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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.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
984715
Report Number(s):
ANL/MSD/JA-66939
Journal ID: 1520-6106; TRN: US201016%%1437
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
J. Chem. Phys. B
Additional Journal Information:
Journal Volume: 114; Journal Issue: 27 ; Jul. 15, 2010
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

Citation Formats

Assary, R S, Redfern, P C, Hammond, J R, Greeley, J, Curtiss, L A, and Northwestern Univ. Computational studies of the thermochemistry for conversion of glucose to levulinic acid.. United States: N. p., 2010. Web. doi:10.1021/jp101418f.
Assary, R S, Redfern, P C, Hammond, J R, Greeley, J, Curtiss, L A, & Northwestern Univ. Computational studies of the thermochemistry for conversion of glucose to levulinic acid.. United States. https://doi.org/10.1021/jp101418f
Assary, R S, Redfern, P C, Hammond, J R, Greeley, J, Curtiss, L A, and Northwestern Univ. Thu . "Computational studies of the thermochemistry for conversion of glucose to levulinic acid.". United States. https://doi.org/10.1021/jp101418f.
@article{osti_984715,
title = {Computational studies of the thermochemistry for conversion of glucose to levulinic acid.},
author = {Assary, R S and Redfern, P C and Hammond, J R and Greeley, J and Curtiss, L A and Northwestern Univ.},
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/984715}, journal = {J. Chem. Phys. B},
number = 27 ; Jul. 15, 2010,
volume = 114,
place = {United States},
year = {2010},
month = {7}
}