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Rate constants of OH radical reactions in gas phase with some fluorinated compounds: A correlation with molecular parameters

โœ Scribed by S. Dhanya; R. D. Saini


Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
136 KB
Volume
29
Category
Article
ISSN
0538-8066

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โœฆ Synopsis


For a number of hydrofluorocarbons (HFCs), E H e z has been found to have a linear correlation with each of the following: (i) log (k /n); (ii) A/n; and (iii) E a /R, where E H ฯญ HOMO energy of the molecule, z ฯญ average fractional positive charge on the abstractable hydrogen atom in the molecule, k ฯญ rate constant of the gas-phase H abstraction reaction of the molecule with OH radical at 298 K, n ฯญ number of abstractable H atoms in the molecule, A ฯญ preexponential factor, and E a /R ฯญ activation temperature of the said reaction. These correlations have been used to estimate the temperature dependent rate constants for the reactions of OH radical with CF 3 CF 2 CH 2 CH 2 CF 2 CF 3 , CF 3 CH 2 CF 2 CH 2 CF 3 , CF 3 CF 2 CH 2 CH 2 F, CF 3 CH 2 CH 3 , CF 3 CH 2 CHF 2 , CF 3 CHFCH 2 F, and CHF 2 CHFCHF 2 as {6.97 ฯซ 10 ฯช13 exp(1481/ T)}, {5.43 ฯซ 10 ฯช13 exp(1754/ T )}, {7.95 ฯซ 10 ฯช13 exp(1308/ T )}, {8.0 ฯซ 10 ฯช13 exp(1300/ T )}, {7.03 ฯซ 10 ฯช13 exp(1470/ T )}, {7.33 ฯซ 10 ฯช13 exp(1417/ T )}, and {8.09 ฯซ 10 ฯช13 exp(1285/ T)}, respectively. These have not yet been measured experimentally. Linear correlation between E H e z and log (k/n) has also been observed for nine halogen substituted acetaldehydes. On the other hand, E H is found to have a better linear correlation with log (k/n) than E H e z in the case of fluorinated ethers and alcohols where the available experimental data are at present limited.


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