Thermodynamics and Chemistry
kiana
(Kiana)
#1
Biographical Sketches
- Biographical Sketches
- Preface to the Second Edition
- From the Preface to the First Edition
- 1 Introduction
- 2 Systems and Their Properties
- 3 The First Law
- 4 The Second Law
- 5 Thermodynamic Potentials
- 6 The Third Law and Cryogenics
- 7 Pure Substances in Single Phases
- 8 Phase Transitions and Equilibria of Pure Substances
- 9 Mixtures
- 10 Electrolyte Solutions
- 11 Reactions and Other Chemical Processes
- 12 Equilibrium Conditions in Multicomponent Systems
- 13 The Phase Rule and Phase Diagrams
- 14 Galvanic Cells
Appendix A Definitions of the SI Base Units
- SHORTCONTENTS
- Appendix B Physical Constants
- Appendix C Symbols for Physical Quantities
- Appendix D Miscellaneous Abbreviations and Symbols
- Appendix E Calculus Review
- Appendix F Mathematical Properties of State Functions
- Appendix G Forces, Energy, and Work
- Appendix H Standard Molar Thermodynamic Properties
- Appendix I Answers to Selected Problems
- Bibliography
- Index
- Biographical Sketches CONTENTS
- Preface to the Second Edition
- From the Preface to the First Edition
- 1 Introduction
- 1.1 Units
- 1.1.1 Amount of substance and amount
- 1.2 Quantity Calculus
- 1.3 Dimensional Analysis
- Problem
- 2 Systems and Their Properties
- 2.1 The System, Surroundings, and Boundary
- 2.1.1 Extensive and intensive properties
- 2.2 Phases and Physical States of Matter
- 2.2.1 Physical states of matter
- 2.2.2 Phase coexistence and phase transitions
- 2.2.3 Fluids
- 2.2.4 The equation of state of a fluid
- 2.2.5 Virial equations of state for pure gases
- 2.2.6 Solids
- 2.3 Some Basic Properties and Their Measurement
- 2.3.1 Mass
- 2.3.2 Volume
- 2.3.3 Density
- 2.3.4 Pressure
- 2.3.5 Temperature
- 2.4 The State of the System
- 2.4.1 State functions and independent variables
- 2.4.2 An example: state functions of a mixture
2.4.3 More about independent variables
- CONTENTS
- 2.4.4 Equilibrium states
- 2.4.5 Steady states
- 2.5 Processes and Paths
- 2.6 The Energy of the System
- 2.6.1 Energy and reference frames
- 2.6.2 Internal energy
- Problems
- 3 The First Law
- 3.1 Heat, Work, and the First Law
- 3.1.1 The concept of thermodynamic work
- 3.1.2 Work coefficients and work coordinates
- 3.1.3 Heat and work as path functions
- 3.1.4 Heat and heating
- 3.1.5 Heat capacity
- 3.1.6 Thermal energy
- 3.2 Spontaneous, Reversible, and Irreversible Processes
- 3.2.1 Reversible processes
- 3.2.2 Irreversible processes
- 3.2.3 Purely mechanical processes
- 3.3 Heat Transfer
- 3.3.1 Heating and cooling
- 3.3.2 Spontaneous phase transitions
- 3.4 Deformation Work
- 3.4.1 Gas in a cylinder-and-piston device
- 3.4.2 Expansion work of a gas
- 3.4.3 Expansion work of an isotropic phase
- 3.4.4 Generalities
- 3.5 Applications of Expansion Work
- 3.5.1 The internal energy of an ideal gas
- 3.5.2 Reversible isothermal expansion of an ideal gas
- 3.5.3 Reversible adiabatic expansion of an ideal gas
- 3.5.4 Indicator diagrams
- 3.5.5 Spontaneous adiabatic expansion or compression
- 3.5.6 Free expansion of a gas into a vacuum
- 3.6 Work in a Gravitational Field
- 3.7 Shaft Work
- 3.7.1 Stirring work
- 3.7.2 The Joule paddle wheel
- 3.8 Electrical Work
- 3.8.1 Electrical work in a circuit
- 3.8.2 Electrical heating
- 3.8.3 Electrical work with a galvanic cell
- 3.9 Irreversible Work and Internal Friction
- 3.10 Reversible and Irreversible Processes: Generalities
- Problems
- CONTENTS
- 4 The Second Law
- 4.1 Types of Processes
- 4.2 Statements of the Second Law
- 4.3 Concepts Developed with Carnot Engines
- 4.3.1 Carnot engines and Carnot cycles
- 4.3.2 The equivalence of the Clausius and Kelvin–Planck statements
- 4.3.3 The efficiency of a Carnot engine
- 4.3.4 Thermodynamic temperature
- 4.4 Derivation of the Mathematical Statement of the Second Law
- 4.4.1 The existence of the entropy function
- 4.4.2 Using reversible processes to define the entropy
- 4.4.3 Some properties of the entropy
- 4.5 Irreversible Processes
- 4.5.1 Irreversible adiabatic processes
- 4.5.2 Irreversible processes in general
- 4.6 Applications
- 4.6.1 Reversible heating
- 4.6.2 Reversible expansion of an ideal gas
- 4.6.3 Spontaneous changes in an isolated system
- 4.6.4 Internal heat flow in an isolated system
- 4.6.5 Free expansion of a gas
- 4.6.6 Adiabatic process with work
- 4.7 Summary
- 4.8 The Statistical Interpretation of Entropy
- Problems
- 5 Thermodynamic Potentials
- 5.1 Total Differential of a Dependent Variable
- 5.2 Total Differential of the Internal Energy
- 5.3 Enthalpy, Helmholtz Energy, and Gibbs Energy
- 5.4 Closed Systems
- 5.5 Open Systems
- 5.6 Expressions for Heat Capacity
- 5.7 Surface Work
- 5.8 Criteria for Spontaneity
- Problems
- 6 The Third Law and Cryogenics
- 6.1 The Zero of Entropy
- 6.2 Molar Entropies
- 6.2.1 Third-law molar entropies
- 6.2.2 Molar entropies from spectroscopic measurements
- 6.2.3 Residual entropy
- 6.3 Cryogenics
- 6.3.1 Joule–Thomson expansion
- 6.3.2 Magnetization
- CONTENTS
- 7 Pure Substances in Single Phases
- 7.1 Volume Properties
- 7.2 Internal Pressure
- 7.3 Thermal Properties
- 7.3.1 The relation betweenCV;mandCp;m.
- 7.3.2 The measurement of heat capacities
- 7.3.3 Typical values
- 7.4 Heating at Constant Volume or Pressure
- 7.5 Partial Derivatives with Respect toT,p, andV
- 7.5.1 Tables of partial derivatives
- 7.5.2 The Joule–Thomson coefficient
- 7.6 Isothermal Pressure Changes
- 7.6.1 Ideal gases
- 7.6.2 Condensed phases
- 7.7 Standard States of Pure Substances
- 7.8 Chemical Potential and Fugacity
- 7.8.1 Gases
- 7.8.2 Liquids and solids
- 7.9 Standard Molar Quantities of a Gas
- Problems
- 8 Phase Transitions and Equilibria of Pure Substances
- 8.1 Phase Equilibria
- 8.1.1 Equilibrium conditions
- 8.1.2 Equilibrium in a multiphase system
- 8.1.3 Simple derivation of equilibrium conditions
- 8.1.4 Tall column of gas in a gravitational field
- 8.1.5 The pressure in a liquid droplet
- 8.1.6 The number of independent variables
- 8.1.7 The Gibbs phase rule for a pure substance
- 8.2 Phase Diagrams of Pure Substances
- 8.2.1 Features of phase diagrams
- 8.2.2 Two-phase equilibrium
- 8.2.3 The critical point
- 8.2.4 The lever rule
- 8.2.5 Volume properties
- 8.3 Phase Transitions
- 8.3.1 Molar transition quantities
- 8.3.2 Calorimetric measurement of transition enthalpies
- 8.3.3 Standard molar transition quantities
- 8.4 Coexistence Curves
- 8.4.1 Chemical potential surfaces
- 8.4.2 The Clapeyron equation
- 8.4.3 The Clausius–Clapeyron equation
- CONTENTS
- 9 Mixtures
- 9.1 Composition Variables
- 9.1.1 Species and substances
- 9.1.2 Mixtures in general
- 9.1.3 Solutions
- 9.1.4 Binary solutions
- 9.1.5 The composition of a mixture
- 9.2 Partial Molar Quantities
- 9.2.1 Partial molar volume
- 9.2.2 The total differential of the volume in an open system
- 9.2.3 Evaluation of partial molar volumes in binary mixtures
- 9.2.4 General relations
- 9.2.5 Partial specific quantities
- 9.2.6 The chemical potential of a species in a mixture
- 9.2.7 Equilibrium conditions in a multiphase, multicomponent system
- 9.2.8 Relations involving partial molar quantities
- 9.3 Gas Mixtures
- 9.3.1 Partial pressure
- 9.3.2 The ideal gas mixture
- 9.3.3 Partial molar quantities in an ideal gas mixture
- 9.3.4 Real gas mixtures
- 9.4 Liquid and Solid Mixtures of Nonelectrolytes
- 9.4.1 Raoult’s law
- 9.4.2 Ideal mixtures
- 9.4.3 Partial molar quantities in ideal mixtures
- 9.4.4 Henry’s law
- 9.4.5 The ideal-dilute solution
- 9.4.6 Solvent behavior in the ideal-dilute solution
- 9.4.7 Partial molar quantities in an ideal-dilute solution
- 9.5 Activity Coefficients in Mixtures of Nonelectrolytes
- 9.5.1 Reference states and standard states
- 9.5.2 Ideal mixtures
- 9.5.3 Real mixtures
- 9.5.4 Nonideal dilute solutions
- 9.6 Evaluation of Activity Coefficients
- 9.6.1 Activity coefficients from gas fugacities
- 9.6.2 Activity coefficients from the Gibbs–Duhem equation
- 9.6.3 Activity coefficients from osmotic coefficients
- 9.6.4 Fugacity measurements
- 9.7 Activity of an Uncharged Species
- 9.7.1 Standard states
- 9.7.2 Activities and composition
- 9.7.3 Pressure factors and pressure
- 9.8 Mixtures in Gravitational and Centrifugal Fields
- CONTENTS
- 9.8.1 Gas mixture in a gravitational field
- 9.8.2 Liquid solution in a centrifuge cell
- Problems
- 10 Electrolyte Solutions
- 10.1 Single-ion Quantities
- 10.2 Solution of a Symmetrical Electrolyte
- 10.3 Electrolytes in General
- 10.3.1 Solution of a single electrolyte
- 10.3.2 Multisolute solution
- 10.3.3 Incomplete dissociation
- 10.4 The Debye–Huckel Theory ̈
- 10.5 Derivation of the Debye–Huckel Equation ̈
- 10.6 Mean Ionic Activity Coefficients from Osmotic Coefficients
- Problems
- 11 Reactions and Other Chemical Processes
- 11.1 Mixing Processes
- 11.1.1 Mixtures in general
- 11.1.2 Ideal mixtures
- 11.1.3 Excess quantities
- 11.1.4 The entropy change to form an ideal gas mixture
- 11.1.5 Molecular model of a liquid mixture
- 11.1.6 Phase separation of a liquid mixture
- 11.2 The Advancement and Molar Reaction Quantities
- 11.2.1 An example: ammonia synthesis
- 11.2.2 Molar reaction quantities in general
- 11.2.3 Standard molar reaction quantities
- 11.3 Molar Reaction Enthalpy
- 11.3.1 Molar reaction enthalpy and heat
- 11.3.2 Standard molar enthalpies of reaction and formation
- 11.3.3 Molar reaction heat capacity
- 11.3.4 Effect of temperature on reaction enthalpy
- 11.4 Enthalpies of Solution and Dilution
- 11.4.1 Molar enthalpy of solution
- 11.4.2 Enthalpy of dilution
- 11.4.3 Molar enthalpies of solute formation
- 11.4.4 Evaluation of relative partial molar enthalpies
- 11.5 Reaction Calorimetry
- 11.5.1 The constant-pressure reaction calorimeter
- 11.5.2 The bomb calorimeter
- 11.5.3 Other calorimeters
- 11.6 Adiabatic Flame Temperature
- 11.7 Gibbs Energy and Reaction Equilibrium
- 11.7.1 The molar reaction Gibbs energy
- 11.7.2 Spontaneity and reaction equilibrium
- CONTENTS
- 11.7.3 General derivation
- 11.7.4 Pure phases
- 11.7.5 Reactions involving mixtures
- 11.7.6 Reaction in an ideal gas mixture
- 11.8 The Thermodynamic Equilibrium Constant
- 11.8.1 Activities and the definition ofK
- 11.8.2 Reaction in a gas phase
- 11.8.3 Reaction in solution
- 11.8.4 Evaluation ofK
- 11.9 Effects of Temperature and Pressure on Equilibrium Position
- Problems
- 12 Equilibrium Conditions in Multicomponent Systems
- 12.1 Effects of Temperature
- 12.1.1 Variation ofi=T with temperature
- 12.1.2 Variation ofi=Twith temperature
- 12.1.3 Variation of lnKwith temperature
- 12.2 Solvent Chemical Potentials from Phase Equilibria
- 12.2.1 Freezing-point measurements
- 12.2.2 Osmotic-pressure measurements
- 12.3 Binary Mixture in Equilibrium with a Pure Phase
- 12.4 Colligative Properties of a Dilute Solution
- 12.4.1 Freezing-point depression
- 12.4.2 Boiling-point elevation
- 12.4.3 Vapor-pressure lowering
- 12.4.4 Osmotic pressure
- 12.5 Solid–Liquid Equilibria
- 12.5.1 Freezing points of ideal binary liquid mixtures
- 12.5.2 Solubility of a solid nonelectrolyte
- 12.5.3 Ideal solubility of a solid
- 12.5.4 Solid compound of mixture components
- 12.5.5 Solubility of a solid electrolyte
- 12.6 Liquid–Liquid Equilibria
- 12.6.1 Miscibility in binary liquid systems
- 12.6.2 Solubility of one liquid in another
- 12.6.3 Solute distribution between two partially-miscible solvents
- 12.7 Membrane Equilibria
- 12.7.1 Osmotic membrane equilibrium
- 12.7.2 Equilibrium dialysis
- 12.7.3 Donnan membrane equilibrium
- 12.8 Liquid–Gas Equilibria
- 12.8.1 Effect of liquid pressure on gas fugacity
- 12.8.2 Effect of liquid composition on gas fugacities
- 12.8.3 The Duhem–Margules equation
- 12.8.4 Gas solubility
- 12.8.5 Effect of temperature and pressure on Henry’s law constants
- CONTENTS
- 12.9 Reaction Equilibria
- 12.10 Evaluation of Standard Molar Quantities
- Problems
- 13 The Phase Rule and Phase Diagrams
- 13.1 The Gibbs Phase Rule for Multicomponent Systems
- 13.1.1 Degrees of freedom
- 13.1.2 Species approach to the phase rule
- 13.1.3 Components approach to the phase rule
- 13.1.4 Examples
- 13.2 Phase Diagrams: Binary Systems
- 13.2.1 Generalities
- 13.2.2 Solid–liquid systems
- 13.2.3 Partially-miscible liquids
- 13.2.4 Liquid–gas systems with ideal liquid mixtures
- 13.2.5 Liquid–gas systems with nonideal liquid mixtures
- 13.2.6 Solid–gas systems
- 13.2.7 Systems at high pressure
- 13.3 Phase Diagrams: Ternary Systems
- 13.3.1 Three liquids
- 13.3.2 Two solids and a solvent
- Problems
- 14 Galvanic Cells
- 14.1 Cell Diagrams and Cell Reactions
- 14.1.1 Elements of a galvanic cell
- 14.1.2 Cell diagrams
- 14.1.3 Electrode reactions and the cell reaction
- 14.1.4 Advancement and charge
- 14.2 Electric Potentials in the Cell
- 14.2.1 Cell potential
- 14.2.2 Measuring the equilibrium cell potential
- 14.2.3 Interfacial potential differences
- 14.3 Molar Reaction Quantities of the Cell Reaction
- 14.3.1 Relation betweenÅrGcellandEcell, eq
- 14.3.2 Relation betweenÅrGcellandÅrG
- 14.3.3 Standard molar reaction quantities
- 14.4 The Nernst Equation
- 14.5 Evaluation of the Standard Cell Potential
- 14.6 Standard Electrode Potentials
- Problems
- Appendix A Definitions of the SI Base Units
- Appendix B Physical Constants
- CONTENTS
- Appendix C Symbols for Physical Quantities
- Appendix D Miscellaneous Abbreviations and Symbols
- D.1 Physical States
- D.2 Subscripts for Chemical Processes
- D.3 Superscripts
- Appendix E Calculus Review
- E.1 Derivatives
- E.2 Partial Derivatives
- E.3 Integrals
- E.4 Line Integrals
- Appendix F Mathematical Properties of State Functions
- F.1 Differentials
- F.2 Total Differential
- F.3 Integration of a Total Differential
- F.4 Legendre Transforms
- Appendix G Forces, Energy, and Work
- G.1 Forces between Particles
- G.2 The System and Surroundings
- G.3 System Energy Change
- G.4 Macroscopic Work
- G.5 The Work Done on the System and Surroundings
- G.6 The Local Frame and Internal Energy
- G.7 Nonrotating Local Frame
- G.8 Center-of-mass Local Frame
- G.9 Rotating Local Frame
- G.10 Earth-Fixed Reference Frame
- Appendix H Standard Molar Thermodynamic Properties
- Appendix I Answers to Selected Problems
- Bibliography
- Index
- Benjamin Thompson, Count of Rumford BIOGRAPHICAL SKETCHES
- James Prescott Joule
- Sadi Carnot
- Rudolf Julius Emmanuel Clausius
- William Thomson, Lord Kelvin
- Max Karl Ernst Ludwig Planck
- Josiah Willard Gibbs
- Walther Hermann Nernst
- William Francis Giauque
- Benoit PaulEmile Clapeyron ́
- William Henry
- Gilbert Newton Lewis
- Peter Josephus Wilhelmus Debye
- Germain Henri Hess
- Franc ̧ois-Marie Raoult
Jacobus Henricus van’t Hoff