Conductance studies of 1-1 electrolytes in N,N-dimethylformamide at various temperatures

Safonova, L. P.; Sakharov, D.V.; Shmukler, L. E.; Kolker, A. M.

doi:10.1039/b006029l

Cited by 29 publications

(22 citation statements)

References 22 publications

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“…As evident from table 1, the transport parameters of CPcation are lower in magnitude than the corresponding DPcation at each specified temperature. The observed differences seem to be on account of different dimensions of ions, degrees of hydration and mobility of solvent molecules in the vicinity of surfactant ions and can be explained in terms of Hubbard and Onsager dielectric friction (HO) theory [22] being a better approach to explain the conducting behaviour of ions in place of Stokes-Einstein-Walden framework [23][24][25][26]. According to the theory, the migrating ions are solvated and thus experiencing a viscous drag.…”

Section: Transport Propertiesmentioning

confidence: 93%

Temperature dependence of transport and equilibrium properties of alkylpyridinium surfactants in aqueous solutions

Bhat

Dar

Amin

et al. 2007

The Journal of Chemical Thermodynamics

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Section: Transport Propertiesmentioning

confidence: 93%

Temperature dependence of transport and equilibrium properties of alkylpyridinium surfactants in aqueous solutions

Bhat

Dar

Amin

et al. 2007

The Journal of Chemical Thermodynamics

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“…Similar to the organic solvents most commonly used in CE, namely, methanol (MeOH) and acetonitrile (ACN), the relative permittivity of DMF is in the range were ionic dissociation might not be complete but ion pair formation can occur. In fact, ion association (or dissociation) constants for some salts in DMF have been reported [42][43][44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Capillary electrophoresis in N,N‐dimethylformamide

Porras

Kenndler

2005

Electrophoresis

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N,N-Dimethylformamide (DMF) is a dipolar protophilic solvent with physicochemical properties that makes it suitable as solvent for capillary electrophoresis (CE). It is prerequisite for the proper application of CE to adjust and to change the pH of the background electrolyte (BGE) in a defined manner. This was done in the present work using benzoic acid-benzoate by selecting different concentration ratios of acid and salt, and calculating the theoretical pH from the activity-corrected Henderson-Hasselbalch equation. The mobilities of the analytes (chloro- and nitro-substituted phenolates) were found to follow reasonably well the typical sigmoid mobility versus pH curve as predicted by theory. The actual mobilities and pK(a) values (at 25 degrees C) of the analytes were derived from these curves. pK(a) values were in the range of 11.1-11.7, being thus 3-4.4 units higher than in water. This pK(a) shift is caused by the destabilization of the analyte anion and the better stability (solubility) of the molecular analyte acid in DMF, which overcome the higher basicity of DMF compared to water. Absolute mobilities were calculated from the actual mobilities; they were between 32x10(-9) and 42x10(-9) m(2)/Vxs. Slight deviations of the measured mobilities from the theoretical mobility versus pH curve were discussed on the bases of ion pairing and heteroconjugation and homoconjugation of either buffer components or buffer components and analytes. Heteroconjugation was used as a mechanism for the electrically driven separation of neutral analyte molecules in a BGE where salicylate acted as complex forming ion. Rough estimation of the complexation constants for the phenolic analytes gave values in the range of 100-200 L/mol. Addition of water to the solvent decreased the effect of heteroconjugation, but it was still present up to the surprisingly high concentration of 20% water. Electrophoretically relevant parameters like ionic mobilities and pK(a) values, and conjugation and ion pairing are dependent on the water content of the solvent. The water uptake of DMF was measured when exposed to humidity of ambient air. The resulted behavior of the water uptake was found rather similar to that for acetonitrile and methanol.

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“…We have not been able to extend our studies to additional solvents simply because of the lack of data on either non-electrolytes or ionic species. Conductance data exists for ions in 2-methoxyethanol [79,80], in N,N-dimethylformamide [66,81] and in formic acid [82], and these could be used to obtain corresponding limiting diffusion coefficients through Eq. 2.…”

Section: Discussionmentioning

confidence: 99%

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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Conductance studies of 1-1 electrolytes in N,N-dimethylformamide at various temperatures

Cited by 29 publications

References 22 publications

Temperature dependence of transport and equilibrium properties of alkylpyridinium surfactants in aqueous solutions

Temperature dependence of transport and equilibrium properties of alkylpyridinium surfactants in aqueous solutions

Capillary electrophoresis in N,N‐dimethylformamide

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

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