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.: Home > Nature and Science > 2016 > Volume 14 Number 4 > Adejoro Isaiah Ajibade, Adeboye Omolara Olubunmi

Computational studies on the α- and β- Elimination Pathways for the Kinetics and Thermodynamics of the Gas-Phase Pyrolysis of Allyl Formates

Adejoro Isaiah Ajibade, Adeboye Omolara Olubunmi
Chemistry Department, University of Ibadan, Nigeria Telephone: 08058584417; E-mail: moadeb5848@yahoo.com
Abstract :

The study of α- and β-elimination pathways for the pyrolysis kinetics and thermodynamics of allyl formate was carried out in the gas-phase using Density Functional Theory (DFT with B3LYP at 6-311++G (2DF, 2P) in Spartan. The two pathways proceeded through a six-centered cyclic transition state. The result obtained for the [Cα-O, (43-46%) Cα-H11 and Cβ-H5 (9-10%)] bond lengthening character in a single step suggested that the reaction is concerted and asynchronous. The energy of formation for the α-elimination pathway that is elimination initiated from the formyl moiety is lower compare with the β-elimination pathway, elimination initiated from the allyl moiety. The activation parameters [Ea=178.59kJ/mol, log A=10.10 s-1 ∆H*=172.79 kJ/mol ∆S*=8.16J/mol.K and ∆G*= 167.20kJ/mol] obtained for the α-elimination pathway are in good agreement with the experimental value than the values obtained for the β-elimination pathway.

Keywords :
Allyl formates, pyrolysis, pathways, Elimination, DFT calculations

Date Deposited : 22 Nov 2016 19:17

Last Modified : 22 Nov 2016 19:17

Official URL: http://www.sciencepub.net/nature/

Volume 14, Number 4, - 2016

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