273.15K时LiCl-Li2SO4-H2O体系热力学性质的等压研究

0℃下用改进的等压设备和改进的实验方法测定了纯水溶液(LiCl 0.5～9.2mol·kg-1,Li2SO40.3～2.5mol·kg-1)以及混合水溶液(离子强度0.5～9.5mol·kg-1)的水活度和渗透系数.该体系的等水活度线与Zdanovskii规则非理想混合溶液表达式的标准偏差为0.0088,当Li2SO4溶液达到饱和后,用Zdanovskii规则扩展式计算,标准偏差为0.0027.根据Pitzer离子相互作用模型对实验数据进行了理论分析,用本文和不同来源的文献数据拟合求取了0℃下该体系的Pitzer纯盐参数和混合参数,计算值与实验值相吻合.     

NaOH-NaAl(OH)4-H2O溶液体系渗透系数的测定及离子作用模型

用等压法测定了在303.15 K时总碱质量摩尔浓度mNaOH(T)从0.61 mol/kg到5.72 mol/kg, 苛性比αK从1.98到7.04的NaOH-NaAl(OH)4-H2O溶液体系的等压平衡浓度和渗透系数, 并得到该溶液体系的水活度. 用Pitzer模型对实验结果进行了参数化研究, 拟合求得了离子相互作用参数. 用Pitzer模型计算的渗透系数值与实验结果一致. 用获得的参数计算了NaOH和NaAl(OH)4在NaOH-NaAl(OH)4-H2O溶液体系中的活度系数, 其值随总碱质量摩尔浓度的增加呈增加的趋势.     

钨酸钠水溶液的活度系数和渗透系数

在周期表第ⅥB族元素Cr、Mo、W六价含氧离子钠盐化合物中,钨酸盐及其在水溶液中的热力学性质是知道得最少的.钨酸钠在水溶液中的活度系数和渗透系数虽然有报道,但由于测量方法不同,给出的结果彼此相差较大.结合着无机盐水溶液热力学性质的研究,我们对钨酸钠在水溶液中的活度系数用等压法进行了测量,浓度范围从0.3到2.5mol·kg~(-1).     

在电解质溶液中测定非电解质溶解度的新方法

提出了一种可以同时测定电解质溶液中非电解质的溶解度和饱和溶液水活度的新方法。该法把等压平衡与传统化学分析统一起来,其优点是：（1）将多元饱和溶液中非电解质溶解度的测定转变为共存离子的溶度测定,避开了对非电解质难于进行精确化学分析的难题;（2）可以同时确定所测饱和体系的水活度。用该法测定了NaCl和KCl溶液中甘露醇的溶解度并与文献值进行了比较,结果表明二者符合得很好。     

LiCl-Li2B4O7-H2O体系在298.15 K下热力学性质的等压研究

用等压法研究了298.15 K下LiCl-Li2B4O7-H2O体系在不同LiB4O7质量摩尔浓度时的等压平衡浓度,  水活度; 计算了LiCl和Li2B4O7混合盐溶液的渗透系数等热力学性质. 用298.15 K下的实验数据对Pitzer离子相互作用模型进行了参数化研究, 拟合求取了298.15 K下Pitzer离子相互作用参数, 用获得的参数计算了LiCl和Li2B4O7在LiCl-Li2B4O7-H2O体系中的活度系数. Pitzer模型计算的渗透系数值与实验结果一致.     

多元系相界上的活度——一种活度计算的递推公式

据等温等压多相平衡Gibbs能最小原理并应用Lagrange未定乘数法导出多元系组元化学位和平衡成分关系式。由此给出三元系两相共存区边界上由一已知组元活度计算它组元活度的解析递推式。该结果被推广到K元K-1相平衡共存区相界。计算结果与实验值符合得较好。     

用于非水介质分析的新型离子选择电极: 水膜电极的设想及验证

本文首次提出了一种新型离子选择电极—水膜电极, 采用水溶液作为液膜, 可分析有机溶液中的组分. 这种电极用于非水介质中的分析 , 有其独特的优点, 可直接测量非水溶液中某种离子的平衡活度(或浓度), 对理论研究有较大的意义. 本文提出的水膜电极能应用于不与水相混溶的低介电常数有机溶剂, 扩展了离子选择电极在非水介质中的研究与应用.     

甲醇-苯混合溶剂中NaI活度系数的测定与计算

测定了甲醇-苯-NaI体系在恒压条件下的汽液平衡数据,采用双标准检验法对数据进行检验,检验结果全部合格.应用P itzer强电解质在水溶液中的活度系数模型,采用全部合格的汽液平衡数据拟合出方程中的维利系数,从而获得在双液比固定条件下盐在甲醇-苯混合溶剂中的活度系数.计算结果表明,正常泡点温度下在具有固定双液比的甲醇-苯混合溶剂中,NaI的平均活度系数随盐浓度的增加先减小,经过一个极小值后又增加.     

亚慢性硝酸钐暴露对小鼠血常规指标的动态影响

探讨亚慢性硝酸钐暴露对小鼠血常规指标的动态影响。ICR小鼠80只,雌雄各半,随机分成5组,分别自由饮用含硝酸钐0,5,50,500,2000 mg.L-1的水溶液90 d,在染毒后30,60,90 d分别测定血常规。雄鼠各处理组在硝酸钐暴露30,60 d后,雌鼠硝酸钐暴露60 d后WBC比对照组显著或极显著升高(P<0.05,P<0.01),但硝酸钐暴露90 d后却显著或极显著下降(P<0.05,P<0.01)。在硝酸钐暴露30,60 d后,Gr#,Ly#,MO#比对照组显著或极显著增加(P<0.05(P<0.01),但暴露90 d后无差异显著性。雌性各染毒组的RBC在硝酸钐暴露30 d显著或极显著升高(P<0.05,P<0.01),雄性2000 mg.L-1组却在硝酸钐暴露60 d后RBC显著下降(P<0.05),而硝酸钐暴露90 d对雌雄各组RBC均无影响。雌雄鼠在硝酸钐暴露30,60 d后的HGB,HCT与对照组相比分别显著或极显著升高(P<0.05,P<0.01),但暴露90 d后各组之间的HGB无显著差异,而雌鼠50,500 mg.L-1组的HCT与对照相比显著升高(P<0.05)。亚慢性硝酸钐暴露可导致小鼠血常规部分指标的改变,且与钐暴露的时间、浓度及性别相关。     

二元表面活性剂水溶液表面张力及其表面过剩量摩尔分数的推算

对于水溶液中表面活性剂分子在表面相达到吸附平衡时,Rosen^[1]等人导出了如下相平衡计算方程式中α:活度,上标:s:表面相、b:体相,bo:参考态.α_i^bo:单一的i组分水溶液在其表面张力与系统表面张力相等时的体相活度.在Rosen等人的工作中对表面相的处理采用单参数的Margules活度系数关联式,对每一个实验点都求出一个参数β值,所得β值并不是一个常数。     

Osmotic coefficients of aqueous sodium carbonate solutions at 25°C

Isopiestic vapor pressure measurements are reported for aqueous sodium carbonate solutions at 25°C using sodium chloride as reference electrolyte. Osmotic and activity coefficients are calculated from the concentrations of the solutions in isopiestic equilibrium. The results are used to calculate the trace activity coefficients of carbonate ion in sodium chloride solutions; these should approximate the trace activity coefficient of carbonate ion in seawater. The solubility of sodium carbonate in water at 25°C has been determined.     

Isopiestic Study of Water + Mannitol(sat) + Sodium Chloride + Ammonium Chloride + Barium Chloride at <Emphasis Type="Italic">T</Emphasis> = 298.15 K and Comparison with the Ideal-Like Solution Model

Isopiestic measurements have been carried out at the temperature 298.15 K for the quinary system (water + mannitol(sat) + sodium chloride + ammonium chloride + barium chloride) saturated with mannitol and its ternary sub-systems (water + mannitol(sat) + sodium chloride), (water + mannitol(sat) + ammonium chloride) and (water + mannitol(sat) + barium chloride). Taking aqueous sodium chloride as reference solutions, osmotic coefficients of the other aqueous solutions were determined. The experimental results show that the isopiestic activities of the quinary system in relation to its ternary sub-systems are in excellent agreement with the ideal-like solution model.     

H2O+KCl(饱和)+NaCl+NH4Cl的等压研究

Isopiestic measurements have been carried out at 298.15 K for the quaternary aqueous solution H2O+KCl(sat)+NaCl+NH4Cl saturated with potassium chloride and its ternary sub systems H2O+KCl (sat)+NaCl and H2O+KCl(sat)+NH4Cl. Taking sodium chloride (aq) or calcium chloride (aq) as reference solutions, osm otic coefficients and water activities of the aqueous solution were determined. The experiment results show that the isopiestic actions of the quaternary system related to its ternary sub-systems are in excellent agreement with the ideal like solution model.     

Isopiestic Determination of Osmotic and Activity Coefficients for Solutions of LiCl, LiBr, and LiNO3 in 2-Propanol at 25°C

The osmotic coefficients of lithium chloride, lithium bromide, and lithium nitrate in 2-propanol have been measured by the isopiestic method at 25^°C. Sodium iodide was used as the isopiestic standard. The molality ranges covered were from 0.2 to 1.5 for LiCl and LiBr, and to 1.9 mol-kg^-1 for LiNO₃. The system of equations developed by Clegg–Pitzer and Pitzer were used to fit each set of osmotic coefficients. The experimental osmotic coefficient data are successfully correlated with these models. The parameters from the fit were used to calculate the mean molal activity coefficients.     

Isopiestic determination of osmotic coefficients and evaluation of vapor pressures for solutions of calcium chloride and calcium nitrate in methanol at 298.15 K

The osmotic coefficients of calcium chloride and calcium nitrate in methanol have been measured by the isopiestic method at the temperature 298.15 K. Sodium iodide served as isopiestic standard for the calculation of osmotic coefficients. The Pitzer model and the self-consistent local composition (SCLC) model developed by Ananth and Ramachandran was used to fit each set of osmotic coefficients. The parameters from the fit were used to calculate the vapor pressures. The osmotic coefficient data are successfully correlated with these models, which provide reliable predictions of vapor pressures.     

Osmotic and activity coefficients of ammonium thiocyanate in aqueous solution at 25°C

Osmotic and activity coefficients of ammonium thiocyanate in aqueous solution at 25°C have been determined by the isopiestic vapor pressure method. The activity coefficients do not agree with values reported previously but are consistent with trends shown by activity coefficients of ammonium chloride and bromide.     

Analysis of variance in determinations of equivalence volume and of the ionic product of water in potentiometric titrations

Homogeneous sets of data from strong acid-strong base potentiometric titrations in aqueous solution at various constant ionic strengths have been analysed by statistical criteria. The aim is to see whether the error distribution matches that for the equilibrium constants determined by competitive potentiometric methods using the glass electrode. The titration curve can be defined when the estimated equivalence volume VEM, with standard deviation (s.d.) sigma (VEM), the standard potential E(0), with s.d. sigma(E(0)), and the operational ionic product of water K(*)(w) (or E(*)(w) in mV), with s.d. sigma(K(*)(w)) [or sigma(E(*)(w))] are known. A special computer program, BEATRIX, has been written which optimizes the values of VEM, E(0) and K(*)(w) by linearization of the titration curve as a Gran plot. Analysis of variance applied to a set of 11 titrations in 1.0M sodium chloride medium at 298 K has demonstrated that the values of VEM belong to a normal population of points corresponding to individual potential/volume data-pairs (E(i); v(i)) of any titration, whereas the values of pK(*)(w) (or of E(*)(w)) belong to a normal population with members corresponding to individual titrations, which is also the case for the equilibrium constants. The intertitration variation is attributable to the electrochemical component of the system and appears as signal noise distributed over the titrations. The correction for junction-potentials, introduced in a further stage of the program by optimization in a Nernst equation, increases the noise, i.e., sigma(pK(*)(w)). This correction should therefore be avoided whenever it causes an increase of sigma(pK(*)(w)). The influence of the ionic medium has been examined by processing data from acid-base titrations in 0.1M potassium chloride and 0.5M potassium nitrate media. The titrations in potassium chloride medium showed the same behaviour as those in sodium chloride medium, but with an s.d. for pK(*)(w) that was smaller and close to the expected instrumental noise, whereas the titrations in nitrate medium had a high noise level and even the determination of VEM was less certain. Procedures are also proposed for obtaining reference sets of data and checking the conformity of the solutions and apparatus to the chosen reference.     

Isopiestic determination of osmotic coefficients and evaluation of vapor pressures for electrolyte solutions of some lithium salts in ethanol

The osmotic coefficients of lithium chloride, lithium bromide and lithium nitrate in ethanol have been measured by the isopiestic method at the temperature 298 K. Sodium iodide served as isopiestic standard for the calculation of osmotic coefficients. The molality range covered in this study correspond to about 0.1–2 mol kg⁻¹. The system of equations developed by Chen, Haghtalab–Vera and Pitzer were used to fit each set of osmotic coefficients. The parameters from the fit were used to calculate the vapor pressures. The osmotic coefficient data are successfully correlated with these models, and the models provide reliable predictions of vapor pressures.     

Thermodynamic Properties of Aqueous Sodium Sulfate Solutions at 40°C

We report osmotic and activity coefficients of aqueous sodium sulfate solutions. The osmotic coefficients were determined at 40°C by the isopiestic method. Sodium chloride served as the isopiestic standard. The molality ranges covered in this study correspond to about 0.2–3.0. The activity coefficients were calculated from the parameters obtained by fitting the Hamer–Wu and Pitzer equations to the experimental osmotic coefficients.