Handbook of Aqueous Electrolyte

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.

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.

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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Handbook of Aqueous Electrolyte Thermodynamics Theory & Application

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