4-(1,2-Diacetoxyethyl)pyridine and Its Chemical Properties

A kinetic study of the reaction of O(3P) with toluene

“…where E and A are the activation energy and preexponential factor of the reaction of oxygen with olefin, and subscripts, T, C , E, and T M E represent toluene, cyclopentene, ethylene, and tetramethylethylene, respectively. By using the flash photolysis-resonance fluorescence technique, Davis and coworkers obtained the absolute rate constant of ethylene + oxygen, k E = lo9 '-' l./rnole.sec [4] and that of tetramethylethylene + oxygen, ~T M E = loy 5+1.6/e l./mole.sec [7], while Furuyama and Cvetanovic obtained k E = lo9 '-' Oie l./mole-sec by using the phase shift-NOz* chemiluminescence method [9]. These absolute rate constants, when combined with eqs.…”

“…Cvetanovic and his colleagues obtained the relative kinetic parameters by applying the competitive reaction-product analysis method as follows [ 1, 131: Oie l./mole-sec by using the phase shift-NOz* chemiluminescence method [9].…”

“…Bonnano and coworkers [l 11 measured the rate constant of the reaction of oxygen with benzene by the rnicrowave discharge-fast-flow method and obtained the rate expression k e = 1010.6-4.4'e l./mole.sec at -18-32"C, where 8 = 2.303RT. However, this kinetic expression differs quite a bit from k g = 109.5-3.1'0, which was obtained by combining the relative rate constants determined by Boocock and Cvetanovic [12] at 120 and 220°C with the recently determined absolute kinetic parameters of the reaction of O ( 3 P ) with ethylene or tetramethylethylene [4,7,9], as will be shown in a later section. As to the kinetics for the reaction of O ( 3 P ) with toluene, the relative rate constant was measured by Jones and Cvetanovic [13] at 120 and 220°C.…”

“…As to the kinetics for the reaction of O ( 3 P ) with toluene, the relative rate constant was measured by Jones and Cvetanovic [13] at 120 and 220°C. When this is combined with the absolute rate constants for the O ( 3 P ) + olefin reactions [4,7,9], we derive k~ = 6.65 X lo7 l./mole.sec, which is close to 4.5 X lo7 l./mole.sec as determined by Atkinson and Pitts [lo], but differs by a factor of two from 1.4 X lo8 l./mole.sec measured by Mani and Sauer I141 at room temperature. This situation, together with the importance of these rate constants in connection with the unique photochemical smog problem created in Japan by blending toluene in gasoline, prompted us to determine the absolute rate constant of the reaction of oxygen atoms with toluene.…”