MOLECULAR-ORGANIZATION OF REAGENTS IN THE KINETICS AND CATALYSIS OF LIQUID-PHASE REACTIONS .6. PECULIARITIES OF THE TEMPERATURE DEPENDENCESOF THE RATE CONSTANTS FOR THE CATALYTIC REACTIONS OF URETHANE FORMATION
Yn. Chirkov et al., MOLECULAR-ORGANIZATION OF REAGENTS IN THE KINETICS AND CATALYSIS OF LIQUID-PHASE REACTIONS .6. PECULIARITIES OF THE TEMPERATURE DEPENDENCESOF THE RATE CONSTANTS FOR THE CATALYTIC REACTIONS OF URETHANE FORMATION, Kinetics and catalysis, 36(5), 1995, pp. 612-615
The temperature dependences of the rate constants for the reaction of
m-chloro-phenylisocyanate with n-butanol in heptane in the presence of
tributyltin acetate and acetic acid as catalysts are investigated, Th
e deviations from the Arrhenius equations are related to the parallel
reaction routes, whose contributions to the observed rate constant var
y with temperature due to the effect of the latter on the equilibrium
of the alcohol association. Considerable differences in the behavior o
f the temperature dependences of the observed rate constants for the n
oncatalytic and catalytic reactions stem from the fact that the latter
involves the monomeric alcohol form, which is virtually inactive in t
he noncatalytic reaction of urethane formation, but plays a crucial ro
le in the catalytic process, forming reactive complexes with the catal
yst.