Measurement and correlation of solubility of 9-fluorenone in 11 pure organic solvents from T = 283.15 to 323.15 K

In this work, the solubility data of 9-fluorenone in 11 pure solvents(methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, acetonitrile, ethyl formate, ethyl acetate, dimethyl sulfoxide, n-hexane)were measured by the gravimetric method from 278.15 K to 318.15 K under atmospheric pressure. The results showed that the solubility of 9-fluorenone in all tested solvents increased with the raised temperature. The solubility data were correlated by the modified Apelblat equation, λh model and NRTL(nonradom two fluid) model. The average relative deviation(ARD) correlated by three thermodynamic models in different solvents was all below 5%, which indicated that the three thermodynamic models fit the solubility data well. Furthermore, the mixing thermodynamic properties of 9-fluorenone in pure solvent systems were calculated via NRTL model. The results indicated the dissolution process of 9-fluorenone is spontaneous and entropically favorable. The solubility and the mixing thermodynamic properties provided in this paper would play an important role in industrial manufacture and follow-up operation of 9-fluorenone.

Determination of metastable zone and induction time of analgin for cooling crystallization

The solubility, metastable zone width, and induction time of analgin for unseeded batch cooling crystallization in ethanol–aqueous system were experimentally determined. The solubility data could be well described by the van't Hoff equation model. The metastable zone width at various cooling rates was measured, and some parameters of nucleation kinetic were calculated using the Ny'vlt theory. Furthermore, the induction period of various temperatures and supersaturation ratios was also measured. According to classical nucleation theory, some nucleation parameters and interfacial energy was calculated through the induction time(t_(ind)) data. Homogeneous nucleation tended to occur when the supersaturation is high, whereas heterogeneous nucleation was more likely to occur when the supersaturation is low.

Thermodynamic properties of metamizol monohydrate in pure and binary solvents at temperatures from(283.15 to 313.15) K

The thermodynamic properties of metamizol monohydrate in pure solvents(methanol,ethanol,n-propanol and isopropanol) and two binary mixed solvent systems including(methanol+ethanol) and(methanol+isopropanol) were measured from 283.15 K to 313.15 K by gravimetric method under atmospheric pressure thought as 0.1 MPa.The modi fied Apelblat equation,the CNIBS/R-K equation,the Hybrid model and the NRTL model were used to correlate the solubility of metamizol monohydrate,respectively.The results show that the solubility of metamizol monohydrate in all the tested solvents increases with the rising temperature which means that it has temperature dependence.What's more,the effects of solvent components of the binary solvent mixtures on solubility were discussed,it illustrates that the increasing of the molar fraction of methanol gives the system a greater dissolving power.Furthermore,according to the NRTL model,the enthalpy,the Gibbs energy and the entropy of the mixing process were also obtained and discussed.

Gelation Mechanism of Erythromycin Ethylsuccinate During Crystallization

In this paper, the gelation mechanism of erythromycin ethylsuccinate(EES) during crystallization is investigated for the first time. The generated semisolid gel-like phase exhibited a 3D fibrillar network morphology and the typical rheological properties of gels. The fibers inside the gel-like phase were confirmed to be new types of EES solvates using powder X-ray diffraction, thermogravimetric analysis/differential scanning calorimetry, and gas chromatography. The gelation and crystallization regions in EES-1-propanol solid–liquid phase diagram were determined. Analyses of solvent parameters showed that moderate solvent polarity may promote EES gelation. Fourier transform infrared spectra, nuclear magnetic resonance spectra, and scanning electron microscopy analyses indicated that through intermolecular hydrogen bonds, EES and solvent molecules assembled into fibers via crystallographic mismatch branching growth. The fibers intertwined into a 3D network microstructure and formed a gel-like phase, completely immobilizing the solution.

Synthesis, Growth, and Characterization of a New Thiourea and Bismuth Chloride Complex with Excellent Nonlinear Optical Properties

Crystals of a new organometallic nonlinear optical(NLO) compound, di-μ-chloro-bis[chlorotri(thiourea)bismuth(Ⅲ)]-pentachloro(thiourea)bismuth-ate(Ⅲ)(DCBPB), have been successfully grown from formic acid aqueous solutions of thiourea and bismuth chloride by a slow evaporation technique. The crystal structure and atomic composition of DCBPB have been confirmed by single crystal X-ray diff raction(SCXRD), Fourier transform infrared spectra, and elemental analysis. The SCXRD results proved that DCBPB crystallizes in triclinic space group P1 with unit cell dimensions of a = 7.0606(2) ?, b = 8.8106(4) ?, c = 16.3247(8) ?, α = 99.242(4)°, β = 95.309(3)°, γ = 105.856(3)°, and Z = 2. DCBPB crystal exhibits excellent transmittance from 500 to 2500 nm and green fluorescence with maximum emission at 508 nm. The thermogravimetricdiff erential scanning calorimetry(TG-DSC) analysis indicates that a solid-phase reaction took place at 170.1 ℃, whereas the decomposition temperature of the crystal material was 189 ℃. The NLO property obtained by the Kurtz powder test showed that the second harmonic generation efficiency of DCBPB crystal is two-seventh of KDP crystal.

Gelation Phenomenon During Crystallization of Cefpiramide Sodium

Unlike the adverse eff ect caused by the gelation during crystallization process, gelation of cefpiramide sodium was found to provide ideal product properties, such as a larger and more regular crystal shape. The causes of the gelation phenomenon and the mechanism of gel-crystal transition during the crystallization of cefpiramide sodium were both investigated in this work. The gel was formed due to the strapping of the solvents by the networks of cefpiramide sodium molecules. The whole gel-crystal transition process was divided into the following three stages:(1) when the temperature decreased, the system reached a metastable-state gelation;(2) the initial microcrystal in the gel grew slowly because of the low supersaturation;and (3) the gel fi nally disappeared, and a larger and more regular crystal was formed. The Hansen solubility parameters were used to analyze the eff ects of the solvents on this gelation;the analysis results can serve as guidance for solvent screening in the actual production process.

Characterization and structure analysis of the heterosolvate of erythromycin thiocyanate

Erythromycin thiocyanate is widely used for the production of other macrolide antibiotics. In this work, a novel heterosolvate of this pharmaceutical compound has been obtained and characterized for the first time, which was transformed from the dihydrate form in the acetone solvent through evaporation crystallization. Thermal behavior together with compositional analysis revealed that both water and acetone molecules participated in the formation of the crystal lattice which is rarely reported before. The general chemical name of the heterosolvate may be defined as erythromycin thiocyanate sesquihydrate hemiacetonate. Furthermore, studies on solid-state spectral analysis provided strong evidence of intermolecular hydrogen bonds in heterosolvate crystals. According to the crystal structure determined by single crystal X-ray diffraction, the formation mechanism of the heterosolvate is proposed in which strong multihydrogen bondings between water and solute molecules form the layer structure. While acetone molecules form single-hydrogen bonds with solutes and reside in channels between layers. This well explains why acetone solvent is easy to escape from the crystal structure during desolvation.

Design and mechanism of agglomeration of aspirin crystals in pure solvents

Agglomeration with improved flowability for platy crystals is desirable in pharmaceutical downstream processing. The formation of agglomerates in pure solvents without the aid of bridging liquids is a convenient and low-cost method compared with complex spherical crystallization. In this work, the adhesion free energies between aspirin crystals in six solvents were calculated using Lifshitz-van der Waals acid-base theory to screen suitable solvents for agglomeration. The maximum stirring rate for agglomeration was determined by adhesion forces and dispersion forces. Then the agglomerates of plate-shaped aspirin were successfully prepared in acetone, methanol, ethanol, 2-propanol, and ethylene glycol without additives by simple cooling crystallization. The interactions between solvent and crystal surfaces were also used to explain the outcomes. A feasible mechanism for the agglomeration process of platy crystals was elucidated, involving the adhesion of dominant crystal facets at the beginning. The effect of stirring rate, cooling rate, and initial supersaturation on agglomeration degree and particle size of aspirin agglomerates were studied. The obtained aspirin agglomerates under the optimal conditions exhibited a uniform particle size distribution, a high agglomeration degree, and superior flowability.

非线性光学晶体3BiCl3·7SC（NH2）2的合成及其转化过程

针对金属有机配合物非线性光学晶体3BiCl3·7SC(NH2)2(DCBPB)合成过程中伴生BiCl3·3SC(NH2)2(β-BTC)的问题,以硫脲与氯化铋为原料,在甲酸-水体系中研究了溶剂配比、反应温度、反应物配比等因素对DCBPB纯度的影响,对反应条件进行了优化,并基于XRD特征峰面积标准曲线法研究了β-BTC与DCBPB之间的转化过程。结果表明,甲酸抑制氯化铋水解且选择性生成DCBPB,氯化铋与硫脲摩尔配比大于1:3时可选择性生成DCBPB。合成过程先生成β-BTC,再由β-BTC转化为DCBPB,甲酸-水体系中氯化铋水解发生在β-BTC生成过程中,且不可避免,导致基于氯化铋直接合成只能获得最高含量为89.91wt%的DCBPB晶体。β-BTC向DCBPB转化率极高且无水解,可获得DCBPB含量大于98wt%的晶体。

Nucleation and growth mechanism of cefodizime sodium at different solvent compositions

The induction time of cefodizime sodium was measured in ethanol-water at different solvent composi- tions by the laser technology measurement. The results indicate that the solvent composition played an important role in the supersaturation and the nucleation process of cefodizime sodium solution. According to the modified classical nucleation theory, the nucleation and growth mechanism were identified. The correlation results show that heterogeneous nucleation dominated the nucleation process at lower supersaturation, where homogeneous nucleation is the most important mechanism at higher supersaturation. Based on the correlated results, the 2D mediated growth mechanism had the highest correlation coefficients （R2）, so this mechanism was selected as the proper growth mechanism for cefodizime sodium.

Discontinuous solid solutions of anthracene-phenanthrene:Thermodynamics and crystallization kinetics

We explored such issues as the formation mechanism,structure and propriety of the solid solutions of anthracene(ANT)-phenanthrene(PHE).Solution crystallization and solid-state grinding were employed to prepare solid solutions under different conditions.The thermal behavior and PXRD scanning results revealed the formation of discontinuous solid solutions,whose melting points and crystal lattices varied linearly with mixed ratio.Combing with Materials Studio,the formation possibility of solid solutions were investigated by evaluating the change of the energy.The crystal morphology of the solid solutions have a positive correlation with the change of the major part.Finally,the solution crystallization process of solid solution were studied using the population balance model.

Thermal properties,structure,and morphology of discontinuous solid solutions between phenanthrene and carbazole

Two methods,namely solid-state grinding and solution crystallization,were used to prepare discontinuous solid solutions of phenanthrene(PHE)-carbazole(CAR)with different PHE and CAR molar fractions.The thermal properties and structure of the solid solutions were analyzed using differential scanning calorimetry,hot stage microscopy,and powder X-ray diffraction,and the experimental results revealed that the two compounds could form discontinuous solid solutions where PHE and CAR alternately acted as the host and guest with limited range.This was demonstrated using molecular simulations based on lattice energy calculations using the Materials Studio 8.0 software.The crystal morphology and solubility of the solid solution changed significantly as the molar fraction of the guest molecules changed.