Kinetics of Decomposition Reactions of Acetic Acid Using DFT Approach
Anand Mohan Verma, Nanda Kishore*
Identifiers and Pagination:Year: 2018
First Page: 14
Last Page: 23
Publisher Id: TOCENGJ-12-14
Article History:Received Date: 17/08/2017
Revision Received Date: 01/12/2017
Acceptance Date: 21/01/2018
Electronic publication date: 08/02/2018
Collection year: 2018
open-access license: This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 International Public License (CC-BY 4.0), a copy of which is available at: https://creativecommons.org/licenses/by/4.0/legalcode. This license permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
Excessive amount of oxygen content in unprocessed bio-oil deteriorates the quality of bio-oil which cannot be used in transportation vehicles without upgrading. Acetic acid (CH3COOH) is a vital component of ‘acids’ catalogue of unprocessed bio-oil produced from thermochemical conversions of most of biomass feedstocks such as switchgrass, alfalfa, etc. In this study, the decomposition reactions of acetic acid are carried out by two reaction pathways, i.e., decarboxylation and dehydration reactions. In addition, the reaction rates of decomposition are analysed in a wide range of temperatures, i.e., 298-900 K and at atmospheric pressure.
All quantum chemical calculations are performed in the gas phase using two DFT functionals, B3LYP and M06-2X, with 6-31g(d) basis set. The dehydration reaction of acetic acid proceeds directly from ground state structure of acetic acid, whereas, decarboxylation reaction forms an unstable intermediate of acetic acid to initiate the proton migration. Barrier height and kinetics study for both reactions and theories are different and illustrated in the reaction pathway and rate profiles, respectively. Furthermore, both levels of theories offer similar structural configurations but they differ slightly in energetics.
The reaction kinetics of both reactions is linearly fitted and the Arrhenius equations corresponding to each decomposition mechanism are generated by fitting the data from line equation.