High-pressure phase behaviour of binary (CO2 + nicotine) and ternary (CO2 + nicotine + solanesol) mixtures

This work paper presents vapour–liquid equilibrium (VLE) data for binary (CO₂ + nicotine) and ternary (CO₂ + nicotine + solanesol) mixtures, at 313.2 K and 6, 8 and 15 MPa. The (CO₂ + nicotine) system exhibits three phases (L₁L₂V) in equilibrium at 8.37 MPa. It is estimated that this system most likely follows the type-III phase behaviour. In the ternary system, the presence of solanesol in the vapour phase was detected only at the pressure of 15 MPa. At this pressure, partition coefficients and separation factors for solanesol/nicotine were calculated for different initial nicotine/solanesol compositions and a strong influence of composition was found. The results were modelled using the Peng–Robinson equation of state (PR EOS) coupled with the Mathias–Klotz–Prausnitz (MKP) mixing rule (PR–MKP model). Good correlations of the binary data, particularly in the case of the (CO₂ + nicotine) mixture, were obtained. However, the model could not correlate the ternary data.     

High-pressure phase equilibrium data for the (carbon dioxide + l-lactide + ethanol) system

Experimental phase equilibrium values (cloud points) for the ternary system involving carbon dioxide, l-lactide and ethanol have been measured in order to provide fundamental values to conduct the polymerization reaction in supercritical carbon dioxide medium. The experiments were performed using a variable-volume view cell over the temperature range from 323 K to 353 K, system pressure between 9 MPa and 25.0 MPa and different mole ratios of ethanol to l-lactide (0.5:1, 1:1 and 1.5:1). Phase transitions of vapour-liquid types were observed. The experimental results were modelled using the Peng–Robinson (PR) equation of state with the Wong–Sandler (PR–WS) mixing rule, providing a good representation of the experimental phase equilibrium values.     

Hydroformylation of propylene in supercritical CO2 + H2O and supercritical propylene + H2O

Hydroformylation of propylene has been carried out in supercritical CO₂ + H₂O and in supercritical propylene + H₂O mixtures using Rh(acac)(CO)₂ and triphenylphosphine trisulfonate trisodium salt (TPPTS), P(m-C₆H₄SO₃Na)₃, as catalyst. Visual observation of the reaction mixtures indicates that in both systems a single phase is present at supercritical temperatures and pressures so that the reaction occurs under homogeneous conditions. After reaction is complete, a biphasic system is formed when the pressure and temperature are reduced to ambient. This facilitates separation of the products in the organic phase and the rhodium catalyst in the aqueous phase. The rhodium concentration in the organic phase was found to be negligible (1.0 × 10⁻⁶ mg/ml). Furthermore, compared with traditional hydroformylation technology, the supercritical reactions also show better activity and selectivity.     

Measurement and modelling of binary (solid + liquid + vapour) equilibria involving lipids and CO2

The development of solid lipid nanoparticles (SLN) using supercritical fluid at room temperature is an innovative alternative compared to traditional pharmaceutical methods and the safety and drug efficacy of SLN made using supercritical CO₂ is increased. One of the micronization techniques which have provided the best results in the production of SLN is particles from gas-saturated solution (PGSS). The solid–liquid–vapour coexistence curve of a solid in a compressed gas is of primary importance in assessing the feasibility of PGSS and the selection of appropriate operating conditions. The objectives of this work are to perform experimental measurements using a high pressure differential scanning calorimeter (DSC) to obtain melting properties as a function of composition and develop a simplified approach to model multiphase equilibria of lipids in compressed CO₂. The selected lipid was tristearin. Before assessment of triestearin and CO₂ phase equilibrium, the performance of this thermodynamic model was evaluated in two other lipids which provided results with high accuracy.     

聚合物-溶剂-超临界CO2三元体系的相行为

研究了聚合物-超临界二氧化碳二元体系溶解性,并考查了添加共溶剂对溶解性的影响,结果表明,添加共溶剂会大大提高CO2的溶解度.此外,还研究了聚合物-溶剂-超临界二氧化碳三元体系在高压时的相行为, 探讨了组分性质、含量等对温度-压力相图的影响.随着CO2含量的增加,压力-温度相图L-LV（单一液相向液气两相共存）边界线的斜率会出现突变点,发生由L-LV边界线向L-LL（单一液相向液液两相共存）边界线的过渡, 而L-LV边界线对不同聚合物并不敏感.     

High-pressure phase equilibrium in the {carbon dioxide (1) + 1-chloropropane (2)} binary system

The current study reports original vapour-liquid equilibrium (VLE) for the system {CO₂ (1) + 1-chloropropane (2)}. The measurements have been performed over the entire pressure-composition range for the T = (303.15, 313.15 and 328.15) K isotherms. The values obtained have been used for comparison of four predictive approaches, namely the equation of state (EoS) of Peng and Robinson (PR), the Soave modification of Benedict–Webb–Rubin (SBWR) EoS, the Critical Point-based Revised Perturbed-Chain Association Fluid Theory (CP-PC-SAFT) EoS, and the Conductor-like Screening Model for Real Solvents (COSMO-RS). It has been demonstrated that the three EoS under consideration yield similar and qualitatively accurate predictions of VLE, which is not the case for the COSMO-RS model examined. Although CP-PC-SAFT EoS exhibits only minor superiority in comparison with PR and SBWR EoS in predicting VLE in the system under consideration, its relative complexity can be justified when taking into account the entire thermodynamic phase space and, in particular, considering the liquid densities and sound velocities over a wider pressure-volume-temperature range.     

Direct quantum mechanical calculation of the F + H2 → HF + H thermal rate constant

Accurate full-dimensional quantum mechanical thermal rate constant values have been calculated for the F+H₂→HF+H reaction on the Stark–Werner ab initio potential energy surface. These calculations are based on a flux correlation functions and employ a rigorous statistical sampling scheme to account for the overall rotation and the MCTDH scheme for the wave packet propagation. Our results shed some light on discrepancies on the thermal rate found for previous flux correlation based calculations with respect to accurate reactive scattering results. The resonance pattern of the all-J cumulative reaction probability is analyzed in terms of the partial wave contributions.     

镧石型碳酸镨钕向碱式碳酸镨钕的相转变反应特征及其应用

镧石型碳酸镨钕[(PrNd)2(CO3)3·8H2O,LPN]在95℃的不同起始pH值的溶液中陈化不同时间所得样品的XRD衍射图证明了LPN向碱式碳酸镨钕[(PrNd)(OH)(CO3),BPN]的相态转变。为此,详细研究了这一相态转变的反应条件以及粒子特征变化。结果表明:LPN是由片状或条状结晶连生而成的聚集体,具有大的粒度和小的堆密度。当在热的水溶液中陈化时,由于水解反应而发生由LPN向BPN的相转变。这一相转变可以在95℃下pH=7以上的溶液中发生,其转化率随起始溶液pH值的升高和陈化时间的延长而增大。随着相转变的进行,溶液的pH值开始下降明显,而后趋于平缓。相应地,大的团聚体颗粒解散成小的单个粒子,导致粒度减小,分布变窄,氯根含量降低和堆密度的增大。而且,这些变化直接与溶液pH值和陈化时间相关。据此,发展了一种新的制备具有高堆密度、低氯根含量、细粒度和窄分布的新方法,而且通过改变相转变条件可以方便地调谐颗粒特征。     

Orthorhombic–orthorhombic phase transitions in Nd2NiO4+δ (0.067≤δ≤0.224)

Variation of the phases of Nd₂NiO_4+δ with the excess oxygen concentration δ has been examined at room temperature in the range 0.067≤δ≤0.224 using the X-ray powder diffraction technique. The phases observed at room temperature are orthorhombic-I (0.21<δ≤0.224), orthorhombic-IV (0.175<δ≤0.21), orthorhombic-II (0.15<δ≤0.175), orthorhombic-II+quasi-tetragonal-I (0.10<δ≤0.15), and quasi-tetragonal-I (0.067<δ≤0.10).     

Vapor–liquid equilibria of the carbon dioxide (CO2) + 2,2-dichloro-1,1,1-trifluoroethane (R123) system and carbon dioxide (CO2) + 1-chloro-1,2,2,2-tetrafluoroethane (R124) system

Binary vapor–liquid equilibrium data were measured for the carbon dioxide (CO₂) + 2,2-dichloro-1,1,1-trifluoroethane (R123) system and the carbon dioxide (CO₂) + 1-chloro-1,2,2,2-tetrafluoroethane (R124) system at temperature from 313.15 to 333.15 K. These experiments were carried out with a circulating-type apparatus with on-line gas chromatography. The experimental data were correlated well by Peng–Robinson equation of state using the Wong–Sandler mixing rules.     

镧石型碳酸镨钕向碱式碳酸镨钕的相转变反应特征及其应用

本文研究了镧石型碳酸镨钕[（PrNd）₂（CO₃）₃·8H₂O,LPN]在95℃的不同起始pH值的溶液中陈化不同时间所得样品的XRD衍射图,证明所得样品为碱式碳酸镨钕[（PrNd）（OH）（CO₃）,BPN]。为此,详细研究了这一相态转变的反应条件以及粒子特征变化。结果表明：LPN是由片状或条状结晶连生而成的聚集体,具有大的粒度和小的堆密度。当在热的水溶液中陈化时,由于水解反应而发生由LPN向BPN的相转变。这一相转变可以在95℃下pH=7以上的溶液中发生,其转化率随起始溶液pH值的升高和陈化时间的延长而增大。随着相转变的进行,溶液的pH值开始下降明显,而后趋于平缓。相应地,大的团聚体颗粒解散成小的单个粒子,导致粒度减小,分布变窄,氯根含量降低和堆密度的增大。而且,这些变化直接与溶液pH值和陈化时间相关。据此,发展了一种新的制备具有高堆密度、低氯根含量、细粒度和窄分布的新方法,而且通过改变相转变条件可以方便地调谐颗粒特征。     

2,5-Dichloro-1-(ROSO2)benzene [R = C6H5, C6F5, and CH2(CF2)4H]: Synthesis, molecular structure, and solubility in supercritical CO2

Highly crystalline phenyl 2,5-dichlorobenzenesulfonate (PDBS, T_melt = 86-87 °C) and pentafluorophenyl 2,5-dichlorobenzenesulfonate (FPDBS, T_melt = 120-122 °C) were synthesized. Single-crystal X-ray molecular structure determinations show that both compounds have similar three-dimensional molecular structures; however, PDBS crystals are thin platelets and FPDBS crystals form hexagonal tube-like structures that are predominately hollow at one end. PDBS crystals exhibit offset π-stacking of the phenoxy-rings that form complete two-dimensional layers each two molecules thick. Hydrogen-bonding interactions are calculated at ∼3.2 Å between the C6-hydrogen and the sulfonyl-oxygen of a neighboring molecule. On the other hand, for FPDBS, π-stacking of the dichloro-substituted ring as well as dipole-dipole interactions of the fluorinated-phenoxy rings appears to be the predominate intermolecular interactions. Neither structure exhibits any kind of side-on interaction of the phenyl rings. PDBS and FPDBS exhibit melting point depressions of 26 and 40 °C, respectively, in the presence of supercritical CO₂. Although both sulfonates exhibit high solubility in CO₂, much lower pressures are needed to dissolve FPDBS compared to PDBS. For example, at 100 °C FPDBS dissolves at 4750 psia and PDBS dissolves at 11,000 psia. The solubility data reinforce the observation that fluorinating a compound can significantly lower the conditions needed to dissolve that compound in CO₂.     

High-pressure phase behavior of CO2 + 1-butyl-3-methylimidazolium chloride system

The phase behavior of carbon dioxide (CO₂) and the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) was measured and correlated at high pressures up to ∼40 MPa and at temperatures between 353.15 K and 373.15 K. The solubility data of CO₂ in [bmim][Cl] were obtained by observing the bubble point pressure at specific temperatures. A variable-volume view cell, which is a high-pressure equilibrium apparatus, was used to measure the CO₂ + [bmim][Cl] system solubility under varying pressure and temperature conditions. In addition, liquid–liquid–vapor (LLV) three-phase behavior was investigated using the equilibrium cell to be able to determine the classification of phase-behavior type by Scott and Van Konynenburg. Based on the LLV phase behavior, this system most likely has type III phase-behavior which is common for IL + CO₂ systems. The resulting data showed that CO₂ dissolved well in the IL at low CO₂ concentrations, but that the pressure derivative of CO₂ solubility dramatically decreased as the mole fraction of CO₂ was increased. The experimental data were well fitted by the Peng–Robinson equation of state with a quadratic mixing rule and cubic parameters estimated by the Joback method.     

Energetics of copper diphosphates – Cu2P2O7 and Cu3(P2O6OH)2

Differential scanning calorimetry and high temperature oxide melt solution calorimetry are used to study enthalpy of phase transition and enthalpies of formation of Cu₂P₂O₇ and Cu₃(P₂O₆OH)₂. α-Cu₂P₂O₇ is reversibly transformed to β-Cu₂P₂O₇ at 338–363 K with an enthalpy of phase transition of 0.15 ± 0.03 kJ mol⁻¹. Enthalpies of formation from oxides of α-Cu₂P₂O₇ and Cu₃(P₂O₆OH)₂ are −279.0 ± 1.4 kJ mol⁻¹ and −538.8 ± 2.7 kJ mol⁻¹, and their standard enthalpies of formation (enthalpy of formation from elements) are −2096.1 ± 4.3 kJ mol⁻¹ and −4302.7 ± 6.7 kJ mol⁻¹, respectively. The presence of hydrogen in diphosphate groups changes the geometry of Cu(II) and decreases acid–base interaction between oxide components in Cu₃(P₂O₆OH)₂, thus decreasing its thermodynamic stability.     

Vibrational spectra of α-Ge(HPO4)2·H2O compound

We have measured Raman and infrared spectra of α-Ge(HPO₄)₂·H₂O compound at room temperature. The analysis of vibrational modes indicated the presence of two non-equivalent HPO₄²⁻ units in agreement with ³¹P nuclear magnetic resonance measurements. A tentative assignment of all the observed modes is proposed based on the previous works reported for other hydrogenphosphate-based compounds.     

Bubble-point measurements for the system CO2 + aqueous ethanol solutions of boldo leaf antioxidant components (boldine and catechin) at high pressures

The bubble-points pressures of solute(s) + ethanol + water + CO₂ mixtures were determined visually using a synthetic method in an experimental apparatus that included a variable-volume equilibrium cell. Tested solutes included boldo leaf tincture, a boldine + catechin mixture, pure boldine, and pure catechin. Uncertainties in bubble-point pressures were estimated to be <5%, based on comparisons with literature values and replicate measurements. The largest effect we observed was an average increase of 205% in the bubble-point pressure when decreasing the ethanol-to-water ratio from 63:37 to 37:63 (w/w). The bubble-point pressure increased 11% when increasing the temperature from 313 to 343 K, and decreased 8.2% when increasing the concentration of solids from 400 to 1500 ppm. The bubble-point pressure was higher for boldo leaf tincture than for a boldine + catechin mixture having the same boldine-to-catechin weight ratio, but this was partially due to a lower content of solids in the tincture. On the other hand, bubble-point pressures of the boldine + catechin mixture were marginally (0.33%) higher than the weighed average of the bubble-point pressures for pure boldine and pure catechin.     

TiO_2纳米带光催化二氧化碳甲烷化

研究了在常温常压下TiO2纳米带光催化CO2催化加氢气反应。在紫外光照射下,二氧化碳的加氢还原产物为甲烷。利用高分辨TEM,XRD,UV-Vis DRS,低温氮吸附-脱附,TG等考察了催化剂与甲烷产率的构效关系。结果表明,在600℃焙烧时得到的双晶材料具有最佳的光催化活性。优异的光催化活性主要得益于TiO2双晶脱水纳米带(DNR Bicrystalline dehydratednanoribbon)。上面形成的纳米晶界能够提高催化剂在紫外区的光吸收能力,TiO2(B)和锐钛矿独特的双晶间隔结构也提高了界面电荷分离的效率。担载贵金属Pt显著地提高了反应速率。     

New isothermal vapor–liquid equilibria for the CO2 + n-nonane,and CO2 + n-undecane systems

Experimental vapor–liquid equilibria (VLE) for the CO₂ + n-nonane and CO₂ + n-undecane systems were obtained by using a 100-cm³ high-pressure titanium cell up to 20 MPa at four temperatures (315, 344, 373, and 418 K). The apparatus is based on the static-analytic method; which allows fast determination of the coexistence curve. For the CO₂ + n-nonane system, good agreement was found between the experimental data and those reported in literature. No literature data were available for the CO₂ + n-undecane system at high temperature and pressure. Experimental data were correlated with the Peng–Robinson equation of state using the classical and the Wong–Sandler mixing rules.     

Development of Fe3O4-poly(l-lactide) magnetic microparticles in supercritical CO2

The Fe₃O₄-poly(l-lactide) (Fe₃O₄-PLLA) magnetic microparticles were successfully prepared in a process of solution-enhanced dispersion by supercritical CO₂ (SEDS), and their morphology, particle size, magnetic mass content, surface atom distribution and magnetic properties were characterized. Indomethacin (Indo) was used as a drug model to produce drug-polymer magnetic composite microparticles. The resulting Fe₃O₄-PLLA microparticles with mean size of 803 nm had good magnetic property and a saturation magnetization of 24.99 emu/g. The X-ray photoelectron spectroscopy (XPS) test indicated that most of the Fe₃O₄ were encapsulated by PLLA, which indicated that the Fe₃O₄-PLLA magnetic microparticles had a core–shell structure. After further loading with drug, the Indo-Fe₃O₄-PLLA microparticles had a bigger mean size of 901 nm, and the Fourier transform infrared spectrometer (FTIR) analysis demonstrated that the SEDS process was a typical physical coating process to produce drug-polymer magnetic composite microparticles, which is favorable for drugs since there is no change in chemistry. The in vitro cytotoxicity test showed that the Fe₃O₄-PLLA magnetic microparticles had no cytotoxicity and were biocompatible, which means there is potential for biomedical application.     

CO2在Na2Cr2O7溶液中的平衡溶解度模型

为研究重铬酸钠(Na₂Cr₂O₇)对CO₂溶解的影响, 本文在带有搅拌的气液相高压平衡釜内, 采用静态法测定了温度在313.2-333.2 K, 压力在0.1-1.9 MPa 范围内, 重铬酸钠浓度分别为0、0.361、0.650、0.901 mol·kg^-1 时, CO₂ 在Na₂Cr₂O₇溶液中的溶解度. 结果表明: (1) Na₂Cr₂O₇对CO₂ 的溶解有盐析效应; (2) CO₂ 在Na₂Cr₂O₇溶液中的溶解符合亨利定律, 并且CO₂溶解度是温度和Na₂Cr₂O₇浓度的函数, 且用改进的Setschenow方程和Peng-Robinson-Pitzer (PR-Pitzer)方程拟合了在此温度、压力及重铬酸钠浓度范围内的实验数据, 拟合效果较好, 并且其平均相对误差分别为4.24%和3.32%.