Gas-phase recombination of chlorine atoms

Abstract

Publication costs assisted by Madison CollegeThe recombination of chlorine atoms in the presence of various chaperons has been studied over the range 195-373°K using kinetic spectroscopy. The rate coefficients obtained, in M -2 sec-l units and expressed as kM = A exp(E/RT) or log kM = B + C log T, were kHe = 1.47 x lo9 exp(260 f 10IRT) or log kHe = 10.55 f 0.12 -(0.48 f 0.009) log T; k~~ = 1.26 X lo9 exp(660 f 20/RT) or log k~~ = 12.74 f 0.26 -(1.27 f 0.02) log T; kAr = 2.5 x los exp(1800 f 50/RT) or log kAr = 18.62 f 0.60 -(3.59 f 0.05) log T; k N z = 5.8 X lo8 exp(1600 f 140/RT) or log kNz = 15.61 f 0.65 -(2.32 f 0.02) log T; ksF6 = 2.4 x lo9 exp(970 f 100/RT) or log ksF6 = 13.72 f 0.76 -(1.47 f 0.02) log T; kCFi = l.62 x log exp(1200 f 200/RT) or log kCF4 = 14.43 f 1.36 -(1.77 f 0.04) log T; kcoz = 1.56 x 109 exp(1500 f 200/RT) or log kcOz = 15.75 f 0.60 -(2.22 f 0.018) log T. Where comparison values are available they are in good agreement with the results of this investigation. The values reported here are compared with the available data for iodine and bromine atom recombination.

Flash photolysis study of the recombination of chlorine atoms in the presence of various inert gases and NO

“…The value given in Table I was determined from experiments in the range of 4-24 atm. Our present results with purer gases now agree much better with the recent results from [13]. They are compared in [ mol cm-3 3 Table I with the third-order rate constants obtained from different studies.…”

“…Low-pressure data for this reaction with the third bodies He, Ar, and Cl2 have been obtained earlier in discharge-flow experiments 19-1 11. Low-pressure flash photolysis experiments with He, Ne, Ar, NP, COP, CF4, and SFfi (and with SiF4 and C2Fs [12]) have been reported in [12,13]. In the present work our earlier experiments have been improved and extended to inert gas pressures of about 100 atm.…”

The Jury Is Still Out on Health Courts

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Recombination rates of chlorine atoms in flash photolysis of chlorine molecules

“…The recombination of chlorine atoms has not attracted much attention because of detection difficulties, due to the low-absorption cross section of the chlorine molecules and the low degree of dissociation of the chlorine molecules obtainable with conventional flashtubes. In the past, the above difficulties were overcome with the use of higher chlorine concentrations [ 1 1 or longer absorbing paths [2]. In this work, we have used a coaxial flashlamp, which can achieve a high degree of dissociation, owing to the close optical coupling between the photolyzing source and the sample.The experiments were performed with a flash photolysis apparatus which employs a coaxial flashlamp and operates in the kinetic mode.…”