The effect of charge upon mobility. A critical examination of the Zwanzig equation

Evans, Denis J.; Chan, C. T.; Lamartine, B.C.

doi:10.1021/ja00462a004

Cited by 88 publications

(25 citation statements)

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“…Hence, at constant T, when D −1 12 is plotted against (η 2/3 M 1/4 2 ρ 1/3 2V m /V f ) for a given solute as in Fig. 3, the slope should be (pV 1 …”

Section: Idealized Relation and Temperature Dependencementioning

confidence: 99%

“…While the SE relation can predict diffusivities of large spherical solutes reasonably well, it nevertheless fails for solutes small in size compared to solvent molecules. [1][2][3] Invalidity of the SE relation has also been a) Author to whom correspondence should be addressed. Electronic mail: tcc.chan@polyu.edu.hk found in computer simulations and theoretical studies.…”

Section: Introductionmentioning

confidence: 99%

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Diffusion of aromatic compounds in nonaqueous solvents: A study of solute, solvent, and temperature dependences

Chan

Tang

2013

The Journal of Chemical Physics

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Tracer diffusivities (limiting mutual diffusion coefficients) of nonassociated aromatic compounds in n-hexane and cyclohexane have been measured at 298.2 K by Taylor's dispersion method. These new data, together with other diffusivities of nonassociated pseudoplanar solutes reported in the literature, are used to determine the separate effects of solute and solvent on tracer diffusion. The data show that for a given pseudoplanar solute diffusing in different solvents at 298.2 K, the tracer diffusivity is dependent not only on the fractional viscosity of the solvent but also on a function of the solvent's molar density, molecular mass, and free volume fraction. For different pseudoplanar aromatic solutes diffusing in a particular solvent at a constant temperature, there is a linear relationship between the reciprocal of the tracer diffusivity and the molecular volume of the solutes. The results are discussed in respect to relevant theories and experimental studies in the literature. An idealized relation, developed on the basis of the Einstein equation by incorporating the newly found solute and solvent dependences, is capable of describing a total of 176 diffusivities of nonassociated pseudoplanar solutes in various solvents at different temperatures to within an average error of ±2.8%. © 2013 AIP Publishing LLC. [http://dx

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“…Hence, at constant T, when D −1 12 is plotted against (η 2/3 M 1/4 2 ρ 1/3 2V m /V f ) for a given solute as in Fig. 3, the slope should be (pV 1 …”

Section: Idealized Relation and Temperature Dependencementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Diffusion of aromatic compounds in nonaqueous solvents: A study of solute, solvent, and temperature dependences

Chan

Tang

2013

The Journal of Chemical Physics

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“…Although the Stokes-Einstein equation describes the diffusion behavior of large spherical solutes fairly well, it nevertheless fails completely for solute molecules small in size compared to the solvent molecules. [1][2][3][4] Recently, there has been a great deal of interest in the use of the roughhard-sphere ͑RHS͒ theory 37,38 for the interpretation of diffusion data. Based on the van der Waals ͑VDW͒ picture of condensed matter, the RHS theory assumes that motions of molecules in a liquid are determined primarily by the size and shape of the molecules ͑i.e., the short-range repulsive intermolecular forces͒; weak dipole-dipole interactions and other attractive forces which vary slowly in space play only a minor role.…”

Section: Introductionmentioning

confidence: 99%

The effects of molecular association on mutual diffusion in acetone

Chan

Chen

1997

The Journal of Chemical Physics

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Limiting mutual diffusion coefficients of aromatic compounds in acetone have been measured at 298.2 K by using the chromatographic peak-broadening method. The data of the polar and nonpolar pseudoplanar solutes are compared, and the effects of molecular association on diffusion as well as the solvation numbers are determined. It is found that the effects of hydrogen bonding are such that -OHϾ-NH 2 Ͼ-SH, and that the solvation numbers are approximately equal for solutes containing the same polar group. Using ab initio molecular orbital theory, molecular solute-acetone interaction energies have been calculated. There exists a nearly linear relationship between the interaction energy and the effect of solute-solvent association on diffusion. The applicability of the rough-hard-sphere theory to the diffusion of associated molecules is discussed. © 1997 American Institute of Physics. ͓S0021-9606͑97͒53330-7͔

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“…Secondary flow effects should be considered [38,42], but can be neglected through use of a sufficiently long column of the correct radius, flow rate, and coil diameter. The accuracy of the apparatus and conditions used were evaluated by measuring two of the test solutes under the same conditions as previously experimentally determined [40].…”

Section: Methodsmentioning

confidence: 99%