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Inne
Experimental and theoretical study of the kinetics and mechanism of the reaction of chlorine atoms with CH3CHClCH3 and CD3CDClCD3
Autorzy
Rok wydania
2018
Czasopismo
Journal of Physical Chemistry A
Numer woluminu
122
Strony
470-481
DOI
10.1021/acs.jpca.7b10031
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The overall rate constants for H-abstraction (kH) from CH3CHClCH3 and D-abstraction (kD) from CD3CDClCD3 by chlorine atoms in the temperature range 298–528.5 K were determined and are described by the expressions: kH = (3.52 ± 0.21) × 10–11 exp(−184 ± 19/T) cm3 molecule–1 s–1and kD = (1.91 ± 0.16) × 10–11 exp(−185 ± 31/T) cm3 molecule–1 s–1 respectively. The results of the experiment show that the value of the kinetic isotope effect (kH/kD) for the overall rate constants is temperature independent and is equal to 1.85 ± 0.17. A theoretical examination of these reaction mechanisms revealed some unusual properties, such as negative values of the activation energy for the H-abstraction reaction from the secondary carbon atom. Moreover, it was proved that in the radical process of H-abstraction from the primary carbon atom of 2-chloropropane the created R–Cl···Cl complex is the most stable structure responsible for the value of the activation energy of this transformation.
Adres publiczny
http://dx.doi.org/10.1021/acs.jpca.7b10031
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