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Title: Reaction dynamics of Cl + CH3SH: Rotational and vibrational distributions of HCl probed with time-resolved Fourier-transform spectroscopy
Journal: J. Chem. Phys.
Volume: 120
Page(s): 1792 - 1800
Year: 2004
Reference type: Journal article
Squib: 2004CHE/WU1792-1800
Reaction:
CH3SH + Cl → CH3S· + HCl
Reaction order:
2
Temperature:
298
K
Pressure: 1.33E-4 - 1.73E-3 bar
Rate expression:
2.9x10-10 [±7.0x10-11 cm3/molecule s]
Bath gas:
Ar
Category: Experiment
Data type:
Absolute value measured directly
Pressure dependence:
None reported
Experimental procedure:
Static or low flow - Data taken vs time
Excitation technique:
Flash photolysis (laser or conventional)
Time resolution:
In real time
Analytical technique:
Fourier transform (FTIR)
Comments:
Combined experimental and theoretical study. Measured rate of reaction of CH3SH + Cl -> CH3S + HCl. Cl atoms produced by 308 nm photolysis of S2Cl2. HCl detected using FTIR. Bath gas Argon. Room temperature measurements but exact temperature not evident in paper - assumed 298 K. Aslo used ab initio calculations MP4/6-311++G(3df,2p) to elucidate details of mechanism for reaction. Experimental measurements by others yield rate expressions with slight negative temperature dependences, suggesting reaction is not direct abstraction, but proceeds through intermediate. Ab initio calcs in this study confirm adduct formation with a heat of about 57 kJ/mol. Transition state for HCl elimination from this adduct is about -7 kJ/mol (lower) relative to reactants, or about 50 kJ/mol above adduct.
In this work also measured branching ratios going into different HCl vibrational states.
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