Non-Isothermal Decomposion Kinetics of Supermolecule Compound [Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]_2·phen·4H_2O

Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C_(10)H_(10)N_2O_4,H_3L) and 1,10-phenan-throline (C_(12)H_8N_2,phen) has been prepared.A yellow prismatic crystal of the compound was obtained,and themolecule crystallized in the triclinic space group P-1.There are two 9-coordinated complex molecules in everystructure unit,where every Eu atom is coordinated by three water molecules and two tridentate C_(10)H_(10)N_2O_4 ligands,forming two stable pentacycles.The coordination polyhedron around Eu~(3+) was described as a single cap squareantiprism.In the crystal cell,there are one free 1,10-phenanthroline and four water molecules.The thermaldecomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry.The Kissinger'smethod and Ozawa's method were used to calculate the activation energy value of the first-step decomposition.Thestages of the decompositions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were ana-lyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equationswere investigated by comparing the kinetic parameters.     

水杨醛-1H-苯并三唑-1-乙酰腙与镧(Ⅲ)配合物的制备、表征及热化学

在甲醇中,利用水杨醛-1H-苯并三唑-1-乙酰腙(C15H13N5O2,简称SBTH)与高氯酸镧反应,制得一新配合物,经元素分析、化学分析并结合热分析确定了其组成为La(C15H12N5O2)( C15H11N5O2)•2.5H2O.利用电导测定、红外光谱、1H NMR和TG-DTG等手段推测了配合物的结构.用微热量计测定了配合物在不同浓度(b)时的溶解焓,用计算机拟合求得该配合物的标准摩尔溶解焓(ΔsolHmΘ=－135.62 kJ•mol－1)及溶解焓(ΔsolH)的经验公式(ΔsolH=－135.62－11633b＋3761.5b1/2),并由此分别推导出配合物的相对表观摩尔焓(Li)、相对偏摩尔焓(Li)以及配合物稀释焓(ΔdilH1,2)的经验公式:Li=－11633b＋3761.5b1/2；Li=－23266b＋5642.2b1/2和ΔdilH1,2=－11633(b21/2－b11/2)＋3761.5(b2－b1).还研究了配合物的热分解过程,利用Kissinger公式计算了配合物主要分解阶段的表观活化能(Ea=470.24 kJ•mol－1).     

Zn(AA)SO4·H2O(AA=Thr,Phe,Val,Met)在水和丙酮混合溶剂中的结晶动力学研究

Zincisanecessarylifeelementinhumanbody．L－α－aminoacidisthebasicunitofproteinrelatedwithlife．L－α－Thr（Threonine），L－α－Phe（Phenylalanine），L－α－Val（Valine）andL－α－Met（Methionine）arein－dispensabletolifewhichhavetobeabsorbedfromfoodbecausetheycannotbesynthesizedinhumanbody．Thecomplexesofzincsaltswithα－aminoacidasad－ditivehaveawideapplicationinmedicine，foodstuffandcosmetics犤１～３犦．Thesynthesismethodsofthecom－plexesofzincsaltswithα－aminoacidhavebeenre－viewed犤…     

ESTIMATION OF THE CRITICAL RATE OF TEMPERATURE INCREASE OF THERMAL EXPLOSION OF NITROCELLULOSE USING NON-ISOTHERMAL DSC

A method of estimating the critical rate of temperature increase of thermal explosion for the first orderautocatalytic decomposition reaction system using non-isothermal DSC is presented. Information is obtained on theincreasing rate of temperature in nitrocellulose containing 13.54% of nitrogen when the first order autocatalytic decomposition converts into thermal explosion.     

Zn(Val)SO4·H2O在丙酮-水混合溶剂中的结晶动力学

确定了Zn(Val)SO4·H2O在水-丙酮中结晶生长的最佳体积比为1:10,用微量热法测定了该结晶生长过程在298.15K时的放热量及产热速率,计算了动力学常数,认为结晶过程符合Burton-Cabrera-Frank位错理论.同时测定了Zn(Val)SO4·H2O于298.15K时在纯水中的溶解焓为(28.46±0.08)kJ·mol-1,计算了Zn(Val)2+(aq)的标准生成焓为(-569.71±3.84)kJ·mol-1.     

Non-isothermal Kinetics of the Thermal Decomposition of 3-Nitro-1,2,4-triazol-5-one Magnesium Complex

Introduction3 Nitro 1,2 ,4 triazol 5 one (NTO)metalcomplexeshavemanyspecialstructuresandsomepotentialusesinammunition .1 4 Wepreviouslypreparedanddeterminedthecrystalstructureofitsmagnesiumcomplex ,5andinthispaper ,wediscusseditsthermalbehaviorbyDSCandTG/DTGtechniquesandstudieditsnon isothermalkineticsbythemeansoftheKissingermethod ,theOzawamethod ,thedifferentialmethodandtheintegralmethod .ExperimentalSample[Mg(H2 O) 6 ](NTO) 2 ·2H2 Owaspreparedasfollows :AcalculatedamountofMg(OH…     

柠檬酸镧催化双基推进剂的非等温热分解反应动力学

采用TG-DTG和DSC技术研究了含二缩三乙二醇二硝酸酯(TEGDN)和硝化甘油(NG)的混合酯、硝化棉(NC)和用作燃烧催化剂的柠檬酸镧组成的双基推进剂在常压和流动态氮气气氛下的非等温热分解反应动力学. 结果表明, 该双基推进剂的热分解过程存在2个失重阶段: 第I失重阶段为混合酯的挥发分解过程; 第II失重阶段为主放热分解反应, 机理服从三级化学反应, 减速型α-t曲线, 动力学参数: Ea=231.14 kJ·mol-1, A=10^23.29 s-1, 动力学方程为dα/dt=10^22.99(1-α)³ e^-2.78×104/T. 由外推起始点温度(Te)和峰顶温度(Tp)计算得出该双基推进剂的热爆炸临界温度值分别为Tbe=463.62 K, Tbp=477.88 K. 反应的活化熵(⊿S^≠)、活化焓(⊿H^≠)和活化能(⊿G^≠)分别为219.75 J·mol-1·K-1, 239.23 kJ·mol-1和135.96 kJ·mol-1.     

3-硝基-1,3,4-三唑-5-酮金属(Li,Na, Pb,Cu)盐的制备反应热动力学

在常压、298.15 K条件下, 用RD496-2000微量热仪开展了3-硝基-1,3,4-三唑-5-酮(NTO)金属(Li, Na,Pb, Cu)盐制备反应的热动力学研究, 得到了反应过程中的热力学参数(活化焓、活化熵和活化自由能), 速率常数和动力学参数(活化能、指前因子和反应级数), 还得到了在25-40℃范围内NTO金属(Li, Na, Pb, Cu)盐制备反应过程的反应焓. 结果表明, NTO金属(Li, Na, Pb, Cu)盐的制备反应较容易发生. 基于Hess定律, 得到了Δ_fH_m⁰ (Li(NTO)·2H₂O, aq, 298.15 K)和Δ_fH_m⁰ (Na(NTO)·H₂O, aq, 298.15 K)的值.     

纳米三氧化钨的制备、表征及对六硝基六氮杂异伍兹烷热分解的影响

采用水热法通过控制前躯体钨酸钠的加入量和反应时间制备了长方体形纳米WO₃,利用X射线粉末衍射(XRD)、透射电镜(TEM)、扫描电镜及能量散射光谱仪(SEM-EDS)对样品进行表征。并运用差示扫描量热法(DSC)研究纳米WO₃对六硝基六氮杂异伍兹烷(CL-20)热分解特性的影响。结果表明:与单组分CL-20相比,纳米WO₃的加入使复合物WO₃/CL-20的热分解峰温降低2.95℃,活化能减小7.74 kJ·mol^-1,因此纳米WO₃能够加速CL-20的热分解。     

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158.84kJ·mol-1和109.85s-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=109.85(1-α)e-1.91×104/T.