氯化钙－正丙醇－水溶液稀释热

使用ＬＫＢ－２１０７型流动式微量热计测量了２８８．１５Ｋ，２９８．１５Ｋ和３０８．１５Ｋ下ＣａＣｌ_２－ｎ－Ｃ_３Ｈ_７ＯＨ－Ｈ_２Ｏ溶液的稀释热。混合溶剂中正丙醇摩尔分数Ｘα：０．００，０．１３，０．２５，０．５０，０．７５，０．８７和１．００。测量结果用扩展的Ｄｅｂｙｅ－Ｈｕｃｋｅｌ方程关联，计算了不同溶剂组成下溶液无限稀释热△Ｈ_Ｄ（ｍ＝０．５，Ｘα）。结果表明：Ｘα相同时，－△Ｈ_Ｄ随温度增加而增加；温度相同时，随Ｘα变化，当Ｘα≈０．８７时，－△Ｈ_Ｄ具最大值。     

氯化锂-乙醇-水溶液稀释热

使用 Ｌ Ｋ Ｂ ２１０７ 型流动式微量热计微机数据采集系统测量了 ２８８．１５ Ｋ、２９８．１５ Ｋ 和 ３０８１５ Ｋ 下 Ｌｉ Ｃｌ Ｃ２ Ｈ５ Ｏ Ｈ Ｈ２ Ｏ 体系在不同混合溶剂浓度下的稀释热。测量结果用扩展的 Ｄｅｂｙｅ Ｈüｃｋｅｌ方程、 Ｐｉｔｚｅｒ 模型和单参数模型关联。计算了方程的参数和溶液无限稀释热（ｍ Ｌｉ Ｃｌ＝ １．０ ｍ ｏｌ／ｋｇ 溶剂）－ Δ Ｈ Ｄ∞ 。结果表明：相同混合溶剂浓度下,－ Δ Ｈ Ｄ ∞ 随温度增加而增加;同一温度下,－ Δ Ｈ Ｄ∞ 与溶剂浓度有关,在 ｘ２ ＝ ０．８５ 左右,－ Δ Ｈ Ｄ∞ 具有最大值。     

竹红菌素在DMF－H_2O混合体系中的电化学研究

本文研究了竹红菌素ＨＡ，ＨＢ以及１３－ＳＯ_３Ｎａ－ＤＤＨＡ在ＤＭＦ－Ｈ_２Ｏ（体积分数＝１）混合体系中的电化学氧化还原性质。结果表明，它们都为两步单电子还原过程，反应机理为：油溶性．水溶性１３－ＳＯ３Ｎａ－ＤＤＨＡ：（第一步）（质子化）；（第二步）．并且，ＨＡ，ＨＢ的单电子还原半醒自由基非常稳定，而１３－ＳＯ_３Ｎａ－ＤＤＨＡ单电子还原半醌自由基存在歧化反应，其速率常数ｋ_ｆ＝０．４０８。     

丙醇－水／氯化钙体系汽液平衡测定和关联

利用改进的Ｏｔｈｍｅｒ釜测量了０．１０１３ＭＰａ下的ｎ－ＰｒＯＨ－Ｈ２Ｏ／ＣａＣｌ２和ｉ－ＰｒＯＨ－Ｈ２Ｏ／ＯａＣｌ２体系恒定盐摩尔分率下ＶＬＥ数据。测定结果用优先溶剂化法、Ｆｕｒｌｅｒ方程及本文提出的Ｆｕｒｌｅｒ方程改进式进行了关联。其中Ｆｕｒｌｅｒ方程改进式关联结果较好，汽相组成平均偏差为０．０１２。     

竹红菌甲素衍生物13－SO_3Na－DDHA电化学及光诱导还原的研究

本工作研究了化合物１３－ＳＯ＿３Ｎａ－ＤＤＨＡ在不同ｐＨ的缓冲溶液中的电化学氧化还原行为．实验证明：化合物中羰基的还原电位与ｐＨ之间存在线性关系，其直线的斜率为６０ｍＶ／ｐＨ．并证明了此过程为一步两电子、两质子还原过程：Ｑ＋２Ｈ￣＋＋２ｅ＝ＱＨ＿２．ＤＭＦ作为非质子溶剂，具有很好的稳定自由基的作用．向缓冲溶液中加入ＤＭＦ后，化合物１３－ＳＯ＿３Ｎａ－ＤＤＨＡ为两步单电子还原过程，相应溶液中的光诱导电子转移吸收光谱证实了以上电化学的结果．     

竹红菌甲素衍生物13—SO3Na—DDHA电化学及光诱导还原的研究

本工作研究了化合物１３－ＳＯ３Ｎａ－ＤＤＨＡ在不同ｐＨ的缓冲溶液中的电化学氧化还原行为。实验证明：化合物中羰基的还原电位与ｐＨ之间存在线性关系，其直线的斜率为６０ｍＶ／ｐＨ。并证明了此过程为一步两电子、两质子还原过程：Ｑ＋２Ｈ＾＋＋２ｅ＝ＱＨ２．ＤＭＦ作为非质子溶剂，具有很好的稳定自由基的作用。向缓冲溶液中加入ＤＭＦ后，化合物１３－ＳＯ３Ｎａ－ＤＤＨＡ为两步单电子还原过程，相应溶液中的光诱导电子转     

竹红菌素在DMF—H2O混合体系中的电化学研究

本文研究了竹红菌素ＨＡ，ＨＢ以及１３－ＳＯ３Ｎａ－ＤＤＨＡ在ＤＭＦ－Ｈ２Ｏ（体积分数ψ＝１）混合体系中的电化学氧化还原性质，结果表明，它们都为两步单电子还原过程，反应机理为：油 ＨＡ，ＨＢ：ＨＡ（ＨＢ）＋ｅ＋Ｈ＾＋－ＨＡ（ＨＢＨ）＋ｅ－ＨＡＨ，水溶性１３－ＳＯ３Ｎａ－ＤＤＨＡ：（第一步）１３－ＳＯ３Ｎａ－ＤＤＨＡ＋ｅ－１３－ＳＯ３ＮａＤＤＨＡ，（质子化）１３－ＳＯ３Ｎａ－ＤＤＨＡ＋Ｈ＾＋－１３－Ｓ     

酸化破乳—Fenton试剂氧化—混凝沉淀处理电子感光废水的研究

用酸化破乳－Ｈ２Ｏ２／ Ｆｅ２＋氧化－混凝沉淀处理印刷线路板感光乳化废水。讨论了 ｐＨ值、Ｈ２Ｏ２的浓度、Ｆｅ２浓度对ＣＯＤ去除的影响。结果表明,酸化破乳、Ｆｅｎｔｏｎ试剂氧化的ｐＨ值控制在３～４,混凝沉淀ｐＨ值控制在９～１０,Ｈ２Ｏ２浓度为０．０６ｍｇ·Ｌ－１,Ｆｅ２＋浓度为０．８ｍｇ·Ｌ－１,反应温度为１４０℃左右时,ＣＯＤ总去除率达９３．６％,具有良好的应用前景。     

异丁烯两段催化氧化制甲基丙烯酸催化剂的研究 Ⅱ．甲基丙烯醛气相氧化制甲基丙烯酸的杂多酸盐催化剂的研究

本文报道用于甲基丙烯醛（ＭＡＬ）选择氧化制甲基丙烯酸（ＭＡＡ）的ＰＭｏＶ杂多酸盐催化剂的研究结果。ＩＲ和ＸＲＤ考察结果表明，本文所研究的催化剂均具有稳定的Ｋｅｇｇｉｎ结构，催化剂物相组成为Ｈ（４－２ｙ－２）ＰＯ４（ＭｏＯ３）（１２－ｘ）（ＶＯ３）ｘＣＵｙＣｓｚ。在３００℃，原料气组成ＭＡＬ：Ｈ２Ｏ：Ｏ２：Ｎ２＝１：１０：３：３２．体积空速１２００ｈ（－１）的条件下，最佳催化剂的ＭＡＬ转化率为９４．１％，ＭＡＡ选择性达８８．７％。     

端羟基丁腈橡胶的合成

在１０Ｌ和５０Ｌ不锈钢聚合釜中，以合成端羟基丁腈橡胶（ＨＴＢＮ）为目的，用Ｈ２Ｏ２作引发剂、乙醇作溶剂，研究了本二烯（Ｂｄ）和丙烯腈（ＡＮ）的溶液共聚合。结果表明，在ＡＮ／Ｂｄ为１０／９０，１５／８５，２０／８０，Ｈ２Ｏ２用量为４．０／８．０ｇ，乙醇用量为７０－８０克，１１０－１２０℃和１２０－１５０ｍｉｎ的聚合条件下，可以得到Ｍ。为２３００－４２００、羟值（ＫＯＨ）为４０．０－８０．０ｍｇ／ｇ、     

Densities of soybean oil/solvent mixtures

Density data for soybean oil/acetone and soybean oil/n-hexane mixtures were measured at 20, 30 and 40 C using a PAAR DMA digital readout calculating precision density meter over the complete range of concentrations. When plotted as molar volume versus molar concentration the mixtures exhibited near ideal linear behavior. To check whether other oil/solvent mixtures behaved in a similar way, data from published literature were replotted in this form and the near ideal linear behavior was observed. Using the data at 20 C, the excess volumes V^E were calculated, from which partial molar volumes for each component were obtained. These showed only slight variation over the composition range, confirming the near ideal behavior of these systems. Therefore, if densities of pure oil and solvent are known, their mixture density can be calculated by linear interpolation with sufficient accuracy for engineering design calculations.     

超临界CO2-共溶剂二元体系溶质的偏摩尔体积及分子间的相互作用

在313.5～323.5 K、7～14 MPa范围内测定了CO₂及CO₂-甲醇、CO₂-乙醇、CO₂-正丁醛、CO₂-异丁醛二元混合流体的表观密度,讨论了压力、第2组分的种类和加入量对CO₂表观密度的影响,在此基础上计算了溶质的偏摩尔体积,讨论了温度、压力和第2组分的性质对溶质偏摩尔体积的影响规律.实验发现：CO₂-共溶剂二元体系在临界点附近溶质的偏摩尔体积出现较大的负值,反映了CO₂与共溶剂之间存在较强的相互作用,使CO₂分子发生聚集现象;CO₂分子聚集程度与共溶剂分子大小及空间结构有关,分子越大或越规则,CO₂分子聚集程度越强.     

Measurement of the PVTx properties of n-heptane in supercritical water

By means of a constant-volume piezometer, measurements have been made of the PVTx properties of water-n-heptane mixtures at supercritical conditions. The measurements cover the temperature range from 573 to 673 K and pressures from 2 to 30 MPa. Values of excess, partial, and apparent molar volumes were obtained from these measurements. Tests on the piezometer and consistency tests on the measurements suggest that the results are free from significant ‘dead volume’ error. The PVT data for the pure components (water and n-heptane) obtained using the piezometer are in excellent agreement with results obtained by other investigators. The overall accuracy of the pressure, density, temperature, and mole fraction are ± 0.15%, ± 0.5%, ± 10 mK and ± 0.002, respectively.Analysis of the results for dilute water-n-heptane mixtures show that the partial molar volume of n-heptane (solute) and the excess molar volume of the mixture near the critical point of pure water (solvent) exhibit remarkable anomalies. Our results contribute to the formulation of supercritical solubility in near-critical fluids.     

Thermodynamic parameters of viscous flow for electrolytic solutions in N,N dimethylformamide—water mixtures

Transition-state treatment has been used for calculation of the contributions per mole of the solute to the free energy of activation for viscous flow of lithium chloride, lithium nitrate and lithium, sodium and potasium perchlorates solutions in dimethylformamide—water mixtures. The values obtained increase with increasing dimethylformamide content in the solvent, except in the case of perchlorates, where a minimum in a water-rich region is observed. This behaviour is interpreted in view of the changes in solvation and molar volumes at infinite dilution of the ions in the different solvent mixtures. Finally, from the free energy-values at different temperatures, the estimated enthalpy and entropy of activation of viscous flow are analysed.     

Mixed-surfactant system of dodecylbenzene sulfonate and alpha-olefin sulfonate: Micellar and volumetric studies

Critical micelle concentrations of sodium salts of dodecylbenzene sulfonate, alpha-olefin (C₁₆) sulfonate, and their mixtures have been evaluated by measuring the surface tensions of solutions at 298.15 K. Interaction parameters for mixed monolayer formation (β^σ) and mixed-micelle formation (β^M) have been calculated from the critical micelle concentration data. Densities of solutions of surfactants and their mixtures were measured with a vibrating-tube densimeter at 298.15 K. Apparent and partial molar volumes have been evaluated from solution density data. Results of the micellar properties have been eplained on the basis of a nonideal multicomponent mixed-micelle model. The mixed-surfactant system exhibits synergism in all aspects when the mole fraction of alpha-olefin sulfonate in the mixture is 0.2. Volumetric properties correlate well, as the partial molar volumes also show a minimum at the same composition of the mixture. Formation of a compact mixed micelle at this composition has been envisaged.     

Implication of solvent structure in the interaction of poly (vinylalcohol) and short chain monohydric alcohols

Viscosity and density data have been obtained for aqueous solutions of a monodisperse sample of 90% hydrolysed poly (vinylalcohol) PvOH and for solutions of PvOH in short chain alcohol/water mixtures. The results are interpreted in terms of a ‘dynamic’ flowing volume and a ‘static’ partial molar volume for the macromolecule. Changes in the size of the dynamic and static volumes of the polymer in alcohol/water solvent mixtures are shown to correlate closely with reported changes in the degree of solvent structure. A tentative explanation of the role of solvent structure in the solution behaviour of the polymer is proposed.     

The influence of solvent type on the viscosity of concentrated polymer solutions

The viscosity of concentrated (17.5 g/dl) solutions of cellulose acetate in 11 single solvents and in four binary solvent mixtures was related to a thermodynamic measure of solvent power. In single solvents, the specific viscosity varied from 4600 in dimethyl sulfoxide to 78,000 in diacetone alcohol, with the specific viscosity increasing with decreasing abolute value of the partial molar free energy of dilution. This behavior can be accounted for by the hypothesis that the number of chain entanglements increases with decreasing solvent power. In solvent mixtures, the specific viscosity often attains a minimum value at a composition where the average solubility parameter locus is near the center of the solubility region of the polymer.     

Molecular Clustering in Supercritical Solutions

Abstract

Molecular explanations have recently identified massive solvent clusters surrounding the dissolved solute as the causative agent of the striking solvent properties of supercritical fluids. Such clusters were first inferred from the large negative values of the solute partial molar volume near the solvent critical point; these clusters were estimated to contain about 100 solvent molecules per solute molecule in excess of the bulk average. Subsequent evidence from visible and ultraviolet absorption and fluorescence spectroscopy and from chemical reaction studies have provided qualitative support for the notion of solvent-solute clusters. Other spcctroscopic evidence suggests the formation of solute-solute aggregates, as well, near the solvent critical point. Such structures on a molecular level are describable in terms of the molecular distribution functions. We present results on the size and radial profile of solvent-solute clusters and on solute-solute aggregation for systems representative of typical dilute, attractive, supercritical solutions calculated from integral equation theories. The microstructure of theoretically-predicted dilute, repulsive, supercritical solutions exhibits a deficit of solvent molecules surrounding the solute. Solute partial molar volume and chemical potential are predicted to increase dramatically in such repulsive mixtures as density is increased toward the critical point at slightly supercritical temperatures.     

转移催化法合成苯甲酸苄酯的研究

主要研究了由苯甲酸钠和氯化苄通过相转移催化法合成苯甲酸苄酯,考察了几种季铵盐类相转移催化剂的亲核取代反应性能。实验表明：季铵盐类相转移催化剂四丁基碘化铵（（C4H9）4NI）对合成苯甲酸苄酯反应的催化性能较好,在原料配比（苯甲酸钠：氯化苄）为1：1．3,反应温度110℃,反应时间2.5-3.0h,催化剂用量为苯甲酸钠的6％,体系pH值为5-6时,苯甲酸苄酯的产率超过了90％。     

氰酸钠法合成磺酰脲类除草剂苄嘧磺隆

研究了以邻甲酸甲酯苄基磺酰氯、2-氨基-4,6-二甲氧基嘧啶和氰酸钠为原料,乙腈为溶剂,在吡啶催化下合成除草剂苄嘧磺隆的新方法。考察了溶剂种类、催化剂用量、氰酸钠用量、反应时间、反应温度等因素对反应的影响。结果表明:邻甲氧羰基苄基磺酰氯、2-氨基-4,6-二甲氧基嘧啶、吡啶和氰酸钠摩尔比为1∶1∶1∶1.2,乙腈为溶剂,在40°C下搅拌反应3 h,产品收率67.8%,纯度97.0%(HPLC)。该方法避免了剧毒光气,简化了工艺路线,是一个对环境友好的磺酰脲除草剂的合成方法。