The calculation of thermal rate constants for gas phase reactions: A semiclassical flux–flux autocorrelation function (SCFFAF) approach

2001 ◽  
Vol 114 (12) ◽  
pp. 5141-5148 ◽  
Author(s):  
Keith Runge ◽  
Marshall G. Cory ◽  
Rodney J. Bartlett
Keyword(s):  
Gas Phase ◽  
Autocorrelation Function ◽  
Rate Constants ◽  
Gas Phase Reactions ◽  
Thermal Rate Constants

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

An experimental study of the reactivity of the hydroxide anion in the gas phase at room temperature, and its perturbation by hydration

1981 ◽  
Vol 59 (11) ◽  
pp. 1615-1621 ◽  
Author(s):  
Scott D. Tanner ◽  
Gervase I. Mackay ◽  
Diethard K. Bohme
Keyword(s):  
Experimental Study ◽  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Gas Phase Reactions ◽  
Flowing Afterglow ◽  
Hydroxide Anion

Flowing afterglow measurements are reported which provide rate constants and product identifications at 298 ± 2 K for the gas-phase reactions of OH− with CH3OH, C2H5OH, CH3OCH3, CH2O, CH3CHO, CH3COCH3, CH2CO, HCOOH, HCOOCH3, CH2=C=CH2, CH3—C≡CH, and C6H5CH3. The main channels observed were proton transfer and solvation of the OH−. Hydration with one molecule of H2O was observed either to reduce the rate slightly and lead to products which are the hydrated analogues of the "nude" reaction, or to stop the reaction completely, k ≤ 10−12 cm3 molecule−1 s−1. The reaction of OH−•H2O with CH3—C≡CH showed an uncertain intermediate behaviour.

Rate Constants for the Gas-Phase Reactions of Methylphenanthrenes with OH as a Function of Temperature

2003 ◽  
Vol 107 (34) ◽  
pp. 6603-6608 ◽  
Author(s):  
Woojin Lee ◽  
Philip S. Stevens ◽  
Ronald A. Hites
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Gas Phase Reactions

ChemInform Abstract: RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF OZONE WITH A SERIES OF CARBONYLS AT 296 K

1982 ◽  
Vol 13 (8) ◽  
Author(s):  
R. ATKINSON ◽  
S. M. ASCHMANN ◽  
A. M. WINER ◽  
J. N. JUN. PITTS
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Gas Phase Reactions

Rate constants of the gas-phase reactions of OH radicals withtrans-2-hexenal,trans-2-octenal, andtrans-2-nonenal

2009 ◽  
Vol 41 (7) ◽  
pp. 483-489 ◽  
Author(s):  
Tingting Gao ◽  
Jean M. Andino ◽  
Carlos C. Rivera ◽  
Misaela Francisco Márquez
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Oh Radicals ◽  
Gas Phase Reactions
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