Nikolay N. Akinfiev

Experimental study of dissociation of HCl from 350 to 500°C and from 500 to 2500 bars: Thermodynamic properties of HCl°(aq)

New values of the dissociation constants of HCl° referring to low density supercritical solutions and near-critical temperatures of water (350–500°C and 500–2500 bars) have been obtained based on comparison of AgCl(s) solubility in NaCl or KCl solutions with Ag(s) solubility in HCl + NaCl or KCl solutions at controlled hydrogen fugacities. During the course of this study the thermodynamic properties of AgCls− were refined with the aid of the revised HKF equation of state (Tanger and Helgeson, 1988). The dissociation constants of HCl° obtained in the present work are higher than that found from electrical conductance measurements (Frantz and Marshall, 1984) by more than an order of magnitude at pressures of about 500 bars, but the difference becomes smaller as the pressure increases. Both sets of dissociation constants agree well at high pressures where the isothermal compressibility of water is less than about 1.42·10−4 bar−1. To reliably compare experimental data obtained by different methods, the Redlikh-Kwong equation of state was applied to available literature data as well as to the results of this study. Finally, the standard state thermodynamic properties and HKF parameters for HCl°(aq) were established. These results allow extrapolation of the thermodynamic properties of HCl°(aq) and consequently the HCl dissociation constant up to 700°C and 5000 bars.

Thermodynamic properties of the Sb(III) hydroxide complex Sb(OH)3(aq) at hydrothermal conditions

Abstract The standard thermodynamic properties and Helgeson-Kirkham-Flowers (HKF) parameters for Sb(OH)3(aq) have been estimated. For this purpose, the available solubility data for senarmontite, valentinite, stibnite, and native Sb in a wide range of temperatures (15 to 450°C) and pressures (1 to 1000 bar), and thermodynamic properties of Sb oxides (senarmontite and valentinite) have been critically analyzed. Published data were complimented by results from new experiments performed by solubility and solid-state galvanic cell methods. Both experimental data and thermodynamic calculations show that the hydroxide complex Sb(OH)3(aq) is primarily responsible for hydrothermal transport of antimony, especially at temperatures above 250°C.

Thermodynamic description of aqueous nonelectrolytes at infinite dilution over a wide range of state parameters

Abstract A new, virial-like equation of state (EoS) for describing the thermodynamic properties of aqueous nonelectrolytes at infinite dilution is proposed. It is based on the accurate EoS for a solvent (H 2 O) given by Hill (1990) and requires only three empirical parameters to be fitted to experimental data, and these are independent of temperature and pressure. Knowledge of the thermodynamic properties of a pure gas, together with these three parameters, enables prediction of the whole set thermodynamic properties of the solute at infinite dilution (chemical potential, entropy, molar volume, and apparent molar heat capacity) over a wide range of temperatures (0 to 500°C) and pressures (1 to 2000 bars), including the near-critical region. In the cases in which experimental thermodynamic data are lacking, the empirical parameters can be estimated solely from the known standard-state properties of the solute. The new EoS is compatible with the Helgeson-Kirkham-Flowers model for aqueous electrolytes, and thus it can be applied to reactions involving minerals, gases, and aqueous ions, in addition to uncharged species.

Gold speciation and transport in geological fluids: insights from experiments and physical-chemical modelling

Abstract This contribution provides an overview of available experimental, thermodynamic, and molecular data on Au aqueous speciation, solubility, and partitioning in major types of geological fluids in the Earths crust, from low-temperature aqueous solution to supercritical hydrothermal-magmatic fluids, vapours, and silicate melts. Critical revisions of these data allow generation of a set of thermodynamic properties of the AuOH, AuCl−2, AuHS, and Au(HS)−2 complexes dominant in aqueous hydrothermal solutions; however, other complexes involving different sulphur forms, chloride, and alkali metals may operate in high-temperature sulphur-rich fluids, vapours, and melts. The large affinity of Au for reduced sulphur is responsible for Au enrichment in S-rich vapours and sulphide melts, which are important gold sources for hydrothermal deposits. Thermodynamic, speciation, and partitioning data, and their comparison with Au and S contents in natural fluid inclusions from magmatic-hydrothermal gold deposits, provide new constraints on the major physical-chemical parameters (temperature, pressure, salinity, acidity, redox) and ubiquitous fluid components (sulphur, carbon dioxide, arsenic) affecting Au concentration, transport, precipitation, and fractionation from other metals in the crust. The availability and speciation of sulphur and their changes with the fluid and melt evolution are the key factors controlling gold behaviour in most geological situations.

CuCl Electrolysis for Hydrogen Production in the Cu–Cl Thermochemical Cycle

The Cu―Cl thermochemical cycle is among the most attractive technologies proposed for hydrogen production due to moderate temperature requirements and high efficiency. In this study, the key step of the cycle, H 2 gas evolution via oxidation of CuCl(s) dissolved in high concentrated HCl(aq), was experimentally investigated. The electrolysis parameters and system performance were studied by linear sweep voltammetry and electrochemical impedance spectroscopy at ambient temperature. Promising performance of the electrolyzer was obtained when pure water was used as catholyte. A thermodynamic model previously developed for speciation of the CuCl―CuCl 2 ―HCl aqueous solutions was used to speculate on the effects of reagent concentration, flow rate, and temperature on electrolysis kinetics. The experimental decomposition potential necessary to initiate the hydrogen evolution reaction was more than 3 times lower than the potential necessary for water electrolysis at the same conditions. Close correspondence of the hydrogen production rate to Faradays law of electrolysis indicated the current efficiency of about 98%, while the voltage efficiency was estimated at 80% at 0.5 V and 0.1 A/cm 2 .

Thermodynamic properties of o-phthalic acid and its products of dissociation at 0–200°C and 1–5000 bar

Values of the pH for four solutions in a KHPh-HCl-KOH system, where Ph denoting C8O4H4, are measured at 25–70°C depending on pressure (1–1000 bar). The experimental results and the available literature data are processed on the base of Helgeson-Kirkham-Flowers (HKF) equation of state [1] and the GIBBS, OptimA, and OptimB programs from the HCh software package [2]. The obtained standard thermodynamic properties and HKF parameters of H2Phaq, HPh−, and Ph2− aqueous species, provides calculation of the pH of phthalate buffers in a wide range of temperatures (up to 200°C) and pressures (up to 5 kbar). The calculated values for the biphthalate buffer (0.05m KHPh) correspond to the IUPAC recommendations (at 0–50°C and 1 bar) with an accuracy of 0.005 pH units, and to the values of pH measured in this study at elevated Tp parameters (25–70°C and pressures of up to 1 kbar) within the limits of ±0.02 pH units.