34 research outputs found

    Kinetics of the gas-phase reactions of chlorine atoms with CH 2 F 2 , CH 3 CCl 3 , and CF 3 CFH 2 over the temperature range 253–553 K

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    Relative rate techniques were used to study the title reactions in 930–1200 mbar of N 2 diluent. The reaction rate coefficients measured in the present work are summarized by the expressions k (Cl + CH 2 F 2 ) = 1.19 × 10 −17 T 2 exp(−1023/T) cm 3 molecule −1 s −1 (253–553 K), k (Cl + CH 3 CCl 3 ) = 2.41 × 10 −12 exp(−1630/T) cm 3 molecule −1 s −1 (253–313 K), and k (Cl + CF 3 CFH 2 ) = 1.27 × 10 −12 exp(−2019/T) cm 3 molecule −1 s −1 (253–313 K). Results are discussed with respect to the literature data. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 401–406, 2009Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62132/1/20398_ftp.pd

    Addition of a chlorine atom to tetrachloroethylene

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    The gas-phase competitive photochlorination Cl2 + C 2Cl4 + 1,2-C2H4Cl2 has been studied at 310°K between 40 and 642 torr in the presence and absence of added CO2 and SF6. The results are explained in terms of a mechanism in which the activated C2Cl*5 radical initially formed by addition of a Cl atom to C2Cl4 is deactivated by collision much more rapidly than it can react. The experimental data, combined with those from a parallel study of the competition Cl 2 + C2Cl4 + C2H6 at 348°K and those from previous studies at higher temperatures, lead to the new values log10k2 (mole-1 l. sec-1) = 10.1 and log10k4 (sec-1) = 13.51-16080/4.576T. for the reactions Cl + C2Cl4 → 2C2Cl5 k2 and C2Cl 5 → 4C2Cl4 + Cl, k4 where C2Cl5 is a thermalized radical. These results, combined with known thermochemical data, yield: D(C2Cl 4-Cl) = 16.9, D(C2Cl5-H) = 95.8 and D(C 2Cl5-Cl) = 72.6 kcal mole-1, ΔH°f,298 (C2Cl5) = 8.4 kcal mole -1 and S°298 (C2Cl5) = 96.4 cal mole-1 deg.-1. The rate constant ka for the reaction C2Cl*5 → C2Cl4 + Cl is estimated to be less than 4 × 107 sec-1. Existing data on addition-substitution competitive photochlorinations of C 2H4, 1,2-C2H2Cl2, C 2HCl3 and C2Cl4 are discussed.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

    Hydrogen abstraction from chlorinated ethanes by chlorine atoms

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    The hydrogen abstraction from the chlorinated ethanes by chlorine atoms has been investigated in the gas phase between 323 and 423°K. Absolute values of the rate constants have been obtained using a competition method with chloroform or methyl chloride as competitor. The activation energies and the pre-exponential factors are discussed.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

    Oxygen-inhibited photochlorination of 1,2-dichloroethane

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    The oxygen‐inhibited photochlorination of 1,2‐dichloroethane has been studied in the gas‐phase between 321 and 489,5°K. The following rate constants have been estimated: (Formula Presented.) These results are compared to those observed for the reactions of C2H6, C2HCl5, C2HCl3 and C2Cl4. Copyright © 1972 Wiley‐VCH Verlag GmbH & Co. KGaA, WeinheimSCOPUS: ar.jinfo:eu-repo/semantics/publishe
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