Kinetics of Cl(2PJ) Reactions with the Chloroethanes CH3CH2Cl, CH3CHCl2, CH2ClCH2Cl and CH2ClCHCl2

Article abstract of DOI:10.1021/j100241a040

The kinetics of the reactions Cl(²P_J) + RHCl -> RCl + HCl were investigated over the temperature range 257-426 K for RHCl = CH3CH2Cl (k₂), CH3CHCl2 (k₃), CH2ClCH2Cl (k₄), and CH2ClCHCl2 (k₅).Cl(²P_J) 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(²P_J) regeneration via a secondary reaction was observed.At 258+/-1 K, deviations of Cl(²P_J) temporal profiles from first-order behavior were attributable to the reactions RCl + Cl2 -> RCl2 + Cl(²P_J)(k_j).By modeling the observed C(²P_J) temporal profiles, we found the rate constant k_j 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 Cl²P_J) with C2HXCl(6-x), x=3-6, are discussed.