ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
For a number of hydrofluorocarbons (HFCs), EHez has been found to have a linear correlation with each of the following: (i) log (k/n); (ii) A/n; and (iii) Ea/R, where EH = HOMO energy of the molecule, z = average fractional positive charge on the abstractable hydrogen atom in the molecule, k = rate constant of the gas-phase H abstraction reaction of the molecule with OH radical at 298 K, n = number of abstractable H atoms in the molecule, A = preexponential factor, and Ea/R = 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 CF3CF2CH2CH2CF2CF3, CF3CH2CF2CH2CF3, CF3CF2CH2CH2F, CF3CH2CH3, CF3CH2CHF2, CF3CHFCH2F, and CHF2CHFCHF2 as {6.97 × 10-13 exp(1481/T)}, {5.43 × 10-13 exp(1754/T)}, {7.95 × 10-13 exp(l308/T)}, {8.0 × 10-13 exp(1300/T)}, {7.03 × 10-13 exp(1470/T)}, {7.33 × 10-13 exp(1417/T)}, and {8.09 × 10-13 exp(1285/T)}, respectively. These have not yet been measured experimentally. Linear correlation between EHez and log (k/n) has also been observed for nine halogen substituted acetaldehydes. On the other hand, EH is found to have a better linear correlation with log (k/n) than EHez in the case of fluorinated ethers and alcohols where the available experimental data are at present limited. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 187-194, 1997.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
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