SCOGS2

A Nonlinear Least-Squares Program for the Evaluation of Formation Constants of Metal Complexes
  • D. D. Perrin
  • H. Stunzi
Chapter
Part of the Modern Inorganic Chemistry book series (MICE)

Abstract

Bjerrum’s enbar (n̅) approach,(1) provided a useful tool in studying quantitatively the stepwise formation of mononuclear complexes, but this method failed if polynuclear, protonated, or hydrolyzed species were present. The use of electronic digital computers overcame this barrier: programs were developed in which formation constants were sought by minimizing the sums of squares of residuals in “analytical hydrogen ion concentrations.” The residual is the difference between the experimental value and the amount calculated from the pH and the concentrations of all species using computed constants. (a general discussion of least-squares calculations has been presented by Wentworth.(2))

Keywords

Stability Constant Formation Constant Ligand Concentration Numerical Differentiation Main Program 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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References

  1. 1.
    J. Bjerram, Metal Ammine Formation in Aqueous Solution, Haase, Copenhagen (1941, reprinted 1957).Google Scholar
  2. 2.
    W. E. Wentworth, Rigorous Least Squares Adjustment. Application to Some Non-Linear Equations, I., J. Chem. Educ. 42, 96–103; II, 162–167 (1965).CrossRefGoogle Scholar
  3. 3.
    L. G. Sillén, High-Speed Computer as a Supplement to Graphical Methods. I. Functional Behaviour of the Error Square Sum, Acta Chem. Scand. 16, 159–172 (1962).CrossRefGoogle Scholar
  4. 4.
    N. Ingri and L. G. Sillén, High-Speed Computers as a Supplement to Graphical Methods. II. Some Computer Programs for Studies of Complex Formation Equilibria, Acta Chem. Scand. 16, 173–191 (1962).CrossRefGoogle Scholar
  5. 5.
    L. G. Sillén, High-Speed Computers as a Supplement to Graphical Methods. III. Twist Matrix Methods for Minimising the Error-square Sum in Problems with Many Unknown Constants, Acta Chem. Scand. 18, 1085–1098 (1964).CrossRefGoogle Scholar
  6. 6.
    N. Ingri and L. G. Sillén, High-Speed Computers as a Supplement to Graphical Methods. IV. An ALGOL version of LETAGROP VRID, Ark. Kemi 23, 97–121 (1964).Google Scholar
  7. 7.
    R. S. Tobias and M. Yasuda, Computer Analysis of Stability Constants in Three-Component Systems with Polynuclear Complexes, Inorg. Chem. 2, 1307–1310 (1963).CrossRefGoogle Scholar
  8. 8.
    D. D. Perrin and I. G. Sayce, Stability Constants of Polynuclear Mercaptoacetate Complexes of Nickel and Zinc, J. Chem. Soc. (A) 1967, 82–89.Google Scholar
  9. 9.
    D. D. Perrin and I. G. Sayce, Computer Calculation of Equilibrium Concentrations in Mixtures of Metal Ions and Complexing Species, Talanta 14, 833–842 (1967).CrossRefGoogle Scholar
  10. 10.
    D. D. Perrin, I. G. Sayce, and V. S. Sharma, Mixed Ligand Complex Formation by Copper (II) Ion, J. Chem. Soc (A) 1967, 1755–1759.Google Scholar
  11. 11.
    I. G. Sayce, Computer Calculation of Equilibrium Constants of Species Present in Mixtures of Metal Ions and Complexing Agents, Talanta 15, 1397–1411 (1968).CrossRefGoogle Scholar
  12. 12.
    I. G. Sayce, Computer Calculation of Equilibrium Constants by Use of the Program SCOGS: A Correction, Talanta 18, 653 (1971).CrossRefGoogle Scholar
  13. 13.
    I. G. Sayce and V. S. Sharma, Computer Calculation of Equilibrium Constants using Program SCOGS. A Further Modification, Talanta 19, 831 (1972).CrossRefGoogle Scholar
  14. 14.
    H. Stunzi, Copper Complexation by Isatin ß-Thiosemicarbazones in Aqueous Solution, Aust. J. Chem. 34, 2549–2561 (1981).CrossRefGoogle Scholar
  15. 15.
    G. Anderegg, Die Anwendung der elektronishchen Rechenmaschine zur Lösung einiger Probleme der Komplexchemie, Helv. Chim. Acta 45, 901–907 (1962).CrossRefGoogle Scholar
  16. 16.
    H. Stunzi, Can Chelation be Important in the Antiviral Activity of Isatin β-Thiosemicarbazones?, Aust. J. Chem., 35, 1145–1155 (1982).CrossRefGoogle Scholar
  17. 17.
    N. K. Davidenko and P. A. Manorik, Mixed-ligand Complexes of Copper(II) and Nickel (II) with Nucleotides and Glycine, Zh. Neorg. Khim. 25, 437–444 (1980).Google Scholar
  18. 18.
    O. Yamauchi, T. Takaba, and T. Sakurai, Solution Equilibria of Histidine-containing Ternary Amino Acid-Copper(II) Complexes in 20% Dioxane-Water, Bull. Chem. Soc. Jpn 53, 106–111 (1980).CrossRefGoogle Scholar
  19. 19.
    N. K. Davidenko, P. A. Manorik, and K. B. Yatsimirskii, Ternary Complexes of the Ions of 3 d Transition Metals with Adenine Nucleotides and Histidine, Zh. Neorg. Khim. 25, 883–890 (1980).Google Scholar
  20. 20.
    B. Spiess, F. Arnaud-Neu, and M. J. Schwing-Weil, Behaviour of Uranium (VI) with some Cryptands in Aqueous Solution, Inorg. Nucl. Chem. Lett. 15, 13–16 (1979).CrossRefGoogle Scholar
  21. 21.
    R. W. Renfrew, R. S. Jamison, and D. C. Weatherburn, Aqueous Solution Equilibria Involving the Ligand 2,2,4-Trimethyl-l,5,9-triazacyclododecane and Nickel(II), Copper(II), and Zinc(II), Inorg. Chem. 18, 1584–1589 (1979).CrossRefGoogle Scholar
  22. 22.
    J. L. Colin and J. Pinart, Etude des chelates mercuriques de pyridyl 2,6-dimethanol, Bull. Soc. Chim. France 1, 7–10 (1979).Google Scholar
  23. 23.
    L. H. J. Lajunen, R. Petrola, P. Schildt, O. Korppi-Tominola, and O. Makitie, Complex Formation between Aluminium and 3-Hydroxy-7-sulpho-2-naphthoic Acid, Talanta 27, 75–78 (1980).CrossRefGoogle Scholar
  24. 24.
    D. J. Leggett and W. A. E. McBryde, General Computer Program for the Computation of Stability Constants from Absorbance Data, Anal Chem. 47, 1065–1070 (1975).CrossRefGoogle Scholar
  25. 25.
    I. Nagypal, General Method for the Calculation of the Concentration, Distribution and Formation Constants in Chemical Equilibrium Systems, Magy. Kem. Foly. 80, 49–55 (1974).Google Scholar
  26. 26.
    D. J. Leggett, POLAG—A General Computer Program to Calculate Stability Constants from Polarographic Data, Talanta 27, 787–793 (1980).CrossRefGoogle Scholar
  27. 27.
    A Sabatini and A. Vacca, A New Method for Least-Squares Refinement of Stability Constants, J. Chem. Soc. (Dalton) 1972, 1693–1698.Google Scholar
  28. 28.
    T. B. Field and W. A. E. McBryde, Determination of Stability Constants by pH Titrations: A Critical Examination of Data Handling, Can. J. Chem. 56, 1202–1211 (1978).CrossRefGoogle Scholar
  29. 29.
    P. Gans and A. Vacca, Application of the Davidon-Fletcher-Powell Method to the Calculation of Stability Constants, Talanta 21, 45–51 (1974).CrossRefGoogle Scholar
  30. 30.
    H. Stunzi and D. D. Perrin, Stability Constants of Metal Complexes of Phosphonoacetic Acid, J. Inorg. Biochem. 10, 309–316 (1979).CrossRefGoogle Scholar
  31. 31.
    H. Stunzi, R. L. N. Harris, D. D. Perrin, and T. Teitei, Stability Constants for Metal Complexation by Isomers of Mimosine and Related Compounds, Aust. J. Chem. 33, 2207–2220 (1980).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1985

Authors and Affiliations

  • D. D. Perrin
    • 1
  • H. Stunzi
    • 1
  1. 1.Medical Chemistry Group, The John Curtin School of Medical ResearchThe Australian National UniversityCanberra CityAustralia

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