Rate Constants for the Reactions of Chlorine Atoms with Deuterated Methanes:  Experiment and Theory†

2001 ◽  
Vol 105 (9) ◽  
pp. 1456-1464 ◽  
Author(s):  
Gwen D. Boone ◽  
Frederick Agyin ◽  
David J. Robichaud ◽  
Fu-Ming Tao ◽  
Scott A. Hewitt
ChemInform ◽  
2010 ◽  
Vol 24 (35) ◽  
pp. no-no
Author(s):  
D. J. SCOLLARD ◽  
J. J. TREACY ◽  
H. W. SIDEBOTTOM ◽  
C. BALESTRA-GARCIA ◽  
G. LAVERDET ◽  
...  

2005 ◽  
Vol 37 (7) ◽  
pp. 420-426 ◽  
Author(s):  
Pablo R. Dalmasso ◽  
Raúl A. Taccone ◽  
Jorge D. Nieto ◽  
Mariano A. Teruel ◽  
Silvia I. Lane

1993 ◽  
Vol 97 (18) ◽  
pp. 4683-4688 ◽  
Author(s):  
D. J. Scollard ◽  
J. J. Treacy ◽  
H. W. Sidebottom ◽  
C. Balestra-Garcia ◽  
G. Laverdet ◽  
...  

1994 ◽  
Vol 59 (6) ◽  
pp. 1368-1383 ◽  
Author(s):  
Jaroslav Včelák ◽  
Anna Friesová ◽  
Roman Řeřicha ◽  
Jiří Hetflejš

The dehalogenation of a series of 9 mono- to pentachlorinated benzenes with the title hydride in toluene has been found to be first order in the substrate and half order in the hydride. The reactivities of the chlorobenzenes, expressed by rate constants for the first-step dehalogenation, increased with increasing number of chlorine atoms over three orders of magnitude. The rate data revealed the unexpected acceleration of benzene formation during exhaustive dehalogenation of the higher chlorinated benzenes. For comparison, dehalogenation of several isomeric dibromobenzenes and bromochlorobenzenes with the same hydride and the product distribution for the dehalogenation of some chlorobenzenes with LiAlH4 are also reported.


2006 ◽  
Vol 84 (12) ◽  
pp. 1686-1695 ◽  
Author(s):  
Anisha Garib ◽  
Qadir K Timerghazin ◽  
Parisa A Ariya

Halogens are suggested as important atmospheric oxidants in the marine boundary layer. The room-temperature kinetics of the chlorine-initiated reactions of three biogenic brominated hydrocarbons and four anthropogenic chlorinated ethenes was investigated by gas chromatography with flame ionization detection (GC–FID) at a pressure of 1 atm (1 atm = 101.325 kPa) in air, using the relative rate technique. The rate constants (× 1013 cm3 molecule–1 s–1) for CH2Br2, CHBr2Cl, and CHBr3 reactions at 298 ± 2 K were found to be 4.25 ± 0.65, 2.03 ± 0.31, and 2.81 ± 0.41, respectively, using methane as a reference compound. Room temperature rate constants (±1011 cm3 molecule–1 s–1) obtained for 1,1-dichloroethene, cis-dichloroethene, trans-dichloroethene, and trichloroethene using ethene as a reference are 13.4 ± 3.3, 9.1 ± 2.3, 7.4 ± 1.8, and 7.7 ± 1.9, respectively. The rate constants of chlorine-atom reactions with various hydrocarbons obtained in this work and taken from literature were correlated with corresponding rate constants of the OH radical available in the literature. The temperature dependences for the reactions of chlorine atoms with chlorinated ethenes were studied within the 298–358 K range. The corresponding Arrhenius expressions for the rate constants are (cm3 molecule–1 s–1): ln k = (–25.26 ± 0.17) – (758 ± 55)/T for 1,1-dichloroethene, ln k = (–25.79 ± 0.10) – (799 ± 34)/T for cis-dichloroethene, ln k = (–26.74 ± 0.09) – (1018 ± 28)/T for trans-dichloroethene, and ln k = (–26.10 ± 0.26) – (846 ± 83)/T for trichloroethene. In addition, product studies for the chlorine-initiated gas phase oxidation reactions of CHBr3 and CHBr2Cl were performed using gas chromatography with mass spectrometric detection (GC–MS). The only identified product for the reaction of CHBr3 with Cl reaction was COBr2, while for the CHBr2Cl + Cl reaction, COBrCl and COCl2 were observed, indicating the possibility of halogen atom release. The atmospheric implications of the results obtained are discussed.Key words: tropospheric reactions, kinetics, chlorine atoms, chlorinated hydrocarbons, brominated hydrocarbons.


1995 ◽  
Vol 99 (35) ◽  
pp. 13156-13162 ◽  
Author(s):  
Peter Beichert ◽  
Lisa Wingen ◽  
Jason Lee ◽  
Rainer Vogt ◽  
Michael J. Ezell ◽  
...  

2011 ◽  
Vol 43 (8) ◽  
pp. 431-440 ◽  
Author(s):  
A. Sharma ◽  
K. K. Pushpa ◽  
S. Dhanya ◽  
P. D. Naik ◽  
P. N. Bajaj

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