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Abstract
Equilibria and kinetics of the 1 : 1 complex formation of TiIII with malonic acid and methylmalonic acid have been investigated at 15 °C, ionic strength I= 0.5 mol dm–3(LiCl). Spectrophotometric measurements yielded for the complex stability constant Kc=[TiL+]/[Ti3+][L2–] values of 3.4 × 106(malonic acid) and 4.0 × 106 dm3 mol–1(methylmalonic acid). The kinetics of the complex-formation process show simple behaviour within the acidity range [H+]= 0.05–0.30 mol dm–3, the apparent second-order rate constant being of the form ka=k[H+]. It is concluded that under these conditions only the reaction path Ti3++ HL– [graphic omitted] [TiL]++ H+ contributes to the complex formation, with k2= 4.2 × 105(malonic acid) and 3.2 × 105 dm3 mol–1 s–1(methylmalonic acid), respectively. Together with data obtained earlier, the results indicate an associativeinterchange mechanism for substitution at [Ti(H2O)6]3+.
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