An activation energy of Ea = 213.73 kJ tool d has been determined for the thermal decomposition of SmC204C1 to SmOCI, CO and CO2. The result is predictable on the basis of the Kahwa-Mulokozi expression + for the activation energy and its extended interpretation.The basis for our mechanistic interpretation of the thermal decomposition kinetics of oxalate is the Kahwa-Mulokozi expression for the activation energy
An activation energy Ea = 195 kJ mol-1 has been determined for the thermal decomposition of NdC204C1 to NdOCI with simultaneous expulsion of CO and CO2. As compared with the value (127 kJ mo1-1) predicted by the Kahwa-Mulokozi empirical expression (i) + for Ln2(C204)3 (Ln = light lanthanide), the presence of C1-in the coordination polyhedron appreciably raises the activation energy, which is consistent with a corresponding increase in the covalent strength of the Ln-oxalate bond. The same conclusion regarding the strength of this bond is drawn from a study of the infrared spectrum.Mechanistically, the breaking of the Ln-oxalate bond is suggested to occur in the kinetic ratedetermining step.The thermal decomposition behaviour of the lanthanide oxalates and their derivatives LnC204X (X = C1 or Br) has been widely investigated [1-37]. The course of the reaction displays pronounced sensitivity to the nature of the bonding, not only with regard to the metal-oxalate interaction, but also as concerns the donor property of X. Those observations are explained in a neat theoretical framework. decomposition of oxalate can proceed via three alternativeThe thermal pathways:
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