The reactions of O(3P) with acetonitrile and propionitrile

1995 ◽  
Vol 73 (5) ◽  
pp. 666-674 ◽  
Author(s):  
Suzanne Budge ◽  
John M. Roscoe
Keyword(s):  
Hydrogen Atom ◽  
Gas Phase ◽  
Rate Constant ◽  
Rate Constants ◽  
Hydrogen Atom Abstraction ◽  
Absolute Rate ◽  
Analytical Results ◽  
Absolute Rate Constant ◽  
Secondary Reactions ◽  
The Absolute

The reactions of O(3P) with acetonitrile and propionitrile have been studied kinetically in the gas phase as a function of temperature and nitrile concentration. The rate constants obtained experimentally for the consumption of O(3P) in these reactions, in the units L mol−1 s−1, obey the following relations: O + acetonitrile: In k = 20.98 ± 0.23 − 2100 ± 200/T; and O + propionitrile: In k = 21.01 ± 0.19 − 1900 ± 200/T. Mechanisms are discussed in which the reaction is initiated by hydrogen atom abstraction and in which initiation is by addition of O(3P) to the nitrile, followed by decomposition of the addition complex. The kinetic and analytical results are best explained by the mechanism in which the reactions are initiated by RCN + O → R + OCN. In the case of the reaction with acetonitrile, the absolute rate constant is smaller than the experimental value by a factor of 7 ± 20%, independent of temperature, as a result of secondary reactions. Keywords: kinetics, reactions of O(3P) with nitriles.

Absolute Rate Constants for Hydrocarbon Autoxidation. Part XX. Oxidation of Some Organic Sulfides

1971 ◽  
Vol 49 (12) ◽  
pp. 2178-2182 ◽  
Author(s):  
J. A. Howard ◽  
S. Korcek
Keyword(s):  
Liquid Phase ◽  
Hydrogen Atom ◽  
Rate Constants ◽  
Hydrogen Atom Abstraction ◽  
Absolute Rate ◽  
Organic Sulfides

Absolute rate constants for the liquid phase autoxidation of some organic sulfides at 30 °C have been measured. The reactivities of organic sulfides towards t-butylperoxy radicals are equal to or somewhat less than the reactivities of structurally analogous ethers. The α-alkylthiylalkylperoxy radicals appear to be about 3–5 times more reactive in hydrogen atom abstraction than the α-alkoxyalkylperoxy radicals.

Absolute rate constants for hydrocarbon autoxidation. VI. Alkyl aromatic and olefinic hydrocarbons

1967 ◽  
Vol 45 (8) ◽  
pp. 793-802 ◽  
Author(s):  
J. A. Howard ◽  
K. U. Ingold
Keyword(s):  
Hydrogen Atom ◽  
Steric Hindrance ◽  
Rate Constants ◽  
Peroxy Radical ◽  
Electron System ◽  
Chain Termination ◽  
The Self ◽  
Hydrogen Atom Abstraction ◽  
Peroxy Radicals ◽  
Absolute Rate

Absolute rate constants have been measured for the autoxidation of a large number of hydrocarbons at 30 °C. The chain-propagating and chain-terminating rate constants depend on the structure of the hydrocarbon and also on the structure of the chain-carrying peroxy radical. With certain notable exceptions which are mainly due to steric hindrance, the rate constants for hydrogen-atom abstraction increase in the order primary < secondary < tertiary; and, for compounds losing a secondary hydrogen atom, the rate constants increase in the order unactivated < acyclic activated by a single π-electron system < cyclic activated by a single Π-system < acyclic activated by two π-systems < cyclic activated by two π-systems. The rate constants for chain termination by the self-reaction of two peroxy radicals generally increase in the order tertiary peroxy radicals < acyclic allylic secondary  [Formula: see text] cyclic secondary  [Formula: see text] acyclic benzylic secondary < primary peroxy radicals < hydroperoxy radicals.

The reactions of O(3P) with 2-propanone, 2-butanone, and 3-pentanone

1986 ◽  
Vol 64 (7) ◽  
pp. 1408-1414 ◽  
Author(s):  
John M. Roscoe
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Substrate Concentration ◽  
Activation Energies ◽  
Absolute Rate ◽  
The Absolute

The reactions of O(3P) with 2-propanone, 2-butanone, and 3-pentanone have been studied kinetically as a function of temperature and substrate concentration. The absolute rate constants for these reactions in the gas phase, in the units M−1 s−1, obey the following relations.[Formula: see text]The activation energies for these reactions are comparable to those for the reactions of O(3P) with alcohols, but the preexponential factors for the reactions of O(3P) with these ketones are significantly smaller than those for the analogous reactions with alcohols. The available data indicate that the reactivity of O(3P) toward ketones shows a variation with polar effects of substituents which is similar to that found for the reactions of OH with ketones.

Dibromosilylene: Determination of the absolute rate constants for its gas-phase reactions with oxygen and nitric oxide

1990 ◽  
Vol 13 (1) ◽  
pp. 43-52 ◽  
Author(s):  
V. Sandhu ◽  
O. P. Strausz ◽  
T. N. Bell
Keyword(s):  
Nitric Oxide ◽  
Gas Phase ◽  
Rate Constants ◽  
Absolute Rate ◽  
Gas Phase Reactions ◽  
The Absolute

scholarly journals Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

2007 ◽  
Vol 19 (6) ◽  
pp. 641-643 ◽  
Author(s):  
Hai-tao WANG ◽  
Yu-jie ZHANG ◽  
Yu-jing MU
Keyword(s):  
Temperature Dependence ◽  
Rate Constant ◽  
Dimethyl Sulfide ◽  
Absolute Rate ◽  
Absolute Rate Constant ◽  
The Absolute
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