16520-13-1Relevant articles and documents
Gas-phase carbene radical anions: New mechanistic insights
Villano, Stephanie M.,Eyet, Nicole,Lineberger, W. Carl,Bierbaum, Veronica M.
, p. 7214 - 7215 (2008)
The gas-phase reactivity of the CHCl?- anion has been investigated with a series of halomethanes (CCl4, CHCl3, CH2Cl2, and CH3Cl) using a FA-SIFT instrument. Results show that this anion primarily reacts via substitution and by proton transfer. In addition, the reactions of CHCl?- with CHCl3 and CH2Cl2 form minor amounts of Cl2?- and Cl-. The isotopic distribution of these two products is consistent with an insertion-elimination mechanism, where the anion inserts into a C-Cl bond to form an unstable intermediate, which eliminates either Cl2?- or Cl- and Cl?. Neutral and cationic carbenes are known to insert into single bonds; however, this is the first observation of such reactivity for carbene anions. Copyright
Kinetics of the reactions of CH2Cl, CH3CHCl, and CH3CCl2 Radicals with Cl2 in the Temperature Range 191-363 K
Rissanen, Matti P.,Eskola, Arkke J.,Timonen, Raimo S.
, p. 4805 - 4810 (2010)
The kinetics of three chlorinated free radical reactions with Cl 2 have been studied in direct time-resolved measurements. Radicals were produced in low initial concentrations by pulsed laser photolysis at 193 nm, and the subsequent decays of the radical concentrations were measured under pseudo-first-order conditions using photoionization mass spectrometer (PIMS). The bimolecular rate coefficients of the CH3CHCl + Cl2 reaction obtained from the current measurements exhibit negative temperature dependence and can be expressed by the equation k(CH3CHCl + Cl 2) =(3.02 ± 0.14) × 10-12)(T/300 K) -1.89±0.19 cm3 molecule-1 s-1 (1.7-5.4 Torr, 191-363 K). For the CH3CCl2 + Cl 2 reaction the current results could be fitted with the equation k(CH3CCl2 + Cl2) =(1.23 ± 0.02) × 10-13)(T/300 K)-0.26±0.10 cm3 molecule-1 s-1 (3.9-5.1 Torr, 240-363 K). The measured rate coefficients for the CH2Cl + Cl2 reaction plotted as a function of temperature show a minimum at about T ) 240 K: first decreasing with increasing temperature and then, above the limit, increasing with temperature. The determined reaction rate coefficients can be expressed as k(CH2Cl + Cl2) = (2.11 ± 1.29) × 10 -14) exp(773 ±183 K/T)(T/300 K)3.26±0.67 cm3 molecule-1 s-1 (4.0-5.6 Torr, 201-363 K). The rate coefficients for the CH3CCl2 + Cl2 and CH2Cl + Cl2 reactions can be combined with previous results to obtain: kcombined(CH3CCl2 + Cl 2) =(4.72 kcombined 1.66) × 10-15) exp(971 ± 106 K/T)(T/300 K)3.07 ±0.23 cm3 molecule -1 s-1 (3.1-7.4 Torr, 240-873 K) and k combined(CH2Cl + Cl2) =(5.18 ± 1.06) ± 10-14) exp(525 ±63 K/T)(T/300 K) 2.52±0.13 cm3 molecule-1 s-1 (1.8-5.6 Torr, 201-873 K). All the uncertainties given refer only to the 1θ statistical uncertainties obtained from the fitting, and the estimated overall uncertainty in the determined bimolecular rate coefficients is about ± 15%. Copyright
Laser Photolysis/Laser Induced Fluorescence Study of OH-C2H5Cl Rate Constants from 294 to 789 K
Kasner, James H.,Taylor, Philip H.,Dellinger, Barry
, p. 3250 - 3253 (1990)
Absolute rate coefficients for the reaction of hydroxyl radical (OH) with ethyl chloride (C2H5Cl) were measured over the temperature range 294-789 K, at atmospheric pressure, by using a laser photolysis/laser induced fluorescence technique.Hydroxyl (OH) was generated via photodissociation of N2O and the subsequent reaction of O(1D) with H2O.Relative radical concentration was monitored versus reaction time by using laser-induced fluorescence.The data were fit to the modified Arrhenius expression k(T) = (2.96 +/- 2.94) * 10-13(T/300)2.59 +/- 0.666 exp(229 +/- 624 cal mol-1/RT), where k is in units of cm3 molecule-1 s-1.Random errors in the measured rate data, as determined by a propagation of error analysis, were typically 10-20percent (+/-2?).Agreement with available room-temperature literature data and proposed methods of rate constant estimation, over extended temperature ranges, are shown.
Kinetics of reactions of Cl atoms with ethane, chloroethane, and 1,1-dichloroethane
Bryukov, Mikhail G.,Slagle, Irene R.,Knyazev, Vadim D.
, p. 6565 - 6573 (2007/10/03)
Reactions of Cl atoms with ethane, chloroethane, and 1,1-dichloroethane were studied experimentally with the discharge flow/resonance fluorescence technique over wide ranges of temperatures and at 2.3-9.2 torr. The rate octane of the reaction of Cl atoms with ethane obtained agreed with the results of earlier low-temperature measurements. Reactivity with respect to Cl atom attack decreased in the sequence of ethane, chloroethane, and dichloroethane. Rate constants of the reactions of Cl with chloroethane and 1,1-dichloroethane demonstrated different temperature dependences in the low-temperature (room temperature to 378 K) and the high-temperature (484-810 K) regions. The differences were due to the regeneration of Cl atoms at higher temperatures as a consequence of the fast thermal decompositions of radical products with a chlorine atom in the β position.
