Reactivity of 2-ethyl-1-hexanol in the atmosphere

Abstract

Rate coefficients at room temperature for the reaction of 2-ethyl-1-hexanol with OH and NO(3) radicals and with Cl atoms have been determined in a 150 L PTFE chamber using GC-FID/SPME and FTIR as detection systems. The rate coefficients k (in units of cm(3) molecule(-1) s(-1)) obtained were: (1.13 +/- 0.31) 10(-11) for the OH reaction, (2.93 +/- 0.92) 10(-15) for the NO(3) reaction and (1.88 +/- 0.25) 10(-10) for the Cl reaction. Despite the high concentrations of 2-ethyl-1-hexanol, especially in indoor air, this is the first kinetic study carried out to date for these reactions. The results are consistent with the expected reactivity given the chemical structure of 2-ethyl-1-hexanol. Calculated atmospheric lifetimes reveal that the dominant loss process for 2-ethyl-1-hexanol is clearly the daytime reaction with the hydroxyl radical.

Prediction of Rate Constants for Gas‐Phase Reactions of Nitrate Radical with Organic Compounds: A New Structure–Activity Relationship

“…these compounds, the agreement between calculated and experimental determination is reasonable, except for the saturated alcohols. The study of Garcia et al [92] shows clearly an increase of the rate constants for alcohols with increasing carbon chain length which can not be reproduced with this SAR. This predictive failure of the SAR is not surprising considering the uncertainties in the values of the measured rate constants for the four saturated alcohols taken into account.…”

“…Thus, we tested our SAR on two saturated alcohols, four unsaturated esters, one unsaturated ketone and three ethylene glycol vinyl ethers for which the rate constants were measured recently by Wang et al, [89,90] Zhou et al [91] and Garcia et al [92] A comparison of the experimental and calculated rate constants is given in Table 10. For Table 9.…”

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

“…From the slopes of the plots (k SA /k R ) and using known values of the rate coefficients for the reference compounds employed (k R ), the value of the absolute rate coefficient for each saturated alcohol (k SA ) was determined. Rate coefficients of the reactions of reference compounds with Cl atom reactions (in 10 −10 cm 3 molecule −1 s −1 ) were 3.40 ± 0.28 for 2methylpropene, 3.38 ± 0.48 for 1-butene (Ezzel et al, 2002), and 2.23 ± 0.31 for propene (Ceacero-Vega et al, 2009); rate coefficients of the reactions of reference compounds with OH radicals (in 10 −11 cm 3 molecule −1 s −1 ) were 2.66±0.40 for propene (Atkinson and Aschmann, 1989), 6.77 ± 1.69 for cyclohexene (Atkinson and Arey, 2003), 0.51 ± 0.008 for isopropanol (IUPAC http://www.iupac-kinetic.ch.cam.ac.uk, last access: 19 December 2017), and 0.36 ± 0.06 for 2methyl-2-butanol (Jiménez et al, 2005); and rate coefficients of the reactions of reference compounds with NO 3 radicals (in 10 −15 cm 3 molecule −1 s −1 ) were 3.14 ± 0.97 for 1butanol and 2.93 ± 0.92 2-ethyl-1-hexanol (Gallego-Iniesta et al, 2010).…”

“…It is known that organic compounds that react in the same way with different atmospheric oxidants present a correlation between their rate coefficients. In this sense, over the years, different correlations have been proposed to allow the estimation of the unknown rate coefficient when the other is known (Wayne et al, 1991;Wayne, 2000;Atkinson, 1994;Calvert et al, 2011;Gallego-Iniesta et al, 2014). The log k Cl -log k OH and log k NO 3 -log k OH correlations have been built for a set of ethers and saturated alcohols by Calvert et Table 2.…”