Nvestigation are realistic. The values on the price constants for the reverse reactions of CH2X + HCl could be derived through the respective equilibrium constants. The hydrogen chloride, HCl is deemed as a one of the most abundant natural chlorine containing compounds in the atmosphere. A greatTable five The price constants calculated for the H/D-abstraction reactions CH3Cl + Cl, CD3Cl + Cl and their reverse processes kTST(CH3Cl+Cl) (cm3molecule-1s-1) 7.28?0-14 two.22?0-13 4.82?0-13 four.95?0-13 9.24?0-13 1.54?0-12 two.36?0-12 3.43?0-12 6.39?0-12 four.3486 3.7226 3.3377 3.3258 three.0565 two.8644 2.7217 2.6122 2.4556 two.3488 two.2705 two.2096 two.1602 1.9963 1.8913 1.8110 1.7448 4.41?0-14 7.88?0-14 1.27?0-13 1.90?0-13 7.43?0-13 1.69?0-12 two.99?0-12 4.58?0-12 4.19?0-12 7.02?0-12 1.07?0-11 1.53?0-11 four.93?0-11 9.50?0-11 1.45?0-10 1.95?0-10 1.06?0-11 1.62?0-11 two.34?0-11 three.23?0-11 1.03?0-10 two.20?0-10 3.79?0-10 five.78?0-10 3.20?0-18 4.11?0-17 two.17?0-16 two.28?0-16 7.91?0-16 two.04?0-15 4.34?0-15 eight.06?0-15 two.12?0-14 two.92?0-15 1.67?0-14 five.51?0-14 five.73?0-14 1.46?0-13 three.09?0-13 5.70?0-13 9.57?0-13 2.20?0-12 3.2499 2.9090 2.7064 two.7002 two.5620 two.4651 2.3936 2.3384 2.2577 two.1998 two.1547 two.1172 two.0849 1.9628 1.8727 1.7993 1.7369 logKp k(CH2Cl+HCl) (cm3molecule-1s-1) k(CD3Cl+Cl) (cm3molecule-1s-1) logKp k(CD2Cl+DCl) (cm3molecule-1s-1) 1.64?0-18 two.06?0-17 1.08?0-16 1.14?0-16 four.01?0-16 1.06?0-15 2.30?0-15 4.39?0-15 1.22?0-14 two.64?0-14 4.92?0-14 8.19?0-14 1.26?0-13 five.37?0-13 1.27?0-12 two.30?0-12 three.58?0-12 KIE 24.49 13.01 eight.55 8.44 6.15 four.84 4.01 3.45 two.75 2.35 2.09 1.92 1.79 1.49 1.39 1.33 1.T (K)k(CH3Cl+Cl) (cm3molecule-1s-1)200 250 298 300 350 400 450 5007.15?0-14 2.17?0-13 4.71?0-13 four.84?0-13 9.01?0-13 1.49?0-12 2.29?0-12 three.30?0-12 six.05?0-700 800 900 1000 1500 2000 25009.84?0-12 1.47?0-11 two.06?0-11 2.75?0-11 7.36?0-11 1.32?0-10 1.93?0-10 two.54?0-J Mol Model (2013) 19:1489?J Mol Model (2013) 19:1489?-11.-1 –11.Knox (1962) Clyne Walker (1973) Manning Kurylo (1977) Orlando (1999) Bryukov et al. (2002) Sarzy ski et al. (2009) this studyCH3Cl+Cl-12.3 H-12.-13.0 1 2 three 1000K/T 4Fig. four Arrhenius plot for the CH3Cl + Cl reaction comparing the obtainable benefits of kinetic measurements with obtained theoretically within this studydeuterated reactants react having a distinct price in comparison to the reaction of non-deuterated molecules.Buy2-Iodoadenosine The knowledge in the rate constants, k(CH3X+Cl) and k(CD3X+Cl) enables a determination of the kinetic isotope effect (KIE), defined by the ratio of k(CH3X+Cl)/k(CD3X+Cl).Formula of 1820673-85-5 Values of KIE and its dependence on temperature can provide helpful information and facts for interpreting the stable isotope composition on the organic compounds in the atmosphere.PMID:25558565 The calculated values of your rate constants k(CD3X+Cl) for the D-abstraction processes might be analytically written within the type: k D3 F ?Cl??9:18 ?10?two ? =300?:97 ?exp 1675=T?cm3 molecule? s? ?three?k D3 Cl ?Cl??8:63 ?ten?two ? =300?:63 ?exp 1490=T?cm3 molecule? s? ?four?k D3 Br ?Cl??8:73 ?ten?two ? =300?:70 ?exp 1560=T?cm3 molecule? s? : ?5?The profiles from the potential power surface show that Dabstraction course of action is associated with the power barrier of 5 kJmol-1 larger than the H-abstraction in the corresponding non-deuterated molecule. These variations inside the height on the energy barrier are reflected in values from the price constants. The abstraction of deuterium from CD3X by Cl atom proceeds slower compared with all the analogous H-abstraction from CH3X. The values of your price constants, k(CD3X+Cl) are distinctly lower than values of their counter.
