Abstract
The Bjerrum ΔKOH method for determining the degree of formation ( n ¯ ) from the titration curves of a ligand with and without metals is derived without approximations. The Calvin and Wilson method is rederived in a form which allows easy comparison between the values calculated by each method. The advantages of the n ¯ comparison method are discussed. Thermodynamic dissociation constants and stoichiometric biligand stability constants are calculated for five tetracycline analogs. Contrary to previous work, the biologically inactive tetracycline derivatives, 4-epi-chlortetracycline and 4-epi-anhydrotetracycline, were found to form 2:1 complexes with cupric ions. The choice of methods for the calculation of the stability constants from n ¯ and [HT−] potentiometric data is discussed. The Bjerrum ΔKOH method for determining the degree of formation ( n ¯ ) from the titration curves of a ligand with and without metals is derived without approximations. The Calvin and Wilson method is rederived in a form which allows easy comparison between the values calculated by each method. The advantages of the n ¯ comparison method are discussed. Thermodynamic dissociation constants and stoichiometric biligand stability constants are calculated for five tetracycline analogs. Contrary to previous work, the biologically inactive tetracycline derivatives, 4-epi-chlortetracycline and 4-epi-anhydrotetracycline, were found to form 2:1 complexes with cupric ions. The choice of methods for the calculation of the stability constants from n ¯ and [HT−] potentiometric data is discussed.
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