水＋3-甲基吡啶＋溴化钠三元溶液动-静态光散射临界行为研究

对水＋3-甲基吡啶＋溴化钠三元电解质溶液的临界跨接行为的认识存在着争议. 部分研究认为由于三甲基吡啶的聚集, 体系存在从非经典的3D-Ising(三维伊辛)行为向经典的平均场行为的非单调跨接; 另一部分研究发现该体系符合3D-Ising临界行为, 并不存在跨接. 采用动-静态光散射研究了溴化钠, 3-甲基吡啶和水三元溶液的临界性质, 得到动态关联长度和静态关联长度, 发现动态关联长度和静态关联长度一致, 且在实验温度范围内(离临界温度0.01～25 K), 体系不违背3D-Ising行为, 也观测不到显著的临界跨接现象.     

水＋乙醇＋碳酸钾三元溶液的跨接临界行为

水＋乙醇＋碳酸钾三元体系在DCP (double critical point)和CDP (critical double point)附近, 存在两个高临界点和一个低临界点. 改变该三元系中醇与水的比例可使DCP和CDP消失, 体系在相当大的温度范围内仅存在一个高临界点,从而使共存曲线的跨接临界行为的研究更简单和直接. 报道了水＋乙醇＋碳酸钾三元体系在醇与水的质量比例分别为0.3699和0.5042时, 温度向单一的高临界点逼近过程中共存曲线从平均场行为到3D Ising行为的跨接, 发现跨接属于非单调的类型, 此结果符合Sengers等的理论.     

2,6-二甲基哌啶+水体系临界性质的氘代同位素影响

用等体积法分别确定2,6-二甲基哌啶+水和2,6-二甲基哌啶+重水体系的临界组成, 并测定各自的临界温度. 采用折射率法在较宽温度范围内测定两个体系的温度-折射率(T-n)共存曲线, 利用标φ曲线法将其转化为温度-摩尔分数(T-x)和温度-体积分数(T-φ)共存曲线, 求得临界指数β、指前因子B、Wegner校正项因子B1及与共存曲线直径ρd相关的参数. 研究结果表明, 氘代后, 体系低临界温度下降了约3.2 K, 临界组成和共存曲线形状不变, 在近临界点临界指数β仍符合三维伊辛模型(3D-Ising)的理论值(0.327).     

DMA+AOT+正辛烷三组分非水微乳体系的临界现象

采用折射率法在离临界温度7 K的范围内测定N,N-二甲基乙酰胺(DMA)与二-(2-乙基己基)琥珀酸酯磺酸钠(AOT)摩尔比为3.46的非水微乳体系(DMA+AOT+正辛烷)的温度-折射率(T-n)共存曲线, 利用标准曲线转化为温度-体积分数(T-φ)共存曲线和温度-有效体积分数(T-ψ)共存曲线, 进而求得临界指数β. 研究结果表明, 该体系的临界指数β与已经报道的微乳液不同, 在较宽的温度范围内均符合Fisher重整化理论值0.365. 分析实验数据, 获得指数因子B、Wegner校正项因子B1和共存曲线的直径籽d, 并讨论所选择的序参量的优劣性.     

苯-水-乙醇三元溶液体系的临界行为

通过等体积滴定法测定了苯-水-乙醇三元部分互溶溶液体系的会溶点曲线；测定了29.00±0.05 ℃时,等溶点附近的等温共存曲线；拟合得到苯-水-乙醇体系序参量临界指数β= 0.38 ± 0.04,序参量临界指前因子K= 1.3 ± 0.2. 说明三元部分互溶溶液体系在等温会溶点附近有非经典临界溶液理论行为, 符合Fisher重正化模型.     

聚阳离子三甲基烯丙基氯化铵-丙烯酰胺共聚物的溶液性质研究

按实用要求对不同阳离子度及分子量的三甲基烯丙基氯化铵 丙烯酰胺共聚物Ｐ（ＴＭ ｃｏ ＡＡＭ）分别在水、水 甲醇、水 乙酸，不同浓度的ＮａＣｌ、ＫＣｌ、ＫＢｒ及Ｎａ２ＳＯ４水溶液中的溶液粘度行为进行了探讨，考察了低阳离子度的Ｐ（ＴＭ ｃｏ ＡＡＭ）的聚电解质行为及其大分子链在溶液中的分子链运动形态．     

水-环己烷-二乙二醇丁醚三元体系的三液相相平衡

用改进的相体积法测定了水-环己烷-二乙二醇丁醚三元体系的相平衡, 给出了不同温度下平衡共存三液相的体积分数及平衡共存三液相的相密度的共存曲线. 实验结果表明, 在平衡共存三液相中, 水、环己烷和二乙二醇丁醚的体积分数随温度改变的变化曲线分别是倒“S”型, 正“S”型, “结”型; 将共存三液相的体积分数转化为对应的相密度后, 相密度随温度改变的变化曲线也是规整的倒“S”型; 而且, 3条“S”曲线形状均表现出不对称的特性. 因此, 密度也可以用作描述体系的相平衡, 而且在描述体系临界标度率时, 密度可能是一个很好的序参量.     

葡萄糖和水混合溶液多组分电解质热力学II. HCl-NaCl-d-Glucose-H2O体系(5-45 ℃)

The thermodynamic properties of HCl-NaCl-d-Glueose-H_2O system was studied by emf measurement without liquid junction. Pt, H_2(1.013×10~5 Pa)|Hel(m), d-Glucose(x), H_2O(1-x)| Agel-Ag (A) Pt, H_2(1.013×10~5Pa)|HCl(m_A), NaCl(m_B), d-Glucose(x), H_2O(1-x)|AgCl-Ag (B) at the mass percentage of d-Glucose x=5%, 15% and 20% in the mixed solution, from 5 to 45 ℃, for cell (B) at constant total ionic strength I=1.00 mol·kg~(-1). The standard electrode potential of Ag-AgCI in the mixed solution have been determined from cell (A). The activity coefficients of HCl, γ_A, in the mixed solution system have been determined from cell (B). The results show that the activity coefficients of HCl in HCl-NaCl solutions still obeye Harned Rule. The standard transfer Gibbs free energies of HCl have calculated. The primary, secondary and total medium effect of HCl have been calculated.     

水+甲烷系统的气液相边界曲线和临界曲线

采用带有蓝宝石视窗和磁力搅拌的可变体积高压斧得出了水+甲烷系统的气液相边界曲线和临界曲线. 实验温度为433.0-633.0 K, 实验压力为30.00-300.00 MPa. 实验确定了甲烷在富水区的亨利系数, 结果显示, 在433.0-603.0 K的温度范围内, 此亨利系数随着温度的升高而下降. 本文还研究了甲烷+水系统的气液分配比以及偏摩尔溶解焓和偏摩尔溶解熵数据. 结果发现, 甲烷和水的内聚能密度差别很大.     

丙酮-水混合溶剂中3-甲基吡啶的电氧化

在以质子交换膜为隔膜的电解槽内, 通过3-甲基吡啶在PbO2电极上的电氧化研究, 发现在丙酮-水混合溶剂中, 与纯水作溶剂相比, 不仅在相同阳极电位下电流密度大幅度上升, 3-甲基吡啶电氧化生成烟酸的选择性和电流效率也明显提高. 通过循环伏安、极化曲线和恒电位电解实验, 研究了在丙酮-水混合溶剂中3-甲基吡啶的电氧化条件, 并比较了不同条件下的选择性和电流效率.     

The measurements of coexistence curves and light scattering for {xC6H5CN + (1 − x)CH3(CH2)6CH3} in the critical region

The coexistence curves and light scattering data for a critical solution of (benzonitrile + octane) have been reported. The critical exponents relating to the difference in the density variables between two coexisting phases β, the osmotic compressibility γ, and the correlation length ν have been deduced and the values are consistent with the 3D-Ising value in the range close to the critical point. The experimental results of the coexistence curves have also been analyzed to examine the Wegner correction terms and the behavior of the diameter of the coexistence curves. The light scattering data are well described by the crossover model proposed by Anisimov and Sengers, and show a monotonic crossover of the critical exponents γ and ν from its 3D-Ising value to the mean-field value as the temperature departures from the critical point. Furthermore, the dependences of the critical amplitudes on the mass of n-alkane for the binary solutions of (benzonitrile + n-alkane) have been discussed.     

水＋甲酰胺＋环己烷＋二乙二醇丁醚拟三元系的三临界现象

用改进的体积法研究了拟三元体系水＋甲酰胺＋环己烷＋二乙二醇丁醚的三临界现象. 以水+甲酰胺作为拟“纯组分”，通过控制甲酰胺在拟“纯组分”中的质量分数w，逐渐向三临界点逼近，当w从0增加到0.206时，三相区范围ΔT从1.500 ℃减小到0.228 ℃. 由实验数据得到体系的临界质量分数w=0.286±0.003，临界温度为（54.8±0.7） ℃. 实验发现平均温度下三相区三角形的水-油边与三角坐标中的水-油边几乎平行，而且三相区三角形水-油边的边长及其对应的高与ΔT的指数关系符合三临界的经典理论.     

The Viscosity Properties of Sodium Silicate Solutions

Using a NDJ-1 rotational viscometer and an AR500 rheometer, both static and dynamic viscosities of sodium silicate solutions were measured with changes of concentration, temperature, modulus (molar ratio of SiO₂ to Na₂O), shear rate and chemical additives. Static results show that viscosity increases monotonously with concentration varying from 15 to 55%, decreases with temperature rising from 15 to 70 °C, and has a minimum value at a modulus of about 1.8. Measured data can be fitted quantitatively either by the Krieger-Dougherty expression or the Arrhenius equation with good agreement. This fact suggests that the sodium silicate solutions exhibit the properties of a suspension, in which the silicate anions, mainly constructed of Q ¹ and Q ² groups, act as a binder; the colloidal particles mainly constructed of Q ³ and Q ⁴ groups and small cations, act as effective rigid particles. Dynamic results show a shear thickening property in the high shear-rate regime, and a Newtonian property in the low shear-rate regime.     

Physical Properties of the Ternary Mixture Ethanol+Water+1-Butyl-3-Methylimidazolium Chloride at 298.15 K

In this work densities, refractive indices, speeds of sound and isentropic compressibilities of the ternary mixture ethanol+water+1-butyl-3-methylimidazolium chloride ([C₄mim][Cl]), and of the binary subsystems containing the ionic liquid, have been measured at 298.15 K and atmospheric pressure.     

Constant-Volume Heat Capacity of H2O + Na2CO3 Solutions Near the Critical Point of Pure Water

The results of new isochoric heat capacity measurements of H₂O + Na₂CO₃ solutions as a function of temperature along several isochores in the near-critical region of pure water are reported. The measurements cover temperatures from 331 to 661 K at Na₂CO₃ mole fraction 0.008869. The experiments were performed at seven densities between 245 and 875 kg-m^–3. The measurements were made in a high-temperature, high-pressure, adiabatic, and nearly constant-volume calorimeter. Uncertainties of the isochoric heat capacity measurements are estimated to be 1–2% in the liquid phase, 2–3% in the vapor phase, and 4–5% near the critical point. Measurements were made in the two-phase (vapor–liquid, liquid–solid, vapor–solid) and three-phase (vapor–liquid–solid) regions. Two peaks in isochoric heat capacity have been found near the critical point of pure water. One of the peaks at T _S1 occurs on the three-phase (L–V–S) curve and another peak at T _S2 corresponds to a two-phase (L–S or V–S) curve. The experimental values of phase transition temperatures T _S() on each isochore was determined. Uncertainty in the phase transition temperature measured was no greater than ±0.03 to 0.05 K.