Computing MOSCED parameters of nonelectrolyte solids with electronic structure methods in SMD and SM8 continuum solvents

Phifer, Jeremy R.; Solomon, Kimberly J.; Young, Kayla; Paluch, Andrew S.

doi:10.1002/aic.15413

Cited by 17 publications

(21 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As might be expected, UNIFAC‐original has a number of advantages over other conventional models since its comprehensive parameter matrix is being obtained from extensive series of VLE and LLE data‐fitted parameters. Nonetheless, interaction parameters are missing for many complex compounds including ionic liquids and dibasic esters, and predictions with existing parameters have shown appreciable error . Recently, to improve the accuracy of phase equilibrium calculations, newly developed equations of state (EOS), such as APACT, SAFT, HM, CPA‐EOS, DFT, and COSMO‐RS, have originated from the statistical fluid theory coupled with quantum chemistry of LLE, wherein efforts are being made to model novel, complex solvent structures …”

Section: Introductionmentioning

confidence: 99%

“…Nonetheless, interaction parameters are missing for many complex compounds including ionic liquids and dibasic esters, and predictions with existing parameters have shown appreciable error. [26] Recently, to improve the accuracy of phase equilibrium calculations, newly developed equations of state (EOS), such as APACT, SAFT, HM, CPA-EOS, DFT, and COSMO-RS, have originated from the statistical fluid theory coupled with quantum chemistry of LLE, wherein efforts are being made to model novel, complex solvent structures. [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] This paper compares the calculations with UNIFAC-original, SERLAS [42,43] (solvation energy relation for liquid associated systems), and modified versions of the latter to give a realistic picture of whether the selected model structure is appropriate for a design application or not.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Estimation of liquid‐liquid equilibrium of type 2 systems (water + valeric acid + monobasic ester or dibasic ester or alcohol) using SERLAS, SERLAS‐modified, and SERLAS‐integrated

2017

View full text Add to dashboard Cite

This paper studies liquid‐liquid equilibrium (LLE) of the type 2 systems (water + valeric acid + dibasic ester or monobasic ester or alcohol) at T = (298.2 ± 0.1) K and p = (101.3 ± 0.7) kPa. Equilibrium distribution of valeric acid onto (water + solvent) two‐phase system is better for more structured diethyl sebacate and ethyl caprylate as compared to less structured diethyl succinate, diethyl malonate, ethyl valerate, and isoamyl alcohol. The two‐phase envelope size and the tie line slope on the phase diagrams are varying as follows: ethyl caprylate > diethyl sebacate > ethyl valerate > diethyl succinate ≈ diethyl malonate > isoamyl alcohol. The SERLAS‐integrated (solvation energy relation for liquid associated systems‐integrated) molecular model with nine physical descriptors, originated from LSER (linear solvation energy relation) principles in conjunction with group‐contribution method, is proposed and applied to the prediction of type 2 LLE properties. By combining SERLAS with UNIFAC‐Dortmund, we are able to get along with a simultaneous impact of both methods for satisfactorily simulating type 2 phase behaviour so long as solvent effects are concerned. SERLAS, SERLAS‐modified, SERLAS‐integrated, and UNIFAC‐original models have been stringently tested for consistency in reproducing phase equilibrium properties with average deviations inferior to 28.8 %, 44.3 %, 21.3 %, and 30.4 %, respectively.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Estimation of liquid‐liquid equilibrium of type 2 systems (water + valeric acid + monobasic ester or dibasic ester or alcohol) using SERLAS, SERLAS‐modified, and SERLAS‐integrated

2017

View full text Add to dashboard Cite

show abstract

“…Interestingly, ref. 42 suggested that results obtained with MOSCED parameters predicted using solvation free energy calculations with the SMx universal solvent model were superior to predictions made with SMx alone. This may result from implicitly including reference data by using MOSCED parameters that were regressed using reference data.…”

Section: Reference Calculationsmentioning

confidence: 92%

“…At present, MOSCED parameters are available for 130 organic solvents and water [20,74]. Efforts have been made to use electronic structure calculations to predict missing MOSCED parameters, including the use of solvation free energy calculations with the SMx universal solvent models [42,[79][80][81][82][83]. While we would not expect the predicted MOSCED parameters to be as good as those regressed using experimental data, the results of the present study nonetheless would suggest they would yield acceptable results, especially for early stage process conceptualization and design applications.…”

Section: Reference Calculationsmentioning

confidence: 99%

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

Roese¹,

Heintz²,

Uzat³

et al. 2020

Preprint

View full text Add to dashboard Cite

The SMx (x= 12, 8, or D) universal solvent models are implicit solvent models which using electronic structure calculations can compute solvation free energies at 298.15 K. While solvation free energy is an important thermophysical property, within the thermodynamic modeling of phase equilibrium, limiting (or infinite dilution) activity coefficients are preferred since they may be used to parameterize excess Gibbs free energy models to model phase equilibrium. Conveniently, the two quantities are related. Therefore the present study was performed to assess the ability to use the SMx universal solvent models to predict limiting activity coefficients. Two methods of calculating the limiting activity coefficient where compared: 1) The solvation free energy and self-solvation free energy were both predicted and 2) the self-solvation free energy was computed using readily available vapor pressure data. Overall the first method is preferred as it results in a cancellation of errors, specifically for the case in which water is a solute. The SM12 model was compared to both UNIFAC and MOSCED. MOSCED was the highest performer, yet had the smallest available compound inventory. UNIFAC and SM12 exhibited comparable performance. Therefore further exploration and research should be conducted into the viability of using the SMx models for phase equilibrium calculations.

show abstract

“…The solvation free energy in this context is defined as taking a solute from a non-interacting ideal gas state to solution at the same molecular density (or concentration). We have shown previously that the solvation free energy is readily related to the limiting activity coefficient (γ ∞ i,j ) as [24,[37][38][39][40][41][42]:…”

Section: Methodsmentioning

confidence: 99%

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

et al. 2020

Self Cite

View full text Add to dashboard Cite

The SMx (x = 12, 8, or D) universal solvent models are implicit solvent models which using electronic structure calculations can compute solvation free energies at 298.15 K. While solvation free energy is an important thermophysical property, within the thermodynamic modeling of phase equilibrium, limiting (or infinite dilution) activity coefficients are preferred since they may be used to parameterize excess Gibbs free energy models to model phase equilibrium. Conveniently, the two quantities are related. Therefore the present study was performed to assess the ability to use the SMx universal solvent models to predict limiting activity coefficients. Two methods of calculating the limiting activity coefficient where compared: (1) the solvation free energy and self-solvation free energy were both predicted and (2) the self-solvation free energy was computed using readily available vapor pressure data. Overall the first method is preferred as it results in a cancellation of errors, specifically for the case in which water is a solute. The SM12 model was compared to both the Universal Quasichemical Functional-group Activity Coefficients (UNIFAC) and modified separation of cohesive energy density (MOSCED) models. MOSCED was the highest performer, yet had the smallest available compound inventory. UNIFAC and SM12 exhibited comparable performance. Therefore further exploration and research should be conducted into the viability of using the SMx models for phase equilibrium calculations.

show abstract

Computing MOSCED parameters of nonelectrolyte solids with electronic structure methods in SMD and SM8 continuum solvents

Cited by 17 publications

References 58 publications

Estimation of liquid‐liquid equilibrium of type 2 systems (water + valeric acid + monobasic ester or dibasic ester or alcohol) using SERLAS, SERLAS‐modified, and SERLAS‐integrated

Estimation of liquid‐liquid equilibrium of type 2 systems (water + valeric acid + monobasic ester or dibasic ester or alcohol) using SERLAS, SERLAS‐modified, and SERLAS‐integrated

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

Contact Info

Product

Resources

About