Kinetics of alcohol oxidation by chloropentamine cobalt(III) chloride in NaOH medium
was investigated via pseudo-first order kinetics using a uv-1800 Shimadzu spectrophotometer
with a thermostated cell compartment and interfaced with a computer. The rate was first order with
respect to [oxidant] and [alcohol] and zero order in [OH-]. Variation of ionic strength did not have
any significant influence on the rate of oxidation, indicating that a non-ionic species is involved in
the rate limiting step. Addition of reaction mixture to aqueous acrylonitrile solution did not initiate
polymerization, showing absence of free radicals. Michaelis-Menten plot showed the presence of
an intermediate complex. Oxidation products were identified from spectral studies and Rf values.
Activation parameters were evaluated from the values obtained from temperature studies. Negative
activation entropy is indicative of ordered transition state for the reaction and same values of
activation free energy shows a common mechanism for the reaction. Therefore, based on the
kinetic results, reaction stoichiometry and oxidation products, a suitable mechanism was proposed.
Keywords: Chloropentamine cobalt(III) chloride, Alcohol, Oxidation, Kinetics and Mechanism.
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