Thermodynamic studies of some binary mixtures containing a self-associated component. II. Excess volumes of some mixtures of tetrahydrofuran with alcohols

Excess volumes of mixing, V^E, for binary mixtures of tetrahydrofuran (THF) with methanol, ethanol, n-butanol, tert-butanol, 2-bromoethanol and ethylene glycol have been determined from the experimental density measurements at 298.15 K over the entire composition range. The V^E data follow the order: ethylene glycol < 2-bromoethanol < methanol < ethanol < n-butanol < tert-butanol. The results have been explained in terms of self-association and the hydrogen bond-donating abilities of alcohols.     

The phase-separation behaviour of aqueous solutions of polyacrylic acid and its partial sodium salts in the presence of sodium chloride

Phase-separation temperatures have been measured for polyacrylic acid dissolved in aqueous sodium chloride solutions over a range of ionic strengths, degrees of neutralisation, polymer concentrations and molecular weights. The data are used to derive θ-temperatures for this system. The dependence of the θ-points on ionic strength and degree of ionisation is discussed and the results are briefly compared with data for other polyelectrolytes.     

The electrical conductance of some molten car☐ylate mixtures

Data are presented for the electrical conductivities in the melt for lead(II) octadecanoate/lead(II) decanoate, lead(II) hexadecanoate/lead(II) decanoate, lead(II) hexadecanoate/zinc hexadecanoate and lead(II) hexadecanoate/cadmium hexadecanoate mixtures over their complete composition ranges. The electrical conductivities are measured as a function of temperature from just above the melting point to just below the decomposition point of the mixtures. The Arrhenius plots for the mixtures are linear in all cases and the activation energies are determined. While the activation energies for lead(II) octadecanoate/lead(II) decanoate and lead(II) hexadecanoate/lead(II) decanoate mixtures are mole fraction independent over the concentration range studied, rendering support to previous models advanced by other workers that the major charge carrier is the free metal cation, the other systems show no such simple behaviour. In these systems there are indications of deviations from ideal behaviour, suggesting that entropy and enthalpy of mixing might be important.     

Oxidation of ferrocene and some substituted ferrocenes in the presence of horseradish peroxidase

The enzyme catalysed oxidation of ferrocene and some substituted ferrocenes to the corresponding ferricinium ions by hydrogen peroxide in the presence of native or immobilized horseradish peroxidase has been studied. Initial and maximum rates of oxidation have been determined. It was found that the oxidation was independent of the hydrogen peroxide concentration. The oxidation of ferrocene was effected also by horseradish peroxidase in a coupled system with glucose oxidase in the absence of any added hydrogen peroxide.     

Thermodynamics of weak interactions: Excess enthalpies of some binary bromoform mixtures

Excess enthalpies of bromoform + toluene, +o-xylene +m-xylene and +p-xylene have been determined at 308.15 K. These compounds have been examined for Barker's theory in order to understand the magnitude and nature of various interactions between the components of these mixtures. It has been concluded that the H-atom and one bromine atom of bromoform interact with the π cloud of the aromatic ring. These conclusions have been supplemented by n.m.r. studies. An approximate distance of the bromoform proton from the plane of the aromatic ring has also been calculated and examined in the light of the proposed geometry of the molecular complexes. Equilibrium constants for the complexations reaction have also been determined.     

Factors influencing the atomization of vanadium in graphite furnace AAS

We have made the determination of V conform to the requirements of the modern (stabilized temperature) furnace technology where the integrated absorbance (A·s) signals are used to quantitate analyte volatilized into a chamber whose temperature is relatively constant during the period when the analyte peak is measured. Graphite tubes with good pyrolytic coating and fast (maximum power) heating are required. We explored the advantages of specially designed tubes, of a cool-down procedure between the char and atomization steps and of very thin platforms. We found that Mg(NO₃)₂ was advantageous as a matrix modifier. With these conditions we found no problems with several matrices reported by earlier workers to be troublesome, for example HNO₃, phosphate, Fe, Mg and Ca. However metals that form very refractory carbides, such as La, Mo, W and Zr may remain troublesome for V, probably because mixed carbides result which include VC. A group of geological samples was analysed for V. Our recommendation is the use of wall atomization from tubes with good pyrolytic coatings, Mg(NO₃)₂ as a matrix modifier and the cool-down procedure to establish a nearly constant temperature along the tube.     

Solvent extraction and spectrophotometric determination of palladium(II) with some nitrogen-containing heterocyclic hydrazones in the presence of chloride ions

Three terdentate hydrazones, all containing the 1-phthalazino grouping in the hydrazine moiety but differing in the heterocyclic substituent in the aldehyde moiety, have been used as analytical reagents for palladium(II), the optimal conditions for the extractive spectrophotometric determination of palladium(II) in the presence of chloride ions being deduced. These compounds are highly selective and sensitive reagents for palladium(II), since they are not extracted into chloroform from sulfuric acid solutions and do not react with other platinum group metals. The desirable spectral properties of the palladium(II) complex of benzothiazole-2-aldehyde-1-phthalazinohydrazone (BAPhH) have also been discussed with respect to preference of the C  N structural form in the heterocyclic ring on the aldehyde moiety of the ligand.     

Cryoscopic studies in molten salts. Dissociation state of some alkali isopolymolybdates and some related molybdenum(VI) compounds in molten K2Cr2O7and KNO3

The dissociation state of the solutes M₂MoO₄, M₂Mo₃O₁₀, M₂Mo₄O₁₃, M₂Mo₅O₁₆ (MRb or Cs), Na₂CrO₄·MoO₃, K₂CrO₄·2 MoO₃, Cr₂Mo₃O₁₂ and V₂MoO₈ was studied cryoscopically in molten K₂ Cr₂O₇ and KNO₃ solvents. The freezing point depression, ΔT, of the solvents was obtained by measuring the cooling curves of the binary salt mixtures over unlimited range of solute concentration. The number of foreign ions obtained ν, showed that the solutes were either simply dissociated in the melt into the probable stable species (MoO₄)^2?, (Mo₃O₁₀)^2?, (Mo₄O₁₃)^2? and (Mo₅O₁₆)^2? or, in some cases after reactions and rearrangements, into (CrMo₂O₁₀)^2? heteropolyions. The solute V₂MoO₈, on the other hand, was found to dissolve without any apparent dissociation. An agreement between the experimental and calculated values of activity, a, based on the Temkin and Random Mixing models and that of Van't Hoff's equation support the proposed simple dissocia- tion scheme for K₂Cr₂O₇Cs₂MoO₄ system.     

Thermodynamics of associated mixtures of the Mecke—Kempter type

A chain-forming associated solution theory based on the UNIQUAC equation is presented for alcohol-unassociated active component liquid mixtures of the Mecke—Kempter type. The capability of the theory in reproducing the excess Gibbs free energy and excess enthalpy data for many binary mixtures is successfully shown. Ternary extension of the theory is presented in the calculations of vapor—liquid and liquid—liquid equilibria and excess enthalpy data from binary data.     

Topological aspects of the thermodynamics of binary mixtures of non-electrolytes

An approach based on the “graph” theory has been evolved to predict molar excess enthalpies, H^E, and molar excess volumes, V^E, for a number of binary mixtures of non-electrolytes. The calculated H^E and V^E values compare reasonably well with their corresponding experimental values. The limitations of this approach have also been discussed.     

Solid—liquid phase diagrams of mixtures containing substituted phenols and amine mixtures

The thermal decomposition of CaCO₃ was studied under high vacuum by means of both TG and the more recently developed constant decomposition rate thermal analysis (CRTA) which allows the monitoring of both reaction rate and the residual pressure over the sample. The reliability of the kinetic results seems to be much higher with the latter technique which actually allows the reduction of the reaction rate and therefore the heat and mass transfer effects over a broad range of sample size. For instance, it was necessary, by conventional TG started under a vacuum of 2 10^?6 torr with a heating rate of 0.5 K min^?1, to lower the amount of sample to 2 mg in order to obtain the same activation energy as that calculated from CRTA with various samples weighing up to 50 mg. The TG experimental conditions quoted above (and which are upper limits of mass and heating rate) are beyond the limit of sensitivity of most available conventional TG equipment.     

Application of the principle of congruence to ternary alkane mixtures

Excess enthalpies and excess volumes at 298.15 K and atmospheric pressure have been measured for mixtures of n-hexane + (an equimolar mixture of n-tridecane + n-nonadecane). The agreement of the results with the corresponding results for mixtures of n-hexane + n-hexadecane is interpreted as confirmation of the applicability of the principle of congruence to multicomponent mixtures.     

Osmotic coefficients of polystyrenesulphonates in dioxane-water mixtures—II. Divalent counterions and mixtures of mono- and divalent counterions

The osmotic pressures of solutions of magnesium and calcium polystyrenesulphonate in water and in 25 wt % mixture of dioxane in water have been measured for concentrations from 0?002 to 0?06 molal in monomer units. The osmotic coefficient derived from these measurements is almost independent of concentration. Its values for solutions in dioxane-water mixtures are much lower than for aqueous solutions. The osmotic coefficients of solutions containing mixtures of polystyrenesulphonic acid and its calcium salt in 25 wt % dioxane have also been determined. The osmotic coefficient of these solutions has a distinct maximum at a certain value of the equivalent fraction of the acid. The experimental results are compared with the predictions of the cylindrical cell model and infinite line charge model. Satisfactory agreement between theory and experiment is found.     

Direct access to ferrocenyliminium salts and their use in synthesis

Reduction of ferrocenylketoximes by titanium trichloride provides a convenient route for the preparation of ferrocenyliminium salts, which have been shown to be useful for the synthesis of new derivatives.