The rate constants of the reactions of nitrosyl chloride with chlorine atoms and COCl radicals

1952 ◽  
Vol 48 ◽  
pp. 52 ◽  
Author(s):  
W. G. Burns ◽  
F. S. Dainton
Keyword(s):  
Rate Constants ◽  
Nitrosyl Chloride ◽  
Chlorine Atoms

ChemInform Abstract: Rate Constants for the Reactions of Hydroxyl Radicals and Chlorine Atoms with Halogenated Aldehydes.

ChemInform ◽  
2010 ◽  
Vol 24 (35) ◽  
pp. no-no
Author(s):  
D. J. SCOLLARD ◽  
J. J. TREACY ◽  
H. W. SIDEBOTTOM ◽  
C. BALESTRA-GARCIA ◽  
G. LAVERDET ◽  
...  
Keyword(s):  
Hydroxyl Radicals ◽  
Rate Constants ◽  
Chlorine Atoms

Rate constants for the reactions of chlorine atoms with hydrochloroethers at 298 k and atmospheric pressure

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

A study of sensitized explosions. IX. Experimental work on the sensitization of ignitions of hydrogen-chlorine mixtures by chloropicrin

1950 ◽  
Vol 203 (1075) ◽  
pp. 472-486 ◽  
Keyword(s):  
Experimental Work ◽  
Reaction Vessel ◽  
Nitrosyl Chloride ◽  
Chlorine Atoms ◽  
Inhibiting Action ◽  
Temperature Range ◽  
Sensitizing Effect ◽  
Increasing Temperature ◽  
Oxygen Reaction

The results of a study of the sensitizing action of chloropicrin upon the hydrogen-oxygen reaction suggested that chloropicrin might also sensitize the hydrogen-chlorine reactions by providing chlorine atoms which would initiate the reaction chains. Experimental work is described which shows that the addition of small proportions of chloropicrin lowers the normal ignition boundary of hydrogen-chlorine mixtures to the temperature range 100 to 200° C. This sensitized boundary separates exceedingly rapid and complete reactions from slow reactions which are further retarded during their course by the formation of nitrosyl chloride from the chloropicrin. At higher temperatures (330 to 370° C) the decomposition of the chloropicrin is sufficiently rapid for the inhibiting action of the nitrosyl chloride to become prominent during the entry of the gases, and the ignition boundary rises with increasing temperature. It rises more sharply with a greater proportion of chloropicrin in the mixtures entering the vessel, and when a longer portion of the entry tube is heated. The sensitized ignitions are suppressed by the addition of small quantities of nitrosyl chloride. A remarkable ‘backfire’ phenomenon, in which ignitions travel back to the cold mixing vessel but not into the hot reaction vessel, is described and shown to be in agreement with the assumption that reaction chains are started by chlorine atoms formed from chloropicrin and are abruptly terminated by nitrosyl chloride also formed from chloropicrin. Experimental work upon the effects of nitrosyl chloride upon the boundary of ignition of mixtures of hydrogen and chlorine show that below 400° C it acts as an inhibitor, but above 400° C it has a slight sensitizing effect.

Rate constants for the reactions of hydroxyl radicals and chlorine atoms with halogenated aldehydes

1993 ◽  
Vol 97 (18) ◽  
pp. 4683-4688 ◽  
Author(s):  
D. J. Scollard ◽  
J. J. Treacy ◽  
H. W. Sidebottom ◽  
C. Balestra-Garcia ◽  
G. Laverdet ◽  
...  
Keyword(s):  
Hydroxyl Radicals ◽  
Rate Constants ◽  
Chlorine Atoms

Dehalogenation of Chlorobenzenes with Sodium Dihydridobis(2-methoxyethoxo)aluminate

1994 ◽  
Vol 59 (6) ◽  
pp. 1368-1383 ◽  
Author(s):  
Jaroslav Včelák ◽  
Anna Friesová ◽  
Roman Řeřicha ◽  
Jiří Hetflejš
Keyword(s):  
Rate Constants ◽  
Product Distribution ◽  
Rate Data ◽  
Chlorine Atoms ◽  
Chlorinated Benzenes ◽  
First Order

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.

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
Keyword(s):  
Rate Constants ◽  
Chlorine Atoms

Chlorine atom initiated reactions of selected tropospheric halocarbons — Kinetic and product studies

2006 ◽  
Vol 84 (12) ◽  
pp. 1686-1695 ◽  
Author(s):  
Anisha Garib ◽  
Qadir K Timerghazin ◽  
Parisa A Ariya
Keyword(s):  
Gas Chromatography ◽  
Chlorine Atom ◽  
Rate Constants ◽  
Room Temperature ◽  
Marine Boundary Layer ◽  
Relative Rate ◽  
Addition Product ◽  
Chlorinated Ethenes ◽  
Oxidation Reactions ◽  
Chlorine Atoms

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.

Rate Constants for the Reactions of Chlorine Atoms with Some Simple Alkanes at 298 K: Measurement of a Self-Consistent Set Using Both Absolute and Relative Rate Methods

1995 ◽  
Vol 99 (35) ◽  
pp. 13156-13162 ◽  
Author(s):  
Peter Beichert ◽  
Lisa Wingen ◽  
Jason Lee ◽  
Rainer Vogt ◽  
Michael J. Ezell ◽  
...  
Keyword(s):  
Rate Constants ◽  
Relative Rate ◽  
Chlorine Atoms ◽  
Self Consistent
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