Rate constant and mechanism of the reaction of oxygen atoms with n-butane

1963 ◽  
Vol 12 (6) ◽  
pp. 890-893 ◽  
Author(s):  
L. I. Avramenko ◽  
R. V. Kolesnikova ◽  
G. I. Savinova
Keyword(s):  
Rate Constant ◽  
Mechanism Of The Reaction ◽  
Oxygen Atoms

Mechanism and rate constant of the reaction of oxygen atoms with acetylene

1965 ◽  
Vol 14 (3) ◽  
pp. 396-399 ◽  
Author(s):  
L. I. Avramenko ◽  
R. V. Kolesnikova ◽  
G. I. Savinova
Keyword(s):  
Rate Constant ◽  
Oxygen Atoms

Reaction of oxygen atoms with ethanol

1967 ◽  
Vol 45 (16) ◽  
pp. 1845-1861 ◽  
Author(s):  
A. Kato ◽  
R. J. Cvetanović
Keyword(s):  
Rate Constant ◽  
Vapor Phase ◽  
Room Temperature ◽  
Initial Reaction ◽  
Reaction Products ◽  
Absolute Value ◽  
Oxygen Atoms

Reaction of O(3P) atoms with ethanol in the vapor phase has been studied at room temperature. The principal initial reaction products are water, acetaldehyde, and 2,3-butanediol. The data are consistent with abstraction of an α-hydrogen from ethanol as the primary step in the reaction. Ethanol is found to react with O(3P) atoms about 3.5 times less rapidly than acetaldehyde. The approximate absolute value of the rate constant of the ethanol reaction at 25 °C is 6.2 × 1010 cm3 mole−1 s−1.As a corollary to the investigation of the reaction of oxygen atoms with ethanol, a brief study has been made of the mercury Hg 6(3P1) photosensitized decomposition of ethanol at room temperature.

Kinetics and mechanism of the reaction of oxygen atoms with hydrogen sulfide

1979 ◽  
Vol 83 (17) ◽  
pp. 2195-2200 ◽  
Author(s):  
Donald L. Singleton ◽  
Robert S. Irwin ◽  
Wing S. Nip ◽  
R. J. Cvetanovic
Keyword(s):  
Hydrogen Sulfide ◽  
Kinetics And Mechanism ◽  
Mechanism Of The Reaction ◽  
Oxygen Atoms

Mechanism of the reaction of oxygen atoms, O(3P) with dimethyl disulfide

1983 ◽  
Vol 61 (5) ◽  
pp. 968-974 ◽  
Author(s):  
D. L. Singleton ◽  
R. S. Irwin ◽  
R. J. Cvetanović
Keyword(s):  
Reaction Mechanism ◽  
Ground State ◽  
Dimethyl Disulfide ◽  
Primary Reaction ◽  
Secondary Chemistry ◽  
Mechanism Of The Reaction ◽  
Oxygen Atoms

The mechanism of the reaction of ground state oxygen atoms, O(3P), with CH3SSCH3 was studied by analysis of the final products. Oxygen atoms were generated by mercury photosensitized decomposition of N2O such that [Formula: see text]. The only detected product was CH3S(O)2SCH3, which accounted for close to 70% of the oxygen atoms reacted. Isomerization of small amounts of cis- or trans-2-butene added to the reaction mixture indicated the presence of CH3S radicals. The results are consistent with the primary reaction O + CH3SSCH3 → CH3SO + CH3S. The effect of small amounts of CH3SH and H2S on the yields of CH3S(O)2SCH3 and the products formed provide further information on the nature of the secondary chemistry. A comprehensive reaction mechanism has been proposed.

Kinetics and mechanism of the reaction of dimethyl acetylphosphonate with water. Expulsion of a phosphonate ester from a carbonyl hydrate

1978 ◽  
Vol 56 (13) ◽  
pp. 1792-1795 ◽  
Author(s):  
Ronald Kluger ◽  
David C. Pire ◽  
Jik Chin
Keyword(s):  
Rate Constant ◽  
Electronic Effect ◽  
Order Rate Constant ◽  
Ion Concentration ◽  
First Order ◽  
Cleavage Reactions ◽  
Ph Range ◽  
Rapid Hydrolysis ◽  
Hydrolysis Of ◽  
Mechanism Of The Reaction

Dimethyl acetylphosphonate (DAP) is rapidly cleaved in water to acetate and dimethylphosphonic acid. The half time for reaction at pH 7, 25 °C is estimated to be 3 s. The reaction is first order in hydroxide ion concentration and first order in DAP concentration. Rates of reaction were measured over the pH range 3.8 to 6.5 at 25 °C, 6.5 and 7.0 at 5 °C, 4.5 to 6.5 at 35 °C, and 4.5 to 6.0 at 45 °C. The average observed second-order rate constant at 25 °C is 2.4 × 106M−1 s−1. DAP is converted rapidly to a hydrated carbonyl adduct. The mechanism for the formation of the observed products is proposed to be analogous to cleavage reactions of other carbonyl hydrates, proceeding from a monoanion conjugate in this case. The estimated rate constant for the unimolecular cleavage of the carbonyl hydrate anion is 2 × 103 s−1. The rapid hydrolysis of DAP results from energetically favourable formation of a hydrate due to the electronic effect of the phosphonate diester. This effect also promoles ionization of the hydrate. The ionized hydrate readily expels the phosphonate diester to achieve the overall rapid hydrolysis.

Kinetics of reactions involving CN emission IV. Study of the reactions of CN by electronic absorption spectroscopy

1968 ◽  
Vol 305 (1480) ◽  
pp. 107-123 ◽  
Keyword(s):  
Absorption Spectroscopy ◽  
Rate Constant ◽  
Electronic Absorption ◽  
Flow Reactor ◽  
Initial Step ◽  
Electronic Absorption Spectroscopy ◽  
Kinetics Of ◽  
Cn Radicals ◽  
Limiting Values ◽  
Oxygen Atoms

The kinetics of the reaction between oxygen atoms and cyanogen have been studied in a capacity flow reactor at temperatures between 570 and 687 °K. The concentration of CN radicals was measured by electronic absorption spectroscopy. This work confirms the previously proposed mechanism (part II). The initial step has a rate constant of k 1 = 2∙5 (± 0∙3) x 10 13 exp ( – 11000±2000/ RT ) cm 3 mole –1 s –1 . CN radicals are removed mainly by reactions (4) and (2) for which k 4 = 6∙3 (±3∙5) x 10 13 exp (–2400±700/ RT ) cm 3 mole –1 s –1 and k 2 = 4∙4 (±2∙0) x 10 12 cm 3 mole –1 s –1 . CN+O = CO+N, (4) CN+O 2 = NCO+O. (2) The rates of reaction of CN with NO and NH 3 were also measured; for CH 4 and H 2 limiting values were obtained.

A graphical method for extracting rate constants from some enzyme-catalyzed reactions not monitored to completion

1978 ◽  
Vol 56 (11) ◽  
pp. 1055-1057 ◽  
Author(s):  
Bernard R. Glick ◽  
Lewis J. Brubacher ◽  
David J. Leggett
Keyword(s):  
Rate Constant ◽  
Graphical Method ◽  
Exponential Phase ◽  
Time Data ◽  
Linear Portion ◽  
Mixed Disulfide ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Rate Of Activation ◽  
Mechanism Of The Reaction

A large number of enzyme-catalyzed reactions can be described by the equation y = At−B(1−e−kt) where y is the amount of product formed, A is the slope of the linear portion of the curve, and B is a constant dependent on the mechanism of the reaction. The methods which are generally used to extract the rate constant, k, from absorbance–time data described by this equation require that the reaction be monitored for some 10 to 15 half-lives. We show herein that the rate constant k is readily obtained from a plot of (y″−y′) vs. (y′−y0) where y0, y′, and y″ are the values of y at times t, t + Δt, and t + 2Δt. This graphical method is simple, reliable, and requires that the reaction be monitored for only three to five half-lives of the exponential phase of the reaction.We have used this method to measure the rate of activation of a mixed disulfide of papain and 2-nitro-5-mercaptobenzoic acid in the presence of substrate.

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