一氧化碳在苯酚+乙醇中的溶解度测量和关联

The solubility of carbon monoxide in phenol＋ethanol mixed solvents at elevated pressures is reported in this article. The experimental results revealed the influence of pressure on the solubility of CO in phenol＋ethanol mixtures. These mixtures are a poorer solvent for carbon monoxide. The solubility of CO is a linear function of pressure, and the extended Henry＇s constants were presented at different concentrations of phenol. The cubic Soave-Redlich-Kwong equation of state was used to correlate the experimental gas liquid equilibrium data and to predict the solubility of CO. At the same time, the binary interaction parameters, kO, for CO-phenol, CO-ethanol and phenol-ethanol systems were estimated by fitting experimental GLE data at 303.15 K and at 2.0-9.0 MPa. Hence, a model was suggested for the solubility of CO in phenol＋ethanol mixed solvents. The agreement between experimental and calculated solubilities with the proposed model was rather satisfactory.     

亚硝酸乙酯在混合溶剂中溶解度的测定与关联

An experimental apparatus was used to measure the solubility of ethyl nitrite in mixed solvents under the lower pressure and higher temperature. The solubilities of ethyl nitrite in mixed solvents of ethanol-water at 15℃-40℃ and ethanol-diethyl oxalate at 20℃--40℃ were determined. A Henry constant model has been improved, and the interaction parameters have been fitted from experimental data. The calculation results have been compared with experimental data; the results obtained are satisfactory.     

Solubility measurement and thermodynamic modeling of carbamazepine(form Ⅲ) in five pure solvents at various temperatures

In this work, the solubilities of carbamazepine(CBZ)(form Ⅲ) in ethyl acetate, methyl acetate, ethylene glycol, chloroform and cyclohexylamine were determined by laser monitoring techniques at pressure above sea level, and the solubility data of CBZ(form Ⅲ) in different pure solvents were fitted by the Modified Apelblat model and λh model. The result shows that the solubility of CBZ(form Ⅲ) in five solvents increases as temperature rises, and the solubility in chloroform was the largest. The experimental solubility values of CBZ(form Ⅲ) in ethyl acetate, methyl acetate, chloroform and cyclohexylamine were in better agreement with the simulated fitting values of the λh model. For ethylene glycol, the r value was much larger than the other four solvents, and it can be seen from the λh model that ethylene glycol was closer to the ideal solution system than the other four solvents.     

用局部组成理论关联纳米流体的剪切黏度

In this study, a new method is presented to correlate the shear viscosity of nanofluids by local composition theory. The Eyring theory and nonrandom two-liquid (NRTL) equation are used for this purpose. The effects of temperature and particle volume concentration on the viscosity are investigated. The adjustable parameters of NRTL equation are obtained by fitting with experimental data. The calculated shear viscosities for nanofluids of CuO/water with 29 nm particle size, Al2O3/water with two different particle diameters, 36 nm and 47 nm, and CuO/(ethylene glycol, water) are compared with experimental data and the average absolute deviation (AAD) is 1.2%, while the results from some conventional models yield an AAD of 190%. The results of this study are in excellent agreement with experimental data.     

Measurement and correlation of solubility of diosmin in four pure solvents and β-cyclodextrin solution at 298.15 K to 333.15 K

The aim of present study was to measure and correlate the solubility of poorly water-soluble flavonoid diosmin in water, ethanol, isopropyl alcohol (IPA), polyethylene glycol-400 (PEG-400) andβ-cyclodextrin (β-CD) aqueous solution (0.02 mol·L-1). The solubility of diosmin was measured using the shake flask method from (298.15 to 333.15) K at atmospheric pressure. The experimental solubilities of diosmin were regressed by the modified Apelblat model with a relative deviation in the range of 0.048%to 5.940%. The correlation coefficients were observed in the range of 0.9957 to 0.9995. The solubility of diosmin was found to be increased with temperature in all sample matrices investigated. The mole fraction solubility of diosmin was found to be higher inβ-CD aqueous solution and PEG-400 as compared to water, ethanol and IPA. Based on solubility data of present study, diosmin was considered as practical y insoluble in water, insoluble in ethanol&IPA and soluble in PEG-400 andβ-CD aqueous solution.     

Measurement and correlation of solubility of meropenem trihydrate in binary (water + acetone/tetrahydrofuran) solvent mixtures

The solubility of meropenem trihydrate in water + acetone mixtures and water + tetrahydrofuran mixtures were determined from T =(278.15 to 303.15) K by static method under atmospheric pressure.Effects of solvent composition and temperature on solubility of meropenem trihydrate were discussed.To extend the applicability of the solubility data,experimental solubility data in two kinds of binary solvent mixtures were correlated by the Apelblat equation and NIBS/Redlich-Kister model.It was found that the two models could satisfactorily correlate the experimental data and the Apelblat equation could give better correlation results.     

Determination and correlation solubility of m-phenylenediamine in (methanol,ethanol, acetonitrile and water) and their binary solvents from 278.15 K to 313.15 K

In this study, the solubility of m-phenylenediamine in four pure solvents(methanol, ethanol, acetonitrile and water) and three binary solvent(methanol + water),(ethanol + water) and(acetonitrile + water) systems were determined in the temperature ranging from 278.15 K to 313.15 K by using the gravimetric method under atmospheric pressure. In the temperature range of 278.15 K to 313.15 K, the mole fraction solubility values of m-phenylenediamine in water, methanol, ethanol, and acetonitrile are 0.0093–0.1533, 0.1668–0.5589,0.1072–0.5356, and 0.1717–0.6438, respectively. At constant temperature and solvent composition, the mole fraction solubility of o-phenylenediamine in four pure solvents was increased as the following order:water b ethanol b methanol b acetonitrile; and in the three binary solvent mixtures could be ranked as follows:(ethanol + water) b(methanol + water) b(acetonitrile + water). The relationship between the experimental temperature and the solubility of m-phenylenediamine was revealed as follows: the solubility of mphenylenediamine in pure and binary solvents could be increased with the increase of temperature. The experimental values were correlated with the Jouyban–Acree model, van't Hoff–Jouyban–Acree model, modified Apelblat–Jouyban–Acree model, Sun model and Ma model. The standard dissolution enthalpy, standard dissolution entropy and the Gibbs energy were calculated based on the experimental solubility data. In the binary solvent mixtures, the dissolution of m-phenylenediamine could be an endothermic process. The solubility data,correlation equations and thermodynamic property obtained from this study would be invoked as basic data and models regarding the purification and crystallization process of m-phenylenediamine.     

取代苯甲酸类化合物在正辛醇中的固液平衡

The solid-liquid equilibrium of benzoic acid derivatives in 1-octanol was first determined in this article. Using a laser monitoring observation technique, the solubility data of o-amino-benzoic acid, p-amino-benzoic acid,o-chloro-benzoic acid, and m-nitro-benzoic acid in 1-octanol were measured by the polythermal method in the temperature range of 20-50℃. The experimental data were regressed with the. Wilson equation and the λH equation. The experimental results showed that the solubility of the four chemicals in 1-octanol increased significantly with temperature. The results indicate that the molecular structure and interactions affect the solubility significantly.The solubility order of the benzoic acid derivatives is as follows： m-nitro-benzoic acid〉o-chloro-benzoic acid〉 o-amino-benzoic acid〉p-amino-benzoic acid. Both the Wilson equation and λH equation are in good agreement with the experimental data.     

基于UNIFAC模型的基团-OCOO-与-CH3,ACH,CH3OH和CH3COO-的交互作用参数估算与验证

Isobaric vapor-liquid equilibria (VLE) are experimentally measured for the binary systems of dimethyl carbonate (DMC) ethylene carbonate and methanol ethylene carbonate at 101.325kPa. The thermodynamic consistency of these experimental data is tested with an available statistic method. Interaction parameters of the carbonate group —OCOO— with the group —CH3, ACH, CH3OH and CHACO0— in UNIFAC model are determined using the experimental and literature VLE data. The results show that the calculated VLE data using the new UNIFAG parameters agree excellently with the experimental data in this work and in literature. These results are useful in the research on DMG and diphenyl carbonate synthesis by transesterification in design of reactor and distillation tower.     

Experimental determination of solubilities and supersolubilities of 2,2′,4,4′,6,6′-hexanitrostilbene in different organic solvents

The laser monitor technique was used to determine solubilities and supersolubilities of HNS in N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone and 1,4-butyrolactone. The experimental solubility values were correlated with λh equation, modified Apelblat equation and NRTL model. Furthermore, the dissolution enthalpy, dissolution entropy and the Gibbs energy of HNS were calculated by the experimental data. The results show that the solubilities of HNS in the above solvents increase with the increasing temperature. Besides, at the same temperature, the order of solubility is N-methyl-2-pyrrolidone dimethyl sulfoxide N,N-dimethylformamide 1,4-butyrolactone acetonitrile. The temperature dependence of predicted solubility is in agreement with the experimental data.     

氨在甲醇乙二醇混合溶剂中的溶解度

采用溶解平衡的方法测定了氨气在甲醇、乙二醇及其混合溶剂中的溶解度,得到了100 kPa和70.0 kPa压力,温度从278.1 K到338.1 K共7个水平,混合溶剂组成(用乙二醇质量分数表示)从0到1.0共11个水平的143组氨溶解度数据。基于扩展的拉乌尔定律和扩展的亨利定律提出了表达上述条件下,混合溶剂中氨溶解度的热力学模型,对实验数据进行关联,取得了较好的结果。     

二水硫酸钙在硫酸铵溶液中的溶解度测定

采用电感耦合等离子体发射光谱法（ICP-AES）测定了二水硫酸钙在硫酸铵溶液中（298.15～348.15 K）的溶解度,利用E-DH方程对实验数据进行关联,总平均相对偏差为2.81%;并考察了E-UDH方程的理论预测值,与实验值对比,总平均相对偏差为4.13%。实验和理论研究结果表明：在同离子效应和盐效应协同影响下,二水硫酸钙在（NH₄）₂SO₄-H₂O体系中溶解度随硫酸铵浓度增加先降低后又增大,在298.15～348.15 K温区内,溶解度突变点硫酸铵浓度为0.07～0.08 mol·kg^-1;随溶液中硫酸铵浓度增加,温度对二水硫酸钙溶解度的影响更趋显著。研究结果对磷石膏矿化烟气CO₂的过程设计具有指导意义。     

Experimental study of methane and carbon dioxide solubility in 1,4 butylene glycol at pressures up to 11 MPa and temperatures ranging from 303 to 423 K

This work reports solubility data of methane and carbon dioxide in 1,4 butylene glycol and the Henry's law constant of each solute in the studied solvent at saturation pressure. The measurements were performed at 303, 323, 373, 398 and 423.15 K and pressures up to 3.8 MPa for mixtures containing carbon dioxide and pressures up to 10.9 MPa for mixtures containing methane. The experiments were performed in an autoclave type phase equilibrium apparatus using a technique based on the total pressure method (synthetic method). All investigated systems show an increase of gas solubility with the increase of pressure. A decrease of carbon dioxide solubility with the increase of temperature and an increase of methane solubility with the increase of temperature were observed. From the variation of solubility with temperature, the partial molar enthalpy and entropy change of each mixture were calculated.     

亚硝酸甲酯在甲醇溶剂中的亨利常数测定

在合成气制乙二醇这一新工艺中,亚硝酸甲酯的再生起着至关重要的作用,但关于亚硝酸甲酯的基础物性数据很少,如在甲醇中的亨利常数。由于亚硝酸甲酯的相关物性数据的缺乏,不能用已报道的一些方法进行估算,因此在改进的静态法测定汽液平衡装置上,测定了293.15—323.15 K亚硝酸甲酯在甲醇中的亨利系数。结果表明,温度升高,亨利系数增大,且亚硝酸甲酯在甲醇中的溶解量很小。通过对亨利系数与温度的关联得出普遍意义的表达式,为亚硝酸甲酯再生的研究提供参考。     

Phase behavior measurement for the ethylene glycol dimethacrylate in supercritical carbon dioxide at temperatures between (313.2 and 393.2) K and pressures from (5.8 to 22) MPa

High pressure experimental data are presented on the phase equilibrium of ethylene glycol dimethacrylate in supercritical carbon dioxide. Pressure-composition (P-x) isotherms were measured in static method at five temperatures of (313.2, 333.2, 353.2, 373.2 and 393.2) K and at pressures up to 22.0MPa. This (carbon dioxide+ethylene glycol dimethacrylate) system has continuous critical mixture curves that exhibit maximums in pressure at temperatures between the critical temperatures of carbon dioxide and ethylene glycol dimethacrylate. At a fixed pressure, the solubility of ethylene glycol dimethacrylate for the (carbon dioxide+ethylene glycol dimethacrylate) system increases with increasing temperature. The (carbon dioxide+ethylene glycol dimethacrylate) system exhibits type-I phase behavior. The experimental result for the (carbon dioxide+ethylene glycol dimethacrylate) system is correlated with Peng-Robinson equation of state using mixing rule including two adjustable parameters. The critical property of ethylene glycol dimethacrylate is predicted with Joback and Lee-Kesler method.     

The effect of [bmim][Br] on the solubility of carbon dioxide and methane in glycols at pressures up to 14 MPa and temperatures ranging from 303 to 423 K

Solubility data of methane in ethylene glycol and 1-4 butylene glycol and carbon dioxide in ethylene glycol and 1-2 propylene glycol in the presence of the ionic liquid 1-butyl-3-methylimidazolium bromide have been measured in the temperature range (303–423) K at pressures up to 14 MPa. Henry's law constant of each solute in the studied solvent at saturation pressure is given. The experiments were performed in an autoclave type phase equilibrium apparatus using the total pressure method. For mixtures containing carbon dioxide and ethylene glycol no influence was observed. For mixtures containing carbon dioxide and 1-2 propylene glycol it was observed salting-out effect at 303.2 K and 323.2 K and salting-in effect at the remaining temperatures. For mixtures containing methane and ethylene glycol or 1-4 butylene glycol salting-in effect was observed.     

The physical solubilities and diffusivities of N<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in aqueous ammonia solutions on the additions of AMP,glycerol and ethylene glycol

Carbon dioxide (CO₂) is a major greenhouse gas, the emissions of which should be reduced. There are various technologies for the effective separation of CO₂. Of these, chemical absorption methods are generally accepted as the most effective. The monoethanolamine (MEA) process is an effective way to remove CO₂, but is an expensive option for the separation of CO₂ from massive gas-discharging plants. Therefore, ammonia solution, which is less expensive and more effective than MEA, was used for the removal of CO₂. In this study, the physical solubility of N₂O in (ammonia+water), (ammonia+2-amino-2-methyl-1-propanol+water), (ammonia+glycerol+water) and (ammonia+ ethylene glycol+water) was measured at 293, 303, 313, 323 K. Additive concentrations of 1, 3, and 5 wt% AMP, glycerol and ethylene glycol were added for each 9 wt% ammonia solution. A solubility apparatus was used to investigate the solubility of N₂O in ammonia solutions. The diffusivity was measured with a wetted wall column absorber. The “N₂O analogy” is used to estimate the solubility and diffusivity of CO₂ in the aqueous ammonia solutions. OriginPro 7.5 was used to correlate the solubility and diffusivity of N₂O in ammonia solutions. The parameters of the correlation were determined from the measured solubility and diffusivity.     

CO2在醇中溶解度的测定与分子连接性指数的关联

用恒定溶剂法测定了303.15K下CO2在乙醇、正丙醇、异丙醇、正丁醇、正戊醇、异戊醇、正己醇、正辛醇、乙二醇、1,2-丙二醇中的溶解度。实验表明:随着碳链的增长,吸收CO2的效果越好,CO2在正辛醇中的溶解度最大,CO2在二元醇中的亨利常数显著大于一元醇。利用线性回归方法建立CO2在醇中的亨利常数lgH与分子连接性指数的相关关系模型,模型计算简单易行,对CO2在醇中的亨利常数有良好的估算和预测能力,相关系数R>0.99,计算值和实验值吻合良好。研究表明:用一阶分子连接性指数1χv、羟基的个数N、经验参数COH三个参数可以描述CO2在醇中的溶解特性lgH,且精确度很高。     

Physical solubility of hydrogen sulfide in several aqueous solvents

The solubility of hydrogen sulfide in several aqueous solutions was measured over the temperature range 25°C to 60°C. The solvents investigated in this work include 0 to 50% aqueous solutions of polyethylene glycol, ethylene glycol, methyldiethanolamine and diethanolamine. The amine solutions used in this work were neutralized by the addition of hydrochloric acid in order to suppress the hydrogen sulfide reaction (H₂S → H⁺ + HS^?) so that only the physical solubility of hydrogen sulfide would be measured. The solubility data determined in this work are expressed in terms of Henry's law. The Henry's law constants found in this work were correlated well by a particularly simple empirical formula based on the molecular weight of the solvent.     

氧气在醋酸水溶液中的Henry系数计算模型

高温下氧气在醋酸水溶液中的Henry系数目前还没有合适的计算方法。胡英等(1985)提出的扩展定标粒子理论虽然可在广泛的温度范围内适用于多种体系,但目前还没有将这一模型应用于有机酸溶液的报道。文中对扩展定标粒子理论进行了二点改进,一是考虑了热力学参数对温度的依赖关系;二是针对有机酸溶液的特点对氧气的有效大小参数进行了调整,建立了氧气在醋酸水溶液中的Henry系数计算模型。模型参数由文献实验数据回归得到,模型计算结果与文献报道值基本一致,所建立的模型可用于关联和预测不同温度(273—500 K)、不同醋酸摩尔分数(0—100%)下氧气在醋酸水溶液中的Henry系数。