.14?0-12?T/298)two.26 xp(-313/T). Regrettably, you’ll find no other studies on the kinetics CH3F+Cl carried out at sufficiently high temperatures, which could confirm this conclusion of Marinkovic et al. [21]. Reaction CH3Cl + Cl The minimum power path for the reaction CH3Cl + Cl is also shown in Fig. 2a. The mechanism of your H-abstraction from CH3Cl by Cl atoms is complex and consists of 3 elementary actions which includes the formation in the pre- and post-reaction adducts, MC1Cl and MC2Cl. The energy barrier for reaction CH3Cl + Cl of eight.1 kJ mol-1 is 1.8 kJ mol-Table 3 Comparison in the experimental Hf0;298 (exp.) and theoretical Hf0;298 (calc.) values in the enthalpy of formation from the reactants CH3X and goods CH2X, (X 0 F, Cl and Br) obtained in the G2 level Molecular technique CH3F CH3Cl CH3Br CH2F CH2Cl CH2Bra)Hf0;298 (calc.) (kJmol-1)-237.7 -81.four -32.0 -28.1 120.4 174.Hf0;298 (exp.) a) (kJmol-1)-238 -81.9 -37.7 -32 117.3 169 ? ?0.six ?1.five ? ?three.1 ?from ref.J Mol Model (2013) 19:1489?505 Fig. two Schematic profiles from the potential energy surfaces for the reactions: a) CH3X + Cl, and b) CD3X + Cl exactly where X 0 F, Cl and Br. The energies are calculated in the G2 level which includes zero-point energy corrections15 10-a9.1-Bromoisoquinolin-4-amine manufacturer 9 8.three eight.1 TS1F TS1Br TS1Cl15 10b15.1 13.5 12.DTS1F DTS1Br DTS1Cl0 -5 -10 -CH3X+Cl-0.CH2F+HCl -5.9 -9.0 MC2F -13.6 MC2Br CH2Cl+HCl -14.2 CH2Br+HClCD3X+Cl0.-0.8 -3.CD2F+DCl CD2Br+DCl-5 -10 –18.7 -10.-6.DMC2F -8.eight CD2Cl+DCl-9.MC1Cl-9.-9.5 DMC1Cl -13.DMC2BrDMC2Cl-16.9 -18.four MC2Cl MC1Br–DMC1Brlower than that for CH3F + Cl. The values of the calculated rate constants, k(CH3Cl+Cl) and kTST(CH3Cl+Cl) are collected in Table five. Our calculated worth of k(CH3Cl+Cl) of four.5?0-13 cm3molecule-1s-1 at space temperature is quite close to these of (four.8?.5)?0-13 cm3molecule-1s-1 [14] and (four.9?.five)?0-13 cm3molecule-1s-1 [12] advised by IUPAC and NASA evaluations, respectively. The calculated value of the price constant at 298 K can be compared together with the reported outcomes of experimental studies [12?4]. Our value of 4.five?0-13 cm3molecule-1s-1 is in line together with the estimate of (4.four?.six)?0-13 obtained by Beichert et al. [27], (4.7?.6)?0-13 of Orlando [28], (four.28269-02-5 Data Sheet eight?.4)?0-13 of Wallington et al. [26], (5.1?.3)?0-13 of Pritchard et al. [23], (5.two?.4)?0-13 of Sarzyski et al. [32], (5.2?.3)?0-13 of Bryukov et al.PMID:23399686 [29], and (five.4?.2)?0-13 cm3molecule-1s-1 of Manning and Kurylo [15]. A related value of (five.1?.7)?0-13 cm3molecule-1s-1 at 298 K may be derived from the expression describing the temperature dependence on the price continuous located by Tschuikow-Roux et al. [16]. A comparison involving the values of the rate constant for the reaction CH3Cl + Cl calculated within this study and obtainable experimental outcomes are shown in Fig. 4. The values of k (CH3Cl+Cl) is usually, in the temperature selection of 200?000 K, expressed as: k H3 Cl ?Cl??six:97 ?10?2 ? =300?:73 ?exp 795=T?cm3 molecule? s? : ??Except for the higher temperature variety, i.e., above 500 K, the reported values on the rate continuous k(CH3Cl+Cl) estimated by diverse experimental tactics are extremely related from one particular to an additional. The discrepancy from the experimental final results is only little. The values calculated from Eq. eight of k (CH3Cl+Cl) reproduce nicely the observed trend in experimental results within a wide temperature range. At temperaturesabove 500 K, the experimental values of k(CH3Cl+Cl) are restricted by the outcomes of Bryukov et al. [29] and Clyne and Walker [25]. The theoretically derived temperature dependence of k(CH3Cl+Cl).