Rate constants for reactions of hydroxyl radicals with alcohol vapours at 292 K

Campbell, Ian; McLaughlin, David F.; Handy, Brian J.

doi:10.1016/0009-2614(76)85174-3

Cited by 68 publications

(23 citation statements)

References 8 publications

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“…They show a small increase with temperature, and over the range 273–343 K give k 6 = (9.8 ± 0.45) × 10 −12 exp[(−172 ± 210)/ T ] cm 3 molecule −1 s −1 No other Arrhenius parameters are available for reaction (6), but Table III compares the values obtained at room temperature. Atkinson et al 13 have remarked that the low value obtained by Campbell et al 18 may have been caused by undetected problems with the experimental technique. The agreement with the other results is excellent when it is considered that both absolute and relative rate techniques were employed, the latter with three different reference compounds.…”

Section: Resultsmentioning

confidence: 95%

Kinetics and mechanism associated with the reactions of hydroxyl radicals and of chlorine atoms with 1‐propanol under near‐tropospheric conditions between 273 and 343 K

Cheema

Holbrook

Oldershaw

et al. 2001

Int J of Chemical Kinetics

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Rate constants for the reactions of OH radicals and Cl atoms with 1-propanol (1-C 3 H 7 OH) have been determined over the temperature range 273-343 K by the use of a relative rate technique. The value of k(Cl + 1-C 3 H 7 OH) = (1.69 ± 0.19) × 10 −12 cm 3 molecule −1 s −1 at 298 K and shows a small increase of 10% between 273 and 342 K. The value of k(OH + 1-C 3 H 7 OH) increases by 14% between 273 and 343 K with a value of (5.50 ± 0.55) × 10 −12 cm 3 molecule −1 s −1 at 298 K, and further when combined with a single independent experimentally determined value at 753 K gives k(OH + 1-C 3 H 7 OH) = 4.69 × 10 −17 T 1.8 exp(422/T) cm 3 molecule −1 s −1 , which fits each data point to better than 2%. Two well-established structure-activity relationships for H abstraction by OH radicals give accurate predictions of the rate constant for OH + 1-C 3 H 7 OH, provided the β-CH 2 group is given an increased reactivity of a factor of about 2 over that for the structurally equivalent CH 2 group in alkanes at 298 K. REACTIONS OF HYDROXYL RADICALS AND CHLORINE ATOMS WITH 1-PROPANOL 111A quantitative product analysis was carried out at 298 K for the Cl-initiated photooxidation of 1-C 3 H 7 OH, using both FTIR and gas chromatography. HCHO, CH 3 CHO, and C 2 H 5 CHO were the only major organic primary products observed, although HCOOH was found in much smaller amounts as a secondary product. A key characteristic of the analysis was that the initial values of the product ratio [CH 3 CHO]/[C 2 H 5 CHO] were effectively constant for NO pressures between 0.15 and 0.3 Torr, but fell by about 35% as the pressure fell to 0.0375 Torr. From a detailed consideration of the mechanism for the oxidation, it is suggested that C 2 H 5 CHO, CH 3 CHO (+HCHO), and 3 molecules of HCHO are formed uniquely from CH 3 CH 2 CHOH, CH 3 CHCH 2 OH, and CH 2 CH 2 CH 2 OH radicals, respectively. On this basis, use of the product yields gives the branching ratios of 56, 30, and 14% for Cl atom reaction at the α-, β-, and γ-C H positions in 1-C 3 H 7 OH at 298 K. Given the very low temperature coefficients involved, little change will occur over tropospheric temperature ranges.

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Section: Resultsmentioning

confidence: 95%

Kinetics and mechanism associated with the reactions of hydroxyl radicals and of chlorine atoms with 1‐propanol under near‐tropospheric conditions between 273 and 343 K

Cheema

Holbrook

Oldershaw

et al. 2001

Int J of Chemical Kinetics

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“…Values of the rate constants for the reaction of OH with alcohols are in reasonable accord with the available data in the literature. A number of relative rate studies [17,20,21] have utilized nonphotolytic techniques to generate OH radicals at atmospheric pressure. The agreement found with the present relative rate studies suggests problems arising from formation of other reactive species in the system by secondary photolysis of products such as aldehydes or ketones must be largely unimportant in this work.…”

Section: Discussionmentioning

confidence: 99%

Absolute and relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols and ethers at 298 K

Nelson

Rattigan

Neavyn

et al. 1990

Int J of Chemical Kinetics

197

201

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Rate constants for the gas-phase reactions of hydroxyl radicals and chlorine atoms with aliphatic alcohols and ethers have been determined at 298 f 2 K and at a total pressure of 1 atmosphere. The OH radical rate data were obtained using both the absolute technique of pulse radiolysis combined with kinetic UV spectroscopy and a conventional photolytic relative rate method. The C1 atom rate constants were measured using only the relative rate method.

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“…Numerous studies have reported the rate coefficients for the reactions of n ‐propanol and iso ‐propanol with OH in the gas phase 5–15. Even though the reported values of k 1 (298 K) agree well with each other, the values of k 1 below 298 K are uncertain.…”

Section: Introductionmentioning

confidence: 95%