p-CH3C6H4SR型硫醚与钯(II)配合物热分解反应动力学

热重分析(TG)和微商热重法(DTG)广泛应用于各个研究领域,用非等温热重法测定固体化合物的热分解动力学参数已有报导.许多作者提出各种不同的数据处理方法.本文用的ρ-CH_3C_6H_4SR 型硫醚对钯的萃取具有选择性好、分配比高、气味较小、易溶于脂肪烃类溶剂、易于合成、是很有发展前途的一类萃取剂.我们合成五种ρ-CH_3C_6H_4SR(R:n-C_4H_9,n-C_6H_(13),n-C_8H_(17),n-C_(10)H_(21),n-C_(12)H_(25))型硫醚与钯(Ⅱ)的配合物,用TG-DTG 法研究它们的热分解过程,用微商法(Freeman-Carroll 方程)及积分法(Coats-Redfern 方程)获得了这些配合物的热分解动力学参数.     

含有羧基配体的蝎型钒氧配合物的合成、结构及其热分解动力学

设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50.     

Applicability of glass fiber as a support material for generation of gaseous standard mixtures using thermal decomposition of the surface compound. Calibration of analytical equipment

The use of glass fiber as a support material for a surface compound serving to generate gaseous standard mixtures of ethene is described. The technique is based on the process of thermal decomposition of the surface compound in a desorber connected on‐line via a multi‐port valve to the calibrated device. The surface compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The method enables on‐line preparation of a standard mixture immediately before the calibration step. Consequently, it can be also applied for the generation of standard mixtures containing volatile, malodorous, unstable, and toxic compounds.     

Resolution method for overlapping peaks based on the fractional-order differential

Equations between the differential order and the maximum of the fractional-order differential for the specified peak signals are developed based on the variation of the maximum of the specified peak signals at different orders. Also, equations between the differential order and the zero-crossing of the fractional-order differential of the specified peak signals are proposed according to the variation of the zero-crossing of the specified peak signals at different orders. Characteristic paramters of the Gaus- sian peak, Lorentzian peak, and Tsallis peak can be estimated using estimator I and estimator II which are obtained by the equations above. As a result, a new method is presented to resolve the overlapped peaks signal. Firstly, a fractional-order differential of the specified peak signals is obtained with the fractional-order differentiation filter. Then, characteristic paramters of the specified peak signals can be extracted using estimator I and estimator II. Finally, the Tsallis peak is used as a model to assign the overlapping peak signals correctly. Experimental results show that the proposed method is efficient and effective for the simulated overlapping peaks and detected overlapping voltammetric peak signals.     

Na3Fe(C2O4)3·5H2O的热解过程和FAB-MS断裂规律

以红外光谱法为主要手段，原位“跟踪”测定铁（Ⅲ）与乙二酸形成的配合物Ｎａ３Ｆｅ（Ｃ２Ｏ４）３．５Ｈ２Ｏ的热解过程，分析了气、固相热解产物。并以色谱分析、差热－热重分析和Ｘ－射线粉末衍射法定性、定量地验证其结果。测定了该配合物快原子轰击质谱，提出了断裂规律。铁的二元羧酸配合物的质谱尚属首见。     

CaO和NaCl焙烧混合稀土精矿过程中的分解反应

用XRD和TG-DTA热分析技术, 研究了含独居石和氟碳铈镧矿的混合稀土精矿在100～1000 ℃焙烧过程中, 添加CaO, NaCl时, REPO4和REFCO3的分解反应. 研究结果表明: 不添加CaO和NaCl时, 仅在377～450 ℃范围内存在REFCO3的分解反应, 其产物是REOF, RE2O3, 以及Ce2O3进一步的氧化产物CeO2, 而REPO4不分解; 添加CaO后在660～750 ℃之间, CaO有3种分解作用: (1) CaO分解REPO4, 其产物是RE2O3和Ca3(PO4)2. (2) CaO分解REOF, 其产物是RE2O3和CaF2. (3) CaO和REOF的分解产物CaF2共同作用分解REPO4, 其分解产物为RE2O3, Ca5F(PO4)3; 添加CaO, NaCl后, 混合精矿的分解率明显提高, NaCl的作用是为反应体系提供了液相, 促进了固相反应物间的传质过程, 加快了反应速度. 与此同时NaCl还可能参加了CaO分解REPO4的反应.     

Influence of Gas Atmosphere on Removal of Sulphate Groups From Titanium Oxide

The studies were devoted to determination of the effect of gas atmosphere and its pressure on the second step of decomposition of hydrated titanium dioxide (HTD) promoted by sulfate groups. It has been found that thermal decomposition of HTD at temperatures above 300°C consists of a number of processes such as dehydroxylation, desulfuration, recrystallization and sintering of solid grains, photochemical processes (if the decomposition proceeds in the presence of light) and adsorption of gas phase components (in the presence of air or SO₂). Kinetic parameters characterizing this step of decomposition have been determined for processes carried out in vacuum and in argon or air atmospheres (at a pressure of 13.33hPa). The kinetic curves of decomposition carried out in the presence of gases capable of being adsorbed on the surface of partly dehydrated HTD are featured by local extrema due to simultaneous processes of decomposition and adsorption of gas components. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

直键与弯键的对称性判据

一穹键的提出人们认为,杂化轨道(HAO)角函数的最大值方向(亦即HAO的方向)指向与之键合的原子,这样形成的化学键称为“直键”。但环丙烷分子中的三个碳原子构成三元环,有60°的键角。而任意两个正交的S-P杂化轨道之间的夹角θ都不可能小于90°,因而形成C-C键的HAO,不可能指向键合原子,环上的C-C键不可能是直键,而是“弯键”(BentBond)。通常,人们认为张力分子环上的键是弯键,其他的键为直键。