Linearized model for error-compensated kinetic determinations without prior knowledge of reaction order or rate constant.
This paper describes a new algorithm for calculation of reaction orders, rate constants, and initial and final values of detector signal from several signal vs time data points. The algorithm utilizes a linearized version of the rate equation and is intended primarily to provide initial estimates of these kinetic parameters for other curve-fitting methods. However, under some circumstances, the linearized model can provide sufficiently reliable results that subsequent processing by other methods is not needed. Simulated data with different levels of superimposed noise, data densities, reaction orders, rate constants, and signal change are used to evaluate the algorithm both for its primary purpose of providing initial estimates for other curve-fitting methods and as an independent method. Results are compared with those obtained with a nonlinear least-squares method and two initial-rate methods. The new algorithm provides less reliable results than those obtained by the nonlinear curve-fitting method for some situations (e.g. reaction orders greater than two, low data densities) but has the advantage that it is applicable to reaction orders at and near unity where the nonlinear method to which it is compared fails.
Larsson
J A
JA
Pardue
H L
HL
D007700:Kinetics; D008956:Models, Chemical