An Alternative Method for Correlation and Evaluation of Mutual Diffusion Coefficients of Solutes in Organic Solvents at Infinite Dilution

Li, Zhiwei; Zuo, Lihua; Wu, Wensheng; Chen, Liuping

doi:10.1007/s10953-018-0804-2

Cited by 3 publications

(7 citation statements)

References 118 publications

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“…There are numerous studies on single ion conductance in methanol (43)(44)(45)(46)(47)48) from which we derived corresponding diffusion coefficients. Diffusion coefficients of nonelectrolytes have been well studied (4,10,34,(39)(40)(41)(42)(49)(50)(51)(52)(53) and we collected data on a total of 96 solutes, ionic plus nonelectrolytes, that yielded Eq. 5.…”

Section: Methanolmentioning

confidence: 99%

“…Data are available for ions [30,45], but, again, there is a lack of data on nonelectrolytes [4,10,39,40,42,47]. We adopted the same stratagem as for propan-1-ol solvent and obtained data on a total of 53 solutes, leading to Eq.…”

Section: Butan-1-olmentioning

confidence: 99%

“…Diffusion coefficients for ions are available from conductance data [46,54] and there is just enough data on diffusion coefficients for nonelectrolytes [3,10,[54][55][56][57] to be able to construct Eq. 8 for a total of 61 solutes.…”

Section: Octan-1-olmentioning

confidence: 99%

“…There is a reasonable amount of data on the conductance of ions in propanone [46,58], and several studies on the diffusion of nonelectrolytes [10,50,[59][60][61][62][63]. We did not use the results of Hejtmanek and Schnelder [63] on crown ethers that were completely out of line.…”

Section: Propanonementioning

confidence: 99%

“…However, since 18 solvents were examined, the number of solutes per solvent is not that large. Li et al [10] used a linear free energy relationship based on the Abraham equation [11], to correlate 743 diffusion coefficients in 25 solvents; again, although a large number of data points was used, the number per solvent is still rather limited.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Limiting Diffusion Coefficients for Ions and Nonelectrolytes in Solvents Water, Methanol, Ethanol, Propan-1-ol, Butan-1-ol, Octan-1-ol, Propanone and Acetonitrile at 298 K, Analyzed Using Abraham Descriptors

Abraham

Acree

2019

J Solution Chem

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We have used literature data on the conductivity of single ions to obtain limiting diffusion coefficients (D o ) of ions in water, alcohols, propanone and acetonitrile. We then used literature data on limiting diffusion coefficients of nonelectrolytes in order to set up linear free energy relationships that combine data for ions and nonelectrolytes, as log 10 (D o ) in the same equation, all values being at 298 K. These equations are for solvents water (N = 377, SD = 0.0474), methanol (N = 96, SD = 0.0332), ethanol (N = 96, SD = 0.0666), propan-1-ol (N = 71, SD = 0.0487), butan-1-ol (N = 53, SD = 0.0600), octan-1-ol (N = 61, SD = 0.0684), propanone (N = 86, SD = 0.0366) and acetonitrile (N = 74, SD = 0.0438) where N is the number of data points, that is ions plus nonelectrolytes, and SD is the standard deviation in log 10 (D o ). It is shown that solute hydrogen bond acidity, solute hydrogen bond basicity and solute volume all lower the diffusion constants of ions and nonelectrolytes in the various solvents studied.

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Section: Methanolmentioning

confidence: 99%

Section: Butan-1-olmentioning

confidence: 99%

Section: Octan-1-olmentioning

confidence: 99%

Section: Propanonementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Limiting Diffusion Coefficients for Ions and Nonelectrolytes in Solvents Water, Methanol, Ethanol, Propan-1-ol, Butan-1-ol, Octan-1-ol, Propanone and Acetonitrile at 298 K, Analyzed Using Abraham Descriptors

Abraham

Acree

2019

J Solution Chem

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A Generalized Bifunctional Correlation for Diffusivities of H-Bonded Aromatic Compounds in Polar Organic Solvents

Chan

Yeung

2022

Ind. Eng. Chem. Res.

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Limiting mutual (tracer) diffusivities of aromatic compounds in different polar solvents were measured by the Taylor dispersion method. The data of the nonassociated disc-like solutes in this work are shown to validate the recently established fractional molecular–hydrodynamic relation [Ind. Eng. Chem. Res. 2019, 58, 20423–20440]. A new model is proposed to account for the tracer diffusivities of the aromatic solutes capable of H-bonding in various polar organic solvents. The model contains two functions: one for the intrinsic nonassociated diffusivity behavior of each individual solute molecule and another for the effect due to its solute–solvent H-bonding on diffusivity. A general equation developed from this model is demonstrated to be capable of correlating and calculating a total of 358 diffusivity data of H-bonded aromatic solutes, which have been measured here and collected from the literature, in different organic solvents at various temperatures to a standard deviation of 3.25% only.

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The macroscopic viscosity approximation: A first-principle relationship between molecular diffusion and viscosity

Gaudin

2020

AIP Advances

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In this article, a new relationship between viscosity and molecular diffusion at infinite dilution is proposed for better rationalization and prediction of these properties, based on a “macroscopic viscosity approximation” (MVA), i.e., by assuming viscosity around a solute as equal to the macroscopic, measurable viscosity of the solvent. This implies that activation energies of the viscous flow and diffusion process are equal. The hypothesis is validated by our correlation analysis (mean difference of 0.10 kcal/mol, R2 = 0.96). The new approach, named “Modified Stokes–Einstein” (MSE), achieves better performance than the widely used Wilke–Chang (WC) correlation both in organic solvents [mean relative error (MRE) of 15% vs 24%, respectively] and in water (MRE of 13% vs 21%, respectively). Contrary to the popular WC correlation as well as all other available approaches in the literature, the MSE approach can be used consistently for water, without requiring any ad hoc association parameter, and is not fitted on diffusion and/or viscosity data, making all of its underlying hypotheses explicit. Based on the MVA and the MSE, a simple atomic count estimation method for the activation energy of the flow allows us to simultaneously predict viscosity and diffusion coefficients with an MRE of 21%–22%, again slightly better than the WC correlation, but not requiring any experimental data as the input. This work provides rationalized and efficient means for prediction of diffusion coefficients at infinite dilution and pure liquid viscosities wherever such properties are required, for example, as inputs for mixing rules to predict flow and transport behavior of complex systems.

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An Alternative Method for Correlation and Evaluation of Mutual Diffusion Coefficients of Solutes in Organic Solvents at Infinite Dilution

Cited by 3 publications

References 118 publications

Limiting Diffusion Coefficients for Ions and Nonelectrolytes in Solvents Water, Methanol, Ethanol, Propan-1-ol, Butan-1-ol, Octan-1-ol, Propanone and Acetonitrile at 298 K, Analyzed Using Abraham Descriptors

Limiting Diffusion Coefficients for Ions and Nonelectrolytes in Solvents Water, Methanol, Ethanol, Propan-1-ol, Butan-1-ol, Octan-1-ol, Propanone and Acetonitrile at 298 K, Analyzed Using Abraham Descriptors

A Generalized Bifunctional Correlation for Diffusivities of H-Bonded Aromatic Compounds in Polar Organic Solvents

The macroscopic viscosity approximation: A first-principle relationship between molecular diffusion and viscosity

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