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- W2904376476 endingPage "191" @default.
- W2904376476 startingPage "170" @default.
- W2904376476 abstract "Aldehydes represent an intermediate redox state of organic carbon and can be precursors to carboxylic acids via disproportionation. A model aldehyde, benzaldehyde, was subjected to hydrothermal experiments (250–350 °C, saturation pressure) to assess the kinetics and mechanisms of the reactions leading to carboxylic acids. The concentration dependence demonstrates the kinetics are second-order in benzaldehyde, consistent with a disproportionation reaction, which is reminiscent of the base-promoted Cannizzaro reaction known at lower temperatures. Arrhenius parameters for these rate constants trend well with data from most, but not all, previous studies for the reaction under supercritical conditions. The rate constants yielded an entropy of activation (ΔS‡) of −161 J mol–1 K–1, consistent with a bimolecular transition state at the rate-limiting step. Experimental yields of benzoic acid and benzyl alcohol were not equal, unlike what is expected for the disproportionation reaction. A kinetic model that included many secondary reactions was developed and was able to reproduce the observed yields of benzyl alcohol and benzoic acid, indicating that disproportionation and subsequent secondary reactions can explain the observed product yields. Experiments at different pH values demonstrated that while the reaction can be expedited by hydroxide, as traditionally understood, at lower pH the rate is independent of pH, indicating the neutral hydrate is capable of hydride donation to another benzaldehyde molecule in the rate-limiting step. Aldehyde disproportionation offers an alternative pathway to ketone oxidation for the formation of carboxylic acids in geologic environments where they are abundant, such as sedimentary basins." @default.
- W2904376476 created "2018-12-22" @default.
- W2904376476 creator A5007970581 @default.
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- W2904376476 date "2018-12-11" @default.
- W2904376476 modified "2023-10-17" @default.
- W2904376476 title "Production of Carboxylic Acids from Aldehydes under Hydrothermal Conditions: A Kinetics Study of Benzaldehyde" @default.
- W2904376476 cites W115743938 @default.
- W2904376476 cites W1965594678 @default.
- W2904376476 cites W1969051824 @default.
- W2904376476 cites W1972125845 @default.
- W2904376476 cites W1976737382 @default.
- W2904376476 cites W1977548550 @default.
- W2904376476 cites W1977927881 @default.
- W2904376476 cites W1978380609 @default.
- W2904376476 cites W1981592573 @default.
- W2904376476 cites W1982578809 @default.
- W2904376476 cites W1982894212 @default.
- W2904376476 cites W1985155518 @default.
- W2904376476 cites W1989951589 @default.
- W2904376476 cites W1990536516 @default.
- W2904376476 cites W1994585846 @default.
- W2904376476 cites W1999166177 @default.
- W2904376476 cites W2001432744 @default.
- W2904376476 cites W2001481384 @default.
- W2904376476 cites W2001937523 @default.
- W2904376476 cites W2002499895 @default.
- W2904376476 cites W2003083308 @default.
- W2904376476 cites W2003484831 @default.
- W2904376476 cites W2004025816 @default.
- W2904376476 cites W2008889869 @default.
- W2904376476 cites W2014365296 @default.
- W2904376476 cites W2014528151 @default.
- W2904376476 cites W2016702532 @default.
- W2904376476 cites W2016880005 @default.
- W2904376476 cites W2017128538 @default.
- W2904376476 cites W2017625487 @default.
- W2904376476 cites W2018807578 @default.
- W2904376476 cites W2021330878 @default.
- W2904376476 cites W2022838773 @default.
- W2904376476 cites W2025877412 @default.
- W2904376476 cites W2028375788 @default.
- W2904376476 cites W2029343525 @default.
- W2904376476 cites W2030709999 @default.
- W2904376476 cites W2031949647 @default.
- W2904376476 cites W2036692849 @default.
- W2904376476 cites W2040735551 @default.
- W2904376476 cites W2043062751 @default.
- W2904376476 cites W2045951612 @default.
- W2904376476 cites W2059072333 @default.
- W2904376476 cites W2064735458 @default.
- W2904376476 cites W2064775421 @default.
- W2904376476 cites W2065364168 @default.
- W2904376476 cites W2069672475 @default.
- W2904376476 cites W2070002206 @default.
- W2904376476 cites W2070247799 @default.
- W2904376476 cites W2071858434 @default.
- W2904376476 cites W2074550123 @default.
- W2904376476 cites W2074968565 @default.
- W2904376476 cites W2083128202 @default.
- W2904376476 cites W2084297777 @default.
- W2904376476 cites W2084840802 @default.
- W2904376476 cites W2087596710 @default.
- W2904376476 cites W2091197819 @default.
- W2904376476 cites W2092725966 @default.
- W2904376476 cites W2102653059 @default.
- W2904376476 cites W2105722596 @default.
- W2904376476 cites W2106051032 @default.
- W2904376476 cites W2115722351 @default.
- W2904376476 cites W2121615354 @default.
- W2904376476 cites W2123134406 @default.
- W2904376476 cites W2125284409 @default.
- W2904376476 cites W2136973503 @default.
- W2904376476 cites W2137698957 @default.
- W2904376476 cites W2147437902 @default.
- W2904376476 cites W2158847234 @default.
- W2904376476 cites W2165738701 @default.
- W2904376476 cites W2171764294 @default.
- W2904376476 cites W2177064492 @default.
- W2904376476 cites W2269577387 @default.
- W2904376476 cites W2317125081 @default.
- W2904376476 cites W2326380944 @default.
- W2904376476 cites W2326802047 @default.
- W2904376476 cites W2329340339 @default.
- W2904376476 cites W2770063217 @default.
- W2904376476 cites W2808547642 @default.
- W2904376476 cites W2892390301 @default.
- W2904376476 cites W2949868638 @default.
- W2904376476 cites W2952087764 @default.
- W2904376476 cites W93093154 @default.
- W2904376476 doi "https://doi.org/10.1021/acsearthspacechem.8b00130" @default.
- W2904376476 hasPublicationYear "2018" @default.
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