Chemical Thermodynamics: Basic Concepts and Methods, 7th Edition

by Irving M. Klotz; Robert M. Rosenberg (Emeritus, Lawrence Univ.)

• ISBN13: 9780470285220
• ISBN10: 0470285222
• Format: eBook
• Copyright: 2008-06-01
• Publisher: Wiley-Interscience

Summary

A completely updated, expanded edition of a longstanding and influential text on chemical thermodynamics Covers the logical foundations and interrelationships of thermodynamics and their application to problems that are commonly encountered by the chemist. Explanations of abstract concepts in a clear and simple, yet still rigorous fashion Logical arrangement of the material to facilitate learning, including worked out examples. Computational techniques, graphical, numerical, and analytical, are described fully and are used frequently, both in illustrative and in assigned problems.

Table of Contents

Preface

Introduction

Origins of Chemical Thermodynamics

Objectives of Chemical Thermodynamics

Limitations of Classic Thermodynamics

References

Mathematical Preparation For Thermodynamics

Variables of Thermodynamics

Extensive and Intensive Quantities

Units and Conversion Factors

Analytic Methods

Partial Differentiation

Exact Differentials

Homogeneous Functions

Exercises

ReferencesA

The First Law Of Thermodynamics

Definitions

Temperature

Work

The First Law of Thermodynamics

Energy

Heat

General Form of the First Law

Exercises

References

Enthalpy, Enthalpy Of Reaction, And Heat Capacity

Enthalpy

Definition

Relationship between Q_v and Q_p

Enthalpy of Reactions

Definitions and Conventions

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

Bond Enthalpies

Definition of Bond Enthalpies

Calculation of Bond Enthalpies

Enthalpy of Reaction from Bond Enthalpies

Heat Capacity

Definition

Some Relationships between C_p and C_v

Heat Capacities of Gases

Heat Capacities of Solids

Heat Capacities of Liquids

Other Sources of Heat Capacity Data

Enthalpy of Reaction as a Function of Temperature

Analytic Method

Arithmetic Method

Graphical or Numerical Methods

Exercises

References

Applications Of The First Law To Gases

Ideal Gases

Definition

Enthalpy as a Function of Temperature Only

Relationship Between C_p and C_v

Calculation of the Thermodynamic Changes in Expansion Processes

Real Gases

Equations of State

JouleaÆthomson Effect

Calculations of Thermodynamic Quantities in Reversible Expansions

Exercises

References

The Second Law Of Thermodynamics

The Need for a Second Law

The Nature of the Second Law

Natural Tendencies Toward Equilibrium

Statement of the Second Law

Mathematical Counterpart of the Verbal Statement

The Carnot Cycle

The Forward Cycle

The Reverse Cycle

Alternative Statement of the Second Law

CarnotaÆs Theorem

The Thermodynamic Temperature Scale

The Definition of S, the Entropy of a System

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

Entropy Changes in Reversible Processes

General Statement

Isothermal Reversible Changes

Adiabatic Reversible Changes

Reversible Phase Transitions

Isobaric Reversible Temperature Changes

Isochoric Reversible Temperature Changes

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

General Equations for the Entropy of Gases

Entropy of the Ideal Gas

Entropy of a Real Gas

Temperaturea??Entropy Diagram

Entropy as an Index of Exhaustion

Exercises

References

Equilibrium And Spontaneity For Systems At Constant Temperature

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

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

The Gibbs Function and Chemical Reactions

Standard States

Pressure and Temperature Dependence of I?G

Useful Work and the Gibbs and Helmholtz Functions

Isothermal Changes

Changes at Constant Temperature and Pressure

Relationship between I?H_p and Q_p When Useful Work is Performed

Application to Electrical Work

Gibbsa??Helmholtz Equation

The Gibbs Function and Useful Work in Biologic Systems

Exercises

References

Application Of The Gibbs Function And The Planck Function To Some Phase Changes

Two Phases at Equilibrium as a Function of Pressure and Temperature

Clapeyron Equation

Clausiusa??Clapeyron Equation

The Effect of an Inert Gas on Vapor Pressure

Variable Total Pressure at Constant Temperature

Variable Temperature at Constant Total Pressure

Temperature Dependence of Enthalpy of Phase Transition

Calculation of Change in the Gibbs Function for Spontaneous Phase Change

Arithmetic Method

Analytic Method

Exercises

References

Thermodynamics Of Systems Of Variable Composition

State Functions for Systems of Variable Composition

Criteria of Equilibrium and Spontaneity in Systems of Variable Composition

Relationships Among Partial Molar Properties of a Single Component

Relationships Between Partial Molar Quantities of Different Components

Partial Molar Quantities for Pure Phase

Escaping Tendency

Chemical Potential and Escaping Tendency

Chemical Equilibrium in Systems of Variable Composition

Exercises

Reference

Mixtures Of Gases And Equilibrium In Gaseous Mixtures

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 I?G^o_m and ln K

The Fugacity Function of a Pure Real Gas

Change of Fugacity with Pressure

Change of Fugacity with Temperature

Calculation of the Fugacity of a Real Gas

Graphical or Numerical Methods

Analytical Methods

JouleaÆthomson 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

JouleaÆthomson Coefficient

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

Exercises

References

The Third Law Of Thermodynamics

Need for the Third Law

Formulation of the Third Law

Nernst Heat Theorem

PlanckaÆs Formulation

Statement of Lewis and Randall

Thermodynamic Properties at Absolute Zero

Equivalence of G and H

I?C_p in an Isothermal Chemical Reaction

Limiting Values of C_p and C_v

Temperature Derivatives of Pressure and Volume

Entropies at 298 K

Typical Calculations

Apparent Exceptions to the Third Law

Tabulations of Entropy Values

Exercises

References

Application Of The Gibbs Function To Chemical Changes

Determination of I?G^o_m from Equilibrium Measurements

Determination of I?G^o_m from Measurements of Cell potentials

Calculation of I?G^o_m from Calorimetric Measurements

Calculation of a Gibbs Function of a Reaction from Standard Gibbs Function of Formation

Calculation of a Standard Gibbs Function from Standard Entropies and Standard Enthalpies

Enthalpy Calculations

Entropy Calculations

Change in Standard Gibbs Function

Exercises

References

The Phase Rule

Derivation of the Phase Rule

Nonreacting Systems

Reacting Systems

One-Component Systems

Two-Component Systems

Two Phases at Different Pressures

Phase Rule Criterion of Purity

Exercises

References

The Ideal Solution

Definition

Some Consequences of the Definition

Volume Changes

Heat Effects

Thermodynamics of Transfer of a Component from One Ideal Solution to Another

Thermodynamics of Mixing

Equilibrium between a Pure Solid and an Ideal Liquid Solution

Change of Solubility with Pressure at a Fixed Temperature

Change of Solubility with Temperature

Equilibrium between an Ideal Solid Solution and an Ideal Liquid Solution

Composition of the Two Phases in Equilibrium

Temperature Dependence of the Equilibrium Compositions

Exercises

References

Dilute Solutions Of Nonelectrolytes

HenryaÆs Law

NernstaÆs Distribution Law

RaoultaÆs Law

VanaÆt HoffaÆs Law of Osmotic Pressure

Osmotic Work in Biological Systems

VanaÆt HoffaÆs Law of Freezing-Point Depression and Boiling-Point Elevation

Exercises

References

Activities, Excess Gibbs Functions, And Standard States For Nonelectrolytes

Definitions of Activities and Activity Coefficients

Activity

Activity Coefficient

Choice of Standard States

Gases

Liquids and Solids

Gibbs Function and the Equilibrium Constant in Terms of Activity

Dependence of Activity on Pressure

Dependence of Activity on Temperature

Standard Partial Molar Enthalpies

Equation for Temperature Derivative of the Activity

Standard Entropy

Deviations from Ideality in Terms of Excess Thermodynamic Functions

Representation of G^E_m as a Function of Composition

Regular Solutions and HenryaÆs Law

Regular Solutions and Limited Miscibility

Exercises

References

Determination Of Nonelectrolyte Activities And Excess Gibbs Functions From Experimental Data

Activity from Measurements of Vapor Pressure

Solvent

Solute

Excess Gibbs Function from Measurement of Vapor Pressure

Activity of a Solute from Distribution between Two Immiscible Solvents

Activity from Measurement of Cell Potentials

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

Measurements of Freezing Points

Exercises

References

Calculation Of Partial Molar Quantities And Excess Molar Quantities From Experimental Data: Volume And Enthalpy

Partial Molar Quantities by Differentiation of J as a Function of Composition

Partial Molar Volume

Partial Molar Enthalpy

Enthalpies of Mixing

Enthalpies of Dilution

Partial Molar Quantities of One Component from those of Another Component by Numerical Integration

Partial Molar Volume

Partial Molar Enthalpy

Analytic Methods for Calculation of Partial Molar Properties

Partial Molar Volume

Partial Molar Enthalpy

Changes in J for Some Processes in Solutions

Transfer Process

Integral Process

Excess Properties: Volume and Enthalpy

Excess Volume

Excess Enthalpy

Exercises

References

Activity, Activity Coefficients, And Osmotic Coefficients Of Strong Electrolytes

Definitions and Standard states for Dissolved Electrolytes

Uni-univalent Electrolytes

Multivalent Electrolytes

Mixed Electrolytes

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

Activity Coefficients of Some Strong Electrolytes

Experimental Values

Theoretical Correlation

Exercises

References

Changes In Gibbs Function For Processes In Solutions

Activity Coefficients of Weak Electrolytes

Determination of Equilibrium Constants for Dissociation of Weak Electrolytes

From Measurements of Cell Potentials

From Conductance Measurements

Some Typical Calculations for I?_fG^o_m

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

General Comments

Entropies of Ions

The Entropy of an Aqueous Solution of a Salt

Entropy of Formation of Individual Ions

Ion Entropies in Thermodynamic Calculations

Exercises

References

Systems Subject To A Gravitational Or A Centrifugal Field

Dependence of the Gibbs Function on External Field

System in a Gravitational Field

System in a Centrifugal Field

Exercises

References

Estimation Of Thermodynamic Quantities

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

Exercises

References

Concluding Remarks

References

Practical Mathematicaltechniques

Analytical Methods

Linear Least Squares

Nonlinear Least Squares

Numerical and Graphical Methods

Numerical Differentiation

Numerical Integration

Use of the Digital Computer

Graphical Differentiation

Graphical Integration

Exercises

References

Index

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