Photochlorination of Chloroform

Chiltz, Georges; Martens, G.; Mahieu, A.

doi:10.1038/1801068a0

Cited by 4 publications

(1 citation statement)

References 8 publications

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“…1) resemble those found by Ashmore and Chanmugaml for the system H2+Cl;!+NO+NOCl. The experimental results are interpreted in terms of a scheme similar to theirs but From the heats of formation of CCl3 18 and the other species,lg we estimate AHo for reactions (7) and ( 8) and deduce that E-7-E7 = 14+3 kcalmole-1 and E-8 -Es = 10 +_ 3 kcal mole-1 (Ei is the activation energy and At the pre-exponential factor of reaction (i)), in agreement with a finding 20 that E-8) 14 kcal mole-1 and approximate estimates 10 of k-7 and keg. It is likely that A-7mAg and A 7 = L g , probably to better than an order of magnitude, and hence k_7/ks can be neglected in comparison with unity and k-7k-B/kg in comparison with k7.…”

Section: Discussionmentioning

confidence: 99%

Kinetics of the effects of nitric oxide and nitrosyl chloride on the gas-phase chlorination of chloroform

Ashmore¹,

Spencer²

1964

Trans. Faraday Soc.

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Section: Discussionmentioning

confidence: 99%

Kinetics of the effects of nitric oxide and nitrosyl chloride on the gas-phase chlorination of chloroform

Ashmore¹,

Spencer²

1964

Trans. Faraday Soc.

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Kinetische Studie über die Konkurrenz bei Photochlorierungsreaktionen

et al. 1960

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Herrn Professor Dr. R i c h a r d Kuhn zurn 60. Geburtstag gewidrnetDie Photochlorierung von Gemischen aus C2CI4 einerseits und CH4, CH3C1, CHzC12 oder CHCI, anderseits, sowie die Photochlorierung von CH4, CH3CI und CH2Cl2 wurden untersucht; die drei letztgenannten Reaktionen sind ebenfalls einer Untersuchung von Gemischen aquivalent, da die Reaktionsprodukte einen starken EinfluB auf den Redktionsverlauf haben. Es werden kinetische Gleichungen abgeleitet; ferner wird eine Reaktionszeit definiert (im wesentlichen das Inverse einer Reaktionsgeschwindigkeitskonstanten) : die Reaktionszeit in einem Gemisch ist gleich der Summe der Reaktionszeiten der Komponenten. Diese kinetischen Betrachtungen gestatten es, den komplizierten Verlauf der Photochlorierung von CH4, CH3CI und CHzClz zu klaren. Unter Zuhilfenahrne einiger Literaturangdben werden so zuverllssige Werte fur etwa 40 Geschwindigkeitskonstanten elementarer Atom-und Radikalreaktionen erhalten. * ) Boursier de I'IRSIA (Institut pour I'Encouragcment de la Recherche Scientifique dans I'Industric et I'Agriculture, Bruxelles).

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Kinetics of the reactions of halogenated methyl radicals (CF₃, CF₂Cl, CFCl₂, and CCl₃) with molecular chlorine

Timonen

Russell

Gutman

1986

Int J of Chemical Kinetics

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The kinetics of four gas-phase reactions involving halogenated methyl radicals (R,==CF,, CF2C1, CFCI,, and eel,) with molecular chlorine have been studied using a tuhular reactor coupled to a photoionization mass spectrometer. The radicals were homogeneously generated by the pulsed photolysis of precursor molecules at 193 nm. The subsequent decays of the radical concentrations were monitored in real-time experiments as a function of Clz concentration to obtain the rate constants of these R + C1, reactions.Where possible, the rate constants were measured as a function of temperature to determine Arrhenius parameters. Apparent discrepancies between these measiired rate constants for CF, and CCl, with Clz and ones obtained in prior indirect studies are explained.The higher activation energies for these R + Clz reactions compared to that of the CH, + Clz reaction are attributed in part to the different polarities of the transition states formed.

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Photochlorination of Chloroform

Cited by 4 publications

References 8 publications

Kinetics of the effects of nitric oxide and nitrosyl chloride on the gas-phase chlorination of chloroform

Kinetics of the effects of nitric oxide and nitrosyl chloride on the gas-phase chlorination of chloroform

Kinetische Studie über die Konkurrenz bei Photochlorierungsreaktionen

Kinetics of the reactions of halogenated methyl radicals (CF₃, CF₂Cl, CFCl₂, and CCl₃) with molecular chlorine

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Photochlorination of Chloroform

Cited by 4 publications

References 8 publications

Kinetics of the effects of nitric oxide and nitrosyl chloride on the gas-phase chlorination of chloroform

Kinetics of the effects of nitric oxide and nitrosyl chloride on the gas-phase chlorination of chloroform

Kinetische Studie über die Konkurrenz bei Photochlorierungsreaktionen

Kinetics of the reactions of halogenated methyl radicals (CF3, CF2Cl, CFCl2, and CCl3) with molecular chlorine

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Kinetics of the reactions of halogenated methyl radicals (CF₃, CF₂Cl, CFCl₂, and CCl₃) with molecular chlorine