T. R. Usacheva

Effect of solvation on the thermodynamics of the formation of molecular complexes of 18-crown-6 ether with glycine in water-dimethylsulfoxide solutions

Complexation of the 18-crown-6 ether (18C6) with glycine (Gly) in mixed H2O-DMSO solvents with the composition of 0.1, 0.2, and 0.25 mole fraction of DMSO (T = 298.15 K) was studied calorimetrically. Thermodynamic characteristics of the reaction of the formation of the molecular Gly18C6 complex (ΔrG°, ΔrH°, TΔrS°) were calculated from the calorimetric data. It was established that the change in the stability of the Gly18C6 complex is mainly determined by the predominance of the enthalpy component of the Gibbs energy over the entropy component. It was shown during the analysis of the enthalpy contributions of the reagents to the enthalpy of the reaction of the formation of Gly18C6 that the change in the enthalpy of the reaction upon a change the solvent composition was due to changes in the solvation state of 18C6.

Studies of the complex formation of silver (I) ion with 18-crown-6 in H2O-DMSO mixtures by calorimetry

The thermodynamic parameters (DrG0, DrH0, TDrS0) of the reaction of [Ag18C6]+ complex formation were obtained for a wide range of H2O-DMSO mixtures from the calorimetric data at 298.15 K. The relation between the thermodynamic parameters of complex formation and solvation of each reagent was investigated.

Complex formation of Ag+ with polyether 18-crown-6

The complex formation of Ag+ with polyether 18-crown-6 (18C6) and their solvation have been studied using calorimetric and potentiometric methods in H2O-EtOH solvents in wide range of ethanol concentration. The standard enthalpies of dissolution AgNO3, AgClO4 and 18C6 in aqueous-ethanol solvents are obtained. The stability of a complex [Ag18C6]+ grows with increasing the EtOH content a solvent. Using the method based on the thermodynamic characteristics of solvation of metal-ion, ligand and complex-ion the interpretation of the results has been given.

Thermodynamic characteristics of alanine-18-crown-6 ether complexes in binary water-acetone solvents

The formation of 18-crown-6 ether (18C6) complexes with D,L-alanine (Ala) in mixed wateracetone solvents with 0.0, 0.08, 0.17, 0.22, and 0.30 mole fractions of acetone (T = 298.15 K) was investigated by means of calorimetry. Thermodynamic characteristics of the reaction of the molecular [Ala18C6] complex formation (ΔrG°, ΔrH°, and TΔrS°) were calculated on the basis of calorimetric data. Analysis of solvation contributions of reagents into the enthalpy of the [Ala18C6] formation reaction showed that the changes in the reaction energy when the solvent composition is varied are determined by the changes in the solvate state of 18C6.

Influence of the composition of aqueous dimethylsulfoxide solvent on thermodynamics of complexing between 18-crown-6-ether and D,L-alanine

Standard thermodynamic parameters (logKo, ΔrHo, TΔrSo) of complexing 18-crown-6 ether (18C6) with D,L-alanine (Ala) in mixed water-dimethysulfoxide (H2O-DMSO) solvents are calculated on the basis of calorimetric titration results. A rise in the DMSO concentration in mixed solvent is found to increase stability and increase the exothermicity of the formation of [Ala-18C6] molecular complex. Changes in the reaction energetic are shown to be determined by changes in the solvation state of 18C6 that is the characteristic of the reactions of molecular complex formation between 18C6 and D,L-alanine or glycine in water-organic solvents.

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 (χDMSO = 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 ΔtrG○(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.

Constants and thermodynamics of the acid-base equilibria of triglycine in water–ethanol solutions containing sodium perchlorate at 298 K

The acid−base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water–ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases pK1) and increases the dissociation constant of the amino group of triglycine (decreases pK2). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

Thermochemistry of solvation of 18-crown-6 ether in binary methanol-acetonitrile solvents

Heat effects of the dissolution of 18-crown-6 ether (18C6) over a wide range of compositions of mixed methanol-acetonitrile solvents are determined via calorimetry at 298.15 K. It is found that passing from methanol to acetonitrile to xAN = 0.6 mole fraction is accompanied by a sharp increase in the exothermicity of 18C6 solvation. It is concluded that a further increase in the aprotic component of a binary mixture leads to no appreciable changes in the enthalpy of solvation of the macrocycle.

Thermodynamics of the formation of Cu2+–glycyl-glycyl-glycine complex in water–ethanol solutions at 298 K

The stability constants of monoligand complexes of copper(II) ions with glycyl-glycyl-glycine zwitterions (triglycine, HL±) and triglycinate ions (L−) in a water–ethanol solvent with 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol at an ionic strength of 0.1 created by sodium perchlorate and temperature Т = 298.15 K are determined by means of potentiometric titration. It is found that an increase of ethanol content improves the stability of the investigated complexes, due mainly to the resolvation of ligands.

Dependence of the thermodynamic characteristics of the complexation of alanine-18-crown-6 on the composition of water-ethanol solvent

Standard thermodynamic parameters (ΔrG○, ΔrH○, TΔrS○) for the complexation reaction of 18-crown-6 ether (18C6) with D,L-alanine (Ala) in mixed water-ethanol (H2O-EtOH) solvents are calculated from the data of calorimetric titrations performed at T = 298.15 K. It is established that an increase in the concentration of EtOH in mixed solvent leads to a rise in stability and an increase in the exothermicity of [Ala18C6] molecular complex formation; changes in the energetics of reaction upon a change in the solvent composition are determined by changes in the solvation state of 18C6, which is typical of the reactions of molecular complex formation of 18C6 with D,L-alanine and glycine in water-organic solvents.