对羟基苯甘氨酸在水-丙酮-硫酸混合溶剂中的溶解度及介稳区

分别采用恒温溶解法和变温溶解法测定了对羟基苯甘氨酸在水-丙酮-硫酸混合溶剂中的溶解度曲线和超溶解度曲线,利用激光监视装置检测测定系统中晶体的消失和产生,实验温度范围约为303~323K。随着混合溶剂中水的增加,溶解度略有增加;酸度增加,溶解度有较大幅度的增加。用经验方程二次多项式关联溶解度与温度的关系,计算的溶解度和实验值符合良好。测得的超溶解度曲线与溶解度曲线基本平行,介稳区宽度以最大过冷度表示约为1.5~2.4K,温度升高时介稳区宽度略有减少。溶剂中水含量或硫酸含量增加将使介稳区宽度变小;降低搅拌速度使介稳区明显变宽。实验结果可应用于优先结晶法拆分对羟基苯甘氨酸。     

普瑞巴林晶型Ⅰ在纯溶剂及丙酮-水混合溶剂中的溶解度测定与关联

通过平衡法测定了283.15~328.15 K温度下普瑞巴林晶型I在水、甲醇、乙醇、丙酮、四氢呋喃、N,N-二甲基甲酰胺、乙酸乙酯及丙酮-水混合溶剂中的溶解度,实验结果表明:普瑞巴林晶型I在所测定的所有纯溶剂及丙酮-水混合溶剂中的溶解度均随温度的升高而增大;在丙酮-水混合溶剂中,溶解度随着丙酮的摩尔分数的增加而降低,在丙酮的摩尔分数达到0.83附近时溶解度最小,接近0。采用修订的Apelblat经验方程和(CNIBS)/Redlich-Kister方程对溶解度数据进行关联,结果令人满意。所得实验数据和拟合模型为普瑞巴林在工业结晶及药物多晶型等方面的研究提供了重要的依据。     

Ⅱ晶型利福平在两种混合溶剂中溶解度的测定和关联

使用平衡法测定了288.15～323.15 K时Ⅱ晶型利福平在正丁醇-丙酮和水-丙酮混合溶剂中的溶解度。实验结果表明Ⅱ晶型利福平在两种混合溶剂中的溶解度均随着温度升高而增大;在正丁醇-丙酮混合溶剂中,溶解度随着正丁醇的摩尔分数增加先增大后减小,在摩尔比0.350附近溶解度最大;在水-丙酮体系中,溶解度随着水的摩尔分数增加而增大。使用Apelblat方程、理想状态方程和(CNIBS)/Redlich-Kister方程关联溶解度数据,Apelblat方程关联结果优于理想状态方程,平均相对偏差小于5%。使用修正的van't Hoff方程计算了两种体系的溶解焓、溶解熵和吉布斯自由能。溶解度数据及拟合方程为利福平研究和工业生产提供了基础数据。     

阿维菌素在不同醇-水溶剂体系中溶解度的测定与关联

工业生产中阿维菌素在不同比例的有机溶剂-水体系中的溶解度是重要的基础数据,本实验采用平衡法测定了阿维菌素在甲醇含量100%～70%、乙醇含量100%～60%的水溶剂中,温度范围为30～70℃的溶解度,并采用多项式经验方程、半经验关联模型对实验测定溶解度数据进行关联,相关系数都在98%以上,结果较为满意。结果表明在甲醇-水溶剂体系中随水的比例增加,溶解度减少较为明显,以32℃时为例,90%甲醇-水溶剂比纯甲醇做溶剂的溶解度下降了67%,而乙醇-水体系随水的比例增加,溶解度减小较缓和,同样条件下,在95%乙醇-水溶剂中溶解度只下降了28%。     

甘氨酸在丙酮-水混合溶剂中溶解度的测定与关联

采用平衡法测定了278.15~313.15 K甘氨酸在纯水及丙酮-水混合溶剂中的溶解度;采用Apelbla t经验方程和(CNIBS)/Redlich-Kister方程分别对甘氨酸在纯水和丙酮-水体系中的溶解度数据进行了关联,并对(CNIBS)/Redlich-Kister方程进行了温度影响分析。结果表明,甘氨酸在纯水中的溶解度随着温度的升高而增大;甘氨酸在丙酮-水混合溶剂中的溶解度随着丙酮与水的质量比的增加而变小;当丙酮与水的质量比达到实验中最大值即4时,甘氨酸的溶解度接近于0;在相同丙酮与水的质量比下,甘氨酸的溶解度随着温度升高而有所增大。甘氨酸在纯水及丙酮-水混合溶剂中的溶解度模型关联的标准方差均能达到1×10-4,精度满足工程需要。实验数据及相应模型为甘氨酸结晶过程分析和设计提供了重要依据。     

二苯基亚砜在有机溶剂中的溶解度测定和拟合

在温度288.30～334.32 K、常压条件下,采用合成法测定二苯基亚砜在乙醇、乙酸乙酯、甲苯、丙酮、氯仿以及一系列浓度的乙醇-水混合溶剂中的溶解度。实验结果表明,在相同温度下,5种纯溶剂中二苯基亚砜的溶解度大小顺序如下,氯仿 > 丙酮 > 甲苯 > 乙酸乙酯 > 乙醇;乙醇-水混合溶剂中溶解度随着乙醇浓度下降而迅速降低;该溶解过程为吸热熵增过程,且随着溶解Gibbs斯自由能增大,溶解度减小。数据采用改进的Apelblat方程和van’t Hoff方程进行拟合,在乙醇-水混合溶剂中的溶解度数据还采用Jouban-Acree方程拟合。拟合结果与实验数据基本吻合。测定的固液平衡数据可为二苯基亚砜的合成与提纯等过程的溶剂选择提供依据。     

阿奇霉素二水合物在水-有机溶剂中溶解度及三元相图测定

采用静态法测定了293.15～323.15 K范围内，阿奇霉素二水合物在丙酮-水和异丙醇-水混合溶剂中的溶解度，并研究阿奇霉素在293.15、298.15、303.15及308.15 K温度下丙酮-水混合溶剂中转晶水活度，根据溶解度特性绘制丙酮-阿奇霉素-水三元相图，溶解度数据用Apelblat方程、λh方程和van’t Hoff方程进行关联。结果表明，阿奇霉素溶解度随着有机溶剂体积分数和温度的升高而增加，转晶水活度随温度的升高增大，阿奇霉素一水二水共存区域随温度的升高减小，Apelblat方程拟合效果更好，R²≥0.988。     

阿奇霉素二水合物在水-有机溶剂中溶解度及三元相图测定

采用静态法测定了293.15～323.15 K范围内,阿奇霉素二水合物在丙酮-水和异丙醇-水混合溶剂中的溶解度,并研究阿奇霉素在293.15、298.15、303.15及308.15 K温度下丙酮-水混合溶剂中转晶水活度,根据溶解度特性绘制丙酮-阿奇霉素-水三元相图,溶解度数据用Apelblat方程、λh方程和van’t Hoff方程进行关联。结果表明,阿奇霉素溶解度随着有机溶剂体积分数和温度的升高而增加,转晶水活度随温度的升高增大,阿奇霉素一水二水共存区域随温度的升高减小,Apelblat方程拟合效果更好,R~2≥0.988。关键词:阿奇霉素二水合物;溶解度;转晶水活度;Apelblat方程;三元相图     

二苯基亚砜在有机溶剂中的溶解度测定和拟合

在温度288.30~334.32 K、常压条件下,采用合成法测定二苯基亚砜在乙醇、乙酸乙酯、甲苯、丙酮、氯仿以及一系列浓度的乙醇-水混合溶剂中的溶解度。实验结果表明,在相同温度下,5种纯溶剂中二苯基亚砜的溶解度大小顺序如下,氯仿丙酮甲苯乙酸乙酯乙醇;乙醇-水混合溶剂中溶解度随着乙醇浓度下降而迅速降低;该溶解过程为吸热熵增过程,且随着溶解Gibbs斯自由能增大,溶解度减小。数据采用改进的Apelblat方程和van’t Hoff方程进行拟合,在乙醇-水混合溶剂中的溶解度数据还采用Jouban-Acree方程拟合。拟合结果与实验数据基本吻合。测定的固液平衡数据可为二苯基亚砜的合成与提纯等过程的溶剂选择提供依据。     

RDX在丙酮-水混合溶剂中溶解度的测定及关联

本文利用激光系统,在20～40℃温度范围内,由溶析结品法洲定了RDX在纯丙酮以及丙酮与水混合溶剂中的溶解度,然后用Apelblat经验方程模拟了RDX在纯丙酮中的溶解度,用(CNIBS)/Redlich-Kister方程模拟了RDX在丙酮和水体系中的溶解度,模拟精度都在99%以上     

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.     

Measurement and correlation of the solubility of sodium acetate in eight pure and binary solvents

The knowledge of solubility of a salt in either the pure solvent or blend solvent is of great importance for studying or operating the crystallization, extraction, and distillation processes. The solubility of sodium acetate (NaAc) in four pure solvents (water, ethanol, acetic acid and 2,2,2-trifluoroethanol) and four binary solvents (water–ethanol, water-acetic acid, acetic acid–ethanol, and acetic acid-ethyl acetate) were measured by using the laser dynamic method at temperatures from 288.15 K to 338.15 K at 0.1 MPa. The results showed that the solubility of NaAc was influenced by either the solution temperature or solvent composition. The aqueous sodium acetate solution possessed the maximal solubility under the experimental conditions. The solubility of NaAc in 2,2,2-trifluoroethanol was found to be decreased with the increase of the solution temperature. While, the solubilities of NaAc in other seven solvents increased as the solution temperature was elevated. Besides, five correlation models, including the van't Hoff model, modified Apelblat model, Yaws model, λh model, and modified Apelblat-Jouyban-Acree model were used to correlate the solubility data of those sodium acetate solutions with acceptable deviation, respectively. Finally, van't Hoff analysis method was selected to analyze the change law of thermodynamic properties of a salt during the dissolution process.     

Solubility measurement and thermodynamic properties of sulfamonomethoxine in pure solvents and sulfamonomethoxine hydrate in acetone + water binary solvent at different temperature

The experimental solubility of sulfamonomethoxine in six different pure solvents (methanol,ethanol,1-propanol,l-butanol,ethyl acetate and acetone) and sulfamonomethoxine hydrate in acetone + water mixture solvents were measured from 294.55 K to 362.15 K by a laser dynamic method under atmospheric pressure.Experimental results indicated that the solubility data of sulfamonomethoxine increased with temperature increasing in pure solvents and the solubility followed this order:acetone ＞methanol ＞ ethanol ＞ ethyl acetate ＞ 1-propanol ＞ 1-butanol,but solubility in ethyl acetate was not affected significantly by temperature.In acetone + water mixture solvent,the solubility of sulfa-monomethoxine hydrate increased with temperature and the acetone concentration.Thermodynamic equations were applied to correlate solubility data of sulfamonomethoxine and sulfamonomethoxine hydrate including the modified Apelblat equation,λh equation,Wilson equation,NRTL equation,Van't Hoff-Jouyban Acree equation and modified Apel-Jouyban-Acree equation.Furthermore,thermodynamic properties △Gd,△Hd and △Sd of sulfamonomethoxine and sulfamonomethoxine hydrate in dissolution process were obtained and discussed with the modified Van't Hoff equation and Gibbs equation.     

TNAZ在乙醇-水二元溶剂中的溶解度

采用动态激光监测技术测定了温度为293.15~323.15K时TNAZ在乙醇-水二元溶剂体系中的溶解度。结果表明,TNAZ在乙醇-水二元溶剂中的溶解度是温度和溶剂比例的函数,溶解度随温度的升高而增大,温度293.15~323.15K时,TNAZ在纯乙醇溶剂中溶解度变化为0.01349~0.03935mol/mol;293.15K,水的摩尔分数0~0.9189时,TNAZ的溶解度变化为0.01349~0.00007mol/mol。实验数据采用Apelblat经验方程(lnx1=a+b/T+clnT)和(CNIBS)/Redlich-Kister方程(lnx1=B0+B1x2+B2x22+B3x23+B4x24)进行关联,关联效果良好(R20.96)。所测定的溶解度数据与关联模型可以作为基础热力学数据和模型在TNAZ结晶生产实践中应用。     

双酚A在苯酚-丙酮-水中溶解度测定与关联

采用差示扫描量热法,以升温扫描速率2K-min^-1,测定了双酚A分别在溶剂苯酚及二元混合溶剂苯酚-丙酮、苯酚．水和三元混合溶剂苯酚．丙酮．水中的溶解度数据,溶质及各溶剂的浓度范围分别为：双酚A 7％～30％(wt)：苯酚70％～93％(wt);丙酮0%～5％(wt)：水0%～5％(wt)。为每一物系,提出了关联实验数据温度与溶解度关系的数学方程式,方程式参数不超过4个,并根据最小二乘法拟合得到。对每一物系进行关联,关于温度的均方根偏差分别为036K,0．68K．0．68K和0．78K,关联结果十分成功。实验结果可用于双酚A结晶过程。     

对苯二甲酸和对羧基苯甲醛在醋酸水溶液中的溶解度

测定了420-505K温度范围内,对苯二甲酸和对羧基苯甲醛在醋酸水溶液中溶解度。在70%-100%醋酸水溶液中,70%醋酸使对苯二甲酸的溶解度对温度最敏感,随着醋酸浓度增加,对苯二甲酸的溶解度减少。当温度低于470K时,对苯二甲酸在水中的溶解性低于醋酸中的溶解度;温度高于470K时,对苯二甲酸在水中的溶解性对温度敏感明显提高。40%醋酸使对羧基苯甲醛的溶解度对温度最敏感, 随着醋酸浓度增加, 对羧基苯甲醛的溶解度增加。实验数据用修正的Apelblat方程进行了对苯二甲酸和对羧基苯甲醛在醋酸水溶液中溶解度关联,计算与实验值吻合良好。     

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.     

Solubility of N-chloro succinimide in different pure solvents in the temperature range from 278.15 K to 333.15K

Solubility data were measured for N-chloro succinimide in pure n-butanol, ethyl acetate, acetone, isopropanol, tetrahydrofuran, acetonitrile and acetic anhydride at the temperature range between 278.15 K and 333.15 K under atmospheric pressure by gravimetric method. The solubility of N-chloro succinimide in those selected solvents increased with increasing temperature. The solubility data were correlated with the modified Apelblat equation and the van??t Hoff equation to obtain the model parameters. The experimental results could be useful for optimizing the process of purification of N-chloro succinimide in industry. Isopropanol could be the excellent solvent in the crystallization of N-chloro succinimide.     

Solubility of argon in acetone + water mixed solvent at 288.15, 298.15 and 308.15 K

Solubilities of argon were determined in acetone + water mixed solvent over the full range of composition using a static method. The gas solubilities were measured at three temperatures of 288.15, 298.15 and 308.15 K. The solubility dependence on the temperature in the mixed solvent was measured and discussed, and the similarity between excess quantities of mixed solvent and those of gas solubilities was examined. The order of gas solubility of argon in acetone + water mixed solvent at the three different temperatures was 288. 15 > 298.15 > 308.15 K in the composition range of 0 ≤ x₂2 ≤ 0.15. However, the reverse relationship with temperature was observed in the range of composition of 0.15 < x₂ ≤ 1.0. For all solubility curves, maximum and minimum values of solubility were observed at lower temperatures, but not at higher temperatures. Furthermore, the excess Ostwald coefficients on the basis of volume fraction which express the non-ideality of gas solubility in non-ideal solutions were defined, and they were expressed by a polynomial equation of the Redlich-Kister (1948) type.