Journal of Physical Chemistry p. 3572 - 3578 (1983)
Update date:2022-08-17
Topics:
Wine, P. H.
Semmes, D. H.
The kinetics of the reactions Cl(2PJ) + RHCl -> RCl + HCl were investigated over the temperature range 257-426 K for RHCl = CH3CH2Cl (k2), CH3CHCl2 (k3), CH2ClCH2Cl (k4), and CH2ClCHCl2 (k5).Cl(2PJ) was produced by 355 nm pulsed laser photolysis of Cl2 and monitored by time-resolved resonance fluorescence spectroscopy.The data are adequately described by the following Arrhenius expressions (units are cm3 molecule-1 s-1, errors are 2? and refer to precision only): k2=(2.34+/-0.42)E-11exp<-(310+/-56)/T>, k3=(8.19+/-1.84)E-12exp<-(554+/-71)/T>,k4=(2.21+/-0.51)E-11exp<-(793+/-73)/T>, and k5=(4.88+/-1.41)E-12exp<-(786+/-88)/T>.Under some experimental conditions evidence for Cl(2PJ) regeneration via a secondary reaction was observed.At 258+/-1 K, deviations of Cl(2PJ) temporal profiles from first-order behavior were attributable to the reactions RCl + Cl2 -> RCl2 + Cl(2PJ)(kj).By modeling the observed C(2PJ) temporal profiles, we found the rate constant kj to lie in the range (5-12)E-14 cm3 molecule-1 s-1 for all RCl investigated.The reactivity trends observed in reactions of Cl2PJ) with C2HXCl(6-x), x=3-6, are discussed.
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