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 modified 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.     

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.     

Measurement and correlation of solubility of xylitol in binary water+ethanol solvent mixtures between 278.00 K and 323.00K

The solubility of xylitol in ethanol+water solvent mixtures was measured at temperatures ranging from 278.00 K to 323.00 K at atmospheric pressure by using a laser technique. The results of these measurements were correlated by the combined nearly ideal binary solvent CNIBS/Redlich-Kister equation. The experimental solubility and correlation equation in this work can be used as essential data and models in the purification process of xylitol. The variant 2 in the CNIBS/R-K models was confirmed to be more adaptable to predict solubility of xylitol in binary ethanol +water system. Using the experimentally measured solubilities, the thermodynamic properties of dissolution of xylitol, such as Gibbs energy, molar enthalpy of dissolution, and molar entropy of dissolution, were calculated.     

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。     

Solubility and solution thermodynamics of ammonium dihydrogen phosphate in the water-methanol system

The solubility of ammonium dihydrogen phosphate (MAP) in the water-methanol system is essential for antisolvent crystallization studies. To investigate the effect of methanol on the solubility of MAP in water, the solubility of MAP in the water-methanol system was determined by dynamic method and static equilibrium method at temperatures ranging from 293.2 to 343.2 K at atmospheric pressure. Results showed that the solubility of MAP increased with the increase of temperature and the increase of water mole fraction in the water-methanol system. The experimental solubility data were correlated with the modified Apelblat equation, the combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) model and the Jouyban-Acree model. The calculated results based on these three models were in very good agreement with the experimental data with the average relative deviations of 0.65%, 0.97%, and 5.38%, respectively. Simultaneously, the thermodynamic properties of the MAP dissolution process in the water-methanol system, including Gibbs energy change, enthalpy, and entropy were obtained by the Van't Hoff equation, which can be used to assess the crystallization process.     

Determination and Correlation of Solubility of Nonivamide in Different Solvents☆

The solubility of nonivamide in dimethyl sulfoxide, methanol, acetone, ethyl acetate, methyl tert-butyl ether, ace-tonitrile, n-hexane and water over the temperature range of 293.2 K to 323.2 K was mea...     

Determination and correlation solubility of 4-nitroimidazole in twelve pure solvents from 278.15 K to 323.15 K

In this paper, the solubility of 4-nitroimidazole in twelve pure solvents (toluene, benzene, 1,4-dioxane, acetonitrile, ethyl acetate, acetone, GBL, ethanol, methanol, n-butanol, DMF and NMP) were determined by using the laser monitoring system from 278.15 K to 323.15 K under 101.1 kPa, which are 0.00018-0.00070, 0.00021-0.00073, 0.00034-0.00092, 0.00038-0.00142, 0.00047-0.00120, 0.00126-0.00303, 0.00225-0.00517, 0.00310-0.00724, 0.00467-0.00982, 0.00453-0.01940, 0.01947-0.04652, and 0.04670-0.07452, respectively. At constant temperature, the mole fraction solubility of 4-nitroimidazole were increased as the following order: toluene < benzene < 1,4-dioxane < (ethyl acetate or acetonitrile) < acetone < GBL < ethanol < (methanol or nbutanol) < DMF < NMP, and the solubility of 4-nitroimidazole in (ethyl acetate, acetonitrile) and (methanol, n-butanol) had an intersection point at 297.55 K and 281.85 K, respectively. The solubility of 4-nitroimidazole could be increased with increasing temperature in twelve pure solvents. The ideal model, modified Apelblat equation, polynomial empirical equation, and λh equation were used to correlate the experimental values. The experimental solubility values were employed to calculate the standard dissolution enthalpy, standard dissolution entropy and Gibbs energy. The dissolution of 4-nitroimidazole could be an endothermic process in twelve pure solvents. The determination and fitting solubility of 4-nitroimidazole have important guiding significance for the purification and crystallization of its preparation process.     

双季戊四醇在3种混合溶剂中的固-液相平衡

采用动态平衡法,在293.15～332.80 K、常压下,测定了双季戊四醇(DPE)在水+(甲醇、乙醇、异丙醇)三种混合溶剂中的溶解度数据。结果表明：DPE在不同质量分数的水+(甲醇、乙醇、异丙醇)混合溶剂中的溶解度随体系温度升高而增大;同一温度下,其在所选取溶剂体系中的溶解度随着甲醇、乙醇或异丙醇质量分数的增大而先增大后减小。λh方程、两参数方程与Apelblat方程均能够对所测定的溶解度数据进行较好的关联;通过修正的van’t Hoff方程计算得到DPE在所选取溶剂体系中Δ_sol H ⁰、Δ_sol S ⁰和Δ_sol G ⁰均大于零,表明DPE在所选取溶剂体系中的溶解过程为吸热、熵增的非自发过程。     

The solubility of cefquinome sulfate in pure and mixed solvents

Solid-liquid equilibrium data of cefquinome sulfate is important to develop industrial crystallization processes for cefquinome sulfate. The solubilities of cefquinome sulfate in five pure solvents (methanol, ethanol, ethylene glycol, acetic acid and water) from 277.15 to 305.15 K and in a binary acetone-water solvent from 278.15 to 293.15 K were measured at atmospheric pressure. The pure-solvent solubility data was correlated to the modified Apelblat and Van’t Hoff equations whereas the mixed-solvent system data was correlated to the modified Apelblat, Van’t Hoff, CNIBS/R-K and Jouyban- Acree models. It was found that the solubilities of cefquinome sulfate in all tested solvents decreased with the increasing of temperature. In addition, the thermodynamic properties of the dissolution processes, including standard Gibbs free energy, enthalpy and entropy changes, were calculated using the Van’t Hoff equation. It was found that the dissolution of cefquinome sulfate is exothermic.

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Determination and correlation solubility of 4-nitroimidazole in twelve pure solvents from 278.15 K to 323.15 K

In this paper, the solubility of 4-nitroimidazole in twelve pure solvents (toluene, benzene, 1,4-dioxane, acetonitrile, ethyl acetate, acetone, GBL, ethanol, methanol, n-butanol, DMF and NMP) were determined by using the laser monitoring system from 278.15 K to 323.15 K under 101.1 kPa, which are 0.00018–0.00070, 0.00021–0.00073, 0.00034–0.00092, 0.00038–0.00142, 0.00047–0.00120, 0.00126–0.00303, 0.00225–0.00517, 0.00310–0.00724, 0.00467–0.00982, 0.00453–0.01940, 0.01947–0.04652, and 0.04670–0.07452, respectively. At constant temperature, the mole fraction solubility of 4-nitroimidazole were increased as the following order: toluene < benzene < 1,4-dioxane < (ethyl acetate or acetonitrile) < acetone < GBL < ethanol < (methanol or n-butanol) < DMF < NMP, and the solubility of 4-nitroimidazole in (ethyl acetate, acetonitrile) and (methanol, n-butanol) had an intersection point at 297.55 K and 281.85 K, respectively. The solubility of 4-nitroimidazole could be increased with increasing temperature in twelve pure solvents. The ideal model, modified Apelblat equation, polynomial empirical equation, and λh equation were used to correlate the experimental values. The experimental solubility values were employed to calculate the standard dissolution enthalpy, standard dissolution entropy and Gibbs energy. The dissolution of 4-nitroimidazole could be an endothermic process in twelve pure solvents. The determination and fitting solubility of 4-nitroimidazole have important guiding significance for the purification and crystallization of its preparation process.     

黑索今在丙酮-水混合溶剂中介稳区的测定及关联

采用溶析结晶法测定了黑索今在纯丙酮以及丙酮与水混合溶剂中的溶解度与超溶解度,得到了黑索今结晶介稳区。用Apelblat经验方程模拟了黑索今在纯丙酮中溶解特性,用（CNIBS）/Redlich-Kister方程模拟了黑索今在丙酮和水体系中溶解特性,模拟精度均在99%以上。     

S-噻吗洛尔-D-酒石酸非对映体盐在有机溶剂中的溶解度测定和预测

实验测定了S-噻吗洛尔-D-酒石酸非对映体盐(S-TTS)在乙醇、正丙醇、丙酮、1,2-二氯乙烷和乙酸乙酯中的溶解度。在相同温度下,S-TTS在这些溶剂中的溶解度(s)顺序是:s(乙醇)>s(正丙醇)>s(丙酮)>s(1,2-二氯乙烷)>s(乙酸乙酯)。用四参数多项式、Apelblat方程、改进的Apelblat方程和λH方程关联了溶解度实验数据,以四参数多项式关联实验数据的结果最好,其相关系数(R2)>0.99,平均绝对相对偏差(AARD)(%)<4。提出了1,2,5-硫氮二茂基团、含手性碳次甲基基团(*CH)等新的基团相互作用参数,并用UNIFAC法预测了S-TTS在这5种溶剂中的溶解度,所得结果的平均绝对相对偏差(%)<53,并与用.H方程等的结果作了比较。     

反式-4-羟基环己基地氯雷他定溶解度测定关联

采用高效液相色谱法测定了常压下在293.15~323.15 K温度范围内反式-4-羟基环己基地氯雷他定在水、质量分数为10% 的甲醇-水、质量分数为20% 的甲醇-水、质量分数为10% 的乙醇-水和质量分数为20% 的乙醇-水中的溶解度,并采用Apelblat方程和λh方程对所得到的溶解度数据进行关联拟合,通过van't Hoff方程计算了其在不同溶剂中的溶解焓和溶解熵。发现反式-4-羟基环己基地氯雷他定的溶解度随着温度的升高和溶剂极性的降低而升高,其溶解过程在实验温度范围内,在所选溶剂中均为吸热熵增过程。     

异烟肼在有机溶剂中溶解度测定及晶习研究

在283.15~323.25 K范围内,利用在线浊度法测定了异烟肼在甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、丙酮、乙腈、乙酸甲酯与乙酸丁酯中的溶解度。数据表明,异烟肼在不同溶剂中的溶解度均随着温度升高而增加。在同一温度下,异烟肼的溶解度与溶剂关系符合如下顺序：甲醇 > 丙酮 > 乙醇 > 正丙醇 > 异丙醇 > 乙酸甲酯 > 异丁醇 > 正丁醇 > 乙腈 > 乙酸丁酯。采用改进的Apelblat、Wilson与NRTL方程对溶解度数据进行了拟合,结果与实验数据有较高的吻合。基于溶解度数据,对异烟肼溶解焓、溶解熵与溶解吉布斯能进行了计算,发现异烟肼溶解过程是吸热熵增过程。分析了甲醇、乙醇、正丙醇与丙酮对异烟肼冷却结晶过程所获产品晶习的影响,确定乙醇为合适的结晶溶剂。     

缬沙坦在乙酸乙酯中的溶解度及介稳区

采用静态平衡法测定缬沙坦在乙酸乙酯中278.15~323.15K的溶解度数据,利用Modified Apelblat、NRTL和λh方程分别对溶解度数据进行了关联,并通过van't Hoff分析计算了缬沙坦在溶解过程中的热力学参数（焓变、熵变和吉布斯自由能）。结果表明,缬沙坦在乙酸乙酯中的溶解度随着温度升高而显著增大,3个模型均具有较好的关联性,平均相对偏差分别为1.03%、3.87%、1.72%,Modified Apelblat方程对溶解度数据关联的效果最好;缬沙坦在乙酸乙酯中的溶解过程为自发吸热熵驱动过程,焓变在溶解过程中对吉布斯自由能贡献较大。利用激光法测定了缬沙坦在乙酸乙酯中的超溶解度,研究了不同搅拌速率、降温速率对结晶介稳区的影响。结果表明,随饱和温度的升高,介稳区显著变宽;搅拌速率越小、降温速率越快,介稳区越宽,降温速率的影响相对较小。     

拉莫三嗪-邻苯二甲酰亚胺药物共晶在有机溶剂中溶解度及三元相图测定

采用静态法测定了拉莫三嗪在正丙醇、异丙醇、正丁醇、异丁醇、丙酸乙酯、乙酸甲酯6种溶剂中的热力学行为,并采用Apelblat方程和λh方程进行了关联,其结果表明拉莫三嗪的溶解度随着温度的升高而升高,溶解行为由低到高为正丁醇>正丙醇>异丁醇>异丙醇,乙酸甲酯>丙酸乙酯,应用的方程拟合度较好,可用于单体拉莫三嗪热力学行为的预测。在此基础上,采用溶液法制备拉莫三嗪-邻苯二甲酰亚胺共晶,在298.15、303.15 K时,建立了共晶体在异丁醇、丙酸乙酯溶剂中的三元相图,结果表明同一溶剂体系内,随着温度的升高,拉莫三嗪-邻苯二甲酰亚胺共晶区域增大,有利于共晶的形成。同一温度下,拉莫三嗪-邻苯二甲酰亚胺共晶在异丁醇体系的对称性优于丙酸乙酯体系,表明拉莫三嗪-邻苯二甲酰亚胺共晶更易于在异丁醇体系中获得。     

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 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.     

Investigation of the Solubility of 3,4‐Diaminofurazan (DAF) and 3,3′‐Diamino‐4,4′‐azoxyfurazan (DAAF) at Temperatures Between 293.15 K and 313.15 K

The solubilities of 3,4‐diaminofurazan (DAF) and 3,3′‐diamino‐4,4′‐azoxyfurazan (DAAF) were investigated in water, dichloromethane, acetonitrile, ethyl acetate, methanol, and acetone between 293.15 K and 313.15 K. The solubility was determined by high‐pressure liquid chromatography with ultraviolet detection. The solubilities of DAF and DAAF are increased with the increasing of temperature in all solvents studied. The enthalpy of solution in each solvent was calculated according to van't Hoff Equation.     

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.