Kinetics of oxidation of monohydric aliphatic alcohols by ozone

Шерешовец, В. В.; Galieva, F. A.; Akhunov, I. R.; Комиссаров, В. Д.; Tsarkov, A. V.; Бикбулатов, И. Х.

doi:10.1007/bf00956138

Cited by 2 publications

(4 citation statements)

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“…As shown in Figure , with only propane in the feed, the CO 2 selectivity is ∼66%. Similarly, high CO 2 selectivity was also reported in gas-phase ozonation of propane at 50 °C. , The C 3 oxygenates are likely much more reactive with ozone compared to propane. , As such, the effect of isobutane addition is even more pronounced for propane compared to n -butane. Adding 33 mole % isobutane doubles the IPA yield compared to neat propane and diminishes the CO 2 selectivity drastically to ∼16% while increasing the overall hydrocarbon conversion.…”

Section: Resultsmentioning

confidence: 65%

“… 27 , 28 The C 3 oxygenates are likely much more reactive with ozone compared to propane. 74 , 75 As such, the effect of isobutane addition is even more pronounced for propane compared to n -butane. Adding 33 mole % isobutane doubles the IPA yield compared to neat propane and diminishes the CO 2 selectivity drastically to ∼16% while increasing the overall hydrocarbon conversion.…”

Section: Resultsmentioning

confidence: 99%

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Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Zhu

Jackson

Subramaniam

2023

JACS Au

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We have demonstrated the oxidation of mixed alkanes (propane, nbutane, and isobutane) by ozone in a condensed phase at ambient temperature and mild pressures (up to 1.3 MPa). Oxygenated products such as alcohols and ketones are formed with a combined molar selectivity of >90%. The ozone and dioxygen partial pressures are controlled such that the gas phase is always outside the flammability envelope. Because the alkane−ozone reaction predominantly occurs in the condensed phase, we are able to harness the unique tunability of ozone concentrations in hydrocarbon-rich liquid phases for facile activation of the light alkanes while also avoiding over-oxidation of the products. Further, adding isobutane and water to the mixed alkane feed significantly enhances ozone utilization and the oxygenate yields. The ability to tune the composition of the condensed media by incorporating liquid additives to direct selectivity is a key to achieving high carbon atom economy, which cannot be achieved in gas-phase ozonations. Even in the liquid phase, without added isobutane and water, combustion products dominate during neat propane ozonation, with CO 2 selectivity being >60%. In contrast, ozonation of a propane+isobutane+water mixture suppresses CO 2 formation to 15% and nearly doubles the yield of isopropanol. A kinetic model based on the formation of a hydrotrioxide intermediate can adequately explain the yields of the observed isobutane ozonation products. Estimated rate constants for the formation of oxygenates suggest that the demonstrated concept has promise for facile and atom-economic conversion of natural gas liquids to valuable oxygenates and broader applications associated with C−H functionalization.

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Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 99%

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Zhu

Jackson

Subramaniam

2023

JACS Au

View full text Add to dashboard Cite

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“…The effect of substitutes on the reactivity for the studied reactions in aqueous solutions is described satisfactorily by the TaR equation (Fig. 3, Table 2): lgk=lgko+ p* a* Methanol [4], phenylcarbinol and tert-pentanol, with which ozone reacts not with a CH-bond but with the hydroxy group of the molecule, fall out of this dependence. A low value of the reaction series constant p* = -2.72, obtained from the experimental data given in Fig.3, indicates that the charge formed in the transient state is insignificant, and it is stabilized to a greater extent by the oxygen atom of the hydroxy group than by the substituent [11 ].…”

Section: Fig 2 Compensation Effect In the Ozone Reaction With Alcoholsmentioning

confidence: 93%

“…The kinetic characteristics of this reaction are obtained for a large number of alcohols in various solvents [2][3][4][5]. At the same time, quantitative data of the reaction of ozone with alcohols in aqueous solutions are not numerous and rather contradictory [1, 3,4].…”

Section: Introductionmentioning

confidence: 99%