Modelling of calcium sulphate solubility in concentrated multi-component sulphate solutions

The chemistry of several calcium sulphate systems was successfully modelled in multi-component acid-containing sulphate solutions using the mixed solvent electrolyte (MSE) model for calculating the mean activity coefficients of the electrolyte species. The modelling involved the fitting of binary mean activity, heat capacity and solubility data, as well as ternary solubility data. The developed model was shown to accurately predict the solubility of calcium sulphate from 25 to 95 °C in simulated zinc sulphate processing solutions containing MgSO₄, MnSO₄, Fe₂(SO₄)₃, Na₂SO₄, (NH₄)₂SO₄ and H₂SO₄. The addition of H₂SO₄ results in a significant increase in the calcium sulphate solubility compared to that in water. By increasing the acid concentration, gypsum, which is a metastable phase above 40 °C, dehydrates to anhydrite, and the conversion results in a decrease in the solubility of calcium sulphate. In ZnSO₄–H₂SO₄ solutions, it was found that increasing MgSO₄, Na₂SO₄, Fe₂(SO₄)₃ and (NH₄)₂SO₄ concentrations do not have a pronounced effect on the solubility of calcium sulphate. From a practical perspective, the model is valuable tool for assessing calcium sulphate solubilities over abroad temperature range and for dilute to concentrated multi-component solutions.     

Calcium carbonate solubility: a reappraisal of scale formation and inhibition

Considerable disparity exists in the published thermodynamic data for selected species in the Ca(2+) /CO(2)/H(2)O system near 25 degrees C and 1 atm pressure. Some authors doubt the significance of CaCO(3)(0)aq) complexes although there is experimental evidence of their occurrence. Evaluation of all the published experimental and estimated data for aqueous calcium carbonate species confirms that the consistent set of constants given by Plummer and Busenberg in 1982 is the best available, and suggests a formation constant log beta = 3.22 for CaCO(3)(0)(aq). This value was confirmed by additional experimental data and calculations using a specially developed computer program. The solubility s and solubility product K(s) are critically evaluated for each solid polymorph (amorphous CaCO(3), ikaite, vaterite, aragonite and calcite) using a hydrated ion pair model and we give coherent explanations for the calcium carbonate precipitation/dissolution process and the existence of supersaturated waters. The practical cases of scale formation and its inhibition by phosphonate-type compounds are discussed and explained with the same model, taking into account the CaCO(3)(0)(aq) species.     

CaCO3超细粉末的低温水热合成与表征

超细碳酸钙有颗粒尺寸小、比表面积大和表面活性高等优良特性,在橡胶、塑料、纸张、涂料、日用化学品等领域有广泛的应用。因此,研究CaCO3超细粉末的制备方法,开发CaCO3超细微粉的用途,具有十分重要的意义。目前其制备方法主要是碳化法,本文利用水热法制备单一相超细CaCO3粉末,通过不同的反应前驱物在120℃和150℃下进行水热反应直接合成出超细CaCO3粉末,并对产品的结构和形貌进行了表征。     

On the modeling of calcium sulfate solubility in aqueous solutions

The electrolyte–NRTL model used in a previous work (B. Messnaoui, T. Bounahmidi, Fluid Phase Equilibr. 237(1–2) (2005) 77–85), was extended for modeling of α-hemihydrate and gypsum solubilities in the complex system Ca²⁺–H⁺–SO₄²⁻–HSO₄⁻–H₂PO₄⁻–H₃PO₄–H₂O, at wide range of temperature and P₂O₅ concentration. The chemical equilibrium constant was evaluated as function of temperature according to the Gibbs–Helmholtz equation. The temperature dependence was taken into account in the expression of the standard state heat capacity of ionic, molecular and cristalline salts species. The standard-state heat capacity of Ca²⁺at 298.15 K is calculated to be 27.30 J mol⁻¹ K⁻¹. It is also shown that the experimental data agree with the predicted values of gypsum and anhydrite solubilities in water, at high temperature, by using only the values of parameters ${\tau }_{{\text{H}}_2\text{O}-(\text{C}{\text{a}}^{2+},\text{S}{{\text{O}}_4}^{2-})}$, ${\tau }_{(\text{C}{\text{a}}^{2+},\text{S}{{\text{O}}_4}^{2-})-{\text{H}}_2\text{O}}$ which were calculated, at 298.15 K from data of gypsum solubilities in phosphoric acid solutions.     

Measurement and modelling of solubility for calcium sulfate dihydrate and calcium hydroxide in NaOH/KOH solutions

The solubility of calcium sulfate dihydrate (CaSO₄·2H₂O) and calcium hydroxide (Ca(OH)₂) in alkali solutions is essential to understand their desilication behavior from Bayer liquor. In this work, solubilities of calcium sulfate dihydrate and calcium hydroxide for the ternary systems of CaSO₄·2H₂O–NaOH–H₂O, CaSO₄·2H₂O–KOH–H₂O, and Ca(OH)₂–NaOH–H₂O were measured by using the classic isothermal dissolution method over the temperature range of 25–75 °C. The Pitzer model embedded in Aspen Plus platform was used to model the experimental solubility data for these systems. The experimental solubility data was employed to obtain the new binary interaction parameters for Ca(OH)⁺–OH⁻, Ca(OH)⁺–Ca²⁺ and Ca(OH)⁺–K⁺, suggesting that the species Ca(OH)⁺ is a dominant species in simulated solubility for alkali systems. Validation of the parameters was performed by predicting the solubility for the ternary systems of Ca(OH)₂–NaOH–H₂O, CaSO₄·2H₂O–NaOH–H₂O and CaSO₄·2H₂O–KOH–H₂O with the overall average relatively deviation (ARD) of 2.12%, 0.75% and 1.63%, respectively.     

Synthesis of precipitated calcium carbonate nanoparticles using a two-membrane system

Precipitated calcium carbonate (PCC) nanoparticles were synthesized using a two-membrane system composed of a combination of a dialysis membrane tubing (DMT) and an emulsion liquid membrane (ELM). During the process, Ca²⁺ was diffused through the DMT, then the ELM, and finally reacted with CO ₃ ^2– ions in the internal water-in-oil (w/o) emulsion droplets. Each individual droplet was used as a microreactor. Results showed that the particle size and morphology of PCC were depended not only on the diffusion rate of Ca²⁺ across the liquid membrane, but also the carrier concentration as well. The PCC particles were mainly in vaterite form and their size increased steadily with the reaction time, as proved by X-ray diffraction and transmission electron microscopy studies.From Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 829–834.Original English Text Copyright © 2004 by Zeshan Hu, Yulin Deng, Qunhui Sun.This article was submitted by the authors in English.     

Crystallization of calcium carbonate with the filtration of aqueous solutions through a microporous membrane

It is established that the filtration of water through a microporous membrane does not change the hardness of the water; it does, however, reduce the amount of scale deposit, due to the crystallization of salts in water in the form of aragonite. The effect is consistently observed in water with a hardness of more than 7.0 H, a content of hydrocarbonate ions of more than 500 mg/L, and a pH ≥ 7.3. It is shown that introducing the seeds of calcite crystals into a filtrate results in the precipitation of calcite rather than aragonite. It is concluded that quasi-softening in the case of hard water microfiltration is caused by the removal of calcite micronuclei, and thus by conditions being created for the crystallization of aragonite as a thermodynamically less stable form.     

Mechanism of intumescence of a polyethylene/calcium carbonate/stearic acid system

In this work, we have investigated the intumescent behaviour of linear low-density polyethylene (LLDPE) containing calcium carbonate (chalk) treated by stearic acid. This system swells during burning and creates a protective layer when exposed to an external heat flux of 50 kW/m² in a mass loss calorimeter. This system has been fully characterized by FTIR, XRD, TGA and SEM. The carbonation/decarbonation temperatures, the swelling phenomenon and the effect of the thermal stress on the swelling have been examined. The residue is composed of a smooth surface made of chalk and CaO and a bulk of only chalk. Stearic acid allows a good dispersion of chalk particles into the LLDPE matrix, and contributes to form a cohesive network during burning when the thermal stress is high enough. A governing parameter of the intumescent effect is the particle size, which permits the formation of an insulating and cohesive mineral network during burning.     

Thermally induced transformations of calcium carbonate polymorphs precipitated selectively in ethanol/water solutions

For the precipitation of calcium carbonate polymorphs in ethanol/water solutions of calcium chloride by the diffusion of the gases produced by sublimation–decomposition of solid ammonium carbonate, polymorph selection and morphology control of the precipitates were demonstrated by the effect of ethanol/water ratio in the mother liquor. The precipitated phases change systematically from gel-like aggregates of hydrated amorphous calcium carbonate in the absolute ethanol solution to well-shaped rhombohedral particles of calcite in the absolute aqueous solution via almost pure phase of vaterite with dendrite structure in 75%-ethanol/25%-aqueous and 50%-ethanol/50%-aqueous solutions. On heating the precipitated sample in flowing dry nitrogen, all the samples transformed to calcite before the thermal decomposition, where the thermal decomposition temperature shifts to higher temperatures with increasing the water content in the mother liquor due to the systematic increase in the particle size of calcite. Accordingly, the present method of controlled precipitation of calcium carbonate polymorphs is also useful to control the particle size and reactivity of calcite produced by heating the precipitates. Selecting vaterite with dendrite structure from the present series of precipitated samples, the structural phase transition to calcite was characterized as the three-dimensional growth of rhombohedral particles of calcite with the enthalpy change ΔH = ? 2.8 ± 0.1 kJ mol^?1 and the apparent activation energy E_a = 289.9 ± 5.8 kJ mol^?1.     

Crystallization of inorganic compounds in polymer solutions. Part I: Control of shape and form of calcium carbonate

Calcium carbonate was precipitated by mixing aqueous solutions of sodium carbonate and calcium nitrate in the presence of water-soluble polymers. When the former was poured into the latter, in which a certain amount of sodium poly(styrenesulfonate) was dissolved, monodisperse spherical crystals were created. The crystal form was vaterite, although, in the absence of the polymer, calcite crystals were obtained in rhombic shape. The factors deciding the shape and form of the crystal were investigated and the role of polymer in the formation of unique crystals was discussed.     

Quantitative calibration of a TPD-MS system for CO and CO2 using calcium carbonate and calcium oxalate

A method is described for calibrating quantitatively a temperature-programmed decomposition, mass-spectrometric (TPD-MS) system by monitoring the gases evolved during the thermal decomposition of a chemical within the TPD reactor. A method for calibrating for evolved CO and CO₂ is described using the thermal decompositions of calcium carbonate and calcium oxalate. The method takes into account the production of CO⁺ ions from CO₂⁺ ions and secondary reactions in the thermal decomposition of calcium oxalate.     

Electrodialysis of calcium and carbonate high concentration solutions and impact on composition in cations of membrane fouling

Fouling, which is the accumulation of undesired solid materials at the phase interfaces of permselective membranes, is one of the major problems in electrodialysis. The objectives of the present work were to investigate the effect of the composition in calcium and carbonate of a model solution to be treated by conventional electrodialysis on their migration kinetics and the composition in cations of the membrane fouling. In the absence of sodium carbonate in the solution, no fouling was visually observed on anion-exchange membranes (AEM) and fouling was observed only at 1600 mg/L CaCl2 on cation-exchange membrane (CEM), while at only 800 mg/L CaCl2 with sodium carbonate, a deposit was observed on both membranes. This difference could be explained by the fact that carbonate has a high buffer capacity, and the time to reach pH 4.0 was then longer than the one without carbonate. Consequently, the migration of the ionic species was carried out over a longer period of time during ED treatment with sodium carbonate addition and in extent the demineralization rates were higher: 43 vs 86%. For treatment with sodium carbonate and 1600 mg/L CaCl2, the higher migration during ED treatment, increased the concentration of calcium, from 14.24 to 93.38 mg/g dry membrane and from 0.74 to 10.27 mg/g dry membrane for CEM and AEM, respectively. Due to the basic pH on the side of the membrane in contact with the NaCl solution, the calcium would precipitate to form calcium hydroxide on CEM while the calcium migrated through the CEM was blocked by the AEM where it formed another fouling.     

Compleximetric determination of calcium in impure calcium carbonate and limestone

Calcium is determined in impure calcium carbonate and limestone samples by titrating with 0.01 M disodium EGTA at pH 12 in the presence of at least 0.6 mg of magnesium and a maximum of 500 μg of iron(III), using a pH 12.5 sodium hydroxide-potassium cyanide-sodium sulfide buffer and Calcon indicator. The results of such titrations are compared with those obtained by titrating at pH 10 the calcium perchlorate solutions derived from calcium oxalate, and with those of a modified LEWIS AND MELNICK method. The results for magnesium (% MgO) obtained by difference are in fair agreement. Magnesium can be titrated compleximetrically as magnesium perchlorate, but the reagent blank must be determined.     

Dielectric properties of propylene carbonate and propylene carbonate solutions

Permittivity data at frequencies from 0.9 to 12 GHz for propylene carbonate and for the solutions of NaI, NaClO₄, Bu₄NI, Bu₄NClO₄, ZnBr₂, and Ca(ClO₄)₂ in propylene carbonate at 25°C are reported and discussed. The contaminating influence of water on the dielectric spectra is shown. Measurements were executed by the method of travelling waves with equipment known to produce data of high precision. Evaluation of the data is performed on the basis of models presupposing one or more relaxation regions. The dielectric spectra of all salts with the exception of ZnBr₂ yield relaxation time distributions with a single critical relaxation time or can be analyzed by assuming two critical relaxation times for the solvent. ZnBr₂ solutions show a supplementary relaxation region at low frequencies which is attributed to the solute. The variation of permittivities at zero frequency with the salt concentration is discussed in the framework of kinetic depolarization. Solvation numbers are estimated.     

Effects of calcium ions on solubility and aggregation behavior of an anionic sulfonate gemini surfactant in aqueous solutions

In this work, a ternary composite, Pt/TiO(2)/RGO (reduced graphite oxide), was prepared via immobilizing Pt particles onto the TiO(2)/RGO composite that was obtained via redox reaction of TiCl(3) and GO. The composite was characterized by different techniques including X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The TiO(2) particles with size less than 10 nm were uniformly distributed throughout the RGO, and almost each Pt particle with size around 3 nm adhered to TiO(2) particles, resulting in high dispersion of all Pt particles on the support. The Pt particles were in the electron-deficient state due to the strong interactions with the TiO(2) particles and the RGO support. The catalytic performance of the composite for nitrobenzene hydrogenation was investigated under solvent-free condition. It was indicated that the Pt/TiO(2)/RGO catalyst exhibited high activity with a turnover frequency (e.g., 59,000 h(-1)) as well as superior selectivity to aniline (e.g., >99%). Moreover, the catalyst can be reused for six times without any activity loss, which resulted from the stable structure of the catalyst.