THE EXTRAPOLATION OF RATE CONSTANTS FOR REACTION OF O((delta)p) WITH KETONES USING TRANSITION-STATE THEORY

Conventional transition-state theory is used for extrapolating rate constant of reactions of O(P-3) atom with ketones to temperature range 200-2000K. Estimations of structural properties of the activated complex necessary for calculating free energy of activation are presented. Expressions of the rate constant with three parameters ore derived. These are as follows (unit(1)cm(-3).molecule(-1).s(-1)). k = 5.34 x 10-(20)T(2.30)exp ( - 12.4/RT) (for butanone) k = 6.64 x 10(-20)T(2.37)exp ( - 14.1/RT) (for 3-pentagone) k = 3.54 x 10(-22)T(3.68)exp ( -0.29/RT) (for iso-butyl ketone) k = 1.29 x 10(-18)T(2.60)exp ( -16.6/RT) (for 3,3-2 methyl-2-butanone) k = 9.47 x 10(-21)T(3.23)exp ( -9.71/RT) (for c-pentagone) k = 5.23 x 10(-20)T(3.16)exp ( -9.92/RT) (for c-hexagone) k((a)) =1.87 x 10(-10)T(2.32)exp ( -29.5/RT) (for acetone) Note: (a) the frequency of C.H.O bend vibration is 200 cm-1. (b) the frequency of C.H.O bend vibration is 700 cm(-1).