Thermodynamics and Statistical Mechanics

Thermodynamics and Statistical Mechanics provides undergraduate chemistry students with a grounding in both classical and statistical thermodynamics. Thermodynamic quantities and relationships are introduced and developed in a coherent way, enabling students to apply thermodynamic analysis to chemical problems with confidence. Each stage in the development is well illustrated with examples. The text aims to help students understand energy, its different forms and transformations, and the key role of entropy, as applied to chemical systems, addressing questions such as: (i) How much work is performed, and how much heat transfer occurs, during chemical processes and reactions, and how do they depend on temperature? (ii) How is it possible for endothermic processes to occur spontaneously, and will a given reaction occur spontaneously? (iii) What determines the equilibrium between phases? (iv) How do temperature and pressure affect equilibrium? (v) What is the meaning of entropy? (vi) How are macroscopic thermodynamic properties related to microscopic energy levels? Ideal for the needs of undergraduate chemistry students, Tutorial Chemistry Texts is a major series consisting of short, single topic or modular texts concentrating on the fundamental areas of chemistry taught in undergraduate science courses. Each book provides a concise account of the basic principles underlying a given subject, embodying an independent-learning philosophy and including worked examples.

Introduction	p. 1
The Laws of Thermodynamics	p. 2
Definitions	p. 3
Exothermic and Endothermic Processes	p. 3
The First Law	p. 5
Internal Energy	p. 5
Heat	p. 6
Work	p. 7
Heat Capacity, Enthalpy and Thermochemistry	p. 16
Heat Capacity, C	p. 16
Enthalpy	p. 19
Thermochemistry	p. 20
Reaction Enthalpy and Hess's Law	p. 20
Temperature Dependence of Enthalpy Changes	p. 22
The Second and Third Laws: Entropy	p. 25
Spontaneous Processes	p. 25
The Clausius Inequality	p. 27
Temperature Dependence of the Entropy, S	p. 29
Free Energy	p. 35
Gibbs and Helmholtz Free Energy	p. 35
Maximum Work	p. 36
Pressure and Temperature Dependence of G	p. 38
Phase Transitions	p. 40
Stability of Phases	p. 40
Effect of Pressure on the Boiling Point	p. 42
Phase Diagrams	p. 42
Clapeyron Equation	p. 42
Clausius-Clapeyron Equation	p. 43
Gibbs Free Energy and Chemical Potential	p. 44
Chemical Equilibrium	p. 49
Extent of Reaction and the Reaction Gibbs Free Energy	p. 49
The Equilibrium Constant	p. 51
Temperature Dependence of the Equilibrium Constant	p. 54
Effect of Pressure on Equilibrium	p. 55
Le Chatelier's Principle	p. 56
The Statistical Definition of Entropy	p. 59
Statistical Entropy	p. 60
Microstates	p. 60
Calculating the Entropy	p. 62
Connecting Microscopic and Macroscopic Properties	p. 67
Ensembles	p. 67
Ensemble Averages	p. 69
What is the Preferred State of a System?	p. 72
The Boltzmann Distribution	p. 74
The Partition Function	p. 77
Definition of the Partition Function	p. 77
The Internal Energy	p. 78
The Helmholtz Free Energy	p. 80
The Entropy	p. 80
The Pressure	p. 81
The Isochoric Heat Capacity	p. 81
An Ideal Gas of Atoms	p. 84
The Ideal Gas	p. 84
The Molecular Partition Function	p. 87
The Translational Partition Function	p. 88
The Internal Energy of a Monatomic Ideal Gas	p. 91
The Heat Capacity of a Monatomic Ideal Gas	p. 93
The Pressure of a Monatomic Ideal Gas	p. 93
The Entropy of a Monatomic Ideal Gas	p. 93
An Ideal Gas of Diatomic Molecules	p. 98
The Rotational Partition Function	p. 99
Rotation and Symmetry	p. 102
The Properties of a Rigid Rotor	p. 104
The Harmonic Oscillator	p. 106
Thermodynamic Properties of the Harmonic Oscillator	p. 110
The Electronic Partition Function	p. 113
Statistical Mechanics and Equilibrium	p. 117
Thermodynamics of Gaseous Molecules	p. 117
The Gibbs Free Energy	p. 118
The Standard Gibbs Free Energy	p. 120
The Equilibrium Constant, K[subscript p]	p. 122
Glossary	p. 126
Answers to Problems	p. 134
Subject Index	p. 159
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Thermodynamics and Statistical Mechanics

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