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Abstract
The kinetics of anation of cis-diaquobis(1,3-diaminopropane) cobalt(III) by oxalic acid and bioxalate anion have been studied at 35°, 40° and 45°C, I=1.0 M(NaClO4). The observed rate law for the formation of Co(tmd)2C2O+ 4,
is valid in the range of [Ox]T=0.03–0.50 M, pH=0.3–2.03. The anation rate constants, k1 and k2, for cis-{Co(tmd)2(OH2)3+ 2, H2C2O4) and cis-{Co(tmd)2(OH2)3+ 2, HC2O4-] ion pairs respectively are found to be virtually the same (k1=10.7 × 10−4 sec−1 and k2=11.0 × 10−4 sec−1 at 40°C). Temperature independent oxalic acid and bioxalate ion-pair association constants (Q1 and Q2) are 1.7(±0.3)M−1 and 11.5(±0.7)M−1, respectively. The activation enthalpy and entropy for k1 and k2 paths are 122.6 kJ mol−1 89.5 JK−1 mol−1 and 103.8 kJ mol−1, 29.3 JK−1 mol−1, respectively. The anation of cis-{Co(tmd)2(OH2)3+ 2, X} ion pairs (X=H2C2O4 or HC2O− 4) is believed to involve Id mechanism. The reaction is catalysed by NO− 3.