配合物[Fe(CTS)2]·5SO4·7H2O的热分解动力学

研究了壳聚糖对Fe2+的吸附行为,并进行了条件优化,得到了较为理想的合成产物.通过红外光谱和紫外光谱进行了表征,进而用化学分析、元素分析确定了配合物的组成,并利用TG-DSC分析,采用常用的22种机理函数,对非等温动力学数据进行了线性回归拟合处理,求得了配合物主要分解阶段热动力学最可机理函数和动力学参数(E和A).     

配合物[Fe(CTS)_2]·SO_4·7H_2O的热分解动力学

研究了壳聚糖对Fe2 + 的吸附行为 ,并进行了条件优化 ,得到了较为理想的合成产物。通过红外光谱和紫外光谱进行了表征 ,进而用化学分析、元素分析确定了配合物的组成 ,并利用TG DSC分析 ,采用常用的 2 2种机理函数 ,对非等温动力学数据进行了线性回归拟合处理 ,求得了配合物主要分解阶段热动力学最可机理函数和动力学参数 (E和A)。     

配合物Zn(Leu)SO4·O.5H2O的合成与热行为

在水-丙酮溶液中制备了zn(Leu)SO4@0.5H2O的配合物.通过热重和红外分析,研究了它的热分解机理,可分为三步完成.第一阶段配合物的脱水过程在60-180℃,形成Zn(Leu)S04,第二阶段,Zn(Leu)SO4进一步分解为Zn(Leu)SO4@9ZnSO4,随后其在728℃完全分解为ZnO.在不同线性升温5.O,10.0,15.0,20.OK@min-1条件下,用两种积分法和三种微分法研究了题目化合物失去配体过程的非等温动力学,相应过程的表观活化能E为133.78KJ@mol-1,指前因子A为1O8.19s-1,配体失去过程为三维扩散机理控制,并建立了反应过程的动力学方程.     

NH4Al(SO4)2·12H2O的热分解动力学研究

采用热分析(TG-DTA/DTG)、X射线衍射(XRD)研究了固态物质NH4Al(SO4)2.12H2O在氩气中的热分解过程。热分析结果表明,NH4Al(SO4)2.12H2O在氩气中分5步分解,其质量变化率与理论计算相吻合。XRD结果表明,NH4Al(SO4)2.12H2O热分解的最终产物为Al2O3。用Friedman法对各步分解过程的活化能Ea进行了计算,依此为初始值,采用多元非线性回归法得到各个分解步骤可能的动力学模型和参数。     

[Ni(CHZ)3]SO4·3H2O的合成、晶体结构及热分解特性

用硫酸镍与碳酰肼(CHZ)反应, 制备得到一种新型含能配合物[Ni(CHZ)3]SO4·3H2O, 通过X射线单晶衍射, 元素分析和傅立叶变换红外(FTIR)光谱对其进行了表征. 晶体结构测试表明, 该化合物晶体属于三斜晶系, P1空间群, a=0.85237(1) nm, b=0.90964(1) nm, c=1.22559(2) nm, β=96.731(2)°, V=0.8849(2) nm3, Z=2, Dc=1.798 g·cm-3. 在该配合物分子中, 碳酰肼作为双齿配体, 以羰基O原子和端基N原子与Ni2+离子发生配位, 形成3个相互垂直的五元平面螯合环. 在氢键、静电引力和范德华力的作用下, 该配合物形成了复杂的三维网状结构. 对碳酰肼分子进行了DFT-B3LYP/6-311+G**量化计算研究, 得到其NBO电荷, 从理论上说明碳酰肼的配位点是羰基O原子和端基N原子. 采用DSC、TG-DTG和FTIR光谱技术对目标化合物的热分解机理进行了研究, 并用Kissinger法和Ozawa-Doyle法对其热分解过程中两个放热峰的非等温反应动力学参数进行了计算. 结果表明, 该配合物具有较高的能量和良好的热稳定性.     

Ho(NO3)3(C2H5O2N)4·H2O的低温热容和热力学函数

合成了稀土(钬, Ho)-氨基酸(甘氨酸, C₂H₅O₂N)二元配合物Ho(NO₃)₃(C₂H₅O₂N)₄·H₂O, 并且通过化学分析、元素分析和红外(IR)光谱对配合物进行了表征. 用高精度全自动绝热量热仪, 测定了该配合物在80-390 K温度区间的定压摩尔热容(C_p,m). 利用实验测定的热容数据, 采用最小二乘法, 将热容曲线上热容峰以外的两段平滑区的摩尔热容对折合温度进行拟合, 建立了热容随折合温度变化的多项式方程. 根据热容与焓、熵的热力学关系,计算出了配合物在80-390 K温度区间内,每隔5 K,相对于298.15 K的摩尔热力学函数(H_T,m-H_298.15,m)和(S_T,m-S_298.15,m). 通过热容曲线分析, 计算出了350 K附近转变过程的焓变(Δ_trsH_m)和熵变(Δ_trsS_m). 用差示扫描量热法(DSC)测定了配合物的热稳定性.     

配合物Zn(His)SO4·H2O(s)的低温热容和热力学性质

通过精密自动绝热热量计测定了配合物Zn(His)SO4*H2O(s)在78～390K温区的摩尔热容,由热容曲线得到其起始脱水温度328.90K;用最小二乘法拟合得到摩尔热容(Cp,m)对温度(T)的多项式方程,并在此基础上计算了它的各种热力学函数.此外,研究了其在惰性气氛下的热分解过程.     

稀土氨基酸配合物RE(Val)Cl3•6H2O(RE = Nd，Sm)的热分解动力学

合成了稀土氨基酸配合物晶体——三氯化缬氨酸六水合钕、钐，对合成样品进行了EDTA滴定、元素分析、红外光谱分析、热重、差热分析以及熔点测定，推测了配合物的热分解机理，采用Achar法和Coats-Redfern法研究了配合物热分解的非等温动力学过程，给出了各配合物样品失水阶段第一步反应和氨基酸骨架断裂阶段第一步反应的活化能（E）、指前因子的对数值（ln(A)）及热分解反应动力学方程式.     

[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构

氯化钆;甘氨酸;固态配合物;[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构     

配合物Zn(Leu)SO_4·0.5H_2O的合成与热行为(英文)

在水-丙酮溶液中制备了Zn(Leu)SO4·0.5H2O的配合物。通过热重和红外分析,研究了它的热分解机理,可分为三步完成。第一阶段配合物的脱水过程在60～180℃,形成Zn(Leu)SO4,第二阶段,Zn(Leu)SO4进一步分解为Zn(Leu)SO4·9ZnSO4,随后其在728℃完全分解为ZnO。在不同线性升温5.0,10.0,15.0,20.0K·min-1条件下,用两种积分法和三种微分法研究了题目化合物失去配体过程的非等温动力学,相应过程的表观活化能E为133.78kJ·mol-1,指前因子A为108.19s-1,配体失去过程为三维扩散机理控制,并建立了反应过程的动力学方程。     

对自旋交叉化合物[Fe(dpq)(py)2(NCS)2]·H2O·py和[Fe(dpq)(py)2(NCSe)2]·1.5H2O的研究

为了研究配体修饰对自旋交叉现象的影响,我们合成了两个Fe(Ⅱ)自旋交叉的配合物[Fe(dpq)(py)₂(NCS)₂]·H₂O·py和[Fe(dpq)(py)₂(NCSe)₂]·1.5H₂O,(dpq=二吡嗪[2,3-f:2′3′-h]喹喔啉,py=吡啶)。通过对这两个配合物磁性质和穆斯堡尔谱的研究,发现和用邻啡咯啉配体合成的配合物比较,配体的修饰对自旋交叉性质以及其临界温度     

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.     

(NH4)3[VO2(SO4)2(H2O)2]·1.5H2O

The title compound, tri­ammonium cis‐di­aqua‐cis‐dioxo‐trans‐disulfatovanadate 1.5‐hydrate, was obtained by oxidizing V^IV to V^V in a 2 M sulfuric acid solution of vanadyl­ sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner‐sharing to form a discrete [VO₂(SO₄)₂(OH₂)₂]^3? anion. The water mol­ecules occupy cis positions in the equatorial plane of the vanadium octahedron.     

配合物Zn(Leu)SO4·0.5H2O的合成与热行为

在水-丙酮溶液中制备了Zn(Leu)SO₄·0.5H₂O的配合物。通过热重和红外分析,研究了它的热分解机理,可分为三步完成。第一阶段配合物的脱水过程在60～180℃,形成Zn(Leu)SO₄,第二阶段,Zn(Leu)SO₄进一步分解为Zn(Leu)SO₄·9ZnSO₄,随后其在728℃完全分解为ZnO。在不同线性升温5.0,10.0,15.0,20.0K·min^-1条件下,用两种积分法和三种微分法研究了题目化合物失去配体过程的非等温动力学,相应过程的表观活化能E为133.78kJ·mol^-1,指前因子A为10^8.19s^-1,配体失去过程为三维扩散机理控制,并建立了反应过程的动力学方程。     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

K2[Hg(SO3)2]·2.25H2O

The characteristic feature of the structure of the title compound, dipotassium bis(sulfito‐κS)mercurate(II) 2.25‐hydrate, is a layered arrangement parallel to (001) where each of the two independent [Hg(SO₃)₂]²⁻ anions are grouped into centrosymmetric pairs and are surrounded by two K⁺ cations to give the overall layer composition {K₂[Hg(SO₃)₂]₂}²⁻. The remaining cations and the uncoordinated water molecules are situated between these layers. Within the [Hg(SO₃)₂]²⁻ anions, the central Hg atoms are twofold coordinated by S atoms, with a mean Hg—S bond length of 2.384 (2) Å. The anions are slightly bent [174.26 (3) and 176.99 (3)°] due to intermolecular O...Hg interactions greater than 2.8 Å. All coordination polyhedra around the K⁺ cations are considerably distorted, with coordination numbers ranging from six to nine. Although the H atoms of the five water molecules (one with symmetry 2) could not be located, O...O separations between 2.80 and 2.95 Å suggest a system of medium to weak O—H...O hydrogen bonds which help to consolidate the structural set‐up. Differences and similarities between the bis(sulfito‐κS)mercurate(II) anions in the title compound and those in the related salts (NH₄)₂[Hg(SO₃)₂] and Na₂[Hg(SO₃)₂]·H₂O are discussed.     

Synthesis and Thermal Decomposition of [Ni2(C4H4O6)2]·7H2O

The paper describes the synthesis, characterization and thermal decomposition of nickel(II) bis(tartrato) nickelate(II) heptahydrate [Ni₂(C₄H₄O₆)₂]·7H₂O. The complex was characterized by elemental analysis, magnetic moment measurement, infrared, ESR and electronic spectroscopy. The experimental evidences indicate that complex is likely to have metal bonding. The thermal decomposition of the complex produced NiO in air at about 360°C and in nitrogen at about 380°C as the final product. Some of the intermediates produced during the thermolysis were isolated by temperature arrest technique and identified by analytical and spectroscopic methods. A tentative reaction mechanism is proposed for the thermal decomposition of the complex in air and nitrogen.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal behaviour of [CoCO3(NH3)4]2SO4 · 3H2O

The thermal behaviour of [CoCO₃(NH₃)₄]₂SO₄ · 3H₂O was studied using X-ray diffraction diagrams, DTA, TG and heating at constant temperatures for different periods of time. The X-ray study was made in order to characterize with the powder diagrams the phases obtained and to follow the reactions of the complex when heated in air up to 800. A parallel infrared spectral study was also made. The results obtained by the various experimental methods were compared with the theoretical weight losses.

---

Zusammenfassung Das thermische Verhalten von [CoCO₃(NH₃)₄]₂SO₄ · 3H₂O wurde durch Röntgendiffraktion, DTA, TG und Erhitzen auf gleiche Temperatur in verschiedenen Zeiten, untersucht. Die röntgenographische Prüfung diente zum Kennzeichnen der erhaltenen Phasen durch Pulverdiagramme und zur Verfolgung der in Luft bis 800 im Komplex verlaufenden Reaktionen. Es wurde parallel auch eine Prüfung durch infrarote Spektroskopie unternommen. Die auf verschiedene Weise erhaltenen Ergebnisse wurden miteinander in Einklang gebracht.

---

Résumé On a étudié le comportement thermique de [CoCO₃(NH₃)₄]₂SO₄ · 3H₂O par diffraction de rayons X, ATD et ATG avec maintien en thermostat. L'étude par rayons X a été menée dans le but de caractériser les phases obtenues par leur diagramme de poudre et de suivre les réactions données par le complexe chauffé dans l'air jusqu'à 800. En raison de l'impossibilité de suivre l'évolution thermique par rayons X, une étude parallèle a été effectuée par spectrographie infrarouge. On a essayé de rapprocher les résultats obtenus à l'aide de ces différentes méthodes.

---

[CoCo₃(NH₃)₄]₂SO₄·3H₂O , , , . 800. . , , , .

---

---

This work has been carried out, in part, through the Ayuda para el Fomento de la Investigación en la Universidad.     

(Et4N)4[V4O12]·2H2O

The title compound, tetrakis(tetraethylammonium) cyclo‐tetra‐μ‐oxo‐tetrakis[dioxovanadium(V)] dihydrate, (C₈H₂₀N)₄[V₄O₁₂]·2H₂O, was obtained by reacting V₂O₅ with (C₂H₅)₄NOH. It consists of a discrete centrosymmetric molecular anion, [V₄O₁₂]^4?, where four tetrahedral VO₄ units share two vertices with each other to form a ring. A water mol­ecule is attached on each side of the ring through hydrogen bonds.