Excess enthalpies of tri-n-butylphosphate + hydrocarbons

Tsimering, L.; Kertes, A.S.

doi:10.1016/0021-9614(74)90001-9

Cited by 16 publications

(12 citation statements)

References 5 publications

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“…For all of the earlier equilibrium properties, it is seen that the Mulliken charge incorporated OPLS-AA force field is the most suitable charge model. The diffusion constant predicted by Mulliken charge is 0.539 × 10 –6 , which is 4 times smaller than that of experimental value but close to that of Cui et al and 2 times smaller than that of Mu et al Overall, our calculation also follows the same line of argument like Cui et al and Mu et al that reparameterization of OPLS-AA force field is perhaps necessary to reproduce the experimental diffusivity data for TBP.…”

Section: Resultssupporting

confidence: 84%

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Molecular Dynamics Simulation for the Calibration of the OPLS Force Field Using DFT Derived Partial Charges for the Screening of Alkyl Phosphate Ligands by Studying Structure, Dynamics, and Thermodynamics

2017

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Molecular dynamics (MD) simulations were performed to calibrate the all-atom optimized potential for liquid simulations (OPLS-AA) force field using partial quantum charges calculated from four different population analysis methods: Mulliken, Löwdin, NPA, and ChelpG for predicting the thermophysical properties of pure liquids like tri-n-butylphosphate (TBP), tri-isoamylphosphate (TiAP), triethylphosphate (TEP), and dodecane to determine a potential solvent for the nuclear fuel cycle. The structural, dynamic, and thermodynamic properties were calculated in NVT ensembles by introducing the partial charges on each atom calculated from density functional theory (DFT). The calculated structural and dynamic properties were affected by the different partial charges on TBP, TiAP, and TEP. The estimated liquid density employing partial charges obtained from Mulliken population analysis with OPLS force field leads to an excellent agreement with the experimental data (within 0.36–1.41%). The diffusivity and the pair correlation function (PCF) for all of the ligands have been calculated and validated wherever literature data is available. The free energies of hydration and solvation for all of the ligands were evaluated using thermodynamic integration technique and the hydration free energy for TEP is within 8.3% of the experimental value, and for other properties they are not available in the literature for comparison. Furthermore, the partition coefficient of the ligands calculated using MD derived free energy difference between the water–dodecane system resembles the trend predicted by DFT/COSMO-RS calculations which is in qualitative agreement with the experimental results. Among the four-charge model, the computed dipole moment of TBP and TEP using the Mulliken charge is found to be in good agreement with the experimental results. Finally, the superiority of TiAP over TBP as an extracting agent for the UO2 2+ ion has been demonstrated by a higher calculated free energy of extraction, ΔG ext, over TBP using DFT. Overall the Mulliken charge embedded calibrated OPLS-AA force field is perhaps the most reliable one as it does not incorporate any arbitrary scaling in the force field or Lennard–Jones parameters and thus can be used indubitably to evaluate the liquid state properties of alkyl phosphates and n-alkanes which eventually assist in the invent of future generation extractants.

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Section: Resultssupporting

confidence: 84%

“…Similarly, for dodecane, the reported self-diffusion (4.883 ± 0.208) × 10 –6 cm 2 /s . The experimental values of the diffusion coefficient for TiAP and TEP are not available. b Reference . …”

Section: Resultsmentioning

confidence: 99%

Molecular Dynamics Simulation for the Calibration of the OPLS Force Field Using DFT Derived Partial Charges for the Screening of Alkyl Phosphate Ligands by Studying Structure, Dynamics, and Thermodynamics

2017

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“… a Experimental values are from Tian and Liu; statistical errors are not given. b Experimental values are from Tsimering and Kertes; statistical errors are not given. …”

Section: Resultsmentioning

confidence: 99%

“…The excess molar enthalpy of mixing, Δ H ex , which represents the heat released or taken up upon the mixing of TBP and n -dodecane liquids, was calculated by subtracting the enthalpies of the pure components from the molar enthalpy of the mixture, using eq where x 1 and x 2 are the mole fractions of TBP and n -dodecane, respectively, H 1 and H 2 are the molar enthalpies of the pure TBP and pure n -dodecane, respectively, H mix is the molar enthalpy of the mixture. The calculated results were compared with the experimental values, as shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

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Comparative Molecular Dynamics Study on Tri-n-butyl Phosphate in Organic and Aqueous Environments and Its Relevance to Nuclear Extraction Processes

Motokawa

Williams

et al. 2016

J. Phys. Chem. B

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A refined model for tri-n-butyl phosphate (TBP), which uses a new set of partial charges generated from our ab initio density functional theory calculations, has been proposed in this study. Molecular dynamics simulations are conducted to determine the thermodynamic properties, transport properties, and the microscopic structures of liquid TBP, TBP/water mixtures, and TBP/n-alkane mixtures. These results are compared with those obtained from four other TBP models, previously described in the literature. We conclude that our refined TBP model appears to be the only TBP model from this set that, with reasonable accuracy, can simultaneously predict the properties of TBP in bulk TBP, in organic diluents, and in aqueous solution. The other models only work well for two of the three systems mentioned above. This new TBP model is thus appropriate for the simulation of liquid-liquid extraction systems in the nuclear extraction process, where one needs to simultaneously model TBP in both aqueous and organic phases. It is also promising for the investigation of the microscopic structure of the organic phase in these processes and for the characterization of third-phase formation, where TBP again interacts simultaneously with both polar and nonpolar molecules. Because the proposed TBP model uses OPLS-2005 Lennard-Jones parameters, it may be used with confidence to model mixtures of TBP with other species whose parameters are given by the OPLS-2005 force field.

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The enthalpies of mixing of organophosphate esters with hydrocarbons

Marcus

Kolařík

1977

J Solution Chem

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Excess enthalpies of tri-n-butylphosphate + hydrocarbons

Cited by 16 publications

References 5 publications

Molecular Dynamics Simulation for the Calibration of the OPLS Force Field Using DFT Derived Partial Charges for the Screening of Alkyl Phosphate Ligands by Studying Structure, Dynamics, and Thermodynamics

Molecular Dynamics Simulation for the Calibration of the OPLS Force Field Using DFT Derived Partial Charges for the Screening of Alkyl Phosphate Ligands by Studying Structure, Dynamics, and Thermodynamics

Comparative Molecular Dynamics Study on Tri-n-butyl Phosphate in Organic and Aqueous Environments and Its Relevance to Nuclear Extraction Processes

The enthalpies of mixing of organophosphate esters with hydrocarbons

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