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For some centuries, first order chemical rate constants were determinedmainly by a linear logarithmic plot of reagent concentration terms against timewhere the initial concentration was required, which is experimentally often achallenging task to derive accurate estimates. By definition, the rate constantwas deemed to be invariant and the kinetic equations were developed with thisassumption. A reason for these developments was the ease in which linear graphscould be plotted. Here, different methods are discussed that does not requireexact knowledge of initial concentrations and which require elementarynonlinear analysis and the ensuing results are compared with those derived fromthe standard methodology from an actual chemical reaction, with itsexperimental determination of the initial concentration with a degree ofuncertain. We verify experimentally our previous theoretical conclusion basedon simulation data [ J. Math . Chem {\bf 43} (2008) 976--1023,arXiv:physics/0608073] that the so called rate constant is never constant evenfor elementary reactions and that all the rate laws and experimentaldeterminations to date are actually averaged quantities over the reactionpathway. We conclude that nonlinear methods in conjunction with experimentscould in the future play a crucial role in extracting information of variouskinetic parameters.

Determination of Rate Constant of Chemical Reactions by Simple Numerical Nonlinear Analysis