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Title: Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory

Abstract

Density functional calculations have been performed on several protonation states of the oxyacids of Si, P, V, As, Cr, and S. Structures and vibrational frequencies are in good agreement with experimental values where these are available. A reasonably well-defined correlation between the calculated gas-phase acidities and the measured pK{sub a} in aqueous solution has been found. The pK{sub a}/gas-phase acidity slopes are consistent with those derived from previous molecular mechanics calculations on ferric hydrolysis and the first two acidity constants for orthosilicic acid. The successive deprotonation of other H{sub n}TO{sub 4} species, for a given tetrahedral anion T are roughly consistent with this slope, but not to the extent that there is a universal correlation among all species.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab., Richland, WA (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20034423
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 104; Journal Issue: 17; Other Information: PBD: 4 May 2000; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; INORGANIC ACIDS; SILICON COMPOUNDS; GROUND WATER; VANADIUM COMPOUNDS; ARSENIC COMPOUNDS; CHROMIC ACID; SULFURIC ACID; PHOSPHORIC ACID

Citation Formats

Rustad, J.R., Dixon, D.A., Kubicki, J.D., and Felmy, A.R. Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory. United States: N. p., 2000. Web. doi:10.1021/jp993421f.
Rustad, J.R., Dixon, D.A., Kubicki, J.D., & Felmy, A.R. Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory. United States. doi:10.1021/jp993421f.
Rustad, J.R., Dixon, D.A., Kubicki, J.D., and Felmy, A.R. Thu . "Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory". United States. doi:10.1021/jp993421f.
@article{osti_20034423,
title = {Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory},
author = {Rustad, J.R. and Dixon, D.A. and Kubicki, J.D. and Felmy, A.R.},
abstractNote = {Density functional calculations have been performed on several protonation states of the oxyacids of Si, P, V, As, Cr, and S. Structures and vibrational frequencies are in good agreement with experimental values where these are available. A reasonably well-defined correlation between the calculated gas-phase acidities and the measured pK{sub a} in aqueous solution has been found. The pK{sub a}/gas-phase acidity slopes are consistent with those derived from previous molecular mechanics calculations on ferric hydrolysis and the first two acidity constants for orthosilicic acid. The successive deprotonation of other H{sub n}TO{sub 4} species, for a given tetrahedral anion T are roughly consistent with this slope, but not to the extent that there is a universal correlation among all species.},
doi = {10.1021/jp993421f},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 17,
volume = 104,
place = {United States},
year = {2000},
month = {5}
}