Equilibrium solubilities of spearmint oil components in supercritical carbon dioxide

The equilibrium solubilities of l-carvone and l-limonene in the binary (l-carvone–CO₂ and l-limonene–CO₂) and ternary (l-carvone–l-limonene–CO₂) systems were obtained at 39°C and 49°C and at pressures ranging from 6 to 10 MPa. The solubilities of these components increased with a pressure increase or a temperature decrease. The solubility of l-limonene was higher than that of l-carvone at the same temperature and pressure. The correlation of the solubilities using Chrastil equation revealed that the solubilities of both components were strongly dependent on the density of CO₂. In the ternary system simulating the actual spearmint oil composition, the solubility of l-carvone was similar but the solubility of l-limonene was lower as compared to their solubilities in the binary systems.     

A high pressure differential thermal analysis apparatus

A high pressure differential thermal analysis apparatus is described which is capable of operation in the pressure range from 1-600 atm of nitrogen gas and at temperatures from 25 to 500°C. Use of the apparatus is illustrated by the deaquation reactions of CuCl₂·2H₂0 and CoSO₄·7H₂O at pressures from 1 to 69 atm.     

A high pressure electrical conductivity apparatus

A high pressure electrical conductivity (EC) apparatus. capable of operation at pressures from 1 to 170 atm in the temperature range from 25 to 500°C, is described. The effects of the sample holder geometry, pressure, and sample packing on the resulting EC curves are given. Operation of the apparatus is illustrated by the deaquation reactions of BaCI₂·2H₂0.     

Solubility of Li2WO4 under hydrothermal conditions

Experimental studies of water solubilities of Li₂WO₄ at temperatures up to 450°C and pressures up to 147 MPa show that this salts with water forms a type 2 binary system, where the solubility of the salt under the vapor pressure decreases as temperature rises to end at the critical end-point p (g=l-s) near the H₂O critical temperature. High-temperature Li₂WO₄ solutions are shown to not react with silica, but they cause corrosion of metallic walls of an autoclave accompanied with gas evolution and formation of dark-colored solid corrosion products.     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006     

Gas—liquid equilibrium in hydrogen + tetralin + diphenylmethane and hydrogen + tetralin + m-xylene

Vapor—liquid equilibrium data in two ternary mixture systems, hydrogen + tetralin + diphenylmethane and hydrogen + tetralin + m-xylene, were determined in a flow apparatus at pressures 20–250 atm¹ for both systems, and temperatures 190–430°C for the first system and 190–310°C for the second. Mixed solvents approximately equi-molal in the organic compounds were studied. Henry constants of hydrogen in the mixed solvents were evaluated from the data. The results show that the solubility of hydrogen in these mixed hydrocarbon solvents can be completely predicted from solubilities in the pure component liquids.     

Solubilities of zinc oxide and cadmium oxide in CsI melt at 700°C

The solubility products of ZnO (pL = 10.0 ± 0.5) and CdO (pL = 6.8 ± 0.2) in CsI melt at 700°C are determined by potentiometric titration with the use of a Pt(O₂)|ZrO₂(Y₂O₃) membrane oxygen electrode. In the Zn-Cd family, metal oxide solubilities grow with increasing metal cation radius. The solubilities in an iodide melt are much lower than in a chloride melt due to a higher basicity of the former; for the Cd²⁺ cation, the difference between solubilities in these melts is lower owing to the formation of Cd²⁺-I⁻ (soft acid-soft base) complexes.     

Measurement of the solubility of metal complexes in supercritical carbon dioxide using a UV–vis spectrometer

A new apparatus based on the circulation method was developed to measure the solubility of metal complexes in supercritical carbon dioxide (scCO₂) at a wide range of temperatures and pressures. A UV–vis spectrometer, which was connected to a small saturation cell through optical fibers, was used to determine solubility. The solubilities of cobalt(III) acetylacetonate (Co(acac)₃) and chromium(III) acetylacetonate (Cr(acac)₃) in scCO₂ were measured to check the validity of both the apparatus and the method and to accumulate new solubility data. The solubility data for Cr(acac)₃ obtained in this study were in good agreement with the data reported in the literature.The measured solubilities of Co(acac)₃ and Cr(acac)₃ were also correlated with the empirical equation including the three adjustable parameters, based on the equation proposed by Chrastil. The parameters were determined by fitting the equation to the experimental data for each metal complex and the calculated results closely replicated the experimental data.     

Isothermal pressure dependence of the solubility of some triazines in supercritical CO2

 The solubility of two related series of each three triazine compounds has been determined in supercritical CO₂, at 40 °C and pressures between 80 and 220⋅10⁵ Pa. A high pressure small volume cell with adjustable optical path and built-in circulation pump has been constructed to be used with quartz windows in a Perkin Elmer UV-VIS spectral photometer. At 220 bar solubilities are between 0.3 and 25 g/L, dependent on the specific triazine structure. The isothermal pressure dependence of the solubility could be modelled using the pressure dependent dielectric constant of CO₂ as the only variable. Received: 30 October 1996/Revised: 3 April 1997/Accepted: 13 April 1997     

Untersuchungen an Systemen aus Salzen und gemischten Lösungsmitteln. VI. Das Verhalten des reziproken Salzpaares Na2SO4 + 2 KCl ⇌ K2SO4+2 NaCl in Methanol-Wasser-Mischungen

The solubility isotherms of the system Na₂SO₄? K₂SO₄? CH₃OH? H₂O at 25,40 and 55°C and the solubilities in the system of the metathetic salt reaction Na₂SO₄+ + 2KCl ? K₂SO₄ + 2NaCl in methanol-water mixtures at 10 and 25°C have been determined and the nature of the solid phases established. The addition of methanol causes an enlargement of the sulphatic existence fields. A flow sheet for the industrial application of the results is communicated.     

Be<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>CO<Subscript>3</Subscript> solubility in carbonate and fluoride aqueous solutions

Be₂(OH)₂CO₃ solubilities at 25°C in 0.7 M NaClO₄ solutions containing variable NaHCO₃ and Na₂CO₃ concentrations has been experimentally determined. The solubilities increase with increasing carbonate alkalinity. The results of the experiments do not contradict the suggestion that the mixed hydroxocarbonate complex Be₂(OH)₂CO ₃ ^2? is the major beryllium solute species. At fluoride concentrations higher than 250 μmol/L, the Be₂(OH)₂CO₃ solubilities noticeably increase as a result of the formation of beryllium fluoride complexes.     

Solubility of Zinc Silicate and Zinc Ferrite in Aqueous Solution to High Temperatures

Crystalline zinc silicate, Zn₂SiO₄, and zinc ferrite, ZnFe₂O₄, were prepared and characterized. The solubilities of these phases were measured using flow-through apparatus from 50 to 350 °C in 100 °C intervals over a wide range of pH. Both solid phases dissolve incongruently, presumably to form ZnO(s) and Fe₂O₃(s) (or the corresponding hydroxide phases at low temperature), respectively. The respective concentrations of zinc(II) and iron(III) matched those of ZnO(cr) and Fe₂O₃(s) (≥150 °C) reported in the literature, whereas the corresponding Si(IV) and Zn(II) concentrations were at least an order of magnitude below the solubility limits for their pure oxide phases. Therefore, the solubility constants for zinc silicate and ferrite were determined with respect to the known solubility constants for ZnO(cr) and Fe₂O₃(s) (≥150 °C), respectively, and the corresponding concentrations of Si(IV) and Zn(II) measured in this study. The results of independent experiments, as well as those reported in the literature provide insights into the mechanism(s) of formation of zinc silicate and ferrite in the primary circuits of nuclear reactors. D.A. Palmer is retired.     

Diffusion and solubility of methane in polyisobutylene

Diffusion coefficients and solubilities of methane in polyisobutylene have been measured at four temperatures between 102 and 188°C. in the pressure range 23–341 atm. Diffusion coefficients extrapolated to atmospheric pressure range from 1.72 × 10^?6 cm.²/sec. at 102°C. to 1.5 × 10^?5 cm.²/sec. at 188°C. corresponding to an activation energy for diffusion of 8.7 ± 0.4 kcal./mole. Solubilities are small, about one molecule of methane for every forty carbon atoms in the polyisobutylene at 300 atm. partial pressure of methane. Solubilities vary little with temperature, but show an apparent minimum between 127 and 188°C. With improved methods of data analysis, diffusion coefficients and solubilities have been recalculated from previously reported studies on nitrogen in branched polyethylene and methane in branched polyethylene, linear polyethylene, and polystyrene. Recalculated diffusion coefficients are essentially the same as those reported previously, but the recalculated solubilities are decreased from 2 to 30%. The solubilities of all five systems show strong deviations from Henry's law, i.e., increases in partial pressure of methane and nitrogen with respect to solubility exceed linearity. The partial pressure (or fugacity)—solubility data may be interpreted in terms of a sorption model in which sorbed molecules are accommodated in widely dispersed, unoccupied volumes or sites in the polymer. An almost equivalent, solution model in which the first sorbed molecules to enter the polymer are accommodated to a large extent in existing volumes in the polymer, with successively sorbed molecules swelling the polymer to a greater extent (i.e., partial molal volume of sorbed molecules, V ₁, increasing with concentration) can also account for these data.     

A study of the reaction Na2SO4·10H2O→Na2SO4+10H2O in the temperature range 0 to 25°C

Thermogravimetry was used to obtain data on the isothermal rate of dehydration and hydration of the reaction Na₂SO₄·10H₂O→Na₂SO₄+10H₂O in the temperature range 10 to 25°C. The thermodynamic functions, ΔH, ΔG and ΔS were calculated and compared with data in the literature. The dissociation pressures of Na₂SO₄·10H₂O at temperatures in the range 0 to 25°C were measured in a volumetric dissociation apparatus. The results obtained were compared with those using thermogravimetry and the accuracy of the two techniques was assessed.     

Gas transport through ethylene-acrylic acid ionomers

Transport properties of several gases in two ethylene-acrylic acid ionomers characterized by a different amount of acrylic acid groups and percentage of neutralization have been investigated. Sorption and permeation experiments have been performed with N₂, O₂, CO₂, CH₄, C₂ H₆, and SF₆ in the 25–65°C range and with C₃H₈ only at 25°C. Gas permeabilities, diffusivities, and solubilities were evaluated along with activation energies and heats of solution. Data obtained in the present investigation were compared to analogous results reported in literature for polyethylene to better highlight the effect of ionic aggregates on the gas transport mechanism. © 1995 John Wiley & Sons, Inc.     

Solubility in the ternary system LiCl + MgCl<Subscript>2</Subscript> + H<Subscript>2</Subscript>O at 60 and 75°C

The solubility of ternary system of lithium, magnesium and chloride and refractive indexes have been determined at 60 and 75°C, respectively. Using the experimental results, the phase diagrams of the ternary system were plotted. The single-salt Pitzer parameters of LiCl and MgCl₂ β⁽⁰⁾, β⁽¹⁾ and C ^ϕ were calculated by using the equations reported by Li Y-H and de Lima at different temperatures, respectively. On the basis of Pitzer ion-interaction model and solubility product equation for mixed electrolytes, the mixing parameters θ_{Li, Mg}, Ψ_{Li, Mg, Cl} and equilibrium constant K _sp were evaluated in this system, which were not reported in literature. A complete phase diagram of the ternary system was predicted at 60 and 75°C. The prediction of solubilities in ternary system was then demonstrated. The calculated solubilities agreed well with the experimental values.     

Hydrogenation and Dehydrogenation of the Clathrate Na<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>136</Subscript>

Samples of the clathrate Na _x Si₁₃₆ were saturated with hydrogen to 100 atm at 25°C in a Sievertstype apparatus and at pressures of 6 and 28 kbar in lentil-type high-pressure apparatuses at 100 and 250°C. X-ray powder diffraction analysis and Raman spectroscopy of the samples quenched after the saturation with hydrogen showed that the phase composition of the clathrates did not change. Heating of the quenched samples to room temperature in a thermal desorption setup produced not hydrogen, but hydrogen-containing gases, as we assumed, silanes. Heating to 650°C leads to decomposition of these compounds to form hydrogen.     

Composés d'addition des chlorures de terres rares avec le méthanol,l'éthanol et le propanol-2. Préparations,solubilités et réactions de transsolvatation

By reaction of hydrated rare earths chlorides (M = La, Nd, Sm, Gd, Dy, Er, Yb, Y) with orthoformates, the following adducts have been prepared: MCl₃· 4MeOH, MCl₃ ·3EtOH (M = La, Nd, Sm, Gd, Yb), MCl₄ · 4 EtOH (M = Dy, Er, Y); adducts MCl₃ · 3iso-PrOH have been prepared by successive action of methyl orthoformate and of 2-propanol. The solubilities of these adducts in the corresponding alcohols at 25° (for the lanthanum adducts equally at 0 and 50°) are given. Two examples of the transsolvatation of these compounds, yielding adducts with weakligands, are described.     

Mise au point d'un appareillage de preparation et de manipulation de melanges anhydres HFNH3MF (M alcalin) — tension de vapeur totale au-dessus de solutions HFNH3 riches en HF

An apparatus for preparing and handling HFNH₃MF mixtures (M alkali metal) has been designed and constructed. The vacuum line made of plastic materials (PVF₂, PTFCE, PTFE) allows the purification of anhydrous hydrogen fluoride, preparation and analysis of HFNH₃ or HFNH₃MF mixtures and their handling for further study or destruction.Total vapour pressures above HFNH₃ binary mixtures rich in HF have been measured and are described as a function of ammonia concentration and temperature (?10 to +20°C).