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The suitability of phenyl‐based deep eutectic solvents (DESs) as absorbents for toluene absorption was investigated by means of thermodynamic modeling and molecular dynamics (MD). The thermodynamic models perturbed‐chain statistical associating fluid theory (PC‐SAFT) and conductor‐like screening model for real solvents (COSMO‐RS) were used to predict the vapor–liquid equilibrium of DES–toluene systems. PC‐SAFT yielded quantitative results even without using any binary fitting parameters. Among the five DESs studied in this work, [TEBAC][PhOH] consisting of triethyl benzyl ammonium chloride (TEBAC) and phenol (PhOH), was considered as the most suitable absorbent. Systems with [TEBAC][PhOH] had lowest equilibrium pressures of the considered DES–toluene mixtures, the best thermodynamic characteristics (i.e., Henry's law constant, excess enthalpy, Gibbs free energy of solvation of toluene), and the highest self‐diffusion coefficient of toluene. The molecular‐level mechanism was explored by MD simulations, indicating that [TEBAC][PhOH] has the strongest interaction of DES–toluene compared to the other DESs under study. This work provides guidance to rationally design novel DESs for efficient aromatic volatile organic compounds absorption. [ABSTRACT FROM AUTHOR]

A new predictive molecular thermodynamic model (i.e., modified COSMO‐SAC‐UNIFAC) was first proposed and extended to predict the solubility of CO2 in pure and mixed ionic liquids (ILs) at the temperatures down to 263.2 K. It is interesting to discover that with equimolar amounts, the solubility of CO2 in such 1:1 IL pairs, that is, [A1][B1] + [A2][B2] and [A1][B2] + [A2][B1], was consistent at the same temperature and pressure in the case of exchanging their respective cations and anions. The molecular dynamic (MD) simulation for CO2 + mixed ILs was performed to deeply analyze and explain this intriguing phenomenon. Not only the CO2 gas drying experiment with the ILs ([C2mim][OAc], [C2mim][dca], and [C2mim][OAc] + [C2mim][dca]) as absorbents but also the corresponding process simulation and optimization were made to stress the effectiveness and applicability of the new thermodynamic model. Thus, this work ranges from molecular level to systematic scale. [ABSTRACT FROM AUTHOR]

In this work, seven acrylonitrile derivatives were selected as potential inhibitors of fat and obesity‐related proteins (FTO) by the aid of fluorescence spectroscopy, ultraviolet visible spectroscopy, molecular docking, and cytotoxicity methods. Results show that the interaction between 3‐amino‐2‐(4‐chlorophenyl)‐3‐phenylacrylonitrile (1a) and FTO was the strongest among these derivatives. Thermodynamic analysis and molecular modeling show that the main force between 1a and FTO is hydrophobic interaction. The cytotoxicity test showed that the IC50 value of 1a was 46.64 μmol/L, which indicated 1a had the smallest IC50 value and had the best inhibitory effect on the proliferation of leukemia K562 cells among the seven derivatives. Both our previous results and this work show that chlorine atoms play important role in the binding of small molecules and FTO. This work brings new information for the study of FTO inhibitors. [ABSTRACT FROM AUTHOR]

This work explores the optimum detergency conditions of alkyl ethoxylate (CXEOY) surfactants with the integrated free energy model (IFEM). IFEM is a molecular thermodynamic model that calculates the free energy of formation of oil‐swollen spherical micelles, with a core solubilization radius Ro, using surfactants from empty (oil‐free) micelles and oil molecules from a continuous oil phase. The described geometry allows for rapid calculations, using a personal laptop (3.4 GHz processor), where each solubilization energy profile (free energy vs. Ro curve) can be solved in 5 min or less. While previous work showed quantitative agreement between IFEM predictions and experimental solubilization of alkanes in CXEOY micelles, this work explores the possibility of using IFEM as a tool in surfactant selection. Experimental work has shown that detergency improved when operating near the phase inversion temperature (PIT) of the surfactant‐hexadecane system. The IFEM simulations in this work show, for the first time, that IFEM can be used to predict the PIT of surfactant‐oil systems, and that the surfactants selected via this method are consistent with the selection guided by experimental observations. [ABSTRACT FROM AUTHOR]

Phosphorus is a nonmetal with several allotropes, from the highly reactive white phosphorus to the thermodynamically stable black phosphorus (BP) with a puckered orthorhombic layered structure. The bulk form of BP was first synthesized in 1914, but received little attention until it was rediscovered in 2014 as a member of the new wave of 2D layered nanomaterials. BP can be exfoliated to a single sheet that acts as a semiconductor with a tunable direct band gap, a high carrier mobility at room temperature, and an in-plane anisotropy. The development of BP applications is hampered by surface degradation, thus efforts to achieve effective BP passivation are ongoing, such as its integration in van der Waals heterostructures. BP has been tested as a novel nanomaterial in batteries, transistors, sensors, and photonics. This Review begins with the origin of the BP story, following the path from a bulk material to modern few/single layers. The physical and chemical properties are summarized, and the state-of-the-art of BP applications highlighted. [ABSTRACT FROM AUTHOR]

Mining and metals processing are not invisible activities and are heavy industries, which require energy, water, chemicals, and land area. Recently more emphasis is given to environmental and societal aspects in mining and processing. Development of good practices with improved resource efficiency, new recovery methods and sustainability thinking are increasingly required. This work shows pH titration method for acid mine drainage (AMD) water incorporated with aqueous thermodynamic model for selective metals precipitation from complex solution. Also two examples on gold recovery methods from aqueous streams are shown: biosorption using fungal matter and solvent extraction using a task-specific ionic liquid. By understanding chemical thermodynamics and natural phenomena, there is a better chance of developing solutions for environmental problems and new industrial processes. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2739-2748, 2015 [ABSTRACT FROM AUTHOR]

Experimental results are presented for the solubility of CO2 in an aqueous solution of phenol and NaOH (molalties in water: phenol: 0.5; NaOH: 1.0) at (314, 354, and 395) K and pressures up to 10 MPa. The experimental work extends recent investigations on the influence of phenol as well as of (phenol + NaCl) on the solubility of CO2 in water. In contrast to those previous investigations, the strong electrolyte reacts with carbon dioxide and also with phenol. The experimental results are compared with predictions from a thermodynamic model. That model combines a model for the 'chemical' solubility of CO2 in aqueous solutions of NaOH with a model for the 'physical' solubility of CO2 in aqueous solutions of phenol. An extension is introduced to account for the chemical reaction between the weak acid phenol and the strong base sodium hydroxide. The prediction results nicely agree with the new experimental data. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2832-2840, 2015 [ABSTRACT FROM AUTHOR]

The permeability of light gases in a series of different glassy polymers is analyzed through a thermodynamic-based approach for solubility and diffusivity. The nonequilibrium thermodynamic model for glassy polymers describes the solubility of the different penetrants; diffusivity is given as the product of a mobility factor and a thermodynamic factor. The latter is predicted by the nonequilibrium lattice fluid thermodynamic model, while the mobility coefficient is determined using the experimental permeability data. For rather soluble penetrants (e.g., CO2), a plasticization factor is also accounted for, considering the mobility to depend exponentially on penetrant concentration, as often observed experimentally. The model is able to describe accurately the experimental behavior in a simple and effective way, considering only two adjustable parameters. The mobility coefficient is found to depend on the penetrant size (critical volume) and on the fractional free volume of the polymer matrix, following rather general and reasonable correlations. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2776-2788, 2015 [ABSTRACT FROM AUTHOR]

Despite great efforts over the past decades, thermodynamic modeling of electrolytes in mixed solvents is still a challenge today. The existing modeling frameworks based on activity coefficient models are data-driven and require expert knowledge to be parameterized. It has been suggested that the predictive capabilities could be improved through the development of an electrolyte equation of state. In this work, the Cubic Plus Association (CPA) Equation of State is extended to handle mixtures containing electrolytes by including the electrostatic contributions from the Debye-Hückel and Born terms using a self-consistent model for the static permittivity. A simple scheme for parameterization of salts with a limited number of parameters is proposed and model parameters for a range of salts are determined from experimental data of activity and osmotic coefficients as well as freezing point depression. Finally, the model is applied to predict VLE, LLE, and SLE in aqueous salt mixtures as well as in mixed solvents. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2933-2950, 2015 [ABSTRACT FROM AUTHOR]

Forward thermodynamic modelling is a commonly used tool for examining the thermobarometric history of a rock. Such models are being applied to a widening range of rock types using increasingly complex model systems. A useful aspect of phase equilibria modelling using pseudosections is the ability to calculate the modal abundance and compositions of phases, in addition to overall phase relations. However, calculating and plotting such data with thermocalc, a popular modelling program, is time consuming. In this article, we provide the methods and a description of a Matlab® computer program, TCInvestigator, which uses thermocalc 3.40 to automatically contour pre-calculated pressure-temperature pseudosections with modal abundance and mineral composition parameters. The ability to calculate, plot and visualize these parameters automatically and rapidly, allows for a more in-depth investigation into the metamorphic evolution of a rock. Data can be contoured for all minerals that are present in all fields on the pseudosection, rather than a selection of fields or phases that are a priori considered relevant. Examples of contoured pseudosections for pelitic and greywacke bulk compositions are presented, along with accompanying data sets, to illustrate the applications of this program. The software and example files are available from the CSIRO Data Access Portal at the following address: doi:. [ABSTRACT FROM AUTHOR]

RATIONALE The unique properties of the PbO-B2O3-SiO2 system, especially its extensive range of glass-forming compositions, make it valuable for various practical applications. The thermodynamic properties and vaporization of PbO-B2O3-SiO2 melts are not well established so far and the data obtained on these will be useful for optimization of technology and thermodynamic modeling of glasses. METHODS High-temperature Knudsen effusion mass spectrometry was used to study vaporization processes and to determine the partial pressures of components of the PbO-B2O3-SiO2 melts. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two quartz effusion cells containing the sample under study and pure PbO (reference substance). Ions were produced by electron ionization at an energy of 25 eV. To facilitate interpretation of the mass spectra, the appearance energies of ions were also measured. RESULTS Pb, PbO and O2 were found to be the main vapor species over the samples studied at 1100 K. The PbO activities as a function of the composition of the system were derived from the measured PbO partial pressures. The B2O3 and SiO2 activities, the Gibbs energy of formation, the excess Gibbs energy of formation and mass losses in the samples studied were calculated. CONCLUSIONS Partial pressures of the vapor species over PbO-B2O3-SiO2 melts were measured at 1100 K in the wide range of compositions using the Knudsen mass spectrometric method. The data enabled the PbO, B2O3, and SiO2 activities in these melts to be derived and provided evidence of their negative deviations from ideal behavior. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: As the Dawn mission approaches a successful conclusion at Ceres, it seems time to assess how its findings have sharpened the picture of Ceres’s evolution. Before Dawn, we inferred from Ceres's bulk density of about 2100 kg m−3 that Ceres contained about 25% water by mass. Thermodynamic modeling of the interior evolution suggested that the original accreted ice had to melt even if only long‐lived radionuclides were present, leading to the aqueous alteration of the original chondritic silicates and differentiation of the altered silicates from any remaining water, consistent with telescopic detection of aqueously altered silicates (serpentine and clay minerals) on Ceres’s surface. Earth‐based observations of Ceres’s shape were not accurate enough to constrain the extent of differentiation of its interior. Dawn's results confirm these early findings and extend them dramatically to reveal an evolved and active small planet, probably even today, due to water/ice‐driven processes. A nearly uniform global distribution of surface mineralogy, which includes Mg‐serpentines, ammoniated clays, and salts including carbonates, suggests extensive, endogenous, planet‐wide aqueous alteration. Local exceptions show salt‐rich deposits of varied composition, which suggests subsurface heterogeneities. Concentration of Fe below carbonaceous chondrite levels suggests chemical fractionation, leading to Ceres being chemically differentiated. The high spatial uniformity of element abundance measurements of equatorial regolith also indicates that some ice‐rock fractionation occurred on a global scale. Even some local exposures of ice are seen, especially in higher latitudes and in low‐illumination regions that must be very young, as surface water ice is unstable on time scales of 1–1000 years under Ceres’s surface temperatures. Subsurface ice is also likely in abundance at higher latitudes in at least the upper few meters of the surface, as suggested by near‐surface H‐rich polar deposits. Observations of bright ice deposits in permanently shadowed regions suggest cold‐trapping of migrating H2O across the surface. Gravity field measurements indicate a concentration of mass toward the center and near isostatic equilibrium, consistent with at least some mass differentiation driven by water‐related processes. Abundant small and midsize craters but relaxed or missing large craters suggest a stiff upper crust with water abundance lower than 30 vol%. A sharp decrease in viscosity at ~40 km depth suggests the occurrence of a small fraction of liquid, consistent with earlier thermophysical models. Surface cryogenic features, such as flows, extrusions, and domes, some geologically very recent, are evidence of active water/ice‐driven subsurface processes. Ceres experienced extensive water‐related processes and at least some mass and chemical fractionation and is probably active today, consistent with previous moderate heating thermodynamic models. Clearly, Ceres is a “wet,” evolved planet at the edge of the inner solar system, as described in this special issue. We conclude with a list of questions suggested by the Dawn findings; they especially regard the state and fate of water and its role in driving past and possibly current chemical and physical activity in this dwarf planet. [ABSTRACT FROM AUTHOR]

Biomass to fuel programs are under research and development worldwide. The largest biomass programs are underway in industrialized countries. In the coming decades, however, developing countries will be responsible for the major increase in transportation fuel demand. Although the lack of existing large-scale infrastructure and primary resources preclude oil refining in developing countries, this provides an opportunity for the rapid implementation of small-scale distributed biorefineries to serve multiple communities locally. The principles for biorefinery design, however, are still in their infancy. This review sets a precedent in combining thermodynamic, metabolic, and sustainability analyses for biorefinery design. We exemplify this approach through the design and optimization of a marine biorefinery for an average town in rural India. In this combined model, we include sustainability and legislation factors, intensive macro algae Ulva farming, and metabolic modeling of the biological two-step conversion of Ulva feedstock by a yeast ( Saccharomyces cerevisiae), and then by a bacterium ( Escherichia coli), into bioethanol. We hope that the model presented here will be useful in considering practical aspects of biorefinery design. © 2013 Society of Chemical Industry and John Wiley & Sons, Ltd [ABSTRACT FROM AUTHOR]