The solubility behavior of sodium arsenate in NaOH solution based on the Pitzer model.

Alkaline leaching is an effective method for dealing with arsenic-containing resources. Arsenic is dissolved in an alkaline solution in the form of arsenate, but the lack of relevant basic data has caused difficulties in the theoretical analysis during production and research. The dissolution behavior of arsenic in the solution was systematically studied in this paper. The solubility behavior of the self-made sodium arsenate in water and NaOH solution were measured. The research on sodium arsenate solution was carried out to obtain the quasi-solubility product using the Pitzer model, and the effect of temperature and NaOH concentration on the solubility and quasi-solubility product of sodium arsenate was clarified.

The Influence of Chemical Activity Models on the Description of Ion Transport through Micro-Structured Cementitious Materials.

The significance of ion activity in transport through a porous concrete material sample with steel rebar in its center and bathing solution is presented. For the first time, different conventions and models of ion activity are compared in their significance and influence on the ion fluxes. The study closes an interpretational gap between ion activity in a stand-alone (stagnant) electrolyte solution and ion transport (dynamic) through concrete pores. Ionic activity models developed in stationary systems, namely, the Debye-Hückel (DH), extended DH, Davies, Truesdell-Jones, and Pitzer models, were used for modeling the transport of ions driven through the activity gradient. The activities of ions are incorporated into a frame of the Nernst-Planck-Poisson (NPP) equations. Calculations were done with COMSOL software for a real concrete microstructure determined by X-ray computed tomography. The concentration profiles of four ions (Na+, Cl-, K+, OH-), the ionic strength, and the electric potential in mortar (with pores) and concrete samples (with aggregates and pores) are presented and compared. The Pitzer equation gave the most reliable results for all systems studied. The difference between the concentration profiles calculated with this equation and with the assumption of the ideality of the solution is negligible while the potential profiles are clearly distinguishable.

Mining minerals and critical raw materials from bittern: Understanding metal ions fate in saltwork ponds.

Seawater represents a potential resource for raw materials extraction. Although NaCl is the most representative mineral extracted other valuable compounds such as Mg, Li, Sr, Rb and B and elements at trace level (Cs, Co, In, Sc, Ga and Ge) are also contained in this "liquid mine". Most of them are considered as Critical Raw Materials by the European Union. Solar saltworks, providing concentration factors of up-to 20 to 40, offer a perfect platform for the development of minerals and metal recovery schemes taking benefit of the concentration and purification achieved along the evaporation saltwork ponds. However, the geochemistry of these elements in this environment has not been yet thoroughly evaluated. Their knowledge could enable the deployment of technologies capable to achieve the recovery of valuable minerals. The high ionic strengths expected (0.5-7 mol/kg) and the chemical complexity of the solutions imply that only numerical geochemical codes, as PHREEQC, and the use of Pitzer model to estimate the activity coefficients of the different species in solution can be adopted to provide valuable description of the systems. In the present work, for the first time, PHREEQC Pitzer code database was extended to include the target minor and trace elements using Trapani saltworks (Sicily, Italy) as a case study system. The model was able to predict: i) the purity in halite and the major impurities contained, mainly Ca, Mg and sulphate species; ii) the fate of minor components as B, Sr, Cs, Co, Ge and Ga along the evaporation ponds. The results obtained pose a fundamental step in critical raw materials mining from seawater brine, for process intensification and combination with desalination.

Volumetric properties of disodium dihydrogen pyrophosphate aqueous solution from 283.15 to 363.15 K at 101.325 kPa.

The purpose of this exploration was to determine the density and volumetric properties of the aqueous solution of Na2H2P2O7 with the molality varied from 0.08706 to 0.88402 mol·kg-1 measured at temperature intervals of 5 K from 283.15 to 363.15 K at 101.325 kPa using Anton Paar Digital vibrating-tube densimeter. The thermal expansion coefficient (α), apparent molar volume (VΦ), expansibility (ϕE), and partial molar volume (VB) of Na2H2P2O7 (aq) against temperature and molality have been evaluated from density data. On the basis of Pitzer ion-interaction apparent molar volume theory, the Pitzer single-salt parameters (ßM,X0v, ßM,X1v, ßM,X2v and CM,Xv, MX = Na2H2P2O7), and their correlation coefficients ai of the temperature-dependence formula f (i, p, T) = a1 + a2ln(T/298.15) + a3(T - 298.15) + a4/(620 - T) + a5/(T - 227) for Na2H2P2O7 were obtained for the first time. It was revealed that predicted apparent molar volumes agreed well with the experimental values indicating the single salt parameters and the temperature-dependent formula are reliable.

Insight into the effect of pH-adjusted acid on thermodynamic properties and crystallization sequence during evaporative-crystallization process of hydrolyzed urine.

The evaporative-crystallization process (ECP) is a frequently used approach for complete nutrient recovery from human urine, and crystallization sequence is related to the selection of seed and the optimization of crystallization process. In this study, three hydrolyzed urine (HU) samples, which were acidified to an initial pH of 4 with HCl, H2SO4, and H3PO4, were used to recover crystallized products by ECP, their crystallization process and thermodynamic properties during ECP were compared, and the detailed crystallization sequence was analyzed using the PHREEQC-2 simulation. The results showed that the pH-adjusted acid has a significant effect on crystal precipitation, and the new crystal in HCl-4-HU, H2SO4-4-HU, and H3PO4-4-HU first appeared at volume concentration factors (CFV) of 19.61, 9.90, and 9.96, respectively. Furthermore, the simulated crystallization process characteristics of HU by PHREEQC-2 have a good fit with the actual experimental data, and crystallization sequence of HCl-4-HU, H2SO4-4-HU, H3PO4-4-HU during ECP were NH4Cl (CFV from 10.25 to 100) / NaCl (CFV from 71.43 to 100), NH4NaSO4 (CFV from 10.25 to 55.56) / NH4Cl (CFV from 20 to 100) / (NH4)2SO4 (CFV from 40.45 to 100), NH4H2PO4 (CFV from 10.25 to 100) / NaH2PO4 (CFV from38.46 to 55.5) / NaCl (CFV from 45.46 to 100), respectively. The present study clearly reveals the crystallization sequence and thermodynamic properties of nutrient elements in acidified HU, which provides an important theoretical basis for the optimization of crystallized products obtained from HU for future study.

Thermochemical study for remediation of highly concentrated acid spill: Computational modeling and experimental validation.

The release of concentrated acid solutions by chemical accidents is disastrous to our environmental integrity. Alkaline agents applied to remedy the acid spill catastrophe may lead to secondary damages such as vaporization or spread out of the fumes unless substantial amount of neutralization heat is properly controlled. Using a rigorous thermodynamic formalism proposed by Pitzer to account short-range ion interactions and various subsidiary reactions, we develop a systematic computational model enabling quantitative prediction of reaction heat and the temperature change over neutralization of strongly concentrated acid solutions. We apply this model to four acid solutions (HCl, HNO3, H2SO4, and HF) of each 3 M-equivalent concentration with two neutralizing agents of calcium hydroxide (Ca(OH)2) and sodium bicarbonate (NaHCO3). Predicted reaction heat and temperature are remarkably consistent with the outcomes measured by our own experiments, showing a linear correlation factor R2 greater than 0.98. We apply the model to extremely concentrated acid solutions as high as 50 wt% where an experimental approach is practically restricted. In contrast to the extremely exothermic Ca(OH)2 agent, NaHCO3 even lowers solution temperatures after neutralization reactions. Our model enables us to identify a promising neutralizer NaHCO3 for effectively controlling concentrated acid spills and may be useful for establishment of proper strategy for other chemical accidents.

Potential water recovery during lithium mining from high salinity brines.

Lithium extraction from continental brines involves the evaporation of large amounts of water in open air ponds, in order to concentrate the brine. The evaporitic technology implies the evaporation of large water volumes, raising environmental concerns. If we envision the use of desalination processes for the concentration of lithium-rich brines, then fresh water production/recovery becomes a process well integrated with lithium extraction. Here we apply the Pitzer thermodynamic model with effective molality to estimate activity coefficients for 8 different native brines, and for the resulting concentrated solutions produced by a hypothetical advanced desalinization technique. In all cases, rational activity coefficients deviate considerably from unity. We calculate next the least work of separation for a hypothetical desalination process for the 8 different brines. Because of the large total salinity, the calculation shows that the least work of separation ranges from 18 until 42 kJ kg-1 at nil recovery ratio, and escalating from those numbers as more water is recovered. We can also predict the boiling point elevation, the vapour pressure lowering, and the osmotic pressure. Our calculations show that results are not strictly proportional to the total dissolved solids. Results are strongly dependent with the specific chemical composition of each brine, with the amount of divalent ions (Mg-Ca-SO42-) in particular strongly influencing calculations. Fresh water and lithium minerals production could be part of a single integrated production system.

Novel method for characterization of aqueous vanadium species: A perspective for the transition metal chemical speciation studies.

Identification the polymerization nature of vanadium bearing solution is difficult, yet it is of great environmental concern due to the possible carcinogenic effects as well as high-value sustainable necessities. Thus, seeking for simple and efficient characterization methods of tracking vanadium species is in urgent demand. In this work, high-resolution electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) coupled with thermodynamic calculations was employed to measure vanadium-containing samples. Evolutions of four characteristic vanadium species, H2VO4- (0-1%), V2 species (0-1%), V4 species (1-20%), and V10 species (60-95%), were comprehensively studied from acidic to neutral conditions, based on which thermodynamic model and vanadium phase diagram were established to visualize transformation pathways. More than 30 types of aqueous vanadium species could be semi-quantitatively detected by employing this method with less than 5% relative error, and the corresponding existing forms and concentration of these vanadium species could be well predicted. The vanadium species identified in MS results were confirmed by NMR. This method can be widely used for the understanding of vanadium speciation in practical examples, especially involving V(V), Cr(VI) ions or organic complexes.

Applying a modified Donnan model to describe the surface complexation of chromate to iron oxyhydroxide agglomerates with heteromorphous pores.

In this study, a modified Donnan model (mDM) is incorporated into surface complexation model (SCM) to better understand the physicochemical processes for adsorption of hexavalent chromium, Cr(VI), on porous iron oxyhydroxide agglomerates (IOAs). The mDM includes a chemical potential term µatt to account for ionic transport and electrostatic interaction in micropores (dmi<2nm) which is usually neglected in typical Donnan model (tDM). To estimate the parameters of mDM in a simple and accurate way, a rigorous protocol was presented. First, the prepared IOAs was characterized with a heteromorphous pore structure (i.e., co-existing micropores and macropores, dma>2nm) demonstrating high Cr(VI) adsorption in a broad range of ionic strengths. The batch data was then fitted with Donnan model in PHREEQC to obtain Stern (ψS) and Donnan (ψD) potentials used for µatt calculation. The decreasing µatt values with ionic strength indicated obstructing effect of electrolyte ions on Cr(VI) uptake in micropores. Finally, the ionic activity coefficients and reaction constants were corrected using Pitzer model due to the high level electrolytes accumulated in the Donnan layer through osmotic and electrostatic attraction. Results of this study have captured the effects of inner structure of IOAs on Cr(VI) uptake and quantitatively discerned the contribution of micropores and macropores for adsorption reactions at different ionic strengths.

Thermodynamically-robust Pitzer equations for volumetric properties of electrolyte solutions.

Pitzer equations are widely employed to correlate and predict the volumetric properties of aqueous electrolyte solutions over broad ranges of pressure and temperature. However, the currently-used pressure and temperature terms are empirical and tend to violate known thermodynamic behaviour. Three functional constraints have been identified that overcome this problem.

Accurate and self-consistent procedure for determining pH in seawater desalination brines and its manifestation in reverse osmosis modeling.

Measuring and modeling pH in concentrated aqueous solutions in an accurate and consistent manner is of paramount importance to many R&D and industrial applications, including RO desalination. Nevertheless, unified definitions and standard procedures have yet to be developed for solutions with ionic strength higher than ∼0.7 M, while implementation of conventional pH determination approaches may lead to significant errors. In this work a systematic yet simple methodology for measuring pH in concentrated solutions (dominated by Na(+)/Cl(-)) was developed and evaluated, with the aim of achieving consistency with the Pitzer ion-interaction approach. Results indicate that the addition of 0.75 M of NaCl to NIST buffers, followed by assigning a new standard pH (calculated based on the Pitzer approach), enabled reducing measured errors to below 0.03 pH units in seawater RO brines (ionic strength up to 2 M). To facilitate its use, the method was developed to be both conceptually and practically analogous to the conventional pH measurement procedure. The method was used to measure the pH of seawater RO retentates obtained at varying recovery ratios. The results matched better the pH values predicted by an accurate RO transport model. Calibrating the model by the measured pH values enabled better boron transport prediction. A Donnan-induced phenomenon, affecting pH in both retentate and permeate streams, was identified and quantified.