Rate constants of OH radical reactions in gas phase with some fluorinated compounds: A correlation with molecular parameters
โ 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
No coin nor oath required. For personal study only.
โฆ 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.
๐ SIMILAR VOLUMES
Using a relative rate method, rate constants have been measured for the gasphase reactions of the OH radical with the dibasic esters dimethyl succinate The rate constants ob-298 ฯฎ 3 K. tained were (in units of ): dimethyl succinate, dimethyl 10 cm molecule s 1.4 ฯฎ 0.6; glutarate, and dimethyl adip
Using a relative rate method, rate constants for the gas-phase reactions of 2methyl-3-buten-2-ol (MBO) with OH radicals, ozone, NO 3 radicals, and Cl atoms have been investigated using FTIR. The measured values for MBO at and total 298 ฯฎ 2 K 740 ฯฎ 5 torr pressure are: ฯช11 3 ฯช1 ฯช1 ฯช18 3 k ฯญ (3.9 ฯฎ 1.
By using relative rate methods, rate constants for the gas-phase reactions of OH and NO 3 radicals with propanal, butanal, pentanal, and hexanal have been measured at 296 ฯฎ 2 K and atmospheric pressure of air. By using methyl vinyl ketone as the reference compound, the rate constants obtained for th
Rate constants for three dimethylbenzaldehydes and two trimethylphenols have been determined for the OH reactions at and atmospheric pressure using a relative rate method. The OH reaction rate constants were placed on an absolute basis using the literature rate constant for 1,2,4-trimethylbenzene of