极谱过程温度效应的研究(Ⅲ)——催化反应速率常数和反应活化能的测定

Investigation on the Temperature Effect in the Polarographic Processes (Ⅲ)--The Determination of the Rate Constant and Activation Energy of Catalytic Reactions

催化反应在极谱分析中的应用及反应速率常数的测定已有报道。通常根据Koutecky公式计算催化反应速率常数,而反应活化能则由不同温度下测定的速率常数,按照Arrhenius公式计算。我们根据前文提出的可逆、不可逆、准可逆、动力和催化过程各种极谱电流——温度关系的普遍方程式,测定了Ti(Ⅳ)-H_(2)SO_(4)H_(2)C2O_(4)-KClO_(3)、Mo(Ⅳ)-H_(2)SO_(4)-NaNO_(3)、Mo(Ⅵ)-H_(2)SO_(4)-NH4NO_(3)体系催化反应速率常数和反应活化能(或表观活化能),结果令人满意。

A new, simple method for the determination of the rate constant, kf, and the activation energy, Ea, of catalytic reaction on the basis of the dependence of catalytic current on the temperature has been developed. The experimental results for several catalytic systems are in a good agreement with those obtained by other methods in the literatures. The new value of kf for the system of Mo(Ⅵ)-H_(2)SO_(4)-NH4NO_(3) was determined. The Ea for these studied systems were reported.