Solubility of Barium Sulfate in Water at Elevated Temperatures and Pressures.

There are few measurements of barium sulfate (BaSO4) solubility in water above 373 K available in the literature. BaSO4 solubility data at water saturation pressure are scare. The pressure dependence on BaSO4 solubility has not previously been comprehensively reported for the pressure range 100-350 bar. In this work, an experimental apparatus was designed and built to measure BaSO4 solubility in aqueous solutions under high-pressure (HP), high-temperature (HT) conditions. The solubility of BaSO4 was experimentally determined in pure water over the temperature range from T = (323.1 to 440.1) K and pressures ranging from p = (1 to 350) bar. Most of the measurements were done at water saturation pressure: six data points were done above the saturation pressure (323.1-373.1 K) and 10 experiments were conducted at water saturation (373.1-440.1 K). The reliability of the extended UNIQUAC model and results generated in this work was demonstrated by comparing with the scrutinized experimental data reported in the literature. The model gives a very good agreement with BaSO4 equilibrium solubility data, demonstrating the reliability of the extended UNIQUAC model. The accuracy of the model at high temperature and saturated pressure due to data insufficiencies is discussed.

Experimental data of the aqueous NH3 and CO2 absorption at temperatures from 15 °C to 35 °C, NH3 concentrations from 5% to 15% and CO2 loadings from 0.2 to 0.6 measured with the Wetted Wall Column.

The absorption between aqueous NH3 and CO2 is studied using the Wetted Wall Column in order to show the effect of the solvent condition on the rate of reaction. A total of 27 different cases are investigated in the region defined by temperatures from 15 °C to 35 °C, NH3 concentrations from 5% to 15% and CO2 loadings from 0.2 to 0.6. The paper reports the data measured during the experiments, the experimental apparatus description and the experimental procedure. The data here presented are both the raw data measured with their uncertainty and the final value of the overall mass transfer coefficient. The overall mass transfer coefficient is the result of the raw data treatment explained in the research paper related to this data. The data here reported are analyzed in the paper by Lillia et al. (2018) [1].

Modeling of dielectric properties of complex fluids with an equation of state.

The static permittivity is a key property for describing solutions containing polar and hydrogen bonding compounds. However, the precise relationship between the molecular and dielectric properties is not well-established. Here we show that the relative permittivity at zero frequency (static permittivity) can be modeled simultaneously with thermodynamic properties. The static permittivity is calculated from an extension of the framework developed by Onsager, Kirkwood, and Fröhlich to associating mixtures. The thermodynamic properties are calculated from the cubic-plus-association (CPA) equation of state that includes the Wertheim association model as formulated in the statistical associating fluid theory (SAFT) to account for hydrogen bonding molecules. We show that, by using a simple description of the geometry of the association, we may calculate the Kirkwood g-factor as a function of the probability of hydrogen bond formation. The results show that it is possible to predict the static permittivity of complex mixtures over wide temperature and pressure ranges from simple extensions of well-established theories simultaneously with the calculation of thermodynamic properties.

Modeling of dielectric properties of aqueous salt solutions with an equation of state.

The static permittivity is the most important physical property for thermodynamic models that account for the electrostatic interactions between ions. The measured static permittivity in mixtures containing electrolytes is reduced due to kinetic depolarization and reorientation of the dipoles in the electrical field surrounding ions. Kinetic depolarization may explain 25-75% of the observed decrease in the permittivity of solutions containing salts, but since this is a dynamic property, this effect should not be included in the thermodynamic modeling of electrolytes. Kinetic depolarization has, however, been ignored in relation to thermodynamic modeling, and authors have either neglected the effect of salts on permittivity or used empirical correlations fitted to the measured static permittivity, leading to an overestimation of the reduction in the thermodynamic static permittivity. We present a new methodology for obtaining the static permittivity over wide ranges of temperatures, pressures, and compositions for use within an equation of state for mixed solvents containing salts. The static permittivity is calculated from a new extension of the framework developed by Onsager, Kirkwood, and Fröhlich to associating mixtures. Wertheim's association model as formulated in the statistical associating fluid theory is used to account for hydrogen-bonding molecules and ion-solvent association. Finally, we compare the Debye-Hückel Helmholtz energy obtained using an empirical model with the new physical model and show that the empirical models may introduce unphysical behavior in the equation of state.

Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.

Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.