硫酸铜与氨水反应实验研究及教学应用

对人教版选择性必修二《物质结构与性质》中的“实验3-3”进行研究,就如何发挥实验教学的功能价值进行了探索。首先,开发硫酸铜与氨水的系列实验,通过几组实验现象的对比,结合理论分析,得出了硫酸四氨合铜晶体的制备条件,增进了学生对实验现象背后的原理的理解;其次,结合不同学段相关内容的学习,将该实验设置为符合学情的任务活动,并将该实验探究过程命制为探究试题,发挥该实验素材在知识的学习、巩固、检验等多方面的作用。

2，3，4，5—四氟苯胺的制备

2，3，4，5—四氟苯胺是一种重要精细化工中间体，广泛应用于医药、农药，和感光材料。目前的合成工艺中存在着较多缺点，现介绍以N—苯基四氟邻苯二甲酰亚胺为原料经酸式水解、甲苯脱水、氨水反应、降解反应及脱羧得产品，收率为43％。

Preparation and characteristic research of anhydrous magnesium chloride with dehydrated ammonium carnallite

Taking the saline lake bischofite and NH4Cl that was removed with the ammonia method and continuously followed by filtration as raw materials with a molar ratio of 1∶1 of MgCl2 to NH4Cl, ammonium carnallite was synthesized. And then the ammonium carnallite was dehydrated to some extent at 160℃ for 4 h. Ammonium carnallite reacted with ammonia at 240℃ for 150 min and the ammonation ammonium carnallite was produced. Finally, the ammonation ammonium carnallite was calcined at 750℃ into anhydrous magnesium chloride containing only 0.1%（mass fraction） of MgO. On the other hand, dehydrated ammonium carnallite was mixed with the solid ammonium chloride at mass ratio 1∶4 at high temperature and with the differential pressure of NH3 above 30.5kPa. The dehydrated ammonium carnallite of mixture was dehydrated at 410℃, and then calcined at 700℃ into anhydrous magnesium chloride with only 0.087%（mass fraction） of MgO. X-ray diffraction and electron microscopy analysis results prove that anhydrous magnesium chloride obtained by both methods hasn’t mixed phases, the particle is large and even has good dispersion, which is suitable for preparation of metal magnesium in the electrolysis.

Hydrolysis Activities of the Particle of Agarose-Ce^(4+) Complex for Compounds Containing Phosphodiester or Peptide Bonds

Hydrolysis activities of PACC (particle of agarose-Ce4+ complex, newly made through double emulsification) forcompounds containing phosphodiester or peptide bonds were studied. The results showed that PACC could hydrolyzeorganophosphorous pesticides not only in water but also in vegetable juice or tea extract. Hydrolysis rates of methamidophos,omethoate and chlorpyrifos in water are 32.39%, 27.12% and 46.62% respectively, those of chlorpyrifos and methami-dophos in mung sprout juice 38.28% and 35.45% respectively, and that of chlorpyrifos in tea extract 59.76%. Hydrolysisrates of BSA (bovine serum albumin) in water and protein in tea extract by PACC increase by 54.30% and 86.46% respec-tively as compared with the control.

Dissolution kinetics of malachite in ammonia/ammonium sulphate solution

The dissolution kinetics of malachite was investigated in ammonia/ammonium sulphate solution. The effects of ammonia and ammonium sulphate concentration, pH, leaching time, reaction temperature, and particle size were determined. The results show that the optimum leaching conditions for malachite ore with a copper extraction more than 96.8% are ammonia/ammonium concentration 3.0 mol/L NHaOH ＋ 1.5 mol/L （NH4）2SO4, liquid-to-solid ratio 25：1 mL/g, leaching time 120 min, stirring speed 500 r/rain, reaction temperature 25 ℃ and particle size finer than 0.045 mm. The dissolution process of malachite with an activation energy of 26.75 k J/tool is controlled by the interface transfer and diffusion across the product layer. A semi-empirical rate equation is obtained to describe the leaching process and the reaction orders with respect to concentration of ammonia and ammonium sulphate are 2.983 0 and 0.941 1, respectively.

Deactivation Behavior of Hollow Titanium Silicalite Zeolite in Aqueous Ammonia Solution under Simulated Industrial Cyclohexanone Ammoximation Conditions

For simulating the real deactivation of hollow titanium silicalite(HTS) zeolite in commercial ammoximation process, HTS was treated by 10% NH_3·H_2O solution at 120 ℃ in stirred autoclave. It is found that a part of HTS zeolite crystals dissolved in the hot NH_3·H_2O solution, and the specific surface area and pore volume continuously decreased with the increase in NH_3 hydrothermal treatment time. Meanwhile, the transformation of framework Ti species into extraframework Ti species was detected by the spectroscopic methods. However, the extraframework Ti species were still in a highly dispersed state after the hydrothermal and thermal treatments as shown by TEM images, while the formation of new acid sites was not detected. Upon combining the results of characterization with catalytic performance of HTS, the main deactivation reason for this material had been determined, which might be attributed to the reduction of specific surface area and active centers after basic treatment and calcination of HTS samples. And then the possible mechanism of simulated deactivation of HTS zeolite was proposed, which could describe the elemental reaction steps much more visually and directly.

Synthesis of Waterborne Polyurethane Modified by Nano-SiO_2 Silicone and Properties of the WPU Coated RDX

A series of nano silica/silicone modified waterborne polyurethane(WPU) have been synthesized from polytetramethylene glycol and isophorone diisocyanate, dihydroxymethyl propionic acid and triethylamine, ethylenediamine, trimethylolpropane, nano-SiO2 and the silane coupling agent KH550. The effect of the dosage of nano-SiO2 on the WPU-Si membrane and the coated RDX(cyclotrimethylenetrinitramine) particles have been studied in terms of their surface properties, mechanical properties, and thermal stability. The results showed that with the increase of Si content, the stability of the emulsion reduced gradually. The material with more Si content displayed an increased thermodynamic stability, an increased high temperature resistance, an increased tensile strength and a decreased elongation at break. With the increase of Si content, the surface tension of the material decreased, the bibulous rate reduced, and the contact angle increased gradually, so that the surface tension of the polyurethane and RDX are close to each other which could improve the performance of coating.

Theoretical Study of Electron Transferin Bimolecular System of NH_3 and H_2O

Mulliken, NPA, MK and CHelpG population analyses have been accomplished at the level of MP2/6-31G（d,p） for the title system. The variations of four kinds of charges on NH3 with intermolecular distance infer that electron transfers from NH3 to H2O. MK and CHelpG population analyses indicate more electron transfer than Mulliken and NPA ones. The atomic charges resulted from MK and CHelpG schemes infer that electron transfers from N in NH3 to H in H2O, which confirms that this bimolecular complex possesses linear structure as H3N…HOH.

Study on the Hydrolysis and Ammonolysis Kinetics of a Monochlorotriazinyl Reactive Dye

To understand the reaction behaviour of the reactive dye with amino groups on protein fibres,the reaction kinetics of competitive hydrolysis and ammonolysis of a monochlorotriazina reactive dye were studied at 50-80℃ and pH=8-10 by high performance liquid chromatography(HPLC).The results showed the pseudo-first-order phenomenon for the general reaction of concurrent hydrolysis and ammonolysis of the dyes.The ammonolysis reaction was always faster than the hydrolysis reaction in the range of temperature and pH employed,but the preference for ammonolysis to hydrolysis reaction decreased with the increase of temperature and pH value.The ratios of ammonolysis/hydrolysis rate constant reduced from 17.6 to 5.4 when the temperature increased from 50 to 80℃ in pH=10,and from 7.2 to 5.4 when the pH value increased from 8 to 10 at 80℃.

Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in supercritical ammonia

Hexamethylenediamine(HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol(HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al_2O_3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al_2O_3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature,time, H_2 and NH_3 pressure were examined, and the reaction processes were discussed in detail.