三元配合物RE(Et2dtc)3(phen)热化学性质的规律性

在无水乙醇中, 用铜试剂(NaEt₂dtc•3H₂O)和邻菲咯啉(o-phen•H₂O)分别与13种低水合氯化稀土合成了三元固态配合物(其中5种尚未见文献报道), 确定它们的组成可用通式RE(Et₂dtc)₃(phen)表示. IR光谱表明配合物中RE³⁺与3个NaEt₂dtc中的6个硫原子双齿配位, 同时与o-phen中的2个氮原子双齿配位. 用RD496-Ⅲ微量热计测定了298.15 K下13种水合氯化稀土盐及两个配体在无水乙醇中的溶解焓, 两个配体醇溶液的混合焓及13种化合物液相生成反应的焓变, 并通过合理的热化学循环, 求得了标题配合物的固相生成反应焓变; 测定了标题配合物298.15 K的比热容. 用RBC-II精密转动弹热量计测定了标题配合物的恒容燃烧热, 计算了它们的标准摩尔燃烧焓和标准摩尔生成焓. 发现系列配合物RE(Et₂dtc)₃(phen) (RE＝La, Pr, Nd, Sm～Lu)的多项热化学性质, 如低水合氯化稀土盐在无水乙醇中的溶解焓以及配合物的液相生成反应焓变和固相生成反应焓变、常温比热容、标准摩尔燃烧焓和标准摩尔生成焓都与稀土原子序数作图呈现“三分组现象”. 较集中地反映出配合物中RE³⁺与配体间的化学键有一定程度的共价性, 这是由于稀土离子5s²5p⁶轨道对4f电子的不完全屏蔽引起的.     

三元配合物RE(Et2dtc)3(phen)热化学性质的规律性

在无水乙醇中, 用铜试剂(NaEt₂dtc•3H₂O)和邻菲咯啉(o-phen•H₂O)分别与13种低水合氯化稀土合成了三元固态配合物(其中5种尚未见文献报道), 确定它们的组成可用通式RE(Et₂dtc)₃(phen)表示. IR光谱表明配合物中RE³⁺与3个NaEt₂dtc中的6个硫原子双齿配位, 同时与o-phen中的2个氮原子双齿配位. 用RD496-Ⅲ微量热计测定了298.15 K下13种水合氯化稀土盐及两个配体在无水乙醇中的溶解焓, 两个配体醇溶液的混合焓及13种化合物液相生成反应的焓变, 并通过合理的热化学循环, 求得了标题配合物的固相生成反应焓变; 测定了标题配合物298.15 K的比热容. 用RBC-II精密转动弹热量计测定了标题配合物的恒容燃烧热, 计算了它们的标准摩尔燃烧焓和标准摩尔生成焓. 发现系列配合物RE(Et₂dtc)₃(phen) (RE＝La, Pr, Nd, Sm～Lu)的多项热化学性质, 如低水合氯化稀土盐在无水乙醇中的溶解焓以及配合物的液相生成反应焓变和固相生成反应焓变、常温比热容、标准摩尔燃烧焓和标准摩尔生成焓都与稀土原子序数作图呈现“三分组现象”. 较集中地反映出配合物中RE³⁺与配体间的化学键有一定程度的共价性, 这是由于稀土离子5s²5p⁶轨道对4f电子的不完全屏蔽引起的.     

配合物[La(pic)3(phen)2]·CH3CN的合成及晶体结构

The Lanthanum picrate complex with 1,10-phenanthroline was synthesized, whose chemical formula can be written in [La(pic)₃(phen)₂]·CH₃CN. The crystal Xray diffraction analysis shows that crystal belongs to monoclinic with space group P2₁/a and unit cell parameters:a=17.072(4),b=16.083(4),c=17.789(4),β=106.34(2)°,V=4687(4)³, Z=4,Dc=1.735g·cm³, μ=10.106cm¹,F(000)=2448,R=0.0589,Rw=0.0589. The coordination number of La³⁺ is nine. Acetonitrile, a solvent molecule is not coordinated. Between three Pic ligands, that possesses 2 bidentate forms six member ring with La. The other is unidentate ligand. As usually, phen is bidentate ligand.     

三元配合物RE [(Pdtc)3(phen)]热化学性质的规律性

Treatment of hydrate rare-earth(RE=La,Pr,Nd,Sm-Lu)chloride with ammonium pyrrolidinyldithiocarboxy-late(apdtc)and 1,10-phenanthroline(phen)gave rise to thirteen complexes with an empirical formulaRE[(pdtc)_3(phen)].The enthalpies of solution of hydrate rare-earth(RE= Sm-Ho,Tm-Lu)chloride,apdtc and phenin ethanol were measured by an RD-496 Ⅲ microcalorimeter at 298.15 K,along with the mixing enthalpy of etha-nol solution of APDC and that of phen and the enthalpies of reaction of formation of the title complexes in ethanol.The enthalpies of reaction of formation of the title complexes in solid were available through a rationally thermo-chemical cycle.Using an RD-496 Ⅲ microcalorimeter,a model was developed for calculating the specific heat ca-pacity and the responding specific heat capacity of the complexes were determined.The thermochemical properties,including the enthalpies of solution of hydrate rare earth chloride in ethanol,the enthalpies of reaction of formationof the title complexes in ethanol,the enthalpies of reaction of formation of the title complexes in solid,the specialheat capacities at room temperature,the standard molar enthalpies of combustion and the standard molar enthalpiesof formation for this series of complexes versus the atomic numbers of rare earth,presented triplet effect,which isrepresentative of certain covalent bond between RE and the ligands and the result of 4f electron not shielded fullyby 5s5p.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

Cu(NO3)2(La(NO3)3)-CO(NH2)2-H2O三元体系的等温溶度研究

本文首次报道三元体系Cu(NO₃)₂-CO(NH₂)₂-H₂O(30℃)和La(NO₃)₃-CO(NH₂)₂-H₂O(25℃)的等温溶度及饱和溶液、折光率,绘制相应的溶度图及折光率-组成图。体系中发现有组成为Cu(NO₃)₂·4CO(NH相似文献   

配合物(ArO)2Yb(NPh2)2K(THF)4(Ar=C6H2-t-Bu3-2,4,6)的合成、分子结构和催化行为

Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile.     

稀土配合物{La［o-C6H4(NO2)(CO2)］3·(DMF)2}2的晶体结构及其荧光性能

合成了一种新的双核倒反中心的稀土镧配合物{La［o-C6H4(NO2)(CO2)］3·(DMF)2}2. 通过元素分析、 核磁共振谱和红外光谱对配合物的组成和结构进行了表征,  用热重分析研究了该配合物的热稳定性,  用X射线单晶衍射法测定了其晶体结构. 镧配合物{La［o-C6H4(NO2)(CO2)］3·(DMF)2}2晶体属三斜晶系, 空间群P1,  晶胞参数a=1.902(2) nm, b=1.245 0(2) nm, c=1.298 7(2) nm, α=64.555(2)°, β=66.348(2)°, γ=71.920(2)°, V=1.569 5(5) nm3, Dc=1.658 Mg/m3, Z=2, μ=1.437 mm-1, F(000)=784. 配合物中有2个La(Ⅲ)被4个邻硝基苯甲酸的羧酸根的负氧离子桥联, 每个La(Ⅲ)的中心离子配位数为9,  配位原子分别来自于7个邻硝基苯甲酸的羧酸根的负氧离子和2个DMF的羰基氧原子. 化合物中的氢键和π…π堆积作用使其成为三维立体结构. 同时发现了标题化合物固体具有光致发光现象, 发光性能测试表明， 配合物具有很好的荧光性质.     

Lu(Et2dtc)3(phen)的生成反应焓变、摩尔热容和恒容燃烧能测定

A ternary solid complex Lu(Et₂dtc)₃(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt₂dtc), and 1,10-phenanthroline (o-phen·H₂O) in absolute ethanol. IR spectrum of the complex indicates that Lu³⁺ binds with sulfur atom in the Na(Et₂dtc)₃ and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, Δ_rH_m^Ө (l), was determined to be (-32.821 ± 0.147 ) kJ·mol^-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, Δ_rH_m^Ө (s), was calculated to be (104.160 ± 0.168) kJ · mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (ΔH_≠^Ө), the activation entropy (ΔS_≠^Ө), the activation free energy (ΔG_≠^Ө), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, c_m, was determined to be (82.23 ± 1.47) J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combustion energy of the complex, Δ_cU, was determined as (-17 898.228 ± 8.59) kJ·mol^-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δ_cH_m^Ө, and standard enthalpy of formation, Δ_fH_m^Ө, were calculated to be (-17 917.43 ± 8.11) kJ·mol^-1 and (-859.95 ±10.12) kJ·mol^-1, respectively.     

混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3的合成晶体结构及性能

[Mn₃O(O₂CCH₂Cl)₆(C₅H₅N)₂(H₂O)]·CH₂ClCOO·H₂O在pH=4.5的HOAcNaOAc的缓冲水溶液中和2,2′联吡啶(bipy)反应,制得了混合价双核锰配合物[(bipy)₂Mn(μ-O)₂Mn(bipy)₂](ClO₄)₃·1.5H₂O。该配位化合物的X射线单晶衍射表明,该晶体属单斜晶系,空间群P2₁/c,晶胞参数:a=1.3854(3),b=1.3943(3),c=2.4225(5)nm,β=103.30°,V=4.554(2)nm³,Z=4,D_c=1.448g·cm^-3。其紫外可见光谱在640nm处有一个峰,可指派为桥配体O^2-到Mn(Ⅲ)的电荷迁移光谱.循环伏安实验说明,此配合物在半波电位E_1/2为1.25V处,有一个可逆的氧化还原峰,这相应于(Ⅲ,Ⅳ)态氧化为(Ⅳ,Ⅳ)态,另外在0.37V处有一阴极峰,相应于(Ⅲ,Ⅳ)态还原为(Ⅲ,Ⅲ)态,在0.81V处有一氧化峰,相应于(Ⅲ,Ⅲ)态氧化为(Ⅲ,Ⅳ)态,这两个峰是不可逆的。     

用微量热法测定稀土含硫有机配合物的比热容

推导了用改进的RD496-III型微热量计测定固态物质比热容的计算式. 用Joule 效应确定了仪器在298.15 K时的量热常数和相对标准偏差分别为(63.901±0.030) μV•mW^－1和0.08%, 用Peltier效应测定总不平衡热. 在该仪器上测定的两种标准物质(基准苯甲酸和α-Al₂O₃)比热容的计算值与文献值相差在0.4%以内. 用本法测定了13种固态配合物RE(PDC)₃(phen) (RE＝La, Pr, Nd, Sm～Lu; PDC＝ )的比热容值, 总偏差在1.0%, 与稀土原子序数Z_RE作图呈现“三分组现象”, 说明配合物中RE^3＋与配体间的化学键有一定程度的共价性, 显示了稀土离子4f电子云的扩大效应.     

Determination of Specific Heats Using Isothermal Microcalorimetry

The specific heat capacities (c_p) for the brain and muscle equivalent liquids were determined with isothermal heat conduction microcalorimetry (IMC) and differential scanning calorimetry (DSC). IMC was found to afford an accurate technique to measure c_p for solid and liquid samples, when an appropriate reference is employed. The accuracy of obtained c_p values was estimated to be better than 0.7% with the equivalent liquids. Intercomparison with a conventional isoperibolic calorimeter showed an excellent agreement within the estimated uncertainty of the isoperibolic calorimeter (±3%). Additionally, suitability of different kinds of IMC sample vessels was tested, and the standard electrical calibration procedure of IMC was evaluated through the determination of c_p with and without a reference material. This revised version was published online in July 2006 with corrections to the Cover Date.     

三元配合物Er(Et2dtc)3(phen)的热化学性质

三元配合物Er(Et2dtc)3(phen)的热化学性质;Er(Et2dtc)3(phen); 微量热法; 热动力学; 恒容燃烧能; 标准摩尔生成焓     

Determination of combustion energies and the standard enthalpies of formation for the complexes of RE(Et_2dtc)_3(phen)

Solid complexes, RE(Et2dtc)3(phen) (RE=La, Pr, Nd, Sm-Lu), were synthesized with sodium diethyldithiocarbamate (NaEt2dtc3H2O),1,10-phenanthroline (o-phen·H2O) and hydrated lanthanide chlorides in absolute ethanol. The constant-volume combustion energies of complexes,ΔcU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion,ΔcHmθ, and standard enthalpies of formation,ΔfHmθ, were calculated for these complexes, respectively. The experiment results showed the "tripartite effect" of rare earth.     

Determination of combustion energies and the standard enthalpies of formation for the complexes of RE(Et2dtc)3(phen)

Solid complexes, RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm—Lu), were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc3H₂O), 1,10-phenanthroline (o-phen•H₂O) and hydrated lanthanide chlorides in absolute ethanol. The constant-volume combustion energies of complexes, Δ _C U, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_CH_m ^θ, and standard enthalpies of formation, Δ_fH_m ^θ, were calculated for these complexes, respectively. The experiment results showed the “tripartite effect” of rare earth.

     

三元配合物Tb(Et2dtc)3(phen)的热化学性质

以铜试剂(NaEt2dtc•3H2O)和邻菲咯啉(o-phen•H2O) 与水合氯化铽(TbCl3•3.75H2O)在无水乙醇中制得了三元固态配合物.化学分析和元素分析确定其组成为Tb(Et2dtc)3(phen).IR光谱研究表明配合物中Tb3＋与NaEt2dtc中的硫原子双齿配位,同时与phen的氮原子双齿配位.用Calvet微热量计测定了298.15 K下液相生成反应的焓变ΔrHmθ(l),为(－21.819±0.055) kJ•mol－1,通过热化学循环计算了固相生成反应焓变ΔrHmθ(s),为(128.476±0.675) kJ•mol－1.改变反应温度,研究了液相生成反应的热动力学.用精密转动弹热量计测得配合物的恒容燃烧能ΔcU为(－17646.95±8.64) kJ•mol－1,经计算其标准燃烧焓ΔcHHmθ和标准生成焓ΔfHmθ分别为(－17666.16±8.64) kJ•mol－1和(－1084.04±9.49) kJ•mol－1.     

三元配合物Ho(Et2dtc)3(phen)的合成及其热化学性质

改进文献方法,以铜试剂(NaEt2dtc·3H2O)和邻菲咯啉(o-phen·H2O)与低水合氯化钬(HoCl3·3.58H2O)在无水乙醇中反应,制得三元固态配合物.化学分析和元素分析确定该配合物的组成为Ho(Et2dtc)3(phen).IR光谱表明配合物中Ho3 与3个NaEt2dtc中的6个硫原子双齿配位,同时与o-phen中的2个氮原子双齿配位,可推测其配位数为8.用微量热量计测定了298.15 K下液相生成反应的焓变△rHm (1),为(-14.697±0.0376)kJ·mol-1,通过合理的热化学循环计算了固相生成反应焓变△rHm (s),为(117.504±0.619)kJ·mol-1;改变反应温度,研究了配合物的液相生成反应的热力学性质.配合物的恒容燃烧能△cU用精密转动弹热量计测定为(-18687.64±8.22)kJ·mol-1,其标准燃烧焓△cHm 和标准生成焓△fHm 经计算分别为(-18706.85±8.22)和(-70.01±9.37)kJ·mol-1.     

A Laser Flash Apparatus for Thermal Diffusivity and Specific Heat Capacity Measurements

We have developed a laser flash apparatus for simultaneous measurements of thermal diffusivity and specific heat capacity of solid materials by introducing recent technical progress: uniform heating by a homogenized laser beam using an optical fiber with a mode mixer, measuring transient temperature of a specimen with a calibrated radiation thermometer, analyzing a transient temperature curve with a curve fitting method, to achieve differential laser flash calorimetry. Thermal diffusivity, specific heat capacity and thermal conductivity of glassy carbon and molybdenum were measured in the temperature range from 300 to 1100 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

RE(C5H8NS2)3(C12H8N2)的标准摩尔生成焓

在无水乙醇中, 使低水合氯化稀土 (RE = Ho, Er, Tm, Yb, Lu) 与吡咯烷二硫代氨基甲酸铵 (APDC)和1,10-菲咯啉 (o–phen•H₂O) 反应, 制得其三元固态配合物. 用化学分析和元素分析确定它的组成为RE(C₅H₈NS₂)₃(C₁₂H₈N₂) (RE = Ho, Er, Tm, Yb, Lu). IR光谱说明RE³⁺ 分别与3个PDC^–的6个硫原子双齿配位, 同时与o–phen的2个氮原子双齿配位, 配位数为8. 用精密转动弹热量计测定了它们的恒容燃烧热△_cU分别为(-16788.46 ± 7.74), (-15434.53 ± 8.28), (-15287.80 ± 7.31), (-15200.50 ± 7.22)和(-15254.34 ± 6.61) kJ•mol^-1; 并计算了它们的标准摩尔燃烧焓△_cH_m^θ和标准摩尔生成焓△_fH_m^θ分别为( -16803.95 ± 7.74), (-15450.02 ± 8.28), (-15303.29 ± 9.28), (-15215.99 ± 7.22), (-15269.83 ± 6.61) kJ • mol^-1和 (-1115.42 ± 8.94), (-2477.80 ± 9.15), (-2619.95 ± 10.44), (-2670.17 ± 8.22), (-2650.06 ± 8.49) kJ•mol^-1.     

N-(乙氧酰基)-N’-(2,4-二硝基苯胺基)硫脲的合成、晶体结构、比热容及热力学性质

以PEG-400为催化剂,利用氯甲酸乙酯和硫氰酸钾反应生成的乙氧酰基异硫氰酸酯为中间体与2,4-二-硝基苯肼反应,得到N-(乙氧酰基)-N′-(2,4-二硝基苯胺基)硫脲,通过IR、元素分析等方法对其结构进行了表征。 在室温条件下,采用缓慢挥发法培养出适合用于X射线衍射测试的单晶。 晶体结构数据表明,晶体属单斜系,P2(1)/c空间群,晶胞参数:a=4.1919(2) nm,b=12.295(6) nm,c=23.828(11) nm,α=γ=90.00°,β=92.467(10)°,V=14397(12),Dc=1.519 g/cm3,μ=0.263 cm-1,F(000)=680,Z=4,R1=0.1121,wR2=0.2540。 并对标题化合物进行了热重分析和比热容测定,计算了热力学函数;证明该化合物有良好的热稳定性。