烟酰胺铬(Ⅲ)配合物的合成及其热分解脱水非等温动力学研究

本文合成了铬（Ⅲ）的一个新的双核配合物Ｃｒ２（Ｎｉｃａ）４Ｃｌ５（ＯＨ）（Ｈ２Ｏ）６（Ｎｉｃａ表示烟酰胺．通过元素分析、摩尔电导、红外光谱、热重．对该配合物进行了表征，表明烟酰胺以吡啶氮与铬（Ⅲ）配位．文章对该配合物进行了热分解脱水非等温动力学研究，运用Ａｃｈａｒ法与Ｃｏａｔｓ—Ｒｅｄｆｅｒｎ法，推断出该热分解脱水反应为二级反应．其动力学方程为ｄα／ｄｔ＝Ａｃ（－Ｅ／ＲＴ）（１－α）２，动力学补偿效应表达式为ＩｎＡ＝０．２９９２Ｅ－１０．５６８２．     

地开石热分解过程及非等温动力学研究

Fourier-transform infrared emission spectroscopy was used to study the dehydroxylation behavior of the thermal decomposition of dickite from Chenxi, Hunan Province, China. Dehydroxylation of dickite was followed by a loss of intensity of the 3620.73, 3695.34 cm-1 OH-stretching bands and 916.06, 1009.33 cm-1 OH bending bands. The thermal decomposition was investigated by thermogravimetric analysis (TGA). A good agreement is found with TG curves of dickite and the mass loss is 13.7% (close to the theoretical value). The non-isothermal kinetics of the thermal decomposition of dickite was studied in TG-DTG curves over the temperature range from 298 K to 1123 K by thermogravimetry and differential thermal analysis in air. Mathematical analysis of TG-DTG data using the integral methods (Coats-Redfern equation, HM equation, MKN equation) and differential method (Achar equation) shows that the thermal decomposition of dickite accords F2 mechanism. The kinetic parameters such as the activation energy (E=131.62 kJ/mol), pre-exponential factor (A=108.30 s-1) and reaction order (n=2.1) are reported. The Ozawa method was used to analyse the activation energy of the same sample at different heating rate and gave 133.07 kJ/mol. The kinetic parameters calculated from different equation are rather close to each other.     

双核Cu(Ⅰ)配合物的热分解非等温动力学

由于钢作为活性配位中心离子，存在干具有生物功能的蛋白质大分子中，近年来钢的配位化学受到广泛关注．普遍认为，咪唤基在铜蛋白的配位化学中起重要作用＊，开展钢与具咪陵基配体所形成配合物的研究，有助于揭示钢在蛋白质中的生物化学功能及其与咪哩基等其它基团相互键合作用的本质．我们曾报导了四种新型具苯并咪吐基双核CIJ（）配合物：［CllZ’（OCTB）flC104h·1．SHZO川，［Cll。’（NMOCTB）］·（CIO。）。·H。O（2），［Cll。’（NBUOCTB）］（CIO。）z切，［Cll。’（NBOCTB）］·（CIO4h·H。O（4）的合…     

Zn(C9H6O5N2)·2H2O配合物热分解非等温动力学的研究

合成了Ｚｎ（Ｃ９Ｈ６Ｏ５Ｎ２）·２Ｈ２Ｏ,用元素分析、红外光谱、摩尔电导对该配合物进行了表征。并用热重（ＴＧ）对其热分解机理进行了研究,推断出了该配合物第三步热分解的非等温动力学方程为： ｄα／ｄｔ＝ Ａｅ－ Ｅ／ＲＴ（１－ α）。     

双核Cu(I)配合物的热分解非等温动力学

Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2•1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2•H2O(2), [Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2•H2O(4) and their kinetics were studied under the non-isothermal conditions by TG-DTG techniques. The non-isothermal kinetic data were analyzed by means of Achar and Coats-Redfern method respectively. The kinetic equation for the second step of the decomposition of complex (1) can be expressed as: dα/dt=A•exp(-E/RT) •(1-α), the mechanism of this reaction corresponds to "Coring and Growth" with n=1; while for the first step of complex (3) decomposition, dα/dt=A•exp(-E/RT)• (1-α)2, which corresponds to the mechanism of "the second-order chemical reaction".     

3,4-二硝基吡唑热分解及非等温动力学

采用TG-DSC综合热分析的方法,对3,4-二硝基吡唑(DNP)的热分解和非等温动力学进行了研究。结果表明DNP的热分解分两阶段进行,并且在升温速率达到15K/min时才能明显区分。分别采用Archar微分法和Coats-Redfen积分法计算了DNP第一阶段热分解反应动力学参数:Ea=91.6kJ.mol-1,lnA=42.7s-1。最可能的DNP热分解机理为随机成核和随后生长机理,符合动力学机理函数Avrami-Erofeev方程,n=3。     

三烟酰胺铬(Ⅲ)配合物的合成及其热分解非等温动力学研究

合成了铬 ( )的一个新配合物 Cr(Nica) 3 (H2 O) 3 (NO3 ) 3 ·H2 O(Nica表示烟酰胺 ) ,并对其进行了热分解非等温动力学研究。通过摩尔电导、紫外可见光谱、红外光谱、X-射线粉末衍射等 ,对其结构进行了表征。运用 Achar法与 Coats- Redfern法 ,对非等温动力学数据进行分析 ,推断第二步热分解反应按动力学方程 dα/ dt=Ae-ERT· 32 (1 α) 23 [(1 α) 1 3 - 1 ] -1进行 ,同时给出了热力学补偿效应表达式。     

一种新的非等温动力学方程

用热分析法研究聚合热降解或固体热分解反应动力学￣［１］，可用微分法和积分法进行数据处理。前者直接从热谱图上读取值，可能引入大的误差，故更多的是采用积分法。而积分动力学方程中有一个不可积项∫ｅｘｐ（—Ｅ／ＲＴ）ｄ＿Ｔ，为了求解，许多作者对该项作了近似处理。本文在以前近似式的基础上，提出了一个新的非等温动力学方程，并对各近似式在不同ｘ（ｘ＝Ｅ／ＲＴ）下与相应的∫ｅｘｎ（－Ｅ／ＲＴ）ｄ＿Ｔ积分值比较，得出各个近似式的误差范围，并以误差σ对ｘ作图。从结果可见，本文提出的方程在使用范围和精度上都有进一步的提高。     

3-硝基邻苯二甲酸锆的制备﹑热分解机理及非等温反应动力学

用3-硝基邻苯二甲酸、氢氧化钠和硝酸氧锆为原料, 制备了3-硝基邻苯二甲酸锆, 采用元素分析、X射线荧光衍射和FT-IR对其结构进行了表征. 用TG-DTG以及变温固相原位反应池/傅里叶变换红外光谱(RSFT-IR)联用技术研究了3-硝基邻苯二甲酸锆的热分解机理, 对主分解反应的DTG峰进行了数学处理, 计算得到了动力学参数和动力学方程. 结果表明, 3-硝基邻苯二甲酸锆的分解反应总共有4个阶段, 其中主分解反应发生在第2阶段, 主分解反应的表观活化能Ea与指前因子A分别为158.84 kJ·mol-1和10^9.85 s-1, 主分解阶段的反应机理服从一级Mample法则, 主分解反应的动力学方程为dα/dt=10^9.85(1-α)e^-1.91×10⁴/T.     

非等温热重分析三聚氰胺热分解动力学

采用非等温热重法对三聚氰胺的热分解动力学进行了研究,选定拟合结果更好的迭代法计算反应活化能,采用积分法结合36种动力学函数来判断三聚氰胺热分解的机理函数.得到了三聚氰胺热分解的动力学参数,即反应的动力学函数为g(α)=(1-α)-3-1,平均活化能Ea为142.38×103J/mol,指前因子A的平均值为1.98×10...     

迪开石热分解及重结晶的非等温动力学

采用热分析(TG-DTG-DSC)和X射线衍射(XRD)技术研究了福州迪开石在动态空气气氛条件下的热分解及重结晶过程, 利用TG和DSC数据分别对迪开石的热分解和重结晶过程进行动力学分析. 由Friedman法求得热分解过程的表观活化能, 以此为初始值, 通过非线性回归法拟合得到了热分解过程最可能的反应机理和动力学参数; 将迭代的等转化率法和最小偏差法相结合计算得到了高温下迪开石重结晶过程最可能的反应机理和动力学参数. 研究结果表明, 迪开石在450~750 ℃内发生热分解, 脱去2个水分子, 生成无定形的准迪开石, 此过程为两步连串反应, 第一步为随机成核和随后生长机理An, 第二步为自催化反应机理CnC; 在975~1050 ℃内, 准迪开石重结晶转化为莫来石, 此过程对应的反应机理为An.     

Non-isothermal Kinetics of the First-stage Decomposition Reaction of Cobalt Oxalate Dihydrate

Introduction Solid state kinetics has been extensively studied by means of thermal analysis methods[1]. The aim of the study is to determine the mechanism function f(α) , the activation energy E and the pre-exponential factor A. In recent years there have been many methods of processing thermal analysis kinetic data[2-11].     

三维网状结构配位聚合物[Cu(HCOO)2(H2O)2]∞晶体的热分解机理

用水热合成法得到了[Cu(HCOO)2(H2O)2]∞的晶体, 采用TG-DTG和DSC法对配合物[Cu(HCOO)2(H2O)2]∞进行了热分解机理和热分解动力学研究. 通过对DSC曲线用Kissinger、Ozawa、积分法和微分法处理的结果进行比较, 得到了脱水过程的动力学模型函数. 并用X射线单晶衍射、元素分析、FTIR光谱技术进行了表征. 结果表明该配位聚合物晶体为单斜晶系, 属P21/c空间群, 晶胞参数为a=0.8533(2) nm, b=0.7151(2) nm, c=0.9463(2) nm, β=96.94(0)°. 晶胞体积V=0.5732(2) nm3, Z=4, 计算得到的晶体密度Dc=2.197 g•cm−3. 在该配位聚合物中, 通过甲酸根作为连接配体将两种铜配位中心连接起来形成三维网状框架结构.     

Non-isothermal Decomposition Kinetics of [Cu（en）2H2O] （FOX-7）2·H2O

The thermal behavior and non-isothermal decomposition kinetics of [Cu（en）2H2O]（FOX-7）2·H2O （en=ethylenediamine） were studied with DSC and TG-DTG methods.The kinetic equation of the exothermal process is dα/dt=（10^17.92/β）4α^3/4exp（-1.688×10^5/RT）.The self-accelerating decomposition temperature and critical temperature of the thermal explosion are 163.3 and 174.8 ℃,respectively.The specific heat capacity of [Cu（en）2H2O]（FOX-7）2·H2O was determined with a micro-DSC method,with a molar heat capacity of 661.6 J·mol^-1·K^-1 at 25 ℃.Adiabatic time-to-explosion was also estimated as 23.2 s.[Cu（en）2H2O]（FOX-7）2·H2O is less sensitive.     

Non-isothermal Kinetic Study of the Heterogeneous Thermal Decomposition of a Mannich Compound

The authors present data concerning the evaluation of kinetic parameters of the decomposition of a Mannich compound by using the classical method of constant heating rate thermal analysis and the new one of controlled rate thermal analysis (CRTA). The data processed using the CRTA method allow to obtain more reliable kinetic parameters according to the proposed reaction mechanism. This revised version was published online in July 2006 with corrections to the Cover Date.     

Characterization and Non-isothermal Decomposition Kinetic Analysis of PS/FeNi3 Nanocomposites

Polystyrene/iron-nickel (PS/FeNi3) nanocomposites were synthesized via an in-situ polymerization route and characterized by XRD,SEM and FTIR. FeNi3 nanoparticles were characterized by TEM and XRD. The pure FeNi3 nanoparticles (100～125 nm) were highly clustered and percolated through the PS matrix. When the content of FeNi3 nanoparticles reached 5 wt%,an interaction between FeNi3 nanoparticles and PS matrix was observed. The thermal decomposition behavior of PS/FeNi3 nanocomposites was investigated by thermal analysis. The activation energies (E) and pre-exponential factors (lnA) were calculated by using Archar method. The results show that the thermal decomposition of pure PS is a one-dimensional diffusion mechanism. A three-dimensional diffusion mechanism appears when FeNi3 nanoparticles incorporate. The E of PS/FeNi3 nanocomposites with different FeNi3 contents is 217.5,225.3,180.6 and 73.0 kJ·mol-1,and the corresponding lnA is 35.6,34.9,27.5 and 10.4 S-1,respectively.     

ZnSO4·CO(NH2)2·2H2O和MgCl2·NH4Cl·6H2O的热分解动力学研究

采用TG-DSC研究了ZnSO4·CO(NH2)2·2H2O和MgCl2·NH4Cl·6H2O的热分解反应,并对其中的脱水过程及部分分解过程进行了动力学计算,由Fridman、Ozawa-Flynn-Wall、ASTME698三种方法得出峰温时的活化能值与指前因子值,通过优化选择出了热分解过程最佳机理函数.