Kinetic study of the reactions of CN with ethane and propane

Journal Article · Thu Aug 24 00:00:00 EDT 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100354a025· OSTI ID:7108164

Hess, W P; Durant, Jr, J J; Tully, F P ^[1]

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1. Sandia National Labs., Livermore, CA (USA)

Absolute rate coefficients for the reactions of CN with ethane, propane, and five of their deuterated isotopes are determined over the temperature range 294-736 K by using the laser photolysis/CW laser-induced-fluorescence technique. The measured rate coefficients for the reactions of CN with C{sub 2}H{sub 6} (k{sub 1}) and C{sub 2}D{sub 6} (k{sub 2}) are well described by the three-parameter modified Arrhenius expressions k{sub 1}(T) = (7.40 {times} 10{sup {minus}15})T{sup 1.29} exp(+512 cal mol{sup {minus}1}/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} and k{sub 2}(T) = (8.32 {times} 10{sup {minus}16})T{sup 1.57} exp(+460 cal mol{sup {minus}1}/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The rate coefficient for the reaction of CN with the half-deuterated ethane compound, CH{sub 3}CD{sub 3} (k{sub 3}), is well described ty (1/2)(k{sub 1} + k{sub 2}). We measure rate coefficients for CN reactions with C{sub 3}H{sub 8} (k{sub 4}), C{sub 3}D{sub 8} (k{sub 5}), C{sub 3}H{sub 6}D{sub 2} (k{sub 6}), and C{sub 3}D{sub 6}H{sub 2} (k{sub 7}) and derive site-specific rate constants for abstraction of primary and secondary hydrogens. These rate coefficients, on a per hydrogen atom basis, are, in the units cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, k{sub H}{sup P}(T) = (3.58 {times} 10{sup {minus}15})T{sup 1.14} exp(+566 cal mol{sup {minus}1}/RT), k{sub D}{sup P}(T) = (2.63 {times} 10{sup {minus}16})T{sup 1.47} exp(+568 cal mol{sup {minus}1}/RT), k{sub H}{sup S}(T) = (3.30 {times} 10{sup {minus}13})T{sup 0.56} exp(+649 cal mol{sup {minus}1}/RT), and k{sub D}{sup S}(T) = (2.96 {times} 10{sup {minus}13})T{sup 0.52} exp(+656 cal mol{sup {minus}1}/RT). The k{sub 4} through k{sub 7} are well represented by the sum of the appropriate three-parameter expressions for H- and D-atom abstraction from primary and secondary sites.

• OSTI ID: 7108164
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:17; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CYANIDES
DATA
DATA ANALYSIS
ETHANE
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOTOPE EFFECTS
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
PROPANE
REACTION KINETICS