Lan-Chi Koenigsberger

Solubility constants reported in the literature for ammonium hydrogenurate (NH4HU), an occasional constituent of urinary calculi in humans, show a large scatter, probably due to the tendency of hydrogenurates to form supersaturated solutions that persist over long periods of time. In this study, the solubility of NH4HU(s) was measured as a function of p[H] = − lg{[H+]/mol dm−3} (4.5–8) and temperature (25 and 37 °C) at constant ionic strength, Ic = 0.300 mol dm−3 NH4Cl, which is similar to the ionic strength of urine. Highly reproducible values for the solubility product (Ks0) of NH4HU(s) were obtained. The first dissociation constant (K1) of uric acid determined in this work agrees well with values obtained in our previous studies of uric acid solubilities in electrolyte solutions relevant to urolithiasis. This study confirms our earlier findings that in the ionic strength range of urine, the solubilities of uric acid and hydrogen urates as a function of p[H] can be described consistently by unique values of their solubility constants (Ks, Ks0) and the first dissociation constant of uric acid (K1). In addition, no appreciable complexation between uric acid or hydrogenurates and other urine constituents has been found.

An internally consistent thermodynamic network for arsenic minerals and aqueous species is being developed based on a high quality starting point: arsenolite and arsenolite solubility. Current research is refining the properties of scorodite solubility as a function of temperature along with improved aqueous species stability constants and activity coefficients for ions and ion pairs based on potentiometric measurements of redox, pH, and conductivity for 5-90 °C. The second and third hydrolysis constants for arsenic acid have been calculated as a function of temperature and thermodynamic properties have been derived.

The extraction of rare earth oxides from fluorapatite rich phosphate concentrates often involves a weak acid leach of fluorapatite and a sulphuric acid bake of the leach residue followed by water leach and precipitation to obtain an intermediate product. The main aim of this study was to determine and rationalize the solubility of rare earth metal ions in synthetic solutions representing various process liquors at the temperatures 40, 60 and 80 °C. The liquors contained different acid and metal ion concentrations with respect to sulphuric acid, phosphoric acid and sulphate salts of sodium, magnesium, aluminium, potassium, calcium and iron(III). A solid of mixed rare earth carbonates was used as the source of rare earth metal ions. The solubility tests and characterisation of solids using XRD were conducted at Murdoch University laboratories as part of the process development for the Arafura Resources Nolans rare earth project. The composition of initial carbonate solids and the solids and solutions formed after saturation were analysed for rare earth and other elements at TSW Analytical Laboratories in Perth using ICP-MS and ICP-OES. The precipitated solid in sodium-rich acidic sulphate solutions is the double salt NaRE(SO4)2 based on the solid assays. However, in acidic solutions free of sodium or of low concentrations of sodium the precipitated solid appears to be RE2(SO4)3.

An internally consistent thermodynamic network for arsenic minerals and aqueous species is being developed based on a high quality starting point: arsenolite and arsenolite solubility. Current research is refining the properties of scorodite solubility as a function of temperature along with improved aqueous species stability constants and activity coefficients for ions and ion pairs based on potentiometric measurements of redox, pH, and conductivity for 5-90°C.

Protonation constants for the biologically-important thioamino acids cysteine (CSH), penicillamine (PSH) and glutathione (GSH), and the formation constants of their complexes with Cu(i), have been measured at 25 °C and an ionic strength of 1.00 mol dm-3 (Na)Cl using glass electrode potentiometry. The first successful characterisation of binary Cu(i)-CSH and Cu(i)-GSH species over the whole pH range was achieved in this study by the addition of a second thioamino acid, which prevented the precipitation that normally occurs. Appropriate combinations of binary and ternary (mixed ligand) titration data were used to optimise the speciation models and formation constants for the binary species. The results obtained differ significantly from literature data with respect to the detection and quantification of protonated and polynuclear complexes. The present results are thought to be more reliable because of the exceptionally wide pH and concentration ranges employed, the excellent reproducibility of the data, the close agreement between the calculated and observed formation functions, and the low standard deviations and absence of numerical correlation in the constants. The present formation constants were incorporated into a large Cu speciation model which was used to predict, for the first time, metal-ligand equilibria in the biofluids of the human eye. This simulation provided an explanation for the precipitation of metallic copper in lens and cornea, which is known to occur as a consequence of Wilson's disease.

The IUPAC Subcommittee on Solubility and Equilibrium Data has been selecting, editing and reviewing projects and manuscripts for publication as part of the IUPAC-NIST Solubility Data Series (SDS). This series provides comprehensive reviews of data from the primary literature for solubilities of gases, liquids and solids in liquids or solids. Data are compiled in a uniform format, critically evaluated and, where high-quality data from independent sources agree sufficiently, recommended values are proposed [1]. SDS Volume 102 was published recently [2]. A current IUPAC project is dealing with solubilities of subs tances related to urolithiasis [3]. Kidney stones consist of a range of inorganic and organic substances that are sparingly soluble in urine, thereby producing ionic and uncharged aqueous species which can undergo a wide variety of protonation and complexation reactions. Using these data as an example, this work explores the features of the JESS solubility database [4] that assist with the presentation, manipulation and critical evaluation of solubility data. In particular, the unique combination of databases available in JESS for speciation equilibria [5], physicochemical properties of solutions [6] and solubilities provides improved evaluation facilities, including the assessment of thermodynamic consistency among solubility, calorimetric and speciation data as described in a recent SDS volume [7]. Systems of different chemical complexity will highlight the benefits of applying the JESS software package to the production of future SDS volumes.

The extraction of rare earth metals from fluoroapatite rich phosphate concentrates often involves a weak acid leach of fluoroapatite and a sulphuric acid bake of leach residue followed by water leach and precipitation to obtain an intermediate product. The main aim of this study was to determine and rationalize the solubility of rare earth metal ions in synthetic solutions representing various process liquors at three temperatures 40, 60 and 80oC containing different acid and metal ion concentrations with respect to sulphuric acid, phosphoric acid and sulphate salts of sodium, magnesium, aluminium, potassium, calcium and iron(III). Solid mixture of rare earth metal carbonates was used as the source of rare earth metal ions. The solubility tests and characterization of solids using XRD were conducted at Murdoch University laboratories. The composition of initial carbonate solids and the solids and solutions formed after saturation were analysed for rare earth and other elements at TSW Analytical Laboratories in Perth using ICP-MS and ICP-OES. The precipitated solid in sodium rich acidic sulphate solutions is the double salt NaRE(SO4)2 based on the solid assays. However, in acidic solutions free of sodium or of low concentrations of sodium the precipitated solid appears to be RE2(SO4)3.

Reliable solubility data for oxides and hydroxides of heavy metals in alkaline solutions are relevant to a number of industrial and geochemical processes, including the production of high-purity alumina in the Bayer process, the formation of ores from geothermal solutions at high pH, hydrometallurgical leaching processes for the extraction of metal values from ores and plant residues, and the storage and processing of certain types of radioactive waste. Recent results obtained for various systems will be reported, including experimental and modelling aspects. A new facility for the storage, handling and processing of solubility data will be outlined.

The solid-liquid solubility data for well defined nonaqueous binary and ternary systems are reviewed. One component includes hydroxybenzoic acid, hydroxybenzoate, and hydroxybenzoic acid salt, and another component includes a variety of organic compounds (hydrocarbons, alcohols, halogenated hydrocarbons, carboxylic acids, esters, et al.) and carbon dioxide. The ternary systems include mixtures of organic substances of various classes and carbon dioxide. The total number of compilation sheets is 270 for six types of system. Almost all data are expressed as mass percent and mole fraction as well as the originally reported units, while some data are expressed as molar concentration. Critical evaluation was carried out for the binary nonaqueous systems of 2-, 3-, and 4-hydroxybenzoic acids and hydroxybenzoates (methylparaben, ethylparaben, propylparaben, and butylparaben) in alcohols, 1-heptane, and benzene.