Bulk Gas-Phase Acidity

被引：15

作者：

Himmel, Daniel ^{[1
,2
]}

Goll, Sascha K. ^{[1
,2
]}

Leito, Ivo ^{[3
]}

Krossing, Ingo ^{[1
,2
]}

机构：

[1] Univ Freiburg, Inst Anorgan & Analyt Chem, Freiburger Mat Forschungszentrum FMF, D-79104 Freiburg, Germany

[2] Univ Freiburg, Freiburg Inst Adv Studies FRIAS, D-79104 Freiburg, Germany

[3] Univ Tartu, Inst Chem, EE-50411 Tartu, Estonia

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2012年 / 18卷 / 30期

关键词：

ab initio calculations; acidity; chemical potential; gas-phase reactions; thermodynamics; NEUTRAL BRONSTED ACIDS; BASIS-SETS; SUPERACIDIC PROPERTIES; CONJUGATE ACIDS; COUPLED-CLUSTER; ENERGIES; ELECTRON; PROTON; SCALE; APPROXIMATION;

D O I：

10.1002/chem.201104025

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The capability of a gaseous Bronsted acid HB to deliver protons to a base is usually described by the gas-phase acidity (GA) value of the acid. However, GA values are standard Gibbs energy differences and refer to individual gas pressures of 1 bar for acid HB, base B-, and proton H+. We show that the GA value is not suited to describe the bulk acidity of a gaseous acid. Here the pressure dependence of the activities of HB, H(HB)n+, and B(HB)m- that result from gaseous autoprotolysis have to be considered. In this work, the pressure-dependent absolute chemical potential of the proton in the representative gaseous proton acids CH4, NH3, H2O, HF, and HCl was worked out and the general theory to describe bulk gas phase aciditythat can directly be compared with solution aciditywas developed.

引用

页码：9333 / 9340

页数：8

共 40 条

[1] ELECTRONIC-STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS - THE PROGRAM SYSTEM TURBOMOLE [J].

AHLRICHS, R ;

BAR, M ;

HASER, M ;

HORN, H ;

KOLMEL, C .

CHEMICAL PHYSICS LETTERS, 1989, 162 (03) :165-169

[2] Determination of Gas-Phase Acidities of Dimethylphenols: Combined Experimental and Theoretical Study [J].

Arnorim Madeira, Paulo J. ;

Costa, Paulo Jorge ;

Fernandez, Maria Tereza ;

Martinho Simoes, Jose A. ;

Leal, Joao Paulo .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2008, 19 (11) :1590-1599

[3] THERMODYNAMICS OF THE ELECTRON AND THE PROTON [J].

BARTMESS, JE .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (25) :6420-6424

[4] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[5] Basis set limit coupled cluster study of h-bonded systems and assessment of more approximate methods [J].

Boese, A. Daniel ;

Martin, Jan M. L. ;

Klopper, Wim .

JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (43) :11122-11133

[6]

Burk P, 1996, J COMPUT CHEM, V17, P30, DOI 10.1002/(SICI)1096-987X(19960115)17:1<30::AID-JCC3>3.0.CO

[7]

2-1

[8] Critical test of performance of B3LYP functional for prediction of gas-phase acidities and basicities [J].

Burk, P ;

Koppel, IA ;

Koppel, I ;

Leito, I ;

Travnikova, O .

CHEMICAL PHYSICS LETTERS, 2000, 323 (5-6) :482-489

[9] An efficient implementation of second analytical derivatives for density functional methods [J].

Deglmann, P ;

Furche, F ;

Ahlrichs, R .

CHEMICAL PHYSICS LETTERS, 2002, 362 (5-6) :511-518

[10] Efficient characterization of stationary points on potential energy surfaces [J].

Deglmann, P ;

Furche, F .

JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (21) :9535-9538

← 1 2 3 4 →