Kinetics of degradation of diclofenac sodium in aqueous solution determined by a calorimetric method

An isothermal heat conduction microcalorimeter has been used to study the stability of diclofenac sodium both alone and its inclusion complex with beta-cyclodextrin in aqueous solution. The rates of heat evolved during degradation of diclofenac sodium have been measured by a highly sensitive microcalorimetric technique as function of concentration, pH and temperature. The calorimetric accessible data have been incorporated in the equations for determination of rate constants, change in enthalpy and order of reaction. The decomposition of diclofenac sodium both alone and its inclusion complex with beta-cyclodextrin in solution corresponds to a pseudo-first order reaction. The values of rate constants, k's at 338.15 K, (calculated from the variation of heat evolution with the time) for the degradation of diclofenac sodium at pH 5, 6, 7, 8 and its inclusion complex with beta-cyclodextrin at pH 7 are found to be 4.71 x 10(-4), 5.69 x 10(-4), 6.12 x 10(-)4, 6.57 x 10(-4) and 4.26 x 10(-4) h(-1) respectively. There is good agreement between calorimetric determined t(0.5) and literature values. It has been found that beta-cyclodextrin retards the degradation of diclofenac sodium. The kinetic parameters have been calculated for the reaction. The negative entropy of activation suggests the formation of an ordered transition state.