Origin of Bath Gas Dependence in Unimolecular Reaction Rates

2019 ◽  
Vol 123 (4) ◽  
pp. 764-770 ◽  
Author(s):  
Akira Matsugi
Keyword(s):  
Reaction Rates ◽  
Unimolecular Reaction

Predicting nonstatistical unimolecular reaction rates using Kramers’ theory

1999 ◽  
Vol 110 (12) ◽  
pp. 5514-5520 ◽  
Author(s):  
Yin Guo ◽  
Dmitrii V. Shalashilin ◽  
Justin A. Krouse ◽  
Donald L. Thompson
Keyword(s):  
Reaction Rates ◽  
Unimolecular Reaction

Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold

2006 ◽  
Vol 329 (1-3) ◽  
pp. 163-167 ◽  
Author(s):  
David M. Leitner ◽  
Peter G. Wolynes
Keyword(s):  
Quantum Theory ◽  
Reaction Rates ◽  
Unimolecular Reaction

Improved formulae for thermal unimolecular reaction rates with randomisation failure

1984 ◽  
Vol 62 (12) ◽  
pp. 2879-2880
Author(s):  
S. R. Vatsya ◽  
H. O. Pritchard
Keyword(s):  
Reaction Rates ◽  
Unimolecular Reaction

On the relation between unimolecular reaction rates and overlapping resonances

1994 ◽  
Vol 101 (11) ◽  
pp. 9672-9680 ◽  
Author(s):  
Uri Peskin ◽  
Hanna Reisler ◽  
William H. Miller
Keyword(s):  
Reaction Rates ◽  
Unimolecular Reaction

scholarly journals The structure of the reaction zone in a flame

1949 ◽  
Vol 197 (1048) ◽  
pp. 90-106 ◽  
Keyword(s):  
Heat Conductivity ◽  
Mathematical Problem ◽  
Reaction Rates ◽  
Successive Approximations ◽  
Method Of Successive Approximations ◽  
Unimolecular Reaction ◽  
Homogeneous Reaction ◽  
One Dimensional ◽  
Mathematical Approximation ◽  
Low Pressures

The structure of one-dimensional flames is shown to be completely determined by constants such as those of heat conductivity, of diffusion, and of the homogeneous reaction rates. The mathematical problem in the most general case is intractable, but three simple cases are solved fully by a mathematical method of successive approximations. The three cases are those in which diffusion is neglected compared with heat conductivity and in which reaction velocities of the following types are considered: unimolecular, bimolecular, and the quasibimolecular form of a unimolecular reaction at low pressures. The method of mathematical approximation is shown to involve errors of the order of only 10 % in some actual cases, an error which is negligible compared with other uncertainties of the problem. In these simple cases it is possible to solve all details of the structure such as the variation of composition and temperature through the flame.

Hydrolysis of ketene catalysed by nitric acid and water in the atmosphere

2020 ◽  
Vol 17 (6) ◽  
pp. 457
Author(s):  
Fang Xu ◽  
Xing-Feng Tan ◽  
Ze-Gang Dong ◽  
Da-Sen Ren ◽  
Bo Long
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Gas Phase ◽  
Energy Barrier ◽  
Reaction Rates ◽  
State Theory ◽  
Direct Reaction ◽  
Unimolecular Reaction ◽  
Atmospheric Water ◽  
Hydrolysis Of

Environmental contextThe detailed mechanism of hydrolysis of gas-phase ketene to form acetic acid is critical for understanding the formation of certain atmospheric contaminants. This study explores the effect of nitric acid and water on the hydrolysis of ketene in the atmosphere. The calculated results show that nitric acid is an effective catalyst in the hydrolysis of ketene to form acetic acid in atmospheric water-restricted environments. AbstractThe gas-phase hydrolysis of ketene and the unimolecular reaction of 1,1-enediol catalysed by nitric acid and water have been investigated using quantum chemical methods and conventional transition state theory with Eckart tunnelling. The theoretical calculation results show that nitric acid exerts a strong catalytic effect on the hydrolysis of ketene in the gas-phase. The calculated energy barrier for the direct reaction mechanistic pathway is reduced from 42.10kcal mol−1 in the reaction of ketene with water to 3.40kcal mol−1 in the reaction of ketene with water catalysed by HNO3. The catalytic ability of nitric acid is further proven in the hydrogen shift reaction of 1,1-enediol because the energy barrier of the unimolecular reaction of 1,1-enediol is decreased from 44.92kcal mol−1 to −4.51kcal mol−1. In addition, the calculated results indicate that there is competition between the direct and indirect mechanistic pathways with the increase of additional water molecules in the reaction of ketene with water catalysed by HNO3 and (H2O)n (n=1, 2). The calculated kinetics results show that the CH2=C=O+H2O+HNO3 reaction is significant in the gas phase of the atmosphere and the other reactions are negligible owing to the slow reaction rates. However, compared with the CH2=C=O+OH reaction, the CH2=C=O+H2O+HNO3 reaction is very slow and cannot compete with the CH2=C=O+OH reaction. CH2=C=O+OH is the main elimination pathway of ketene in the gas phase of the atmosphere. Our findings reveal that acetic acid may be formed through the hydrolysis of ketene in atmospheric water-restricted environments of the surfaces of aqueous, aerosol and cloud droplets.

Monte Carlo Calculations. VI. A Re‐evaluation of the RRKM Theory of Unimolecular Reaction Rates

1968 ◽  
Vol 48 (2) ◽  
pp. 772-776 ◽  
Author(s):  
Don L. Bunker ◽  
Merle Pattengill
Keyword(s):  
Monte Carlo ◽  
Reaction Rates ◽  
Unimolecular Reaction ◽  
Rrkm Theory ◽  
Monte Carlo Calculations
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