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Tables of Contents for The Bases of Chemical Thermodynamics
Thermodynamic Systems: Definitions
1
12
Interactions of Thermodynamic Systems with their Environment
2
1
System in a State of Equilibrium
3
1
Thermal reservoir. Heat Source
4
1
Diathermal and Adiabatic Enclosures
4
1
State Function and State Variables. Intensive and Extensive Variables
4
3
Definitions and Properties4
2
Isobaric Coefficient of Thermal Expansion. Isothermal Compressibility Coefficient6
1
Change of a State Variable as the Result of a Thermodynamic Process
7
4
General Process7
1
Cyclic Process8
1
Expansion and Compression of a Gas9
1
Mathematical Properties of a State Function10
1
Reversible and Irreversible Processes
11
1
Definition14
1
Work and Volume Change15
1
Examples16
2
Various Forms of Energy
19
1
Various Expressions for Work
20
1
First Law of Thermodynamics
21
6
Internal Energy. First Law
22
3
General Aspects. Expression of the First Law of Thermodynamics22
1
Application to a Closed System23
2
Internal Energy - A Look at the Molecular Scale
25
2
Second Law of Thermodynamics
27
38
Spontaneous Processes. Illustration at the Molecular Scale
27
4
Spatial rearrangement27
1
Heat Transfer28
1
A First Glance at Entropy29
2
First Formulation of the Second Law
31
1
Carnot Cycle. Heat Engine. Thermodynamic Temperature
32
3
Carnot Cycle. Operation of an Engine32
1
Reversible Cycles of Two Distinct Systems33
1
Definition of the Thermodynamic Temperature34
1
Entropy. Reversible and Irreversible Processes
35
15
Definition35
1
Entropy is a State Function36
2
Implications of the Second Law towards Entropy and Spontaneity of Processes38
3
System in Contact with a Single Thermal Reservoir41
1
System in Contact with Several Thermal Reservoirs42
1
Other Formulations of the Second Law. Equilibrium Condition43
1
Thermal Equilibrium43
2
Differential Expression for the Internal Energy of a Closed System45
1
Maximum Usable Work during a Process46
1
Entropy Change during a Monothermal Expansion of an Ideal Gas47
3
Carnot Cycle of an Ideal Gas
50
5
Isothermal (Reversible) Process of an Ideal Gas50
1
Reversible Adiabatic Process of an Ideal Gas51
1
Properties of the Cycle52
3
Heat Engines, Refrigerators, Heat Pumps
55
3
Thermal Machines55
1
Efficiency of an Engine55
1
Refrigerator, Air Conditioner, Heat Pump56
2
Internal Combustion Engine
58
2
The Otto Cycle or Beau de Rochas Cycle58
1
Efficiency of an Engine59
1
Stirling Cycle60
3
Joule Cycle63
2
Auxiliary Functions: Enthalpy, Helmholtz Energy, Gibbs Energy
65
24
Constant Volume Process (Isochoric Process)66
1
Constant Pressure Process (Isobaric Process)67
1
Characteristic Variables. Fundamental Equations. Open Systems
68
5
Generalities68
1
Internal Energy69
1
Enthalpy70
1
Helmholtz Function (Helmholtz Energy, Free Energy)70
1
Gibbs Function (Gibbs Energy, Free Enthalpy)71
1
Chemical Potential. Summary72
1
Thermodynamic Equation of State
75
3
General Case75
2
Equation of State for an Ideal Gas77
1
Properties of CP and CV
78
3
Relation between CP and CV78
2
Variation of CV with Volume and of CP with Pressure80
1
Physical Meaning of the Auxiliary Functions
81
8
Helmholtz Function (Free Energy, Helmholtz Energy)81
3
Gibbs Function (Gibbs Energy, Free Enthalpy)84
2
Spontaneous Evolution of a System. Equilibrium Condition86
3
Pure Substances and Mixtures: Molar Quantities and Partial Molar Quantities
89
16
Homogeneous Functions and their Properties
89
1
Extensive Variables: Essential Property
90
1
Explicit Expressions for Various Extensive Variables
93
2
Partial Molar Quantities
96
4
Definition96
1
Relation between Partial Molar Quantities97
1
Pure Substance98
1
Other Relations98
2
Measurement of Partial Molar Volumes
100
5
Thermodynamics of Gases
105
28
Chemical Potential of a Pure Ideal Gas105
1
Selection of the Standard State Pressure106
1
Mathematical Expressions of other Thermodynamic Functions of Ideal Gases106
1
Entropy Change of an Ideal Gas due to a Change of State107
1
Mixtures of Ideal Gases
108
8
Basic Properties, Ideal Gas Mixture108
2
Entropy of Mixing, Gibbs and Helmholtz Energy of Mixing of Two Ideal Gases Forming an Ideal Gas Mixture110
3
Irreversible Mixing of Two Ideal Gases113
1
Chemical Potential of an Ideal Gas in an Ideal Gas Mixture of Two Gases113
1
Several Gases, Partial Molar Quantities, Functions of Mixing114
2
Molecular Interactions in Real Gases116
2
Chemical Potential of a Pure Real Gas118
1
Fugacity Coefficient of a Pure Real Gas119
1
The Virial Equation119
1
The van der Waals Equation of State120
4
Joule-Thomson Effect124
3
Mixtures of Real Gases
127
3
Chemical Potential of a Real Gas in a Mixture127
1
Variables of Mixing for Real Gases128
2
Ideal Mixtures of Gases
130
3
General Remarks130
2
The Lewis-Randall Rule132
1
Systems Made up of Several Phases with No Chemical Reaction
133
20
Differential Expressions of State Functions
134
3
Fundamental Relations134
1
Chemical Potentials at Equilibrium135
1
General Expressions for Open Systems136
1
Spontaneous Transfer of a Species from One Phase to Another
137
1
Equilibrium of Two Phases of a Pure Substance
139
7
The Clapeyron Equation139
2
Equilibrium between a Gaseous Phase and a Condensed Phase (Liquid or Solid) of a Pure Substance141
1
Schematic Representation of some of the Thermodynamic Functions in the Vicinity of a Phase Change142
2
Effect of an Inert Gas on the Vapor Pressure of a Pure Substance144
1
Effect of Temperature on the Latent Heat of Phase Change and on the Equilibrium Pressure145
1
Phase Diagram of a Pure Substance
146
7
The Solid Exists in only One Crystalline Form146
4
The Solid May Exist in Several Crystalline Forms150
3
Problems and Solutions Chapters 1 through 8
153
1
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