Temperature dependence of the kinetic isotope effect for a gas-phase SN2 reaction: Cl- + CH3Br

1991 ◽  
Vol 113 (24) ◽  
pp. 9404-9405 ◽  
Author(s):  
A. A. Viggiano ◽  
John Paschkewitz ◽  
Robert A. Morris ◽  
John F. Paulson ◽  
Angels Gonzalez-Lafont ◽  
...  
Keyword(s):  
Temperature Dependence ◽  
Gas Phase ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Kinetic Isotope ◽  
Sn2 Reaction

Deuterium Kinetic Isotope Effect and Temperature Dependence in the Reactions of CH[2Π] with Methane and Acetylene

1997 ◽  
Vol 101 (10) ◽  
pp. 1881-1886 ◽  
Author(s):  
Holger Thiesemann ◽  
John MacNamara ◽  
Craig A. Taatjes
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Kinetic Isotope

Quantum Mechanical Tunneling in Homodienyl Sigmatropic [1,5]-Hydrogen Shifts of (Hydroxymethyl)styrylcyclopropanes

1990 ◽  
Vol 43 (6) ◽  
pp. 1071 ◽  
Author(s):  
GG Pegg ◽  
GV Meehan
Keyword(s):  
Low Temperature ◽  
Temperature Dependence ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Natural Compounds ◽  
Quantum Mechanical ◽  
Strong Temperature Dependence ◽  
Quantum Mechanical Tunneling ◽  
Hydrogen Migration ◽  
Kinetic Isotope

The strong temperature dependence of the deuterium kinetic isotope effect observed for homodienyl [1,5]-hydrogen migration of [hydroxy (D)methyl] styrylcyclopropanes (1c,d) in hexane solvent is suggestive of a significant tunnelling contribution to the mechanism. While the hydroxy substituent at the migration origin appears to influence the thermolytic behaviour of these molecules, attempts to promote oxy anionic homodienyl rearrangement in the isotopically natural compounds (1a,b) at low temperature were unsuccessful.

Kinetic isotope effect in gas-phase base-induced elimination reactions

1985 ◽  
Vol 107 (9) ◽  
pp. 2818-2820 ◽  
Author(s):  
Veronica M. Bierbaum ◽  
Jonathan Filley ◽  
Charles H. DePuy ◽  
Martin F. Jarrold ◽  
Michael T. Bowers
Keyword(s):  
Gas Phase ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Kinetic Isotope ◽  
Elimination Reactions

Primary kinetic isotope effect in the gas phase photochlorination of ethyl chloride-1-d1

1984 ◽  
Vol 62 (5) ◽  
pp. 899-906 ◽  
Author(s):  
Jan Niedzielski ◽  
T. Yano ◽  
E. Tschuikow-Roux
Keyword(s):  
Activation Energy ◽  
Gas Phase ◽  
Isotope Effect ◽  
Ground State ◽  
Rate Constants ◽  
Kinetic Isotope Effect ◽  
Kinetic Isotope ◽  
Primary Reference ◽  
Hydrogen Deuterium ◽  
Increasing Temperature

The abstraction of hydrogen/deuterium from CH3CHDCl by ground state chlorine atoms produced photolytically from Cl2 has been investigated at temperatures betwen 280 and 368 K. The relative rates for the internal competition[Formula: see text]are found to conform to an Arrhenius rate law:[Formula: see text]These data, taken together with the external competition results for the C2H5Cl/CH3CHDCl system, in conjunction with the competitive results using CH4 as a primary reference, have yielded the rate constants (cm3 s−1):[Formula: see text]The relatively weak primary kinetic isotope effect, kH/kD, decreases with increasing temperature from 1,855 at 280 K to 1.66 at 365 K. The results are compared with those obtained based on the BEBO method. While both the trend and the magnitude of the kinetic isotope effect are satisfactorily predicted, the activation energy is not.

Intramolecular kinetic isotope effect in gas-phase proton-transfer reactions

1979 ◽  
Vol 101 (8) ◽  
pp. 2242-2243 ◽  
Author(s):  
Keith M. Wellman ◽  
Maria E. Victoriano ◽  
Paulo C. Isolani ◽  
Jose M. Riveros
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Transfer Reactions ◽  
Kinetic Isotope ◽  
Proton Transfer Reactions
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