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Author(s):   Rodriguez, D.; Aranda, A; de Mera, Y.D.; Ballesteros, B.; Martinez, E.
Title:   Kinetic and mechanistic study of Cl reactions with aliphatic thiols. Temperature dependence
Journal:   Phys. Chem. Chem. Phys.
Volume:   5
Page(s):   514 - 519
Year:   2003
Reference type:   Journal article
Squib:   2003ROD/ARA514-519

Reaction:   iso-C3H7SH + ClHCl + (CH3)2CHS
Reaction order:   2
Temperature:   260 - 333 K
Pressure:  1.33E-3 bar
Rate expression:   4.1x10-10 [±1.0x10-10 cm3/molecule s] e-1039 [±175 J/mole]/RT
Bath gas:   He
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure independent
Experimental procedure:   Flow tube - Data taken vs distance
Excitation technique:   Discharge
Time resolution:   By end product analysis
Analytical technique:   Mass spectrometry
Comments:   Measured reaction of Cl with alkane thiols. Typical pressure 1 torr He. Typical concentration of thiols 1E12 to 1E13 cm-3. Cl atoms produced by microwave discharge of Cl2. Cl concentrations measured by titration with Br2 at end of reactor and detecting BrCl with a Mass spec. Reaction time varied by sliding injector.

Low barrier to reaction and other evidence suggest strongly that abstraction is of S-H, with C-H abstractions not contributing under these conditions.

View full bibliographic record.


Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
260 2.54E-10
275 2.60E-10
300 2.70E-10
325 2.79E-10
333 2.82E-10