Theoretical study of the first acid dissociation of H2SO4 at a model aqueous surface

被引：30

作者：

Bianco, R ^{[1
]}

Wang, SZ

Hynes, JT

机构：

[1] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA

[2] Ecole Normale Super, CNRS, Dept Chim, UMR 8640, F-75231 Paris, France

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2005年 / 109卷 / 45期

关键词：

D O I：

10.1021/jp055107t

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Electronic structure calculations on the H2SO4.(H2O)(4.6) model system embedded at the surface of an aqueous layer have been performed to examine the feasibility of the first acid dissociation of H2SO4 to an HSO4-.H3O+ contact ion pair over a wide temperature range, with a special focus on the 190-250 K range relevant for atmospheric sulfate aerosols. The results indicate that the acid dissociation can be either thermodynamically favored or disfavored depending on the degree of solvation of the acid and the produced ions, as well as on the temperature.

引用

页码：21313 / 21321

页数：9

共 74 条

[11]

BIANCO R, IN PRESS

[12]

BIANCO R, IN PRESS ACC CHEM RE

[13]

BIANCO R, UNPUB

[14] Semiempirical QM/MM method for studying HCl adsorption on ice [J].

Bolton, K .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2004, 96 (06) :607-614

[15] Heterogeneous reactions on stratospheric background aerosols, volcanic sulfuric acid droplets, and type I polar stratospheric clouds: Effects of temperature fluctuations and differences in particle phase [J].

Borrmann, S ;

Solomon, S ;

Dye, JE ;

Baumgardner, D ;

Kelly, KK ;

Chan, KR .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1997, 102 (D3) :3639-3648

[16] Structure and vibrational spectroscopy of salt water/air interfaces: Predictions from classical molecular dynamics simulations [J].

Brown, EC ;

Mucha, M ;

Jungwirth, P ;

Tobias, DJ .

JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (16) :7934-7940

[17] Modeling the composition of liquid stratospheric aerosols [J].

Carslaw, KS ;

Peter, T ;

Clegg, SL .

REVIEWS OF GEOPHYSICS, 1997, 35 (02) :125-154

[18] The effective fragment model for solvation: Internal rotation in formamide [J].

Chen, W ;

Gordon, MS .

JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (24) :11081-11090

[19] EFFICIENT DIFFUSE FUNCTION-AUGMENTED BASIS SETS FOR ANION CALCULATIONS. III. THE 3-21+G BASIS SET FOR FIRST-ROW ELEMENTS, LI-F [J].

CLARK, T ;

CHANDRASEKHAR, J ;

SPITZNAGEL, GW ;

SCHLEYER, PV .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1983, 4 (03) :294-301

[20] An effective fragment method for modeling solvent effects in quantum mechanical calculations [J].

Day, PN ;

Jensen, JH ;

Gordon, MS ;

Webb, SP ;

Stevens, WJ ;

Krauss, M ;

Garmer, D ;

Basch, H ;

Cohen, D .

JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (05) :1968-1986

← 1 2 3 4 5 6 7 8 →