Addison-Wesley Publishing Company, 1972. 444 p. ISBN:
0201073587
Contents
Symbols Used in This Book
Introduction
Temperature and the zeroth law Section
Energy Conservation: the First Law of Thermodynamics Energy forms
Accumulated energy 3 Transitory energy forms
Graphical representation of work Reversible work processes
Efficiency
Reversible expansion and compression 8 Equivalence of all energy forms
Equivalence of heat and work energy
Equivalence of mass and energy
System
Surroundings
First law or the conservation of energy
The sign convention
Accumulated inteal energy and the thermodynamic state U: a state property
Enthalpy
General procedure for analyzing problems
Specific heat
Phase change
Ideal gas
Reversible work: ideal-gas systems Exact and inexact differentials; thermodynamic surfaces Exact and inexact differentials: some mathematical characteristics
Cyclical process
Steam: a nonideal gas
Application of the first law to irreversible processes: the free expansion process
The infinitesimal free expansion process
Flow processes: open systems
Steady-flow processes
Frictionless, reversible steady-flow processes
Engineering applications
Nuclear energy
Thermochemistry
Standard enthalpies of formation
Standard enthalpy of combustion
Standard enthalpy change for any chemical reaction process at 25°C, 1 atm
Enthalpy of solution
Enthalpy of atomization
Enthalpy change of a chemical process at any temperature
Adiabatic chemical processes: flame temperatures
Section 3 Entropy and the Second Law of Thermodynamics
Work from heat
The second law of thermodynamics (and spontaneous change)
Heat reservoirs
Reversibility
Characteristics of reversible and irreversible processes
Converting heat into work: noncyclical process
Converting heat into work: Caot cycle
Thermal efficiency of a heat engine
Refrigeration cycle
Maximum thermal efficiency
Temperature and the efficiency of a reversible engine
The thermodynamic temperature scale
Entropy
Entropy and integrating factors
Computing changes in entropy
Temperature-entropy diagram: Caot cycle
Free expansion: entropy increase for an irreversible process
Other irreversible processes
Entropy change during chemical reactions
Entropy of phase change
Trouton's law
Third law of thermodynamics: absolute entropy
Absolute entropy and molecular structure
Work functions
Gibbs free energy
dG for any system
Applications of free-energy equations
Effect of total pressure on vapor pressure: the Poynting effect
The Helmholtz function
Equilibrium and spontaneous change
Work functions and equilibrium
Equilibrium criteria for systems that do work other than expansion work
Caot engine and the measurement of available work energy
Supplementary remarks on reversible work, energy and entropy change, lost work, and the Clausius inequality
Power and Refrigeration Cycles
Gasoline engines: the Otto cycle
The Diesel engine cycle
Steam engines: the Rankine cycle
Gas turbine: the Joule cycle
Refrigeration cycles
Properties of refrigerants
Vapor-compression cycle
Air conditioners and heat pumps
Absorption refrigeration
Steam jet refrigeration
Air liquefaction
Statistical Thermodynamics
Connecting the microscopic and macroscopic
Allowed energies
Multiparticle quantum states
Additional hypothesis
Maximizing uncertainty
Partition functions
Changing 0 and \jj 8 The nature of 0
Negative temperatures
Probability and partition function for single-particle quantum states.
N-particle partition function from single-particle partition functions
Reversible work
Work and heat
Entropy
The meaning of entropy
The Clausius inequality
Increase in entropy when heat is added to a system
Maxwell's distribution
Other distributions: open systems
The nature of a
Bose-Einstein and Fermi-Dirac distribution
Other approaches to statistical thermodynamics
Statement of basic problems
Ensemble of states
Ergodic hypothesis
Equal a priori probabilities
True ensemble average
Contents
Most likely condition
Mathematical necessity
Information-theory approach
Relations Among Thermodynamic Properties
Combined first and second law
The state principle
Relations among thermodynamic properties
Differential property relationships
The Maxwell relations
The Clapeyron equation
Jacobians
Specific heats and expansion coefficients
Thermodynamic properties as functions of measurable properties
Evaluation of changes in thermodynamic properties
Equations of State 1 Deviation from ideal-gas behavior; compressibility factor
Real gases
The van der Waals equation
Other two-constant equations of state
Benedict-Webb-Rubin equation
Virial equations of state
The generalized equation of state
Improved generalized correlation
Thermodynamic properties from equations of state
Effect of different equations of state on property computation
Departure functions
Generalized equation of state: departure functions
The need for experimental data
Presentation of thermodynamic data
Thermodynamic properties of liquids and solids
Fugacity and Activity
Fugacity
Fugacities computed from the generalized equation of state
Fugacity of liquids and solids
The effect of pressure on fugacity of liquids and solids
Activity
Activity of liquids and solids
General dependence of fugacity and activity on pressure and temperature
Contents
Thermodynamics of Mixing and Composition Change 1 Ideal solutions y
Ideal solutions of ideal gases; Dalton's and Amagat's laws
Ideal solutions of liquids; Raoult's law
Entropy of mixing ideal solutions: statistical approach
Entropy of mixing ideal solutions: macroscopic approach
Entropy, free energy, and Helmholtz function of mixing ideal gases
Free energy of mixing: ideal liquid solutions
Composition change and chemical work
Minimum work of separation
Ideal solutions of real materials
Compressibility and fugacity of real gas solutions: pseudocritical properties
Ideal solution of real gases
Solutions of real liquids; Henry's law
Ideal solutions of real liquids
K factors; composition of vapor and liquid phases in equilibrium
Real liquid solutions: activity coefficients
Partial molar properties
Partial molar volume
Partial molar enthalpies of a nonideal binary solution
Graphical computation of partial molar properties
Energy-conservation equation for variable work systems
Differential relations in chemical work systems
Gibbs-Duhem equation
Equilibrium in multiphase systems: constancy of Mi
Phase rule
Chemical Equilibrium
The chemical-equilibrium state
AG of equilibrium chemical-reaction process
AG of a chemical-reaction process at standard conditions.
Graphical representation of the AG? computation path
The equilibrium constant
Tabulations of AGformatjon
Additivity of standard free energies: calculation of AGjiaction
Absolute entropy and standard free energy of reaction
Composition of chemical equilibrium mixtures
Effect of pressure on AGreaction and the equilibrium constant K
Effect of temperature on the equilibrium constant
Equilibrium mixtures of real gases
Homogeneous reactions in liquid or solid phases
Heterogeneous reactions
Simultaneous reactions
Electrochemical processes
Contents
Standard electrode voltages
Fuel cells
Irreversible Thermodynamics
The steady state
Coupled flows
Supplementary postulates
Applications: the thermocouple
Peltier effect
Thomson effect
Thermal transpiration
Other transport processes
Appendix I
Appendix II
Appendix III
Index
Answers to Selected Problems
Contents
Symbols Used in This Book
Introduction
Temperature and the zeroth law Section
Energy Conservation: the First Law of Thermodynamics Energy forms
Accumulated energy 3 Transitory energy forms
Graphical representation of work Reversible work processes
Efficiency
Reversible expansion and compression 8 Equivalence of all energy forms
Equivalence of heat and work energy
Equivalence of mass and energy
System
Surroundings
First law or the conservation of energy
The sign convention
Accumulated inteal energy and the thermodynamic state U: a state property
Enthalpy
General procedure for analyzing problems
Specific heat
Phase change
Ideal gas
Reversible work: ideal-gas systems Exact and inexact differentials; thermodynamic surfaces Exact and inexact differentials: some mathematical characteristics
Cyclical process
Steam: a nonideal gas
Application of the first law to irreversible processes: the free expansion process
The infinitesimal free expansion process
Flow processes: open systems
Steady-flow processes
Frictionless, reversible steady-flow processes
Engineering applications
Nuclear energy
Thermochemistry
Standard enthalpies of formation
Standard enthalpy of combustion
Standard enthalpy change for any chemical reaction process at 25°C, 1 atm
Enthalpy of solution
Enthalpy of atomization
Enthalpy change of a chemical process at any temperature
Adiabatic chemical processes: flame temperatures
Section 3 Entropy and the Second Law of Thermodynamics
Work from heat
The second law of thermodynamics (and spontaneous change)
Heat reservoirs
Reversibility
Characteristics of reversible and irreversible processes
Converting heat into work: noncyclical process
Converting heat into work: Caot cycle
Thermal efficiency of a heat engine
Refrigeration cycle
Maximum thermal efficiency
Temperature and the efficiency of a reversible engine
The thermodynamic temperature scale
Entropy
Entropy and integrating factors
Computing changes in entropy
Temperature-entropy diagram: Caot cycle
Free expansion: entropy increase for an irreversible process
Other irreversible processes
Entropy change during chemical reactions
Entropy of phase change
Trouton's law
Third law of thermodynamics: absolute entropy
Absolute entropy and molecular structure
Work functions
Gibbs free energy
dG for any system
Applications of free-energy equations
Effect of total pressure on vapor pressure: the Poynting effect
The Helmholtz function
Equilibrium and spontaneous change
Work functions and equilibrium
Equilibrium criteria for systems that do work other than expansion work
Caot engine and the measurement of available work energy
Supplementary remarks on reversible work, energy and entropy change, lost work, and the Clausius inequality
Power and Refrigeration Cycles
Gasoline engines: the Otto cycle
The Diesel engine cycle
Steam engines: the Rankine cycle
Gas turbine: the Joule cycle
Refrigeration cycles
Properties of refrigerants
Vapor-compression cycle
Air conditioners and heat pumps
Absorption refrigeration
Steam jet refrigeration
Air liquefaction
Statistical Thermodynamics
Connecting the microscopic and macroscopic
Allowed energies
Multiparticle quantum states
Additional hypothesis
Maximizing uncertainty
Partition functions
Changing 0 and \jj 8 The nature of 0
Negative temperatures
Probability and partition function for single-particle quantum states.
N-particle partition function from single-particle partition functions
Reversible work
Work and heat
Entropy
The meaning of entropy
The Clausius inequality
Increase in entropy when heat is added to a system
Maxwell's distribution
Other distributions: open systems
The nature of a
Bose-Einstein and Fermi-Dirac distribution
Other approaches to statistical thermodynamics
Statement of basic problems
Ensemble of states
Ergodic hypothesis
Equal a priori probabilities
True ensemble average
Contents
Most likely condition
Mathematical necessity
Information-theory approach
Relations Among Thermodynamic Properties
Combined first and second law
The state principle
Relations among thermodynamic properties
Differential property relationships
The Maxwell relations
The Clapeyron equation
Jacobians
Specific heats and expansion coefficients
Thermodynamic properties as functions of measurable properties
Evaluation of changes in thermodynamic properties
Equations of State 1 Deviation from ideal-gas behavior; compressibility factor
Real gases
The van der Waals equation
Other two-constant equations of state
Benedict-Webb-Rubin equation
Virial equations of state
The generalized equation of state
Improved generalized correlation
Thermodynamic properties from equations of state
Effect of different equations of state on property computation
Departure functions
Generalized equation of state: departure functions
The need for experimental data
Presentation of thermodynamic data
Thermodynamic properties of liquids and solids
Fugacity and Activity
Fugacity
Fugacities computed from the generalized equation of state
Fugacity of liquids and solids
The effect of pressure on fugacity of liquids and solids
Activity
Activity of liquids and solids
General dependence of fugacity and activity on pressure and temperature
Contents
Thermodynamics of Mixing and Composition Change 1 Ideal solutions y
Ideal solutions of ideal gases; Dalton's and Amagat's laws
Ideal solutions of liquids; Raoult's law
Entropy of mixing ideal solutions: statistical approach
Entropy of mixing ideal solutions: macroscopic approach
Entropy, free energy, and Helmholtz function of mixing ideal gases
Free energy of mixing: ideal liquid solutions
Composition change and chemical work
Minimum work of separation
Ideal solutions of real materials
Compressibility and fugacity of real gas solutions: pseudocritical properties
Ideal solution of real gases
Solutions of real liquids; Henry's law
Ideal solutions of real liquids
K factors; composition of vapor and liquid phases in equilibrium
Real liquid solutions: activity coefficients
Partial molar properties
Partial molar volume
Partial molar enthalpies of a nonideal binary solution
Graphical computation of partial molar properties
Energy-conservation equation for variable work systems
Differential relations in chemical work systems
Gibbs-Duhem equation
Equilibrium in multiphase systems: constancy of Mi
Phase rule
Chemical Equilibrium
The chemical-equilibrium state
AG of equilibrium chemical-reaction process
AG of a chemical-reaction process at standard conditions.
Graphical representation of the AG? computation path
The equilibrium constant
Tabulations of AGformatjon
Additivity of standard free energies: calculation of AGjiaction
Absolute entropy and standard free energy of reaction
Composition of chemical equilibrium mixtures
Effect of pressure on AGreaction and the equilibrium constant K
Effect of temperature on the equilibrium constant
Equilibrium mixtures of real gases
Homogeneous reactions in liquid or solid phases
Heterogeneous reactions
Simultaneous reactions
Electrochemical processes
Contents
Standard electrode voltages
Fuel cells
Irreversible Thermodynamics
The steady state
Coupled flows
Supplementary postulates
Applications: the thermocouple
Peltier effect
Thomson effect
Thermal transpiration
Other transport processes
Appendix I
Appendix II
Appendix III
Index
Answers to Selected Problems