A differential technique which is independent of initial conditions for calculating the rate constant of a second‐order reaction

It has been shown that experimental errors of the initial conditions of a second‐order reaction can cause erroneous results with the rate constant calculated directly from the differential or integrated rate expression. By means of a computer method, a differential technique has been developed so that precise initial reactant conditions are not necessary for calculating a second‐order rate constant if continuous measurements of a single reaction variable are available. The technique has been successfully applied to the data of Kistiakowsky and Lacher on the condensation of acrolein and butadiene.