马丁—侯状态方程向固相发展

ＭＨ－８１状态方程式经过进一步改进后，其使用范围可扩展到固相。在该方程中增加了三个常数，Ａ６、Ｂ７和ｂｓ后变为：Ｐ＝ＲＴ／Ｖ－ｂ＋Ａ２＋Ｂ２Ｔ＋Ｃ２ｅ－５．４７５Ｔ／Ｔｃ／（Ｖ－ｂ）＾２＋Ａ３＋Ｂ３Ｔ＋Ｃ３ｅ－５．４７５Ｔ／Ｔｃ／（Ｖ－ｂ）＾３＋Ａ４＋Ｂ４Ｔ／（Ｖ－ｂ）＾４＋Ｂ５Ｔ／（Ｖ－ｂ）＾５＋Ａ６／（Ｖ－ｂｓ）＾６＋Ｂ７Ｔ／（Ｖ－ｂ）＾７改进后的状态方程对于一般物质，如二氧化碳、氩、甲烷及氮     

8─羟基喹啉─5─磺酸柱前衍生反相HPLC分离测定痕量Al（Ⅲ）、Co（Ⅲ）、Fe（Ⅲ）和Pd（Ⅱ）

本文采用８－羟基喹啉－５－磺酸（ＨＱＳ）为柱前衍生试剂，用含有１０ｍｍｏｌ·Ｌ－１的四丁基溴化铵（ＴＢＡ＋Ｂｒ－）、７．５×１０－５ｍｏｌ·Ｌ－１的ＥＤＴＡ和２０ｍｍｏｌ·Ｌ－１的ｐＨ５．６乙酸－乙酸钠缓冲溶液的甲醇－水（４５：５５，Ｖ／Ｖ）溶液为流动相，以Ｃ１８硅烷化载体为固定相，１６ｍｉｎ内分离测定了Ｃｏ（Ⅲ）、Ｆｅ（Ⅲ）、Ａｌ（Ⅲ）和Ｐｄ（Ⅱ）的ＨＱＳ的配合物、信噪比为３时，检出限分别为：Ｃｏ（Ⅲ）０．９ｐｐｂ、Ｆｅ（Ⅲ）１．５ｐｐｂ和Ｐｄ（Ⅱ）５．４ｐｐｂ，方法灵敏度高，干扰少，用于测定试剂级盐酸，硝酸和中国红茶样品中的这些离子，结果良好。     

高效液膜分离富集镍基合金镀层中稀土总量

用ＴＢＰ－ＴＴＡ（协同流动载体）、ＳＰＡＮ８０和煤油高效液膜体系，研究∑ＲＥ＾３＋迁移行为。在适宜条件下，１０ｍｉｎ内，∑ＲＥ＾３＋的迁移率达９９．５％以上。在同样条件下，常见共存金属离子如Ｆｅ＾３＋、Ａｌ＾３＋、Ｎｉ＾２＋、Ｃｒ＾３＋、Ｍｏ＾６＋、Ｃｕ＾２＋、Ｃｏ＾２＋、Ｚｎ＾２＋、Ｃｄ＾２＋等均不被迁移；大量碱金属、碱土金属、Ｃｌ、ＮＯ３、ＣｌＯ４、Ｆ、ＳｉＯ３＾２－、ＳＯ４＾２－等离子也不影     

无机盐对染料与非离子表面活性剂相互作用的影响

用光度法研究了对非离子表面活性剂ＴＸ－１００有盐溶、盐析作用的两种无机电解质（Ｎａ_２ ＳＯ_４和ＫＳＣＮ）对离子染料（漂蓝６Ｂ）与ＴＸ－１００相互作用的影响,得到了３种体系的相互作用常数 Ｋ及临界胶团浓度 ＣＭＣ。对于 ＥＣＡＢ＋ ＴＸ－ １００, ＥＣＡＢ＋ ＴＸ－ １００＋ Ｎａ_２ ＳＯ_４和 ＥＣＡＮ＋ ＴＸ－ １００＋ ＫＳＣＮ ３种体系,其 Ｋ值分别为 ２５５０, ７５３２和２４００ｄｍ_３· ｍｏｌ~（－１）; ＣＭＣ值分别为 ２． ５ × １０~（－４）,１．８７×１０~（－４）和１．８３×１０~（－４）ｍｏｌ·ｄｍ~（－３）。对所得结果作了合理解释。     

磷酸三丁酯为载体的乳状液膜体系迁移钇(Ⅲ)的研究

用磷酸三丁酯（ＴＢＰ）－ＬＭＳ－２－磺化煤油乳状液膜体系研究了Ｙ（Ⅲ）的迁移行为。当膜相体积分数为５．０％ＴＢＰ和２．０％ＬＭＳ－２,内相为０．０１ｍｏｌ／ＬＮａＨＣＯ３,外相含６ｍｏｌ／ＬＮＨ４ＮＯ３,酸度为ｐＨ＝３时,Ｙ（Ⅲ）能快速并完全迁移。常见过渡元素离子如Ｆｅ２＋,Ｃｏ２＋,Ｎｉ２＋,Ｍｎ２＋,Ｚｎ２＋等均不迁移,故可以从这些离子的混合液中分离Ｙ（Ⅲ）,回收率可达９８％以上。     

不同引发速率下的苯乙烯乳液聚合

研究了在引发速率相差千倍的情况下，胶乳粒子的成核机理，胶乳粒子和自由基的静电相互作用对乳液聚合动力学以及胶乳粒子的成核和成长的影响。当反应温度为６０℃，引发剂为过硫酸钾／［ＶＯ（Ｈ２Ｏ）５］＾２＋（ＶＯ＾２＋）或叔丁基过氧化氢（ｔ－ＢＨＰ）／ＶＯ＾２＋时，引发速率由精确计量泵的注入量来控制，其最低和最高值分别为５．３×１０＾－７ｍｏｌ／（ｄｍ＾３·ｍｉｎ）和４．６×１０＾－４ｍｏｌ／（ｄｍ＾３·ｍ     

Pd~(2+)-I~--TBAB三元缔合物萃取光度法测定钯含量

介绍了Ｐｄ２＋－Ｉ－－ＴＢＡＢ（四丁基溴化铵）三元缔合物萃取光度法测定钯的方法。该方法以Ｌ（＋）抗坏血酸作为掩蔽剂，干扰离子Ｃｕ２＋，Ｆｅ３＋的允许量均为２．５μｇ／ｍＬ，Ｐｄ２＋浓度为０～４μｇ／ｍＬ，完全符合比耳定律（萃取剂作参比），方法的相关摩尔吸光系数ε为２．０９×１０４Ｌ／（ｍｏｌ·ｃｍ），桑德尔灵敏度Ｓ为５．０７×１０－３μｇ／ｃｍ２。工作曲线的应用范围为１～４μｇ／ｍＬ。     

2-乙酰基-7-甲胺基酮与TMB等取代芳香醛的反应

本文探讨了２－乙酰基－７－甲胺基卓酮与３，４，５－三甲氧基苯甲醛（ＴＭＢ）等取代芳香醛的羟醛缩合反应。２－乙酰基－７－甲胺基卓酮与ＴＭＢ、丁香醛、二溴醛等取代芳香醛进行反应分别生成了２－（３，４，５－三甲氧基）肉桂酰基－７－甲胺基卓酮；２－（４－羟基－３，５－二甲氧基）肉桂酰基－７－甲胺基卓酮；２－（４－羟基－３，５－二溴）肉桂酰基－７－甲胺基卓酮等三种尚未见文献报道的新化合物。它们的结构经红外光谱、核磁共振谱及元素分析得以证实。     

新型阻燃剂TBT的合成

研究了新型阻燃剂５，６，７，８－四溴－１，２，３，４－四氢化萘（ＴＢＴ）的合成方法，并对工艺条件进行了研究。总收率可达５０．３％。     

可溶金属盐离子提取茶多酚的最佳工艺与参数研究

研究了Ｃａ￣（２＋）、Ｍｇ￣（２＋）、Ｂａ￣（２＋）、Ｆｅ￣（３＋）、Ｚｎ￣（２＋）、Ａｌ￣（３＋）６种离子提取茶多酚（ＴｅａＰｏｌｙｐｈｅｎｏｌｓ，ＴＰ）的条件，确定了最佳工艺和参数。采用最佳工艺提取ＴＰ，提取率可达１０．５％，纯度＞９９．５％。     

EXTENSION OF MARTIN-HOU EQUATION OF STATE INTO LIQUID REGION

The range of application of the equation of state proposed by Martin and Hou for gases was extendedinto liquid region.The improvement was achieved by retaining the constant,B_,in the original equation,namelyP=(RT)/(V-b)+(A_2+B_2T+C_2e~(-5.475))T_r+(A_3+B_3T+C_3e~(-5·475))T_r+(A_4+B_4T)/(V-b)~4+(B_5T/(V-B)~5)and imposing the condition,PdV=P_0(V_v-V_l),on the equation.The constant,B_4,was then evaluatedfor a given compound.The calculated values of the saturated liquid molar volumes for carbon dioxide,normal butane,argon,methane and nitrogen,were compared with the data reported,in the reduced temperature rangefrom about 0.65 to 1.0.The average deviation was less than 5% in each case,without loss of accuracyin gaseous region.Furthermore,no additional data were required for evaluation of the constants of theimproved equation.     

新铃兰醛饱和蒸汽压测定和关联

采用静态法,利用Rose釜测定了新铃兰醛在391.85~416.35K范围的饱和蒸汽压,并用Antoine方程lnP=A-B/(T+C)进行关联,确定了蒸汽压方程的三个参数A=10.701,B=558.048,C=-296.730。新铃兰醛饱和蒸汽压测定值与上述Antoine方程关联值吻合较好,相对误差均在1%以内。所得饱和蒸汽压方程对新铃兰醛精馏分离设计和操作具有重要意义。     

发展马丁-侯方程作为水的专用方程

发展了适用于极性物质水的MH方程。由线性最小二乘法拟合单相区和汽液共存区的PVT及相平衡数据 ,得到方程常数 ,并用统计方法检验了方程的有效性。计算结果表明 ,饱和蒸汽压和摩尔体积误差一般小于0 .6。单相区体积和压力平均误差分别为 0 .3 %和 2 .5 %。与Bender方程相比 ,新方程准确度更高     

甲基烯丙醇饱和蒸汽压的测定与关联

采用静态法测定了甲基烯丙醇在335.05~388.29 K温度区间的饱和蒸汽压数据,并用Antoine方程lnps=AB/(T+C)进行了关联,获得Antoine常数A、B、C分别为15.0499、3020.65和-98.10。Antoine方程计算得到的饱和蒸汽压值与实验数据吻合较好,平均相对误差为0.86%。通过Clausius-Clapeyron方程计算得到甲基烯丙醇在335.05~388.29 K范围内的平均摩尔蒸发热为46.47 kJ·mol-1。实验所得饱和蒸汽压方程对甲基烯丙醇的精馏分离过程设计具有重要意义。     

Measurement and correlation of solubility of disperse anthraquinone and azo dyes in supercritical carbon dioxide

The solubility of three disperse anthraquinone dyes and two azo dyes in supercritical CO₂ was measured. The tested dyes are Celliton fast blue B, l-amino-2-methylanthraquinone, 1-methylaminoanthraquinone, disperse Red 1 and 4-[4-(phynylazo)phenylazo]-o-cresol. Solubility measurements were made at 313.15-393.15 K and 10-25 MPa in a high-temperature autoclave phase equilibrium apparatus. Pure physical properties of the dyes such as critical constants, molar volumes and vapor pressures were estimated based on semi-empirical methods. Also, the data were quantitatively modeled by both an empirical density correlation and a quantitative equation of state recently proposed by the present authors based on nonrandom lattice theory. We found that anthraquinone disperse dyes in general show higher solubility than azo disperse dyes in supercritical CO₂ within the experimental ranges.     

尿素生产中高温高压条件下NH_3-CO_2-H_2O-NH_2CONH_2体系的汽液平衡研究

提出了一个适用于尿素合成条件下(T=438.15～478.15K,P=6.87～24.5MPa,NH_3/CO_2=2.6～5.0,H_2O/CO_2=0.2～1.2)NH_3-CO_2-H_2O-NH_2CONH_2体系的热力学模型,该模型用PHS状态方程和Wilson方程来分别修正气液两相的非理想行为,用本模型可对尿素合成体系进行有效的汽液平衡计算.     

碳酸二甲酯相关二元体系粘度和密度的测定及关联

在常压下采用U形振动管密度计测定了碳酸二甲酯-甲醇的混合液在293．15～323．15K和碳酸二甲酯-氯苯的混和液在293．15～343．15K下的密度;用乌氏粘度计测定了这两个混合溶液在相应温度下的粘度,并由密度数据计算出超额体积V^E、由粘度数据计算出了不同温度和组成下的混合粘度的变化Δη,前者V^E、Δη均为负值。后者V^E为正值,Δη基本聚集在0附近。对不同温度下的超额体积、混合粘度变化与组成的关系按Redlich-Kister方程进行了关联,最大标准偏差小于5％;说明这两体系适合采用此方程回归。     

变阱宽方阱链流体状态方程模拟制冷剂的汽液平衡

应用作者先前基于二阶微扰理论和PY2近似积分方程建立的可变阱宽方阱链流体状态方程模拟了纯制冷剂及其混合体系的汽液平衡。通过关联不同温度下制冷剂的饱和蒸气压和液体体积得到了18种纯制冷剂的分子参数,新方程计算的饱和蒸气压和液体体积总的平均偏差分别为1.11％和0.92％。结合简单混合规则,将此方程扩展到混合体系。研究发现,建立的方程可满意预测制冷剂二元混合体系除临界区附近外的汽液平衡,对两个三元体系汽液平衡的预测也取得了满意的效果,当引入一个与温度无关的可调参数时,关联精度大为提高,预示着新的方程可模拟制冷剂的汽液平衡。     

Ternary phase diagrams and solvate transformation thermodynamics of omeprazole sodium in different solvent mixtures

Omeprazole sodium(OMS), a typical non-hydrogen bond donors API, is only available in solvates so far, including monohydrate, ethanol solvate and methanol solvate. The methanol solvate was found for the first time. Solvate transformation thermodynamics of OMS was studied in this paper. First, the ternary phase diagrams forming two solvates for OMS in binary solvent mixtures including methanol + water, ethanol + water, and methanol+ ethanol were measured at temperature ranging of T =(278.15 to 313.15) K under atmospheric pressure. Further, the standard equilibrium constants of the solvate transformation reactions were evaluated according to the chemical reaction isothermal equation. The standard molar Gibbs free energy, the standard molar enthalpy, and the standard molar entropy of solvate transformation reactions were then calculated based on van't Hoff equation. Moreover, the thermodynamic stability of the OMS solvate was analyzed based on phase diagram. The results are of great importance to develop a crystallization process for manufacturing OMS solvate, and could be helpful to other solvate transformation research.     

A generalized vapor pressure equation for hydrocarbons

A reduced vapor pressure relationship of the following form has been developed: The optimum value of n was established to be 8.00 from vapor pressure data for n-heptane. A method was developed for the determination of the constants A, B, C and D from one reliable vapor pressure point. By this procedure vapor pressures were calculated for 33 hydrocarbons, including saturated and unsaturated paraffins, naphthenes, and aromatics, and were compared with corresponding experimental values. For these substances the overall average deviation between calculated and actual vapor pressure was 0.38% (1879 points). This relationship was also applied to seven additional hydrocarbons not included in its development, and for these substances the resulting average deviation was 0.36% (99 points).