16519-99-6Relevant academic research and scientific papers
Temperature dependence of the kinetic isotopic effect of the reaction of Cl atoms with C2H5Cl between 298 and 550 K
Sarzyński, Dariusz,Gola, Agnieszka A.,Brudnik, Katarzyna,Berkowski, Ryszard,Jodkowski, Jerzy T.
, p. 20 - 26 (2012)
The kinetics of the gas-phase reactions of chlorine atoms with chloroethane and chloroethane-d5 was studied experimentally. The relative rate method was applied using Cl + CH3Cl as the reference reaction. The overall rate constants for H-abstraction from C2H5Cl (kH), D-abstraction from C2D5Cl (k D), the site-specific rate constants for H-abstraction from α-carbon (kH,α) and β-carbon (kH,β) atoms of C2H5Cl were measured in the temperature range of 298-550 K at a total pressure of 100 Torr. The derived temperature dependencies of the rate constants are given by kH = (2.41 ± 0.21) × 10-11 × exp(-316 ± 11/T), kH,α = (1.36 ± 0.09) × 10-11 × exp(-202 ± 8/T), k H,β = (1.14 ± 0.11) × 10-11 × exp(-592 ± 16/T) and kD = (1.58 ± 0.14) × 10 -11 × exp(-474 ± 13/T) cm3 molecule -1 s-1. The values of the kinetic isotope effect, k H/kD were also estimated.
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 (2003)
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.
Kinetics of the reactions of chlorine atoms with C2H4 (k1) and C2H2 (k2): A determination of ΔHf,298° for C2H3
Kaiser,Wallington
, p. 4111 - 4119 (2007/10/03)
The rate constant (k1) for the reaction of Cl atoms with C2H4 has been measured as a function of pressure (0.2-100 Torr) at 297 K using the relative rate technique in two reactors with either FTIR or GC analysis. The results of these and previous experiments (100-3000 Torr) can be described to within ±10% by a Tree expression with the limiting rate constants k1(∞) = (3.2 ± 0.15) × 10-10 cm3 molecule-1 s-1; and k1(0) = (1.42 ± 0.05) × 10-29 cm6 molecule-2 s-1 using Fcent = 0.6. The stated uncertainties are statistical only, and the true uncertainties in the limiting rate constants must include uncertainty in Fcent. Temperature-dependent (297-383 K) measurements of k1 were carried out in the low-pressure regime (0.2-2 Torr) yielding the rate constant expression k1(0) = (1.7 ± 0.3) × 10-29(T/298)-3.28 cm3 molecule-1 s-1. The rate constant, k1b, for the abstraction channel of reaction 1 to form the vinyl radical was determined at 300, 343, and 383 K. This measurement of k1b in combination with literature values of k-1b allows a determination of the heat of formation of the vinyl radical by the third law method [ΔHf,298o(C2H3) = 70.6 ± 0.4 kcal/mol]. Using the same data with the second law yields ΔHf,298o(C2H3) = 69.6 ± 1.6 kcal/mol. These measurements agree satisfactorily with a recent negative-ion photoelectron spectroscopy determination of this quantity (71.6 ± 0.8 kcal mol-1). The pressure dependence of the rate constant (k2) for the reaction of Cl with C2H2 was determined over the range 0.3-700 Torr. The results of these and previous experiments (100-6000 Torr) can be described to within ±10% by a Troe expression with the limiting rate constants k2(∞) = (2.0 ± 0.1) × 10-10 cm3 molecule-1 s-1 and k1(0) = (6.1 ± 0.2) × 10-30 cm6 molecule-2 s-1 using Fcent = 0.6.
Evidence for the Three-Center Elimination of HCl from CH3CHClO
Maricq, M. Matti,Shi, Jichun,Szente, Joseph J.,Rimai, L.,Kaiser, E. W.
, p. 9686 - 9694 (2007/10/02)
Time-resolved IR spectral photography and transient diode laser absorption measurements reveal a yield of HCl from the photolysis of Cl2 in the presence of C2H5Cl and O2 which is 78percent larger than expected from Cl + C2H5Cl.The HCl formation occurs in two steps: a rapid rise to = 0, followed by a secondary rise to = 1.780 with a rate constant of k3 = (5.2 +/- 1.3)E-12 cm3s-1.In the presence of NO, the rate of secondary HCl formation is greatly enhanced, but its yield (84percent) is comparable to that in the absence of NO.The secondary HCl is explained as an elimination product from the CH3CHClO, which can be generated by the reaction of CH3CHClO2 with itself of with NO.The fact that the secondary HCl yield increases by 12percent when using CD3CH2Cl shows that the secondary HCl is formed mainly by three-center elimination from the 1-chloroethoxy radical.We also report UV absorption cross sections for CH3CHClO2, which has a broad maximum of ?max = 0.029 Angstroem2 from 215 to 248 nm, and CH2ClCH2O2, with ?max = 0.045 Angstroem2 at 240 nm.The self-reaction rate constants are (5.2 +/- 1.3)E-12 cm3s-1 and (6.0 +/- 0.8)E-12 cm3s-1, respectively.Finally, the rate constant for the reaction Cl + C2H5Cl = C2H4Cl + HCl (1) is determined to be k10 = (7.3 +/- 0.9)E-12 cm-3s-1.
