Pressure dependence of the rate constants for the electron/atom self-exchange between MII (cp2 and MIV) (cp)2 = X+ (M = ruthenium, osmium; X = bromide, iodide; cp = cyclopentadienide) as a function of solvent

1992 ◽  
Vol 31 (12) ◽  
pp. 2605-2608 ◽  
Author(s):  
Kim A. Anderson ◽  
Karl Kirchner ◽  
Harold W. Dodgen ◽  
John P. Hunt ◽  
Scot Wherland
Keyword(s):  
Pressure Dependence ◽  
Rate Constants ◽  
Electron Atom

REACTION OF OXYGEN ATOMS WITH BUTADIENE

1960 ◽  
Vol 38 (11) ◽  
pp. 2187-2195 ◽  
Author(s):  
R. J. Cvetanović ◽  
L. C. Doyle
Keyword(s):  
Pressure Dependence ◽  
Rate Constants ◽  
Room Temperature ◽  
Relative Rate ◽  
Excess Energy ◽  
General Mechanism ◽  
Arrhenius Parameters ◽  
Heats Of Reaction ◽  
Relative Rate Constants ◽  
Oxygen Atoms

Reaction of oxygen atoms with 1,3-butadiene has been investigated at room temperature. It is found that it conforms to the general mechanism established previously for the analogous reactions of monoolefins. Only 1,2-addition occurs, and the addition products, butadiene monoxide and 3-butenal, possess excess energy when formed as a result of high heats of reaction. The pressure dependence of the formation of the addition products yields the values of the "lifetimes" of the initially produced "hot" molecules. The relative rate constants have been determined at 25 and 127 °C and from these the relative values of the Arrhenius parameters have been calculated.

Computational study on the mechanisms and kinetics of the CH2CCl + O2 reaction

2020 ◽  
Vol 98 (8) ◽  
pp. 395-402
Author(s):  
Yunju Zhang ◽  
Bing He ◽  
Yuxi Sun
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Pressure Dependence ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Energy Surface ◽  
Computational Study ◽  
Tddft Calculations ◽  
Temperature And Pressure ◽  
Kinetics Of

The potential energy surface for the CH2CCl + O2 reaction has been investigated by using the CCSD(T)/cc-pVTZ//B3LYP/6-311++G(d,p) method. Two type reaction mechanisms have been located. The H-abstraction of CH2CCl by O2 generates CHCCl + HO2 surmounting a 20.86 kcal/mol barrier. The addition between O2 and CH2CCl proceeds to an intermediate CH2CClO2 (IM1t and IM1c) without a barrier, which can further dissociate or isomerize to various products with the complicated processes. The temperature and pressure dependence rate constants for the CH2CCl + O2 reaction were computed by means of multi-channel RRKM-TST theory. Moreover, TDDFT calculations imply that IM1t, IM1c, IM2, IM4, IM5t, and IM5c will photolyze under the sunlight.

The pressure dependence of the rate of isomerization of cyclopropane at 897 K

1982 ◽  
Vol 60 (7) ◽  
pp. 916-920 ◽  
Author(s):  
Hlroshi Furue ◽  
Philip D. Pacey
Keyword(s):  
High Pressure ◽  
Pressure Dependence ◽  
Rate Constants ◽  
Flow Reactor ◽  
Average Energy ◽  
Increasing Temperature

The isomerization of cyclopropane has been studied in a flow reactor at 897 K and from 4 to 406 Torr. The pressure dependence of the rate constants from this work and from the literature have been compared with predictions obtained from two models based on the theory of Yau and Pritchard and from three RRKM models. The collisional deactivation efficiency was found to generally decline with increasing temperature. The average energy removed per collision was calculated by the method of Tardy and Rabinovitch and was found to have values from 15 to 23 kJ mol−1 at 897 K. Combining the results of this work with data from the literature from 690 to 1038 K, the limiting high pressure rate constants follow the relation log k∞ = 15.50 ± 0.14 – (276.0 ± 2.1 kJ mol−1)/2.3RT.

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