Characteristics of polarographic catalytic waves observed with bovine-serum albumin: kinetic or diffusion control

Conditions are described under which the catalytic Brdicka currents observed in ammoniacal buffer solutions containing cobalt(III) hexammine chloride or cobalt(II) and very little bovine-serum albumin (0.1-0.2 muM) are purely kinetically controlled. Under these conditions the kinetic current at pH 9.3-10.3 exhibits a sharp maximum followed by a decrease of the current to a well-defined minimum. The maximum and minimum are eliminated in the presence of 5 mM or more concentrated calcium chloride when a short plateau occurs at the potential of the maximum followed by a well-defined second wave. Both currents are kinetically controlled. When the albumin concentration is 2 muM or greater, the kinetic currents approach diffusion control, the rate of diffusion of cobalt(III) or (II) being close to rate determining. Under these conditions the currents become proportional to the cobalt(III) or (II) concentration in the concentration range between 25 and 200 muM.