铜离子在合金硫化镍矿浸出过程的化学动力学

建立了在常压氧化硫酸浸出合金硫化镍矿过程中通氧反应结束后铜离子浸出镍的动力学方程,反应的表观活化能为129.88 kJ.K-1.mol-1.根据该动力学方程,可以进一步对硫酸氧化浸出合金硫化镍矿过程中镍的浸出速率进行推导.     

新催化动力学光度法(木音)花青-H2O2体系测定痕量铬(Ⅵ)

在六次甲基四铵-盐酸介质中, 痕量铬(Ⅵ)显著催化 H2O2 氧化花青褪色的指示反应, 催化反应的表观活化能为 6.84 kJ·mol-1, 建立了测定痕量铬(Ⅵ)的动力学分析法, 线性测定范围为 0～150 μg·L-1,检出限为 0.8 μg·L-1.常见离子中,除 Al3+,Cu2+,Fe3+,Fe2+ 外,其余离子不影响测定.其中 Al3+ 的干扰可用 F- 掩蔽消除, Cu2+,Fe3+,Fe2+ 的干扰可用 EDTA 掩蔽消除.本法已用于测定湖水,矿井水和电镀废水中的铬(Ⅵ).     

酸性溶液中硝基苯在WC电极上的电化学还原

以聚四氟乙烯为粘接剂制成碳化钨(WC)电极.采用循环伏安法、线性扫描法和恒电位阶跃法研究了硝基苯在酸性溶液中WC电极上的电化学行为.实验表明:WC电极对硝基苯的还原具有较好的活性,电极过程受扩散和电化学步骤混合控制;表观活化能为23.7kJ·mol 1,其中,电化学步骤的活化能10.91kJ·mol 1.     

罗丹明S-高碘酸钾体系催化光度法测定痕量铑

研究了铑(Ⅲ)催化高碘酸钾氧化罗丹明S的褪色反应,据此建立了测定微量铑的催化光度分析法,研究了该催化氧化还原褪色反应的最佳条件及动力学参数.结果表明:在以硫酸为介质及90±0.5℃的条件下,罗丹明S-高碘酸钾体系测定微量铑的方法具有较高的灵敏度,线性范围为10~140μg/LRh(Ⅲ),检出限为5.0×10-9g/mL,表观活化能为64.86 kJ/mol.方法灵敏,准确,应用于合成样品中微量铑的测定,结果令人满意.     

海沙钛铁矿在硫酸溶液中的电化学溶解研究（英文）

采用电化学技术研究了孟加拉国海沙里钛铁矿在硫酸溶液中不同温度下的溶解行为.循环伏安研究表明,在没有添加碳粉的条件下钛铁矿的溶解非常困难.为探明钛铁矿的溶解过程,考察了钛铁矿-碳比例、硫酸浓度和温度对钛铁矿电化学溶解行为的影响.结果显示,钛铁矿在低还原电位和低温下的溶解速率较慢.施加更负的还原电位和在较高的温度下溶解速率加快.增加硫酸浓度(最大浓度达到1 mol·L~(-1))也可提高溶解速率,但在较高的硫酸浓度和还原电位下,由于氢气析出导致钛铁矿的溶解速率降低且气体吸附,最后使得钛铁矿的活性表面积减小.计算得到活化能数值在高温区间为50±10 kJ·mol~(-1),而低温区间为~15±5 kJ·mol~(-1),说明低温区间为扩散控制过程,而高温区间为化学控制过程.     

铜氨配合物还原动力学研究--硫酸四氨合铜

氨(或胺)常被用作液相还原法镀铜或制备铜纳米线的还原剂,但氨(胺)对铜离子还原过程及动力学的影响缺乏系统的研究。本研究通过计时电量法测定了硫酸四氨合铜溶液中不同温度下在不同阶跃电位时Cu(NH₃)4²⁺还原为Cu的反应速率常数,进而求得标准速率常数K 0(4.12×10^-5 m·s^-1~7.33×10^-5m·s^-1)及表观活化能(23.60 kJ·mol^-1)。所得参数为研究氨(胺)对铜离子还原反应影响规律提供基础数据,并可为铜纳米线制备过程中长径比的调控提供参考。     

锗烟尘中锗浸出过程动力学研究

本文对锗烟尘中锗浸出过程的动力学和反应机制进行了研究.结果表明,锗烟尘浸出符合不生成固体产物层的"未反应核缩减型"模型,动力学方程遵从1-2a/3-(1-a)1/3=kt.锗烟尘中锗浸出的表观活化能12.603kJ/mol,这表明锗烟尘中锗的浸出过程为边界层扩散所控制.在浸出时间3小时内,锗的浸出反应为2级反应.提高酸的浓度、温度、搅拌强度均可加速锌浸出速度,提高浸出率.     

有色金属冶炼废水处理二次污泥中银的硫氰酸铵浸出动力学

以硫氰酸铵作为浸银剂,从除砷提铜后的有色金属冶炼废水处理的二次污泥中提取银,研究了银的浸出过程动力学.结果表明,硫氰酸铵浸出银的过程符合收缩核动力学模型,浸出活化能Ea为14.87kJ·mol-1,扩散系数D′为2.3×10-5exp(-1 487/RT)cm0.5·mol 0.5·s-1.根据该模型可知,硫氰酸铵浸出银的决定步骤是固体膜扩散.     

Zn(Ac)2/超高比表面积活性炭催化剂上乙炔法合成醋酸乙烯宏观动力学

在接近工业生产条件下研究了Zn(Ac)2/超高比表面积活性炭 (AＢＥＴ=2713m2/g) 催化剂上，乙炔法合成醋酸乙烯 (VAc) 反应宏观动力学，并与Zn(Ac)2/日本普通椰壳炭 (AＢＥＴ=1 384 m2/g) 催化剂进行了比较。实验结果求得两种不同比表面积载体催化剂的宏 观动力学方程分别为：υ1=28.22pＣ２Ｈ２1.00p VAc -0.62和υ2=25.03pＣ２Ｈ２1.01 p VAc -0.52，即合成 VAc的反应对乙炔是1级反应，对VAc是负的反应级数，载体的比表面积越高催化剂的 催化反应活性越高。求得在160 ℃～175 ℃两种催化剂反应的平均表观活化能分别为： 52.49 (kJ·mol-1)和53.87(kJ·mol-1)，均小于文献报道的反应真实活化能87.80(kJ·mol-1)。     

硫酸铵焙烧法从低品位菱镁矿提取镁及其反应动力学研究

将低品位菱镁矿经900 ℃煅烧3 h,产物轻烧镁粉按比例与硫酸铵均匀混合后焙烧,MgO转化为MgSO4,产生的氨气用水吸收得到氨水.焙烧产物经过水溶、过滤,得到硫酸镁溶液.采用TG-DTA和XRD技术分析了轻烧镁粉与硫酸铵的反应历程,计算了反应过程的动力学,采用正交实验确定了反应的最佳工艺条件.研究表明:轻烧镁粉与硫酸铵的焙烧反应分3个阶段完成,第1阶段MgO转化为(NH4)2Mg2(SO4)3;第2阶段 (NH4)2Mg2(SO4)3与MgO反应生成MgSO4;第3阶段 (NH4)2Mg2(SO4)3分解生成MgSO4;3个阶段反应的表观活化能分别为(99.10±1.50),(97.51±1.85)和(133.65±0.46) kJ*mol-1,反应速率常数为2.21,1.07和1.56,并得到每个阶段反应的速率方程.当焙烧温度为475 ℃,焙烧时间为4 h,硫酸铵与氧化镁的物质的量比为1.1∶1时,镁的转化率可达91.4%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.