《物理化学（英文版）Physical Chemistry》为十三五江苏省高等学校本科重点教材（新编）。本书是在继承既有物理化学中文、英文教材体系成果的基础上编写而成的，在新工科理念指导下，注重借助数学、物理等基础科学的理论原理及新实验技术手段研究化学变化中的基本规律。本书共包括九章内容，分别是气体的性质、热力学定律、热力学第二定律、多组分系统热力学、化学平衡、相平衡、电化学平衡、化学动力学和界面化学，每章均配有与章节基本概念、公式和知识内容相对应的不同难度的例题、练习题和思考题，有助于巩固掌握基础知识，增强解题及逻辑思维能力。

本书注重提高学生的学习兴趣和效果，培养多学科基础厚实、工程能力强、综合素质高且能实现跨界整合的复合型人才。本书既可作为高等院校化工类、化学类、材料类、生工制药类、环境类等专业基础物理化学课程的全英文教学用书，也可供其他相关专业使用，并可作为相关科研和工程技术人员的参考用书。

前言

本书是为本科物理化学课程英文教学而设计编写的。物理化学是化学的理论基础，使用物理的原理和方法来研究化学中基本的规律和理论，为学生开启了将化学的描述性、理论性和数学知识进行融汇贯通之路。因此本书内容着眼于通过定义体系，研究其状态，并分析其状态改变的过程。

本书分九章，首先以热力学的三个基本定律为基础，研究宏观化学体系在气态、液态、固态、溶解态等平衡态的物理化学性质及其规律性；然后研究由于化学或物理因素的扰动而引起的体系的化学变化过程速率和变化机理。每一章都包含例题和习题，以便读者理解并运用相关知识点。

本书由景苏、王强任主编，各章执笔人分别是裴文博（章），美国得克萨斯南方大学Jacob Xin Wei 和Yuanjian Deng、景苏（第二章），姚敏霞（第三章），王芳（第四章），林志华（第五章），王强（第六章），韩明娟和吴雅静（第七章），王小辉（第八章），李冀蜀（第九章）。全书承蒙黄岭教授和美国得克萨斯南方大学Jacob Xin Wei 教授详细审阅并提出宝贵的修改意见。

由于编者水平有限，书中疏漏及不当之处在所难免，恳请读者提出宝贵意见。



编者

2021年1月





Preface

This is a textbook designed for an undergraduate physical chemistry course. Physical chemistry is one of the traditional sub-disciplines of chemistry and is concerned with the application of the concepts and theories of physics to the analysis of the chemical properties and reactive behavior of matter. The physical chemistry course is often the first opportunity that a student has to synthesize descriptive, theoretical, and mathematical knowledge about chemistry into a coherent whole. To facilitate this synthesis, the book is constructed about the idea of defining a system, studying the states in which it might be found, and analyzing the processes by which it can change its state.

The book is divided into nine chapters. Based on the three basic laws of thermodynamics, it firstly focuses on the study the macroscopic properties of gases, liquids, solids and solutions; the following dynamics includes chemical change caused by the disturbance of chemical or physical factors. Each chapter contains examples that illustrate various kinds of calculations, as well as exercises placed within the chapter. Both these exercises and the problems at the end of each section are designed to provide practice in applying techniques and insights obtained through study of the chapter.

This book is edited by Jing Su and Wang Qiang. The authors of each chapter are Pei Wenbo (Chapter 1), Jacob Xin Wei and Yuanjian Deng of Texas Southern University, Jing Su (Chapter 2), Yao Minxia (Chapter 3), Wang Fang (Chapter 4), Lin Zhihua (Chapter 5), Wang Qiang (Chapter 6), Han Mingjuan and Wu Yajing (Chapter 7), and Wang Xiaohui (Chapter 8), Li Jishu (Chapter 9). Professor Huang Ling and Professor Jacob Xin Wei of Southern University of Texas reviewed the manuscript and put forward valuable suggestions for revision.

The authors encourage students and instructors to comment on any part of the book; please send comments and suggestions to the authors attention.

Chapter 1 The Properties of Gases 1

1.1 State Equation of the Ideal Gas 1

1.1.1 Empirical Laws of Gases 1

1.1.2 State Equation of Ideal Gas 2

1.1.3 Model and Definition of Ideal Gas 4

1.2 The Properties of Mixtures of the Ideal Gases 5

1.2.1 Composition of Mixtures 5

1.2.2 Daltons Law of Partial Pressures 6

1.2.3 Amagats Law of Partial Volumes 7

1.3 State Equations of Real Gas 8

1.3.1 The van der Waals Equation 8

1.3.2 Generalized Equation of State for Real Gases 9

1.4 Isothermal Curves and Liquefaction of Real Gas 10

1.4.1 Saturated Vapor Pressure of the Liquid 10

1.4.2 Isothermal Curves and Liquefaction 12

1.4.3 Critical Parameters and Critical Compression Factor Zc 14

1.5 Exercises 15



Chapter 2 The First Law of Thermodynamics 17

2.1 Basic Concepts 17

2.1.1 System and Surroundings 17

2.1.2 Property, State, and State Function 18

2.1.3 Process and Route 19

2.1.4 Work, Heat, and Energy 20

2.2 The First Law of Thermodynamics 22

2.2.1 The First Law of Thermodynamics 22

2.2.2 Internal Energy 23

2.3 Heat, Enthalpy, and Heat Capacities 23

2.3.1 Heat in Isochoric Conditions, and Internal Energy 23

2.3.2 Heat in Isobaric Conditions, and Enthalpy 25

2.3.3 Hesss Law 26

2.3.4 Heat Capacities 27

2.4 Pressure-Volume Work and Reversible Processes 29

2.4.1 Pressure-Volume Work 29

2.4.2 Reversible Processes 30

2.5 Isoenthalpic Processes 36

2.5.1 The Joule-Thomson Effect 36

2.5.2 Adiabatic Joule-Thomson Coefficient 37

2.6 Thermochemistry 37

2.6.1 Standard Enthalpy of Formation 38

2.6.2 Enthalpy of Reaction 39

2.6.3 Temperature-Dependence of Standard Enthalpy of Reaction 40

2.7 Exercises 41



Chapter 3 The Second Law of Thermodynamics 42

3.1 Statements of the Second Law of Thermodynamics 42

3.1.1 Spontaneous Process 42

3.1.2 Conversion of Heat and Work 43

3.1.3 Statements of the Second Law of Thermodynamics 43

3.2 Carnot Cycle and Carnot Theorem 44

3.2.1 Carnot Cycle 44

3.2.2 Carnot Theorem 45

3.3 Entropy and Clausius Inequality 46

3.3.1 Derivation and Definition of Entropy 46

3.3.2 The Clausius Inequality 47

3.3.3 The Principle of the Increase of Entropy 47

3.3.4 Physical Significance of Entropy 48

3.4 The Calculation of Entropy Changes 49

3.4.1 The Calculation of Entropy Changes in Simple pVT Process 49

3.4.2 The Calculation of Entropy Changes for Phase Changes 51

3.5 The Standard Molar Reaction Entropy Change of Chemical Reaction 52

3.5.1 The Third Law of Thermodynamics 52

3.5.2 Absolute Entropy and Standard Molar Entropy of Matter 52

3.5.3 Calculation of Entropy Changes for Chemical Reactions 53

3.6 The Gibbs and Helmholtz Functions 55

3.6.1 Helmholtz Function 55

3.6.2 Gibbs Function 56

3.7 The Calculation of A and G 57

3.7.1 Simple pVT Change Process 57

3.7.2 Phase Change Processes 57

3.7.3 Chemical Change Processes 58

3.8 The Fundamental Equation of Thermodynamics 59

3.8.1 The Fundamental Equations of Thermodynamics 59

3.8.2 The Relations of Characteristic Function 60

3.8.3 The Maxwell Relations 61

3.9 The Application of the Second Law of Thermodynamics in the Phase Equilibria of Single Component Systems 62

3.9.1 The Clapeyron Equation 62

3.9.2 The Clausius-Clapeyron Equation 63

3.9.3 The Effect of Total Pressure on the Vapor Pressure 64

3.10 Exercises 65



Chapter 4 The Thermodynamics of Multi-Component Systems 68

4.1 Composition scale of multi-component systems 68

4.1.1 Mass Concentration 68

4.1.2 Amount of Substance concentration 68

4.1.3 Molality 69

4.2 Partial Molar Quantities 69

4.2.1 Definition of Partial Molar Quantity 70

4.2.2 Collected Formula of Partial Molar Quantity 71

4.2.3 The Gibbs-Duhem Equation 71

4.3 Chemical Potential 72

4.3.1 Definition of Chemical Potential 72

4.3.2 Equilibrium Criterion of Material 73

4.3.3 Application of Chemical Potential in Phase Equilibrium 74

4.4 Chemical Potential of Gas 75

4.4.1 Chemical Potential of a Pure Ideal Gas 75

4.4.2 Chemical Potentials in an Ideal Gas Mixture 76

4.5 Raoults law and Henrys law 77

4.5.1 Raoults Law 77

4.5.2 Henrys Law 78

4.5.3 Comparison of Raoults Law and Henrys Law 79

4.6 Mixture of Ideal Liquid 79

4.6.1 Definition and Features of Mixture of Ideal Liquid 79

4.6.2 Chemical Potential of Arbitrary Component in Mixture of Ideal Liquid 80

4.6.3 Mixing Properties of Mixture of Ideal Liquid 81

4.7 Ideal Dilute Solution 82

4.7.1 Definition of Ideal Dilute Solution 82

4.7.2 Chemical Potential of the Solvent and Solute in Ideal Dilute Solution 82

4.8 Real Liquid Solution 83

4.8.1 The Solvent Activity 83

4.8.2 The Solute Activity 84

4.9 Colligative Properties 84

因字数限制，仅展示部分目录