A gas-phase kinetic study of the reaction of silylene with germane: absolute rate constants, temperature dependence and mechanism

1998 ◽  
Vol 94 (24) ◽  
pp. 3569-3572 ◽  
Author(s):  
Rosa Becerra ◽  
Sergey Boganov ◽  
Robin Walsh
Keyword(s):  
Kinetic Study ◽  
Temperature Dependence ◽  
Gas Phase ◽  
Rate Constants ◽  
Absolute Rate

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.

Absolute rate constants for the gas-phase ozonolysis of isoprene and methylbutenol

2004 ◽  
Vol 36 (3) ◽  
pp. 152-156 ◽  
Author(s):  
N. Klawatsch-Carrasco ◽  
J. F. Doussin ◽  
P. Carlier
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Absolute Rate

The reactions of O(3P) with the butanols

1983 ◽  
Vol 61 (12) ◽  
pp. 2716-2720 ◽  
Author(s):  
John M. Roscoe
Keyword(s):  
Free Energy ◽  
Gas Phase ◽  
Rate Constants ◽  
Substrate Concentration ◽  
Kinetic Data ◽  
Absolute Rate ◽  
Gas Phase Reactions ◽  
Linear Free Energy ◽  
Different Types ◽  
Energy Relations

The reactions of O(3P) with the butanols were studied kinetically as a function of temperature and substrate concentration. The absolute rate constants for the gas phase reactions, in the units M−1 s−1, obey the following relations.[Formula: see text]The results suggest that although the α-CH bond in these alcohols is the most reactive one, reaction of O(3P) with other CH bonds in the alcohols is also appreciable. The kinetic data for these and other alcohols are separated into contributions from the different types of CH bonds and the results are discussed in terms of linear free energy relations.

Tautomerism of 5-nitro-2-furylnitromethane

1981 ◽  
Vol 46 (12) ◽  
pp. 3122-3127
Author(s):  
Iva Sroková ◽  
Pavel Vetešník ◽  
Adolf Jurášek ◽  
Jaroslav Kováč
Keyword(s):  
Kinetic Study ◽  
Temperature Dependence ◽  
Thermodynamic Parameters ◽  
Rate Constants ◽  
Strong Acid ◽  
Ion Pair ◽  
Aprotic Solvents ◽  
Protic Solvents ◽  
Parallel Reactions ◽  
Experimental Values

UV study of properties of 5-nitro-2-furylnitromethane (I) in various solvents has shown that this compound is a very strong acid (pKa 3.98) forming an ion pair in protic solvents (water, alcohols) and existing exclusively as nitro-form in aprotic solvents (tetrachloromethane, chloroform, n-hexane, diethyl ether, dioxane). Kinetic study of tautomerism in water has given experimental values of combined rate constants of parallel reactions. Thermodynamic parameters of the tautomeric transformations have been calculated from temperature dependence of the rate constants.

A kinetic study of the reactions of OH radicals with fluoroethanes. Estimates of C—H bond strengths in fluoroalkanes

1983 ◽  
Vol 61 (5) ◽  
pp. 861-865 ◽  
Author(s):  
Jean-Pierre Martin ◽  
George Paraskevopoulos
Keyword(s):  
Kinetic Study ◽  
Gas Phase ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Oh Radicals ◽  
Bond Dissociation Energies ◽  
Time Resolved ◽  
Dissociation Energies ◽  
Bond Strengths ◽  
Vacuum Uv

A kinetic study of the reactions of OH radicals with a series of fluoroethanes in the gas phase is presented. OH radicals were generated by flash photolysis of H2O vapor in the vacuum uv (λ > 165 nm) and were monitored in absorption by time-resolved attenuation of resonance radiation at 308.15 nm [OH(A2Σ+ → X2Π)]. The following absolute rate constants (in units of 109 cm3mol−1 s−1 at the 95% confidence limit) were determined at [Formula: see text][Formula: see text][Formula: see text][Formula: see text][Formula: see text]From a linear correlation of the present and previously published rate constants with bond dissociation energies, the following quantities (in kcal mol−1 at 298 K) were estimated to be: D(CH3CHF—H) = 96.3 ± 1.5, D(CH2FCHF—H = 98.8 ± 1.0, D(CF3CHF—H) = 103.5 ± 1.0, D(CHF2CF2—H) = 103.0 ± 1.5, and [Formula: see text][Formula: see text]

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