Reactions of some Carboxylic Acid Esters with O(<sup>3</sup>P) Atoms

Mix, K.-H.; Schliephake, V.; Wagner, H. Gg.

doi:10.1524/zpch.1986.150.1.017

Cited by 6 publications

(8 citation statements)

References 6 publications

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“…4. In general, the results obtained in this work were comparable to those reported by Mix et al (2), which are also plotted in Fig. 4 for comparison.…”

Section: Reactions Of O(~p) With Carboxylic Acidssupporting

confidence: 91%

“…The observation that the Arrhenius preexponential factors increase systematically with increasing size of the -OR group also supports this assumption. The rate constants for reactions [2] and [3] are known from previous work (8,17) and, with the results of our experiments, permit estimation of the relative importance of reactions [I. ]- [3].…”

Section: Mechanisms and Productssupporting

confidence: 58%

“…]- [3]. In all our experiments, the rate of reaction [3] was at least a factor of four larger than the rate of reaction [2], so the dominant fate of OH was reaction with the ester rather than reaction with o(~P). This is borne out by measurements of the yields of water in the reaction of o(~P) with methyl acetate, presented in Table 2, in which the water yields were nearly equal to the amount of o(~P) consumed.…”

Section: Mechanisms and Productsmentioning

confidence: 59%

“…For personal use only. ever, the reactions of some acetate and formate esters have been studied from approximately 300 to 420 K by measuring the rate of loss of the organic reagent under conditions of excess o (~P ) in a flow system (2). In that work, the Arrhenius preexponential factors were approximately an order of magnitude larger than those for the reactions with ketones and the activation ener ies were significantly larger than those for the…”

Section: Introductionmentioning

confidence: 99%

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The reactions of O(³P) with some carboxylic acids and esters

Caravan¹,

Budge²,

Roscoe³

1996

Can. J. Chem.

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The reactions of o(~P) with formic acid, acetic acid, methyl acetate, ethyl acetate, n-propyl acetate, and isopropyl acetate have been studied kinetically as a function of temperature. The rate constants were measured in a discharge-flow system under pseudo-first-order conditions with a large excess of the organic reagent. No reaction could be found between o(~P) and either formic acid or acetic acid in the temperature range 300-420 K. The acetate esters, on the other hand, reacted with 0c3P) at readily measurable rates over the same temperature range. The temperature dependence of the rate constants for these reactions in the temperature range 300-580 K is given, in the units L mol-' s-I, by: Le fait qu'il ne se produise pas de rCactions a des vitesses mesurables avec les acides carboxyliques, qu'il y a une augmentation systCmatique dans le facteur prkexponentiel avec l'augmentation du groupe ester et que l'on observe la formation d'acide acCtique avec un rendement significatif parmi les produits des rCactions avec les esters indique que l'attaque par o(~P) se fait surtout au niveau de la fonction ester. On a utilisC des corrClations linCaires d'Cnergie libre pour comparer les resultats pour les esters avec ceux pour des rCactions de o(~P) avec d'autres composts organiques contenant de l'oxygkne.Mots clis : cinetique, mecanisme, rtactions du o(~P) avec les esters.

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“…4. In general, the results obtained in this work were comparable to those reported by Mix et al (2), which are also plotted in Fig. 4 for comparison.…”

Section: Reactions Of O(~p) With Carboxylic Acidssupporting

confidence: 91%

Section: Mechanisms and Productssupporting

confidence: 58%

Section: Mechanisms and Productsmentioning

confidence: 59%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The reactions of O(³P) with some carboxylic acids and esters

Caravan¹,

Budge²,

Roscoe³

1996

Can. J. Chem.

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“…Arthur and Newitt, 19 and Ferguson and Pearson 20 both measured rate constants for H-abstraction from MA by CH 3 at low temperature. Peukert et al 21 computed the rate constants for H-abstraction from MA by H and CH 3 and also obtained the experimentally derived coefficients for abstraction by H in the temperature range 1222−1313 K. Caravan et al 22 and Mix et al 23 studied the total consumption rates of MA by O( 3 P) in an O atom-rich environment and concluded that the abstraction reactions contributed most to the total rates. Most of these experiments were conducted over small temperature ranges and could not measure the branching ratio of the two Habstraction channels from the two methyl groups in MA, which largely determines the product distributions from combustion.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Kinetics of Hydrogen Abstraction from Methyl Acetate by Hydrogen, Methyl, Oxygen, Hydroxyl, and Hydroperoxy Radicals

et al. 2015

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The kinetics of hydrogen abstraction by five radicals (H, O((3)P), OH, CH3, and HO2) from methyl acetate (MA) is investigated theoretically in order to gain further understanding of certain aspects of the combustion chemistry of biodiesels, such as the effect of the ester moiety. We employ ab initio quantum chemistry methods, coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) and multireference averaged coupled pair functional theory (MRACPF2), to predict chemically accurate reaction energetics. Overall, MRACPF2 predicts slightly higher barrier heights than CCSD(T) for MA + H/CH3/O/OH, but slightly lower barrier heights for hydrogen abstraction by HO2. Based on the obtained reaction energies, we also report high-pressure-limit rate constants using transition state theory (TST) in conjunction with the separable-hindered-rotor approximation, the variable reaction coordinate TST, and the multi-structure all-structure approach. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predictions are in good agreement with available experimental results. Abstractions from both of the methyl groups in MA are expected to contribute to consumption of the fuel as they exhibit similar rate coefficients. The reactions involving the OH radical are predicted to have the highest rates among the five abstracting radicals, while those initiated by HO2 are expected to be the lowest.

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