated as reversible.2. If irreversible. Comment: The Helmholtz free energy is deﬁned as A = U − T S . Thus. wother . is that the equilibrium constant K is o related to the standard free energy per mole. the change in G at constant P and T has to be equal to the non-P V work. where U and S are properties of the system only. the right-hand side of Eq. molar enthalpy. Comments: It should be noted that the quantities ∆Gf . as will be shown later. 5. . as indicated above. refer to the molar free energy.8d) Again. This function is useful when the volume is constant. Free Energy Changes in Chemical Reactions It is important to distinguish between reaction free energies under standard conditions.The Free Energy Functions 35 surroundings.P ≤ wother (5. and under all other conditions. An example (to be discussed later) is the determination of the free energy from work measurements in electrochemical studies. indicated by the superscript o . the change has to be less. ∆H = −T ∆Ssurr + wother For ﬁxed T and P . qsys = −qsurr = −T ∆Ssurr . ∆GT. ∆Gm .T and wother is very useful. and not to the actual free energy ∆G.

such as νi .4 kJ + 298.14 = −137. on the other hand.93 − 3 × 205.12b) (5.11) (5. all that is needed is multiplication of the ﬁnal molar quantities by the unit mol.1.4 kJ o o o (5. To obtain the real dimensions of free energies or enthalpies. 1) From ∆H o and S o .2 − 0) = 326. where mol0 is the unit mol. Any combination with stoichiometric coeﬃcients.15 × 137.36 Elementary Physical Chemistry etc.7 − 3 × 0 = 285. and the standard entropy. This is indeed happening in the upper atmosphere. Find ∆Go for the reaction 3O2 (g) → 2O3 (g) at 298.15 K.4 + 41. and according to what was said before. S o . ni . one should use mole numbers. will produce values of units J/mol. and thus the dimensions are the dimensions of energy or Joules per mole. ∆H o = 2∆Hf (O3 ) − 3∆Hf (O2 ) = 2 × 142. has a negative ∆G and can proceed spontaneously. where ozone is converted to oxygen. .56 JK ∆G = ∆H o − T ∆S o = 285.12a) (5. ∆Hf . ∆Gf . The reverse reaction. The standard free energy can be obtained from the standard enthalpy o of formation. listed in many handbooks. the reaction as written cannot proceed spontaneously.56/1000 kJ = (285.0) kJ = 326. it follows that to obtain energy dimensions in J. O3 → O2 .4 kJ 2) From ∆Gf o o −1 o o o (5. Considering that ni = νI mol0 . Example 5. or from the standard free o energy of formation.13) Note that the sign of ∆G is positive. as in the reaction free energies or enthalpies. instead of stoichiometric numbers.12c) ∆Gf = 2∆Gf (O3 ) − 3∆Gf (O2 ) = (2 × 163.4 kJ ∆S = 2S o (O3 ) − 3S o (O2 ) = 2 × 238.

dG = dq − Pext dV + P dV + V dP − T dS (5. including mixtures. dG = (nRT /P )dP and ∆G = nRT f i (5. 5. The activity. the pressure is often replaced with an eﬀective pressure. we obtain at constant T dG = dH − T dS = dU + P dV + V dP − T dS and if only P V work is present.14a) (5. This is accomplished by introducing a new concept. ai .14b) for a reversible change (P being the system pressure. we get dG = T dS − P dV + P dV + V dP − T dS Thus.15) (5.20) Comment: This expression can be used only if the gas is ideal. the activity. we can write ∆G = G − Go = nRT ln P/P o (5. for reversible change and P V work only. Variation of G with T and P From G = H − T S.3.19) If we deﬁne P o as a standard pressure (say 1 atm or 1 bar at 298. Generalization of the Free Energy.The Free Energy Functions 37 5.17) (5.4.18) dp/P = nRT ln Pf /Pi (5. dG = V dP For an ideal gas.15 K) corresponding to the standard free energy. at constant T . Activity The form (but not the actual values) of the ideal gas formulas is also used in the treatment of other types of materials. called fugacity. Go . If the gas is not ideal. Pext = P ). .16) (5.

is deﬁned as Gi = Gi + ni RT ln ai o (5. etc. to obtain the exact value of ai . V = nA VA.m The subscript m refers to molar quantity. In general. i. . Partial Molar. one must know the value of Gi .m and.38 Elementary Physical Chemistry of species. pressure. However. What is done often is to approximate the activity as follows: For an (ideal) gas ai = Pi /P o For a pure liquid or solid ai = 1 For a solution ai = ci /c o (5.2325 kPa). 5.5. such as H . mole fractions. It can be shown that if a system is homogeneous. n2 . and co represents the standard concentration (1 mol dm−3 or 1 kg m−3 ). ∗ ∗ V = VA . the total volume will not be the sum of the individual values. which is generally not known exactly.24) (5. ci denotes the concentration of species i. and VB . causing deviations from the sum rule. [This applies also to the other thermodynamic functions.22c) The symbol P o stands for standard pressure (760 Torr or 1 atm or 101.22b) (5.21) Note that the activity is deﬁned in terms of G. in a two-component system.] The reason why this is so is that molecules attract or repel each other. n1 . . i.e.23b) (5. + VB . P. then in Denoting the molar volumes of A and B respectively as VA general. Molal Quantities Suppose we have a mixture of nA moles of pure A and nB moles of pure B.22a) (5. etc. the total volume is V = Σi ni Vi. Denoting .23a) The partial molar volume of species i is deﬁned as the derivative of V with respect to ni holding constant P. . which is a true value of the system. The Gibbs free energy can be written conveniently as G = G(T. the volume of a mixture depends on temperature. T. ∗ ∗ . in particular. and all nj not equal to ni . G. S .m + nB VB.) (5.

(5.26b) Similar considerations apply to the Gibbs free energy ∗ G = nA G∗ A .25) The total volume of all species of a homogeneous system can be written as V = Σi ni Vi∗ and in particular in a two-component system.V. ∗ ∗ V = nA VA . as G = nA µA + nB µB (5. (5.28b) (5. it is common practice to express the free energy of.P nj =ni (5.P. +nB VB . as in Eq.nj =ni (5.29) . Thus. Thus. The Chemical Potential The partial molar free energy is often called the chemical potential and is denoted as µi = (∂G/∂ni )T. instead of writing the Gibbs free energy in terms of the partial molar quantities.26a) (5. The chemical potential. say.nj =ni (5. the partial internal energy.The Free Energy Functions 39 the partial molar or molal volume of i as Vi∗ = (∂V /∂ni )T.28c) (5.6.27) 5. can be deﬁned also as the partial Helmholtz free energy.28a). a two-component system. (6. µi .P.10). +nB GB .V. as well as the partial enthalpy. it makes sense to give these partials a special name.nj =ni µi = (∂H/∂ni )S. they are all equal to Eq.28a) Comment: The partial Gibbs free energy transcends ordinary properties of partials. the name is chemical potential. µi = (∂A/∂ni )T.nj =ni µi = (∂U/∂ni )S. (5.28d) As can easily be shown (not in this course). namely.

aA + bB cC + dD (5. we can express the free energy change of the reaction as o o o ∆r G = {cGo C + dGD − aGA − bGB +RT [c ln aC + d ln aD − a ln aA − b ln aB ]} = ∆G + RT o o d a b ln(ac C aD /aA aB ) (5. we can write for component i. Relation of ∆Go ¯ to the Equilibrium Constant.27)] G∗ = Go∗ + RT ln a or µ = µo + RT ln a In a mixture.30) (5. which depends on T and P as well as on the composition but not on the amount. (5. G∗ = Go∗ + RT ln Pf /P o In terms of activities [Eq.32) (5. ∆G = 0 and so ln K = −∆Go (5. We have shown in the last section that for one mole of a one-component system at pressure P .40 Elementary Physical Chemistry Comment: It should be emphasized that the chemical potential is an intensive property.31) (5.33) ∗ Denoting the molar quantities of A as m∗ A and of B as mB .35c) = ∆G + RT ln K At equilibrium.7.35a) (5. K Consider the reaction.36a) . µi = µi + RT ln ai 5.35b) (5.34) o (5.

∆G. Thus.37b) (5. but to the free energy change in the standard state. we have: at a constant temperature T ln K = −∆Go /RT = −∆H o /RT + ∆S o /R and at a diﬀerent constant temperature T ln K = −∆Go /RT = −∆H o /RT + ∆S o /R resulting in ln K = ln K + ∆H o /R(1/T − 1/T ) (5. a) Calculate w.37a) Example 5. Variation of K with T Assuming that ∆H o and ∆S o vary negligibly with temperature.4 L) = −8.8 L/22. An ideal gas. q = −w and so q = 1. initially at T = 273 K.763 JK−1 = −1. ∆U. q.3145 JK−1 mol−1 × 273 K × ln 2 = −1. ∆H. The process is reversible so that w=− Pext dV = −nRT dV /V = −RT ln Vf /Vi = −RT ln(44. 5. 573.2.573 kJ .4 L expands isothermally and reversibly to a ﬁnal volume.8 L.573 kJ ∆H = ∆U + ∆(P V ) = 0 + ∆(RT ) = 0 ∆S = qrev /T = 1.573 kJ ∆U = 0 (ideal gas at constant temperature).The Free Energy Functions 41 or K = exp(−∆Go /RT ) (5. ∆S. Vf = 44.8.3 J/273 K = 5.38) (5.36b) Comment: It is important to note that the equilibrium constant is not related to the actual free energy change (which is zero). P = 1 atm and Vi = 22.763 JK−1 ∆G = ∆H − T ∆S = 0 − 273 K × 5.

Calculate w. w = 0 because Pext = 0 and thus q = 0. ∆G.763 kJ and ∆G = −1. q. ∆S. ∆H = 0. The other functions are state functions with the same initial and ﬁnal states as in Part (a) and so the ∆ values must be the same as in Part (a).573 kJ. ∆S = 5. In other words. ∆U. ∆H. .42 Elementary Physical Chemistry b) The gas expands into a vacuum from the same Vi to the same Vf as in Part (a). ∆U = 0.

namely a plot of P vs. There are three areas and three lines. 6. Phase Equilibrium We will treat here phase equilibria involving one-component systems and two-component systems. The point where the lines meet is called the triple point.1. mole fraction.1. T . 6. The Phase Rule The Phase Rule tells how many independent intensive variables (pressure.1. F stands for the variance or degrees of freedom. The phase rule reads F = c − p + 2. we will take up chemical reactions. temperature.Chapter 6 Phase and Chemical Equilibria Two important applications of thermodynamics are phase equilibria and chemical equilibria.) there are that can be varied in each region. No chemical reactions are assumed to occur. In the next section. 43 . liquid–solid and solid–gas phases.1) Here. The lines represent regions of coexistence of gas–liquid. Figure 6. (6. etc. These variables are normally referred to as degrees of freedom.1 depicts a phase diagram of a one-component system. c represents the number of components and p the number of phases. The areas represent the phases gas. liquid and solid.

Along lines you can specify either the temperature or pressure but not both.2) where the subscript trans refers to the particular transition. say liquid– vapor or solid–liquid.44 Elementary Physical Chemistry Fig. and must obey the Clapeyron equation: dP/dT = ∆Htrans /(T ∆Vtrans) (6.3b) . 6.1 Pressure–temperature phase diagram of a one-component system.3a) (6. For example. F = 1 − 1 + 2 = 2 when p = 1 (in the areas) F = 1 − 2 + 2 = 1 when p = 2 (along the lines) F = 1 − 3 + 2 = 0 when p = 3 (at the triple point) The phase rule tells us that in areas you can choose both the temperature and pressure. At the triple point you cannot choose any variable: the variables are ﬁxed.2. in a one-component system. From G = H − TS we get the diﬀerential form dG = dH − T dS − S dT = dU + P dV + V dP − T dS − S dT (6. 6.1. The Clapeyron equation is easy to derive. The Clapeyron Equation The slopes of the phase diagram lines can also be predicted thermodynamically.

3e) Note: This is a generalization of an expression derived earlier where P was constant. the following are obtained: liquid–gas dP/dT = ∆Hvap /T Vvap ≈ ∆Hvap /(RT 2 /P ) dlnP/dT = ∆Hvap /(RT 2 ) solid–vapour dP/dT = ∆Hsubl /(T Vvap ) solid–liquid dP/dT = ∆Hfus /[T (Vliq − Vsol )] (6. Then.4c) α α β β (6. The G’s will then change to Gα + dGα and Gβ + dGβ .4b) If a transition occurs between a liquid or solid and the vapor.3d) (6. and treating the vapor as an ideal gas. Consider two phases.7) . dG = dq − P dV + P dV + V dP − T dS − S dT = T dS + V dP − T dS − S dT = −S dT + V dP (6. we must have Gα + dGα = Gβ + dGβ and so dGα = dGβ −S dT + V dP = −S dT + V dP which yields (V α − V β )dP = (S α − S β )dT ∆V dP = ∆S dT and thus. α and β .6) (6. Now consider an inﬁnitesimal change from T to T + dT . the volume of the condensed system will be very much smaller than the volume of the gas. If at the new temperature.4a) (6. then in general.Phase and Chemical Equilibria 45 and. for a reversible transition with PV work only.5b) (6.4d) (6. T + dT .3c) (6. the systems are again in equilibrium.5a) (6. Neglecting the volume of the liquid. Gα = Gβ . dP/dT = ∆S/∆V = ∆H/(T ∆V ) (6. in equilibrium at temperature T .

∗ . obeys Raoult’s Law. liq.5b) is also known as the Claussius– Clapeyron equation. Mixtures There are three ways to characterize mole fractions: (1) Molar concentration. [x] = nx /Vsolution (x is the solute) (2) Molal concentration. and fus refer respectively to vapor.1. where PA (6. (dP/dT )liq−gas < (dP/dT )sol−liq and (dP/dT )sol−liq > 0. (H2 O is an exception. The solvent of all substances.2. Equation (6. mx = nx /Msolvent (usually mole/kg of solvent) (3) Mole fraction. that is ∗ PA = xA PA ∗ is the vapor pressure of pure A.2. subl. in general. Chemical Equilibrium.46 Elementary Physical Chemistry The subscripts vap.10) (6. PA = xA PA An Ideal Solution is a solution in which every component obeys Raoult’s Law over the entire range of compositions.11) The reason for this behavior can be rationalized that in very dilute solutions.) Problem: Explain why. Note: ∆Hsubl > ∆Hvap and. 6. Ideal Solutions. but at a concentration of xA . Hence. sublimation and fusion.8) (6. Raoult’s Law Let us adopt the convention that the solvent will be denoted as A and the solute as B. when suﬃciently dilute. . a molecule A is surrounded essentially by other A molecules. Vliq > Vsol. liquid. in general. xA /n (n = total number of moles) 6.9) (6.

Henry’s ∗ . The drawn line is the total pressure. ∗ ∗ Note: Each partial pressure is xA PA or xB PB and the total pressure is the sum of the two.12) .2). Henry’s Law constant. Henry’s Law Ideal solutions are not very common. where KB is a constant. 6. (5. when solutions are very dilute. However.Phase and Chemical Equilibria 47 Fig. A solution in which the solvent obeys Raoult’s Law and the solute obeys Henry’s Law o (6. 6. Most solutions will show deviations from ideality. the solvent will obey Raoult’s Law (as noted) and the solute will obey Henry’s Law. 6. An example of an ideal solution is a mixture of benzene and toluene (see Fig. the chemical potential becomes µA = µA + RT ln xA and thus aA = xA [see also Eq. Ideal Dilute Solutions.2. generally not equal to the pressure of pure B. Henry’s Law states that PB = xB KB .2. PB Law can also be deﬁned in terms of the molarity PB = mB KH .33)]. The dashed lines are the partial pressures of components A and B. It can be shown that when a substance obeys Raoult’s Law.2 Schematic diagram of an ideal solution.

27/(431. (c) the mole fraction of CH4 in the gaseous phase.01 × 10−2 ) × 300 Torr = 296.27 × 104 Torr at 298 K.2. The O2 molar fraction is xO2 = (4 × 10−3 g L−1 /32. Predict whether natural water can support life. there are 55. It is known that to support aquatic life. PO2 = xO2 KO2 = 2 × 10−6 × 3. If Henry’s Law constant is equal to PB .01 × 10−2 . What must the partial pressure of O2 in air be to achieve that concentration? In a liter of water.5 mol L−1 = 2 × 10−6 (6. Example 6. The pressure of pure benzene is Pbenz = 300 Torr at 298 K. ﬁnd (a) the partial pressure of CH4 at 298 K. xmeth = Pmeth /(Pmet + Pbenz) = 431. Methane (CH4 ) and benzene (C6 H6 ) form an ideal dilute solution.27 Torr (b) The solvent obeys Raoult’s Law o Pbenz = xbenz Pbenz = (1 − 1.48 Elementary Physical Chemistry ∗ is called an ideal dilute solution.27 + 296.13) Henry’s Law constant for O2 is 3. (b) the partial pressure of C6 H6 .1. the concentration of O2 must be 4 mg/L. This is the minimum pressure O2 must have in the air.01 × 10−2 × 4.00 g mol−1 )/55. The actual pressure of O2 in the air is . Henry’s Law constant of the solute (methane) is Kmeth = 4.97) = 0.27 × 104 Torr = 431.79 × 107 Torr in water at 25◦ C. Pmeth = xmeth Kmeth = 1. then the ideal dilute solution becomes ideal.97 Torr (c) Assuming ideal behavior in the gaseous phase. Solution (a) By Henry’s Law.60 × 107 Torr = 70 Torr. Thus. If the mole fraction of CH4 in the liquid phase is xmeth = 1.5 moles of H2 O and a negligible amount of O2 .529 Example 6.

6. pure A in the liquid phase and of A in the solvent.2. one assumes that (1) the solute is not volatile. Colligative Properties There are several properties. Figure 6. Again the solution curve is lower than the liquid curve. • Production of osmotic pressure.3. Thus. pure A in the solid phase and A in solution.4 shows the variation of the chemical potentials with temperature of pure A in the liquid phase. Thus. The pure liquid curve cuts the solution curve at a lower temperature than the pure liquid curve. there is more than ample O2 in the air to sustain life in water on earth. . They are • Elevation of boiling point. Depression of Freezing Point The easiest way to ascertain why there is a boiling point increase or a freezing point decrease is to observe the variation of the chemical potential with temperature. 6. Notice that the solvent curve is lower than the liquid phase curve. when a water solution freezes. The pure vapor phase curve cuts the pure liquid curve at a lower temperature than the solution phase. all resulting from lowering the pressure of the solvent that can be observed in solutions. as it should be because of the lower chemical potential. as it should be. the frozen solid is pure ice. Figure 6. Elevation of Boiling Point.3 shows three curves: the chemical potential of pure A in the vapor phase. In the simplest cases. indicating that the solution freezing point is lower. • Depression of freezing point.2. (2) the solute does not precipitate.Phase and Chemical Equilibria 49 about 21% of 1 atm or 0. indicating that the boiling point of the solution is higher.21 × 760 Torr = 160 Torr.4.

3 Schematic diagram of the chemical potentials responsible for the elevation of the boiling point. .4 Schematic diagram of the chemical potentials responsible for the depression of the freezing point. 6. Fig.50 Elementary Physical Chemistry Fig. 6.

the liquid phase is the stable phase. the chemical potentials of the two phases must be equal. (These constants can readily be related to thermodynamic functions. and write mb = . Below the normal boiling temperature. The boiling-point elevation constant.3.0 g of solute in 1 L of H2 O(l) is m = 30. and the chemical potential of the vapor will be lower than that of the pure liquid. and the chemical potential of the liquid will be the lowest. Similar considerations apply to the chemical potentials responsible for the lowering of the freezing point (see Fig. Tb . mb . the most favored state is the one with the lowest µ. If a system can exist in two diﬀerent states.) Example 6. Thus. where the equal sign pertains to equilibrium and the unequal sign to non-equilibrium situations. say at the normal boiling point.77 × 10−2 mol and thus the molarity of the solute is 8.Phase and Chemical Equilibria 51 Comment: The way the chemical potential behaves is similar to the behavior of the free energy.77 × 10−2 mol/L.51 K kg mol−1 .0 g of solute in 1 L of water. The normal boiling point of H2 O(l) is 373. the vapor phase is the more stable state. but will not be developed in this course. We can write ∗ ∆Tb = Tb − Tb = mb Kb (6.14a) (6. Calculate the boiling point of a solution of 250 cm3 of H2 O(l) containing 7.25 K.5 g of a solute. Assuming that 1 L of water at the normal boiling point weighs essentially 1 kg. we can equate the molarity m to the molality.0 g/342 g mol−1 = 8. 6. The molecular weight of the solute is M = 342 g mol−1 .14b) ∆Tf = Tf∗ − Tf = m f K f where mb is the molality of solute and Kb and Kf are respectively the boiling point elevation constant and freezing point depression constant. Solution 7. Let us denote the normal boiling point and normal freezing point of the ∗ and Tf∗ and the boiling and freezing points pure liquid respectively as Tb of the actual solutions as Tb and Tf . Above the normal boiling temperature.4).5 g in 250 cm3 of water is equivalent to 30. The mole fraction of 30. When liquid and vapor ∗ are at equilibrium (coexist). we have ∆µ ≤ 0. Kb is 0.

The elevation of the boiling point is ∆Tb = Tb − 373.25 + 0. The increased pressure in the tube is called osmotic pressure.52 Elementary Physical Chemistry 8.5. If pistons are placed on both compartments. 6. The compartments are separated by a semi-permeable membrane.0447)K = 373. the other compartment contains the pure solvent. One compartment contains a solution of solute and solvent. Figure 6. which allows solvent molecules to move freely between the compartments but forbids the solute molecules to move across the boundary. Thus. 6.51 K kg mol−1 = (373. the bladder swelled.5 shows a container divided into two compartments.25 K + 8.29 K. the pressure on the pure solvent compartment is the atmospheric pressure PA . Osmotic Pressure It was observed a long time ago that when a cylinder containing wine was covered with animal membranes and placed in a bucket of water. . Solvent molecules will diﬀuse into the solution causing the liquid in that compartment to rise.2.77 × 10−2 mol/kg.25 K = mb Kb . Fig.5 Schematic diagram of osmotic pressure determination Π is the extra pressure that must be applied to prevent the solvent from ﬂowing into the solution compartment. The following is a more common approach to study osmosis.77 × 10−2 mol/kg × 0. Tb = 373.

to good approximation. what is required is µA (P + Π. To prevent that piston to rise. This is similar to the variation of G with P . so µA (P + Π. where Vm is the molar volume. the chemical potential of the pure solvent is µ∗ A. where [B] = nB /V . namely. we have µA (P + Π. Assuming that V ∗ is constant. It turns out that. For the pure solvent. and of the solvent component A in solution is µA . so that Raoult’s Law is applicable. we get ∗ ∗ µ∗ A (P + Π) − µA (P ) = V P +Π P dP (6.Phase and Chemical Equilibria 53 The piston on the solution compartment will rise. xA = 1 and the pressure is P . xA = 1) (6. Osmotic pressure is the extra pressure that must be applied to the solution to prevent the ﬂow of solvent. Assuming the solution to be suﬃciently dilute.17b) = V ∗ (P + Π − P ) = ΠV ∗ Finally. More explicitly. Π = [B]RT . since µA (solution) = µA (pure solvent).16) Next consider the variation of the chemical potential with pressure: dµ = Vm dP . These two chemical potentials diﬀer not only because the concentrations diﬀer. xA ) = µ∗ A ∗ µ∗ A (P + Π) + RT ln xA = µA (P ) ∗ ∗ µ∗ A (P ) + ΠV + RT ln xA = µA (P ) (6. extra pressure. At equilibrium.18) . Proof.15) First consider the non-starred µ. say Π. dG = V dP . xA ) = µ∗ A (P . but also because their pressures are diﬀerent. xA ) = µ∗ A (P + Π) + RT ln xA (6. For the solution the mole fraction is xA and the pressure is P + Π.17a) (6. must be applied.

e. K = P (CO2 ) and not on the other substances.6. a) From the free energy or chemical potentials. Here. but the relation of the activities to pressure. .20) (6. we can derive for the reaction aA + bB · · · = cC + dD · · · producing the quilibrium constant d a b K = ac C aD .22a–c). to concentration. CaCO3 (s) = CaO(s) + CO2 (g) (6.2. Activities are equal to the mole fraction times activity coeﬃcients. etc.22) It is found that K depends only on the partial pressure P (CO2 ) of the gas.54 Elementary Physical Chemistry and Π = −RT /V ln xA ≈ −RT /[V ln(1 − xB )] = xB RT /V ≈ nB /[(nA + nB )(RT /Vm )] = (nB /V )RT ≈ [B]RT (6. as shown in Eqs. i. are approximate. b) Consider the heterogeneous reaction. Chemical Reaction Equilibria The relation between K and ∆Go was already discussed in previous chapters. (5.21) where the activities are related to partial pressures or to concentrations. The expression of K in terms of the activities is exact. /aA aB (6. and the activity of the gas is to a good approximation equal to the partial pressure. Reason: the activity of each solid is 1. . we will make a few remarks which were not suﬃciently emphasized before.19) 6. which are not easily calculated. .

∆Hcomb .24) (6. ∆Ucomb .0 kJ. CO2 (g) and H2 O(l) are respectively −386. The combustion reaction is C6 H5 COOH(s) + and so (a) ∆Hcomb = 7∆Hf [CO2 (g)] + 3∆Hf [H2 O(l)] − ∆Hf [C6 H5 COOH(s)] = 7(−285. and o (b) the standard energy. of combustion of [C6 H5 COOH(s)]. yielding an equilibrium constant.1 kJ (b) o ∆Ucomb o o o o o 15 O2 (g) → 7CO2 (g) + 3H2 O(l) 2 = ∆Hcomb − ∆(P V ) o ∆(P V ) = 7P Vm [CO2 (g)] + 3P V m [H2 O(l)] − P Vm [C6 H5 COOH(s)] 15 − P Vm [O2 (g)] 2 . −285.5 kJ.4. consider the equilibrium constant for the reaction 2H2 O(l) = H3 O+ (aq) + OH− (aq) A neutral system in equilibrium has [H3 O+ ] = [OH− ] = 10−7 mol/L (6. Calculate (a) the standard enthalpy.25) Example 6. denoted as Kw . equal to Kw = 10−14 (6.23) The activity of the pure liquid is essentially constant.5) − (−386.8 kJ and −393.0) = −2795. The standard enthalpies of formation of C6 H5 COOH(s).8) + 3(−393.Phase and Chemical Equilibria 55 c) Also.

36] kJ = 3.24] kJ = −2793. Thus. K < K . be greater or smaller than K ? ln K (T ) = ln K (T ) + [∆H o (T )/R] × (1/T − 1/T ) ∆o H > 0.36 J K−1 . Elements of Electrochemistry. The standard enthalpy change of formation in the reaction H2 (g) + I2 (s) → 2HI(g) is ∆Hf = 52. 1 o ∆Ucomb = −2795. If T < T the quantity (1/T − 1/T ) will be negative. ∆Go = ∆o H − T ∆S o = [52.1 + 1.38 kJ K = exp (−∆Go /RT ) = exp [−3380 J/(8. we get )RT = − 1 RT .9 kJ Example 6. K . the second term in the formula will be negative and ln K < ln K . 6.5.2.1 kJ + × 8. Neglecting the molar volumes of the solid and liquid and replacing P V by RT (assuming ideal gas behavior). There are two types: (a) Electrolytic Cells.7.3145 J K−1 × 298 K 2 = [−2795. Example: the production of H2 and O2 from H2 O.366 = 0.96 kJ. and we will only touch on the highlights which are relevant to thermodynamics. (a) Calculate the equilibrium constant K at T = 298 K.166. ∆[P V (g)] = (7 − 15 2 2 Thus. which produce non-spontaneous reactions by an external electrical current.56 Elementary Physical Chemistry Vm are the molar volumes.96 − 298 × 0.3145 JK−1 × 298 K)] = e−1.1 kJ + RT 2 1 = −2795. The standard entropy change is ∆Sf = 166. Thus. will the equilibrium constant. Electrochemical Cells Much of electrochemistry is covered in other courses. o o .255 (b) If T < 298 K.

The half-cell potentials of the reduction and oxidation reactions referred to above are respectively +0. This provides the link with thermodynamics. (6. Examples are dry battery cells.28) the oxidation half-reaction will deposit electrons on the cathode pole via the external circuit. As an example. if there is a gain of electrons.27a) (6.18 volt.2. The electrical work. etc. Half-Reactions. lithium-ion cells.8. for the Cu–Zn cell is (observing that . the electrical work produced by the cell will be wother = ∆GT.34 and +0. the half-reaction is referred to as reduction. fuel cells. consider the redox (oxidation–reduction) reaction Cu2+ (aq) + Zn(s) → Cu(s) + Zn2+ (aq) which is assumed to be composed of the two half-reactions Cu2+ (aq) + 2e− → Cu(s) Zn(s) → Zn 2+ (6.27b) (aq) + 2e [oxidation of Zn] If these are used in a cell (for example. which extract energy as non-PV work in spontaneous reactions. the Daniell Cell) which may be characterized as Zn(s)|ZnSO4 (a) CuSO4 (a)|Cu(s) (6. 6. giving an overall sum value of E o = 1.P = −n E o . the half-reaction is referred to as oxidation.485 coulomb/mol−1 of electrons and E o is the total potential of the half-cells. If this reaction is carried out reversibly by letting the produced current act against a maximum resistance. If there is a loss of electrons.76 volt.29) where n is the number of moles of electrons. is the Faraday constant equal to 96. Any electrochemical reaction can be expressed as the sum of two half-reactions. Redox Reactions A half-reaction is a process in which there is a transfer of electrons from one substance to another.26) [reduction of Cu2+ ] − (6.Phase and Chemical Equilibria 57 (b) Galvanic Cells.

∆G = 0 and therefore.18 volt = −227. ∆GT. analogous to the determination of the enthalpy ∆HP. The electrode chosen to be assigned zero is the hydrogen electrode. ∆GT. If the reaction is in equilibrium. it follows that 0 = −n E o + RT ln K . wother must be zero. wother must also be zero.P = −n E o = −2 × 96. Finally.T from P V work. we used the published electrode potentials to evaluate wother .2. Note: One can rationalize the above by recalling that. one electrode can be assigned the value 0 and the other electrode can then be assigned a value obtained from the measured total potential. When the system is in equilibrium.30) The foregoing illustrates that the Gibbs free energy. Thus. but the reaction was not in a state of equilibrium. can be obtained from non-P V work (which is not a state function). equal to zero (why?).P must be greater than wother .485 coulomb × 1. the current was produced by the Cu–Zn reaction. 6. and so ln K = −n E o /RT (6. In the above example. in general. This is done to obtain results under quasi-static (reversible) conditions.P ≤ wother .046. Note: Although the potential of a single electrode cannot be measured.P must be less than wother and if it is in a reverse direction. Thus.9. there would be no current ﬂow. a state function. if the reaction is to move in a forward direction. Cells at Equilibrium It should be emphasized that in the above example.31) . since ∆G = ∆Go + RT ln K and thus.58 Elementary Physical Chemistry 1 J = 1 C × 1 V) wother = ∆GT.60 J ≈ −227 kJ (6. Such potentials were originally obtained by measuring voltage changes under maximum resistance between the electrodes. ∆GT.

∆GT. The reduction potentials for the following reactions are Cd+2 + 2e− → Cd Cd + 2OH− → Cd(OH)2 + 2e− Calculate (a) The standard cell potential at 298 K for the reaction Cd+2 + 2OH− → Cd(OH)2 . Solutions (a) Cd+2 + 2e− → Cd Cd + 2OH− → Cd(OH)2 + 2e− Cd2+ + 2OH− → Cd(OH)2 o E o = −0.81 V Ecell = 0.6.485 × 103 coulomb mol−1 (C mol−1 ) ∆Go = −2 × 96.P + RT ln K and ∆GT. (c) The electrical work produced at constant T and P when the reaction is in equilibrium. the electrical work (a form of wother ) is zero. Thus. At equilibrium ln K = ∆Go /RT and ∆GT.40 V E o = +0.12 × 103 Jmol−1 /(8.P ≤ wother.12 kJ mol−1 K = exp[79.41 V o (b) ∆Go = −ν Ecell . o Ecell = potential diﬀerence in volts (1 V = 1 JC−1 ) o .3145 J K−1 mol−1 × 298 K)] = 7.81 V E o = −0.Phase and Chemical Equilibria 59 Example 6.38 × 1013 (c) In general.485 × 103 C mol−1 × 0. (b) The equilibrium constant K at 298 K for the reaction in Part (a).P = ∆GT.40 V E o = −0.P = wother = 0.41 JC−1 = −79. ν = 2 (mol of electrons) = 96.

7.) while the reaction is proceeding. 60 . called the rate constant. Thermodynamics enables us to determine whether reactions will proceed or will not proceed.2) (7.1) where [c] is the concentration of the unreacted sucrose. Several experimental methods are available for determining reaction rates. (2) Analyzing the reaction (using physical methods such as colorimetry. This method is continuous. The Rates of Reactions Reaction rates were already studied quantitatively as far back as the 1850s. the rate of the reaction H2 O + C12 H22 O11 → C6 H12 O6 + C6 H12 O6 sucrose glucose fructose was found to satisfy the relation d[c]/dt = k [c] (7. and k is a constant. spectral absorption etc. Thermodynamics will also determine the conditions that must be satisﬁed to obtain equilibrium. but thermodynamics will not predict how fast equilibrium will be reached.Chapter 7 Chemical Kinetics Much of physical chemistry is concerned with chemical reactions. For example. Chemical kinetics does this.1. They basically fall into two categories: (1) Removal of successive samples from the reaction mixture — and analyzing the mixture (hard to come by if the reaction is fast).

r. . r and 3r.7) . Thus. Order of Reaction The reaction rate is often found to be proportional to the concentration of the reactants raised to some power. is 2r.4b) (7. and the rate of appearance or disappearance of a substance. etc. r = −(1/a)d[A]/dt = k [A]m [B ]n . the rate of appearance of NH3 is twice the rate of disappearance of N2 and 2/3 times the rate of disappearance of H2 .4c) (7.3) Note that there is a diﬀerence between the rate of reaction. whereas the rates of disappearance of N2 and H2 are respectively.4d) (7. on the other hand.2.Chemical Kinetics 61 Reaction rates are usually expressed as the rate of decrease of a given reactant. d[N H3 ]/dt = 2d[N2 ]/dt = 2 d[H2 ]/dt 3 (7. for the reaction N2 (g) + 3H2 (g) → 2NH3 (g) the following applies r = −d[N2 ]/dt = −1/3d[H2]/dt = 1/2d[N H3 ]/dt (7. as a rate increase r = +(1/c)d[C ]/dt r = +(1/d)d[D]/dt (7.5) It should also be noted that the rate of formation of NH3 . For example. .6b) 7. For example. the rate of appearance of D. Thus. the rate is expressed as the rate of increase of a particular compound. (7.6a) (7.4a) (7. For example. is deﬁned as +d[D]/dt. the rate r for the reaction aA + bB → cC + dD can be written as a rate decrease r = −(1/a)d[A]/dt r = −(1/b)d[B ]/dt or. the rate of disappearance of A is deﬁned as −d[A]/dt. Occasionally.

This clearly shows that there is no connection between the order of reaction and the stoichiometric coeﬃcients in these reactions. [c]t−1 ↔ k [c]2 and thus k has the dimension [c]−1 t−1 . k Since the rate r = d[c]/dt has the dimention of concentration divided by time.10a) In a zero-order reaction. b. When a reaction order is mentioned.62 Elementary Physical Chemistry where k is the reaction rate constant. .10b) (7. but are determined experimentally. The exponents m. the rate is independent of the concentration.9a) (7.8a) (7. the order of the reaction with respect to A is m. Sometimes the order of a reaction can be zero or fractional. 7. . For example. [c]t−1 ↔ k [c] and so k has the dimension of t−1 . In a second-order reaction. Relation of order of reaction to stoichiometric coeﬃcients Consider the two reactions: 1) 2N2 O5 → 4NO2 + O2 2) 2NO2 → 2NO + O2 The rates of these two reactions are respectively 1 1) r = − d[N2 O5 ]/dt = k [N2 O5 ] 2 1 2) r = − d[NO 2 ]/dt = k [NO 2 ]2 2 (7. etc. The overall order of reaction is the sum of all the exponents. reaction (2) is second order. the rate law for CH3 CHO → CH4 + CO is r = k [CH 3 CHO ]3/2 (7. n. etc. reaction (1) is ﬁrst order. it follows that the product k [A]m [B ]n . in a ﬁrst-order reaction. it generally refers to the overall order unless otherwise stated. Thus. Units of the Reaction Rate Constant.9b) (7. that appear in the reaction.8b) Obviously. with respect to B is n. must have the same dimention. . in the above example. . are not necessarily the coeﬃcients a. Thus. . The order of reaction is given by the exponents of the concentrations in the rate law.3. .

Example 7.13) . For example. 7. of unknown order m.4.12b) (7.11) The rate law is now eﬀectively ﬁrst order.2. we can write ln(r2 /r1 ) = m ln{[A]2 /[A]1 } from which we can obtain the order m and from r the value of k .12a) (7.Chemical Kinetics 63 If a rate law is not of the form [A]m [B ]n [C ]o . So. Had [A] rather than [B ] been in excess. . 7. . one measures instantaneous rates at the beginning of several diﬀerent concentrations of a particular reactant. Consider the rate expression r = k [A]m .2. Example 7. Denoting the initial rate of a particular sample as r1 and of another sample as r2 . and is called pseudo-ﬁrst order. Consider a reaction which has the rate expression r = k [A][B ]2 .1. Determination of the Rate Law 7. . Initial Rate Method In this approach.4. holding all other reactants constant. Isolation Method This method is used when all reactants except one are in great excess so that their concentrations virtually do not change.4. the reaction has no order.1. the rate would have been pseudosecond order. Assuming that [B ] is in large excess so that it can be considered constant and equal to its initial value. and the corresponding initial concentrations as [A]1 and [A]2 . (7. the rate of formation of HBr (in a particular reaction to be developed later) has the form d[HBr ]dt = {k [H2 ][Br 2 ]3/2 }/{[Br 2 ] + [HBr ]} This reaction has no order. we could express the rate as r = k [A] where k = k [B ]2 (7.

15) (7.5.14) Note that it is kA = ak and not k that enters the expression for the integrated rate.18c) (7. when the concentration is [A]0 and the time t. In a ﬁrst-order reaction. 7. First-Order Reaction Consider the ﬁrst-order reaction r = −(1/a) d[A]/dt = k [A]1 The rate of consumption of A is −d[A]/dt = a k [A] = kA [A] (7.16) Integration between t = 0. (7.17) Note that dx/x = d ln x and so Eq. a plot of ln [A] vs. −d[A]/[A] = kA dt (7.5. whose slope is −kA .1. t gives a straight line.17) becomes ln [A]/[A]0 = −kA t or ln [A]0 /[A] = kA t [A] = [A]0 e−kt (7. Integrated Rate Law Rate laws are diﬀerential equations which must be integrated to obtain concentrations as a function of time. The integrated rate laws are directly related to experimental observables of concentration and time.1). 7. gives A A0 d[A]/[A] = − t 0 kA dt (7. Conversely. . if the order of a reaction is not known.18a) Comment: An important class of ﬁrst-order reactions are nuclear reactions.18b) (7. this indicates that the reaction is ﬁrst order. when the value is [A].64 Elementary Physical Chemistry 7. t gives a straight line (Fig. and a plot of ln[A] vs.

gives 1/[A] − 1/[A]0 = kA t Accordingly. 7. t in a second-order reaction. such as −d[A]/dt = kA [A]2 −d[A]/[A]2 = kA dt (7.1 Plot of ln[A] vs. 7. (7. t in a ﬁrst-order reaction.19a) (7. for a reaction of the type A + B → C in which the concentrations of A and B are not equal. For example.2 Plot of 1/[A] vs. 7. the rate law is much more complicated. In a second-order reaction. Fig. .19b) between the limits [A]0 and [A].19b) we have dx/x2 = −1/x and so integration of Eq.Chemical Kinetics 65 Fig. (7. t gives a straight line (Fig.19c) Note: The foregoing does not apply to all second-order reactions. a plot of 1/[A] vs.2).

3.4. t1/2 = ln 2/kA (7.28 mmol L−1 . Example 7. kA t1/2 = ln{[A0 ]/[A]} = ln{[A0 ]/{(1/2)[A0]} and thus.66 Elementary Physical Chemistry 7. b) If k = 1. the half-life depends on the initial concentration.022 × 10−3 s−1 Since kA t = ln 1.6.4687 we obtain t = 690 s.20a) Example 7.e. t1/2 . Solution kA = ln 2/138 s = 5.73 × 10−5 s−1 what is the half-life of N2 O5 ? . If the initial concentration [A]0 = 1. In a ﬁrst-order reaction. d[NO2 ]/dt. But in a second-order reaction. The reaction rate for the reaction 2N2 O5 → 4NO2 + O2 is of the form r = −1/2d[N2O5 ]/dt = k [N2 O5 ] a) Write an expression in terms of k [N2 O5 ] for the rate of production of NO2 .18b).28 mmol L−1 /0. Exercise: Show that t1/2 = 1/{kA [A]0 }.040 mmol L−1 . is the time taken for the concentration of the substance to reduce to half its value. the half-life is independent of concentration. The half-life of an enzyme-catalyzed reaction is t1/2 = 138 s. How long will it take for the concentration to fall to 0.20b) (7. The reaction is ﬁrst order. Note: In a ﬁrst-order reaction. from Eq.040 mmol L−1 = 3. (7. i. Half-Lives The half-life of a reaction.

21a) A plot of [A] vs. (7.7.73 × 10−5 )t t = 6. t1/2 = ln 2/(2 × 1.73 × 10−5 s−1 ) = 20.21c) (7. Other Reaction Orders 7.22b) (7. −d[A]dt = kA. 7. t1/2 = ln 2/kA .1)[A]0 = ln 10 = (2 × 1. Third-Order Reactions The rate of decomposition of a third-order reaction is −d[A]/dt = kA [A]3 yielding −d[A]/[A]3 = kA t. Integration gives [A]0 − [A] = kA t and the half-life t1/2 = 1/2[A]0 /kA . can be written also as r = −1/2d[N2O5 ]/dt.7.Thus. Zero-Order Reactions The rate decomposition of a zero-order reaction is independent of concentration.65 × 104 s 7. t yields a straight line with a negative slope (Fig. (7.7.21b) (7. and so −d[N2 O5 ]/dt = 2k [N2 O5 ] = kA [N2 O5 ] showing that the rate of reaction is of ﬁrst order.3).Chemical Kinetics 67 c) After a time period. Consequently. t. r.22a) . 7.1.2. the concentration of N2 O5 is 10% of the initial value.0 s c) ln[A]0 /[A] = kA t ln[A]0 /(0. What is the value of t? Solutions a) r = 1 d[NO 2 ]/dt = k [N2 O5 ] 4 The rate of formation of N2 O5 is d[NO 2 ]/dt = 4 k [N2 O5 ] b) The rate.

3 Plot of [A] vs.e. or. 7. [P ] = [A]0 − [A] (7. Concentration of Products So far. Example 7.5.23) . integrated kA t = 1 −2 1 [A] − [A0 ]−2 2 2 (7. In general. 7. Exercise: Show that t1/2 = 1/kA {3/(2[A0 ]2 )}. t gives a straight line of slope kA (Fig..22c) Plotting 1/[A]2 vs.4). 7. Fig. we have considered only reactant concentrations.4 Test for a third-order reaction. they are easy to obtain from the reactant concentrations. Occasionally. 7. product concentrations are of greater interest. The P created must equal the A destroyed.8. i. Consider the reaction A → P . t in a zero-order reaction.68 Elementary Physical Chemistry Fig.

25) ˜ is the so-called pre-exponential factor and Ea is the activation where A energy. . at a given T . 7. from Eq.5 Plot of ln k vs. (7. it is easy to determine the constant at another T . The Arrhenius Equation Arrhenius found that many reactions obey the Law ˜ − Ea /RT ln k = ln A ˜e−Ea /RT k=A (7. 7.18c) [P ] = [A0 ][1 − exp(−kA t)] (3) In second-order. (7. Test of the The Arrhenius Equation. ln(k /k ) = (Ea /R) T (1/T − 1/T ) (7.5). 1/T . (7.24a) (7.9. 1/T gives a straight line whose slope is −Ea /R (Fig. from Eq. If A and Ea are known.21b) [P ] = [A0 ] − [A] = kA t (2) In ﬁrst-order. A plot of ln k vs. Assuming that Ea and A are constant.Chemical Kinetics 69 (1) In zero-order.24c) (7.24b) (7.19c) 1/[A] − 1/[A0 ] = kA t [P ] = kA t[A0 ]2 /{1 + kA t[A0 ]} 7.26) Fig. Temperature-Dependent Reaction Rates. from Eq.

6.992 × 10−3 2 −4. The decomposition of urea (in 0. Solution [Note: ln = 2.4 J mol−1 ) = 14.147 − 4.558 2.303 × 8.992) × 10−3 K−1 = 128.303 × (8. According to this theory.77 × 10−5 Calculate A and Ea .722 Arrhenius’ qualitative explanation of activation energy was based on the assumption that in every system there is an equilibrium between normal and active molecules and only active molecules can take part in chemical reactions.558) (2.05 0.904 × 10−3 Ea = 2.3145 J K−1 mol−1 )(5.1 M HCl) 2− NH2 CONH2 + 2H2 O → 2NH+ 4 + CO3 is ﬁrst order with rate constants at two diﬀerent temperatures k (min−1 ) Exp T (◦ C) 1 61.70 Elementary Physical Chemistry Example 7.147 2. (2) Activated Complex Theory.303 log] Exp log k 1/T 1 −5.558 + 128.86678 A = 1.713 × 10−5 2 71.25 2.904 − 2.100 J mol−1 /(2.3145 × 344.100 J mol−1 log A = −4. increasing the temperature results in (1) an increase in the number of collisions. . 7.10. Reaction Rate Theories There are two theories that purport to explain reaction rates quantitatively: (1) Collision Theory. and (2) an increase in the concentration of active molecules.

However. The graph (called the reaction proﬁle. molecules must collide with suﬃcient energy to carry them over the activation barrier. At left is the potential energy of the reactants when they approach each other.Chemical Kinetics 71 7. rate = k [A][B ].6) depicts the potential energy of two molecules as they interact with each other.6 Reaction proﬁle of two approaching molecules. It can be shown that the number of collisions per unit time is proportional to the product of the concentrations of A and B. 7. where A ˜ is a proportionality constant.e. Considering that the actual reaction rate is k [A][B ]. Collision Theory This is the older of the two theories. the potential energy increases because the bond bends and starts to break. The reaction can obviously not occur more often than the number of collisions between A and B.10.1. . The potential energy reaches a peak when the molecules are most distorted. it ˜e−Ea /RT . For reactions to succeed. As the molecules get closer. Only the collisions which give rise to a kinetic energy exceeding Ea are eﬀective. Thereafter the energy decreases as new bonds are formed. follows that k = A Fig. Consider the reaction A + B → · · · . It can be shown (by statistical mechanics) that the fraction of molecules having a kinetic energy exceeding Ea is e−Ea /RT . Hence. i. see Fig. the theoretical reaction rate has to be proportional to [A][B ]e−Ea /RT . 7. not all collisions lead to reactions.

the maximum corresponds to a complex molecule. be measured. The measured A ˜ is The value of A generally smaller than the one calculated. it assumes that there is an equilibrium involving the reactants and the activated complex.10. the potential energy goes through a maximum. In essence. in principle. “steric” factor. In the activated complex theory (see Fig. Hence. and this will give rise to a ˜e−Ea /RT . But in the activated complex theory. 7. giving rise to an Fig. The collision theory is generally limited to classical gases.7 Plot of potential energy in activated complex theory. The activated complex theory was developed in 1933 by Eyring (and also by Polanyi).72 Elementary Physical Chemistry ˜ can. An activated complex at peak potential energy is often referred to as transition state. PA . . which has a deﬁnite composition and a loose structure. k = PA A 7. It is said that the relative orientation must also be taken into account. Activated Complex Theory This is the modern theory of reaction rate.2. The complex can turn into products or collapse back into reactants. 7.7). as in the collision theory. The activated complex theory makes use of quantum mechanical and statistical mechanical concepts.

27) Moreover. it is assumed that the rate of formation of the product is proportional to the concentration of the activated complex. Rate Law Mechanisms This section deals with explanations of reaction kinetics in terms of reaction mechanisms.11. ∆H ‡ = Ea ˜ = RT /N he∆S and PA A ‡ ‡ /R −∆H ‡ /RT e (7.30) /R where N is the number of molecules and h is Planck’s constant. Comparing this rate of formation of the product with the actual formation rate = k [A][B ] shows that k = αK ‡ → αe−∆G ‡ /RT = αe∆S ‡ /RT −∆H ‡ /RT e (7. • Order is an empirical quantity obtained experimentally. k = (RT /N h)e∆S in which. • Molecularity indicates how many molecules come together to react in an elementary reaction. Before discussing the reasons.28) where α is the proportionality symbol and A and B are reactants. Hence.Chemical Kinetics 73 “equilibrium constant”. it is important to distinguish between the concept of order and the concept of molecularity. Rate = αK ‡ [reactants] = αK ‡ [A][B ] (7. 7. deﬁned as K ‡ = [activated complex]/[reactants] (7. More precisely (not derived here). .29) This has the form of the Arrhenius equation and will be equal to it if we set ∆H ‡ = Ea and αe∆S ‡ /R ˜ = Pa A.

not elementary. It is therefore assumed that d[I ]/dt = 0.) The order is ﬁrst order. two molecules must combine but the order is not necessarily second order. Example 7. in general. exact solutions are not feasible. Question: Why is there no direct correspondence between molecularity and order of reaction? The reason is that most reactions are complex.33) (7.74 Elementary Physical Chemistry Note: In a unimolecular reaction.32) (7. one generally resorts to approximations. The Steady State Approximation Complex reactions usually involve intermediate species that do not appear in the overall reaction. Reactions that tend to cause complications are 1) Opposing or reverse reactions A + B ↔ C B 2) Complex reactions A C 3) Consecutive reactions A → B → C (7. If [A] represent a reactant. 7. Consider the reaction 2NO(g) + O2 (g) → 2NO2 (g) (7. In a bimolecular reaction. This is the steady-state assumption. in fact it could be any order. (Radioctive decay is a good example.7. then it is generally true that [I ] is much smaller than [A] or [P ]. The reason is that intermediates are reactive.12. It may be ﬁrst order. zero order .31) Such reactions greatly complicate the diﬀerential equations and. . and generally do not accumulate to any extent. 2) Rate-Determining (or Rate-Limiting) Step or Equilibrium Approximations. The most common approximations are 1) Steady-State Approximation. reactions go through many intermediate steps. When there are many intermediate steps. a single molecule breaks apart.34) . [P ] a product and [I ] an intermediate. In general. .

the rates of consumption of NO and O2 are respectively −d[NO ]/dt = 2r and −d[O2 ]/dt = r and the rate of formation of NO2 is +d[NO 2 ]/dt = 2r (7. the following mechanisms have been suggested.37a) Obviously. if r represents the rate of reaction. To explain the observed rate law.38) . then 1 1 r = − d[NO ]/dt = −d[O2 ]/dt = d[NO 2 ]/dt 2 2 (7.36) On the other hand.Chemical Kinetics 75 It is found experimentally that the reaction obeys the rate law d[NO 2 ]/dt = k [NO ]2 [O2 ] (7.40) slow − d[N2 O2 ]/dt = k1 [N2 O2 ] − d[N2 O2 ]/dt = k2 [N2 O2 ][O2 ] Note: These k ’s are not the kA which are the product of k and a. Thus.37c) (7. It is assumed that N2 O2 is the intermediate and that the following elementary reactions take place. the rate law. (7. when the order of the reactions can be determined from the stoichiometric coeﬃcients.35) Caution.39) (7. r. It is important to distinguish between rate of reaction and rate of consumption or rate of production.37b) (7.] 1) NO + NO → N2 O2 d[N2 O2 ]/dt = k1 [NO ]2 2) N2 O2 → NO + NO 3) N2 O2 + O2 → 2NO2 fast (7. [Note that reactions are said to be elementary. does not represent the rate of formation of the product NO2 .

76 Elementary Physical Chemistry The overall rate for d[N2 O2 ]/dt is zero. This reaction is followed by a slow step which. the reaction mechanism is assumed to consist of one or more reversible reactions that stay close to equilibrium during most of the reaction.45) 7. (7. [N2 O2 ] = k1 [NO ]2 /{k1 + k2 [O2 ]} (7. which is the slow reaction and thus the reaction determining step. assuming that k1 is much greater than k2 .43) and thus the rate of production of NO2 is d[NO 2 ]/dt = 2k1 k2 [NO ]2 [O2 ]/(k1 + k2 [O2 ]) (7.46) .13.42) (7. The Rate-Determining Step (or Equilibrium) Approximation Here.41) The product NO2 is produced only in reaction (3). r= 1 d[NO 2 ]/dt = k2 [N2 O2 ][O2 ] 2 (7.47) Br− (7.44) Finally. So. yielding d[NO 2 ]/dt = 2(k1 k2 /k1 )[NO ]2 [O2 ] = k [NO ]2 [O2 ] which is the expression obtained experimentally. is the ratedetermining step. Example 7. For this reaction. k1 [NO ]2 − k1 [N2 O2 ] − k2 [N2 O2 ][O2 ] = 0 Hence. we can neglect the term k2 [O2 ] in the denominator. Consider the reaction catalyzed by Br− H+ + HNO2 + C6 H5 NH2 −→ C6 H5 N+ 2 + 2H2 O The observed reaction rate law is r = k [H + ][HNO 2 ][Br − ] (7.8. as noted before.

has both bimolecular and unimolecular steps. 7.14. it must acquire enough energy.52) which yields.50) + Br → ONBr + H2 O C6 H5 N+ 2 (3) ONBr + C6 H5 NH2 → + H2 O + Br The rate constants for reactions (7.53a) Equating the empirical constant k with k2 k1 /k1 gives the observed reaction rate law. But that is a bimolecular reaction.49) fast (7. .53b) (7.48)–(7.Chemical Kinetics 77 Proposed mechanisms: (1) H+ + HNO2 (2) H2 NO+ 2 − H2 NO+ 2 rapid equil. 7.48) (7. Unimolecular Reactions First order gas phase reactions are usually called unimolecular reactions. (3) k3 (forward →) The rate-determining step (Step 2) gives − r = k2 [H2 NO + 2 ][Br ] (7.1. How does it do that? By colliding with another molecule. The overall reaction. But for a molecule to break up. it turns out. slow − (7. (2) k2 (forward →) . r = k2 K [H + ][H2 NO 2 ][Br − ] or r = (k2 k1 /k1 )[H + ][HNO 2 ][Br − ] (7.50) are respectively (1) k1 (forward →) and k1 (reverse ←).51) From (1) we get the equilibrium constant + K = k1 /k1 = [HNO + 2 ]/{[H ][HNO 2 ]} (7.14. The Lindemann Mechanism This was the ﬁrst successful explanation of a unimolecular reaction.

78 Elementary Physical Chemistry It is assumed that a molecule A collides with another molecule A to produce an energetically excited molecule A∗ . and k2 . we obtain thus k1 [A∗ ] = k1 /k1 [A] = k [A} and therefore. −d[A∗ ]/dt = d[P ]/dt = k [A] which is ﬁrst order. by undergoing a unimolecular reaction 3) A∗ → P −d[A∗ ]/dt = k2 [A∗ ] slow Assuming that A∗ is the intermediate. if (not always true) reaction (3) is very much slower than (2).57b) (7. 1) A + A → A∗ + A d[A∗ ]/dt = k1 [A]2 (7.56) (7.58a) . The following reactions (assumed to be elementary) occur. and thus d[A∗ ]/dt = 0 = k1 [A]2 − k1 [A∗ ][A] − k2 [A∗ ] which gives [A∗ ] = k1 [A]2 /{k2 + k1 [A]} (7.57a) (7. the rate constants k1 and k2 are in the forward direction.54) The A∗ molecule may lose its energy by colliding with another molecule A. In all these reactions. (7.55) Finally.58b) (7. and k1 is in the reverse direction. 2) A∗ + A → A + A −d[A∗ ]/dt = k1 [A∗ ][A] fast or A∗ may shake itself apart.

It is customary to characterize the various reactions by names.15. etc. 1) Initiation Br2 → 2Br• 1/2d[Br •]/dt = ka [Br 2 ] 2) Propagation Br• + H2 → HBr + H• −d[Br •]/dt = d[H •]/dt = kb [Br •][H2 ] H• + Br2 → HBr + Br• −d[H •]/dt = d[Br •]/dt = kb [H •][Br 2 ] 3) Retardation H• + HBr → H2 + Br• −d[H •]/dt = d[Br •]/dt = kc [H •][HBr ] 4) Termination Br• + Br• + M → Br2 + M 1 − d[Br •]/dt = kd [Br •]2 2 (7. the latter generates another intermediate.64) (7. Again.60) (7.59) The proposed mechanism involves chain reactions and free radicals.61) (7. such as initiation step.65) . etc. consider the reaction H2 (g) + Br2 (g) → 2HBr(g) The rate law is found to be d[HBr ]/dt = k [H2 ][Br 2 ]3/2 /([Br 2 ] + k [HBr ]) (7. Chain Reactions Many liquid and gaseous reactions are chain reactions. As an example.63) (7.62) (7. The ﬁnal results must not contain intermediate free radicals.Chemical Kinetics 79 7. meaning that an intermediate produced in one step generates an intermediate in a subsequent step. propagation step. all reaction constants are in the forward direction. termination step. A radical is denoted by a dot after the atomic symbol.

kd . we consider d[Br •]/dt = 2ka [Br 2 ] − kb [Br •][H2 ] + kb [H •][Br 2 ] + kc [H •][HBr ] − 2kd [Br •]2 = 0 d[H •]/dt = kb [Br •][H2 ] − kb [H •][Br 2 ] − kc [H •][HBr ] = 0 (7. Example 7. The following mechanism has been suggested 1) I2 2I rapid equilibrium 2) 2I + H2 → 2HI slow The forward and reverse reaction constants of Eq. The concentration of M has been absorbed in the reaction rate constant.66) (7.69) The ﬁnal expression for the rate law. (There are other recombination reactions. when replacing k by 2kb (ka /kd ) and k by kc /kb . Determine the rate law d[HI ]/dt and express the result in terms of the reaction constants k1 . M is a third body which removes energy. combines Eqs.62)–(7. gives the experimental rate law.9. (7. (1) are k1 and k1 . k2 .70) which. such as 2H• → H2 and H• + Br• → HBr.67) Thus. Using the steady state approximation. k1 .64) to give d[HBr ]/dt = kb [Br •][H2 ] + kb [H •][Br 2 ] − kc [H •][HBr ] Substitution of the values for [H •] and [Br •] gives d[HBr ]/dt = 2kb (ka /kd )1/2 [H2 ][Br 2 ]3/2 /{[Br 2 ] + (kc /kb )[HBr ]} (7. which is in terms of the production of HBr.80 Elementary Physical Chemistry Here. The production of HI in the reaction H2 + I2 → 2HI obeys the rate law d[HI ]/dt = k [H2 ][I2 ]. there are two equations with two unknowns.71) (7.68) 1/2 1/2 [H2 ][Br 2 ] }/{kb [Br 2 ]kc [HBr ]} (7. . but these are unimportant and will be ignored. (2) is k2 . the (forward) reaction constant of Eq. Solving them gives [Br •] = (ka /kd )1/2 [Br 2 ]1/2 [H ] = {kb (ka /kd ) • (7.) The ﬁnal reaction rate must not contain free radicals Br• or H•.

we have k1 [I2 ] − k1 [I ]2 − k2 [I ]2 [H2 ] = 0 and so [I ]2 = k1 [I2 ]/(k1 + k2 [H2 ]). it means that k2 neglecting the k2 term in the denominator gives d[HI ]/dt ≈ (2k2 k1 /k1 )[I2 ][H2 ] which is the same as in Part (a). K = [I ]2 /[I2 ] = k1 /k1 . I. k1 and so .Chemical Kinetics 81 Solutions a) Equilibrium Approximation: k1 [I2 ] = k1 [I ]2 . [I ]2 = (k1 /k1 )[I2 ] The rate-determining step is Step (2). is formed in Step (1) forward direction: 1 2 d[I ]/dt = k1 [I2 ] 1 d[I ]/dt = k1 [I ]2 reduced in Step (1) reverse direction: − 2 1 reduced in Step (2) − 2 d[I ]/dt = k2 [I ]2 [H2 ] Since the intermediate substance must disappear. using Step 2 gives d[HI ]/dt = 2k2 [I2 ][H2 ] = 2k2 k1 [I2 ][H2 ]/(k1 + k2 [H2 ]) Realizing that Step (2) is the slow step. Thus. 2 r=1 2 d[HI ]dt = k2 [I ] [H2 ] d[HI ]/dt = 2k2 [I2 ] = (2k2 k1 /k1 )[I2 ][H2 ] b) Steady-State Approximation: The intermediate substance.

To be 82 . the subjects that were well developed were (1) Mechanics (dealing with motion) (2) Light (electromagnetic radiation). Speciﬁcally. Speciﬁcally. by what is now known as classical theory. quantum theory will be applied to atoms and molecules. in principle. aufbau (build-up) principle. atomic spectra. energy levels.Chapter 8 Introduction to Quantum Theory This chapter traces the historical development that led to the adoption of quantum theory.). In subsequent chapters. molecules. and to spectroscopy. elegant disciplines. the present chapter deals with the following topics: (1) Failure of classical mechanics (2) Wave-particle duality (3) The Schr¨ odinger equation and the Born interpretation of wavefunctions (4) The Uncertainty Principle and the Superposition of State (5) Structure of atoms — atomic orbitals. to translational. rotational and vibrational motion. All known phenomena could be explained. electricity and magnetism (3) Thermodynamics and statistical mechanics However. when these classical theories were applied to systems of microscopic dimension (atoms. Historical Development Around 1900.1. science in general and physics in particular were considered to be a self-contained. etc. they generally failed. radius and ionization energy 8.

Black-Body Radiation When a body is heated to incandescence. bright red light is emitted. one should observe two lit points on the second screen. the appearance of diﬀraction patterns when light was passed through two adjacent oriﬁces (Young’s Experiment) and the prediction of Maxwell’s Theory of Electromagnetic Radiation. The distribution of the light colors (really in terms of frequencies or wavelengths) could be measured by shining the emitted light onto a prism. establishing the wave theory as the proper one. but as time went on. clearly established light to be wave-like. . Then. First. 8. which formulated a uniﬁed treatment of electricity. the light emanating from the two holes was observed on a screen. Furthermore. the light emanating from the two holes would set up new waves that would interfere with each other (constructively and destructively). dull red light is emitted. In Young’s experiment (∼1850). Failure of Classical Theories Important experiments which deﬁed classical explanations around 1900 were black-body radiation. The experiment clearly showed the latter. Maxwell’s Theory of Electromagnetic Radiation. is given oﬀ and eventually blue light is emitted. photo-electric eﬀect and heat capacity of solids.2. thus producing interference patterns. In the 17th century there were two theories of light: (1) The corpuscular theory (proposed by Isaac Newton). magnetism and light (called electromagnetic radiation). suggesting that light consists of waves. If light were wave-like. Thereafter yellow light etc.Introduction to Quantum Theory 83 cognizant of the confusion and disappointment these failures caused. By the end of the 20th century. clearly favored the wave theory. (2) The wave theory of light (proposed by Huygens). First. as temperature is increased. the corpuscular theory was most favored as it could account for the sharp shadows. 8. the particle theory of light was as dead as a doornail. If light were corpuscular. which stated that light consists of “particles” shot out of the luminous body.2.1. light is emitted. it is well to mention some of the disputes scientists engaged in.

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The prism separates the light, which is a mixture of several frequencies (colors), thus providing information on the distribution of the frequencies (or colors). The theoretical prediction of the way frequencies should vary with temperature did not agree with the experimental results. Classically, it was assumed that the electromagnetic ﬁeld is made up of a collection of oscillators. If an oscillator is excited to a frequency ν it will emit radiation of that frequency. Planck noticed that if he would disregard one of the most sacred rules of science, namely that energy varies continuously, he could explain the black-body radiation. Planck then postulated that the oscillator energies varied discontinuously — that the energies are discrete, not continuous. Basically, Planck suggested that in the black-body experiment, energy can be absorbed from the heat source only in discrete units, called quanta. 8.2.2. Photo-Electric Eﬀect When a beam of light shines on a metal, it may cause electrons to be ejected from the metal. This is referred to as the photo-electric eﬀect. However, there is a minimum (or threshold) frequency (diﬀerent for diﬀerent metals) below which electrons are not ejected, regardless of how intense the light beam is.

Note: If light consisted of waves, as was generally assumed in those days, there was no reason why there ought to be threshold frequency. As long as the beam is suﬃciently intense, it should emit electrons regardless of frequency.

Could Planck’s ideas shed some light on this problem? Planck’s suggestion of 1900 was essentially forgotten until Einstein, a patent clerk at Bern, Switzerland, published a paper in 1905, which not only revived Planck’s ideas but plunged science into a state of turmoil that lasted for more than a quarter of a century. Einstein felt that Planck’s explanation of the black-body radiation, though revolutionary, was incomplete. While Planck’s theory clearly suggested that energy absorbed from the heat source by the black-body must do so in quanta, not much was said about the fate of the energy of the emitted radiation. It was generally assumed that the emitted radiation would obey

Introduction to Quantum Theory

85

the Laws of Maxwell, in other words, would be wave-like. But Einstein argued that these ideas are inconsistent. He maintained that if energy is absorbed from the heat source in quanta, it must also emit radiation energy in the form of quanta, clearly implying that radiation is particle-like. Einstein then introduced the notion that light consists of indivisible units (later called photons), the energy of which is ε = hν , where h is Planck’s constant and ν the frequency. Planck’s constant has the value h = 6.626 × 1034 J s or h = 6.626 kg m2 s−1 . Comment: It is ironical that Einstein who brought down Newton’s classical mechanics with relativity resurrected Newton’s corpuscular theory of light.

Einstein’s idea was not based strictly on logic, as compelling as that was; but by postulating the existence of indivisible light units, he was able to explain the photo-electric eﬀect. According to Einstein, electrons in a metal are knocked out by photons. The energy of a photon must be equal to or exceed the attractive energy between the electron and the positive charge of the metal. This energy is called the work-function and is denoted as φ. If there is excess energy, it is carried oﬀ by the emitted electron in the form of kinetic energy. Thus, KEelecr = εphot − φ. 8.2.3. Heat Capacity of Solids Solids consist of atoms which are oscillating. According to classical theory, the average energy of an oscillator in 3-D is 3kT , where k is the Boltzmann constant equal to R/NA , (NA being Avogadro’s number). The vibrational molar energy is 3RT and the heat capacity is CV = 3R (the value of Dulong and Petit). The actual heat capacity, as shown in Fig. 8.1, is constant with a value of 3R; but as the temperature is lowered, the heat capacity decreases, and at 0 K it is zero. To explain this, Einstein invoked Planck’s hypothesis that the energy of an oscillator has to be quantized. This produced a heat capacity curve which is very similar to the observed one. The formula was further improved by Debye who did essentially what Einstein did but considered the solid to vibrate with a range of frequencies rather than a single frequency as Einstein had done.

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Elementary Physical Chemistry

Fig. 8.1

Plot of variation of CV with T .

8.2.4. Wave or Particle? So what is light? The photo-electric eﬀect clearly established light to be particle-like. Young’s experiment on interference diﬀraction and Maxwell’s theory of electromagnetic radiation clearly established light to be wave-like. How could the same entity, light, be such a contradictory thing? 8.3. The Rutherford Atom The Rutherford experiment (∼1911) is one of the most important experiments ever performed, for it established unequivocally the structure of the atom (Fig. 8.2). (1) The experimental set-up. In this experiment, a narrow beam of α rays from a radioactive source (radium) was aimed at a very thin gold foil. Behind the gold foil was a screen coated with a chemical (zinc sulﬁde), which has the following property: it ﬂashes when hit by an α-particle.

Note: Some naturally occurring heavy atoms (e.g. uranium, radium, polonium, etc.) have the ability to emit rays. The rays are of three types: α-rays, β -rays and γ -rays. The α-rays are bare positively charged helium nuclei (helium atoms stripped of the electrons); β -rays are electrons; γ -rays are the most energetic forms of electromagnetic radiation.

What Rutherford observed was that most of the α-particles passed through the gold foil undeﬂected. the planets revolve around the sun. The Planetary Model of the Atom. (He could tell by observing the scintillations on the screen. (3) Interpretation. The results led to the following conclusions: (a) The gold foil is for the most part empty space since most of the α-particles passed through the foil undeﬂected. otherwise they would be pulled into the sun by the force of gravity. In the solar system. but there is an essential diﬀerence between planets moving around the sun and electrons moving around a nucleus. Again.) Some α-particles were deﬂected. 8. What emerged from the Rutherford experiment was a model that in many ways resembles the solar system.Introduction to Quantum Theory 87 Fig. Similarly. the Rutherford model was referred to as the planetary model of the atom.2 The Rutherford experiment. (b) The few α-particles that passed through deﬂected indicated that most of the atomic mass is concentrated in a tiny nucleus. (c) The gold nucleus must be positively charged. (d) α-particles colliding with electrons cause no noticeable eﬀect. They have to be in motion. otherwise they would fall into the nucleus. the positively charged nucleus and negatively charged electrons attract each other. the electrons must be in motion. The fact that an atom behaved so similar to our solar system must have been most pleasing to scientists. The . (2) Observation. in atoms. Only positive nuclei can cause positively charged α-particles to deﬂect from the original path. In fact.

(2) An electron moving in a stationary state does not emit electromagnetic radiation. En and Em being two energy levels of the hydrogen atom. a photon is emitted. He further postulated that (1) An electron in an atom is limited to certain discrete values E1 . Fig. a photon is absorbed. 2.88 Elementary Physical Chemistry sun and planets are neutral (not electrically charged) bodies. And. The energy of the photon is εphoton = hν = (En − Em ). (3) Radiation is emitted or absorbed only when an electron jumps from one level to another. using Planck’s idea of quantization of energy (Fig. . If En > Em . 8. E2 . and (5) There were certain limitations of angular momentum. as noted before.3). 8. etc. a planetary atom should not exist. In other words. . when a charged particle (an electron in this case) moves in an electromagnetic ﬁeld. thereby losing energy. called stationary states of levels. the nucleus and electrons are electrically charged. when an electron moves around the nucleus it should lose energy and eventually spiral into the nucleus. .3 Diagram depicting orbitals and energy levels of the Bohr atom. 8. requiring energy levels to have the form En = −hcRH /n2 n = 1. The Bohr Theory of the Hydrogen Atom Bohr developed a theoretical model for Rutherford’s atom.1) where c is the speed of light and RH is the Rydberg constant for the hydrogen atom. it should emit radiation (light). Thus. namely RH = 1.4. (4) The electron moves in circular orbits (paths). (8. .0946 × 10−5 cm−1 . if En < Em .

followed by swift decline. Louis de Broglie. . but not when in motion. a physics student at the Sorbonne. Bohr was able to generate the well-known empirical formulas for the emission of radiation by excited hydrogen atoms. was so disturbing that many scientists were beginning to have serious doubts about the generality of science. Bohr’s prediction of radiation of the hydrogen atom was in almost perfect agreement with experiments.2a) (8.2c) Note: Bohr’s theory was essentially classical in nature except for the assumption of quantization of energy (really of angular momentum of the moving electron) and the photon nature of radiation. in 1923. Lyman Series Balmer Series Paschen Series (8. . and when applied to heavier atoms. suggesting that the theory of he atom was solved.2b) (8. for photons h/mc = h/p = c/ν = λ (8. . .5. the theory failed miserably.Introduction to Quantum Theory 89 With these assumptions.3a) . They are ν/c = RH (1/12 − 1/n2 ) ν/c = RH (1/2 − 1/n ) ν/c = RH (1/3 − 1/n ) 2 2 2 2 n = 2. . . submitted a dissertation in which he made a startling discovery. 4. . he concluded that matter must consist of waves — matter waves. . But when the theory was applied to He. ε = hν . Photons have zero rest mass. This forced him to postulate the conditions 4 and 5. 5. p being the momentum. 3.3b) (8. 8. Using Einstein’s relativity formula E = mc2 and his expression for the photon energy ε = hν = mc2 produced hν/c = mc = p. His reasoning (highly simpliﬁed here) may have been based on the following kinds of analogies: For photons. n = 3. the results were not good. Rummaging through Einstein’s theory of relativity. Thus. Louis de Broglie Then. . The phenomenal success of the Bohr theory of the hydrogen atom. n = 4.

who analyzed diﬀraction patterns of electrons by crystals and observed interference patterns similar to inference by light. Schr¨ odinger set out to discover the matter wave-equation. (2) Heisenberg went to Helgoland trying to get rid of a severe bout of hay-fever. They are referred to as (1) Wave-Mechanics (Schr¨ odinger) (2) Matrix Mechanics (Heisenberg. Rather than focusing on de Broglie’s ideas. diﬀerent conceptually and philosophically from the old theories.” Schr¨ odinger did that. Three diﬀerent formulations of the new theory emerged between 1925 and 1927. as Schr¨ odinger did.626 × 10−34 m2 s−1 /70 kg m s−1 = 9. Jordan) (3) Quantum Theory (Dirac) The three formulations looked mathematically diﬀerent. “Erwin. a person weighing 70 kg moves with a velocity of v = 1 m s−1. (1) There is a story that Debye at Zurich Polytechnic said to Schr¨ odinger (a younger faculty member).3c) In other words.5 × 10−36 m. There he worked on problems involving quantum theory. the wavelength is λ = 6. For example. there must be a waveequation describing those waves. It became clear to Schr¨ odinger that if there was such a thing as matter waves. The new ideas that were introduced next were so strange and weird that only the most gifted scientists could understand them. since you are not doing anything useful these days why don’t you ﬁnd out what de Broglie is up to and tell us about it. but turned out to be equivalent. analogous to the Maxwell equations describing electromagnetic waves. By the de Broglie equation. he . Following are some anecdotal details of the new developments. The de Broglie hypothesis was conﬁrmed a few years later by Davisson and Germer. a particle moving with a velocity v has a wave associated with it.90 Elementary Physical Chemistry de Broglie suggested that a similar expression applies to a particle moving with a velocity v λ = h/mv = h/p (8. What ﬁnally emerged was not just a generalization of classical theories but an entirely new framework. Born.

(3) By now Dirac came on the scene. Dirac’s formulation is lean in comparison with Heisenberg’s. there are concepts that can be measured and concepts that cannot be measured. Heisenberg argued that all we know for sure about the atom are such things as frequencies. on a visit to Cambridge University. not knowing that mathematicians had done that ∼100 years earlier under the name of matrix multiplication. Heisenberg found that he could obtain the correct results for the harmonic oscillator and the hydrogen atom by replacing the classical dynamical variables. Dirac’s formulation is most elucidating in its generality and is sometimes referred to as symbolic quantum mechanics. Heisenberg. he showed his work to Born. because of the form. showed his work to Prof. In Bohr’ theory. asking him for his opinion. but formulated a quantum theory in terms of operators. accomplishing with ease what Heisenberg. only changes in energy levels. Heisenberg decided to develop a theory based solely on concepts that have been measured. The Bohr theory uses such quantities as energy levels. No one has seen orbits — out they go. In fact. Heisenberg. frequencies. which depend on single numbers. Born and Jordan could accomplish only with great diﬃculty. a young faculty member at Gottingen. and asked him for comments. He even worked out the mathematics on how to handle multiplication of arrays of numbers. intensities of the emitted light. but what Heisenberg actually had developed laid the foundation of a new and diﬀerent theoretical framework of mechanics. by matrices which are arrays of numbers. who immediately recognized that Heisenberg’s work was not a mere mathematical scheme for handling arrays of numbers (which was not new). The phenomenal success of Bohr’s theory of the hydrogen atom could not be entirely accidental. Fowler gave the material to Dirac. . he reasoned. Born and Jordan formulated a general theory of quantum mechanics which. is also referred to as matrix mechanics. When Heisenberg returned to Gottingen. Fowler. Together with Jordan. no one has seen energy levels. Dirac not only did that. There must be some essential validity to that approach. intensities and orbits.Introduction to Quantum Theory 91 went back to the Bohr theory of the hydrogen atom. a student of Fowler.

5) where r is the distance of the electron from the nucleus.1. [The wavefunction is in general complex and the ψ ∗ denotes the complex conjugate. it is a diﬀerential equation which has to be solved to produce the properties of the system under consideration. The Schr¨ odinger Equation Schr¨ odinger’s treatment is mathematically the simplest. Solving this equation produces two types of information: (1) A set of energy levels: E1 .6) (a) What is the probability of ﬁnding the electron within a volume of ∆v = 1 pm3 around the nucleus? (b) What is the probability of ﬁnding the electron within a volume of 1 pm3 at a distance a0 from the nucleus? Solution The probability expression is (ψ is real) 3 2 Prob = ψψ dv = (8/πa3 0 ) {exp(−2r/a0 )} dv In this problem. associated with each energy state. The wave-function ψ has no physical signiﬁcance. is −(h2 /8π 2 m) d2 ψ/dx2 + V ψ = Eψ (8. (2) A set of wave-functions.9 × 10−12 m = (52. and a0 = 52. Bohr. The product of the wave-function and its complex conjugate is always real. E2 . ψn (x). However. the r’s are constant and dv = 1 pm3 . Today’s accepted interpretation (due to Born) is that ψ ∗ ψ represents a probability density. the Schr¨ odinger equation of a particle moving in one dimension. and that ψ ∗ ψδ v denotes the probability of ﬁnding the particle within the volume element δv .9 pm) (8. Basically. Schr¨ odinger believed that the wave function described the position of the particle. who invited him to Copenhagen. For example.6.] Example 8.4) where V is the potential energy.92 Elementary Physical Chemistry 8. and is most often used in calculations. Originally. The ground state of He+ is 1/2 ψ = (8/πa3 exp (−2r/a3 0) 0) (8. quickly convinced him that that was not the case. etc. E is the energy of the particle and ψ is the wave-function. . having a mass m.

referred to as the Copenhagen Interpretation. if ∆p and ∆x represent respectively the uncertainty in momentum and the uncertainty in position.72 × 10−5 (b) At r = a0 .7) .93 pm3 )}(exp − 2)2 pm3 = 3. (2) The Copenhagen Interpretation. r = 0 and 3 Prob = (8/πa3 0 ) × (1pm) = {8/(π × 52.7. (b) The Heisenberg formulation through the Uncertainty Principle. In 1927. which is deterministic. Einstein never did. the leading scientists met at Lake Como for the purpose of arriving at some consensus of the meaning of quantum mechanics. They can exist either as particles or as waves. More precisely. Another notable scientist who had problems with some of the Copenhagen Interpretation was Schr¨ odinger. 3 Prob = (8/πa3 0 ) × {exp (−2a0 /a0 )} (1pm) 2 = {8/(π × 52. This resulted in an interpretation. The most important conclusions of the Copenhagen Interpretation are (a) The dual nature of light and of matter. (8.93 pm3 )}(1pm3 ) = 1. then quantum theory requires that ∆p × ∆x ≥ h/4π 8.15 × 10−7 The probabilistic nature of quantum mechanics manifests itself in (a) The Schr¨ odinger formulation through the wave function. which states that it is not possible to know with complete certainty both the momentum and position of a particle. unlike classical mechanics. because of the leadership of Bohr. Most scientists of those days accepted the Copenhagen Interpretation as the true meaning of quantum mechanics.Introduction to Quantum Theory 93 (a) At the nucleus. Summary and Conclusions (1) Quantum mechanics is probabilistic.

(d) One of the consequences of the above is that if a system can exist in several diﬀerent states. one can separate the observation of the system from the measuring device. In classical mechanics. The same considerations apply to all measurements of large bodies in classical mechanics. the process of measurement will have profound eﬀect on the results. Note: As an example of the contrast of observations in classical and quantum mechanics. But the amount of heat is so small. the wave-function “collapses” to a particular state and only that state is observed. a cat is conﬁned in a lower compartment separated from an upper compartment by a glass ceiling (Fig. In this thought-experiment. the size of an electron. So the reading on the thermometer represents the temperature of the person after the heat loss. and may not be ignored. In quantum mechanics. that is a mixture of all these states (sometimes referred to as “ghost” states). What really takes place is heat ﬂowing from the person to the thermometer. .4). The upper compartment contains a poisonous gas. In the upper compartment. But if a measurement is made. consider the measurement of the temperature of a person with a thermometer. that for all practical purposes it is negligible. the operation of observation is built into theory and the observed results are the properties of the system as perturbed by the measurement. In quantum mechanics. the operation of observation is built into theory and the results are properties of the system as perturbed by the measurement. Schr¨ odinger’s Cat Schr¨ odinger had diﬃculties accepting this interpretation and he published a “thought experiment”. However. 8. if an observation is made on a microscopic system of say.94 Elementary Physical Chemistry (b) The importance of observation or measurement. (c) The laws of quantum mechanics have meaning only if measurements are done on the system. The measurement causes the collapse. which goes under the name of “Schr¨ odinger’s Cat”. 8. the state of the system will be a superposition.8.

the Uncertainty Principle. A half-life of an hour means that there is a 50–50 chance that an α-particle was emitted and a 50–50 chance that a particle was not emitted. there is a radioactive material which emits α-particles with a half-life of 1 hour. Finally. What is the de Broglie wavelength λ? . The emitted particle triggers a contraption which releases a hammer that shatters the glass. which acts as an observation. an amoeba. “Does that make any sense?” Schr¨ odinger asked. the cat is obviously dead and in the non-decayed state the cat is alive. The question was raised: “what if it is not a cat. An electron moves with an energy of 10 Mev. and Probability Density. Only after an observation will the combined state collapse to either the decayed state or the non-decayed state. the state of the system after an hour is in a state of decay and a state of non-decay coexisting simultaneously. the cat is simultaneously dead and alive.2. a bacterium?” The Schr¨ odinger Cat controversy was never resolved.Introduction to Quantum Theory 95 Fig.4 Schr¨ odinger’s Cat. the de Broglie wavelength. The counter-argument was that a cat has consciousness. before taking up applications of Quantum Mechanics in the next chapters. let us examine in some more detail the topics mentioned here. what if it is a rat. namely. Example 8. In the decayed state. According to the Copenhagen Interpretation. if no observation is made. 8. In other words.

Prob.0 × 10−3 kg × 1. The probability is ψψ δv = (8/πa3 0 )(e At nucleus r = 0.15 × 10−7 .054 × 10−34 kg m2 s−2 s ∆x = h/(4π ∆p) = 5. = (8/πa3 0 ) δv = (8/π )(52. Prob.39 pm (pm = 10−12 m) Example 8. (b) at a distance a0 from the nucleus. The uncertainty in speed of a particle weighing 1 g is ∆v = 10−6 m s−1 . p= E = 1/2me v2 .72 × 10−5 −2a/a 2 At r = a0 . a0 = 52.707 × 10−21 ) kg m s−1 = 0.9 pm.707 × 10−21 λ = (6.6 × 10−19 J/eV (kg J) = 1. where r is the distance from the nucleus.707 × 10−21 ) kg m s−2 = (6.0 × 10−6 m s−1 = 5. (a) around the nucleus. J = kg m2 s−2 2 × 9. = (8/πa3 ) δv = 1.4.626 × 10−34 ) kg m2 s−2 s/(1.3.707 × 10−21 kg m s−1 = 1. Solution −2r/a 2 ) δv.3 × 10−26 m 1/2 Example 8.626 × 10−34 )J s1 /(1. and a0 is the Bohr radius. What is the probability of ﬁnding the electron within volume element δv = 1 pm3 . p= (2me E ). The ground-state wave-function of He+ is ψ = (8/πa3 0) −2r/a e .11 × 10−31 kg × 107 eV × 1.96 Elementary Physical Chemistry Solution λ = h/p.267 × 10−35 kg m2 s−1 1.72 × 10−5 × e −4 0 )(e = 3.9)−3 × (1)3 = 1.388 × 10−12 m = 0. What is the uncertainty in position? Solution ∆x∆p = h/4π = 1.

2.0 eV [Note: I J = 1 N m = 1 kg m s−2 m = 1 kg m2 s−2 .0 nm and an electron in the box is excited from state 5 to state 6. . Example 9. 9. Particle-in-a-Box Consider a particle of mass m in a one-dimensional box of length L. .1. what is the transition energy? Solution The energy diﬀerence between level 5 and level 6 is ∆E6←5 = 11 h2 /(8 mL2 ) = 11 × (6. 2.3) = 1.10939 × 10−31 kg × (2. When L becomes very large (of macroscopic dimensions). (9.2) n = 1.6554 × 10−19 J ≈ 1. 1 eV = 1.6260 × 10−34 )2 J2 s2 8 × 9. . . the energy distribution becomes practically continuous.1) Note that the spacing between energy levels increases with increasing n and decreases with increasing L. . If L = 2. .Chapter 9 Applications of Quantum Theory 9.0 × 10−9 )2 m2 (9.607 × 10−19 J] 97 .1): En = n2 h2 /8 mL2 and wave-function ψn = (2/L)1/2 sin(nπx/L) n = 1. Assuming that the potential energy is V = 0 inside box and V = ∞ outside the box. (9. Translational Motion.1. A conjugated polyene molecule is sometimes simulated by a one-dimensional-box. the solution of the Schr¨ odinger equation yields the energy (see Fig.

. n = 1. 9. He+ . . .1 Particle-in-a-box wave-functions.98 Elementary Physical Chemistry Fig. Hydrogenic Atoms (H. etc. Li2+ . The hydrogenic wave-functions are characterized by 3 quantum numbers: 1) The principle quantum number. RH = me e4 /8 ε0 h2 (9. . Most often.2. .) The Schr¨ odinger equation yields the following solution: En = −hcZ 2 RH /n2 (9.4) where Z is the atomic number and RH is the Rydberg constant for the H atom. 2. which determines the energy of the electron in the atom. the combination Z 2 is used where R deﬁnes the particle Rydberg constant.5) me being the mass of the electron and ε0 the vacuum permeability. + 9.

the orbital is denoted as p. and are usually denoted by the symbols s. yielding for He+ = 4 × 13. which determines the orbital angular momentum of the electron. ±3. . and so EHe+ /EH = Z 2 = 4. 3.4. In all other atoms.9 eV. etc. M. . ml = 0. . Examples: √ ψ100 = (1/ π )(Z/a0 )3/2 e−Zr/a0 .6) (9. preceded by a number which indicates the principal quantum number. . . 3) The magnetic quantum number.8) . . L. Shells and Subshells (a) In hydrogen and hydrogenic atoms. Ionization Energy The ionization energy is the maximum energy needed to remove an electron from the ground state of an atom. . One-Electron Wave-Functions One-electron wave-functions of hydrogenic atoms are called orbitals. When l = 0. which determines the angular momentum of an electron along a particular axis. There are three diﬀerent p’s — px . . pz — which indicate the directions. It is standard practice to refer to all electrons with the same n as belonging to the same shell. . 1. ±2. 1s √ ψ200 = [1/(4 2π )](Z/a0 )3/2 (2 − Zr/a0 )eZr/2a0 . Often. . 2s √ ψ210 = [1/(4 2π )](Z/a0 )5/2 e−Zr/2a0 rcosθ.2. p. (9. the energy depends only on the principal quantum number n. . referring respectively to n = 1. 9. 2. the shells are denoted by capital letters K.59 eV = 54.7) (9. py . ±1. . representing l = 0. etc. l = 0. the only diﬀerence is Z . . . 2. when l = 1. 9. .5. N.Applications of Quantum Theory 99 2) The azimuthal quantum number. d. the energy depends also on the quantum number l.36 eV. the orbital is denoted as s. 2. 2pz 9. Example 9.3. etc. what is it for He+ ? Solution Obviously. Knowing that the ionization for H is I = 13. 1.

2. 5 orbitals Fig. 0.6. the increase in energy does not always correspond to an increase in n. When n = 1. the 4s energy is lower than the 3d energy. 9. etc. pertaining to l = 0. 2. = ψ ∗ ψ 4πr2 dr (9.9) . etc. −1. etc. Subshells are denoted as s. Thus. (b) Orbitals with the same n but diﬀerent l’s form subshells of the given shell. δV = 0. The number of orbitals of a subshell may be calculated from 2l + 1. The probability of ﬁnding the electron in that volume element is Prob. 3. in the subshell p there are 3 orbitals. 0 (3pz ). When n = 2. Why? Reason: The quantity ψ ∗ ψ is maximum at the center. f. subshells. g . one is interested in the distance of an electron from the nucleus (regardless of angles) rather than in a given volume element. yet the probability of ﬁnding the electron there is zero. except hydrogenic atoms. For example. Shapes of Orbitals Shapes of orbitals play an important role in determining how atoms bind to form molecules. and orbitals. and the subshell can have only one orbital 1s. subshells. In many atoms. l can have only one value. l. Radial Distribution Function Most often. 1. p.100 Elementary Physical Chemistry n (shell) 1 (K ) 2 (L) 3 (M ) l (subshell) 0 (s ) 0 (s ) 1 (p ) 0 (s ) 1 (p ) 2 (d ) ml (orbital) 0 (1s) 0 (2s) −1 (2px ). Question: An s orbital has its maximum at the center. and orbitals. but it has to be multiplied by the volume element. which is zero at the center. 0. To obtain a working formula.2 Relations between n. ml and shells.2 shows relations between shells. 1 (3py ) −2. 0 (2pz ). d. 4. giving rise to the two subshells s and p. in the subshell 1s there is one orbital. 9. 1. 1 (2py ) 0 (3s) −1 (3px ). note that the volume element is δV = 4πr2 dr. Figure 9. l can have the values 0 and 1. etc.

ms . If ms = −1/2 the electron spin is called β and denoted by an arrow pointing downward.325 × 10−6 9. the spin is often called α and denoted by an upward pointing arrow ↑. or −1/2. Electron Spin This is the intrinsic angular momentum of the electron. ν1 ←4 .097 × 10 cm = 4. It may be thought of as the electron spinning about its axis. If the spin quantum number is ms = 1/2.292 × 10−11 m))3 exp − 2 × 2 × (ao /ao ) 2 × (10−12 m)3 = 2. which can have the value 1/2 which means it spins in the clockwise direction. Spin is a quantum mechanical concept and the above classical analogue should not be taken too seriously.Applications of Quantum Theory 101 The quantity 4πr2 ψ ∗ ψ is the radial distribution function [sometimes denoted as g (r)] and represents the probability of ﬁnding the electron between r and r + dr in an atom.7.114 × 105 cm−1 (b) ψ 2 δV = (1/π )(Z/ao )3 exp(−2Zr/ao )δV 1 = (1/π )(2/(5. ↓. (b) What is the probability of ﬁnding the He+ electron within a volume element δV = (1 pm)3 at a distance r = 1 2 ao ? Solution (a) The atomic number of He is Z = 2. ∗ (a) Calculate the radiation frequency. . An electron spin is characterized by a spin quantum number.3. Example 9. resulting from the transition of n = 4 to n = 1 in the Lyman Series of the spectrum of He+ . which means it spins in the anti-clockwise direction. and so ∗ 2 2 2 5 −1 (1 − 1/16) ν1 ←4 = Z RH (1/1 − 1/4 ) = 4 × 1.

and ml . Transitions and Selection Rules We have already mentioned that in a hydrogenic atom.8. Thus. . Structure. Pauli Exclusion Principle This Principle states that no more than two electrons can occupy the same orbital. −2. n = 1.10. . In all other cases. 4s precedes 3d. . . Each energy level is n2 -fold degenerate. .9. l. solutions are approximate. d. The Zeﬀ values are diﬀerent for s. etc. 9. where σ is a shielding constant that can be approximated. +2. −1. This eﬀective nuclear charge. Ze (e being the absolute value of an electronic charge) but Ze−σ = Zeﬀ . the nuclear charge an electron “sees” is not the actual charge.10) where ψ (1) is the orbital of electron 1. although it may be smaller. (9.e. Actually. the Pauli Exclusion Principle really states that in an atom . . i. n − 1 ml = 0. . the p electron has greater penetration than the d electron. the s electron has greater penetration to the nucleus than the p electron. meaning that there are n2 states which have the same energy. But there are exceptions. Zeﬀ . Many-Electron Atoms The Schr¨ odinger equation can only be solved exactly for hydrogenic atoms. 9. Ψatom = ψ (1)ψ (2)ψ (3). . is the charge of the nucleus shielded by the other electrons. yielding exact analytic expressions for the wave-functions. ms = +1/2. . . For example. the electron can have three quantum numbers n. −1/2 Note that l cannot exceed n − 1. This rule is true only for hydrogenic atoms and does not apply to other atoms. We must now also add ms . one can think of the wave-function of the atom as the product of the wave-functions of the individual electrons. ψ (2) the orbital of electron 2. for example. but with nuclear charge that is modiﬁed by the presence of all other electrons. . As a ﬁrst approximation. .102 Elementary Physical Chemistry 9. 1. orbitals. l = 0. +1. 2. Thus. etc. etc. p.

Thus. . and is essential for determining atomic structures by applying Hund’s Rule. no other electron can be put in this orbital. 9. opposite spin quantum numbers). two spin quantum numbers will have to be equal. and this violates Pauli’s Principle. l. and angular momentum is conserved. the ionization energy decreases down the group and increases across the period.11b) (9. which is one.11a) enabling one to determine which transitions are allowed and which are forbidden. 2p < 3s. This can be explained by observing that the orbital “radius” progresses as follows: 1s < 2s. +1 or −1) and that ∆n = unrestricted (9. and ml but must have diﬀerent spin quantum numbers (i. The reason behind these rules has to do with the spin of a photon. Hund’s rule states that “the most stable conﬁguration favors unpaired electrons among degenerate orbitals”. 4p . . Periodic Trends Recall from freshman chemistry that the atomic radius increases down the group in the periodic table and decreases across the period. If two electrons are in the same orbital. On the other hand.e. If another electron is put in this orbital.11. . Selection Rules for Spectroscopic Transitions These rules require that ∆l = 1 or −1 (also that ∆ml = 0. they will have the same quantum numbers n.Applications of Quantum Theory 103 no two electrons can have the same four quantum numbers. 3p < 4s. Obviously. The emitted photon carries oﬀ this unit. Pauli’s Principle forms the basis for the Aufbau (Built-up) Principle. if an atomic electron jumps from a p orbital to an s orbital there is a loss of one unit of angular momentum.

As in atoms. Furthermore. the Aufbau Principle is used to determine the electron conﬁguration of molecules. But there are exceptions to the octet rule — sometimes there are more than 8 electrons. promotion.N. Valence Bond Theory.Chapter 10 Quantum Theory. The theory introduces the concepts of σ and π bonds. 1. Lewis in 1916. 2. The starting point is the concept of shared electron pairs. Among these was the Octet Rule. There are two quantum mechanical theories of electronic structure of molecules: Valence Bond Theory and Molecular Orbital Theory. The Chemical Bond Concepts developed in previous chapters. normally denoted by dots. Molecular Orbital Theory. especially those involving orbitals. the theory is remarkably successful in predicting shape. 104 . The idea is that there are orbitals (wavefunctions) that spread over all atoms in the molecule. but when coupled with VSEPR (Valence Shell Electron Pair Repulsion). the original theory could not account for the shape of molecules. sometimes less. it is well to mention treatments based on ideas introduced by G. Preceding the quantum mechanical description of molecular structures. hybridization. can be extended to describe electronic structures of molecules. Lewis already recognized before the advent of quantum theory that there are two major types of bonds: covalent bonds (in which electrons are shared) and ionic bonds (in which cohesion is due to electrostatic attraction between positive and negative ions). stating that an atom in a molecule likes to be surrounded by 8 electrons.

An approximaion.1). yielding the two functions Ψ and Ψ* Ψ = ψ1sA (1)ψ1sB (2) + ψ1sA (2)ψ1sB (1) Ψ∗ = ψ1sA (1)ψ1sB (2) − ψ1sA (2)ψ1sB (1) (10.1 Variation of potential energy of an electron with internuclear distance. The Chemical Bond 105 Fig. 10.1b) A better description of the bond is a linear combination of both functions. The only molecule that can be solved exactly is the hydrogen molecule + . H2 tion that greatly simpliﬁes quantum-mechanical treatments of molecules is the Born–Oppenheimer Approximation. the wave-function of H2 can be written ψ1sA (1)ψ1sB (2) (10. which assumes that nuclei (being much heavier than electrons) move so slowly that they can be considered stationary. All other molecules must be solved approximately.Quantum Theory. This approximation enables one to solve the Schr¨ odinger equation and obtain the potential energy curves of an electron as a function of the internuclear distance (see Fig.1a) where (1) and (2) refer to electrons 1 and 2. An equally valid description is ψ1sA (2)ψ1sB (1) (10. 10. For example.1. 10. if Ψ1sA and Ψ1sB denote the orbitals on atom A and on atom B respectively.1c) (10.1d) . Valence Bond Theory The electrons that participate in bond formation are described by wavefunctions that allow each electron to be on both atoms.

can only combine with the orbital function Ψ* given in (10. [β1 β2 ]. Solution First note that the electron conﬁguration of the N atom is 1s2 2s2 2p1 x 1 2p1 y 2pz . which is anti-symmetric. a bond between A and B is Ψ(A − B) = ψA (1)ψB (2) + ψA (2)ψB (1) (10. the fourth spin function is anti-symmetric.2) Example 10. It is common practice to take the Z -axis to be the internuclear axis. Accordingly. Denoting the spins as α (spin up) and β (spin down). In quantum mechanics. while . the ﬁrst three spin functions of Eq. The 1s electrons are so deeply embedded that they are unlikely to take part in the bond formation and are ignored. namely [α1 α2 ].1e) where the subscripts refer to electrons 1 and 2. In general. It establishes that you cannot say whether electron 1 is on A and electron 2 on B or vice versa. being symmetric. (a) Describe the valence bond between two N atoms.106 Elementary Physical Chemistry Neither of these functions represent correctly the H2 molecule. The fourth spin function. Thus. we can construct four types of spin functions. [α1 β2 − β1 α2 ] (10. Only 2p electrons will be considered to participate in bond formation. the function must change sign upon interchange of two electrons. Note: A linear combination (singlet or triplet) is the only formula which gives a correct description of combing atoms. What is missing are electron spin contributions. There is an important rule that stipulates that for a wave-function to be proper.1a). the ﬁrst three are symmetric with respect to exchange of the electrons (do not change sign). in contrast to classical mechanics where they are not.1c). there is one Ψ function and there are 3 Ψ* functions. The 2s electrons are also more deeply embedded than the p electrons and will also be ignored in bond formation. (10. which is anti-symmetric. characterized by Ψ. The state. is called singlet state and the state characterized by Ψ* is called triplet state. The 2pz orbitals of the two atoms point towards each other.1a). identical particles are indistinguishable.1. can only combine with the symmetric function Ψ of (10. Note that of the four spin functions [ ]. [α1 β2 + β1 α2 ].

2.3) This form gives rise to constructive interference between the two components in the intermediate region (see Fig.4) The bonds described so far are σ bonds. The arguments are similar as for N2 except that the bond orbitals are 3pz orbitals. 10. A σ bond has cylindrical symmetry along the internuclear axis.2). the px and py orbitals.Quantum Theory. Ψ(Cl − Cl) = ψ3pz A (1)ψ3pz B (2) + ψ3pz A (2)ψ3pz B (1) (10. . The Chemical Bond 107 Fig. The electron 2 1 conﬁguration of Cl is [Ne] 3s2 3p2 x 3py 3pz . They give rise to π orbitals. The valence conﬁguration of O is 2s2 1 1 2p2 x 2py 2pz . So. the wavefunction for the N2 molecule is Ψ(N − N) = ψ2pz A (1)ψ2pz B (2) + ψ2pz A (2)ψ2pz B (1) (10. In the case of N2 . The two unpaired electrons can each pair with a H1s orbital. 10. Polyatomic Molecules Consider the water molecule H2 O. the x and y orbital are perpendicular towards the bond axis. there are other orbitals of level 2. (b) Describe the valence-bond ground state of Cl2 .2 Schematic representation of two overlapping atoms showing constructive interference. 10. These can overlap if the internuclear distance is short.

rather than belonging to a particular bond. However. Ethylene makes use of sp2 orbitals which are planar and 120◦ apart. The large lobes point towards the corners of a tetrahedron. has 3 unpaired electrons. the bond angle turns out to be 104◦. two additional concepts had to be introduced. Each of these hybrid orbitals consists of a small and a large lobe. one of the 2s electrons is promoted to a 2p state. namely 2px . the concept of promotion and the concept of hybridization.108 Elementary Physical Chemistry Fig.3. Another example is NH3 . The essential features of molecular orbital theory are illustrated by H+ 2 which has an exact solution. These orbitals form four hybrid orbitals. 10. The valence electron conﬁguration of N. for example. However. PCl5 . each consisting of the combination of 1s and 3p’s. 10.3 Diagram representing sp2 hybrids in CH2 =CH2 . for example ethylene. 2py and 2pz and thus can form 3 σ bonds with H which should be perpendicular to each other. These orbitals are called sp3 orbitals. for example. in the case of CH4 . the valence bond theory is not a good predictor of the bond angles. . HC≡CH. Molecular Orbital Theory It is assumed here that the electrons spread over the entire molecule. 1 1 1 1 forming a 2p1 x orbital. 10. The valence electron conﬁguration 1 ◦ of C is 2s2 2p1 y 2pz and should have 2 bonds separated by 90 . Speciﬁcally. To overcome this deﬁciency. Other hybrid orbitals have been introduced to explain other molecules. CH2 =CH2 (Fig. thus giving rise to the C conﬁguration 2s 2px 2py 2pz . Thus. But CH4 has ◦ 4 bonds about 109 apart. each of the experimental angles of the pyramidal molecule is 107◦ . as noted before. Even sp hybrids have been used to explain some structures.3). But where valence bond theory is particularly deﬁcient is in predicting the shape of the molecule CH4 . Sometimes d orbitals must be included to explain certain structures. resulting in two σ bonds that should be 90◦ apart.

a bonding and an anti-bonding one. The principles on which these results are based are the same as for atomic orbitals. Anti-bonding orbitals have higher energy and cause a reduction in cohesion. The molecular orbital in the above example is a σ -orbital because of its cylindrical symmetry. Ψ = ψA + ψB Ψ = ψA − ψ B ∗ bonding orbital anti-bonding orbital (10.5. The π orbitals .7a) (10. result in lowering the (electron) energy. binding them. as compared with the energy of the atom (causing an increase in cohesion). 10. as customary. namely the Aufbau Principle.5) where the two wave-functions on the right are respectively the orbitals centered on A and B and Ψ is the molecular orbital. Bonding and Anti-bonding Orbitals From the linear combination of atomic orbitals.4 and 10. if occupied.6) Here. 2 is the probability density of ﬁnding the electron on A. An electron can interact with both nuclei. Each MO can hold a maximum of two electrons having opposite spins. The probability density of the molecule can be written as 2 2 + ψ1sB + 2ψ1sA ψ1sB Ψ2 = ψ1sA (10. (Here. • 2ψ1sA ψ1sB is the overlap density arising from the constructive interference of the atomic wave-functions. one can construct two molecular orbitals. 10. Note that these diagrams show energy levels of both separated and combined atoms. Hund’s Rule.4. The Chemical Bond 109 To a good approximation.Quantum Theory. Examples of MO representation diagrams are shown in Fig. • ψ1sA 2 • ψ1sB is the probability density of ﬁnding the electron on B. anti-bonding orbitals are denoted by *). depicting atomic and molecular orbitals. etc.7b) Bonding orbitals. the wave-function of the hydrogen-molecule ion is Ψ = ψ1sA + ψ1sB (10. This type of approximation is referred to as linear combination of atomic orbitals (LCAO) and the molecular orbital is referred to as LCAO-MO.

8) (10.5). 10. Fig.9) (10.110 Elementary Physical Chemistry Fig. Example 10. F2 . (depicted on the diagrams by double lines).11) Ne2 : 1σ 1σ 2σ 1π 1π 2σ ∗4 .4a MO representation of H2 . 10. Write down the electronic conﬁguration of the following molecules N2 . O2 . 10. Solution The electronic conﬁgurations are N2 : 1σ2 1σ ∗2 1π 4 2σ2 O 2 : 1σ 1σ 2σ 1π 1π F2 : 1σ 1σ 2σ 1π 1π 2 ∗2 2 4 2 ∗2 2 4 2 ∗2 2 4 ∗2 ∗4 ∗2 (10. are degenerate.4b MO representation of He2 .10) (10. Note that for molecules heavier than N2 there is a reversal of the 1π and 2σ orbitals (Fig.2. and Ne2 .

Which molecule has the greater ionization energy: (1) N2 or N+ 2? (2) F2 or F+ 2? . Example 10. 0. the bond orders are respectively 3. The greater the order is. O2 . F2 and Ne2 . which is the diﬀerence between the number of bonding and anti-bonding orbitals divided by 2. the shorter the bond is. Thus.5b Diagram of MO orbitals of diatomic atoms greater than N.Quantum Theory. Fig. the bonds are characterized by an order. 2. for N2 . Bond Order Often. 10.5a MO diagram of diatomic molecules of atoms up to and including N. The Chemical Bond 111 Fig. 10. 10.3. 1.5.

5. σu 10. N2 has larger ionization energy.0). for F it is 18. whereas the π * orbitals have even parity. Na(0.12) Fig. This is a concept that tells whether the wave-function changes sign or remains unchanged upon reﬂection through a center of symmetry. Here are electronegativity values of some light elements: H(2. 10. F2 has greater ionization energy. the energy of F is ∼5 eV lower.112 Elementary Physical Chemistry Solution (1) The bond order of N2 is 3. πg . Homonuclear diatomic molecules are also characterized by parity. The σ orbitals have even parity (do not change sign) whereas the σ * orbitals have odd parity (do change sign). that is the energy levels of F and H are not equal.0). 10. Accordingly. It is common practice to designate the even and ∗ ∗ .01). Polar Covalent Molecules Electron pairs between identical atoms are shared equally by the two atoms.6. But when the atoms are diﬀerent. + (2) The bond order of F2 is 1 and of F+ 2 is 3/2. N(3.5). the atoms are pulled closer to one atom than the other. In the case of HF. The ability of an atom to draw electrons close to it is called electronegativity.0). Thus.8 eV.1). The π orbitals have odd parity. Ψ(HF) = cH ψ (H) ± cF ψ (F) (10.6). F(4. Be(1.5). as we have seen.5).9).6 Diagram of MO orbitals of diatomic molecules of unequal atoms. πu . The electronic conﬁguration 2 2 4 1 of N+ 2 is 1σ 1σ * 1π 2σ with bond order of 2. The ionization energy of H is 13. Why do some atoms pull electrons closer to themselves than others? The rationale for this may be inferred by analyzing the HF molecule.6 eV. Li(1. C(2. Thus we can write σg . odd parities by the subscripts g and u. B(2. O(3. . it would take about 5 eV more to pull oﬀ an electron from F than from H. Thus. The MO for a heterogeneous diatomic molecule must have diﬀerent weighting factors for the atomic orbitals (Fig.

Delocalization is an important feature of MO bonding. 10.94 and cF = 0. gives (10. each molecular orbital is a linear combination of all the atomic orbitals.7. for example. N 2 ∫0 dx sin2 nπ/L = 1. Thus.14) N= 2/L (10. The Chemical Bond 113 where cH = 0. we can write Ψ = ψA + ψ B N2 Ψ2 dv = N 2 2 ψA dv + 2 ψB dv + 2 ψA ψB dv (10.94ψ (F) Ψantb = 0. the six C atomic orbitals are sp2 hybrids. The π bonds are delocalized and each pair helps to bind several atoms.13b) (10. the ground state wave-function for H. 10. For example.33 and cF = 0.94ψ (H) − 0. In benzene (C6 H6 ). Normal Constants The wave-functions of all systems should be normalized. forming σ bonds at 120◦ angles.Quantum Theory. meaning that the square wave-function should integrate to 1.13a) (10.8. Structure of Polyatomic Molecules In the molecular orbital approach (LCAO-MO).94 in bonding and cH = 0.33ψ (F) 10. Normalization. is √ 3 ψ1s = (1/ π )(Z/a) 2 e −(Z/a)r which includes the normalization factor. Normalization Molecules (MO) Assuming that the atomic orbitals are already normalized.16a) = N 2 [1 + 1 + 2S ] = 1 .33ψ (H) + 0.9. Thus. Particle-in-a–box: ψ = N sin nπx/L L Normalization.33 in anti-bonding orbitals. Ψbnd = 0.15) It is customary to include the normalization factor in atoms with the wave-function. The p orbitals form π bonds that spread over the entire molecule.

17) ψsA ψsB dv + λ2 2 =1 ψsB N 2 [1 + 2λS + λ2 ] = 1 N = {1/(1 + 2λS + λ2 )}1/2 (10. Obviously.16c) (10.16b) called the overlap integral.18) .114 Elementary Physical Chemistry where S is S= ψA ψB dv (10. the molecular normalization coeﬃcient is N = 1/ 2(1 + S ) A heteronuclear diatomic molecule has the wave-function Ψ = ψsA + λΨsB Normalization gives N2 2 ψsA dv + 2λ (10.

one can devise selection rules. A spectrum shows only transitions of energy. which has the dimensions of Hz (s−1 ) and is deﬁned as B = (h/8π 2 I ) or. 1. These rules tell whether certain quantum jumps are allowed or not allowed. Rotational Selection Rules Spectral absorption or emission corresponds to transitions between pairs of levels. especially their symmetry properties. Actual energy levels are not directly measurable. Vibration–Rotation Spectra of Diatomic Molecules Two points should be emphasized: 1. as noted before. The results are generally expressed in terms of the rotational constant. But not all possible levels may be combined. Selection rules do not tell whether the intensities are weak or strong. B . (11.1. and I is the moment of inertia. in terms of B∗ . 2. The rotational energy levels of a linear molecule are EJ = J (J + 1)(h/2π )2 /2I J = 0.2a) (11. 11. .1) where J is the rotational quantum number. deﬁned as B ∗ = B/c 115 (11.2b) . By theoretical studies of the wave-functions. 2.2.Chapter 11 Elements of Molecular Spectroscopy 11. namely I = µd2 (d being the internuclear distance and µ the reduced mass). . .

The energy can be expressed as ∗ Ev = (v + 1/2)hcνo (11. as ∗ νv←v (v ) = (v − v )ν0 (11.3a) where. which frequency. 11. νo −1 has the dimension of cm .6) The selection rule for harmonic oscillators requires that ∆v be +1 or −1. 11. yielding a transition frequency in s−1 νJ ←J = (EJ − EJ )/h = [J (J + 1) − J {J + 1)]h/(8π2 I ) = [J (J + 1) − J {J + 1)]B (11.3b) For pure rotation.4. . the selection rule requires that ∆J be either +1 or −1.2c) The transition frequency is often expressed in wave-numbers. yielding values in cm−1 . Vibrational Selection Rules The vibrational energy of a diatomic molecule (simulated by a harmonic oscillator) is Ev = (v + 1/2)hνo v = 1. . (11.4) where v is the vibrational quantum number and νo is the vibration ∗ = νo /c. in wave-numbers cm−1 . often expressed in terms of wave-numbers.5) and the transition frequency. ν ∗ = ν/c.3. B ∗ = B/c = h/(8π2 cI ) (11. Further Requirements The foregoing selection rules are necessary but not suﬃcient conditions: . . ∗ ∗ νJ ←J = [J (J + 1) − J (J + 1)]B (11. The energy of radiation of a transition from J to J is hνJ ←J = EJ − EJ .116 Elementary Physical Chemistry which has the dimensions of cm−1 (c is the velocity of light). 2.

8b) (11.e. In particular. namely from v = 0 to v = 1.7b) (11.5.6. Pure Rotational Spectra These spectra are observed in the far infrared and the microwave region. (2) the equilibrium separation of the two nuclei (or bond-length). ∗ νJ +1←J = (EJ +1 − EJ )/hc (11.7c) (11. implying that at ordinary temperatures the molecules are in their ground state. Exercise: The spacing between adjacent rotational lines in the far IR of HCl is 20. The dipole moment must not vanish upon vibration. with or without accompanying rotational transitions.8c) Note: Spacing between adjacent absorption peaks equals 2B ∗ (i. It is then reasonable to assume that there is only one vibration transition. (2) For a vibration transition. Vibration–Rotation Spectra Vibrational energy levels are generally widely separated.Elements of Molecular Spectroscopy 117 (1) For rotational transitions with no change in vibrational quantum number. the molecule must have a non-vanishing dipole moment derivative.7a) ∗ = [(J + 1)(J + 2) − J (J + 1)]B = 2(J + 1)B ∗ ∗ νJ −1←J = (EJ −1 − EJ )/hc (11. 11. it is constant).8a) = [(J − 1)(J ) − J (J + 1)]B = −2JB ∗ ∗ (11. . 11. the transition frequencies for absorption and emission are respectively.5 cm−1 . the molecule must have a dipole-moment. Calculate (1) the moment of inertia.

9) (11.92 (see Fig.1 depicts several rotational transitions between the vibrational level v = 0 and v = 1. 2906.2). Accordingly. v = 0 → 1. Note that (1) The spacing between two adjacent levels in either the R.11)] and the highest peak of the P-branch is obtained when J = 1 [Eq.or P-branch is ∆ν ∗ = 2B ∗ . Figure 11. 2944.12)]. R-branch P-branch (11. J → J + 1. 11.118 Elementary Physical Chemistry Fig.58. (11. (11.25. 2843.91.10) The transition frequencies (in wave-numbers) are respectively. 2865. ∗ ∗ νR = vo + 2B ∗ (J + 1) ∗ ∗ = vo − 2B ∗ J νP (11.11) (11.1 Diagram representing transitions between v = 0 and v = 1 and J → J + 1 and J → J − 1. 2925. The vibration–rotation spectrum of 1 H 35 Cl has peaks at ν ∗ (cm−1 ): 2821. J → J − 1.12) Example 11.10. there are two kinds (branches) of the spectrum: v = 0 → 1. 11. The spacing between these two peaks is 4B∗ .1.63. . (2) The lowest peak of the R-branch is obtained when J = 0 [Eq.

25. which is twice as large. d.13a) = ∗ νo + 2B × 1 ∗ ∗ ∗ J = 1 → 0 νR = νo − 2B ∗ × 1 ∗ ∗ = νo − 2B ∗ × 2 P J = 2 → 1 νR ∗ ∗ J = 3 → 2 νR = νR − 2B ∗ × 3 (11. This gap separates the R. Thus.and P-branches.13b) It is clear that by adding the lowest R peak and the highest P peak.Elements of Molecular Spectroscopy 119 Fig.6 cm−1 (11.34 cm−1 . The spacing between all adjacent lines is the same except the spacing between the lines 2865. The above information suggests that J =2→3 R J =1→2 J =0→1 ∗ ∗ νR = νo + 2B ∗ × 3 ∗ ∗ = νo + 2B ∗ × 2 νR ∗ νR (11. from which we can obtain the moment of inertia. ∗ = 1/2 (2906.2 Vibration–rotation spectrum of 1 H35 Cl. I . and the internuclear distance.25 + 2865. and ∗ dividing the sum by 2 we can determine ν0 .10 and 2906.10) cm−1 ν0 = 2995. 11. .14) This immediately gives B ∗ = 10.

2.) 120 . viscosity and a host of other phenomena. (The interaction energy varies as Q1 Q2 /R. How do these simple molecules interact to form larger aggregates? This occurs via intermolecular forces. Ion–Ion Forces These take place between ions in solution. (The interaction energy varies as µ1 µ2 /R3 . 12.1. 12. (The interaction energy varies as Qµ/R2 . The forces (interaction energies) can be dubbed valence forces.1.1. Types of Intermolecular Forces 12. Electrostatic Forces 12.1. for formation of liquids and solids.Chapter 12 Elements of Intermolecular Forces So far. which attract and repel each other. 12.1. These forces account for the deviation from ideal behavior of gases. where the Q’s are the charges of the ions and R is the distance between them.) 12.2).1. Ion-Dipole Forces These exist between an ion and the (partial) charge of a polar molecule (see Fig.1.1.1.3. the emphasis has been on bonds between atoms and between ions.1.) 12. there is attraction between the positive end of one molecule and the negative end of another (Fig.1). for surface tension. For example. However. NaCl dissolved in water contains Na+ and Cl− ions. Dipole–Dipole Forces The molecules have dipole moments but are neutral. where Q is the charge and µ the dipole moment.

2. Fig.1. The interaction energy has. Note that this interaction energy is temperature-dependent.2.2.1) The inverse R6 accounts for the a/V 2 term in the van der Waals equation of state.1.2 Dipole–dipole interaction.1. 12. van der Waals Forces 12. A polar molecule can induce a dipole moment in another molecule by distorting its charge distribution. Orientation Forces These exist between rotating dipolar molecules that arise from the correlative rotational motion of the permanent dipole moments in neighboring molecules.1 Ion–dipole interaction. . 12.1. Induction Forces These forces exist between a polar and another (polar or nonpolar) molecule. 12. 2 Er = − µ2 µ2 /(R6 kT ) 3 1 2 (12.Elements of Intermolecular Forces 121 Fig.2. 12. The negative sign indicates that the interaction energy is attractive.

the dispersion energy is 3 Edis = − α1 α2 R−6 I1 I2 /(I1 + I2 ) 2 (12. O or N and an unshared pair of electrons on a neighboring F. denoted as α.1. as noted before. The van der Waals or London dispersion forces arise from the correlative motion of these instantaneous dipole moments in neighboring molecules. 3) Dispersion forces could be explained only after the advance of quantum mechanics. (Note: Hydrogen bondings are always the strongest of the intermolecular forces.2. atoms. The negative sign indicates that energy is attractive.) . London Dispersion Forces These forces exist between all kinds of molecular species (polar. For a diatomic molecule. Ei = −α1 µ2 /R−6 . even at absolute zero. O or N. 2) The London forces are generally greater (stronger) than the orientation or induction forces.2) where I1 and I2 are the ionization energies of the two atoms. Classically. The induction energy has the form. resulting in V −2 dependent term of the equation of state. Note that the dispersion energy is temperature-independent. ions. Comments: 1) The van der Waals forces vary as R−6 . but weaker than the electrostatic forces.3.122 Elementary Physical Chemistry Comment: The ease with which a charge distribution can be distorted is called the polarizability. they have instantaneous dipoles.2. In quantum mechanics there is motion. etc. Hydrogen Bonding This exists between a H atom bonded covalently to either F. nonpolar molecules. 12.) Even though nonpolar neutral molecules or atoms do not possess permanent dipole moments. 12. all motion ceases at T = 0 K.

thus depending on intermolecular forces. (2) Dipole–dipole forces are present between polar molecules in liquids and in solids (where rotation is restricted or hindered). in the liquid there are dipole–dipole and London forces.1. orientation and induction forces are also preset in gases. This is the temperature at which the vapor pressure equals the atmospheric pressure. only London forces. Weak intermolecular forces give high vapor pressure. If molecules are polar. hence. Thus. Hydrogen bonding exists only between molecules containing F–H. the lower the boiling point is. 1. Therefore. dipole–dipole and London forces. the boiling point is highest for liquids with strong intermolecular forces (IF). .Elements of Intermolecular Forces 123 Summary for neutral (non-ionic) molecules: (1) London forces are always present. and lowest for liquids with weak IF. even in nonpolar molecules. These forces are the next strongest of the intermolecular forces. The ease or diﬃculty with which molecules leave the liquid depends on the strength of attraction to other molecules. (b) Boiling Points. it has hydrogen bonding. (c) Butanol has H attached to O. Strong intermolecular forces give low vapor pressure. What kind of intermolecular forces are present in the following substances? (a) CH4 . O–H and N–H bonds. (b) CHCl3 is unsymmetrical and has polar bonds. These are the strongest of the intermolecular forces. (b) chloroform (CHCl3 ). the higher the vapor pressure.3. 12. (c) butanol (CH3 CH2 CH2 CH2 OH) Solution (a) CH4 is nonpolar. Example 12. In other words. Intermolecular Forces and Liquid Properties Properties that are dependent on intermolecular forces are: (a) Vapor Pressure. The van der Waals forces are the weakest of the intermolecular forces.

12.4. Properties of Liquids M H2 O CO2 C5 H12 C3 H8 O3 CHCl3 CCl4 CHBr3 18 44 72 92 119 154 253 BPt 100 −78.3 × 104 4. Except .8 × 10−4 9.4 × 102 1. Its structure is Notes: 1) Except for H2 O and glycerol.2 × 10−2 Visc (kg m) 1 × 10−3 7. the interactions are due to the London forces. The stronger the inter molecular forces.1 × 10−5 2.7 × 10−2 4. with exception of water and glycerol. it is necessary to pull the molecules apart against the attractive forces. the surface tension increases with strength of IF. The liquids are listed in order of increasing molecular weight.124 Elementary Physical Chemistry (c) Surface Tension.0 × 10−3 Note: C3 H8 O3 stands for glycerol.2 290 61.8 × 101 4. there should be a decrease in vapor pressure going down the list.5 × 10o 5.5 36. To increase the surface.7 149.3 × 10−2 1.7 × 10−4 2.7 × 10−2 2. 2) London forces vary as α2 .5 V Pr (mmHg) 1. which increase with molecular weight. Thus.0 × 10o Surf Ts (Jm−2 ) 7.6 × 10−4 1.7 × 101 3. and there is.4 × 10−4 1.7 × 102 8. and in a few cases to dipole–dipole forces. This is a measure of the resistance to ﬂow.6 × 10−2 6.3 × 10−2 2. the higher the viscosity. Thus. (d) Viscosity. This is the energy needed to increase the surface area of liquids.3 76.2 × 10−3 1.

In water. but these are not discussed here. These bonds hold atoms together. . Note that the boiling point increases with increasing weight (larger polarizabilities.) Figure 12. In other cases. the London force is dominant and increases going down the list. and it does. 4) Viscosity should increase with increasing molecular weight and it does. 12. ions) which are strongly attracted to one another to give a rigid substance. for H2 O and C3 H8 O3 .3 Variation of the boiling point of hydrogen-bonded molecules with molecular weight.5. Classiﬁcation of Solids by Types of Intermolecular Forces All solids consist of structural units (atoms. Water has by far the strongest intermolecular forces and should have a much higher boiling point. such as entanglements. molecules. 12. there are in addition to the London forces dipole–dipole forces and hydrogen bonding. the structural units are molecules held together by intermolecular forces. stronger London forces) except for water. or covalent bonds). (It should be mentioned that there are other factors involved. In some cases. The diagram clearly shows this. Therefore the boiling point should increase. ionic.Elements of Intermolecular Forces 125 Fig. the forces binding the structural units are chemical bonds (they can be metallic. 3) Surface tension should increase with increasing weight. and it does.3 depicts the boiling point variation of several hydrogencontaining compounds with molecular weight.

Molecular Solid.126 Elementary Physical Chemistry There are four diﬀerent kinds of solids: 1. Examples are diamond and graphite sheets. Examples are iron. held together by a “sea” of delocalized electrons. . Covalent Solid. Examples are solid Ne. This is a solid composed of a positive charged core of atoms. solid H2 O. Ionic Solid. This is a solid that consists of cations and anions held together by the attraction of opposite charges (ionic bonds). 4. Examples are CsCl and NaCl. Metallic Solid. and silver. This is a solid held together by a large network or chain of covalent bonds. copper. This is a solid held together by intermolecular forces. 3. and solid CO2 2.

7. 127 .300 g of Ar occupying a volume of 400 dm3 at 450 K.36 nm2 . occupying a volume of 250 cm3 at a pressure of 175 atm and a temperature of 300 K. A gas in a balloon has a pressure of 100 kPa. Calculate the pressure at 250◦C. a temperature of 25◦ C and a volume of 10 cm3 . What is the volume of the air in the balloon at a depth of 30 m? 5. λ. The cross-section of Ar is σ = 0. 3.025 g/cm3 and assumed to be constant. of an Ar atom at a pressure of 1 bar and a temperature of 298 K. Chapter 1 1. the mean free path. Calculate the partial pressure of N2 . The gravitational constant is g = 9. The temperature is also assumed to be constant. A gas mixture is composed of 300 mg of CH4 and 200 mg of N2 . and collision frequency. Calculate the molar mass of 40 mg of a gas. the total pressure of the mixture and the volume of the mixture. What will the volume of the balloon be if it rises to an altitude where the atmospheric pressure is 100 Pa and the temperature is −50◦C? 4. The density of sea water is 1. The balloon of Problem 3 is lowered at sea to a depth of 30 m. 6. Calculate the pressure of 0. The partial pressure of CH4 is 120 kPa at 300 K. 8. A gas in a constant volume container has a pressure of 150 kPa at 25◦ C. Calculate the root-meansquare speed. the diameter. The pressure of the gas is 1 bar (105 Pa) and the temperature is 25◦ C.81 ms−2 . Calculate the root-mean-square speed. 2. crms . The atmospheric pressure is 100 kPa. crms . z .Appendix A Homework Problem Sets Problem Set I. d.

A room of volume 110 m3 contains a gas (air). The enthalpy of combustion of diamond is −395.4 kJ mol−1 and of graphite is −393.4 JK1 mol−1 . The heat of fusion of Na is 27.2 kJ mol−1 .83 kJ mol−1 . One mol of O2 is heated at constant pressure from 250 K to 275 K. How many kilojoules of heat are required to melt 250 kg of Na? 4. 9. What is the standard enthalpy of combustion? (The standard enthalpies of formation of CO2 (g) and of H2 O(l) are respectively −393. 3. The standard enthalpy of combustion of C8 H18 (l) (octane) is −546.1 kJ mol−1 . qV .m = 21. ∆H.1 kJ mol−1 .m .6 kJ mol−1 and of Cl− (aq) it is −167. ∆U . whose molar heat capacity at constant pressure is Cp. The standard enthalpy of formation of AgCl(s) is −127.5 K from 100 cm3 to 300 cm3 . calculate the heat required to accomplish this.4 cal/g at 370.2 g mol−1 .6 g of glucose (M = 180.0 kJ mol−1 . 1.5 kJ mol−1. Calculate the work. The molar volume of the gas at T = 300 K is 25 L mol−1 . How much heat is released? . The standard enthalpy of formation of Ag+ (aq) is 105.95 K. What is the standard enthalpy of formation? 8. 6. Calculate CV.51 kJ mol−1 and −285.) burns in air (combines with oxygen) at constant pressure and temperature. Calculate the enthalpy of conversion of graphite into diamond.m = 29.) 2. Chapter 2 1. How much work is required to raise an object weighing 25 kg to a height of 5 m on the surface of the earth? (The gravitational constant is 9. Calculate the standard enthalpy of solution of AgCl in H2 O. 5 moles of a gas is expanded isothermally and reversibly at 298. The standard enthalpy of combustion of sucrose is −2808 kJ mol−1 . The molar heat capacity at constant pressure is Cp. The standard enthalpy of formation of CH3 C6 H5 (methyl benzene) is +50. qP . Develop the van der Waals equation of state in virial form and obtain explicit expressions for the virial coeﬃcients B and C in terms of the van der Waals parameters a and b. 10.0 JK−1 .81 ms−2 . 5. If the room is heated from 300 K to 310 K (at constant volume).128 Elementary Physical Chemistry 9.) 7. [Note: The expansion of 1/(1 − x) ≈ 1 + x + x2 + · · · ] Problem Set II.

Appendix A: Homework Problem Sets

129

11. The standard enthalpy of combustion of l-butene (C4 H8 , g) is −2710 kJ mol−1 and the standard enthalpy of vaporization of liquid l-butene is 18 kJ mol−1 . Calculate the standard enthalpy and the standard energy of combustion of liquid l-butene. Problem Set III. Chapters 3, 4, 5 1. 250 kg of Al is cooled from 298.15 K to 200 K at constant pressure. The molar heat capacity of Al is 24.4 JK−1 mol−1 . Calculate the heat emitted and the change in entropy. 2. 20 L of CO2 at 275 K and 1 atmosphere pressure is compressed to a volume Vf . The change in entropy is −12.0 JK−1 . Calculate Vf . 3. The enthalpy of vaporization of a substance is 30 kJ mol−1 at the normal boiling point Tb = 350 K. What is the entropy of vaporization of the substance, and what is the entropy change of the surroundings? 4. Calculate the standard reaction enthalpies for (a) Hg(l) + Cl2 (g) → HgCl2 (s) (b) Zn(s) + Cu2+ (aq) → Zn2+ + Cu(s) 5. The enthalpy of combustion of C6 H5 OH(s) at 298 K is −3055 kJ mol−1 . The standard entropy of this compound at 298 K is 146 JK−1 mol−1 . Calculate the (a) (b) (c) (d) (e) enthalpy of formation of C6 H5 OH(s) entropy of formation of C6 H5 OH(s) Gibbs free energy of formation of C6 H5 OH(s) Gibbs free energy of the combustion reaction the non-PV work, wother

6. Assuming that at 2000 K and 100 kbar the transition reaction C (graphite) C (diamond)

is reversible (in equilibrium), calculate the ∆S for this reaction. The o = standard enthalpy change at this temperature and pressure is ∆Hreac −1 1.91 kJ mol . 7. The standard Gibbs free energy of transformation of trans-2-pentane to cis-2-pentane at 127◦C is ∆Go = 3.7 kJ mol−1 . Calculate the equilibrium constant for the isomerization of cis-2-pentane to trans2-pentane.

130

Elementary Physical Chemistry

8. The standard Gibbs free energy for a given reaction is ∆Go = 40 kJ mol−1 at 1500 K. The enthalpy change for the reaction is ∆H = 250 kJ mol−1 at 1500 K and approximately constant. (a) Calculate the equilibrium constant at T = 1500 K. (b) Calculate the temperature at which the equilibrium constant is K = 1. 9. Which of the following reactions has a K > 1? (a) NH4 Cl → HCl(g) + NH3 (g) (b) Fe(s) + 2H2 S(g) → FeS2 (s) + 2H2 (g) (c) H2 SO4 (l) + 2H2 (g) → 2H2 O + H2 S(g) 10. Which of the reactions in Problem 9 will be enhanced (yield more products) by increasing the temperature? Problem Set IV. Chapter 6 1. A liquid in equilibrium with its vapor consists of substances A, B and C. If the volume of the vapor phase is 100 m3 at 298.15 K and the partial pressures of the three substances are respectively, Pa (A) = 2.33 kPa, Pa (B) = 1.43 kPa and Pa (C) = 0.26 kPa, calculate (a) the mole fraction of each substance in the vapor phase, (b) the number of moles of each substance in the vapor phase. 2. The partial molar volumes of benzene [C6 H6 (l)] and cyclohexane [(C6 H12 (l)] are respectively 75 and 80 cm3 mol−1 . The mole fraction of benzene is 0.6. (a) What is the mole fraction of cyclohexane? (b) What is the weight per mole of the combined substances? (c) What is the volume of a solution whose total mass is 500 g? 3. The mole fraction, xB , and partial pressure, PB , of three solutions of a substance is xB PB /kPa 0.010 64.0 0.024 153.8 0.038 243.6

Calculate Henry’s Law constant, KH . 4. (a) The partial vapor pressure of oxygen [O2 (g)] in air at sea level is 21.0 kPa at 298.15 K. Henry’s Law constant at that temperature

Appendix A: Homework Problem Sets

131

5.

6.

7.

8.

is KH = 74.68 kPa m3 mol−1 . What is the solubility (molarity) of oxygen in water at that temperature? (b) If the minimum concentration of O2 (g) in water necessary to sustain life is 4 mg/L, what is the minimum partial pressure of O2 (g)? The vapor pressure of a pure solvent at 80.0◦ C is 400 Torr. When 0.15 g of a solute is dissolved in 6.5 g of this solvent, the pressure is reduced by 15 Torr. The molar mass of the solvent is Msolvent = 80.0 g mol−1 . What is the molar mass, Msolute of the compound? The addition of 30.0 g of a substance to 7.0 g of CCl4 lowered the freezing point of the solvent by 7.5 K. The freezing point lowering constant is Kf = 40 K/mol per 1 kg of solvent. What is the molar mass of the compound? The osmotic pressure of an aqueous solution of a solid in H2 O(l) is 125 kPa at 298.15 K. The mass number of the solid is M = 180.16 g mol−1 . The freezing point constant for water is Kf = 1.86 K kgsolvent /molsolute . The normal freezing point of H2 O(l) is Tf∗ = 273.15 K. Calculate the freezing point of the solution. Calculate the number of moles (the solubility) of CO2 in water at 298.15 K when the partial pressure of CO2 is (a) 2.0 kPa , (b) 200 kPa .

Henry’s Law constant of CO2 in water at 298.15 K is KH = 2.937 kPa m3 mol−1 and the atmospheric pressure is 1 atm or 101 kPa at 298.15 K. 9. Calculate the boiling point of 250 cm3 of water containing 7.5 g of sucrose. The normal boiling point of water is 373.15 K and the boiling 1 point elevation constant is Kb = 0.51 K kgsolv mol− solute . 10. (a) Solute B and solvent A form an ideal dilute solution. The partial pressure of the solute is 30 Torr when the mole fraction of the solute is xA = 0.20. Find Henry’s Law constant KB . (b) If the partial pressure of the solvent at that composition is 250 Torr, what is the pressure of the pure solvent? 11. An aqueous solution containing a substance whose concentration is 7.50 g/L has an osmotic pressure of 1150 Torr at 77 K. (a) What is the molecular weight of the solute? (b) What is the osmotic pressure of a solution at 27◦ C that contains 1.00 g of this solute in 500 mL of solution?

r = kA [N2 O5 ]. Chapter 7 1. What is the rate of formation of D? What is the rate of disappearance of A? 2.00 × 103 Pa. . what is the total pressure of the gases? 1. The oxidation of ethanol is ﬁrst order in C2 H5 OH.00 × 103 Pa and at 730 K it is 11. What are the units of k ? 3. for this reaction.e. (a) Calculate the equilibrium constant K at T = 700 K and the equilibrium constant K at T = 730 K. The rate of formation of C in the reaction 3A + B → 2C + D is 2 mol L−1 s−1 . (b) Calculate the standard enthalpy change. Calculate the equilibrium constants at 298 K for the reactions (a) Sn(s) + Sn4+ (aq) → 2Sn2+ (aq) (b) Fe(s) + Hg2+ (aq) → Hg(l) + Fe2+ (aq) (c) Cu2+ (aq) + Cu(s) → 2Cu+ (aq) Problem Set V. The rate constant kA = 3. after 1 hour? 4. after 10 seconds? 2.132 Elementary Physical Chemistry 12.46 × 10−5 s−1 at 298 K.22 × 104 s.2 × 105 Pa. The standard state pressure is P o = 101. The reaction of Problem 1 was found to obey the reaction law r = k [A][B ][D]. The rate of reaction 2N2 O5 (g) → 4NO2 (g) + O2 is ﬁrst order in N2 O5 . calculate the rate constant of the reaction. NH4 Cl(s) dissociates in accordance with the reaction NH4 Cl(s) NH3 (g) + HCl(g) The total pressure at 700 K is 6. If the concentration of ethanol decreased from 440 mmol L−1 to 112 mmol L−1 in 1. Calculate the standard potentials for the cell reactions (a) Fe(s) + Pb2+ (aq) → Fe2+ (aq) + Pb(s) (b) H2 (g) + I2 (g) → 2HI(aq) 14. ∆H o . [Assume that within this temperature range ∆H o is constant] 13. (a) Calculate t1/2 for this reaction (b) If the initial pressure of N2 O5 is 75.0 kPa. i.

The activation energy of the ﬁrst-order decomposition of N2 O into N2 and O is Ea = 250 kJ/mol. the rate constant is k = 2. If the half-life of the reactant is t1/2 = 7.75 L mol−1 s−1 . Estimate the temperature at which the reaction rate would be 15% greater than the rate at 300 K.624 ∞ 11. how long would it take for the concentration of A to change from 0. and k = 4. 12. 6.44 × 104 s. 14 C decays with a half-life of 5750 years. How long will it take for the substance to reduce to 10% of its initial value? 8. Calculate the rate constant of this reaction. The activation energy of a given decomposition reaction is Ea = 125 kJ mol−1 . Calculate the Arrhenius parameter A.400 60 0.40 mol L−1 to 0. (a) What is the rate constant for the reaction? (b) How long will it take for all ammonia to disappear? 7.460 80 0. what will it be at 773 K? The mechanism for the reaction (catalyzed by Br− ) 2H2 O2 (aq) → 2H2 O(l) + O2 (g) . 13.306 40 0. The reaction 2A → P is of second order.0 × 10−4 L mol−1 s−1 at T = 298 K. 15.Appendix A: Homework Problem Sets 133 5.178 20 0. The concentration of B in the reaction A → 2B was measured at 20 min intervals and gave the following results: [B ]/mol L−1 t/ min 0 0 0. The reaction is ﬁrst order. 14. If the percentage of 14 C in a skeleton contains 90% of 14 C that is present in living matter. The concentration of a reactant in a second-order reaction dropped from 440 mmol L−1 to 112 mmol L−1 in 2. If kA = 0.02 mol L−1 ? 10.5 × 106 s at 673 K. The reaction is of ﬁrst order. k ? For a given reaction. Estimate the activation energy of the decomposition. Food decomposes (rots) 50 times faster at 30◦ C than at 0◦ C. What is the order of the reaction and what is the value of the rate constant.5 × 10−3 L mol−1 s−1 at T = 345 K. The decomposition of ammonia is a zero-order reaction in NH3 . The partial pressure of NH3 drops from 20 to 10 kPa in 750 s. how old is the skeleton? 9. The half-life of a substance is 250 s. with r = k [A]2 .

(a) What is the energy release for this process? (b) What is the wavelength of the emitted radiation? .) (slow) What is the rate law for the formation of P? 17. what fraction is the uncertainty in speed. 16.5 × 10−18 J and the speed of the electron is 106 ms−1 . r.0 × 10−10 m.0 × 10−20 kg m s−1 is ∆x = 9. An electron in a one-dimensional box of length L = 5. A photon knocks an electron out of an atom. what is the frequency of the incident photon? 3. [MN] −→ b [O•] + [Q] ii. 1J = 1 kg m2 s−2 . ∆p. If the ionization potential of the atom is 2. what is its velocity? [The electron mass is me = 9. [MN] + [O•] −→ d [P] iv. If the wavelength of an electron is 500 × 10−12 m. What is the reaction order with respect to [MN]? Problem Set VI. If the uncertainty in position of a particle moving with a momentum of 5. and the order of the reaction with respect to H2 O2 and with respect to Br− . kd are the reaction constants of the chain reactions. [M•] −→ c [M•] + [R] iii. kb . [M•] + [O•] −→ k k k k The ka .1094 × 10−12 kg.] 2. Planck’s Constant is h = 6. of the actual momentum of the particle? 4. kc . A hydrogen atom in a one-dimensional box of length L = 10−9 m jumps from level 3 to level 2.134 Elementary Physical Chemistry obeys the following rules H2 O2 (aq) + Br− (aq) → H2 O(l) + BrO− BrO− (aq) + H2 O2 (aq) → H2 O(l) + O2 (g) + Br− (aq) (slow) (fast) Determine the reaction rate. Chapters 8.626 × 10−34 J s. A2 2A A+B→P (rapid equil. The mechanism for a chain reaction involving free radicals obeys the following rules: a [M•] + [N•] i. How much energy is released? 5. 9 1. A reaction is found to obey the following mechanism.0 × 10−9 makes a transition from level 5 to level 3.

(c) l = 4. 12. (c) 4d → 3p. Chapters 10.0 ms−1 . 9. (b) 700 nm. what will be the kinetic energy of the emitted electron? 8.Appendix A: Homework Problem Sets 135 6. and if so. The work function of a metal is 2. (b) 450 nm (violet). (e) O2 . (b) l = 2. 13.577 × 10−5 cm is observed in the spectrum of H. The wavelength λ = 6. (c) 150 pm (X-rays)? 7. (d) N2 . Which of the molecules in Problems 1 would you expect to be stabilized by (a) the addition of an electron? (b) the removal of an electron? Explain. The probability of ﬁnding the electron in the H-atom in a small volume element at a radius r is 40% of its maximum value. (f) F2 . 12 1. . Show that this is a transition line in the Balmer Series. If the metal is subjected to radiation of wavelength (a) 250 nm. Give the ground state electron conﬁguration of (a) H2 . Calculate the radius r. 2. (b) 2p → 1s. What is the energy of radiation corresponding to the following wavelength: (a) 650 nm (red). Explain. 11.0 eV. will an electron be emitted. Calculate the de Broglie wavelength of (a) a particle of mass of 1 g traveling with a speed of 2. (e) 5p → 2s. What is the frequency of the transition of line n = 6 (a) in the Balmer series? (b) in the Paschen series? 10. 11. (c) C2 . What is the wavelength of the next higher line? Problem Set VII. (b) Li2 . (d) 3d → 2s. (b) a He atom traveling with a speed of 103 ms−1 . Which of the following electronic transitions in an atom are allowed? which are forbidden? Why? (a) 3s → 2s. How many electrons can occupy a subshell whose value is (a) l = 0.

136 Elementary Physical Chemistry 3.25. the higher the boiling temperature. Arrange in accordance with increasing or decreasing bond length: − + + (a) F− 2 . (b) N2 . free electrons are treated as particles in a box. calculate the excitation energy from the highest occupied level to the lowest unoccupied level.58. (c) rotational constant? Explain. 2906. If the 1 H in Problem 5 were replaced by 2 H (deuterium). 2865. Explain.92 cm−1 . (b) moment of inertia. 1 HCl or 2 HCl. ∗ . 5. (b) the bond length.10. In the FEMO (free electron molecular orbital) theory of conjugation. The boiling points of several hydrogen-containing compounds increase as follows: H2 S < H2 Se < H2 Te < H2 O Note that the heavier the molecule is. The vibration–rotation spectrum of 1 H35 Cl has peaks at 2821. What kind of intermolecular forces are present in the (a) C2 H6 . 2944. (b) CHCl3 . N2 . 7. Calculate (a) the moment of inertia. (b) the vibration frequency vo 6.91. Calculate (a) the rotation constant B ∗ . Give reason(s) for your choice. N2 . will have the greater (a) vibration frequency. Taking the size of the box to be 560 × 10−12 m. 2925. (c) CH3 COH? 9.5 cm−1 . . The spacing between successive rotational lines in the far infrared of 1 35 H Cl is 20. except for H2 O. 8. In butadiene there are 4 free electrons occupying the 2 lowest energy levels of the box. which molecule. F2 . which is the lightest of these substances. 4.63. F2 . 2843.

Appendix B

Thermodynamic Data

Table B.1. Standard enthalpies and free energies of formation in kJ mol−1 and molar entropies in J mol−1 , all at T = 298.15 K.

o ∆Hf ¯ (kJ) Ag+ (aq.) Al(s) Al3+ (aq.) Ar(g) AgCl AgBr(s) Br2 (l) C(graphite) C(diamond) CH4 (g) C2 H6 (g) CH3 COOH(l) CH3 CHO(g) C2 H5 OH(l) C3 H8 (g) C6 H6 (l) C10 H8 (s) C6 H5 OH(s) C12 H22 O11 (s) CH3 OH(l) CHCl3 (l) CCl4 (l) Cl2 (g) Cl− (aq.) CO2 (g) Cu(s) Cu2+ (aq.) Fe(s) Fe2 O3 (s) 105.56 0 −531.36 0 −127.02 −100.37 0 0 1.88 −74.74 −84.68 −487.02 −166.19 −277.65 −103.85 49.64 78.53 −165.0 −248.1 −238.66 −134.47 −139.49 0 −167.16 −393.51 0 64.77 −822.16 o ∆G¯ f (kJ) −77.11 0 −485.34 0 −109.70 −96.90 0 0 2.89 −50.79 −32.88 −219.17 −128.88 −187.32 −23.49 167.36 −50.0 −156.4 −166.81 −73.72 −68.74 0 −131.32 −394.36 0 65.49 −740.99 So ¯ m (J) 73.9 28.32 321.75 154.72 96.11 107.11 152.21 5.69 1.59 186.18 229.49 159.02 250.33 160.67 209.91 202.92 146.0 200.4 126.72 201.67 214.43 223.09 56.5 213.74 33.15 −99.8 27.28 84.96 (Continued) 137

138

Elementary Physical Chemistry

Table B.1.

o ∆Hf ¯ (kJ) FeS2 (s) FeSO4 (s) H2 (g) H2 O(l) H2 O2 (l) H2 S(g) H2 SO4 (l) HNO3 (l) HCl(g) H3 PO4 (l) Hg(l) HgCl2 (s) I2 (s) LiF(s) K2 O(s) Na(s) NH3 (g) NH4 Cl(s) N2 O(g) O2 (g) Na2 O(s) P(white) P(red) SO2 (g) Zn(s) Zn2+∗ (aq.) ZnS(s) −177.91 −928.43 0 −285.86 −187.78 −10.63 −813.99 −174.05 −92.29 −1279.05 0 −224.3 0 −612.12 −361.49 0 −46.19 −315.38 82.05 0 −415.89 0 −17.57 −296.96 0 −153.89 −205.98

(Continued)

o ∆G¯ f (kJ) −166.69 −820.90 0 −237.19 −120.41 −33.56 −690.11 −80.79 −95.27 −1119.22 0 −178.8 0 −584.09 −322.17 0 −16.61 −208.89 104.20 0 −376.66 0 −12.13 −300.07 0 −147.08 −201.29 So ¯ m(J) 53.14 100.58 130.58 69.96 109.62 206.79 156.90 155.60 186.69 110.49 76.02 146.0 116.15 35.98 98.52 51.21 192.50 94.56 219.85 205.48 72.89 41.09 22.81 248.52 41.63 −112.1 111.29

Appendix C

Standard Reduction Potentials

**Table C.1. The standard (reduction) half-reaction potentials at 25◦ C for a number of ions.
**

E ∗ /V Cd2+ + 2e− → Cd Cu+ + e− → Cu Cu2+ + 2e− → Cu Fe2+ + 2e− → 2H+ + 2e− → H2 2H2 O + 2e− → H2 + 2OH− Hg2 Cl2 + 2e− → 2Hg + 2Cl− O2 + 4H+ + 4e− → 2H2 O O2 + H2 O + 2e− → HO2 + OH− − PbSO4 +2e− → Pb + SO2 4 Sn2+ + 2e− → Sn Sn4+ + 2e− → Sn2+ Fe2+ + 2e− → Fe Pb2+ + 2e− → Pb I2 + 2e− → 2I− −0.40 +0.52 +0.34 −0.44 0 −0.83 +0.27 +1.23 −0.08 −0.36 −0.14 +0.15 −0.44 −0.36 0.54

139

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Index activated complex. 112. 74. 113 approximation Born–Oppenheimer. 95 degenerate. 44. 117. 136 boiling temperature. 55. 112. 2. 18. 69–72. 131. 101. 80. 60–62. 133. 89. 113. 30. 70. 121 dipole moment. 113. 102. 88. 22. 69–72. 112. 127. 136 bond σ and π . 117. 58–60. 130. 53. 131 equilibrium. 122 diﬀusion. 31. 23. 70. 96 boiling point. 72. 84 Bohr. 111. 117. 75–77. 135 Debye. 123. 93. 26 cathode. 73 atomic radius. 96 Bohr radius. 104 chemical. 114 Planck. 41. 125. 114–116. 99. 125. 105 Born–Oppenheimer approx. 84. 34. 85. 77. 111. 76. 83. 120–123 valence. 129. 80. 12. 49–51 elevation. 129. 90 depression. 29. 98 Copenhagen Interpretation. 60–62. 126 ionic. 29. 60 Clapeyron. 67. 40. Niels. 103. 135 bar. 134 chemical kinetics. 80. 127 black-body radiation. 46 colligative properties. 110 delocalized. 111. 85 de Broglie. 81. 13. 91–93. 85. 109 steady-state. 89. 45. 51. 73. 90–92. 35. 49–52. 112 polar. 136 order. 25. 89. 104. 48. 105 orbital. 49 constant Boltzmann. 66. 47. 88. 126 diatomic molecule. 130. 81 Arrhenius equation. 14. 6. 132 gravitational. 43. 72–74. 46. 103 Balmer. 67. 103 anti-bonding orbital. 37. 69. 89. 104–108 Born. 105 Carnot cycle. 128 Henry’s Law. 134 rates. 75–77. 73 angular momentum. 22. 104 covalent. 82. 3. 104. 109. 46 Claussius–Clapeyron. 57 141 chain reaction. 51. 126 length. 88. 90. 131 normalization. 133. 134 Rydberg. 49–52. 21. 134 reaction rate. 56. 88. 120–122 . 95. 79. 7. 66. 80. 8–10 dipole–dipole interaction.

12. 122. 48. 3. 17. 56. 83–86 . 2. 102–113. 38. 83–85. 106 Gibbs free energy. 55. 103 phase rule. 102. 93 electrode. 73. 130. 105. 132 standard enthalpy. 47. 113. 98–100. 129. 20. 82. 14–23. 57 harmonic oscillator energy. 2. 39. 117. 105. 34. 131 Gibbs free energy. 85. 10. Wolfgang. 85. 109 internal energy. 19. 135 Lindemann mechanism. 94. 128. 12. 132. 32. 124 dipole–dipole. 121 dipole–induced dipole. 59. 125 hydrogenic atom. 25–27. 121 van der Waals. 15. 73. 11. 88 electronegativity. 105 van der Waals. 121–123 interaction. 15. 18. 136 hybrid.142 Elementary Physical Chemistry dispersion interaction. 100. 29. 10. 58 electromagnetic radiation. 82. 33 Joule–Thomson. 11. 10. 135 Pauli. 63. 32. 84. 115. 128 virial. 93 Henry’s Law. 14. 128. 130. 89. 128. 136 osmotic pressure. 97. 109. 44 photoelectric eﬀect. 11. 32. 101 molality. 55. 10 kinetic energy. 29. 34. 98. 35. 18. 131 P-branch. 2. 71. 99. 58. 102. 136 Newton. 129 rate of. 117. 89. 30. 27. 134 energy level. 121. 86. 131 Hund’s Rule. 116 heat. 90. 94. 112 energy as heat. 118 partial molar Gibbs energy. 7. 49. 83–85. 15. 89. 33. 10. 113 moelecular. 88. 128 perfect gas. 129 heat capacity. 73 Schr¨ odinger. 30 formation bond. 122. 61. 21. 91. 77. 122 Dulong and Petit. 82. 121–123 orbital. 92. 104. 130 and equilibrium constant. 91. 137 freezing point. 102 induction forces. 128. 85. 49–51. 89. 97. 77 Lyman Series. 88. 120. 4 Paschen Series. 90. 11. 109. 10. 103. 123. 16. 136 enthalphy. 109 hybrid orbital. 121–123. 129 equation Arrhenius. 17. 129. 11. 52. 115. 132 half-reaction. 36. 83 nonpolar molecules. 128 dispersion. 88. 2. 51 moment of inertia. 69. 39 isolated system. 39 pascal. 129 hydrogen. 31. 108. 15. 75. 99. 85. 21. 128 equation of state. 67. Albert. 11. 129. 14–23. 108 hydrogen bonding. 34. 83. 41. 128–132 entropy. 112. 91. 108. 19. 103. 30. 82. 21. 29. 129 Heisenberg. 39 photon. 43. 3 van der Waals. Isaac. 85 Einstein. 92–95. 25–27. 83. 56. Werner. 40. 122 internal energy. 85. 102. 119. 53. 122 First Law.

18. 58 subshell. 77. 6. 125. 73 covalent. 9–11. 59. 52. 38. 14. 38. 28. 38. 108. 12. 102. 56. 48. 11–18. 53. 112. 131 triple point. 6. 46–49. 135 PV-work. 105 solution. 135 surrounding. 129 work function. 85. 5. 41. 106. 58. 103. 88–91. 101. 66. 28. 42. 70. 57. 35. 88. 37. 35. 104–108 van der Waals. 134 polar bond. 2. 91. 100. 82 Rydberg constant. 34. 97. 82. 98 Schr¨ odinger. 49 spin. 23. 83–85. 115. 108. 21–25. 93 promotion. 29. 136 theory. 88. 6. 11. 70. 55. 29. 4. 94. 12. 92–95. 137 standard Gibbs free energy. 51–53. 56. 82. 3. 129 temperature. 34. 59. 109 standard enthalpy. 32. 49. 27. 126 molecular orbital (MO). 57. 12.Index 143 photon. 19. 45–48. 93. 67. 11. 46–49. 92. 18. 46–49. 70–72. 123 polarizability. 104. 82. 95 unimolecular reaction. 49. 30. 47. 74. 51. 93. 48. 31–35. 44 uncertainty principle. 130. 101. 15. 113 thermodynamics. 104. 52. 110. 123. 53 rotational constant. 72. 69. 118 Raoult’s Law. 7. 128. 1–4. 36. 34. 38. 22–24. 21. 109. 104. 16. 21. 105. 128. 20. 136 rotational spectroscopy. 57. 129. 56. 51. 30 Torr. 74. 120. 22. 131 ideal dilute. deterministic. 136 activated complex. 85. 94. 117. 9. 121–123. 120. 122 probabilistic. 78 valence bond. 37. 108. 131 solvent chemical potential. 17–19. 5. 104 work. 37. 104. 21. 3. 51. 103. 70. 106. 131 solvent. 43. 32. 43. 17. 30 Second law. 131 solute. 12–15. 112. 32. 8. 10. 14. 137 First law. 20. 41. 130 state function. 135 . 46–48. 15. 102. 96–99. 82–86. 30 Third law. 21. 99. 97. 89. 132. 45. 121–123. 38. 34. 9. 129. 98. 20. 60. 127–133. 81. 24. 131 ideal. 43–45. 90. 108 R-branch. 27–30. 128 VSEPR (Valence Shell Electron Pair Repulsion). 16. 17. 28. 18.

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