High-temperature measurements of the reactions of OH with small methyl esters: methyl formate, methyl acetate, methyl propanoate, and methyl butanoate.

Abstract

The overall rate constants for the reactions of hydroxyl radicals (OH) with four small methyl esters, namely methyl formate (CH(3)OCHO), methyl acetate (CH(3)OC(O)CH(3)), methyl propanoate (CH(3)OC(O)C(2)H(5)), and methyl butanoate (CH(3)OC(O)C(3)H(7)), were investigated behind reflected shock waves using UV laser absorption of OH radicals near 306.69 nm. Test gas mixtures of individual methyl esters and tert-butyl hydroperoxide (TBHP), a fast source of OH at elevated temperatures, diluted in argon were shock-heated to temperatures spanning from 876 to 1371 K at pressures near 1.5 atm. The overall rate constants were determined by matching the measured OH time-histories with the computed profiles from the comprehensive chemical kinetic mechanisms of Dooley et al. (2010) and Dooley et al. (2008), which were originally developed for the oxidation of methyl formate and methyl butanoate, respectively. These measured values can be expressed in Arrhenius form as k(CH(3)OCHO+OH) = 2.56 × 10(13) exp(-2026/T) cm(3) mol(-1) s(-1), k(CH(3)OC(O)CH(3)+OH) = 3.59 × 10(13) exp(-2438/T) cm(3) mol(-1) s(-1), k(CH(3)OC(O)C(2)H(5)+OH) = 6.65 × 10(13) exp(-2539/T) cm(3) mol(-1) s(-1), and k(CH(3)OC(O)C(3)H(7)+OH) = 1.13 × 10(14) exp(-2515/T) cm(3) mol(-1) s(-1) over the temperature ranges studied. Detailed error analyses were performed to estimate the overall uncertainties of these reactions, and the estimated (2σ) uncertainties were found to be ±29% at 913 K and ±18% at 1289 K for k(CH(3)OCHO+OH), ± 29% at 930 K and ±17% at 1299 K for k(CH(3)OC(O)CH(3)+OH), ± 25% at 909 K and ±17% at 1341 K for k(CH(3)OC(O)C2H(5)+OH), and ±24% at 925 K and ±16% at 1320 K for k(CH(3)OC(O)C(3)H(7)+OH). We believe these are the first direct high-temperature rate constant measurements for the reactions of OH with these small methyl esters. These measured rate constants were also compared with the estimated values employed in different comprehensive kinetic mechanisms. Additionally, the structure-activity relationship from Kwok and Atkinson (1995) was used to estimate these four rate constants, and the estimations from this group-additivity model are in good agreement with the measurements (within ~25%) at the present experimental conditions.

• Authors: King-Yiu Lam, David F Davidson, Ronald K Hanson
• Journal: The journal of physical chemistry. A (J Phys Chem A) Vol. 116 Issue 50 Pg. 12229-41 (Dec 20 2012) ISSN: 1520-5215 [Electronic] United States
• PMID: 23194350 (Publication Type: Journal Article, Research Support, U.S. Gov't, Non-P.H.S.)

Chemical References

• Acetates
• Esters
• Formic Acid Esters
• Propionates
• Butyric Acid
• methyl formate
• Hydroxyl Radical
• methyl acetate

Topics

• Acetates (chemistry)
• Butyric Acid (chemistry)
• Esters
• Formic Acid Esters (chemistry)
• Hydroxyl Radical (chemistry)
• Kinetics
• Propionates (chemistry)
• Structure-Activity Relationship
• Temperature