Crystallization kinetics of MgSO4 · 7 H2O in presence of tenside

The effect of sodium dodecyl sulfate (SDS) on crystallization kinetics and crystal habit of MgSO₄ · 7 H₂O from aqueous solutions at 25 °C was investigated in batch experiments. It highly depends on the supersaturation level. Both increasing supersaturation and rising concentration of the tenside promote the production of needle-like crystals but the influence of the driving force is much more pronounced. SDS increases the crystallization rate and the linear crystal growth rate in length direction of the crystals. To a high degree it also influences properties of the crystallizing solution such as surface tension and viscosity.     

Effect of supersaturation on the crystallization of phenylbutazone polymorphs

The article describes the effect of degree of supersaturation, σ, on the crystallization of specific polymorphs of phenylbutazone from its methanolic solution at 20 °C. At low initial supersaturation, σ ≤ 2.0, the fraction of the metastable α polymorph in the crystallized product exceeds that of the δ polymorph, while at σ ≥ 5.0, the fraction of the stable δ polymorph increases in the crystallized product. The results are explained by the effect of supersaturation on the relative rates of nucleation and crystal growth of the polymorphs. Furthermore, the mechanism of nucleation and crystal growth also change with supersaturation. Supersaturated methanolic solutions of phenylbutazone exhibit a critical temperature at which the nucleation rates of the polymorphs decrease drastically. This effect is partly explained by the decreased mobility of phenylbutazone molecules at lower temperatures. Nucleation is most rapid when the crystallization temperature is close to the transition temperature, T_t(α ⟷ δ), between the polymorphs, α and δ. The nucleation rate decreases as the temperature difference between T_t(α ⟷ δ) and the crystallization temperature increases. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the kinetic of crystallization of zinc oxalate (II). Determination of the specific surface energy at the crystal solution interface by kinetic studies

An apparatus based on turbidimetry was constructed for studying the kinetics of crystallization of sparingly soluble salts. The kinetics of crystallization of zinc oxalate was investigated at various supersaturations and pHs of the medium. The specific surface energy at the crystal-solution interface was determined from the induction periods of the S-shaped curves by means of the classical theory of nucleation. The calculations were made using the slope of the logarithmic dependence of I or τ, respectively, on supersaturation (equations 1 and 2) and the critical supersaturation which was also determined on the basis of kinetic data. Various values of σ were found for the different supersaturations. Different values for this quantity were also obtained when supersaturation was presented by the concentration ratio (S = C/C₀) or by the ratio of the product of the two ions concentrations in the supersaturated solution to that in the saturated one (S = ab/L_p). These σ values were lower than those obtained using the critical supersaturations at the two different solution pHs. For the present it is impossible to give a definite explanation of the results obtained. The experiments for determining the specific surface energy at the crystal-solution interface will be continued.     

Crystallization and Characterization of Orthorhombic β‐MgSO4 · 7H2O

In solution, the growth rate and the crystal habit are influenced by a number of factors such as supersaturation, temperature, pH of the solution, cooling rate, agitation, viscosity, initial state of the seed crystal and the presence of impurities. The crystallization of orthorhombic β‐MgSO₄ · 7H₂O, from low temperature aqueous solution by slow cooling process was studied. The metastable zone width, the induction periods (τ) for different supersaturations and the effect of pH on the growth rate of the crystals were investigated. The increase of pH yielded bigger crystals. The structural, optical, thermal and mechanical properties of β‐MgSO₄ · 7H₂O have been studied using FT‐IR, X‐ray diffraction, TGA‐DTG and micro hardness analyses.     

The influence of concentration and supersaturation ratio of CuI·HI on CuI crystal growth by decomplexation method

The fundamental role of solubility and supersaturation of solute for crystal growth from solution has been widely realized. In order to optimize the process of CuI crystal growth by CuI·HI decomplexation in HI acid, the solubility and supersaturation curves of CuI in HI‐H₂O mixed solvent were measured, and then a modified concentration programming scheme was designed, which could grow high quality CuI single crystals of 2.5 mm on edge successfully. In this scheme, the concentration distribution of CuI·HI complex and HI acid in silica gel along their diffused direction were measured with spectrophotometer, and the evolution of CuI·HI complex supersaturation ratio was analysed. It was found that the excess CuI·HI complex concentration would lead to the high supersaturation ratio and the formation CuI dendrites. The condition for regular CuI single crystal growth in silica gel was measured as follow: when the crystal nuclei appears, the CuI·HI complex concentration in HI‐H₂O solvent should be kept in the range of 0.033–0.050 mol/L and its corresponding supersaturation ratio is 1.24–1.45, and then they should be respectively declined to a range of 0.025–0.033 mol/L and 1.14–1.26 at the stage of crystal growth. The results may provide a useful clue for further improvement of the experimental scheme. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of a polyacrylate antiscalant on gypsum nucleation and growth

Calcium sulphate dihydrate (gypsum) crystallization was studied under conditions, of supersaturation and temperature, simulating a brackish water desalination unit using solar energy. The effect of an commercial sodium salt of poly(acrylic acid), based compound known as RPI, on homogeneous nucleation and growth of gypsum was also examined. Gypsum was precipitated by mixing aqueous CaCl₂ and Na₂SO₄ solutions. It was found that, with increasing temperature or supersaturation, the induction time decreases and the growth rate increases. By using classical nucleation theory, the interfacial tension and the nucleation rate values were estimated. It was shown that the interfacial tension is temperature dependent. The addition of increasing quantities of RPI, in the same conditions of temperature and supersaturation, prolongs the induction time, decreases the nucleation rate and increases the interfacial tension. The addition mode of RPI (in calcium or in sulphate solution) was found as an important parameter in controlling the inhibition process of gypsum crystallization. XRD and SEM analysis showed that RPI antiscalant strongly affected the texture and the morphology of the deposit gypsum. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnesium Sulphite Hexahydrate Supersaturated Solutions Stability

Wet purification of crude MgSO₃ · 6 H₂O obtained at flue gases desulphurization is based on its dissolution, separation of solid ash followed by crystallization of a clear supersaturated solution. The stability of supersaturated solutions during ash separation represents a requisite condition for realization of this process. The stability of agitated supersaturated solutions containing from 5 to 8 wt% of MgSO₃ is assessed in the temperature range from 80° to 95 °C based on experimentally determined induction period of crystallization, t_ind, and desupersaturation curves. Time necessary for complete dissolution of MgSO₃ · 6 H₂O at the studied conditions, t_D, is also determined. A plot of (t_ind – t_D) versus solution initial supersaturation facilitates selection of suitable processing conditions for the wet purification.     

Crystallization of potassium sulphate from glaserite

The crystallization of K₂SO₄ from aqueous solutions of glaserite (a double salt of sodium and potassium sulphate) was investigated in an MSMPR cooling apparatus at 35 °C. The precipitation of K₂SO₄ at an average purity of 93 wt.% was obtained and the crystallization kinetics were derived from the experimental data. The nucleation and growth rates here obtained were, respectively, remarkably higher and slightly lower than those relevant to pure K₂SO₄: this behaviour may be explained by a faster nucleation and a slower growth of crystals containing also Na₂SO₄. The effect of small (0.05%) calcium additions to the feed was also tested, which caused an increase of supersaturation and a depression of the growth kinetics, whereas the nucleation one was not appreciably modified.     

Kinetic studies on the influence of temperature and growth rate history on crystal growth

Crystallization experiments of sucrose were performed in a batch crystallizer to study the effect of temperature and growth rate history on the crystal growth kinetics. In one of the growth methods adopted, the isothermal volumetric growth rate (R_V) is determined as a function of supersaturation (S) at 35, 40 and 45 ºC. In the other, crystals are allowed to grow at constant supersaturation by automatically controlling the solution temperature as the solute concentration decreased. Using the latter method R_V is calculated as the solution is cooled. The obtained results are interpreted using empirical, engineering and fundamental perspectives of crystal growth. Firstly, the overall activation energy (E_A) is determined from the empirical growth constants obtained in the isothermal method. The concept of falsified kinetics, widely used in chemical reaction engineering, is then extended to the crystal growth of sucrose in order to estimate the true activation energy (E_T) from the diffusion‐affected constant, E_A. The differences found in the isothermal and constant supersaturation methods are explained from the viewpoint of the spiral nucleation mechanism, taking into account different crystal surface properties caused by the growth rate history in each method. Finally, the crystal growth curve obtained in the batch crystallizer at 40 ºC is compared with the one obtained in a fluidized bed crystallizer at the same temperature. Apparently divergent results are explained by the effects of crystal size, hydrodynamic conditions and growth rate history on the crystallization kinetics of sucrose. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Kinetics of crystal growth of mirabilite in aqueous supersaturated solutions

The crystallization of sodium sulfate decahydrate (Na₂SO₄·10H₂O, mirabilite) from supersaturated solutions was investigated using stable supersaturated solutions seeded with mirabilite seed crystals. The experiments were done in batch, stirred reactors in which the supersaturated solutions were prepared either by dissolution of sodium sulfate anhydrous at 32 °C followed by cooling to 18 or 20 °C or by mixing equal volumes of equimolar ammonium sulfate and sodium hydroxide solutions at 20 °C. Inoculation of the solutions supersaturated only with respect to mirabilite with seed crystals was accompanied with temperature increase of the thermostated solution. Despite the fact that crystal growth was initiated with seed crystals, the process started past the lapse of induction times inversely proportional to the solution supersaturation. The rates of crystal growth were measured both from the temperature rise and from the concentration–time profiles, which were linearly correlated. The measured crystal growth rates showed a parabolic dependence on supersaturation at low supersaturations. For higher values this dependence changed to linear, a behavior consistent with the BCF spiral crystal growth model. The morphology of the crystals growing at 20 °C showed typical prismatic habit, while at 18 °C when crystallized from cooled sodium sulfate solutions changes in the crystal habit to a leaf like morphology were observed.     

Design of agitated crystallizers

The evaluation and/or design method for crystallization, based on the system constant B_N, has been applied on crystallization data of various substances published in the literature. A correlation of the B_N values with the relative kinetic exponent of crystallization, n/g, demonstrates that the applicability of the method is independent of the size of equipment, mode of crystallization and mode of supersaturation creation.     

A study of primary nucleation of calcium oxalate monohydrate: I‐Effect of supersaturation

There are various organic and inorganic constituents in kidney stones. Among them, calcium oxalate monohydrate (COM) is the primary inorganic constituent of kidney stones. However, the mechanisms of formation of kidney stones are not well understood. In this regard, a basic study is carried out for better understanding of nucleation, crystal growth and/or aggregation of formed COM crystals. The primary nucleation of calcium oxalate monohydrate is studied at the laboratory scale using turbidity measurements. Calcium chloride and potassium oxalate solutions are mixed and then added to a Turbidimeter tube for continuous recording of turbidity. Induction time (time to induce formation of detectable crystals) is estimated from time‐turbidity graphs. The effect of some urinary species, such as oxalate and calcium, on nucleation and crystallization characteristics of COM is determined by particle size distribution analysis, measuring weight of crystals and calculation of relative supersaturation. The classical nucleation theory is applied at high supersaturation ratios (SR) ranging from 1.6 to 2.2. The results indicate that nucleation rate increases with increasing supersaturation ratio from 0.81 × 10²⁸ nuclei/cm³.sec at 1.6 SR, to 18.02 × 10²⁸ nuclei/cm³.sec at 2.2 SR. On the other hand, free energy change and radius of critical nucleus are decreased as supersaturation ratio is increased. The nucleation rates are higher than those reported in literature. Such discrepancy is discussed on the bases of differences in experimental techniques. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth aspects of barium oxalate monohydrate single crystals in gel medium

Single crystals of barium oxalate monohydrate (BaC₂O₄.H₂O, BOM) were grown in pure form by controlled diffusion of Ba²⁺ using the gel technique at different temperatures. Starting from aqueous Ba²⁺ chloride (BaCl₂) and acetic acid (C₂H₂O₄) in gel, this method offers a low‐cost and an easiest alternative to other preparation methods for the production of barium oxalate bulky single crystals. The optimal conditions for the growth of BOM crystals in silica gel were found by investigating different growth parameters such as gel pH, gel aging and crystallization temperature. Irrespective of all such crystallization environments, growth rate of the crystals were initially less and then exhibited supersaturation effect leading to non‐linearity. Gel aging and temperature has profound effect on nucleation density that resulted less number of crystals of maximum size in the gel matrix. Perfect single crystals were grown on gels of higher pH. The macropore morphology and porosity was controlled by changing age of the gel. It has been found that temperature has a fabulous effect in controlling the nucleation density by altering the supersaturation conditions for the formation of critical nuclei. The entire growth kinetics informed that the grown crystals were derived by the one dimensional diffusion controlled process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of strontium chloride hexahydrate by batch‐cooling crystallization: Control of crystal size and morphology

The effects of initial supersaturation, cooling rate, and stirring rate on the morphology of strontium chloride hexahydrate (SrCl₂·6H₂O) crystals were investigated by batch‐cooling crystallization, providing optimal operating conditions. Uniform needle‐like crystals with a length of 1200.50 μm and a width of 100.92 μm on average were obtained. The corresponding aspect ratio of length to width was about 11.90. Moreover, the morphological modification of SrCl₂·6H₂O crystals using cetyltrimethylammonium chloride (CTAC) was studied. When 20.30 mmol·L⁻¹ of CTAC was added, the length and width of crystals were 792.71 μm and 233.25 μm, respectively, and the corresponding aspect ratio decreased to 3.40. The shape of SrCl₂·6H₂O crystal changed to granule‐like, probably because of the strong interaction of CTAC with the SrCl₂·6H₂O facets with a denser distribution of Cl⁻ ions. This study offers a simple, flexible, and highly efficient approach to regulate the morphology of SrCl₂·6H₂O crystals and opportunities for multiple applications of SrCl₂·6H₂O.     

Polymorphic composition and morphology of calcium carbonate as a function of ultrasonic irradiation

This paper reports on the precipitation of CaCO₃ polymorphs, having various crystal morphologies under different conditions. In particular, systems that were subject to ultrasonic irradiation were compared to the corresponding reference systems in the absence of such a treatment. The application of ultrasonic irradiation predominantly resulted in a change of particle size distribution and polymorphic composition of the precipitate, in comparison to the reference systems. Thus, it was found that the supersaturation and temperature influenced the size distribution, in both the reference and sonicated systems. A mixture of calcite, vaterite and aragonite was obtained in all reference systems, at 25 °C. At this temperature, the sonication caused the vaterite content to increase, while aragonite was not detected. In reference and sonicated systems at 80 °C, only aragonite precipitated. The results also indicate that the principle parameter responsible for the morphology of vaterite was the initial supersaturation: at higher supersaturation spherical vaterite particles precipitated, while at lower supersaturation hexagonal platelets were obtained. The morphological investigations also indicated different mechanisms of vaterite formation in the systems in which precipitation was initiated at higher supersaturation: spherulitic growth of vaterite was observed in sonicated systems, while the aggregation of primary particles was predominant in the reference systems. At lower supersaturation, the effect of c(Ca²⁺)/c(CO₃²⁻) on the morphology of hexagonal platelets of vaterite was observed as well. By varying the c(Ca²⁺)/c(CO₃²⁻), significant changes of the polymorphic composition were observed only in the sonicated systems, at 25 °C.     

Influence of clay suspensions on the precipitation of CaCO3 in seawater

The effect of montmorillonite and kaolinite, most common clay in marine water, on nucleation and growth of calcium carbonate in standard sea water was studied. Crystallization was induced by the degasification of the dissolved carbonic gas. It was shown by XRD and SEM analysis that CaCO₃ crystallize under its aragonite polymorph some either the clay concentration or type. It was also found that tested clays inhibited significantly the crystallization of calcium carbonate, especially for concentrations higher than 25 mgL^–1. From the fine analyses of the formed solid, it was suggested that the tested clays have an indirect effect on nucleation and growth of aragonite by increasing the Mg ions concentration, strong inhibitor of CaCO₃ formation, in the neighbourhood of clay particles where supersaturation is the higher and than crystallization can occur. In addition to its indirect role, kaolinite can interact with aragonite by adsorbing on their faces and blocking growth sites (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Supersaturation and Temperature on the Growth Morphology of Ammonium Oxalate Monohydrate Crystals Obtained from Aqueous Solutions

The experimental results of a study of the effect of supersaturation and temperature on the growth morphology of ammonium oxalate monohydrate [(NH₄)₂C₂O₄H₂O; AO] single crystals obtained from aqueous solutions at 30 and 40 °C and supersaturation up to 9% are presented. The observations are analysed in terms of theoretical morphology, growth models and attachment energy for growth units in steps of growing faces.     

Study of growth kinetics of ammonium oxalate monohydrate crystals from aqueous solutions

Experimental results of the dependence of linear growth rates of ammonium oxalate monohydrate [(NH₄)₂C₂O₄ · H₂O; AO] single crystals on solution supersaturation are presented. The AO crystals were grown by constant-temperature, constant-supersaturation method at 30 and 40 °C in the supersaturation range of 1–9%. It was observed that the supersaturation dependence of growth rates follows the parabolic growth law. Analysis of the supersaturation dependence of linear growth rates of AO crystals showed (1) that growth models involving surface diffusion and direct incorporation of growth units give kinetic parameters similar to those reported for other compounds grown from solutions, and (2) that the the BCF model of cooperating screw dislocations is also applicable. An inverse relationship between the estimated values of the length, L, of the line containing the dislocations and growth rate, R, and a direct relationship between L and interplanar distance, d_hkl, of the face {hkl} were found. Both these relationships are associated with the process of generation of screw dislocations in the growing layer.     

The induction time,interfacial energy and growth mechanism of maltitol in batch cooling crystallization

Maltitol is crystallized with seeds by cooling mode in industry, often with large amount of fine crystals and wide crystal size distribution. To eliminate the fine nucleation, it's necessary to understand the nucleation kinetics. In this work, the solubility of maltitol in water was measured by the gravimetric method, the nucleation kinetics of maltitol in batch cooling crystallization was investigated using focus beam reflectance measurement (FBRM), and a novel method was proposed to determine the induction time from the trend of the crystal median chord given by FBRM. Based on the relationship between the induction time and the supersaturation, the nucleation mechanism was obtained, including homogenous nucleation at high supersaturation and heterogenous nucleation at low supersaturation. Additionally, combining the classical nucleation theory (CNT) and Arrhenius’ principle, the crystal‐solution interfacial energy and the energy barrier of homogenous nucleation were calculated. From the scanning electron microscope (SEM) images, the growth mechanism of maltitol was identified as surface nucleation growth and the surface entropy factor calculated from the kinetic analyses of t_ind data corroborated this growth mechanism.     

Precipitation of nesquehonite from homogeneous supersaturated solutions

The homogeneous (unseeded) precipitation of nesquehonite (MgCO₃·3H₂O) was studied over the temperature range of 10‐40 °C. Precipitation was triggered by the supersaturation created by mixing MgCl₂ solution (0.5‐1.5 M) with Na₂CO₃ solution in the same concentration range. The Meissner's method was adopted in the calculation of supersaturations during the MgCl₂‐Na₂CO₃ reaction to monitor the precipitation. Solids were identified using X‐ray diffraction (XRD) analysis and scanning electron microscope (SEM) images. In the temperature range of 10‐40 °C, MgCO₃·3H₂O with needle‐like or gel‐like morphology was precipitated. It was seen that the length, width and surface smoothness of the particles changed with reaction temperature and supersaturation. The supersaturation (S) was in the range of 1.09‐58.68 during titration of Na₂CO₃ solution. The dimension of the crystals increased with longer addition time (or lower initial concentration of reactant) at the same temperature. Slower addition via titration of 2 h followed by 2 h of equilibration at 40 °C proved successful in producing well developed needle‐like MgCO₃·3H₂O crystals of 30‐50 μm long and 3‐6 μm wide. MgCO₃·3H₂O obtained were calcined to produce highly pure magnesium oxide (MgO) at 800 °C. The morphology of MgO was similar to that of their corresponding precursors. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)