Journal article
Acidity of M(VI)O 2 (OH) 2 for M = Group 6, 16, and U as Central Atoms
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.121(5), p.1041
02/09/2017
Handle:
https://hdl.handle.net/2376/114187
PMID: 28075585
Abstract
Gas-phase acidities and aqueous solution pK
's are predicted for MO
(OH)
, where the center atom M is a main Group 6, 16, and U atom using the Feller-Peterson-Dixon approach based on coupled cluster CCSD(T) calculations with additional corrections. The gas-phase acidities of the MO
(OH)
compounds are essentially the same for elements (M) of the same group, 304-310 kcal/mol at 298 K. All of the Group 6 compounds are 5-6 kcal/mol less acidic in the gas phase than H
SO
. The gas-phase acidity of UO
(OH)
is calculated to be up to 338.0 kcal/mol, ∼10% less acidic in the gas phase than the other MO
(OH)
acids. The most acidic molecule in aqueous solution is predicted to be H
SO
. Overall, for the Group 16 compounds, the pK
's increase going down the group, with H
PoO
predicted to be slightly more acidic than nitric acid. H
CrO
is the most acidic of the Group 6 transition metal compounds. The aqueous acidities of H
MoO
and H
WO
are comparable and about 3 pK
units less acidic than H
CrO
and comparable in acidity to HNO
. H
UO
is not acidic at all in aqueous solution with a pK
near 20 pK
units and is also not predicted to readily undergo hydrolysis reactions.
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Details
- Title
- Acidity of M(VI)O 2 (OH) 2 for M = Group 6, 16, and U as Central Atoms
- Creators
- Rulin Feng - Department of Chemistry, Washington State University , Pullman, Washington 99164-4630, United StatesMonica Vasiliu - Department of Chemistry, The University of Alabama , Shelby Hall, Tuscaloosa, Alabama 35487-0336, United StatesKirk A Peterson - Department of Chemistry, Washington State University , Pullman, Washington 99164-4630, United StatesDavid A Dixon - Department of Chemistry, The University of Alabama , Shelby Hall, Tuscaloosa, Alabama 35487-0336, United States
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.121(5), p.1041
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900547416601842
- Language
- English
- Resource Type
- Journal article