The oxidation of formic acid bybis-(2,2′-bipyridyl)copper(II) permanganate (BBCP) is first order with respect to BBCP. The order with respect to formic acid is less than one in the absence of perchloric acid whereas in the presence of perchloric acid, it is more than one but less than two. Thus in both the cases Michaelis-Menten type kinetics were observed with respect to formic acid. The overall formation constants for the formic acid-BBCP complexes and their rates of decomposition have been evaluated. Thermodynamic parameters for complex formation and the activation parameters for their decomposition have also been calculated. The hydrogen-ion dependence has the formkobs=a+b[H+]+c[H+]2. The oxidation of deuterioformic acid showed the presence of a primary kinetic isotope effect (kH/kD≈4). An increase in the amount of acetic acid in the solvent mixture, acetic acid and water, increases the rate. The addition of 2,2′-bipyridine and acrylonitrile has no effect on the rate. Suitable mechanisms have been proposed.
Volume 135, 2023
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