CORRELATION-ANALYSIS OF COMPLEX KINETIC SYSTEMS - A NEW SCHEME FOR UTILIZING SENSITIVITY COEFFICIENTS

A procedure for designing and evaluating kinetic experiments on complex chemical systems is presented. This procedure uses he temporal integral of products of sensitivity coefficients (which may be calculated by standard methods) (1) to calculate the relative importance of reactions affecting the kinetic behavior of a specific observable and (2) to evaluate the correlation between any of the above reactions. The advantages of this procedure are that it is directly related to the analysis of experimental data, conceptually simple, easy to implement, and it provides a quantitative means for assessing the relative accuracy of different experiments. In addition, it provides a new, efficient, and systematic method for calculating the correlation between reactions and determines how the uncertainties in the rate coefficients of these reactions propagate in an analysis of experimental errors We illustrate the essential features of the approach by analyzing recent measurements of the rate coefficients for H-2 + M 2H + M and H + O2 OH + O [J. Chem. Phys. 96, 1077 (1992)].