KINETIC CATALYTIC ANALYSIS - EXTENDED THEORY OF CONTINUOUS ADDITION OF CATALYST TO A REFERENCE SOLUTION FOR NONEQUAL REFERENCE AND SAMPLE INITIAL SIGNALS
G. Lopezcueto et al., KINETIC CATALYTIC ANALYSIS - EXTENDED THEORY OF CONTINUOUS ADDITION OF CATALYST TO A REFERENCE SOLUTION FOR NONEQUAL REFERENCE AND SAMPLE INITIAL SIGNALS, Analytica chimica acta, 335(3), 1996, pp. 185-199
The theory of kinetic catalytic determinations by continuous addition
of a catalyst to a reference solution is extended to the general case
where the initial signals used for monitoring the reaction kinetics in
the sample and reference solutions may or may not be the same. A gene
ralized treatment for pseudo-first-order reactions is developed and di
scussed. Two intersection times which could be either positive or nega
tive, real or imaginary, have to be considered. When real and positive
, the intersection times are used as the input analytical variable. A
suitable nonempirical algorithm to determine the concentration of the
analyte without resorting to a calibration plot is derived, and its va
lidity is evaluated by means of experimental as well as simulated dete
rminations. Conditions have been chosen to cover a wider range. The ef
fects of the relative values of the sample and reference initial signa
ls as well as dilution of the reference solution on the determination
error are discussed.