Phase Equilibria and Critical Curves of Binary Ammonia–Hydrocarbon Mixtures

Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described.     

Concentrated electrolyte solutions at high temperatures and pressures

A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H₂O and CO₂–H₂O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Physicochemical Principles of Extraction with Supercritical Gases

The present review considers some physicochemical properties of fluid mixtures that are of importance for fluid extraction and supercitical fluid chromatography (SFC). Firstly, the important types of phase diagrams are treated, the occurrence of solid phases also being considered in some simple cases. Specific examples are given of mixtures of a highly volatile component I (e.g. CO₂, C₂H₆) with a relatively involatile component II (e.g. squalane) of very different molecular size, shape, structure, and/or polarity, and it is shown how the rather complicated types of phase diagrams can be calculated and correlated. The importance of fluid mixtures extends far beyond the fields of science and technology reviewed.     

Isolation of Some Soluble and Dispersed Materials of Oregano Water

Recent results obtained on determining the extraction efficiency and composition of organic volatiles in Oregano Water obtained from Origanum onites L. are described. Oregano Water was subjected to liquid-liquid extraction with a range of solvents with different polarities and each extract was analyzed by GC/MS.     

Voltammetry in Undiluted Acetic Acid. In Situ Determination of Water

Water present in undiluted acetic acid can be monitored in situ with Pt and Au microelectrodes using differential pulse and square‐wave voltammetries. Both reduction and oxidation peaks can be obtained. The best quantitative analytical results were obtained for the anodic peak, the Pt microelectrode, and differential pulse voltammetry. The anodic water peak is located at +1.55 V vs. the quasi reference Pt electrode. The voltammetric peak obtained at Pt electrode is apparently not a diffusional one, however, the calibration plot obtained by employing this peak is linear over a wide concentration range, up to 4 mol dm^?3. The detection limit has been estimated as 2.3 mM or 0.0043 v/v%. The developed method may be particularly useful, since the Karl Fischer method can not be used to determine water in glacial acetic acid due to the estrification reaction of acetic acid with methanol. A voltammetric wave of undiluted acetic acid could not be obtained in the positive and negative ranges of potential.     

Chromatography with Supercritical Fluids

Chromatography with supercritical fluids unites the features of both gas chromatography and liquid chromatography, yet retains special characteristics of its own. The diffusion coefficient and particularly the viscosity of fluid phases may approach values for low-pressure gases, while the solvent power may be similar to that of liquids. However, with supercritical fluids it is possible to control chromatographic separations very effectively by pressure programming, since the solubility increases with increasing density. Temperature programming, on the other hand, can have the opposite effect to that in gas- or liquid-chromatography since the density decreases with increasing temperature at a given pressure. Supercritical fluid chromatography is primarily of interest for the separation of higher molecular weight compounds. The efficiency of this method of separation is demonstrated on several homologous series. Thus, a styrene oligomer with nominal M_w=2200 can be resolved by a pressure and temperature program into 40 species.     

Synthesis of α, ω perfluoropolyether iodides

Perfluoropolyether (PFPE) diacyl halides of formula XCOCF₂O[(CF₂O)_n(CF₂CF₂O)_m]_pCF₂COX, with X = Cl, F and molecular weight (MW) 400-4000 g mol⁻¹ are smoothly converted in high yields to the corresponding α, ω diiodides in the absence of solvent, employing KI or LiI at 210 °C with extrusion of CO. During the reactions, β-elimination of COF₂ from the terminal difluoromethylene oxide units (CF₂O, C₁ unit) occurs to some extent until a tetrafluoroethylene oxide unit (OCF₂CF₂, C₂ unit) is encountered yielding a OCF₂CF₂I terminus. This considerably alters the MW distribution of the final diiodide especially for low MW PFPEs. Operating in supercritical conditions of CO (scCO) or both scCO and CO₂ (scCO₂) on low (<600 g mol⁻¹) MW diacyl halides, lowers β-elimination from 95 to 52 mol% if KI is used or from 43 to 30 mol% if LiI is used. With higher MW (>600 g mol⁻¹) β-elimination is lowered from 15 to <1 mol% in scCO conditions employing KI.     

Interactions of Pb(II) with particles of a polluted river

Pb(II) interactions with the surface of suspended matter from a polluted river was studied using differential pulse anodic stripping voltammetry (DPASV) technique. Three sampling sites were selected and studies have been done with samples collected in different times of the year (winter, autumn and summer). The values have been compared with those obtained in spring in the same conditions [Sci. Total Environ. 151 (1994) 101].Particles were separated by centrifugation and suspensions of the freeze-dried particles were titrated with Pb(II), being measured the labile metal fraction by DPASV. For comparison, suspensions of river water without any separation have also been titrated.Results show that surface metal complexes are inert, within the time scale of the analytical technique and desorbed organics from surfaces, form labile Pb(II) complexes in solution. For each sample it was determined the capacity for Pb complexation of particles and desorbed organics and the differential function has been estimated. Despite the heterogeneity of ligands, the systems interpreted in a discontinuous way, present one or two kinds of dominant ligands with Pb affinity.     

Influence of Cycle Temperatures on the Thermochemical Heat Storage Densities in the Systems Water/Microporous and Water/Mesoporous Adsorbents

The adsorption equilibrium of water on microporous adsorbents (zeolites of NaA-, NaY- and NaX-type as well as their ion exchanged forms) and on mesoporous adsorbents (different silica gels and composite material i.e. silica gel + salt hydrate) has been studied experimentally and theoretically. Using the Dubinin theory of pore filling the characteristic curves of the adsorption systems and other relevant dependences such as isotherms, isobars, isosteres and the curve of the differential heat of adsorption were calculated. For all systems investigated the adsorption were calculated. A_ads and the desorption potential A_des of the closed heat storage system were estimated. These values define the working range of the adsorption/desorption cycle and allow to calculate the specific heat storage density Δ h_sp. On the basis of Δ h_sp the different adsorbents were compared in order to select the optimal porous storage material for a given application. The presented experimental and theoretical investigations show that the adsorption systems water-zeolite and water-composites are promising working pairs for thermochemical heat storage processes for hot tap water supply and space heating of single family dwellings. The advantage of the water-composite system is the low desorption temperature (solar energy) the main shortcoming the low temperature lift. The advantage of the water zeolite system is the high temperature lift, the shortcoming are the relative high desorption temperatures.     

Supercritical Propanol-Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles

Highly crystalline anatase TiO₂ nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.