Thermodynamics of the dissolution of acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene in aqueous ethanol

The solubility of acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene in water and aqueous ethanol at various temperatures is studied over a wide solvent composition range. The solubilities of both compounds increase as the temperature or ethanol concentration is raised, particularly in the case of acetoacetylferrocene. The dissolution of both β-diketones is accompanied by positive changes in enthalpy and entropy.     

Thermodynamics and molecular dynamics of some ferrocene derivatives

The heat capacities of acetylferrocene, 1,1′-diacetylferrocene, and 1,1′-diethylferrocene were investigated by low-temperature adiabatic calorimetry in the temperature range from 5 to 300 K and their thermodynamic functions were calculated. The enthalpies of combustion of the substances were determined by calorimetry of combustion, and the thermodynamic functions of their formation were calculated by quantum chemistry methods. Inter- and intramolecular interactions of the ferrocene derivatives were also studied by the methods of molecular mechanics and molecular dynamics. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1668–1676, September, 1999.     

Temperature dependence of excited-state proton transfer in water electrolyte solutions and water-methanol solutions

The reversible proton dissociation and geminate recombination of a photoacid is studied as a function of temperature in water electrolyte solutions and binary water-methanol mixtures, containing 0.1 and 0.2 mole fractions of methanol. 8-Hydroxypyrene-1,3,6-trisulfonate trisodium salt (HPTS) is used as the photoacid. The experimental data are analyzed by the reversible geminate recombination model. We found that the slope of the logarithm of the proton-transfer rate constant as a function of the inverse of temperature (Arrhenius plot) in the liquid phase of these samples are temperature-dependent, while in the solid phase, the slope is nearly constant. The slope of the Arrhenius plot in frozen electrolyte solution is larger than that of the water-methanol mixtures, which is about the same as in pure water. Careful examination of the time-resolved emission in ice samples shows that the fit quality using the geminate recombination model is rather poor at relatively short times. We were able to get a better fit using an inhomogeneous kinetics model assuming the proton-transfer rate consists of a distribution of rates. The model is consistent with an inhomogeneous frozen water distribution next to the photoacid.     

Permeation of electrolyte water-methanol solutions through a Nafion membrane

The volume flux through a cation-exchange membrane (Nafion 117) separating two equal electrolyte water-methanol solutions as a function of the pressure difference was determined under different experimental conditions. The results show that permeation rates through the membrane are strongly dependent on the methanol content of the solutions, thus the value of the flux increases when the methanol percentage increases. The effect of the electrolyte concentration of the solution on the membrane permeability is less important, although its influence becomes significant at low electrolyte concentration and high methanol content on solvent. This behavior is explained in terms of the amount of solvent sorbed by the membrane. Typical flux behaviors observed with pressure difference are linear at low pressures, exhibiting a positive deviation at higher pressure difference values.     

Thermodynamics of dissolution of thiourea in triethylene glycol

The solubility of thiourea in triethylene glycol was determined in the temperature range of 318.35–357.75 K. The experimental data were approximated by the modified Apelblat equation. The dissolution enthalpy and dissolution entropy were calculated from the experimental data. The mutual interactions between solvent and solute were discussed in brief. The obtained data may be useful for development of the processes involving thiourea.     

Thermodynamics of polyether solutions

Measurements are reported of the vapor pressures and the heats and volumes of mixing of solutions of poly(ethylene glycol dimethyl ether) in chloroform and in carbon tetrachloride. The measurements have been used to calculate the thermodynamic mixing functions for mixing with zero volume change. These values have been compared with the predictions of the lattice theory of mixtures at three different levels of approximation, viz., the generalized “first approximation” theory of Barker, the “zeroth approximation” theory, and the Flory theory. In the hydrogen-bonding chloroform solutions the Barker theory is more successful than the other forms of the lattice theory. The results have also been used, in conjunction with those for solutions of poly(propylene glycol dimethyl ether) in the same two solvents, to test the ability of the Barker theory to correlate the properties of related systems. Good correlation is found between the two carbon tetrachloride solutions but not between the chloroform solutions. It is probable that the side-chain methyl groups in the propylene oxide repeating unit cause the hydrogen-bonding interaction to be weaker in this polymer than it is in the polymer with the ethylene oxide repeating unit.     

Thermoelectrochemical determination of standard entropy parameters for hydrogen ion in water-methanol solutions

The initial temperature coefficients are measured for the voltage of a thermogalvanic cell composed of two silver chloride electrodes in water-methanol solutions (WMS) of hydrogen chlorite at 298 K. The experimental results and earlier studies of thermoelectric properties of WMS of alkali metal halides are used to determine the entropy and partial molar entropy of the hydrogen ion moving in solution, the entropy change during its solvation, and the entropy carried by the hydrogen ion and a stoichiometric mixture of H⁺ and Cl^- ions in various WMS. The influence of composition of a mixed solvent on the entropy characteristics of the hydrogen ion is analyzed.     

Thermodynamics of the dissolution of crystalline L-methionine in water

The enthalpies of dissolution of crystalline L-methionine in water and aqueous solutions of potasium hydroxide at 298.15 K are measured by means of direct calorimetry. The standard enthalpies of formation are calculated for L-methionine and products of its dissociation in aqueous solution.     

Thermodynamics of dissolution of non-electrolytes and electrolytes in non-aqueous solvents

Experimental results on the H _soln of noble gases, polar non-electrolyte molecules, porphyrins, their metallocomplexes and organic electrolytes in individual and mixed solvents are discussed. Xe was shown to indicate changes in solvent mixtures and also to exert a noticeable influence on the character of intermolecular interactions in solutions. The thermodynamic characteristics of the solvation of a series of non-polar and polar molecules are given and their dependence on the solvent nature, composition, isotopy and temperature is shown. For the first time the thermodynamic characteristics of porphyrins and metalloporphyrins in different non-aqueous solvents have been found by direct calorimetry. The possibility of axial coordination of porphyrin metallocomplexes is treated and a method is proposed for estimation of the influence of the functional substituents and the metal atom on the electronic effects in them. Compared to simple inorganic electrolyte solutions, the dependence of H _soln on various factors reveals a specific character.

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Zusammenfassung Experimentelle Daten zur Lösungswärme H _soln von Edelgasen, polaren Nichtelektrolyten, Porphyrinen und ihren Metallkomplexen und organischen Eletrolyten in einfachen und gemischten Lösungsmitteln werden diskutiert.Es wird gezeigt, dass Xe nicht nur auf Veränderungen in der Zusammensetzung von Lösungsmittelmischungen anspricht, sondern selbst einen merklichen Einfluss auf den Charakter der intermolekularen Wechselwirkungen ausübt. Thermodynamische Charakteristika der Solvatation einer Reihe unpolarer und polarer Moleküle werden aufgeführt und die Abhängigkeit von der Natur, Zusammensetzung (auch isotopisch) und Temperatur des Lösungsmittels wird gezeigt. Erstmalig werden die thermodynamischen Charakteristika von Porphyrinen und Metallporphyrinen in verschiedenen Lösungsmitteln direkt kalorimetrisch bestimmt. Die Möglichkeit einer axialen Koordination an Metall-Porphyrin-Komplexen wird gezeigt und eine Methode zum Abschätzen des dabei wirkenden Einflusses der funktioneilen Substituenten und des Metallatoms auf die elektronischen Effekte vorgeschlagen. Verglichen mit einfachen anorganischen Elektrolyt-Lösungen ist' die Abhängigkeit von H _soln von verschiedenen Faktoren sehr substanzspezifisch.

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Electrophoretic enantioseparation of profens in water-methanol solutions using eremomycin as a chiral selector

The possibility of the electrophoretic enantioseparation of profens in water-methanol solution of eremomycin was demonstrated. The effect of the methanol content, phosphate buffer pH, and chiral selector concentration on enantioresolution was studied. Water-methanol background electrolyte was shown to provide better reproducibility of migration times and baseline stability compared to aqueous buffers. The time of analysis in nonaqueous conditions is less than 15 min.     

Thermodynamics of caffeine in aqueous denaturant solutions

The effects of urea, guanidinium chloride, and potassium chloride on the solution properties of caffeine have been investigated by solubility and partition experiments and by measuring heats of dilution, solution, and mixing. Thermodynamic transfer properties are used to discuss the possible mechanism of action of the two denaturants. The ability of caffeine to form stacked aggregates is taken as possible evidence for a direct interaction of this solute with urea and guanidinium ion. The data are discussed both in terms of an ideally associating system and in terms of the virial expansion following the McMillan-Mayer solution theory.Part of this paper was presented at the Journées de Calorimetrie et d'Analyse Thermique, Torino, Italy, June 28–30, 1978.     

Thermodynamics of aqueous solutions of polyvinylpyrrolidone

Densities, viscosities and water activities of aqueous solutions of polyvinylpyrrolidone have been determined experimentally at T=(298.15, 308.15, 318.15 and 328.15) K. From the density data, the apparent specific volume of polymer and the partial specific volume of polymer and water have been calculated. From the viscosity data, the viscosity and number average molecular weight of polymer have been calculated. From the water activity data, the vapour pressure of solutions has been calculated. Densities, viscosities and water activities have been correlated successfully with an general equation which takes into account the influence of the polymer concentration and the temperature.     

Electrochemical dissolution of magnetite in acid solutions

The present paper deals with the electrochemical behavior of magnetite microcrystals in an acid medium. A voltammetric method employing a carbon-paste electroactive electrode (CPEE) with an organic binder was used. It was found that the cathodic voltammograms, which were recorded at different scan rates, formed a set bounded in the space of i–E parameters by a generalizing voltammetric curve corresponding to the effective potential scan rate _eff. In other words, all curves are situated under one enveloping curve, just as the smaller dolls sit in the largest doll of a Russian doll. Reverse currents (a cathodic current in the anodic direction of the potential scan) were observed on the cyclic voltammogram. Forward and reverse currents obey the same laws and have one and the same generalizing curve, which could be taken as the magnetite characteristic.     

Chemical dissolution of iron in aqueous solutions

By anodic oxidation of hydrogen on the Pt ring of a metal-disk-Pt-ring rotating electrode in aqueous acid (pH 0.5–3) sulfate solutions, it is shown that during the polarization of the metal disk hydrogen coevolves by two parallel reactions. One is the well known electrochemical charge transfer process, while the other one is a direct chemical reaction of the metal, i.e. iron, with water molecules from the electrolyte. This process was proposed a long time ago by Kolotyrkin and co-workers, but their experimental results were subjected to serious criticism which is taken care of in the present paper. The chemical reaction is potential- and pH-independent and, depending on the actual conditions during the corrosion processes (actual potential, pH, etc.), can be of greater or smaller importance in the overall process. The consequences of the existence of this direct chemical reaction of metal with water molecules (i.e. H₂O-induced corrosion or chemical corrosion) on pitting and stress corrosion cracking of metals is discussed. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth. This article was submitted by the authors in English.     

Thermodynamics of aqueous carbohydrate surfactant solutions

The paper deals with the application of the micelle formation theory, developed by Nagarajan and Ruckenstein [R. Nagarajan, E. Ruckenstein, Langmuir 7 (1991) 2934–2969] and Nagarajan [R. Nagarajan, in: K. Esumi (Ed.), Structure–Performance Relationships in Surfactants, Dekker, New York, 1997, pp. 1–81; R. Nagarajan, Adv. Colloid Interface Sci. 26 (1986) 205-264] to various n-alkyl-β-d-glucopyranoside surfactants, differing in the surfactant tail length (n-octyl-β-d-glucopyranoside C₈G₁, n-decyl-β-d-glucopyranoside C₁₀G₁ and dodecyl-β-d-glucopyranoside C₁₂G₁). The model predicts that the carbohydrate surfactant molecules assemble for energetic reasons in spherical bilayer vesicles. The critical micellar concentration as function of the temperature shows a minimum value. The formed micellar aggregates exhibit a broad distribution of sizes. It is demonstrated in this study that the thermodynamic theory in combination with phase separation thermodynamics can be used successfully to described the phase separation, which occurs for the system C₁₀G₁+water and C₁₂G₁+water at low surfactant concentrations.     

Diffusion of ferrocene methanol in super-cooled aqueous solutions using cylindrical microelectrodes

The diffusion of ferrocene methanol in super-cooled aqueous solutions containing sucrose has been studied, using disk and cylindrical microelectrodes, over a wide viscosity range. The solution viscosity and the reduced temperature T/T_g (T_g being the glass transition temperature) were varied by changing the sucrose concentration and the temperature of the system. The voltammetric limiting current obtained with a disk microelectrode and the i(t) response on a cylindrical microelectrode after a potential step were used to determine diffusion coefficients from 7 × 10⁻⁶ cm² s⁻¹ down to 2 × 10⁻¹¹ cm² s⁻¹. The electrochemical procedure described in this work allows a simple and accurate measurement of the dynamics of electroactive solutes in glass-forming liquids.