推算渗透系数及离子平均活度系数的新型半经验方程

提出了一新的推算二元电解质水溶液渗透系数及平均活度系数的热力学模型．该模型不仅考虑到离子间的长程静电作用和近程范德华作用，还考虑到近程有序的溶剂化作用．所提出的计算二元电解质水溶液渗透系数的半经验方程为三参数方程式，计算离子平均活度系数γ±的半经验方程为四参数方程．用该方程关联２９８．１５Ｋ的二元电解质水溶液的实验数据精度高于同类型的其它方程式．     

用渗透系数推算单电解质二元无机水溶液的方法

本文提出了一种推算单电解质二元无机水溶液(火用)值的方法。其中,根据Pitzer普遍方程所得到的渗透系数公式和Gibbs—Duhem方程,推算出二元无机水溶液的化学值计算式,利用该计算式推导出NaCl、NH_4Cl和NaNo_3三种无机水溶液的化学与浓度的关系式,可方便地计算出不同浓度及溶液的化学,进而计算溶液     

碳酸二甲酯—苯二元系在293K～323K温度范围的密度和过剩摩尔体积

用比重天平测定了碳酸二甲酯—苯二元系在293.15 K,298.15 K,303.15 K,308.15 K,313.15 K,318.15 K,323.15 K下的密度值,求得过剩摩尔体积V_m~E。每一温度下V_m~E都是正值,且随温度升高V_m~E值逐渐减小。实验数据用Redlich-Kister方程关联,用线性回归方法求得参数。     

液相活度系数关联式的参数温度依赖关系

在文[1]中提出了一个新的液相活度系数关联式,并用该式子关联了二元体系的等温汽液平衡数据。本文对关联式的两个参数α和β及对温度的依赖关系作了探讨,用这个参数温度关系对12套等压汽液平衡数据进行了关联,并和Wilson方程,NRTL方程,UNIQHAC方程进行了比较,用这组参数-温度关系,对同一个二元体系在不同条件下进行互相推算,计算了九组不同的二元体系。从推算结果来看,该方程略优于Wilson方程。     

新的电解质混合溶剂体系的Gibbs过量自由能模型

提出一个新的电解质混合溶剂体系的Gibbs过量自由能模型，该模型由三项组成：Debye-Hueckel项、溶剂－溶剂相互作用项和溶剂化作用项，其表达形式简洁、满足热力学一致性，仅从298.15K下关联的二元参数就可以预测单一电解质混合溶剂体系的热力学性质，用以熔融盐为标准态扩展到混合溶剂体系的Debye-Hueckel项，能正确地预测此类体系的盐析效应。     

磷酸水溶液的相互作用参数值的求取

本文用 Pitzer 电解质溶液理沦关联了25℃时磷酸水溶液在0.1～19.0mol/1000gH_2O浓度范围内的渗透系数,得出了适用于较高浓度磷酸水溶液的相互作用参数值。     

低温下磷酸的密度和黏度的测定及其关联

分别采用液体比重天平和乌氏黏度计测定了在248.15～298.15 K下及质量分数为0.70～0.85时的磷酸密度和黏度.将测定的磷酸密度和黏度分别与温度和质量分数关联得到相应的关联式.在测定范围内,用相应的关联式计算磷酸水溶液的密度,与测定值相比,最大正相对偏差0.21%,最大负相对偏差-0.23%,平均相对离差0.068%;用相应的关联式计算磷酸水溶液的黏度,与测定值相比,最大正相对偏差3.0%,最大负相对偏差-5.0%,平均相对离差绝对值1.83%.     

甲醇-四氟丙醇汽液相平衡研究

利用汽液相平衡仪测定了甲醇-四氟丙醇二元体系在常压下的汽液平衡数据,并采用Herington半经验法对所得数据进行了热力学一致性检验,采用Wilson模型和NRTL模型进行了关联计算。研究结果表明:试验测定的甲醇-四氟丙醇体系汽液相平衡数据符合热力学一致性要求;经关联计算,得到甲醇-四氟丙醇二元体系在Wilson模型中的交互作用能量参数(λ12-λ11)/R为-223.99 K,(λ21-λ22)/R为174.12 K;该体系在NRTL模型中的交互作用能量参数(g12-g11)/R为478.41 K,(g21-g22)/R为-624.15 K。     

离子液体BMIBF4水溶液体积性质的研究

在283.15-318.15 K范围内,测定了离子液体四氟硼酸-1-甲基-3-丁基咪唑（BMIBF4）水溶液的密度,计算了其表观摩尔体积^φVB,讨论Pitzer-Simonson方程在278.15～338.15 K温度范围内对离子液体水溶液的适用性,以纯离子液体为参考态,根据实验数据拟合得到了相关的P-S方程体积参数,从拟合偏差得出P-S方程在较稀的BMIBF4离子液体水溶液中偏差较大的结论。     

298K时KCl—K2CO3—K2B4O7—H2O相平衡及平衡液相物化性质的研究

采用等温溶解平衡法研究了298 K时KCl-K2CO3-K2B4O7-H2O体系的相平衡及平衡液相物化性质(密度、粘度、折光率、电导率、pH),该体系298 K等温溶解度图有3个相区KCl,K2CO33/2H2O,K2B4O7*4H2O,1个共饱点,3条单变量曲线,该体系属简单四元体系.由渗透系数及三元体系溶解度数据拟合了有关K2B4O7的Pitzer方程参数,并运用Pitzer方程对该四元体系溶解度进行理论计算,计算值与实验值基本吻合.     

Universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong electrolyte aqueous solution and its application in the NaCl-KCl-H2O system

A universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong electrolyte aqueous solution has been developed based on the ion and molecule coexistence theory, and verified in the NaCl-KCl-H₂O ternary system at 298.15 K. To compare the difference of the thermodynamic model in binary and ternary strong electrolyte aqueous solutions, the mass action concentrations of components in the NaCl-H₂O binary strong electrolyte aqueous solution were also computed at 298.15K. A transformation coefficient was required to compare the calculated mass action concentration and reported activity because they were obtained at different standard states and concentration units. The results show that the transformation coefficients between calculated mass action concentrations and reported activities of the same components change in a very narrow range. The calculated mass action concentrations of components in the NaCl-H₂O and NaCl-KCl-H₂O systems are in good agreement with the reported activities. This indicates that the developed thermodynamic model can reflect the structural characteristics of solutions, and the mass action concentration also strictly follows the mass action law.     

Universal thermodynamic model of calculating the mass action concentrations of omponents in a ternary strong electrolyte aqueous solution and its application in the NaCl-KCl-H_2O system

A universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong elec-trolyte aqueous solution has been developed based on the ion and molecule coexistence theory,and verified in the NaCl-KCl-H2O ternary system at 298.15 K. To compare the difference of the thermodynamic model in binary and ternary strong electrolyte aqueous solutions,the mass action concentrations of components in the NaCl-H2O binary strong electrolyte aqueous solution were also com-puted at 29...     

Universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong electrolyte aqueous solution and its application in the NaCl-KCI-H2O system

A universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong elec-trolyte aqueous solution has been developed based on the ion and molecule coexistence theory, and verified in the NaCl-KCl-H2Oternary system at 298.15 K, To compare the difference of the thermodynamic model in binary and ternary strong electrolyte aqueous solutions, the mass action concentrations of components in the NaCI-H20 binary strong electrolyte aqueous solution were also com-puted at 298.15K. A transformation coefficient was required to compare the calculated mass action concentration and reported activ-ity because they were obtained at different standard states and concentration units. The results show that the transformation coeffi-cients between calculated mass action concentrations and reported activities of the same components change in a very narrow range.The calculated mass action concentrations of components in the NaCl-H2O and NaCl-KCl-H2O systems are in good agreement with the reported activities. This indicates that the developed thermodynamic model can reflect the structural characteristics of solutions,and the mass action concentration also strictly follows the mass action law.     

Calculating models of mass action concentrations for NaBr（aq）, LiNO3（aq）, HNO3（aq）, and KF（aq） binary solutions

The calculating models of mass action concentrations for electrolyte aqueous solutions NaBr-H2O, LiNO3-H2O, HNO3-H2O, and KF-H2O have been developed at 298.15 K and their molalities ranging from 0.1 mol/kg to saturation according to the ion and molecule coexistence theory as well as mass action law. The calculated mass action concentration is based on pure species as the standard state and the mole fraction as the concentration unit, and the reported activities are usually based on infinite dilution as the standard state and molality as the concentration unit. Hence, the calculated mass action concentration must be transformed to the same standard state and concentration unit. The transformation coefficients between calculated mass action concentrations and reported ac- tivities of the same component fluctuate in a very narrow range. Thus, the transformed mass action concentrations not only agree well with reported activities, but also strictly obey mass action law. The calculated results show that the new developed models can embody the intrinsic structure of investigated four electrolyte aqueous solutions. The results also indicate that mass action law has its wide- spread applicability to electrolyte binary aqueous solutions.     

氨基酸氟硼酸离子液体摩尔溶解焓的研究

以甘氨酸(Gly)、丙氨酸(Ala)和氟硼酸为原料,采用一步法合成了2种氨基酸氟硼酸离子液体,并在298.15K下利用恒温溶解热测定系统对合成的氨基酸阳离子型离子液体进行摩尔溶解热的研究。首先对不同浓度的离子液体稀水溶液进行溶解焓的测定,然后借助Pitzer电解质溶液理论计算得到各化合物的标准摩尔溶解焓及相应的Pitzer焓参数,估算了离子液体的水化焓,并且将不同类型离子液体的结果进行了比较。估算出的甘氨酸阳离子的水化焓小于咪唑类阳离子,而甘氨酸阴离子的水化焓也小于氟硼酸阴离子。     

二元非理想溶液过量体积的测定与研究

采用改进的倾斜式稀释膨胀溶液在298.15K 测定液体苯(1)——环已烷(2)的过量体积,并与文献值比较证明倾斜式稀释膨胀计测得数据可靠。又对未见报导的二甲苯(1)——环已烷(2)溶液在299.15K、288.15K 测定不同浓度下的摩尔过量体积数值,并用 Redich—Kister 方程对全浓度范围内的摩尔过量体积进行关联计算,从而为溶液热力学提供有价值的热力学数据。     

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO_4-H_2O and NaF-H_2O binary solutions and NaClO_4-NaF-H_2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that tran...     

碱金属卤化物的热力学性质的研究

本文用国产RD496—L型微热量热计测定了25℃时NaCl,KCl,RbCl,csCl系列在水中的溶解热,用Nriss—Cobble方法外推得到四种的标准溶解热,并与文献值进行了比较。对这四种盐在水溶液中的热力学行为进行了简单的计论。     

替硝唑在水溶液中溶解度的实验测定及关联

通过自制的固-液平衡装置,采用高效液相色谱法分别测定了温度在278．15～318．15K时替硝唑在纯水、5％葡萄糖溶液和0．9％氯化钠溶液中的溶解度,并对实验数据分别采用理想溶液模型和经验方程进行了关联．对于纯水体系和0．9％氯化钠溶液体系,实验数据用理想溶液模型关联能较满意地表征实验结果．两种关联方法中,经验方程能较好地关联所测得的溶解度数据,误差较小．