Chemical Thermodynamics: Basic Concepts and Methods. Seventh Edition Irving M. Klotz, Robert M. Rosenberg

Chemical Thermodynamics: Basic Concepts and Methods.
Seventh Edition
Irving M. Klotz, Robert M. Rosenberg

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1 INTRODUCTION
1.1 Origins of Chemical Thermodynamics
1.2 Objectives of Chemical Thermodynamics
1.3 Limitations of Classic Thermodynamics

2 MATHEMATICAL PREPARATION FOR THERMODYNAMICS
2.1 Variables of Thermodynamics
Extensive and Intensive Quantities
Units and Conversion Factors
2.2 Analytic Methods
Partial Differentiation
Exact Differentials
Homogeneous Functions

3 THE FIRST LAW OF THERMODYNAMICS
3.1 Definitions
Temperature
Work
3.2 The First Law of Thermodynamics
Energy
Heat
General Form of the First Law

4 ENTHALPY, ENTHALPY OF REACTION, AND HEAT CAPACITY
4.1 Enthalpy
Definition
Relationship between QV and QP
4.2 Enthalpy of Reactions
Definitions and Conventions
4.3 Enthalpy as a State Function
Enthalpy of Formation from Enthalpy of Reaction
Enthalpy of Formation from Enthalpy of Combustion
Enthalpy of Transition from Enthalpy of Combustion
Enthalpy of Conformational Transition of a Protein from Indirect Calorimetric Measurements
Enthalpy of Solid-State Reaction from Measurements of Enthalpy of Solution
4.4 Bond Enthalpies
Definition of Bond Enthalpies
Calculation of Bond Enthalpies
Enthalpy of Reaction from Bond Enthalpies
4.5 Heat Capacity
Definition
Some Relationships between CP and CV
Heat Capacities of Gases
Heat Capacities of Solids
Heat Capacities of Liquids
Other Sources of Heat Capacity Data
4.6 Enthalpy of Reaction as a Function of Temperature
Analytic Method
Arithmetic Method
Graphical or Numerical Methods

5 APPLICATIONS OF THE FIRST LAW TO GASES
5.1 Ideal Gases
Definition
Enthalpy as a Function of Temperature Only Relationship Between CP and Cv
Calculation of the Thermodynamic Changes in Expansion Processes
5.2 Real Gases
Equations of State
Joule–Thomson Effect
Calculations of Thermodynamic Quantities in Reversible
Expansions

6 THE SECOND LAW OF THERMODYNAMICS
6.1 The Need for a Second Law
6.2 The Nature of the Second Law
Natural Tendencies Toward Equilibrium
Statement of the Second Law
Mathematical Counterpart of the Verbal Statement
6.3 The Carnot Cycle
The Forward Cycle
The Reverse Cycle
Alternative Statement of the Second Law
Carnot’s Theorem
6.4 The Thermodynamic Temperature Scale
6.5 The Definition of S, the Entropy of a System
6.6 The Proof that S is a Thermodynamic Property
Any Substance in a Carnot Cycle
Any Substance in Any Reversible Cycle
Entropy S Depends Only on the State of the System
6.7 Entropy Changes in Reversible Processes
General Statement
Isothermal Reversible Changes
Adiabatic Reversible Changes
Reversible Phase Transitions
Isobaric Reversible Temperature Changes
Isochoric Reversible Temperature Changes
6.8 Entropy Changes in Irreversible Processes
Irreversible Isothermal Expansion of an Ideal Gas
Irreversible Adiabatic Expansion of an Ideal Gas
Irreversible Flow of Heat from a Higher Temperature to a Lower Temperature
Irreversible Phase Transitions
Irreversible Chemical Reactions
General Statement
6.9 General Equations for the Entropy of Gases
Entropy of the Ideal Gas
Entropy of a Real Gas
6.10 Temperature–Entropy Diagram
6.11 Entropy as an Index of Exhaustion

7 EQUILIBRIUM AND SPONTANEITY FOR SYSTEMS AT CONSTANT TEMPERATURE
7.1 Reversibility, Spontaneity, and Equilibrium
Systems at Constant Temperature and Volume
Systems at Constant Temperature and Pressure
Heat of Reaction as an Approximate
Criterion of Spontaneity
7.2 Properties of the Gibbs, Helmholtz, and Planck Functions
The Functions as Thermodynamic Properties
Relationships among G, Y, and A
Changes in the Functions for Isothermal Conditions
Equations for Total Differentials
Pressure and Temperature Derivatives of the Functions
Equations Derived from the Reciprocity Relationship
7.3 The Gibbs Function and Chemical Reactions
Standard States
7.4 Pressure and Temperature Dependence of DG
7.5 Useful Work and the Gibbs and Helmholtz Functions
Isothermal Changes
Changes at Constant Temperature and Pressure
Relationship between DHP and QP When Useful Work is Performed
Application to Electrical Work
Gibbs–Helmholtz Equation
The Gibbs Function and Useful Work in Biologic Systems

8 APPLICATION OF THE GIBBS FUNCTION AND THE PLANCK FUNCTION TO SOME PHASE CHANGES
8.1 Two Phases at Equilibrium as a Function of Pressure and Temperature
Clapeyron Equation
Clausius–Clapeyron Equation
8.2 The Effect of an Inert Gas on Vapor Pressure
Variable Total Pressure at Constant Temperature
Variable Temperature at Constant Total Pressure
8.3 Temperature Dependence of Enthalpy of Phase Transition
8.4 Calculation of Change in the Gibbs Function for
Spontaneous Phase Change
Arithmetic Method
Analytic Method

9 THERMODYNAMICS OF SYSTEMS OF VARIABLE COMPOSITION
9.1 State Functions for Systems of Variable Composition
9.2 Criteria of Equilibrium and Spontaneity in Systems of Variable Composition
9.3 Relationships Among Partial Molar Properties of a Single Component
9.4 Relationships Between Partial Molar Quantities of Different Components
Partial Molar Quantities for Pure Phase
9.5 Escaping Tendency
Chemical Potential and Escaping Tendency
9.6 Chemical Equilibrium in Systems of Variable Composition

10 MIXTURES OF GASES AND EQUILIBRIUM IN GASEOUS MIXTURES
10.1 Mixtures of Ideal Gases
The Entropy and Gibbs Function for Mixing Ideal Gases
The Chemical Potential of a Component of an Ideal Gas Mixture
Chemical Equilibrium in Ideal Gas Mixtures
Dependence of K on Temperature
Comparison of Temperature Dependence of DG8m and ln K
10.2 The Fugacity Function of a Pure Real Gas
Change of Fugacity with Pressure
Change of Fugacity with Temperature
10.3 Calculation of the Fugacity of a Real Gas
Graphical or Numerical Methods
Analytical Methods
10.4 Joule–Thomson Effect for a Van der Waals Gas
Approximate Value of a for a Van der Waals Gas
Fugacity at Low Pressures
Enthalpy of a Van der Waals Gas
Joule–Thomson Coefficient
10.5 Mixtures of Real Gases
Fugacity of a Component of a Gaseous Solution
Approximate Rule for Solutions of Real Gases
Fugacity Coefficients in Gaseous Solutions
Equilibrium Constant and Change in Gibbs Functions and
Planck Functions for Reactions of Real Gases

11 THE THIRD LAW OF THERMODYNAMICS
11.1 Need for the Third Law
11.2 Formulation of the Third Law
Nernst Heat Theorem
Planck’s Formulation
Statement of Lewis and Randall
11.3 Thermodynamic Properties at Absolute Zero
Equivalence of G and H
DCP in an Isothermal Chemical Reaction
Limiting Values of CP and CV
Temperature Derivatives of Pressure and Volume
11.4 Entropies at 298 K
Typical Calculations
Apparent Exceptions to the Third Law
Tabulations of Entropy Values

12 APPLICATION OF THE GIBBS FUNCTION TO CHEMICAL CHANGES
12.1 Determination of DG8m from Equilibrium Measurements
12.2 Determination of DG8m from Measurements of Cell potentials
12.3 Calculation of DG8m from Calorimetric Measurements
12.4 Calculation of a Gibbs Function of a Reaction from Standard Gibbs Function of Formation
12.5 Calculation of a Standard Gibbs Function from Standard Entropies and Standard Enthalpies
Enthalpy Calculations
Entropy Calculations
Change in Standard Gibbs Function

13 THE PHASE RULE
13.1 Derivation of the Phase Rule
Nonreacting Systems
Reacting Systems
13.2 One-Component Systems
13.3 Two-Component Systems
Two Phases at Different Pressures
Phase Rule Criterion of Purity

14 THE IDEAL SOLUTION
14.1 Definition
14.2 Some Consequences of the Definition
Volume Changes
Heat Effects
14.3 Thermodynamics of Transfer of a Component from    One Ideal Solution to Another
14.4 Thermodynamics of Mixing
14.5 Equilibrium between a Pure Solid and an Ideal Liquid Solution
Change of Solubility with Pressure at a Fixed Temperature
Change of Solubility with Temperature
14.6 Equilibrium between an Ideal Solid Solution and an Ideal Liquid Solution
Composition of the Two Phases in Equilibrium
Temperature Dependence of the Equilibrium Compositions

15 DILUTE SOLUTIONS OF NONELECTROLYTES
15.1 Henry’s Law
15.2 Nernst’s Distribution Law
15.3 Raoult’s Law
15.4 Van’t Hoff’s Law of Osmotic Pressure
Osmotic Work in Biological Systems
15.5 Van’t Hoff’s Law of Freezing-Point Depression and Boiling-Point Elevation

16 ACTIVITIES, EXCESS GIBBS FUNCTIONS, AND STANDARD STATES FOR NONELECTROLYTES
16.1 Definitions of Activities and Activity Coefficients
Activity
Activity Coefficient
16.2 Choice of Standard States
Gases
Liquids and Solids
16.3 Gibbs Function and the Equilibrium Constant in Terms of Activity
16.4 Dependence of Activity on Pressure
16.5 Dependence of Activity on Temperature
Standard Partial Molar Enthalpies
Equation for Temperature Derivative of the Activity
16.6 Standard Entropy
16.7 Deviations from Ideality in Terms of Excess Thermodynamic Functions
Representation of Gm E as a Function of Composition
16.8 Regular Solutions and Henry’s Law
16.9 Regular Solutions and Limited Miscibility

17 DETERMINATION OF NONELECTROLYTE ACTIVITIES AND EXCESS GIBBS FUNCTIONS FROM EXPERIMENTAL DATA
17.1 Activity from Measurements of Vapor Pressure
Solvent
Solute
17.2 Excess Gibbs Function from Measurement of Vapor Pressure
17.3 Activity of a Solute from Distribution between Two Immiscible Solvents
17.4 Activity from Measurement of Cell Potentials
17.5 Determination of the Activity of One Component from the Activity of the Other
Calculation of Activity of Solvent from That of Solute
Calculation of Activity of Solute from That of Solvent
17.6 Measurements of Freezing Points

18 CALCULATION OF PARTIAL MOLAR QUANTITIES AND EXCESS MOLAR QUANTITIES FROM EXPERIMENTAL DATA: VOLUME AND ENTHALPY
18.1 Partial Molar Quantities by Differentiation of J as a Function of Composition
Partial Molar Volume
Partial Molar Enthalpy
Enthalpies of Mixing
Enthalpies of Dilution
18.2 Partial Molar Quantities of One Component from those of Another Component by Numerical Integration
Partial Molar Volume
Partial Molar Enthalpy
18.3 Analytic Methods for Calculation of Partial Molar Properties
Partial Molar Volume
Partial Molar Enthalpy
18.4 Changes in J for Some Processes in Solutions
Transfer Process
Integral Process
18.5 Excess Properties: Volume and Enthalpy
Excess Volume
Excess Enthalpy

19 ACTIVITY, ACTIVITY COEFFICIENTS, AND OSMOTIC COEFFICIENTS OF STRONG ELECTROLYTES
19.1 Definitions and Standard states for Dissolved Electrolytes
Uni-univalent Electrolytes
Multivalent Electrolytes
Mixed Electrolytes
19.2 Determination of Activities of Strong Electrolytes
Measurement of Cell Potentials
Solubility Measurements
Colligative Property Measurement: The Osmotic Coefficient
Extension of Activity Coefficient Data to Additional Temperatures with Enthalpy of Dilution Data
19.3 Activity Coefficients of Some Strong Electrolytes
Experimental Values
Theoretical Correlation

20 CHANGES IN GIBBS FUNCTION FOR PROCESSES IN SOLUTIONS
20.1 Activity Coefficients of Weak Electrolytes
20.2 Determination of Equilibrium Constants for Dissociation of Weak Electrolytes
From Measurements of Cell Potentials
From Conductance Measurements
20.3 Some Typical Calculations for DfG8m
Standard Gibbs Function for Formation of
Aqueous Solute: HCl
Standard Gibbs Function of Formation of Individual Ions: HCl
Standard Gibbs Function for Formation of Solid Solute in Aqueous Solution
Standard Gibbs Function for Formation of Ion of Weak Electrolyte
Standard Gibbs Function for Formation of Moderately Strong Electrolyte
Effect of Salt Concentration on Geological Equilibrium
Involving Water
20.4 Entropies of Ions
The Entropy of an Aqueous Solution of a Salt
Entropy of Formation of Individual Ions
Ion Entropies in Thermodynamic Calculations

21 SYSTEMS SUBJECT TO A GRAVITATIONAL OR A CENTRIFUGAL FIELD
21.1 Dependence of the Gibbs Function on External Field
21.2 System in a Gravitational Field
21.3 System in a Centrifugal Field

22 ESTIMATION OF THERMODYNAMIC QUANTITIES
22.1 Empirical Methods
Group Contribution Method of Andersen, Beyer, Watson, and Yoneda
Typical Examples of Estimating Entropies
Other Methods
Accuracy of the Approximate Methods
Equilibrium in Complex Systems

APPENDIX A PRACTICAL MATHEMATICALTECHNIQUES
A.1 Analytical Methods
Linear Least Squares
Nonlinear Least Squares
A.2 Numerical and Graphical Methods
Numerical Differentiation
Numerical Integration
Use of the Digital Computer
Graphical Differentiation
Graphical Integration