scholarly journals Full rate constant matrix contraction method for obtaining branching ratio of unimolecular decomposition

2016 ◽  
Vol 38 (2) ◽  
pp. 101-109 ◽  
Author(s):  
Yosuke Sumiya ◽  
Tetsuya Taketsugu ◽  
Satoshi Maeda
Keyword(s):  
Rate Constant ◽  
Branching Ratio ◽  
Unimolecular Decomposition ◽  
Constant Matrix ◽  
Contraction Method ◽  
Full Rate ◽  
Matrix Contraction

scholarly journals Understanding CO oxidation on the Pt(111) surface based on a reaction route network

2019 ◽  
Vol 21 (26) ◽  
pp. 14366-14375 ◽  
Author(s):  
Kanami Sugiyama ◽  
Yosuke Sumiya ◽  
Makito Takagi ◽  
Kenichiro Saita ◽  
Satoshi Maeda
Keyword(s):  
Co Oxidation ◽  
Kinetic Analysis ◽  
Rate Constant ◽  
Local Minima ◽  
Reaction Route ◽  
Constant Matrix ◽  
Route Network ◽  
Matrix Contraction ◽  
The Impact ◽  
Induced Reaction

Kinetic analysis by the rate constant matrix contraction on the reaction route network of CO oxidation on the Pt(111) surface obtained by the artificial force induced reaction reveals the impact of entropic contributions arising from a variety of local minima and transition states.

Rate Constant and Branching Ratio for the Reactions of the Ethyl Peroxy Radical with Itself and with the Ethoxy Radical

2021 ◽  
Author(s):  
Mirna Shamas ◽  
Mohamed Assali ◽  
Cuihong Zhang ◽  
Xiaofeng Tang ◽  
Weijun Zhang ◽  
...  
Keyword(s):  
Rate Constant ◽  
Branching Ratio ◽  
Peroxy Radical

Unimolecular decomposition of methyl chloride. II. Some refinements of the calculations

1967 ◽  
Vol 45 (24) ◽  
pp. 3169-3176 ◽  
Author(s):  
W. Forst ◽  
P. St. Laurent
Keyword(s):  
Angular Momentum ◽  
Rate Constant ◽  
Degrees Of Freedom ◽  
Methyl Chloride ◽  
Computational Procedure ◽  
Intramolecular Energy Transfer ◽  
Collision Theory ◽  
Unimolecular Decomposition ◽  
Rational Argument ◽  
Quantum Version

The quantum version of the statistical collision theory is applied to the unimolecular decomposition of methyl chloride in the second-order region using an improved computational procedure and a more realistic physical model. An attempt is made to determine active degrees of freedom, i.e. degrees of freedom participating in intramolecular energy transfer, by rational argument. These considerations point to at least one overall rotation as active, in addition to all nine vibrations as active. Conservation of angular momentum is explicitly considered in the case of one active rotation and an appropriate correction factor is included in the calculated rate constant, as is a correction for anharmonicity. The theoretical rate constant so computed is within less than a factor of two of the experimental value.

Thermal Rate Constant and Branching Ratio for CN + HD → HCN/DCN + D/H fromT= 293 to 375 K

1998 ◽  
Vol 102 (39) ◽  
pp. 7653-7661 ◽  
Author(s):  
G. He ◽  
I. Tokue ◽  
Lawrence B. Harding ◽  
R. Glen Macdonald
Keyword(s):  
Rate Constant ◽  
Branching Ratio ◽  
Thermal Rate Constant

Anharmonic effect of the decomposition reaction of the CF3CCl2O radical

2012 ◽  
Vol 90 (2) ◽  
pp. 186-194 ◽  
Author(s):  
Qian Li ◽  
Wenwen Xia ◽  
Li Yao ◽  
Ying Shao
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Decomposition Reaction ◽  
Unimolecular Decomposition ◽  
Anharmonic Effect ◽  
Canonical Systems ◽  
Bond Scission

The rate constant of the unimolecular decomposition reaction of the CF3CCl2O radical was calculated by using the method proposed by Yao and Lin (YL method). Two important channels of decomposition occurring via C–C and C–Cl bond scission were investigated. The results show that C–Cl bond scission is the dominant channel during the decomposition of the CF3CCl2O radical. Especially, the reasonable anharmonic effect on the decomposition reaction was investigated. The results show that the harmonic rate constants are higher than those of the anharmonic case in both microcanonical and canonical systems. The anharmonic effect is more evident with increasing energy.

The homogeneous decomposition reactions of gaseous formic acid

1960 ◽  
Vol 255 (1283) ◽  
pp. 444-455 ◽  
Keyword(s):  
Formic Acid ◽  
Kinetic Parameters ◽  
Rate Constant ◽  
Ion Pairs ◽  
Order Rate Constant ◽  
Second Order ◽  
Unimolecular Decomposition ◽  
Order Component ◽  
First Order ◽  
Homogeneous Decomposition

By use of reaction vessels with specially treated surfaces the homogeneous decomposition of formic acid has been studied kinetically in the range 436 to 532°C. Neither of the two simultaneous reactions ( a ) HCOOH = CO 2 + H 2 , ( b ) HCOOH = CO + H 2 O, is retarded by the usual inhibitors of chain processes. Each appears to be molecular. Reaction ( a ) is of the first order in the range 3 to 650 mm, the first-order rate constant being given by k CO 2 = 10 4⋅8 exp (–30600/ RT )s -1 . It is suggested tentatively that the abnormal kinetic parameters might be explained by regarding the reaction as a decarboxylation of (H + ) (HCOO¯) ion pairs present in minute concentration. Reaction ( b ) shows a pressure dependence most simply explained by a superposition of a predominant second-order component with a small first-order component. The most satisfactory interpretation of the second-order reaction is that it represents the unimolecular decomposition of dimer molecules, known to be present in formic-acid vapour. On this basis the rate constant is given by k CO dimer = 10 13⋅58 exp (–42600/ RT )s -1 , the kinetic parameters thus being in the normal range. The various alternative interpretations are discussed.

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