Rates of hydroxyl radical reactions. Part 14. Rate constant and mechanism for the reaction of hydroxyl radical with formic acid

Jolly, G.; McKenney, D. J.; Singleton, D. L.; Paraskevopoulos, G.; Bossard, Alain R.

doi:10.1021/j100282a028

Cited by 44 publications

(48 citation statements)

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“…The yields of OH from reaction (4) [30,31] and NO3 from reaction (5) [32] are known to be near unity, and dark reactions of HN03 (and a small amount of impurity N02) with the sulfides appear to be negligible on the time scale of the experiment. The above NO3 production scheme does, however, have one important drawback.…”

Section: Daykln and Winementioning

confidence: 98%

A study of the reactions of NO₃ radicals with organic sulfides: Reactivity trend at 298 K

Daykin

Wine

1990

Int J of Chemical Kinetics

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A laser flash photolysis-long path laser absorption technique has been employed to investigate the kinetics of NO3 reactions with CH3SCH3(kl), CDsSCD3(kz), and CzH5SCzHS(k3) in 500 torr air at 298 K. The dependence of k l on total pressure (20-500 torr) and oxygen partial pressure (0-100 torr) has also been investigated, with no dependence observed. Measured rate coefficients in units of cm3 molecule-' s-' are kl = 13 2 3, k p = 3.4 2 0.8, and k3 = 48 2 12, where the quoted uncertainties are %estimates of absolute accuracy. The magnitude of NO3 + sulfide rate coefficients and negative activation energies for k l (reported by other investigators) suggest that reaction does not proceed via a direct hydrogen abstraction mechanism. However, the reactivity trend observed in this study provides evidence that the reaction mechanism does involve breaking a carbon-hydrogen bond.

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Section: Daykln and Winementioning

confidence: 98%

A study of the reactions of NO₃ radicals with organic sulfides: Reactivity trend at 298 K

Daykin

Wine

1990

Int J of Chemical Kinetics

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“…Figure 3 shows such a correlation for the reactions of o(~P) and OH with a selection of aldehydes, ketones, ethers, and alcohols (9,12,13). The intersections of the vertical lines with the regression line indicate the rate constants to be expected for the reactions of o (~P ) with formic acid and acetic acid if the mechanisms of their reactions were consistent with the rest of the correlation.…”

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

confidence: 77%

“…The sample contained 92% formic acid and 8% water, which is necessary for stability. The formic acid was used without drying since it has been found that dry formic acid gives erratic kinetic results (9). Acetic acid (BDH 99.7%), acetone (Anachemia, toxigraphic, distilled in glass), methyl acetate (Aldrich, anhyd., 99%+), ethyl acetate (Aldrich, anhyd., 99.8%), n-propyl acetate (Aldrich, 99%), and isopropyl acetate (Aldrich, 99%) were analysed by gas chromatography and contained no detectable organic impurities.…”

Section: Methodsmentioning

confidence: 99%

“…It has been found that (9,12,13), in the reactions of OH with formic acid and acetic acid, the monomeric form of the acid is much more reactive than the dimer. The possibility that the apparent lack of reactivity might be due to dimerization of the acid was tested by calculating the monomerldimer concentration ratios for our experiments using the equilibrium data reported by Biittner and Maurer (14).…”

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

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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“…At ambient conditions, it's well accepted that Å OH preferably attacks the O-H bond (e.g. HCO(O-H) (Wine et al, 1985;Jolly et al, 1986;Dagaut et al, 1988;Singleton et al, 1988), however, photolysis experiments at higher temperatures (25-172°C and 400°C) suggest that hydrogen extraction from the H-C site is also significant (Singleton et al, 1988;Hess and Tully, 1989;Akiya and Savage, 1998). The latter might play a role in the d 13 C kinetic isotope effect observed in our study for dissolved HCOOH (aq) evolving through Fenton processes.…”

Section: Resultsmentioning

confidence: 99%

Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

Foustoukos

Stern

2012

Geochimica et Cosmochimica Acta

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In order to evaluate the oxidation effect of dissolved hydrogen peroxide and the catalytic role of iron oxides on the kinetics of formic acid decarboxylation, a series of flow-through hydrothermal experiments was conducted at temperatures ranging from 80 to 150°C and pressures of 172-241 bar. d 13 C composition of residual HCOOH (aq) was also monitored to examine kinetic isotope effects associated with oxidation processes. Our results reveal that decomposition of H 2 O 2(aq) in presence of magnetite follows pseudo first order kinetics, highly enhanced relative to the homogeneous H 2 O 2(aq) -HCOOOH (aq) -H 2 O system, which possibly reflect synthesis of hydroxyl radicals ( Å OH) through Fenton processes. The kinetic rate constants of HCOOH (aq) decarboxylation to CO 2(aq) are also elevated relative to those previously measured in H 2 O 2(aq) free experiments. However, reaction kinetics are slightly slower in the case of H 2 O 2(aq) aqueous solutions coexisting with magnetite than in the absence of mineral phases. This behavior is attributed to the possible formation of Fe-bearing hydroxyl formate aqueous species that could serve as stable transition states leading to a decrease in the activation entropy of formic acid decomposition.d 13 C values of residual formic acid in the homogeneous H 2 O 2(aq) -HCOOH (aq) -H 2 O system are consistent with previous studies. However, magnetite-bearing experiments produce a negative shift in d 13 C of residual formic acid, perhaps specific to Å OH-imposed oxidation of organic compounds. This would indicate that isotopic fractionations by this oxidation pathway are opposite to kinetic fractionation effects expected in biologically driven oxidation processes. This could have important implications for putative H 2 O 2(aq) -bearing Martian subsurface environments and the evolution of organics at low-temperature hydrothermal conditions.

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Rates of hydroxyl radical reactions. Part 14. Rate constant and mechanism for the reaction of hydroxyl radical with formic acid

Cited by 44 publications

References 1 publication

A study of the reactions of NO₃ radicals with organic sulfides: Reactivity trend at 298 K

A study of the reactions of NO₃ radicals with organic sulfides: Reactivity trend at 298 K

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

Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

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Rates of hydroxyl radical reactions. Part 14. Rate constant and mechanism for the reaction of hydroxyl radical with formic acid

Cited by 44 publications

References 1 publication

A study of the reactions of NO3 radicals with organic sulfides: Reactivity trend at 298 K

A study of the reactions of NO3 radicals with organic sulfides: Reactivity trend at 298 K

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

Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

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A study of the reactions of NO₃ radicals with organic sulfides: Reactivity trend at 298 K

A study of the reactions of NO₃ radicals with organic sulfides: Reactivity trend at 298 K

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