Catalytic dehydration of alcohols by OH. 2-Propanol: An intermediate case

Journal Article · Thu Jun 17 00:00:00 EDT 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100126a021· OSTI ID:6073340

Dunlop, J R; Tully, F P ^[1]

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1. Sandia National Lab., Livermore, CA (United States)

The authors describe a laser photolysis/cw, laser-induced fluorescence kinetic study of the reaction-between OH and 2-propanol, measured over the temperature range 293--745 K. The rate coefficient for hydrogen atom abstraction by OH from 2-propanol is best fit by the expression k(T) = 1.044 [times] 10[sup [minus]17] T[sup 1.86] exp(736/T)cm[sup 3] molecule [sup [minus]1] s[sup [minus]1]. Chain-catalytic dehydration of 2-propanol by OH is an important component of the reaction mechanism. By using isotopic substitution, they determine, as a function of temperature, the branching ratio for H atom abstraction by OH from the [beta]-sites of 2-propanol. Between 500 and 600 K, biexponential [OH] decays result from the unimolecular decomposition of the H[sub 2]CCH(OH)CH[sub 3] intermediate. The authors characterize the dissociation kinetics of this HO-propene intermediate by fitting biexponential [OH] decays to a reaction model. From these results and previously established kinetic and thermodynamic data, they estimate the strength of a methyl C-H bond in 2-propanol. Measurements above T = 600 K demonstrate a role for two minor reaction channels. 24 refs., 8 figs., 6 tabs.

• OSTI ID: 6073340
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 97:24; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEHYDRATION
REACTION KINETICS
PROPANOLS
CATALYSIS
CHROMATOGRAPHY
DECOMPOSITION
FLUORESCENCE
HYDROXYL RADICALS
LASERS
OXYGEN 16
OXYGEN 18
PHOTOLYSIS
THEORETICAL DATA
ALCOHOLS
CHEMICAL REACTIONS
DATA
EVEN-EVEN NUCLEI
HYDROXY COMPOUNDS
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
LUMINESCENCE
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN ISOTOPES
PHOTOCHEMICAL REACTIONS
RADICALS
SEPARATION PROCESSES
STABLE ISOTOPES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
400500 - Photochemistry