Determination and Use of Stability Constants

by ;
Edition: 2nd
Format: Hardcover
Pub. Date: 1996-12-17
Publisher(s): Wiley-VCH
List Price: $309.11

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Summary

This book describes potentiometric methods for determining stability constants and explains how these constants can be used to describe metal ion speciation in complex environmental and biological systems. It also provides three original computer programs on a disk for calculating stability constants and for using stability constants to calculate concentrations of molecular species in solution. The author gives examples of calculations for simple metal chelates, for metal complexes of large organic molecules, and for mixtures containing several metal ions and complexing agents in aqueous solution. They also describe common errors in calculating stability constants and how to avoid them. This carefully revised second edition is now even more useful to the reader, and, in particular, to those who make use of the program disk. Each program has been revised to improve speed, control, and error trapping.

Author Biography

Arthur E. Martell was a Distinguished Professor of Chemistry at Texas A&M University and award-winning researcher in the field of inorganic chemistry.
His research centered on metal chelate compounds, macrocyclic complexes and cryptates. Ramunas J. Motekaitis is the author of Determination and Use of Stability Constants, 2nd Edition, published by Wiley.

Table of Contents

1 Introduction
1.1 Stability Constants - Early Work
1.2 Recent Developments
1.3 Historical Evolution of Computational Methods
1.4 Purpose of This Book
2 Equilibrium Constants, Protonation Constants, Formation Constants
2.1 Concentration Constants and Activity Constants
2.2 Conventions Employed for Expressing Equilibrium Constants
2.3 Equilibrium Constants and Stability Constants for Ca(II)-EDTA
2.4 Species Distribution Curves
3 Experimental Methods for Measuring Equilibrium Constants
3.1 Methods Available
3.2 Potentiometric pH Measurements
3.3 Displacement Methods
3.4 pH and p[H]
4 Experimental Procedure for Potentiometric p[H] Measurement of Metal Complex Equilibria
4.1 Materials
4.2 The Reaction Mixture
4.3 Calibration of the Potentiometric Apparatus
4.4 The Experimental Runs
4.5 Computation of Stability Constants
5 Common Errors and Their Elimination or Minimization
5.1 Measurement Errors
5.2 Calibration and Electrode Care
5.3 Reagents
5.4 Equilibrium Measurements
5.5 Calculations
5.6 Selection of the Model
6 Examples of Stability Constant Determinations
6.1 Iminodiacetic Acid (IDA)
6.2 Procedure for IDA
Calibration
Checking the electrode system
Initial data for IDA
Final calculation for IDA protonation constants
Lead(II)/IDA system
6.3 C-Bistren
6.4 Procedure for C-Bistren
CBT alone
Cu(II)/CBT system
Computation of Cu(II)/CBT stability constants
6.5 Determination of Stability Constants in the Presence of Competing Ligands
7 Macroscopic and Microscopic Constants
7.1 Some Definitions and Concepts
7.2 Ionization of Tyrosine
7.3 Macroscopic and Microscopic Protonation Equilibria of DOPA
7.4 General Comments and Conclusions
8 Determination of Stability Constants and Species Concentration of Complex Systems
8.1 A Mixed-Ligand Binuclear Dioxygen System
8.2 Non-aqueous Solvents
8.3 Complex Multicomponent Systems
8.4 Equilibrium with Solid Phases
8.5 Equilibrium Involving Hydrolytic Species
8.6 Species Distributions of Hydroxo and Fluoro Complexes of Al(III)
9 Critical Stability Constants and Their Selection
9.1 General Criteria
Essential experimental control
Selection of a constant from a number of reported values
Reliability of investigator
Single investigator
Bibliography
9.2 Examples of Critical Data Selection
9.3 Need for Additional Critical Constants
10 Development of a Complete Critical Metal Complex Data Base
10.1 Introduction
10.2 Linear Stability Constant Correlations
10.3 Estimation of Stability Constants Not Measured Experimentally
10.4 Metal Speciation in Sea Water With and Without Added Ligands
Appendix I
Program PKAS
Appendix II
Program Best
Appendix III
Program SPE
Appendix IV
Scientific and Technical Fields Requiring Stability Data
Appendix V
Minimum Requirements

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