Computational Methods for the Determination of Formation Constants

Transcription

1 Computational Methods for the Determination of Formation Constants Edited by DAVID J. LEGGETT Dow Chemical USA Texas Division Freeport, Texas Plenum Press New York and London

2 Contents 1 The Determination of Formation Constants: An Overview of Computational Methods for Data Processing DAVID J. LEGGETT 1. Introduction 1 2. Direct Search and Univariate Methods Grid, Star, and Composite Designs Fibonacci and Golden Section Hooke and Jeeves, Simplex Quadratic and Cubic Interpolation Methods Summary 4 3. Least-Squares Methods Newton-Raphson Gauss-Newton Levenberg and Marquardt Objective Function Differentiation Other Methods Curve Fitting HOSKMethod Summary References 13 2 Strategies for Solution Equilibria Studies with Specific Reference to Spectrophotometry JOSEF HAVEL and MILAN MELOUN 1. Elucidation of the Equilibrium Model Introduction Experimental Techniques 21 xi

3 xä 1.3. Data Analysis Adequacy of the Selected Model Determination of pk a 's from Absorbance ph Studies Introduction Measurement of Absorbance vs. ph Data Preliminary Data Handling Curve-Fitting Analysis of the Absorbance vs. ph Curve Matrix Regression Analysis Thermodynamic Dissociation Constants Initial Methods for Investigating Complex Equlibria Introduction Graphical Analysis of Absorbance vs. ph Curves Analysis of Absorbance vs. ph Curves Using PRCEK Continuous Variation Techniques Mole Ratio Techniques Method of Corresponding Solutions Conclusions References 34 3 MAGEC: A Program for the Definite Calibration of the Glass Electrode PETER M. MAY and DAVID R. WILLIAMS 1. Introduction Descrition of the Program MAGEC Theory Use of MAGEC for Electrode Calibration Conclusions References Instructions for the Use of MAGEC Basic Principles Data Input Requirements Presentation of the Program Listing of MAGEC Input Data 70 4 SCOGS2: A Nonlinear Least-Squares Program for the Evaluation of Formation Constants of Metal Complexes D.D. PERRIN and H. STUNZI 1. Introduction Description of the Program SCOGS General 72

4 xiii 2.2. MAIN Program of SCOGS2-SCOGSH Option SCOGSM Option Subroutine COGSNR Limits of SCOGS Some Examples of the Use of SCOGS Using SCOGS2 to Build an Equilibrium-Model References Instructions for SCOGS Presentation of the Program Listing of SCOGS InputData Data for the System Copper(II)-Phosphonoacetate Data for the System Copper(II)-Histidine (3-hydroxo-lmethylpyridin-4-(lH)-one) Data for the System Copper-p-Sulfonatobenzaldehyde thiosemicarbazone 97 5 MINIQUAD and MIQUV: Two Approaches for the Computation of Formation Constants from Potentiometrie Data ALBERTO VACCA and ANTONIO SABATINI 1. Introduction Description of the Programs Program MINIQUAD ProgramMIQUV Comments References Instructions for the Programs Details of the Input File Description of the Output Presentation of the Programs Listing of the MINIQUAD InputData Listing of MIQUV InputData SQUAD: Stability Quotients from Absorbance Data DAVID J. LEGGETT 1. Introduction Description of the Program SQUAD Mathematical Algorithms 160

5 xiv 2.2. Principles of Data Input Suggestions for the Use of SQUAD Modifications to SQUAD References Instructions for SQUAD Introduction Details of the Data Input Presentation of the Program Listing of SQUAD Input Data General Computer Programs for the Determination of Formation Constants from Various Types of Data JOSEF HAVEL and MILAN MELOUN 1. Multiparametric Curve Fitting Using ABLET Introduction The "Pit-Mapping" Technique Description of the Program ABLET Routines Specific to the Model Basic Routines of the ABLET Family Data Input Instructions Introduction Data Input Requirements Algorithmic and Heuristic Strategies Listing of ABLET MRLET: Formation Constants of M m L from Mole Ratio Data Model Formulation Description of MRLET Data Input Requirements Presentation of MRLET Listing of MRLET InputData POLET: Formation Constants from Potentiometrie Data Model Formulation Description of POLET Data Input Requirements Presentation of POLET Listing of POLET InputData 268

6 xv 4. EXLET: Formation Constants and Related Parameters from Spectrophotometric Extraction Data Model Formulation Description of EXLET Data Input Requirements Presentation of EXLET Listing of EXLET InputData Other Programs of the ABLET Family DHLET: Estimation of Thermodynamic Dissociation Constants and Extended Debye-Huckel Parameters DCLET: Estimation of Successive Dissociation Constants from ph-absorbance Data NCLET: Evaluation of Competitive Equilibria in a Chelatometric Titration Listing of MAIN, DATA, VBBE, and SKRIK for NCLET References PSEQUAD: A Comprehensive Program for the Evaluation of Potentiometrie and/or Spectrophotometric Equilibrium Data Using Analytical Derivatives L. ZEKANY and I. NAGYPAL 1. Introduction Description of the Program PSEQUAD Calculation of the Free Concentrations Refinement of the Formation Constants and/or the Molar Absorptivities Model Selection by PSEQUAD Estimation of Parameter Correlation Program Limits References Program Instructions Introduction Input of Potentiometrie and/or Photometrie Data Data Processing Options and Instructions Presentation of the Program Listing of PSEQUAD InputData Experimental Details Data for the System Copper(II)-Nitriloacetic Acid Output from PSEQUAD 352

7 xvi 9 STBLTY: Methods for Construction and Refinement of Equilibrium Models ALEX AVDEEF 1. Introduction Program Descripticn Computer Generation of Potentiometrie Data and Distribution of Species Data Reduction and Bjerrum Analysis Free-Ion Concentration in Solution (FICS) Methodology Average Composition of Species in Solution (ACSS) Methodology Linear Least-Squares Refinement of Constants Nonlinear Least-Squares Refinement of Constants: ph Data Nonlinear Least-Squares of Constants: pm, pl, and ph Data Nonlinear Least-Squares Refinement of the Total Concentrations Analysis of Variance Acknowledgments References Description of Batch Input Protocol FANTASY CALCULATION Instructions for Data Input Input Data for FANTASY CALCULATION DATA REDUCTION Instructions for Data Input Input Data for DATA REDUCTION VARIATION PX FROM VARIATION STOICHIOMETRIC COEFS Instructions for Data Input Input Data for VARIATION, PX FROM VARIATION, and STOICHIOMETRIC COEFS LINEAR LS REFINE NONLINEAR LS REFINE Instructions for Data Input Input Data for NONLINEAR LS REFINE ANALYSIS OF VARIANCE Instructions for Data Input Input Data for ANALYSIS VARIANCE Source Listing of STBLTY 413 INDEX 475