Kinetics of Thermal Decomposition for Complex [Zn(C_(16)H_(18)FN_3O_3)_2(NO_3)_2]·2H_2O

1 ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｉｎｔｅｒａｃｔｉｏｎｂｅｔｗｅｅｎｎｏｒｆｌｏｘａｃｉｎａｎｄｃｅｒｔａｉｎｍｅｔａｌｌｉｃｉｏｎｓｈａｓｂｅｅｎｖａｌｕｅｄｗｉｄｅｌｙ[1～ 4].Ｂｕｔｔｈｅｎｏｎ ｉｓｏｔｈｅｒｍａｌｋｉｎｅｔｉｃｓｏｆ[Ｚｎ(ＮＦＡ) 2 (ＮＯ3) 2 ]·2Ｈ2 Ｏｔｈｅｒｍａｌｄｅｃｏｍ ｐｏｓｉｔｉｏｎｈａｓｒａｒｅｌｙｂｅｅｎｓｔｕｄｉｅｄ .Ｉｎｔｈｉｓｐａｐｅｒ ,ｗｅｄｉｓｃｕｓｓｅｄｉｔｓｔｈｅｒｍａｌｄｅｃｏｍｐｏｓｉ ｔｉｏｎｂｅｈａｖｉｏｒｂｙ…     

Thermal decomposition mechanism and non-isothermal kinetics of the polyoxometalate of ciprofloxacin with 12-tungstoboric acid

The polyoxometalate complex (CPFX·HCl)4H5BW12O40·12H2O was prepared in aqueous solution for the first time, and characterized by elemental analysis, IR spectrum, and TG-DTG. The TG-DTG curves showed that its thermal decomposition was a four-step process     

Kinetics Study on the Thermal Decomposition of Europium p-methyl-benzoate Complex with 1,10-penanthroline under Non-isothermal Con-ditions

The special strUcture and iflteresting luminescent character of Eu(lll) complex made it veryimportant in applied researches as well as in theoretical Studies. The cryStal stricture and luminescence spectrum of europium p-methylbenzoate complex with l, 10-penanthroline were reported [l]. Its non-isothermal kinetics and thermal decomposition mechanism, however, hasrarely been studied. In the paped, the thermal decomposition behavior of europium p-methylbenzoate complex with l, 10-penanthroline…     

Non-isothermal decomposition kinetics and lifetime ofTb2(O-MBA)6(PHEN)2

The thermal decomposition of Tb2(O-MBA)6(PHEN)2 (O-MBA: o-methylbenzoate; PHEN: 1,10-phenanthroline)and its kinetics were studied under the non-isothermal condition by thermogravimetry-derivafive thermogravimetry (TG-DTG) techniques. Kinetic parameters were obtained from analysis of TG-DTG curves by the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as dα/dt = Aexp(-E/RT) @ 3(1 - α)2/3. The lifetime equation at mass loss of 10% was deduced as lnτ= -28.7429 + 19797.795/T by isothermal thermogravimetric analysis.     

Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu(Ⅲ) with 1-(6-hydroxy-1-naphthyl)-1,3-butanedione (HNBD) was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu(Ⅲ) ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu3+ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods (Coat-Redfern equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation). The kinetic parameters of the first stage are E* = 164.02 kJ·mol-1, A = 1.31 × 1015 s-1, △S*= 42.27 J·K-1·mol-1, △H*= 159.51 kJ·mol-1, △G*= 136.54 kJ·mol-1, and n = 3.1, those of the second stage are E*= 128.52 kJ·mol-1, A = 1.44 × 106 s-1, △S*= - 136.89 J·K-1·mol-1,△H*= 120.41 kJ·mol-1, △G*=283.85 kJ·mol-1, and n = 1.1.     

Crystal structure and properties of terbium o-methylbenzoate complex with 1,10-phenanthroline [Tb（o-CH3C6H4COO）3（C12H8N2）]2

A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen (where o-MBA =o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solution and its crystal structure was deter-mined by X-ray diffraction. The crystal of the complex Tb(o-MBA)_3phen belongs to triclinic crystal system and P 1 (#2)space group. The crystal data are as follows: a=1.4371(4)nm, b=1.7387(2)nm, c=1.3109(2)nm, α=96.37(1)°,β=107.21(2)°, γ=82.78(2)°, V=3.094(1)nm~3, Z=2, M_r=1489.12, D_c=1.598g·cm, μ=2.330mm~(-1) and F(000)=1488.00.The final R and R_w are 0.038 and 0.047 for 8668Π>2σ(Ⅰ)] unique reflections, respectively. In the complex each Tb~(3 ) ion iseight-coordinated by one 1,10-phenanthroline molecule, one bidentate carboxytate group and four bridging carboxylategroups. The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and the bridging biden-tate. Excitation and luminescence data observed at room temperature show that the title complex emits     

水合草酸镧的热分解动力学(英文)

以PEG20000为表面活性剂在撞击流反应器中制备La2O3超细粉体的前驱体十水草酸镧(La2(C2O4)3.10H2O)。在室温至900°C下研究La2(C2O4)3.10H2O的热分解过程,通过FTIR和DSC-TG对其反应中间物及最终固体产物进行分析。结果表明,该热分解过程由5个连续的反应阶段组成。采用Flynn-Wall-Ozawa(FWO)和Kissinger-Akahira-Sunose(KAS)法对活化能E进行求取,结果显示E值随着α的变化而变化,说明草酸镧的分解为复杂的热分解过程。采用多元非线性回归分析法对动力学方程和相关动力学参数进行拟合,得到动力学模型为G(α)=[1-(1+α)1/3]2。采用该动力学模型求得的活化能平均值与采用FWO法和KAS法计算而得的活化能平均值十分接近,其拟合曲线与样品的热重分析曲线吻合。     

铂和钯的羟基四氨配合物的合成、表征及性能研究

合成了2种用作前驱体的新型水溶性的金属复合离子型化合物羟基四氨合铂二水合物([Pt(NH3)4](OH)2.2H2O)和羟基四氨合钯([Pd(NH3)4](OH)2)。采用元素分析、红外光谱以及¹H-NMR对产物进行了结构表征;用热重-差热(TG-TDA)测试其热分解特性,考察配合物的热稳定性能;对比评价制备DOC催化剂的性能。结果表明,TG-DTA测试显示这2种配合物分解温度均在200~400℃范围内,热稳定性能良好,制备得到的DOC催化剂具有较好的催化活性。     

Thermal Decomposition Kinetics of Ni(Ⅱ) Complex with Norfloxacin

１ＩｎｔｒｏｄｕｃｔｉｏｎＮｏｒｆｌｏｘａｃｉｎｂｅｌｏｎｇｓｔｏｔｈｅｃｏｍｐｏｕｎｄｏｆｔｈｅｓｅｒｉｅｓｏｆｃａｒｂｏｓｔｙｒｉｌｃｏｎｔａｉｎｉｎｇｆｌｕｏｒｉｎｅ．Ｉｔｉｓａｂｒｏａｄｓｐｅｃｔｒｕｍａｎｔｉｍｉｃｒｏｂｉａｌ，ａｎｄ...     

纳米亚铬酸镍的制备及其催化特性

以硝酸铬和硝酸镍为原料,采用溶胶-凝胶法制备了纳米Ni Cr2O4,并用XRD和SEM对纳米亚铬酸镍(nano-NiCr_2O_4)的微观结构进行了表征。同时,采用TG-DTG研究了nano-NiCr_2O_4对六硝基六氮杂异伍兹烷(CL-20)和高氯酸铵(AP)热分解的催化作用,用Kissinger法、Ozawa法计算了非等温动力学参数,发现nano-NiCr_2O_4使CL-20和AP的热分解峰温降低,热分解表观活化能减小。     

Synthesis,luminescent properties,and theoretical study of novel Sm~(3+) and Dy~(3+) complexes containing β-diketone and 1,10-phenanthroline

Two new ternary complexes of 1-(2-thienyl)-3-(p-phenylethynylphenyl)-1,3-propanedione (HTPP) and 1,10-phenanthroline (phen) with Sm³⁺ and Dy³⁺ were synthesized. The composition of the ternary complexes was characterized as Sm(TPP)₃phen and Dy(TPP)₃phen, respectively, by infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. At room temperature, under UV light excitation, the Sm³⁺ and Dy³⁺ complexes exhibit characteristic emissions of the central ions. It is found that the fluorescence intensity of Sm(TPP)₃phen is stronger than that of Dy(TPP)₃phen. In order to explain this phenomenon, an accurate quantum chemistry calculation was carried out, and the result is in good agreement with the experiment data.     

Synthesis and photoluminescence properties of Eu(pzc)3(phen) and Eu(mpzc)3(phen)

Novel europium(III) complexes, (2-pyrazinecarboxylato)(phenanthroline) europium(III) [Eu(pzc)₃(phen)] and (5-methyl-2-pyrazinecarboxylato) (phenanthroline)europium(III) [Eu(mpzc)₃(phen)] have been designed and synthesized. These complexes were characterized by FT-IR, UV-Vis, and X-ray photoelectron spectroscopy. Photoluminescence (PL) studies showed that the two complexes emitted remarkably red luminescence. When powder samples of Eu(pzc)₃(phen) and Eu(mpzc)₃(phen) were examined using time-resolved spectroscopic analysis, the luminescence lifetimes were found to be 1.05 and 2.36 ms, respectively. Thermogravimetric analysis showed that the europium complexes possessed good thermal stability up to 345–350 °C.     

Thermal decomposition kinetics and lifetime of the complex of Tb2（BA）6（PHEN）2

The thermal behavior of Tb2(BA)6(PHEN)2 (BA: benzoate, and PHEN: 1,10-phenanthroline) in a static air atmospbere was investigated by TG-DTG, SEM and IR techniques. By the kinetic method of processing thermal analysis data put forward by Malek et al., it is defined that the kinetic model for the first-step thermal decomposition is SB(m, n). The activation energy E for this step reaction is 99.07 kJ/mol, the entropy of activation ΔS^≠ is -84.72 J/mol, the enthalpy of activation ΔH^≠ is 94.26 kJ/mol, the free energy of activation ΔG^≠ is 144.77 kJ/mol and the pre-exponential factor lnA is 20.93.The lifetime equation at mass-loss of 10% was deduced as lnτ = -29.0312 19760.83/T by isothermal thermogravimetric analysis.     

Mechanism and Kinetic Parameters of Thermal Decomposition of Cobalt Dichloride Hexahydrate

1 ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｃｏｂａｌｔｄｉｃｈｌｏｒｉｄｅｈｅｘａｈｙｄｒａｔｅｉｓｗｉｄｅｌｙｕｓｅｄａｓｏｉｌｖａｒｎｉｓｈｄｅｓｉｃｃａｎｔ ,ａｍ ｍｏｎｉａａｂｓｏｒｂｅｒ ,ｇａｓｓｈｉｅｌｄ ,ｗｅｔａｎｄｄｒｙｉｎ ｄｉｃａｔｏｒｓ ,ｂａｒｏｍｅｔｅｒ ,ｃｅｒａｍｉｃｔｉｎｔａｇｅａｇｅｎｔ ,ｋｉｎｄｓｏｆｃｒｙｓｔａｌｓａｎｄｍｅｄｉｃａｌａｇｅｎｔｓａｎｄｓｏｏｎ .ＴｈｅｋｉｎｅｔｉｃｓｏｆｔｈｅｒｍａｌｄｅｃｏｍｐｏｓｉｔｉｏｎｏｆＣｏＣｌ2 ·6Ｈ2 Ｏｈａｓｂｅｅｎｓｔｕｄｉ…     

Thermochemistry on coordination behavior of samaric chloride hydrate with diethylammonium diethyldithiocarbamate

The complex of samaric chloride lower hydrate-with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N2 atmosphere. The title complex was identified as Et2NH2[Sm(S2CNEt2)4] by chemical and elemental analyses, the bonding characteristics of which was characterized by IR.T he enthalpies of solution of samaric chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et2NH2[Sm(S2CNEt2)4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy, and the activation free energy), the rate constant, and three kinetic parameters (the apparent activation energy, the pre-exponential constant, and the reaction order) of liquid phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.     

Studies on the interaction between lanthanide ions and ligands, in solid complexes of lanthanide hexacyanometalates. Part II. The kinetics of thermal dehydration of lanthanide hexacyanocobaltate (III) hydrates, Ln[Co(CN)6]·nH2O and yttrium hexacyanocobaltate (III) tetrahydrates

Series complexes of lanthanide hexacyanocobaltates (III), Ln[Co(CN)₆]·nH₂O (Ln=lanthanide ions; n=5,4) and yttrium hexacyanocobaltates (III) tetrahydrate were prepared, and the kinetics of the thermal dehydrations of these hydrates was studied. The dehydrations of Ln[Co(CN)₆]·5H₂O (Ln=La to Nd) took place through at least three stages, and those of Ln[Co(CN)₆]·4H₂O (Ln=Ce to Lu, and Y) through at least two stages. The each dehydration stage was found to be described as a first order reaction, F₁. Activation energy for each stage was determined on the basis of thermogravimetry. The relationship between the activation energy for the each dehydration stages and the thermal stability of the series hydrates which was changing with the decrease of the ionic radii of lanthanide ions, was discussed.     

Preparation and characterization of bis(dimolybdo-nonatungstogermanate)lanthanates of potassium

The heteropoly complexes K12[Ln(GeW9Mo2O39)2] · nH2O (Ln = La, Ce, Pr, Nd, and Sm) were prepared for the first time and characterized by chemical analysis, infrared (IR) spectrum, ultraviolet (UV) spectrum, X-ray powder diffraction, and thermal analysis. IR, UV spectra, and X-ray powder diffraction studies show that the structure of the heteropoly complexes is a square antiprism consisting of eight oxygen atoms of two GeW9Mo2O398-, heteropolyanions and a lanthanide ion. The thermostability of heteropoly complexes is lower than that of saturated Keggin structure dodecatungstogermanate.     

钛催化氢化铝钠的贮氢性能

通过加入钛系、锆系催化剂以及碳等添加剂可以显著改善配位氢化物的吸放氢动力学性能,加入催化剂可以使配位氢化物的可逆贮氢量达3.1%~4.2%(质量分数)。采用机械合金化法在NaAlH4中加入钛的化合物作为催化剂,在很大程度上改进了其热力学和动力学性能,可逆吸氢量可达4.0%以上,可逆放氢量也能达3.0%以上。并对试样进行了X射线衍射、扫描电镜以及X射线光电子能谱分析,证明了可逆反应的发生,探讨反应的机理。     

Synthesis and crystal structure of an organic-inorganic complex [Cu(DMF)3(H2O)2]2[SiMo12O40]·2H2O

The synthesis and crystal structure of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)2]2[SiMo12O40]·2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper(Ⅱ) centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.     

Ag2O-石墨混合物非等温分解的动力学分析

根据模型拟合Malek法、积分主曲线法和无模型的先进等转化率法,采用差示扫描量热仪系统研究了Ag2O-石墨混合物热分解的动力学。结果表明,热分解包含两个阶段,在第一阶段,Ag2O分解形成多孔银颗粒,该过程复杂,至少存在两种机制;在第二阶段,多孔粒子发生结构变化而形成大块银晶体,此过程为单步过程。