Water-catalyzed mechanism for the pyrolysis of formic acid

Citation
Bs. Wang et al., Water-catalyzed mechanism for the pyrolysis of formic acid, CHEM PHYS, 243(1-2), 1999, pp. 27-34
Citations number
14
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
CHEMICAL PHYSICS
ISSN journal
03010104 → ACNP
Volume
243
Issue
1-2
Year of publication
1999
Pages
27 - 34
Database
ISI
SICI code
0301-0104(19990501)243:1-2<27:WMFTPO>2.0.ZU;2-W
Abstract
The water-catalyzed mechanism for the pyrolysis of formic acid was studied by the ab initio quantum chemical calculations. The dehydration and decarbo xylation reactions of formic acid occur via five- and six-member-ring hydro gen bonding complexes and transition states, respectively. The role of the water molecule is to serve as a proton relay acting simultaneously as a hyd rogen-atom donor and acceptor. The corresponding potential energy surface w as obtained at G2(MP2) level of theory. The large scatter in the reported e xperimental activation barriers for the dehydration and decarboxylation rea ction of formic acid was explained reasonably. (C) 1999 Elsevier Science B. V. All rights reserved.