Enthalpies of mixing of tributylphosphate with hydrogen-bonding solvents

Tsimering, L.; Kertes, A.S.

doi:10.1021/je60073a019

Cited by 9 publications

(5 citation statements)

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“…Since the ∠O2PO2 angle is less than 90°, the arrangement in Figure d provides favorable electrostatic interaction between two TBP molecules with the two TBP dipoles in antiparallel alignment with the positively charged P and the negatively charged O2 closest to each other. Thus, the geometry from MD simulation provides an explicit realization for the TBP molecule dimerization conjectured from a variety of experimental evidence. − …”

Section: Resultsmentioning

confidence: 97%

“…An analysis of the PCFs is also useful from a theoretical perspective in providing insight into macroscopic properties of the system as well as how molecules interact in the liquid state bulk phase. Based on a host of experimental techniques, namely, distribution coefficient experiments, infrared spectroscopy, nuclear magnetic resonance, calorimetry, − and vapor pressure osmometry, , it has been suggested that TBP in liquid environment has a tendency for self-association. More recently, Motokawa et al have carried out X-ray and neutron scattering experiments on TBP/ n -octane mixture, and reported observing a peak in X-ray scattering intensity at wave vector q ≈ 0.63–0.68 (corresponding to a wavelength of λ = 2π/ q ≈ 0.94–0.98 nm) which the authors attributed to the average P–P distance in the mixture.…”

Section: Resultsmentioning

confidence: 99%

“…The investigation of TBP and its mixture has led to the probing of molecular level behaviors. In particular, a variety of experiments, such as, distribution coefficient experiments, infrared spectroscopy, nuclear magnetic resonance, calorimetry, − and vapor pressure osmometry, , have been carried out to study the self-association of TBP molecules in the liquid environment.…”

Section: Introductionmentioning

confidence: 99%

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Molecular Dynamics Simulations of Tri-n-butyl-phosphate/n-Dodecane Mixture: Thermophysical Properties and Molecular Structure

2014

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Molecular dynamics simulations of tri-n-butyl-phosphate (TBP)/n-dodecane mixture in the liquid phase have been carried out using two recently developed TBP force field models (J. Phys. Chem. B 2012, 116, 305) in combination with the all-atom optimized potentials for liquid simulations (OPLS-AA) force field model for n-dodecane. Specifically, the electric dipole moment of TBP, mass density of the mixture, and the excess volume of mixing were computed with TBP mole fraction ranging from 0 to 1. It is found that the aforementioned force field models accurately predict the mass density of the mixture in the entire mole fraction range. Commensurate with experimental measurements, the electric dipole moment of the TBP was found to slightly increase with the mole fraction of TBP in the mixture. Also, in accord with experimental data, the excess volume of mixing is positive in the entire mole fraction range, peaking at TBP mole fraction range 0.3-0.5. Finally, a close examination of the spatial pair correlation functions between TBP molecules, and between TBP and n-dodecane molecules, revealed formation of TBP dimers through self-association at close distance, a phenomenon with ample experimental evidence.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Molecular Dynamics Simulations of Tri-n-butyl-phosphate/n-Dodecane Mixture: Thermophysical Properties and Molecular Structure

2014

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“…c Half from Kharchenko et al (1964) at 25 °C. Half from Tsimering and Kertes (1977) at 25 °C. d Fomin and Rudenko (1965) at 25 °C.…”

Section: Model Descriptionmentioning

confidence: 99%

Molecular Interactions in Tri-n-butyl Phosphate−Diluent Mixtures

Choi

Tedder

1996

Ind. Eng. Chem. Res.

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This model considers both specific chemical and nonspecific physical contributions to excess Gibbs energy. Competitive chemical equilibria are evaluated to describe specific chemical interactions. Molecular size, shape difference, and regulation solution terms, based on the "true" species, are used to describe nonspecific physical interactions. Parameter estimates are obtained by fitting vapor-liquid equilibrium and hydrogen and phosphorus NMR shift data for three tri-n-butyl phosphate (TBP) and diluent binary mixtures. The thermodynamic equilibrium constant for the TBP dimer is a shared parameter since this complex apparently exists in all binary mixtures. At 22°C, its value is 6.65 based on the behavior of TBP diluted with either benzene, chloroform, or n-heptane. Thermodynamic equilibrium constants for the 1:1 TBP/ chloroform and TBP/benzene complexes are 37.88 and 1.34, respectively. The 1:2 chloroform/ TBP dimer complex has an equilibrium constant of 37.57. Model parameters are used to predict excess molar volumes and enthalpies. Commonly reported stability constants are shown to be concentration dependent.

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“…**Fenby (1987); Huggins et al (1955); Bourrelly et al (1975); Chand et al (1975). 'Kharchenko et al (1964); Choi (1995); Tsimering and Kertes (1977); Choi and Tedder (1995).…”

Section: Chemical Shij2mentioning

confidence: 99%