Anhydrous hydrogen fluoride: Vapor pressure and liquid density

Sheft, I.; Perkins, Alfred J.; Hyman, Herbert H.

doi:10.1016/0022-1902(73)80055-7

Cited by 34 publications

(22 citation statements)

References 9 publications

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“…For proton-containing solutions, the deviation between pHA C H T U N G T R E N N U N G (real) = Àlog a and pHA C H T U N G T R E N N U N G (ideal) = Àlog c is described by Equation (18) and the chemical potential decrease of the proton is according to Equation (19 ). [59,60] is one of the most important solvents in superacid chemistry. It is known that the HF molecules are strongly associated to one another and the structure in solution is a complex mixture of oligomers, far away from an ideal continuum.…”

mentioning

confidence: 99%

Anchor Points for the Unified Brønsted Acidity Scale: The rCCC Model for the Calculation of Standard Gibbs Energies of Proton Solvation in Eleven Representative Liquid Media

Himmel

Goll

Leito

et al. 2011

Chemistry A European J

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The COSMO cluster-continuum (CCC) solvation model is introduced for the calculation of standard Gibbs solvation energies of protons. The solvation sphere of the proton is divided into an inner proton-solvent cluster with covalent interactions and an outer solvation sphere that interacts electrostatically with the cluster. Thus, the solvation of the proton is divided into two steps that are calculated separately: 1) The interaction of the proton with one or more solvent molecules is calculated in the gas phase with high-level quantum-chemical methods (modified G3 method). 2) The Gibbs solvation energy of the proton-solvent cluster is calculated by using the conductor-like screening model (COSMO). For every solvent, the solvation of the proton in at least two (and up to 11) proton-solvent clusters was calculated. The resulting Gibbs solvation energies of the proton were weighted by using Boltzmann statistics. The model was evaluated for the calculation of Gibbs solvation energies by using experimental data of water, MeCN, and DMSO as a reference. Allowing structural relaxation of the proton-solvent clusters and the use of structurally relaxed Gibbs solvation energies improved the accordance with experimental data especially for larger clusters. This variation is denoted as the relaxed COSMO cluster-continuum (rCCC) model, for which we estimate a 1σ error bar of 10 kJ mol(-1) . Gibbs solvation energies of protons in the following representative solvents were calculated: Water, acetonitrile, sulfur dioxide, dimethyl sulfoxide, benzene, diethyl ether, methylene chloride, 1,2-dichloroethane, sulfuric acid, fluorosulfonic acid, and hydrogen fluoride. The obtained values are absolute chemical standard potentials of the proton (pH=0 in this solvent). They are used to anchor the individual solvent specific acidity (pH) scales to our recently introduced absolute acidity scale.

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mentioning

confidence: 99%

Anchor Points for the Unified Brønsted Acidity Scale: The rCCC Model for the Calculation of Standard Gibbs Energies of Proton Solvation in Eleven Representative Liquid Media

Himmel

Goll

Leito

et al. 2011

Chemistry A European J

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“…The nonpolarizable models tend to predict densities much higher than experiment, especially in the case of the TIPS model. However, it is noteworthy that the densities given by Pártay and co-workers for the TIPS model at states C (1.276 ± 0.021 g/cm 3 ) and D (1.300 ± 0.041 g/cm 3 ) are within uncertainty of each other, suggesting that the qualitatively incorrect trend of the TIPS model may be due to convergence issues.…”

Section: Densitymentioning

confidence: 76%

“…Densities of the 11 states in g/cm 3 from XPHF compared to several other models and experiment. Unless otherwise noted, all values for the other models originate from 4 Notice that the polarizable models (XPHF, PJV-P, JV-P) predict densities in better qualitative and quantitative agreement with experiment than the non-polarizable models (JV-NP, HF-Kr, TIPS).…”

Section: Densitymentioning

confidence: 99%

“…In 1984, Cournoyer and Jorgensen introduced the three-site TIPS model for liquid HF, 25 which greatly improved the accuracy of computed thermodynamic properties of the liquid state as compared to experiment. [3][4][5] The following year, the first neutron diffraction study of deuterium fluoride (DF) was published, 6 providing structural information, including radial distribution functions at 293 K. A direct comparison to predictions from the TIPS model was provided in that study, showing TIPS to be surprisingly accurate at 293 K.…”

Section: Introductionmentioning

confidence: 99%

“…1 It is commonly used in industrial applications such as glass etching, where it reacts with silicon dioxide to produce hexafluorosilic acid Although progress has been made, 1,[3][4][5][6][7][8][9][10][11][12][13][14] the amount of experimental data concerning the structure and physical properties of HF is scarce in comparison to other simple fluids of small molecules, due to experimental difficulties. As a result, there is great interest in developing computational models for HF, which can produce accurate dynamic and thermodynamic properties across a wide range of temperatures and pressures.…”

Section: Introductionmentioning

confidence: 99%

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Quantum mechanical force field for hydrogen fluoride with explicit electronic polarization

Mazack

Gao

2014

The Journal of Chemical Physics

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The explicit polarization (X-Pol) theory is a fragment-based quantum chemical method that explicitly models the internal electronic polarization and intermolecular interactions of a chemical system. X-Pol theory provides a framework to construct a quantum mechanical force field, which we have extended to liquid hydrogen fluoride (HF) in this work. The parameterization, called XPHF, is built upon the same formalism introduced for the XP3P model of liquid water, which is based on the polarized molecular orbital (PMO) semiempirical quantum chemistry method and the dipole-preserving polarization consistent point charge model. We introduce a fluorine parameter set for PMO, and find good agreement for various gas-phase results of small HF clusters compared to experiments and ab initio calculations at the M06-2X/MG3S level of theory. In addition, the XPHF model shows reasonable agreement with experiments for a variety of structural and thermodynamic properties in the liquid state, including radial distribution functions, interaction energies, diffusion coefficients, and densities at various state points.

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