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Title: Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid

Abstract

The thermochemistry of the conversion of glucose to levulinic acid through fructofuranosyl intermediates is investigated using the high-level ab initio methods G4 and G4MP2. The calculated gas phase reaction enthalpies indicate that the first two steps involving water molecule elimination are highly endothermic, while the other steps, including additional water elimination and rehydration to form levulinic acid, are exothermic. The calculated gas phase free energies indicate that inclusion of entropic effects makes the dehydration steps more favorable, although the elimination of the first water is still endothermic. Elevated temperatures and aqueous reaction environments are also predicted to make the dehydration reaction steps thermodynamically more favorable. On the basis of these enthalpy and free energy calculations, the first dehydration step in conversion of glucose to levulinic acid is likely a key step in controlling the overall progress of the reaction. An assessment of density functional theories and other theoretical methods for the calculation of the dehydration and hydration reactions in the decomposition of glucose is also presented.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
990114
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry B, 114(27):9002-9009
Additional Journal Information:
Journal Volume: 114; Journal Issue: 27; Journal ID: ISSN 1520-6106
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DEHYDRATION; ENTHALPY; FREE ENERGY; FUNCTIONALS; GLUCOSE; HYDRATION; LEVULINIC ACID; WATER; Environmental Molecular Sciences Laboratory

Citation Formats

Assary, Rajeev S, Redfern, Paul C, Hammond, Jeffrey R, Greeley, Jeffrey P, and Curtiss, Larry A. Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid. United States: N. p., 2010. Web. doi:10.1021/jp101418f.
Assary, Rajeev S, Redfern, Paul C, Hammond, Jeffrey R, Greeley, Jeffrey P, & Curtiss, Larry A. Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid. United States. https://doi.org/10.1021/jp101418f
Assary, Rajeev S, Redfern, Paul C, Hammond, Jeffrey R, Greeley, Jeffrey P, and Curtiss, Larry A. Thu . "Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid". United States. https://doi.org/10.1021/jp101418f.
@article{osti_990114,
title = {Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid},
author = {Assary, Rajeev S and Redfern, Paul C and Hammond, Jeffrey R and Greeley, Jeffrey P and Curtiss, Larry A},
abstractNote = {The thermochemistry of the conversion of glucose to levulinic acid through fructofuranosyl intermediates is investigated using the high-level ab initio methods G4 and G4MP2. The calculated gas phase reaction enthalpies indicate that the first two steps involving water molecule elimination are highly endothermic, while the other steps, including additional water elimination and rehydration to form levulinic acid, are exothermic. The calculated gas phase free energies indicate that inclusion of entropic effects makes the dehydration steps more favorable, although the elimination of the first water is still endothermic. Elevated temperatures and aqueous reaction environments are also predicted to make the dehydration reaction steps thermodynamically more favorable. On the basis of these enthalpy and free energy calculations, the first dehydration step in conversion of glucose to levulinic acid is likely a key step in controlling the overall progress of the reaction. An assessment of density functional theories and other theoretical methods for the calculation of the dehydration and hydration reactions in the decomposition of glucose is also presented.},
doi = {10.1021/jp101418f},
url = {https://www.osti.gov/biblio/990114}, journal = {Journal of Physical Chemistry B, 114(27):9002-9009},
issn = {1520-6106},
number = 27,
volume = 114,
place = {United States},
year = {2010},
month = {7}
}