Evaluating the Thermodynamic Consistency of Experimental Data for HF + H<sub>2</sub>O at 101.325 kPa

and, Christina M. Smith; Visco, Donald P.

doi:10.1021/je034154g

Cited by 4 publications

(3 citation statements)

References 13 publications

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“…This is mainly because of the deficiency of the model in incorporating the strong HF−water interactions. Such complex interactions in this system are also reinforced by the evaluation of the thermodynamic consistency of three experimental data sets available for this mixture at 1 atm ,, and also from molecular simulation studies on this mixture. Both approaches indicate that the dilute HF and dilute water regions of this mixture may result in unusual infinite dilution fugacity coefficients and a fluorophobic-like effect, which only goes toward providing more evidence as to the complexity of this mixture and the modeling challenges this system possesses.…”

Section: Introductionmentioning

confidence: 75%

Association Patterns in (HF)_m(H₂O)_n (m + n = 2−8) Clusters

2007

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In an attempt to understand the phase behavior of aqueous hydrogen fluoride, the clustering in the mixture is investigated at the molecular level. The study is performed at the mPW1B95/6-31+G(d,p) level of theory. Several previous studies attempted to describe the dissociation of HF in water, but in this investigation, the focus is only on the association patterns that are present in this binary mixture. A total of 214 optimized geometries of (HF)n(H2O)m clusters, with m + n as high as 8, were investigated. For each cluster combination, several different conformations are investigated, and the preferred conformations are presented. Using multiple linear regressions, the average strengths of the four possible H-bonding interactions are obtained. The strongest H-bond interaction is reported to be the H2O...H-F interaction. The most probable distributions of mixed clusters as a function of composition are also deduced. It is found that the larger (HF)n(H2O)m clusters are favored both energetically and entropically compared to the ones that are of size m + n < or = 3. Also, the clusters with equimolar contributions of HF and H2O are found to have the strongest interactions.

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Section: Introductionmentioning

confidence: 75%

Association Patterns in (HF)_m(H₂O)_n (m + n = 2−8) Clusters

2007

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“…The phase equilibrium properties of the binary mixture are obtained by considering all 14 different association schemes for HF and with a 1−2 association scheme for water. The binary interaction parameter is optimized for minimum deviation from the experimental T − x − y results. − While optimizing the θ ij , it was important to achieve a balance in accuracy on both the correlation of the T − x−y data in the region of higher concentrations of HF and the composition at which the azeotrope was reported. All of the self-association schemes showed approximately 1% deviation from the experimental data.…”

Section: Mixture Resultsmentioning

confidence: 99%

Methodology for the Development of Thermodynamic Models Describing Substances That Exhibit Complex Association Interactions

Baburao

Visco

2011

J. Chem. Eng. Data

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This work describes a methodology for the development of a thermodynamic model describing the substances that show strong self- and cross-association interactions. The methodology is fundamentally based on the chemical theory of association interactions. The system used as a case study in this work is a binary mixture containing hydrogen fluoride and water (HF + H2O). Earlier studies have failed to provide a reasonable description of this binary mixture because of the complex association interactions between these compounds, which were not adequately modeled. In this work, the phase behavior of this mixture is understood by exploring these complex association interactions. Pure HF was modeled using 14 different association schemes that allow the formations of different physically meaningful oligomers with different distribution schemes (1−2, 1−6, 1−2−6, etc.), where the 1−2 scheme allows the formation of monomers and dimers and likewise. The parameters for these pure component schemes were obtained by correlating the phase coexistence properties of pure HF and were also used to predict several other pure component properties (ΔH vap, C P , C v , Z, etc.) The dominance of these association patterns and their distribution were understood on the basis of their predictive ability. The pure component association schemes that were developed for HF and water were extended to the binary mixture. The phase coexistence properties were correlated using different association patterns for the pure components with and without considerations for the strong association between them. The significance of these self- and cross-association patterns are studied and understood on the basis of the correlative and the predictive ability of the association schemes. The effect of including the cross-associates that are most likely to be formed in this mixture, from a molecular level hybrid meta-density functional theory study, is also discussed. The methodology described in this work can be utilized to understand and predict the bulk-phase thermodynamic properties of substances that show complex association interactions at a molecular level.

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“…14,15 The thermodynamic modelling of these systems is also shown to be difficult possibly due to the inaccuracy of the model which fails to incorporate strong HB interactions between HF and water molecules correctly. [16][17][18] The HF and H 2 O both form strong selfassociating F-HÁ Á ÁF and O-HÁ Á ÁO and cross-associating F-HÁ Á ÁO and O-HÁ Á ÁF HB interactions in these HF-water mixtures. 19 Thus, in order to understand the properties of HF-water mixtures, it is indispensable to have quantitative estimates of these different HB interactions.…”

Section: Introductionmentioning

confidence: 99%

Assessment of hydrogen bond strengths and cooperativity in self- and cross-associating cyclic (HF)_m(H₂O)_n(m+n= 2 to 8) clusters

et al. 2022

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Evaluating the Thermodynamic Consistency of Experimental Data for HF + H₂O at 101.325 kPa

Cited by 4 publications

References 13 publications

Association Patterns in (HF)_m(H₂O)_n (m + n = 2−8) Clusters

Association Patterns in (HF)_m(H₂O)_n (m + n = 2−8) Clusters

Methodology for the Development of Thermodynamic Models Describing Substances That Exhibit Complex Association Interactions

Assessment of hydrogen bond strengths and cooperativity in self- and cross-associating cyclic (HF)_m(H₂O)_n(m+n= 2 to 8) clusters

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Evaluating the Thermodynamic Consistency of Experimental Data for HF + H2O at 101.325 kPa

Cited by 4 publications

References 13 publications

Association Patterns in (HF)m(H2O)n (m + n = 2−8) Clusters

Association Patterns in (HF)m(H2O)n (m + n = 2−8) Clusters

Methodology for the Development of Thermodynamic Models Describing Substances That Exhibit Complex Association Interactions

Assessment of hydrogen bond strengths and cooperativity in self- and cross-associating cyclic (HF)m(H2O)n(m+n= 2 to 8) clusters

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Evaluating the Thermodynamic Consistency of Experimental Data for HF + H₂O at 101.325 kPa

Association Patterns in (HF)_m(H₂O)_n (m + n = 2−8) Clusters

Association Patterns in (HF)_m(H₂O)_n (m + n = 2−8) Clusters

Assessment of hydrogen bond strengths and cooperativity in self- and cross-associating cyclic (HF)_m(H₂O)_n(m+n= 2 to 8) clusters