Pj. Ogren et Jp. Hessler, SENSITIVITY AND CORRELATION-ANALYSIS OF THE PHYSICAL PARAMETERS IN ABSORPTION, 4-WAVE-MIXING, AND SCHLIEREN EXPERIMENTS, International journal of chemical kinetics, 27(7), 1995, pp. 719-738
Experimental data that are used to determine rate coefficients depend
not only upon reaction rates but also the physical properties of the m
easured species. Sensitivity coefficients are presented for the physic
al parameters of three general experimental techniques: a signal linea
rly dependent on the concentration of a species, a signal quadraticall
y dependent on concentration, and a schlieren signal, which depends up
on a bulk property of the system. With these, both the physical and ch
emical parameters of a model may be treated on a comparable basis. The
similarities and differences between these techniques are illustrated
in a simple example of radical formation via first-order precursor de
composition followed by second-order recombination. The results are th
en applied to two important examples: H-2 + O-2 and CH3 + CH3. In almo
st all cases, the experimental data contains more information about th
e physical parameters, such as the optical cross section, than the kin
etic rate coefficients. Furthermore, if a physical parameter is not pr
operly treated; strong correlations between it and rate coefficients w
ill introduce significant systematic biases in the rate coefficient. (
C) 1995 John Wiley and Sons, Inc.