Spectrophotometric evaluation of stability constants of 1: 1 weak complexes from continuous variation data

A bilogarithmic hyperbolic cosine method for the spectrophotometric evaluation of stability constants of 1:1 weak complexes from continuous variation data has been devised and applied to literature data. A weighting scheme, however, is necessary in order to take into account the transformation for linearization. The method may be considered a useful alternative to methods in which one variable is involved on both sides of the basic equation (i.e. Heller and Schwarzenbach, Likussar and Adsul and Ramanathan). Classical least squares lead in those instances to biased and approximate stability constants and limiting absorbance values. The advantages of the proposed method are: the method gives a clear indication of the existence of only one complex in solution, it is flexible enough to allow for weighting of measurements and the computation procedure yield the best value of log beta(11) and its limit of error. The agreement between the values obtained by applying the weighted hyperbolic cosine method and the non-linear regression (NLR) method is good, being in both cases the mean quadratic error at a minimum. (c) 2006 Elsevier B.V. All rights reserved.