电感耦合等离子体原子发射光谱法测定化学合成反应液中铑含量

为了更加快速准确的测定化学合成反应液中铑含量,建立微波消解前处理与电感耦合等离子体原子发射光谱的组合监测方法。采用硝酸-硫酸混合酸体系对样品进行微波消解前处理,将有机铑络合物体系转化为无机酸体系。在相同的条件下分别选用铑元素233.477 nm、249.077 nm、343.489 nm三个波长进行样品的测定,铑元素的质量浓度在(0~1.0)mg·L^(-1)线性良好,线性相关系数r≥0.9997,方法检出限分别为0.01 mg·L^(-1)、0.03 mg·L^(-1)、0.10 mg·L^(-1)。波长343.489 nm具有更好的灵敏度,更适合铑元素的检测,样品回收率98.0%~102.5%,相对误差为2.8%~3.4%,相对标准偏差为0.2%~1.1%。该方法是在密闭空间进行样品前处理,避免了元素的损失,操作简便,耗时短,精密度高,适用于化学合成反应液中铑含量检测。

Reaction kinetics for synthesis of sec-butyl alcohol catalyzed by acid-functionalized ionic liquid

The acid-functionalized ionic liquid([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance(NMR) and Fourier transform infrared spectroscopy(FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a homogeneous kinetic model was established. The results show that the reaction heat ΔH is 10.94 × 103J·mol-1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea-are 60.38 × 103 and 49.44 × 103J·mol-1,respectively.

SYNTHESIS OF FUNCTIONAL MACROMOLECULE INTERMEDIATE THROUGH COUPLING REACTION CATALYZED BY [bmim]Cl/FeCl_3 IONIC LIQUID

To obtain new functional aromatic polymer materiul. 3,3＇-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid （[bmim]CI/FeCl3） at mild reaction condition. Pure 3,3＇-biacenaphthene was obtained hy recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, SHNMR arid FTIR analysis. The influence of various reaction conditions on the yield of 3,3＇-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are, as following： the molar ratio of FeCl3 to [BmimlCl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperamre being 20 ℃ the reaction time being 4h and the solvent of the reaction system being PhNO2 Under those conditions, the yield of the 3.3＇-biacenaphthene will be 48.71% and selectivity, of that will be 78.56 %. Farther more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.