四氯合锌酸十六烷基铵-四氯合锌酸十八烷基铵二元体系亚固相相图

合成了具有层状结构的热致相变材料四氯合锌酸十六铵(n-C16H33NH3)2ZnCl4,C16Zn)和四氯合锌酸十八铵(n-C18H37NH3)2ZnCl4,C18Zn)(在340~370 K的温度范围内存在着焓值较大的可逆固-固相变)。 并将此2种材料在乙醇溶液中结晶出一系列二元体系。 对二元体系利用差热分析(DTA)和X射线衍射技术进行测定,构筑了C16ZnC18Zn二元体系亚固相相图。 根据相图,确定了w(C16Zn)=41.11%处有中间化合物(n-C16H33NH3)(n-C18H37NH3)ZnCl4的存在,并测定在w(C16Zn)=16.19%和w(C16Zn)=63.07% 2处存在着2个不变的共析点,2个共析点温度分别约为356和353 K。 与同类体系的其它相图相比,在此相图的左右边界存在端际固溶体（α和β）和中间区域存在非化学计量相（γ）。     

四氯合金属(II)酸正烷铵在280-500K间的热力学性质和相变 II: 四氯合锌(II)酸正十二烷铵

研究了四氯合锌(II)酸正十二烷铵(C12H25NH3)2ZnCl4(1)]在280-500K间的热力学性质和相变热参数. 据报导(RNH3)MX4型化合物在300-380K间有相变焓很大的固-固相变, 是很有开发前景的固-固相变低温储能材料, 本文为(1)的应用提供了精确的热数据.     

四氯合锌酸正九烷铵的晶体结构及热化学性质

合成了四氯合锌酸正九烷铵复合物(C₉H₁₉NH₃)₂ZnCl₄(s) (C₉Zn(s)), 并使用X射线单晶衍射、化学分析以及元素分析确定了其晶体结构和化学组成. 利用其晶体学数据推导了C₉Zn(s)的晶格能U_POT=952.94 kJ·mol^-1. 在298.15 K下, 利用恒温环境溶解-反应热量计测定了C₉Zn(s)在不同质量摩尔浓度下的摩尔溶解焓. 在Pitzer电解质溶液理论基础上确定了C₉Zn(s)的无限稀释摩尔溶解焓Δ_sΗ_m^∞=20.09 kJ·mol^-1, 以及Pitzer焓参数组合(4β_C9H19NH3,Cl^(0)L+2β_Zn,Cl^(0)L+θ_C9H19NH3,Zn^L)和(2β_C9H19NH3,Cl^(1)L+β_Zn,Cl^(1)L)的值.     

四氯合锌酸烷基铵层形结构配合物的Raman光谱研究

测定了[n-CnH2n+1NH3]2ZnCl(n=7～12, 16)配合物在碳氢伸缩、碳氢弯曲、碳碳伸缩和低频区的Raman光谱。发现它们的频率和相对强度与分子中烷基链的链长有关, 并且表现出碳原子数的奇偶效应。从不同的分子堆积结构和分子间相互作用的角度讨论了光谱变化。     

相变储热材料C10CoCl/C18CoCl二元体系相图

合成了具有层状钙钛矿结构的固-固相变材料四氯合钴酸癸铵(n-C10H21NH3)2CoCl4和四氯合钴酸十八铵(n-C188H37NH3)2CoCl4,并制得一系列C10CoCl/C18CoCl二元体系.利用差示扫描量热(DSC)技术测定其相变温度,并在此基础上绘制了C10CoCl/C18CoCl二元体系相图.在实验相图中确定了新的稳定化合物(n-C10H21NH3)(n-C18H37NH3)CoCl4的存在和2个不变的共晶点,共晶点温度分别为70和73℃.     

相变贮热材料四氯合钴酸铵共析物的制备和热性能

在温度353 K的乙醇溶液中, 采用热回流法合成了热致相变化合物四氯合钴酸铵(1-C_nH_2n+1NH₃)₂CoCl₄(n=10, 18)(分别简写为C₁₀Co、C₁₈Co)及其二元混合物. 利用差示扫描量热和X射线法对二元体系进行了表征.根据测定实验数据构筑二元相图, 所得相图结果表明, 在w_C10Co=52.51% (质量分数)处存在中间化合物(1-C₁₀H₂₁NH₃)(1-C₁₈H₃₇NH₃)CoCl₄. 相图还包括两个三相线, 相对应的两个共析温度分别为(347±1)和(343±1) K, 共析点分别在w_C10Co=38.50%和w_C10Co=69.86%处. 并且, 在相图的左右边界存在端际固溶体(α、β)及中间区域存在非化学计量相(γ). 四氯合钴酸铵及其二元混合体系作为相变材料贮热时, 相变温度范围为340-370 K, 相变焓大小范围在2.13到141.12 J·g^-1之间.     

四氯合镉酸正十一烷铵的合成、晶体结构及低温热容

合成了四氯合镉酸正十一烷铵配合物(C₁₁H₂₃NH₃)₂CdCl₄(s)[简写: C₁₁Cd(s)]. 用X 射线单晶衍射技术、化学分析和元素分析确定其晶体结构和化学组成. 利用其晶体学数据计算出晶格能为: U_POT＝908.18 kJ·mol^-1. 利用精密自动绝热热量计测定了它在78～395 K 温区的低温热容, 结果表明, 该配合物在此温区出现两次连续的固-固相转变, 计算出两次相变的峰温、摩尔焓及摩尔熵分别为: T_trs,1＝(321.88±0.07) K, Δ_trsH_m,1＝(37.59±0.17) kJ·mol^-1, Δ_trsS_m,1＝(117.24±0.12) J·K^-1·mol^-1, T_trs,2＝(323.81±0.30) K, Δ_trsH_m,2＝(12.42±0.02) kJ·mol^-1 和Δ_trsS_m,2＝(38.36±0.09) J·K^-1·mol^-1. 用最小二乘法将实验摩尔热容对温度进行拟合, 得到热容随温度变化的多项式方程. 用此方程进行数值积分,得到此温区每隔5 K 的舒平热容值和相对于298.15 K 时的热力学函数值.     

四氯合镍酸三乙醇铵的固相合成及其热色性

可逆热变色材料作为感温防伪显示材料 ,它的应用已扩展到生产及日常生活的各个领域。例如 ,美国财政部已在新版的美元上使用了可逆热色性油墨[1 ] ;Nature公司生产了热色性釉料图案陶瓷杯 ,室温呈夜幕景色 ,倒入热水后显示白天景象 ,来显示水的冷热 ,给人以赏心悦目之感。在一些无法用常规仪器测温的场合 ,热色性示温涂料有着独特的优越性。本文通过固相反应合成了新化合物四氯合镍酸三乙醇铵 ,并借助光谱数据 ,探讨了该化合物的可逆热致变色机理。IFS 48FTIR傅立叶变换红外分光光度计 ,KBr压片 ;紫外 可见 近红外光谱采用UV 340 0分…     

粉状白钙酸的研究III.从粉状白钨酸制备偏钨酸铵和偏钨酸有机铵酸以及它们的性质研究

本文继活性状白钨酸的制得,用其制备偏钨聚钠后,进一步报道了以粉状白钨酸为出发点的偏钨酸铵(NH4)6[H2(W3O10)4].nH2O、偏钨酸乙基铵、二乙基铵、三乙基铵和四乙基铵盐的合成及部分性质研究。同法还制得偏钨酸三正丁基铵,经化学分析其组成接近[(n-C4H9)3NH]6[H2(W3O10)4],与文献报道的"酸式盐"[(n-C4H9)2NH]5H[H2(W3O10)4]不同。     

四氯合锌酸二(正十一烷基铵)晶体相变的Raman光谱

用Raman光谱研究了[n-C_(11)H_(23)NH_3]_2ZnCl_4(简记为C_nZn)配合物的固-固相变.结果表明,配合物产生的固-固相变主要与烷烃链的堆积结构和分子构象变化有关.在 T_(c1)=25℃的相变是由于烷烃链的侧向堆积和分子构象的有序到部分无序变化.在中间相,分子链局部产生旁式构象.在T_(c2)=87℃的相变主要来源于烷烃链从部分构象有序到完全无序的变化.高温相形成了构象完全无序相.相应于烷烃链的“熔化”.     

Crystal Structure, Phase Transition, and Thermodynamic Properties of Bis-dodecylammonium Tetrachlorozincate (C12H25NH3)2ZnCl4(s)

The crystal structure and composition of (C₁₂H₂₅NH₃)₂ZnCl₄(s) were characterized by chemical and elemental analysis, X‐ray powder diffraction technique and X‐ray crystallography. The lattice energy of the title compound was calculated to be U_POT=888.82 kJ·mol^?1. Low temperature heat capacities of the title compound have been measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 403 K. An obvious solid to solid phase transition occurred in the heat capacity curve, and the peak temperature, molar enthalpy and molar entropy of the phase transition of the compound were determined to be T_trs= (364.02±0.03) K, (_trsH_m= (77.567±0.341) kJ·mol^?1, and (_trsS_m= (213.77±1.17) J·K^?1·mol^?1, respectively. Experimental molar heat capacities before and after the phase transition were respectively fitted to two polynomial equations. The smoothed molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were calculated and tabulated at an interval of 5 K.     

Syntheses, Spectroscopic Properties and Crystal Structures of （2-Cl-C6H4CH2）3SnS2CN（C5H10） and （2-Cl-C6H4CH2）3SnS2CN（C4H9N）

1 INTRODUCTION The chemistry of organotin(IV) complexes was extensively studied due to their biological activity and coordination chemistry[1～7]. More recently, phar- maceutical properties of alkyltin(IV) complexes with dithiocarbamate ligands have bee…     

Evaluation of Transient Absorption Spectra of N, N, N, N- Tetra - ( p -methylphenyl ) - 4, 4- diamino - 1, 1- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C_(60) / C_(70) ) by Laser Flash Photolysis

Fullerenes C60 and C70 have high electron affinity ( 2.6 - 2.8 ev ) and readily form anions on electronchemical reduction1, which were famous as electron acceptor in photo-excitation because of symmetrical shape, large size, and properties of its p - electron system2. After observation of molecular ferromagnetism3 in the tetrakis (dimethylamino ) ethylene salt of C60 as well as the occurrence of ultra-fast photoinduced electron transfer within the dimethyl aniline - C60 complex4, prompted us…     

层状钙钛矿化合物 (n-CnH2n+1NH3)2ZnCl4非等温固-固相变动力学的确定

确定了具有层状钙钛矿结构,脂肪链C原子数从12到18四氯合锌酸二烷基铵(C_nH_2n+1NH₃)₂ZnCl₄系列化合物的非等温固-固相变动力学。采用Kissinger和Ozawa两种动力学模型,对不同温度下测定的每个样品DSC热分析曲线进行数据处理,计算固-固相变过程的活化能E_a。实验结果表明,随着C原子数的增加,脂肪链的有序度和刚度降低,导致固-固相变活化能E_a随C原子数的增大而降低。两种模型方法的计算活化能E_a的结果相一致。并且各个化合物的固-固相变反应级数不随升温速率和烷基链长变化而变化,总保持为1。     

Beiträge zur Chemie des Phosphors. 237. Reaktion von Diphosphan(4) mit Peroxoverbindungen: Bildung von Phosphinophosphinsäure,H2PPH(O)OH,und Bis(phosphino)phosphinsäure, (H2P)2P(O)OH

Contributions to the Chemistry of Phosphorus. 237. On the Reaction of Diphosphane(4) with Peroxo Compounds: Formation of Phosphinophosphinic Acid, H₂PPH(O)OH, and Bis(phosphino)phosphinic Acid, (H₂P)₂P(O)OH Diphosphane(4) reacts with peroxo compounds such as hydrogen peroxide, tetraline hydroperoxide, trifluoroperoxyacetic acid, and cumene hydroperoxide (which is particularly suited for preparative work) at ?30°C to furnish phosphino-phosphinic acid, H₂PPH(O)OH ( 1 ), as the primary product. Compound 1 disproportionates to a major extent in statu nascendi to give phosphanes (above all PH₃) and monophosphorus acids of various oxidation states as well as some bis(phosphino)phosphinic acid, (H₂P)₂P(O)OH ( 2 ). The acids 1 and 2 can be trapped and stabilized as their triethylammonium salts. The structures of these salts have been determined by spectroscopic investigations.     

An Fe(III) Complex with the Dianionic form of 2,6-Diacetylpyridine Bis(Acylhydrazone). The Crystal Structure of [Diaqua-2′,2′′′-(2,6-PyridinediyldiEthylidyne)Dioxamohydrazide]Iron(III) Perchlorate Trihydrate, [Fe(dapsox)(H2O)2]ClO4·3H2O

The title compound was prepared by a template synthesis from 2,6-diacetylpyridine, dioxamohydrazide and Fe(ClO₄)₃·6H₂O(mol ratio 1:2:1) in MeOH/H₂O(3:1) solution and its structure determined by single-crystal X-ray diffraction; triclinic, space group P1, a = 7.5186(7), b = 10.9730(9), c = 14.6110(10) Å, α = 95.866(1), β = 100.252(1), γ = 92.895(1), z = 2. The polydentate ligand is coordinated as a dianionic pentadentate while water molecules occupy apical positions in the structure. This is the first example of a monomeric, pentagonal bipyramidal structure of an Fe(III) complex with a dianionic bis(acylhydrazone) derivative of 2,6-diacetylpyridine.     

LiCl-(2ZnCl2•KCl)-(ZnCl2•2KCl)系中的三个赝二元系

用目测变温、DTA和XRD法研究了LiCl-(2ZnCl2•KCl)-(ZnCl2•2KCl)赝三元系中的三个侧边赝二元系. 结果表明, 在LiCl-(2ZnCl2•KCl)系中有一个组成为3LiCl•2KCl•4ZnCl2或Li3K2Zn4Cl13的三元固液同组成化合物生成, 熔点245 ℃; 在LiCl-(ZnCl2•2KCl)系中有一个组成为12LiCl•2KCl•ZnCl2或Li12K2ZnCl16的三元固液异组成化合物生成, 转熔(包晶)温度432 ℃, 而在另一个赝二元系(2ZnCl2•KCl)-(ZnCl2•2KCl)中有一个固液异组成的二元化合物4ZnCl2•5KCl或K5Zn4Cl13生成, 转熔温度249 ℃.     

C3N6H6(H3BO3)2的合成及晶体结构

以三聚氰胺和硼酸为原料在水溶液中反应合成出了一种新的BCN化合物先驱体C3N6H6(H3BO3)2。XRD表征结果表明三聚氰胺和硼酸的最佳配比为1∶3(物质的量比)。用单晶X-射线衍射分析法测定了该化合物的晶体结构。该化合物属单斜晶系,空间群为P21/C,晶胞参数为a=0.3597(7)nm,b=2.0105(4)nm,c=1.4112(3)nm,α=90,°β=92.07(3),°γ=90,°V=1.0199(3)nm3,Z=4,D c=1.627g.cm-3,μ(MoKα)=0.144mm-1,F(000)=520。晶体结构经全矩阵最小二乘法修正,最终可靠因子R1=0.0519,wR2=0.1361。该化合物是由C3N6H6分子和H3BO3分子通过氢键加合组装形成的三维超分子结构化合物。     

Synthesis of 1,8-dioxo-octahydroxanthenes and bis(indolyl)methanes catalyzed by [Et3NH][H2PO4] as a cheap and mild acidic ionic liquid

Triethyl ammonium dihydrogen phosphate was used as a cheap and mild acidic ionic liquid catalyst for synthesis of 1,8-dioxo-octahydroxanthenes and bis(indolyl)methanes. This methodology offers several advantages, such as good yields, short reaction times, simple procedure, and mild conditions.     

C28X4（X=H,Cl）,CX4（X=H,Cl）的结构和电子光谱的理论研究

用ＩＮＤＯ法对Ｃ２８Ｘ４（Ｘ＝Ｈ，Ｃｌ）和ＣＸ４（Ｘ＝Ｈ，Ｃｌ）进行几何构型优化，得到Ｔｄ对称性的构型Ｃ２８Ｘ４有４种键、４种不等同原子，基态为稳定的闭壳层分子，以此构型为基础计算了上述分子的电子光谱，并预测Ｃ２８Ｘ４的电子光谱。