A Comparison of the Solvation Properties of 2-Nitrophenyloctyl Ether, Nitrobenzene, and <i>n</i>-Octanol as Assessed by Ion Transfer Experiments

Gulaboski, Rubin; Galland, Alexandra; Bouchard, Géraldine; Caban, Karolina; Kretschmer, Ansgar; Carrupt, Pierre‐Alain; Stojek, Zbigniew; Girault, Hubert H.; Scholz, Fritz

doi:10.1021/jp037670m

Cited by 82 publications

(92 citation statements)

References 44 publications

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“…This equation is obtained by applying equation (6) to each simulation (denoted by subscripts I and II), and combining both expressions to eliminate ξ (assuming that this value does not depend on the box size). The bulk correlation length itself can then be extracted from equation (6) using the value of γ cw calculated in equation (10).…”

Section: Interfacial Tensionmentioning

confidence: 99%

Molecular Dynamics Study of the Interface between Water and 2-Nitrophenyl Octyl Ether

Jorge

Cordeiro

2008

J. Phys. Chem. B

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We present results of molecular dynamics simulations of the interface between water and 2-nitrophenyloctyl ether (NPOE). This system is analyzed in detail using a procedure to calculate intrinsic profiles of several important properties (density, radial distribution functions, hydrogen bonds, molecular orientation, self-diffusion). The interface was found to be molecularly sharp, but corrugated by thermal fluctuations. Using a method based on capillary wave theory, we have estimated the interfacial tension and obtained good agreement with values calculated from the virial route. The results were compared to simulations of the water/nitrobenzene interface. The presence of an alkyl chain in NPOE introduces an added degree of hydrophobicity, which causes an increase in the interfacial tension. Furthermore, interfacial NPOE molecules are less organized than nitrobenzene and show a distinct dynamic response. These results shed light on the observed differences between these two organic liquids in electrochemical studies.

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Section: Interfacial Tensionmentioning

confidence: 99%

Molecular Dynamics Study of the Interface between Water and 2-Nitrophenyl Octyl Ether

Jorge

Cordeiro

2008

J. Phys. Chem. B

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“…3 In the past decade, 2-nitrophenyl n-octyl ether (NPOE) has emerged as a viable alternative, and it is seen as one of the most promising solvents in ion transfer studies across liquid|liquid interfaces. 2,[4][5][6][7][8][9][10][11][12] Compared to the other organic solvents, NPOE has a relatively low solubility in water, a low vapor pressure, and is not known to be highly toxic. 3 In addition, NPOE has a high molar volume and a medium permittivity ( rel ) 24.2), which makes it also a good solvent for ionic solutes.…”

Section: Introductionmentioning

confidence: 99%

“…6,[8][9][10] It is also worth mentioning that a recent study has shown that the solvation properties of nitrobenzene and NPOE toward ionic species are very similar. 11,12 In contrast, few theoretical studies have been devoted to probe such organic solvents. NB has been studied by molecular simulation in the context of light scattering, 13 and of liquid|liquid interfaces, [14][15][16] as well as for the optimization of force-field parameters.…”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Study of 2-Nitrophenyl Octyl Ether and Nitrobenzene

et al. 2006

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The pure organic liquids nitrobenzene (NB) and 2-nitrophenyl octyl ether (NPOE) have been studied by means of molecular dynamics simulations. Both solvents are extremely important in various interfacial processes, mainly connected with ion transfer taking place across the interface with water. Thermodynamic (mass density, enthalpy of vaporization, isothermal compressibility, dipole moment) and dynamic (viscosities and self-diffusion coefficients) properties of both liquids have been calculated and are in very good agreement with the experimental data. In the case of NB, several potentials have been tested and the obtained results compared and discussed. In most cases, the OPLS all-atom potential gives results that are in better agreement with available experimental values. Atomic radial distribution functions, dihedral and angle distributions, as well as dipole-orientation correlation functions are used to probe the structure and interactions of the bulk molecules of both organic solvents. These were seen to be very similar in terms of structure and thermodynamics, but quite distinct in terms of dynamic behavior, with NPOE showing a much slower dynamic response than NB. A simulation study of the simple Cl -and K + ions dissolved in both solvents has been also undertaken, revealing details about the diffusion and solvation mechanisms of these ions. It was found that in both liquids the positive potassium ion is solvated by the negative end of the molecular dipole, whereas the negative chloride ion is solvated by the positive end of the dipole.

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“…Details of all the log P values for ions and ionic species are in Table 5 In addition to log P values for ions obtained from solubility or distribution experiments, there are a number of log P values from electrochemical experiments [43][44][45][46][47][48]. Unfortunately, there is no consistency between the two sets of log P values.…”

Section: Resultsmentioning

confidence: 99%

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

Abraham

Acree

2011

Thermochimica Acta

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Equations have been constructed for the transfer of 64 neutral solutes from water and from the gas phase to the solvent benzonitrile. The equations contain five descriptors and can be used to predict further values of the water-benzonitrile and gas-benzonitrile partition coefficients for a wide range of solutes. The water-benzonitrile equation has been extended to include ions and ionic species derived from acids by loss of a proton and bases by acceptance of a proton. Only two further descriptors are needed, one for anions and one for cations. A previous equation for transfer of neutral solutes from water to nitrobenzene has also been extended to include ions and ionic species. Comparison of the equations for transfer to benzonitrile and to nitrobenzene shows that the two solvents behave quite similarly, although benzonitrile as a solvent is a stronger hydrogen bond base.

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A Comparison of the Solvation Properties of 2-Nitrophenyloctyl Ether, Nitrobenzene, and n-Octanol as Assessed by Ion Transfer Experiments

Cited by 82 publications

References 44 publications

Molecular Dynamics Study of the Interface between Water and 2-Nitrophenyl Octyl Ether

Molecular Dynamics Study of the Interface between Water and 2-Nitrophenyl Octyl Ether

Molecular Dynamics Study of 2-Nitrophenyl Octyl Ether and Nitrobenzene

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

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