RE（NO_3）_3·［CH_3CH（NH_2）COOH］_4·H_2O的燃烧热

用转动弹量热计测定了稀土（Ｃｅ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｅｒ、Ｙｂ）硝酸盐与ＤＬ－ａ－丙氨酸（１：４）配合物的燃烧热－△_ｃｕ（Ｊ·ｇ￣（－１）），其结果依次为９５９６．１，８８７４．７，８７１０．１，８９３７．３，８９６１．３，８７５１．８，８７００．０和８６５６．４。据此计算的生成焓－△_ｆＨ（ｋＪ·ｍｏｌ￣（－１））分别为３３９３．５３，３６７１．３７，３７４０．８２，３４９５．２１，３４９７．５２，３６２６．７９，３６４１．６４和３５６８．５８。这些结果不但为稀土元素的三分组提供了可靠的实验依据，亦发现了ＲＥ（ＮＯ_３）_３·（ＣＨ_３ＣＨＮＨ_２ＣＯＯＨ）_４·Ｈ_２Ｏ配合物稳定性之变化规律与稀土原子序数的关系。     

RE[CH2（CH2）4CONC4H9]3（NO3）3（RE=La,Dy）的合成和晶体结构

采用Ｘ－射线四园衍射仪测定了Ｄｙ「Ｃｈ２（ＣＨ２）４ＣＯＮＣ４Ｈ９」３（ＮＯ３）３和Ｌａ「ＣＨ２（ＣＨ２）４ＣＯＮＣ４Ｈ３」３（ＮＯ３）３的晶体结构。两个配合物具有相似的结构，均属单斜晶系，空间群为Ｐ２１／ｃ。晶体参数：Ｄｙ「Ｌａ」：ａ＝１．８５６４（３）「１．８５６４（２）」ｎｍ，ｂ＝０．９７６９（２）「０．９８３４（１）」ｎｍ，ｃ＝２．１８６３（６）「２．２００３８（７）」ｎｍ，β＝９６．０８     

希土元素异硫氰酸盐与二甲基乙酰胺配合物的标准生成焓的测定

本文测量了298.15K时La、Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Yb、Y十一种希土元素异硫氰酸盐水合物[RE(NCS)₃·nH₂O]在二甲基乙酰胺(DMA)水溶液中的积分溶解热以及相应的十一种希土元素异硫氰酸盐二甲基乙酰胺配合物[RE(NCS)₃·mDMA]在水中的积分溶解热。藉助于本文所设计的热化学循环,用本文所测得的积分溶解热数据和文献数据,求得了这十一种RE(NCS)₃·mDMA的标准生成焓,进而计算出了它们的晶格能。此外,还对Tb、Er、Tm、Lu四种RE(NCS)₃·mDMA的相应数据进行了估算。     

[（C5H4CH3）2HoN4cpH]2.[（C5H4CH3）（C5H5）HoN4CPh]2的合成和晶体结构2

（Ｃ５Ｈ４ＣＨ３）３Ｈｏ和（Ｃ５Ｈ４ＣＨ３）２Ｈｏ（Ｃ５Ｈ５）与５－本基四唑在ＴＨＦ中反应，得到了复合产物「（Ｃ５Ｈ４ＣＨ３）２ＨｏＮ４ＣＰｈ」２．「（Ｃ５Ｈ４ＣＨ３）（Ｃ５Ｈ５）ＨｏＮ４ＣＰｈ」２，该晶体属三斜晶系，Ｐ１空间群，晶胞参数为ａ＝９．３８６（３），ｂ＝１３．０７１（３），ｃ＝１６．５７１（２）Ａ，α＝８６．９０（１），β＝７４．６１（２），γ＝７７．３０（２）°，Ｖ＝１９１２．８（８     

RE(C5H8NS2)3(C12H8N2)(RE=La,Pr,Nd,Sm)的标准摩尔生成焓测定研究

在无水乙醇中,使低水合氯化稀土(RE=La, Pr, Nd, Sm)与吡咯烷二硫代氨基甲酸铵(APDC)和1,10-邻二氮菲(σ-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们的组成为RE (C₅H₈NS₂)₃(C₁₂H₈N₂) (RE= La, Pr, Nd, Sm).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σ-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Δ_cU,分别为-17776.94±7.72, -17810.41±7.93, -17762.71±7.91和-17482.42±9.35 kJ·mol^-1;并计算了它们的标准摩尔燃烧焓和标准摩尔生成焓,分别为-17792.43±7.72, -17825.90±7.93, -17778.20±7.91, -17497.91±9.35 kJ*mol^-1和-83.05±8.60, -64.70±9.40, -104.77±8.78, -388.70±10.13 kJ·mol^-1.估算出未研究的同类配合物Ce(C₅H₈NS₂)₃(C₁₂H₈N₂)和Pm(C₅H₈NS₂)₃(C₁₂H₈N₂)的和分别为-17815, -17660 kJ·mol^-1和-60, -217 kJ·mol^-1.     

Thermochemistry of the Ternary Complex Nd（Et2dtc）3（phen）

Introduction A series of lanthanide sulfide complexes have beenlargely used for ceramics and thin film materials1 andthese complexes could be prepared from the precursorswhich are the compounds containing lanthanide-sulfurbonds.2-4 For instance, the compounds synthesized with[(alkyl)2dtc]-, phen?H2O and lanthanide salts were usedas the volatile precursors for preparing lanthanide sul-fide, its friction properties in lubricant was investigatedin literature 5 and the preparation and propertie…     

RE（NO_3）_3·（GLy）_3·nH_2O配合物的合成和表征

本文在水溶液中合成了镧、镨、钐和钆四种稀土硝酸盐与甘氨酸的固态配合物。化学分析表明，它们的化学组成分别是Ｌａ（ＮＯ＿３）＿３·（ＧＬｙ）＿３·Ｈ＿２Ｏ、Ｐｒ（ＮＯ＿３）＿３·（ＧＬｙ）＿３·Ｈ＿２Ｏ、Ｓｍ（ＮＯ＿３）＿３·（ＣＬｙ）＿３·３Ｈ＿２Ｏ和Ｇｄ（ＮＯ＿３）·（ＧＬｙ）＿３·３Ｈ＿２Ｏ。用红外光谱法和Ｘ射线衍射法测定了配合物的结构特征，表明它们是一类完全不同于稀土硝酸盐和甘氨酸的新化合物。同时，考察了配合物在几种常见溶剂中的溶解性。     

稀土元素异硫氰酸盐二甲基亚砜配合物标准生成焓的测定

合成了通式为RE(NCS)_3·5DMSO的7种稀土元素异硫氰酸盐与二甲基亚砜的固态配合物(RE=La,Ce,Pr,Nd,Sm,Eu,Gd)。运用本文设计的热化学循环,采用量热法,测定了上述7种配合物在298.15K时的标准生成焓,并计算了它们的晶格能。     

Zn(Met)Ac2·H2O固态配合物的制备及标准生成焓

水合醋酸锌;L-a-蛋氨酸配合物;Zn(Met)Ac2·H2O固态配合物的制备及标准生成焓     

Macro-, Micro-, Nano- and Crystal Structures of a Homodinuclear Complex [NH3（ CH2）3NH3]2{Na2[（C6H4O2）2]（C6H4O2H）2}

A homodinuclear complex （NH3CH2CH2CH2NH3）2 {Na2[（C6H4O2）2] （C6H4O2H）2} （1） has been synthesized by a solution-based self-assembly route. It crystallized in monoclinic system with space group P21/c. Every sodium ion coordinates in a tetragonal prism fashion with two O atoms of a terminal chelating catecholate ligand and three O atoms from two bridging catecholate ligands. Two neighboring NaO5 tetragonal prisms are edge-shared and centrosymmetric with regard to the inversion center to form a binuclear cluster {Na2[（C6H4O2）2]（C6H4OOH）2}^4- anion. The complex anions were aligned parallelly by n-n interaction and linked with the protonated 1,3-propylenediamine through hydrogen bonds which were assembled into a multi-lamellar structure with channels. The crystal exhibits rectangular geometry with an interior triangle hollow structure under optical microscopy. And the scanning electron microscopy （SEM） indicates that the wall of the tubes shows multi-lamella morphologies. Further, the transmission electron microscopy （TEM） reveals that the crystal is composed of multi-lamellar nano-tubes with diameters less than 100 nm. The molecular structure of the complex was compared with that of its isomer complex 2.     

抗坏血酸锌的制备及标准生成焓测定

合成了一种新的补锌剂抗坏血酸锌,通过元素分析、红外光谱、热重、电导和化学分析确定了配合物的组成。用新型的具有恒定温度环境的反应热量计,在298·2K条件下分别测定了ZnO(s) C6H8O6(s)配位反应中反应物和生成物在2mol/L HCl溶液中的溶解焓,设计了一个新的热化学循环,得到固相配位反应焓。进而计算出配合物Zn(C6H7O6)2·4H2O(s)的标准生成焓:ΔfHm[Zn(C6H7O6)2·4H2O,s]=-3528·9±0·5kJ/mol。     

Thermochemistry on the Complex of Erbium Perchlorate with L-α-Glutamic Acid [Er2（L-Glu）2（H2O）6]（ClO4）4·6H2O（s）

A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be： （308.73±0.45） K, （10.49±0.05） kJ·mol^-1 and （33.9±0.2） J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O（s）＋2L-Glu（s）＋6NaClO4·H2O（s）] and the mixture {[Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）＋6NaCl（s）} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4（1）} in the solution A＇ at T=298.15 K were measured to be, △dHm,1=（31.552±0.026） kJ·mol^-1, △dHm,2 = （41.302±0.034） kJ·mol^-1, and △dHm,3 = （ 14.986 ± 0.064） kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-（7551.0±2.4） kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle.     

Solvothermal Synthesis and Crystal Structure of [H2N（CH2）2NH3]{Co[H2N（CH2）2NH2]3}[SbSe4]

1 INTRODUCTION The chalcogenidometallates with open frame- works have attracted considerable interest as pos- sible zeolite-like materials, of which highly interes- ting properties could be expected. Over the last de- cades a large number of thioanti…     

Zn(Met)Ac_2·H_2O固态配合物的制备及标准生成焓

在水 丙酮混合溶剂中合成了Zn(Met)Ac2 ·H2 O固态配合物 ,通过化学分析、元素分析、IR、DSC和TG DTG对其组成、结构及热稳定性进行了表征。得出其脱水过程和分解过程的焓变分别为 15 30J/ g和35 7 80J/ g。用转动弹热量计测得其恒容燃烧能ΔcE为 (- 6 4 72 11± 2 2 0 )kJ/mol,计算得其标准燃烧焓ΔcH0m 和标准生成焓ΔfH0m 分别为 (- 6 4 75 2 1± 2 2 0 )kJ/mol和 (- 4 2 9 0 4± 2 5 9)kJ/mol。     

Dy(Tyr)(Gly)3Cl3·3H2O的热化学和热分解动力学研究

以氯化镝、甘氨酸和L-酪氨酸为原料合成了配合物Dy(Tyr)(Gly)₃Cl₃·3H₂O. 用溶解-反应热量计测得配合物在298. 15K时的标准摩尔生成焓为–(4287. 10±2. 14) kJ / mol. 并用TG-DTG技术对配合物进行了非等温热分解动力学研究, 推断出配合物第二步热分解反应的动力学方程为: dα/dT＝3. 14 ×10²⁰ s^-1/βexp(-209. 37 kJ / mol /RT)(1-α)².