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Hydrogen Atom Attack on Fluorotoluenes: Rates of Fluorine Displacement
Author(s) -
Manion Jeffrey A.,
Tsang Wing
Publication year - 1996
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199600037
Subject(s) - chemical technology , hydrogen atom , library science , chemistry , engineering physics , engineering , computer science , group (periodic table) , organic chemistry , manufacturing engineering
Rates of hydrogen atom attack on o ‐fluorotoluene ( o ‐FTOL) and m ‐fluorotoluene ( m ‐FTOL) at temperatures of 988–1144 K and pressures of 2–2.5 bar have been determined in a single‐pulse shock tube study. Hydrogen atoms, generated from the decomposition of hexamethylethane, were allowed to react with the substrates and the characteristic products observed. Rate constants for two reaction channels, displacement of fluorine or methyl, were determined relative to displacement of methyl from 1, 3,5‐trimethylbenzene (135TMB). Evidence is presented that abstraction of F is unimportant over the studied temperature range. With k (H + 135TMB → m ‐xylene + CH 3 ) = 6.7 × 10 13 exp(–3255/ T ) cm 3 mol −1 s −1 , the following rate expressions have been derived: k (H + o ‐FTOL → C 6 H 5 CH 3 + F) = 8.38 × 10 13 exp(–6041/ T ) cm 3 mol −1 s −1 ; (1012–1142 K) k (H + o ‐FTOL → C 6 H 5 F + CH 3 ) = 2.37 × 10 13 exp(–2938/ T ) cm 3 mol −1 s −1 ; (988–1142 K) k( H + m ‐FTOL → C 6 H 5 CH 3 + F) = 1.33 × 10 14 exp(–6810/ T ) cm 3 mol −1 s −1 ; (1046–1144 K) k (H + m ‐FTOL → C 6 H 5 F + CH3) = 2.04 × 10 13 exp(–3104/ T ) cm 3 mol −1 s −1 ; (1008–1144 K) Uncertainties in the relative rate constants are estimated to be factors of about 1.1, while the above absolute values have estimated expanded uncertainties of about a factor of 1.4 in rate, 10 kJ mol −1 in the activation energy, and a factor of 3 in the A‐factor. The present data are compared with relevant literature data. From our data and the thermochemistry, a model of the elementary steps comprising displacement of F is developed. On the basis of the model fit to our data, rate constants for the addition of atomic fluorine to toluene at 1100 K are derived. Rate expressions for fluorination reactions of toluene are also determined. The significance of the present results is discussed in the context of the formation of fluorinated byproducts in high‐temperature systems.