Enthalpies of solution of urea in water–alkanol mixtures and the enthalpic pair interaction coefficients of urea and several nonelectrolytes in water

Piekarski, Henryk; Somsen, G.

doi:10.1139/v86-284

Cited by 24 publications

(12 citation statements)

References 20 publications

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“…The h,, values for interactions of 13 nonelectrolytes with urea gave similar correlation (9). It seemed interesting to verify whether a similar relation could be found also in the case of electrolyte-nonelectrolyte interactions in water solution.…”

Section: Enthalpic Pair Interaction Coeficientssupporting

confidence: 56%

Dissolution enthalpy of NaCl in aqueous nonelectrolyte solutions at 298.15 K. Analysis of electrolyte–nonelectrolyte enthalpic pair interaction coefficients in aqueous solution

Piekarski¹

1986

Can. J. Chem.

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HENRYK PIEKARSKI. Can. J. Chem. 64, 2127Chem. 64, (1986. Enthalpies of solution of NaCl in aqueous solutions of isopropanol, s-butanol, 2-methoxyethanol, 2-ethoxyethanol, acetone, and N,N-dimethylformamide were measured. The results of enthalpy measurements were analyzed from the point of view of the effect of added nonelectrolyte on water structure, and enthalpic pair interaction coefficients h,, {(Na' + C1-)-nonelectrolyte} were calculated and compared with appropriate data for (Na' + I-)-nonelectrolyte pairs. The group additivity concept appeared to be useful for the analysis of calculated h,, coefficients. The correlations between h,, and the functions characterizing different properties of the solutes under study were examined. It was shown that the correlation with the heat capacity of transfer of the nonelectrolyte molecule from the vapour phase to high dilution in water was the most promising. The interpretation of observed correlations was proposed.HENRYK PIEKARSKI. Can. J. Chem. 64, 2127Chem. 64, (1986. On a mesurC les enthalpies de solution du NaCl dans des solutions aqueuses d'isopropanol, de s-butanol, de mCthoxy-2 Cthanol, d'Cthoxy-2 Cthanol, d'acetone et de N,N-dimCthylformamide. On a analysC les rtsultats des mesures d'enthalpies en fonction de l'effet de I'addition d'Clectrolytes sur le structure de l'eau; de plus, on a calculC les coefficients d'interaction entre les paires enthalpiques [h,,{(NaL + C1)-nonelectrolyte}] et on les a cornparks avec les donnCes appropriCes relatives aux paires (Na+ + I)-nonelectrolyte. Le concept d'additivitk de groupe semble utile pour I'analyse des coefficients h,, calculCs. On a examink les corrClations qui existent entre h,, et les fonctions qui caractkrisent les diverses propriCtCs des solutes CtudiCs. On a dCmontrC que la corrClation avec la capacitC calorifique de transfert de la molCcule nonClectrolyte de la phase vapeur a une grande dilution dans I'eau est celle qui offre le plus de promesses. On propose une interpretation des corrilations observtes.[Traduit par la revue]Thermochemical properties of electrolyte solutions in the mixtures of water with nonelectrolytes are frequently studied in many scientific centres. The obtained results are explained from the point of view of mixed solvent structure as well as solute -mixed solvent interactions. Enthalpic pair interaction coefficients between the solute and cosolvent in solvent water are often regarded as a measure of the interactions that can appear in these systems (1). As it is known the above mentioned coefficients can be calculated among others from experimentally determined enthalpy of transfer of the solute from water to water-cosolvent mixture ( 2 , 3). From the numerous papers devoted to the analysis of the pair interaction coefficients, the most refer to the nonelectrolyte-nonelectrolyte pairs. Only a few papers concern the interactions between an electrolyte and a nonelectrolyte. One of them is a previous publication, prepared in our laboratory, that presents the systematic investigations of...

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Section: Enthalpic Pair Interaction Coeficientssupporting

confidence: 56%

Dissolution enthalpy of NaCl in aqueous nonelectrolyte solutions at 298.15 K. Analysis of electrolyte–nonelectrolyte enthalpic pair interaction coefficients in aqueous solution

Piekarski¹

1986

Can. J. Chem.

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“…This opinion is confirmed by a similar correlation obtained when the NaI is replaced by NaCl [10] or by polar nonelectrolyte such as urea [10] (Fig. 7) or DMF [19], although in the latter case, the C p (hydrat) better correlates the h xy values. The effect of the properties of substance X (NaI, NaCl, urea, DMF), in these correlations manifests itself in a different slope of the correlating lines.…”

Section: Enthalpies Of Solution and Enthalpies Of Transfersupporting

confidence: 68%

Application of calorimetric methods to investigations of interactions in solutions

Piekarski¹

1999

Pure and App Chemis

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Abstract:The results of calorimetric measurements of dissolution enthalpy of electrolytes and nonelectrolytes in aqueous mixed solvents are discussed with regard to the intermolecular interactions that occur in the solution. Particular attention is given to the systems where hydrophobic hydration can play a significant role. Several ways for analysis of the hydrophobic hydration effects are presented. In the case of the dissolution enthalpies of simple inorganic electrolyte in water-organic solvent mixtures a shape of the dependence of the standard dissolution enthalpy on the mixed solvent composition can serve as a source of information about the hydrophobic properties of the organic co-solvent. A quantitative measure of the hydrophobic properties of some organic compounds can be obtained from the analysis of the organic molecule-electrolyte (used here as a probe) enthalpic pair interaction coefficients in water, determined calorimetrically. In some cases, the 'cage model' can be used for determination of hydrophobic hydration energetic effect. This model has been applied in our laboratory for analysis of hydrophobic properties of crown ethers. It is noteworthy, that all presented methods lead to qualitatively consistent results.

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“…In three-component systems including, solute X, solvent S, cosolvent Y, the enthalpic pair interaction coefficients, h xy , illustrate the heat effect of interaction between the solute molecule X and the cosolvent molecule Y in the solvent S. As these interactions are solvent mediated, it can be assumed that their values are the sum of two essential energetic effects, namely partial desolvation of interacting species and direct interaction between them [4][5][6][7]. The values of pair interaction coefficients in three-component systems can be calculated from the enthalpy of solution or enthalpy of mixing [8].…”

Section: Introductionmentioning

confidence: 99%

Thermochemistry of electrolyte solutions

Piekarski

2011

J Therm Anal Calorim

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The results of calorimetric investigations of electrolyte solutions in the mixtures of water, methanol, N,N-dimethylformamide, and acetonitrile with numerous organic cosolvents are discussed with regard to the intermolecular interactions that occur in the solution. Particular attention is given to answer the questions how and to what extent the properties of the systems examined are modified by the cosolvent added and how much the properties of the cosolvent are revealed in the mixtures with the solvents mentioned above. To this goal, the analysis of the electrolyte dissolution enthalpies, single ionic transfer enthalpies, and enthalpic pair interaction coefficients as well as the preferential solvation (PS) model are applied. The analysis performed shows that in the case of the dissolution enthalpies of simple inorganic electrolytes in waterorganic solvent mixtures, the shape of the dependence of the standard dissolution enthalpy on the mixed solvent composition reflects to a large extent the hydrophobic properties of the organic cosolvent. In the mixtures of methanol with organic cosolvents, the ions are preferentially solvated either by methanol molecules or by molecules of the cosolvent, depending on the properties of the mixed solvent components. The behavior of inorganic salts in the mixtures containing N,N-dimethylformamide is mostly influenced by the DMF which is a relatively strongly ion solvating solvent, whereas in acetonitrile mixtures, the thermochemical behavior of electrolyte solutions is influenced to a large extent by the properties of the cosolvent particularly due to the PS of cation by the cosolvent molecules.

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Enthalpies of solution of urea in water–alkanol mixtures and the enthalpic pair interaction coefficients of urea and several nonelectrolytes in water

Cited by 24 publications

References 20 publications

Dissolution enthalpy of NaCl in aqueous nonelectrolyte solutions at 298.15 K. Analysis of electrolyte–nonelectrolyte enthalpic pair interaction coefficients in aqueous solution

Dissolution enthalpy of NaCl in aqueous nonelectrolyte solutions at 298.15 K. Analysis of electrolyte–nonelectrolyte enthalpic pair interaction coefficients in aqueous solution

Application of calorimetric methods to investigations of interactions in solutions

Thermochemistry of electrolyte solutions

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