A kinetic investigation of the tris(4-morpholinecarbodithionato-S,S') cobalt(III) complex formation by the intralattice and interlattice reactions

Abstract

The kinetics of tris-(4-morpholinecarbodithionato-S,S) cobalt(III) formation by the intralattice and interlattice reactions of hexaaminecobalt(III) cation with dithiocarbamato anion was investigated under isothermal conditions. The intralattice reaction, conducted in the solid hexaaminecobalt(III) 4-morpholinecarbodithionate salt, proceeded well at temperatures of 50-80°C, conforming to the phase boundary Rn reaction mechanism (Ea = 92.6 kJ mol-1, A = 5.28 × 109 s-1). The interlattice reaction, conducted in the mixture of hexaaminecobalt(III) chloride and potassium 4-morpholinecarbodithionate powders, proceeded well at temperatures of 140-200° C. The effect of the particle size of the powders and of the powder packing pressure on the kinetic parameters were also investigated. In the first half of the reaction, the random nucleation F1 mechanism seems to operate (Ea = 200-265 kJ mol-1, A = 8.6 × 1018-3.6 × 1027s-1); later the diffusional mechanism prevails. In addition, a fast initial process in the interlattice reaction has been discovered and investigated at lower temperatures (80-115° C). It conforms to the random nucleation F1 reaction mechanism (Ea = 63 kJ mol-1, A = 1.6 × 105 s-1). © 1993.