# Thermodynamic Properties of Nonelectrolyte Solutions

## 1st Edition

**Authors:**William Acree

**eBook ISBN:**9780323140676

**Imprint:**Academic Press

**Published Date:**1st January 1984

**Page Count:**318

## Description

Thermodynamic Properties of Nonelectrolyte Solutions reviews several of the more classical theories on the thermodynamics of nonelectrolyte solutions. Basic thermodynamic principles are discussed, along with predictive methods and molecular thermodynamics. This book is comprised of 12 chapters; the first of which introduces the reader to mathematical relationships, such as concentration variables, homogeneous functions, Euler’s theorem, exact differentials, and method of least squares. The discussion then turns to partial molar quantities, ideal and nonideal solutions, and empirical expressions for predicting the thermodynamic properties of multicomponent mixtures from binary data. The chapters that follow explore binary and ternary mixtures containing only nonspecific interactions; the thermodynamic excess properties of liquid mixtures and ternary alcohol-hydrocarbon systems; and solubility behavior of nonelectrolytes. This book concludes with a chapter describing the use of gas-liquid chromatography in determining the activity coefficients of liquid mixtures and mixed virial coefficients of gaseous mixtures. This text is intended primarily for professional chemists and researchers, and is invaluable to students in chemistry or chemical engineering who have background in physical chemistry and classical thermodynamics.

## Table of Contents

Preface

1 Mathematical Relationships

A. Concentration Variables

B. Partial Derivatives

C. Total Derivative

D. Implicit Differentiation

E. Chain Rule

F. Cycle Rule

G. Homogeneous Functions

H. Euler's Theorem

I. Exact Differentials

J. Method of Least Squares

Problems

2 Partial Molar Quantities

A. Partial Molar Volumes

B. Other Partial Molar Quantities

C. The Gibbs-Duhem Equation

D. Apparent Partial Molar Quantities

E. Determination of Partial Molar Quantities

F. Interpretive Descriptions

Problems

3 Ideal and Nonideal Solutions

A. Fugacity

B. Activity

C. The Ideal Solution

D. Vapor-Liquid Equilibrium in an Ideal Solution

E. Behavior of Ideal Dilute Solutions

F. Thermodynamic Excess Functions

G. Vapor-Liquid Equilibrium in Nonideal Solutions

Problems

4 Empirical Expressions for Estimating Multicomponent Properties from Binary Data

Text

Problems

5 Binary and Ternary Mixtures Containing Only Nonspecific Interactions

A. The Theory of Van Laar

B. The Scatchard-Hildebrand Model

C. The Flory-Huggins Model

D. The Wilson Model

E. The Nonrandom Two-Liquids (NRTL) Model

F. The UNIQUAC and Effective UNIQUAC Models

G. Summary

Problems

6 Prediction of Thermodynamic Excess Properties of Liquid Mixtures Based on Group Contribution Methods

A. Analytical Solution of Groups Model (ASOG)

B. The Analytical Group Solution Model (AGSM)

C. The UNIQUAC Functional Group Activity Coefficients Model (UNIFAC)

D. Summary

Problems

7 Simple Associated Solutions

A. Thermodynamic Properties in Associated Solutions

B. The Ideal Associated Solution Model: Systems Having a Single AB-type Complex

C. The Ideal Associated Solution Model: Systems Having Both AB-type and AB2-type Complexes

D. Summary

Problems

8 Estimation of Thermodynamic Excess Properties of Ternary-Alcohol Hydrocarbon Systems from Binary Data

A. Kretschmer-Wiebe Association Model

B. Mecke-Kempter Association Model

C. Attenuated Equilibrium Constant (AEC) Model

D. Two-Constant Kretschmer-Wiebe Association Model

E. Summary

Problems

9 Vapor-Liquid Equilibria and Azeotropic Systems

A. Isothermal Vapor-Liquid Equilibrium in Binary Systems

B. Isothermal Vapor-Liquid Equilibrium in Ternary Systems

C. Isobaric Vapor-Liquid Equilibrium in Binary Systems

D. Isobaric Vapor-Liquid Equilibrium in Ternary Systems

E. Azeotropes in Binary Mixtures Under Isobaric Conditions

F. Prediction of Ternary Azeotropes from Binary Data

Problems

10 Solubility Behavior of Nonelectrolytes

A. Solid-Liquid Equilibrium in an Ideal Solution

B. The Scatchard-Hildebrand Solubility Parameter Model

C. Stoichiometric Complexation Model of Higuchi

D. The Nearly Ideal Binary Solvent Theory (NIBS), Solubility in Binary Solvents of Nonspecific Interactions

E. The Nearly Ideal Binary Solvent Model (NIBS), Monomeric and Dimeric Treatment of Carboxylic Acids

F. Extension of the Nearly Ideal Binary Solvent Model to Systems Having Solute-Solvent Complexation

G. Solubility Predictions Using the UNIFAC Group Contribution Method

Problems

11 Liquid-Liquid Equilibrium: Distribution of a Solute between Two Immiscible Liquid Phases

A. Liquid-Liquid Equilibrium in Binary Systems

B. Distribution of a Solute between Two Immiscible Solvents

C. Partitioning of a Solute between a Binary Organic Phase and Water

Problems

12 Physio-Chemical Applications of Gas-Liquid Chromatography to Nonelectrolyte Solutions

A. The Nearly Ideal Binary Solvent Theory: Gas-Liquid Partition Coefficients in Noncomplexing Systems

B. The Kretschmer-Wiebe Association Model: Gas-Liquid Partition Coefficients of Alcohol Solutes on Binary Solvent Mixtures of Inert Hydrocarbons

C. The Nearly Ideal Binary Solvent Theory: Gas-Liquid Partition Coefficients in Systems Containing Solute-Solvent Complexation

D. Gas-Liquid Chromatographic Partition Coefficients of Inert Solutes on Self- Associating Binary Solvent Systems

E. Summary

Problems

Appendix A Solubility Parameters and Molar Volumes at 25°C

Appendix B UNIQUAC Structural Parameters

Appendix C Constants and Conversion Factors

Appendix D Answers to Selected Problems

References

Index

## Details

- No. of pages:
- 318

- Language:
- English

- Copyright:
- © Academic Press 1984

- Published:
- 1st January 1984

- Imprint:
- Academic Press

- eBook ISBN:
- 9780323140676