Constant-time integral method kinetic measurement

The rates of liquid-phase reactions can generally be obtained by measuring the time-dependent concentrations of reactants and/or products in a constant-volume batch reactor. From experimental data, the reaction kinetics can be analyzed either by the integration method or by the differential method ... 

Kinetic studies at several temperatures followed by application of the Arrhenius equation as described constitutes the usual procedure for the measurement of activation parameters, but other methods have been described. Bunce et al. eliminate the rate constant between the Arrhenius equation and the integrated rate equation, obtaining an equation relating concentration to time and temperature. This is analyzed by nonlinear regression to extract the activation energy. Another approach is to program temperature as a function of time and to analyze the concentration-time data for the activation energy. This nonisothermal method is attractive because it is efficient, but its use is not widespread. ... 

A chemical transformation depends on temperature, concentrations and time. The measurements are therefore generally carried out at a constant temperature and at different times. There is no method by which to directly measure the kinetic properties of a reactioa The measurement methods are most often performed by the measurement of quantities that are related to the extent or fractional extent versus time, and we thus obtain the integral curves. The derivation of these data with respect to time leads to the rate of transformation at any time and then to the different derivative curves. 

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