Handbook of Aqueous Electrolyte Thermodynamics Theory & Application

by Zemaitis, Joseph F.; Clark, Diane M.; Rafal, Marshall; Scrivner, Noel C.

• ISBN13: 9780816903504
• ISBN10: 0816903506
• eBook ISBN(s): 9780470938409
• Edition: 1st
• Format: Hardcover
• Copyright: 1986-06-15
• Publisher: Wiley-AIChE
• More Book Details
• Purchase Benefits

Summary

Expertise in electrolyte systems has become increasingly important in traditional CPI operations, as well as in oil/gas exploration and production. This book is the source for predicting electrolyte systems behavior, an indispensable "do-it-yourself" guide, with a blueprint for formulating predictive mathematical electrolyte models, recommended tabular values to use in these models, and annotated bibliographies. The final chapter is a general recipe for formulating complete predictive models for electrolytes, along with a series of worked illustrative examples. It can serve as a useful research and application tool for the practicing process engineer, and as a textbook for the chemical engineering student.

Author Biography

The late Joseph F. Zemaitis, Jr. was President of Chem Solve, Inc. Prior to the formation of Chem Solve, he was Vice-President of OLI Systems, Inc. Dr. Semaitis worked for 9 years at ESSO Research Engineering as Principal Consultant in fluid dynamics and engineering technology. A graduate of Drexel Tech, he received his M.S. and Ph.D. from Carnegie-Mellon University. He was a Lecturer in Physics at Drew University and Mathematics at the County College of Morris. Dr. Zemaitis was a member of AICHE, ACS and AAPT.

Diane M. Clark is presently a Senior Scientist at OLI System, Inc. Prior to this she worked for Chem Solve, Inc. She received a B.S. in Mathematics and Computer Science from Clarkson College of Technology (now Clarkson University) and is a member of AICHE.

Marshal Rafal is President and founder of OLI Systems, Inc. a world leader in computer software for simulation of aqueous chemistry. Prior to founding OLI in 1971, Dr. Rafal worked at ESSO Mathematics and Systems, Inc. for five years. He received a B.Ch.E. from the Cooper Union and an M.S. Ch.E. and Ph.D. from Northwestern University. Dr. Rafal is a member of AICHE.

Noel C. Scrivner, as a Senior Consultant at the Du Pont Company, consults on the problems of thermodynamics and kinetics company-wide. His current interest is in the application of electrolyte thermodynamics to geochemistry problems. He received a B.A. and a B.S. from Rice University and an M.S. and Ph.D. from Carnegie-Mellon University—all in Chemical Engineering. He is currently chairman of the Design Institute for Physical Property Data (DIPPR) Aqueous Electrolyte Thermodynamic Database project. He is member of AICHE, ACS, Sigma Xi, and American Geophysical Union.

Table of Contents

Introduction

Thermodynamics of Solutions

Basic Thermodynamic Functions

Solutions – Basic Definitions and Concepts

Equilibrium – Necessary Conditions

Activities, Activity Coefficients and Standard States

Equilibrium Constants

Ionic and/or Reaction Equilibrium in Aqueous Solutions

Solubility Equilibria Between Crystals and Saturated Solutions

Vapor-Liquid Equilibria in Aqueous Solutions

Temperature Effects on the Equilibrium Constant

Estimating Temperature Effects on Heat Capacity and Other Thermodynamic Properties

Equilibrium Constants from Tabulated Data

Pressure Effects on the Equilibrium Constant

Appendix 3.1 – Criss and Cobble Parameters

Activity Coefficients of Single Strong Electrolytes

History

Bromley’s Method

Meissner’s Method

Pitzer’s Method

Chen’s Method

Temperature Effects

Application

Bromley’s Extended Equation

Comparison of Temperature Effect Methods

Appendix 4.1 – Values for Guggenheim’s ß Parameter

Table 1: ß Values for Uni-univalent Electrolytes

Table 2: ß and B Values of Bi-univalent and Uni-bivalent Electrolytes from Freezing Points

Methods for Calculating ß

Appendix 4.2 – Bromley Interaction Parameters

Table 1: B Values at 25°C Determined by the Method of Least Squares on Log ¿ to I=6.0 (or less of limited data)

Table 2: Individual Ion Values of B and ¿ in Aqueous Solutions at 25°C

Table 3: Bivalent Metal Sulfates at 25°C

Appendix 4.4 – Pitzer Parameters

Table 1: Inorganic Acids, Bases and Salts of 1-1 Type

Table 2: Salts of Carboxylic Acids (1-1 Type)

Table 3: Tetraalkylammonium Halides

Table 4: Sulfonic Acids and Salts (1-1 Type)

Table 5: Additional 1-1 Type Organic Salts

Table 6: Inorganic Compounds of 2-1 Type

Table 7: Organic Electrolytes of 2-1 Type

Table 8: 3-1 Electrolytes

Table 9: 4-1 Electrolytes

Table 10: 5-1 Electrolytes

Table 11: 2-2 Electrolytes

Appendix 4.5 – Pitzer Parameter Derivatives

Table 1: Temperature Derivatives of Parameters for 1-1

Electrolytes Evaluated from Calorimetric Data

Table 2: Temperature Derivatives of Parameters for 2-1 and 1-2

Electrolytes Evaluated from Calorimetric Data

Table 3: Temperature Derivatives of Parameters for 3-1 and 2-2

Electrolytes Evaluated from Calorimetric Parameters

Appendix 4-6 Chen Parameters

Table: ¿ Values Fit for Molality Mean Ionic Activity Coefficient Data of Aqueous Electrolytes at 298.5 K

Activity Coefficients of Multicomponet Strong Electrolytes

Guggenheim’s Method for Multicomponent Solutions

Bromley’s Method for Multicomponent Solutions

Meissner’s Method for Multicomponent Solutions

Pitzer’s Method for Multicomponent Solutions

Application

Phase Diagram Calculations

Appendix 5.1 – Values for Pitzer’s ¿ and ¿ Parameters

Table 1: Parameters for mixed electrolytes with viral coefficient equations (at 25°C)

Table 2: Parameters for the viral coefficient equations at 25°C

Table 3: Parameters for binary mixtures with a common ion at 25°C

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