Title

Chemical Reaction Co+Oh• → Co2+H• Autocatalyzed By Carbon Dioxide: Quantum Chemical Study Of The Potential Energy Surfaces

Abstract

The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

Publication Date

8-4-2016

Publication Title

Journal of Physical Chemistry A

Volume

120

Issue

30

Number of Pages

6023-6028

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1021/acs.jpca.6b03242

Socpus ID

84982798163 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/84982798163

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