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Gas‐phase reactions of Cl atoms with propane, n ‐butane, and isobutane
Author(s) -
Sarzynski Dariusz,
Sztuba Barbara
Publication year - 2002
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.10096
Subject(s) - chemistry , isobutane , butane , reaction rate constant , propane , chlorine atom , medicinal chemistry , hydrogen , atmospheric temperature range , analytical chemistry (journal) , kinetics , organic chemistry , catalysis , meteorology , physics , quantum mechanics
Using the relative kinetic method, rate coefficients have been determined for the gas‐phase reactions of chlorine atoms with propane, n ‐butane, and isobutane at total pressure of 100 Torr and the temperature range of 295–469 K. The Cl 2 photolysis (λ = 420 nm) was used to generate Cl atoms in the presence of ethane as the reference compound. The experiments have been carried out using GC product analysis and the following rate constant expressions (in cm 3 molecule −1 s −1 ) have been derived: (7.4 ± 0.2) × 10 −11 exp [‐(70 ± 11)/ T ], Cl + C 3 H 8 → HCl + CH 3 CH 2 CH 2 ; (5.1 ± 0.5) × 10 −11 exp [(104 ± 32)/ T ], Cl + C 3 H 8 → HCl + CH 3 CHCH 3 ; (7.3 ± 0.2) × 10 −11 exp[−(68 ± 10)/ T ], Cl + n ‐C 4 H 10 → HCl + CH 3 CH 2 CH 2 CH 2 ; (9.9 ± 2.2) × 10 −11 exp[(106 ± 75)/ T ], Cl + n ‐C 4 H 10 → HCl + CH 3 CH 2 CHCH 3 ; (13.0 ± 1.8) × 10 −11 exp[−(104 ± 50)/ T ], Cl + i ‐C 4 H 10 → HCl + CH 3 CHCH 3 CH 2 ; (2.9 ± 0.5) × 10 −11 exp[(155 ± 58)/ T ], Cl + i ‐C 4 H 10 → HCl + CH 3 CCH 3 CH 3 (all error bars are ± 2σ precision). These studies provide a set of reaction rate constants allowing to determine the contribution of competing hydrogen abstractions from primary, secondary, or tertiary carbon atom in alkane molecule. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 651–658, 2002

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