The influence of solvation on the formation of Ag<Superscript>+</Superscript> complexes with 18-crown-6 ether in water-dimethyl sulfoxide solvents

The Gibbs energies of transfer of 18-crown-6 ether from water into water-dimethyl sulfoxide (DMSO) solvents (χ_DMSO = 0.0–0.97 mole fractions) at 298.15 K were determined by the interphase distribution method. Changes in the composition of the aqueous-organic solvent did not cause noticeable changes in the stability of 18-crown-6 ether solvato complexes. Reagent solvation contributions to shifts of complex formation equilibrium between silver(I) and 18-crown-6 ether when water was replaced with dimethyl sulfoxide were analyzed.     

Studying the Iodide Ion Solvation in Water–Dimethyl Sulfoxide Mixtures by the Method of Volta Potential Differences

Real and chemical thermodynamic parameters of resolvation of the iodide ion in water–dimethyl sulfoxide mixtures at 298 K are determined by the method of Volta potential differences. The real parameters, as those of chloride and bromide ions earlier studied in similar solvents are positive, which is due to the restructuring of a surface layer at the solution/gas phase interface. An analysis of chemical energies of the iodide ion resolvation shows that anions that are capable of forming hydrogen bonds with proton-donor solvents are weakly solvated in aprotic solvents.     

Complex formation of silver(I) with glycinate ion in aqueous ethanol and dimethyl sulfoxide solutions

The complex formation reaction of silver(I) with glycinate ion in aqueous ethanol and dimethyl sulfoxide solutions of variable compositions was studied by potentiometric titration at 298 K. The stabilities of Ag(I) glycinate complexes were found to increase with the increasing content of the organic cosolvent. The contribution of ΔG° of the reagent resolvation to the change in the Gibbs energy of the complex formation reaction was estimated using the literature data. The change in the ligand solvate state was shown to give the main contribution to the stability of the title complexes in water-organic solvents.     

Thermodynamic Characteristics of Resolvation of Bromide Ions in Water–Dimethyl Sulfoxide Mixtures

Real and chemical thermodynamic characteristics of resolvation of bromide ions in water–dimethyl sulfoxide mixtures and a surface potential of dimethyl sulfoxide are presented and analyzed. The data are obtained by the method of Volta potential differences. The real thermodynamic characteristics of the bromide ion transport are positive (as those of the chloride ion studied earlier). This is due to structural rearrangement of the surface layer at the solution/gas interface when passing from water to water–organic substance mixtures. According to an analysis of the chemical energy of the bromide ion resolvation, anions that are capable of forming hydrogen bonds with proton-donor solvents are weakly solvated in aprotic solvents.     

Thermochemistry of Benzene Solution in Water-Aprotic Solvent Binary Mixtures

The enthalpies of solution of benzene in the mixed solvents water-1,4-dioxane, water-acetone, and water-dimethyl sulfoxide were determined in the entire ranges of their compositions at 25°C and compared with thermochemical characteristics of n-alkanes. Correlation dependences were obtained that allow one to describe the enthalpies of solution of benzene in the mixtures under study and to predict the corresponding values for other water-aprotic solvent mixtures.     

The dissociation constant ofm-nitroanilinium ion in water-acetone solvents at 25°C

The dissociation constants ofm-nitroanilinium ion have been determined in seven water-acetone mixtures at 25°C. The results are compared with similar data for water-dimethyl sulfoxide solvent mixtures.     

Thermodynamics of the Solvation and phase distributions of ethylenediamine in acetonitrile-dimethylsulfoxide-hexane systems

The enthalpies of dissolution and solvation of ethylenediamine over the range of compositions of a mixed acetonitrile-dimethylsulfoxide solvent at 298 K are determined calorimetrically. It is found that with an increase in the acetonitrile concentration, the solvation exothermicity of ethylenediamine declines, owing to the resolvation of amino groups. The Gibbs energies of transfer of ethylenediamine from dimethylsulfoxide into its mixtures with acetonitrile are determined from the distribution of a substance between immiscible phases. It is found that increasing the acetonitrile concentration in a binary solvent improves the stability of the ethylenediamine solvatocomplex, owing to a change in the entropy component of the Gibbs energy.     

The influence of composition of acetonitrile-dimethyl sulfoxide solvent on stability of silver(I)-ethylenediamine complexes

The influence of the composition of acetonitrile-dimethyl sulfoxide solvent on shifting complexation equilibrium between silver(I) and ethylenediamine was studied potentiometrically at 298.15 K. The stability of the monoethylenediamine complex with silver(I) was found to increase with increasing acetonitrile content in the mixed solution, while the stability of bis-complexes changes only insignificantly. A decrease in the Gibbs energy of formation of [AgEn]⁺ ion was found to be caused by resolvation of the monoligand ion and a reduced stability of the solvation complex of silver(I). The Gibbs energy for the second coordination step remained constant due to the mutual compensation for the solvation contributions from all reagents.     

Heat Effect of the Protonation of Glycine and the Enthalpies of Resolvation of Participating Chemical Species in Water–Dimethylsulfoxide Solvent Mixtures

Enthalpies of the protonation of glycine in water?dimethylsulfoxide (DMSO) mixed solvents are determined calorimetrically in the range of DMSO mole fractions of 0.0 to 0.9, at T = 298.15 K and an ionic strength μ = 0.3 (NaClO₄). It is established that the protonation of glycine becomes more exothermic with an increasing mole fraction of DMSO, and the enthalpies of resolvation of glycine and glycinium ions in water?DMSO solvent mixtures are calculated. It is shown that the small changes in the enthalpy of protonation observed at low mole fractions of DMSO are caused by the contributions from the solvation of proton and protonated glycine cancelling each other out. The enthalpy term of the Gibbs energy of the reaction leading to the formation of glycinium ion is estimated along with the enthalpy of resolvation of the reacting species in the water?DMSO mixed solvent.     

Enthalpies of glycylglycinate ion transfer from water to water-dimethyl sulfoxide solvent

The thermal effects of sodium glycylglycinate dissolution are determined calorimetrically at 298.15 K, and the enthalpies of glycylglycinate ion transfer from water to water-dimethyl sulfoxide solvent are calculated for compositions between 0.00 and 0.99 mole fractions of dimethyl sulfoxide. It is shown that when the concentration of the nonaqueous component is increased, the endothermicity of glycylglycinate ion transfer in the solution is considerably enhanced, weakening the solvation of anions.     

Measurement of real free energies of transfer of individual ions from water to other solvents with the jet cell

Resolution of the activities of solutions of electrolytes into the individual ionic contributions cannot be carried out rigorously and requires the introduction of extrathermodynamic assumptions which have inherent uncertainties. The most commonly used approaches are basically similar in that they are based on the assumed solvent independence of the difference in the enthalpy or Gibbs energy of transfer of pairs of model solutes, e.g., tetraphenylarsonium and tetraphenylborate ions, or ferricinium ion and ferrocene. In this work we follow an alternative approach pioneered by Parsons involving measurement in the jet (Kenrick) cell of outer-potential differences between solutions of the same electrolyte in two solvents. These potential differences provide the real free energies of transfer of individual ions which, in turn, differ from the usual Gibbs energies of transfer by the work required to transfer the ion through the dipolar layers at the two solvent-gas interfaces. One objective of this work was to improve the reliability of real free energy of transfer measurements, which are experimentally demanding, to within ca. ±0.5 kJ-mol^–1 in order to match typical uncertainties in Gibbs transfer energies of electrolytes. This goal was met, in most instances, by careful evaluation of experimental parameters (particularly jet pressure). A major improvement over previous measurements was made by adding a supporting electrolyte which allowed stable potentials to be obtained at test electrolyte concentrations as low as 10^–4M. Real free energy changes are reported for the transfer of silver ion from water to methanol, ethanol, acetonitrile, propylene carbonate and dimethyl sulfoxide, as well as for the transfer of chloride ion from water to methanol and ethanol. Reliable data of this kind may lead to improved understanding of either the properties of the surfaces of solvents or the interactions of model solutes with solvents, depending on which of the two fields develops most.     

Gibbs energies of transferring triglycine from water into H2O-DMSO solvent

The Gibbs energies of transferring triglycine (3Gly, glycyl-glycyl-glycine) from water into mixtures of water with dimethyl sulfoxide (χ_DMSO = 0.05, 0.10, and 0.15 mole fractions) at 298.15 K are determined from the interphase distribution. An increased dimethyl sulfoxide (DMSO) concentration in the solvent slightly raises the positive values of Δ_tr G ^○(3Gly), possibly indicating the formation of more stable 3Gly-H₂O solvated complexes than ones of 3Gly-DMSO. It is shown that the change in the Gibbs energy of transfer of 3Gly is determined by the enthalpy component. The relationship of 3Gly and 18-crown-6 ether (18C6) solvation’s contributions to the change in the Gibbs energy of [3Gly18C6] molecular complex formation in H₂O-DMSO solvents is analyzed, and the key role of 3Gly solvation’s contribution to the change in the stability of [3Gly18C6] upon moving from H₂O to mixtures with DMSO is revealed.     

Sorption of phenol on cellulose from binary aqueous-organic mixtures

Sorption of phenol on cellulose from water-dimethyl sulfoxide and water-acetonitrile mixtures was studied. Different shape of the isotherms of phenol sorption form these mixtures is due to different character of phenol solvation in different concentration regions of water-dimethyl sulfoxide and water-acetonitrile mixtures.     

Variation of thermodynamic parameters of crown ether-metal complex formation and reactant solvation in binary nonaqueous solvent mixtures

General trends in the variation of thermodynamic parameters of complex formation of crown ethers with d-metal ions in binary nonaqueous solvent mixtures were determined. An equation was proposed for predicting variation of the stability of coordination compounds upon replacement of one nonaqueous solvent by another on the basis of the change in the Gibbs energy of solvation of the central ion. Calculation of the Gibbs energies for the formation of the [Ag18C6]⁺ ion in acetonitrile and a number of nonaqueous solvents confirmed the predictive ability of the proposed equation.     

KBPh4由水到系列水-醇混合溶剂的迁移自由能

由于四苯硼盐在分析化学、生物学、电化学等各领域中的广泛用途及其大阴离子在研究与计算单个离子迁移热力学函数中所具有的特殊作用,人们对四苯硼盐的溶液热力学性质进行了广泛研究,特别是对四苯硼钠和可作为参考电解质的四苯硼盐进行了深入细致的研究 [1, 2],得到了一些重要的的结论,为溶液理论的研究提供了有力的实验基础 .但是文献中对难溶碱金属四苯硼盐由单一到不同混合溶剂中的迁移热力学性质的系统研究较少 .在前文 [3]对 KBPh4由水到水-异丙醇和由甲醇到甲醇-异丙醇混合溶剂的迁移自由能进行研究的基础上,我们系统地对 KB…     

Thermodynamics of the solvation and phase distributions of 2,2′-dipyridyl in acetonitrile-DMSO-hexane and methanol-DMSO-hexane systems

The Gibbs energies of 2,2′-dipyridyl when transferred from dimethyl sulfoxide to its mixtures with acetonitrile and methanol are determined from the distribution of substance between immiscible phases. It is found that moving from dimethyl sulfoxide to acetonitrile and methanol weakens the solvation of 2,2′-dipyridyl due to a change in the solvation of amino groups and the hydrocarbon substituent, which is reflected in a reduction in the entropy component of the Gibbs energy.     

The thermodynamic characteristics of formation of nickel(II) complexes with L-tyrosine in aqueous-ethanolic solvents

Acid dissociation constants of L-tyrosine (H₂Tyr) and the constants of complex formation between L-tyrosine and nickel(II) ions in water-ethanol mixtures were determined potentiometrically. The Gibbs energies of transfer of tyrosine, HTyr⁻ tyrosinate anion, and [NiHTyr]⁺ complex from water into binary solvents were calculated. An increase in the stability constants of the [NiHTyr]⁺ and [Ni(HTyr)₂] complexes in solvents with a high content of ethanol was caused by weakening of the solvation of amino ligand donor groups.     

The solvation of fluoride ions. I. Free energies for transfer from water to aqueous alcohol and acetonitrile mixtures

The solubilities of NaF and LiF have been measured in mixtures of water with methanol, ethanol, ethylene glycol and acetonitrile over the whole composition range. Gibbs free energies of transfer of the fluoride ion from water to the mixed and pure solvents have been calculated from the solubility data via the tetraphenylarsonium tetraphenylborate assumption. The values so obtained indicate that the fluoride ion is preferentially solvated by water as a result of its strong hydrogen-bonding capabilities. Desolvation of the fluoride ion is especially marked in acetonitrile-rich solutions.     

The Solubility and Solvation of Salts in Mixed Nonaqueous Solvents. 2. Potassium Halides in Mixed Protic Solvents

The solubilities of potassium fluoride, chloride, and bromide in ethanol, formamide, and N-methylformamide and in binary mixtures of these solvents were determined at 25°C. The standard molar Gibbs energies of solution, Δ_soln G ^o, in the neat solvents were related to their hydrogen bonding abilities. The values of Δ_soln G ^o in the mixtures were fitted with expressions of the quasilattice quasichemical theory, and the preferential solvation of the ions was thereby established.     

Effect of Water–Ethanol Solvents on the Protonation Constants of Cryptand[2.2.2]

The protonation constants of cryptand[2.2.2] are determined potentiometrically at 298 K in water–ethanol solvents of variable composition. An increase in the concentration of a solution’s nonaqueous component reduces the equilibrium constants of the reactions of mono- and biprotonated cryptand[2.2.2] formation. The contribution from the resolvation of reagents to the change in the Gibbs energy of the studied reactions is estimated. The reduction in the protonation constants of cryptand[2.2.2] in water–ethanol solvents is mainly due to enhancement of the solvation of protons in water–ethanol mixtures.