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Title: Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions

Abstract

Bio-oil produced from biomass fast pyrolysis often requires catalytic upgrading to remove oxygen and acidic species over zeolite catalysts. The elementary reactions in the mechanism for this process involve carbenium and oxonium ions. In order to develop a detailed kinetic model for the catalytic upgrading of biomass, rate constants are required for these elementary reactions. The parameters in the Arrhenius equation can be related to thermodynamic properties through structure-reactivity relationships, such as the Evans-Polanyi relationship. For this relationship, enthalpies of formation of each species are required, which can be reasonably estimated using group additivity. However, the literature previously lacked group additivity values for oxygenates, oxonium ions, and oxygen-containing carbenium ions. In this work, 71 group additivity values for these types of groups were regressed, 65 of which had not been reported previously and six of which were newly estimated based on regression in the context of the 65 new groups. Heats of formation based on atomization enthalpy calculations for a set of reference molecules and isodesmic reactions for a small set of larger species for which experimental data was available were used to demonstrate the accuracy of the Gaussian-4 quantum mechanical method in estimating enthalpies of formation for species involvingmore » the moieties of interest. Isodesmic reactions for a total of 195 species were constructed from the reference molecules to calculate enthalpies of formation that were used to regress the group additivity values. The results showed an average deviation of 1.95 kcal/mol between the values calculated from Gaussian-4 and isodesmic reactions versus those calculated from the group additivity values that were newly regressed. Importantly, the new groups enhance the database for group additivity values, especially those involving oxonium ions.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [1]
  1. Department of Chemical and Biological Engineering, Northwestern University, Evanston, Illinois 60208, United States
  2. National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1402557
Report Number(s):
NREL/JA-2700-70342
Journal ID: ISSN 0888-5885
DOE Contract Number:
AC36-08GO28308
Resource Type:
Journal Article
Resource Relation:
Journal Name: Industrial and Engineering Chemistry Research; Journal Volume: 56; Journal Issue: 37
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; bio-oils; biomass; pyrolysis

Citation Formats

Dellon, Lauren D., Sung, Chun-Yi, Robichaud, David J., and Broadbelt, Linda J.. Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions. United States: N. p., 2017. Web. doi:10.1021/acs.iecr.7b02605.
Dellon, Lauren D., Sung, Chun-Yi, Robichaud, David J., & Broadbelt, Linda J.. Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions. United States. doi:10.1021/acs.iecr.7b02605.
Dellon, Lauren D., Sung, Chun-Yi, Robichaud, David J., and Broadbelt, Linda J.. 2017. "Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions". United States. doi:10.1021/acs.iecr.7b02605.
@article{osti_1402557,
title = {Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions},
author = {Dellon, Lauren D. and Sung, Chun-Yi and Robichaud, David J. and Broadbelt, Linda J.},
abstractNote = {Bio-oil produced from biomass fast pyrolysis often requires catalytic upgrading to remove oxygen and acidic species over zeolite catalysts. The elementary reactions in the mechanism for this process involve carbenium and oxonium ions. In order to develop a detailed kinetic model for the catalytic upgrading of biomass, rate constants are required for these elementary reactions. The parameters in the Arrhenius equation can be related to thermodynamic properties through structure-reactivity relationships, such as the Evans-Polanyi relationship. For this relationship, enthalpies of formation of each species are required, which can be reasonably estimated using group additivity. However, the literature previously lacked group additivity values for oxygenates, oxonium ions, and oxygen-containing carbenium ions. In this work, 71 group additivity values for these types of groups were regressed, 65 of which had not been reported previously and six of which were newly estimated based on regression in the context of the 65 new groups. Heats of formation based on atomization enthalpy calculations for a set of reference molecules and isodesmic reactions for a small set of larger species for which experimental data was available were used to demonstrate the accuracy of the Gaussian-4 quantum mechanical method in estimating enthalpies of formation for species involving the moieties of interest. Isodesmic reactions for a total of 195 species were constructed from the reference molecules to calculate enthalpies of formation that were used to regress the group additivity values. The results showed an average deviation of 1.95 kcal/mol between the values calculated from Gaussian-4 and isodesmic reactions versus those calculated from the group additivity values that were newly regressed. Importantly, the new groups enhance the database for group additivity values, especially those involving oxonium ions.},
doi = {10.1021/acs.iecr.7b02605},
journal = {Industrial and Engineering Chemistry Research},
number = 37,
volume = 56,
place = {United States},
year = 2017,
month = 9
}