Complex Formation of Crown Ethers and Cations in Water–Organic Solvent Mixtures: Part XII. Effect of the Acid–Base Properties of the Mixture on the Thermodynamic Functions of Complex Formation of Benzo-15-Crown-5 with Na<Superscript>+</Superscript> in Water–Methanol Mixtures at 298.15 K

The enthalpies of solution of benzo-15-crown-5 ether in methanol–water mixtures and methanol–water–sodium iodide systems have been measured at 298.15 K. The values of standard enthalpies of solution of benzo-15-crown-5 ether are positive in the mixtures of water and methanol within the whole range of mixture composition. The equilibrium constants of complex formation of benzo-15-crown-5 ether with the sodium cation have been determined by conductivity measurements at 298.15 K. The thermodynamic functions of the formation of these complexes have been calculated. The Gibbs energy of complex formation depends on the base–acid properties of methanol–water mixture.     

Complex Formation of Crown Ethers with Cations in the Water–Organic Solvent Mixtures. Part VII. Thermodynamic of Interactions of Na+ Ion with 15-Crown-5 Ether in the Mixture of Water with N,N-Dimethylacetamide at 298.15 K

The thermodynamic functions of the complex formation of 15-crown-5 ether with sodium cation in mixtures of water with N,N-dimethylacetamide at 298.15K are calculated. The equilibrium constants of complex formation of 15-crown-5 ether with sodium cation have been determined by conductivity measurements. The enthalpic effect of complex formation has been measured by a calorimetric method at 298.15K. The complexes are enthalpy-stabilized but entropy-destabilized in this mixed solvent. A quantitative dependence of the excess molar enthalpy and entropy of complex formation on the structural and energetic properties of interactions between water and organic solvent molecules in the mixtures of water with N,N-dimethylacetamide, N,N-dimethylformamide and dimethylsulfoxide has been found. The linear entropy–enthalpy relationship for complex formation is also presented. The solvation enthalpy of the complex in the water–N,N-dimethylacetamide mixtures is discussed.     

Complex Formation of Crown Ethers with Cations in Water–Organic Solvent Mixtures. Part IV. Thermodynamics of Interaction of Na+ Ion with Benzo-15-crown-5 Ether in the Mixtures of Water with Acetonitrile at 298.15 K

The equilibrium constants of complex formation of benzo-15-crown-5 ether with sodium ion have been determined by molar conductance at various molar ratios of benzo- 15-crown-5 ether and sodium iodide in mixtures of water with acetonitrile at 298.15 K. The thermodynamic quantities of complex formation of benzo-15-crown-5 ether with sodium cation are calculated. The enthalpy of solvation of benzo-15-crown-5 ether and sodium ion complex is discussed together with solvation enthalpies of the cation and ligand. The contribution of the benzene ring to the thermodynamic properties of complex formation and to the enthalpy of solvation of the crown ether/ Na⁺ complex in the mixtures of water with acetonitrile are analyzed and discussed.     

Conductance and Thermodynamic Study of Thallium and Silver Ion Complexes with Crown Ethers in Different Binary Acetonitrile–Water Solvent Mixtures

The complexation reactions between Ag⁺ andTl⁺ ions with 15-crown-5 (15C5) and phenyl-aza-15-crown-5(PhA15C5) have been studied conductometrically in 90%acetonitrile-water and 50% acetonitrile - water mixed solvents attemperatures of 293, 298, 303 and 308 K. The stability constants of theresulting 1 : 1 complexes were determined, indicating that theTl⁺ complexes are more stable than the Ag⁺complexes. The enthalpy and entropy of crown complexation reactions were determined from the temperature dependence of the complexation constants.The enthalpy and entropy changes depend on solvent composition and the T S⁰ _o–H⁰ plotshows a good linear correlation, indicating the existence of entropy –enthalpy compensation in the crown complexation reactions.     

Preferential Solvation of Some Sulfonamides in Propylene Glycol + Water Solvent Mixtures According to the IKBI and QLQC Methods

The preferential solvation parameters, which represent differences between the local and bulk mole fractions of the solvents near to the solute, in solutions of some sulfonamides in propylene glycol + water binary mixtures are derived from their thermodynamic properties by means of the inverse Kirkwood?Buff integrals (IKBI) and the Quasi-Lattice Quasi-Chemical (QLQC) method. From solvent effect studies, it is found that sulfonamides are sensitive to solvation effects; the preferential solvation parameter, δx _PG,S, is negative in water-rich mixtures but positive in compositions from 0.20 to 1.00 in mole fraction of propylene glycol according to IKBI method and positive in all co-solvent compositions if the QLQC method is considered. It is conjecturable that in water-rich mixtures, hydrophobic hydration around the aromatic ring and/or other non-polar groups plays a relevant role in the solvation. The greater solvation by propylene glycol mixtures of similar solvent compositions and in co-solvent-rich mixtures could be due mainly to polarity effects and acidic behavior of the sulfonamides, in contrast to the more basic solvent propylene glycol.     

Effect of the Composition of the Water–Dimethyl Sulfoxide Solvent on the Thermodynamics of the Formation of the [Ag(18-Crown-6)]+Complex

The effect of a water–dimethyl sulfoxide solvent (X _DMSO= 0–0.97, where X _DMSOis the mole fraction of DMSO) on the thermodynamics of complexation between Ag⁺and 18-crown-6 and the solvation of all reagents involved in this equilibrium were studied. In aqueous solutions, the complex is stable mainly because of the enthalpy contribution to _r G°. For X _DMSO> 0.3, the contributions from entropy and enthalpy become comparable in magnitude, but they are opposite in sign. In the binary solvent, the complex is most stable at X _DMSO= 0.2 to 0.3. Analysis of the enthalpy characteristics of reagent solvation showed that this solvent effect was due to the superposition of two opposite solvation contributions occurring with an increase in the DMSO concentration in the binary solvent, namely, the destabilization of the ligand solvate sphere and the formation of stable Ag⁺complexes with DMSO.     

Enthalpies of 1,4-Dioxane, 1,2-Dimethoxyethane, and Ethylacetate Solvation in the Water–1-Propanol and Water–Glycerol Binary Mixtures

The enthalpies of 1,4-dioxane, 1,2-dimethoxyethane, and ethylacetate solution in binarymixtures of water with 1-propanol and glycerol were measured at 25°C using a precise isoperibol calorimeter. The enthalpies of the solute solvation were calculated and compared with the experimental data for other solutes. The results obtained were interpreted in terms of universal and specific solute solvation using parameters of a solvent polarity. It was found that the extreme shape of the curve _solv H° vs. X for ethylacetate in the mixtures of water with 1-propanol results from peculiarities of carbotylate-group solvation and appears to be not connected with the influence of alcohol microaggregates in the mixed solvent.     

Theoretical Description of Excess Molar Functions in the Case of Very Small Excess Values. Investigation of Excess Molar Volumes of Propan-2-ol + Alkanol Mixtures

The densities of propan-2-ol + pentan-1-ol, + hexan-1-ol, + heptan-1-ol, + octan-1-ol + nonan-1-ol and speeds of sound in propan-2-ol + pentan-1-ol, + heptan-1-ol, + nonan-1-ol have been measured over the whole composition range at 298.15 K. Excess molar functions determined from the experimental data have been plotted as functions of composition. The excess molar volumes have been interpreted on the basis of the Symmetrical Extended Real Associated Solution Model (S-ERAS).     

Solubility and Dissolution Thermodynamics of Cefmetazole Acid in Four Neat Solvents and Preferential Solvation in Co-Solvent Mixtures of (Methanol,Ethanol or Isopropanol) + Water

The solubilities of cefmetazole acid in methanol, ethanol, isopropanol and water were determined experimentally by using the saturation shake-flask method within the temperature range from (278.15 to 303.15) K under pressure p?=?101.1 kPa. At a fixed temperature, the cefmetazole acid solubility falls in the order methanol?>?ethanol?>?isopropanol?>?water. The apparent dissolution enthalpy, dissolution entropy and Gibbs energy change were calculated. The acquired solubilities were correlated with Apelblat’s equation. The largest value of relative average deviation for mole fraction solubility was 0.45 × 10^?2, and of root-mean-square deviation, 0.747 × 10^?5. The type and extent and direction of solute–solvent interactions were identified using the concept of Linear Solvation Energy Relationship. In addition, the preferential solvation parameters (δx_1,3) of cefmetazole acid in co-solvent mixtures of methanol (1)?+?water (2), ethanol (1)?+?water (2) and isopropanol (1)?+?water (2) were derived via the inverse Kirkwood–Buff integrals method. At 298.15 K, the magnitude of preferential solvation of cefmetazole acid by the co-solvent is highest in methanol mixtures, followed by ethanol mixtures, and finally by isopropanol mixtures.     

Formation of Diazepam–Lanthanides(III) Complexes in the 50–50 Volume % Ethanol–Water Solvent System and Study of the Effect of Temperature on the Complex Formation Constants

Diazepam (7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one) is an important derivative of the 1,4-benzodiazepine compound commercially distributed as Valium. The complex formation constants of diazepam with some light lanthanide(III) metal ions have been studied by potentiometric measurements. All titrations were performed in 50–50% (volume/volume) ethanol–water solvent mixtures at constant ionic strength (0.10 mol⋅dm⁻³). The ionic strength was maintained by using sodium perchlorate. The complex formation constants were determined at 25.00, 35.00 and 45.00 °C. With increasing temperature, a decrease was observed in the protonation constant (pK) of diazepam.     

Effect of Base–Acid Properties of Mixtures of Ethanol with Water on the Enthalpy of Solution of Cyclic Ethers in these Mixtures at <Emphasis Type="Italic">T</Emphasis> = 298.15 K

The enthalpies of solution of the cyclic ethers 1,4-dioxane, 12-crown-4 and 18-crown-6 in mixtures of ethanol and water have been measured within the whole mole fraction range at T = 298.15 K. The enthalpy of solvation has been calculated. In pure ethanol and pure water, the solvation enthalpy of the investigated cyclic ethers depends linearity on the number of –CH₂CH₂– groups in the cyclic ether molecules. Based on the analysis of the preferential solvation model proposed by Waghorne, it can be concluded that the 1,4-dioxane, 15C5 and 18C6 molecules are preferentially solvated by water molecules in the range of low water content in these mixtures. The effect of base–acid properties of ethanol–water mixtures on the enthalpy of solution of cyclic ethers in these mixtures has been analyzed. The enthalpy of solution of cyclic ethers correlates with the acidic properties of ethanol–water mixtures in the range of high and medium water content. The results presented are compared with analogous data obtained for the methanol–water and propan-1-ol–water mixtures.     

Study of Complex Formation of Dibenzo-18-Crown-6 with Ce3+, Y3+, $\mathrm{UO}_{2}^{2 +}$ and Sr2+ Cations in Acetonitrile–Dioxane Binary Solvent Mixtures

The complexation reactions of dibenzo-18-crown-6 (DB18C6) with Ce³⁺, Y³⁺, UO₂^{2 +}\mathrm{UO}_{2}^{2 +} and Sr²⁺ cations were studied in acetonitrile–dioxane (AN–dioxane) binary solvent solutions at different temperatures by the conductometric method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance–mole ratio data. The results show that dibenzo-18-crown-6 does not exhibit selectivity for the cation whose ionic size is closest to the cavity size of this macrocyclic ligand in AN–dioxane binary solvent solutions. A nonlinear relationship was observed between the stability constants (log ₁₀ K _f) of these complexes with the composition of the AN–dioxane binary solvent. Values of thermodynamic parameters (DH_c^°, DS_c^°\Delta H_{\mathrm{c}}^{\circ}, \Delta S_{\mathrm{c}}^{\circ}) for complexation reactions were obtained from the temperature dependence of the stability constants. The results show that the values along with the sign of these parameters are influenced by the nature and composition of the mixed solvent.     

On the Role of the Solvent and Substituent on the Protonation Equilibria of Di-Substituted Anilines in Dioxane–Water Mixed Solvents

Protonation constants of a number of di-substituted anilines were determined potentiometrically in 0, 20, 30, 40, 50, and 60% (v/v) dioxane–water mixtures at (25.00 ± 0.02) ^∘C with an ionic strength of 0.10 mol-dm⁻³ sodium perchlorate. The data are discussed in terms of the electronic character of the substituents. Two different methods were used to study the effects of the solvents on the protonation constants; one involved a single polarity parameter, the Dimroth–Reichardt parameter E_T(30); the other involved the Kamlet–Taft multi-parametric method. The protonation constants of di-substituted anilines correlate with the molecular parameters for the dipolarity/polarizability of the solvent, π^∗, and its hydrogen-bond acceptor ability, β.     

Thermodynamic Data for the Formation of 1:1 and 2:1 Complexes of α,ω-Diamino Dihydrochlorides with 18-Crown-6 in Aqueous Solution

Calorimetric titrations are used to study the interactions between the crown ether 18-crown-6 and several α,ω-diamino dihydrochlorides in aqueous solution. These complexes are formed by ion-dipole interactions between the positively charged nitrogen atoms and the oxygen donor atoms of the crown ether. Depending on the experimental conditions, the formation of 1:1 or 2:1 complexes (ligand:diamines) can be studied. The solvation of the ligand and the amines are responsible for the observed thermodynamic values. The number of water molecules released during the reaction were calculated from the determined reaction entropies. Formation of 1:1 complexes distorts the solvation shell around the molecules. As a result, the number of solvent molecules released during the formation of the 2:1 complexes is slightly smaller than the number released from formation of the 1:1 complex. No experimental evidence is observed for the formation of complexes between one crown ether and two protonated amino groups.     

Study of Solvent Effects on the Protonation of Functional Group of Disubstituted Anilines: Factor Analysis Applied to the Correlation between Protonation Constants and Solvatochromic Parameters in Ethanol–Water Mixtures

Summary. The stoichiometric protonation constants (log β) of some disubstituted aniline derivatives in ethanol–water mixtures (0–90% ethanol by volume) at 25.0 ± 0.1°C were firstly submitted to factor analysis in order to obtain the number factors which affect the variation of the whole data sets and, afterwards, submitted to target factor analysis to identify these factors. The influence of solvatochromic parameters in the interactions between aniline derivatives and the solvent studied was identified and quantified. The general equation of Kamlet and Taft was reduced for these mixtures to two terms using combined factor analysis (FA) and target factor analysis (TFA): the independent term and the hydrogen-bond donating ability, α (HBD), solvatochromic parameters. Further, the quasi-lattice quasi-chemical (QLQC) theory of preferential solvation has been applied to quantify the preferential solvation by water of electrolytes in ethanol–water mixtures. The effects of the substituents on the protonation constants, the additivities of these effects, and the applicability of the Hammett equation to the behavior of substituents are also discussed. Further, Hammett’s reaction constant for the protonation of disubstituted anilines has been obtained for all the solvent mixtures and correlates well with α (HBD) of the solvent.     

Interfacial and Thermodynamic Properties of Formation of Water‐in‐Oil Microemulsions with Surfactants (SDS and CTAB) and Cosurfactants (n‐Alkanols C5–C9)

The interfacial and thermodynamic properties of water‐in‐oil microemulsion systems consisting of water, isopropyl myristate, n‐alkanol, and surfactant have been investigated using the method of dilution. The surfactants used were hexadecyl trimethylammonium bromide and sodium dodecylsulfate, and the cosurfactants were n‐alkanols with varying chain length from (C₅–C₉). The distribution of cosurfactant (n‐alkanol) between the interface of water and oil regions at the threshold level of stability as well as the energetics of the transfer of the cosurfactant from the oil to the interfacial region have been examined as a function of varying cosurfactant chain length (C₄–C₉) and temperature. The structural parameters (including dimension, population density and effective water pool radius) of the dispersed water droplets in the oil phase have also been evaluated and correlated with alkanol chain length.     

A Proton NMR Study of the Stoichiometry and Stability of 18-Crown-6 Complexes with K+, Rb+ and Tl+ Ions in Binary Dimethyl Sulfoxide-Nitrobenzene Mixtures

Proton NMR spectroscopy was used to study the complexation reaction of 18-crown-6 (18C6) with K⁺, Rb⁺ and Tl⁺ ions in a number of binary dimethyl sulfoxide-nitrobenzene mixtures. In all cases, the exchange between free and complexed crowns was fast on the NMR time scale and only a single population average ¹H signal was observed. Formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of dimethyl sulfoxide in the mixed solvent. It was found that, in all solvent mixtures used, Rb⁺ ion forms the most stable complex with 18-crown-6 in the series.     

The Role of Iron–Carbon Galvanic Contact in the Formation of Dispersed Iron Hydr(oxides) in Water and Electrolyte Solutions

The comparative analysis of phase formation on the iron surface in aqueous medium in the presence and absence of iron–carbon (coke) galvanic contact was carried out. The role of galvanic contact in phase formation processes was determined. It was shown that, in the presence of galvanic contact almost complete oxidation of iron ions on the surface of an iron half-element and a rather efficient stationary formation of dispersed phases serving as sorbents of heavy metals from solutions take place. The effect of anionic composition of solution on the parameters of phase formation was studied. It was established that maximal amount of iron–oxygen-containing phases is formed in zinc chloride solution. The presence of sulfate and nitrate ions in solution decreased significantly the rate of phase formation in iron–carbon galvanic contact.