Computational Methods for the Determination of Formation Constants

1 The Determination of Formation Constants: An Overview of Computational Methods for Data Processing.- 1. Introduction.- 2. Direct Search and Univariate Methods.- 2.1. Grid, Star, and Composite Designs.- 2.2. Fibonacci and Golden Section.- 2.3. Hooke and Jeeves, Simplex.- 2.4. Quadratic and Cubic Interpolation Methods.- 2.5. Summary.- 3. Least-Squares Methods.- 3.1. Newton-Raphson.- 3.2. Gauss-Newton.- 3.3. Levenberg and Marquardt.- 3.4. Objective Function Differentiation.- 4. Other Methods.- 4.1. Curve Fitting.- 4.2. HOSK Method.- 5. Summary.- 6. References.- 2 Strategies for Solution Equilibria Studies with Specific Reference to Spectrophotometry.- 1. Elucidation of the Equilibrium Model.- 1.1. Introduction.- 1.2. Experimental Techniques.- 1.3. Data Analysis.- 1.4. Adequacy of the Selected Model.- 2. Determination of pKa’s from Absorbance pH Studies.- 2.1. Introduction.- 2.2. Measurement of Absorbance vs. pH Data.- 2.3. Preliminary Data Handling.- 2.4. Curve-Fitting Analysis of the Absorbance vs. pH Curve.- 2.5. Matrix Regression Analysis.- 2.6. Thermodynamic Dissociation Constants.- 3. Initial Methods for Investigating Complex Equlibria.- 3.1. Introduction.- 3.2. Graphical Analysis of Absorbance vs. pH Curves.- 3.3 Analysis of Absorbance vs. pH Curves Using PRCEK.- 3.4. Continuous Variation Techniques.- 3.5. Mole Ratio Techniques.- 3.6. Method of Corresponding Solutions.- 4. Conclusions.- 5. References.- 3 MAGEC: A Program for the Definite Calibration of the Glass Electrode.- 1. Introduction.- 2. Descrition of the Program MAGEC.- 2.1. Theory.- 2.2. Use of MAGEC for Electrode Calibration.- 2.3. Conclusions.- 3. References.- 4. Instructions for the Use of MAGEC.- 4.1. Basic Principles.- 4.2. Data Input Requirements.- 5. Presentation of the Program.- 5.1. Listing of MAGEC.- 5.2. Input Data.- 4 SCOGS2: A Nonlinear Least-Squares Program for the Evaluation of Formation Constants of Metal Complexes.- 1. Introduction.- 2. Description of the Program SCOGS2.- 2.1. General.- 2.2. MAIN Program of SCOGS2—SCOGSH Option.- 2.3. SCOGSM Option.- 2.4. Subroutine COGSNR.- 2.5. Limits of SCOGS2.- 2.6. Some Examples of the Use of SCOGS.- 2.7. Using SCOGS2 to Build an Equilibrium-Model.- 3. References.- 4. Instructions for SCOGS2.- 5. Presentation of the Program.- 5.1. Listing of SCOGS2.- 5.2. Input Data.- 5.2.1. Data for the System Copper(II)-Phosphonoacetate.- 5.2.2. Data for the System Copper(II)-Histidine (3-hydroxo-1-methylpyridin-4-(1H)-one).- 5.2.3. Data for the System Copper-p-Sulfonatobenzaldehyde thiosemicarbazone.- 5 MINIQUAD and MIQUV: Two Approaches for the Computation of Formation Constants from Potentiometric Data.- 1. Introduction.- 2. Description of the Programs.- 2.1. Program MINIQUAD.- 2.2. Program MIQUV.- 2.3. Comments.- 3. References.- 4. Instructions for the Programs.- 4.1. Details of the Input File.- 4.2. Description of the Output.- 5. Presentation of the Programs.- 5.1. Listing of the MINIQUAD.- 5.1.1. Input Data.- 5.2. Listing of MIQUV.- 5.2.1. Input Data.- 6 SQUAD: Stability Quotients from Absorbance Data.- 1. Introduction.- 2. Description of the Program SQUAD.- 2.1. Mathematical Algorithms.- 2.2. Principles of Data Input.- 2.3. Suggestions for the Use of SQUAD.- 2.4. Modifications to SQUAD.- 3. References.- 4. Instructions for SQUAD.- 4.1. Introduction.- 4.2. Details of the Data Input.- 5. Presentation of the Program.- 5.1. Listing of SQUAD.- 5.2. Input Data.- 7 General Computer Programs for the Determination of Formation Constants from Various Types of Data.- 1. Multiparametric Curve Fitting Using ABLET.- 1.1. Introduction.- 1.2. The “Pit-Mapping” Technique.- 1.3. Description of the Program ABLET.- 1.3.1. Routines Specific to the Model.- 1.3.2. Basic Routines of the ABLET Family.- 1.4. Data Input Instructions.- 1.4.1. Introduction.- 1.4.2. Data Input Requirements.- 1.4.3. Algorithmic and Heuristic Strategies.- 1.5. Listing of ABLET.- 2. MRLET: Formation Constants of MmLn from Mole Ratio Data.- 2.1. Model Formulation.- 2.2. Description of MRLET.- 2.3. Data Input Requirements.- 2.4. Presentation of MRLET.- 2.4.1. Listing of MRLET.- 2.4.2. InputData.- 3. POLET: Formation Constants from Potentiometric Data.- 3.1. Model Formulation.- 3.2. Description of POLET.- 3.3. Data Input Requirements.- 3.4. Presentation of POLET.- 3.4.1. Listing of POLET.- 3.4.2. Input Data.- 4. EXLET: Formation Constants and Related Parameters from Spectrophotometric Extraction Data.- 4.1. Model Formulation.- 4.2. Description of EXLET.- 4.3. Data Input Requirements.- 4.4. Presentation of EXLET.- 4.4.1. Listing of EXLET.- 4.4.2. InputData.- 5. Other Programs of the ABLET Family.- 5.1. DHLET: Estimation of Thermodynamic Dissociation Constants and Extended Debye-Huckel Parameters.- 5.2. DCLET: Estimation of Successive Dissociation Constants from pH-Absorbance Data.- 5.3. NCLET: Evaluation of Competitive Equilibria in a Chelatometric Titration.- 5.3.1. Listing of MAIN, DATA, VBBE, and SKRIK for NCLET.- 6. References.- 8 PSEQUAD: A Comprehensive Program for the Evaluation of Potentiometric and/or Spectrophotometric Equilibrium Data Using Analytical Derivatives.- 1. Introduction.- 2. Description of the Program PSEQUAD.- 2.1. Calculation of the Free Concentrations.- 2.2. Refinement of the Formation Constants and/or the Molar Absorptivities.- 2.3. Model Selection by PSEQUAD.- 2.4. Estimation of Parameter Correlation.- 2.5. Program Limits.- 3. References.- 4. Program Instructions.- 4.1. Introduction.- 4.2. Input of Potentiometric and/or Photometric Data.- 4.3. Data Processing Options and Instructions.- 5. Presentation of the Program.- 5.1. Listing of PSEQUAD.- 5.2. Input Data.- 5.2.1. Experimental Details.- 5.2.2. Data for the System Copper(II)-Nitriloacetic Acid.- 5.3. Output from PSEQUAD.- 9 STBLTY: Methods for Construction and Refinement of Equilibrium Models.- 1. Introduction.- 2. Program Description.- 2.1. Computer Generation of Potentiometric Data and Distribution of Species.- 2.2. Data Reduction and Bjerrum Analysis.- 2.3. Free-Ion Concentration in Solution (FICS) Methodology.- 2.4. Average Composition of Species in Solution (ACSS) Methodology.- 2.5. Linear Least-Squares Refinement of Constants.- 2.6. Nonlinear Least-Squares Refinement of Constants: pH Data.- 2.7. Nonlinear Least-Squares of Constants: pM, pL, and pH Data.- 2.8. Nonlinear Least-Squares Refinement of the Total Concentrations.- 2.9. Analysis of Variance.- 2.10. Acknowledgments.- 3. References.- 4. Description of Batch Input Protocol.- 4.1. Fantasy Calculation.- 4.1.1. Instructions for Data Input.- 4.1.2. Input Data for Fantasy Calculation.- 4.2. Data Reduction.- 4.2.1. Instructions for Data Input.- 4.2.2. Input Data for Data Reduction.- 4.3. Variation.- 4.4 PX From Variation.- 4.5 Stoichiometric Coefs.- 4.5.1. Instructions for Data Input.- 4.5.2. Input Data for Variation, PX From Variation, and Stoichiometric COEFS.- 4.6. Linear LS Refine.- 4.7. Nonlinear LS Refine.- 4.7.1. Instructions for Data Input.- 4.7.2. Input Data for Nonlinear LS Refine.- 4.8. Analysis of Variance.- 4.8.1. Instructions for Data Input.- 4.8.2. Input Data for Analysis Variance.- 5. Source Listing of Stblty.