Magnetische Messungen in den Systemen Co—Se,Ni—Se und Co—Ni—Se

The magnetic behavior of the binary systems Co?Se and Ni?Se was investigated within the temperature region from 100 to 300 K. Both phases Co_1?x Se and CoSe₂ behave like antiferromagnetics following theCurie-Weiss law with magnetic moments between 2.22 and 3.16 μ_B. For the corresponding phases Ni_1?x Se and NiSe₂ the results indicate a feeblePauli paramagnetism. For some alloys a slight positive temperature coefficient could be observed. Three quasibinary sections of the ternary phase (Co_1?y Ni _y )_1?x Se and one section of (Co_1?y Ni _y )Se₂ were investigated in the ternary system Co?Ni?Se. For all sections the increase of the Ni-content resulted in a continuous shift fromCurie-Weiss behavior toPauli paramagnetism. Due to the change from negative to positive temperature coefficients some ternary alloys have a temperature-invariant paramagnetism.     

L－苏糖酸钴的制备及标准生成焓

以L－苏糖酸钙与草酸的复分解反应得到的L－苏糖酸溶液，在80℃下与过量 CoO反应较长时间，滤液浓缩后加无水乙醇制得L－苏糖酸钴粉红色粉末。用化学分 析及元素分析确定其组成为Co(C4H7O5)·H2O,IR光谱分析结果表明新化合物中苏糖 酸以羧基氧原子与Co^+配位。TD－DTG结果说明，它在热分解中有一定稳定性，经 脱水生成Co-(C4H7O5)2,最后生成CoO。用转动弹热量计测得其恒容燃烧能ΔcE为（ －3504.47±1.64)kJ·mol^-1，计算得其标准燃烧焓和标准生成焓ΔfHm^θ分别为 （－3501．99±1．64）和（－2170．67±1.97)kJ·mol^-1。     

Thermochemische Untersuchungen zu Systemen M2O3/SeO2 — Bestimmung der molaren Wärmekapazitäten

Aus‐Thermochemical Investigations on Systems M₂O₃/SeO₂ — Determination of Specific Heat Capacities The experimental determination of the molar heat capacities of the ternary compounds M₂Se_xO_3+2x (M = Bi, Y, Nd, Sm) and the comparison with theoretical derivatives are described. It is shown, how the functions of the binary parent compounds M₂O₃ and SeO₂ are verified. For the determination of the C_p‐function of SeO₂ at higher temperatures an indirect method is developed.     

Crystal Structure, Thermal Decomposition Behavior and the Standard Molar Enthalpy of Formation of a Novel 3D Hydrogen- Bonded Supramolecular [Co（HnicO）2·（H2O）2]

Hydrothermal synthesis and X-ray characterized 3D supramolecular networks were constructed by [Co（HnicO）2·（H2O）2] （HnicOH=2-hydroxynicofinic acid） （1） as building block via abundant dimeric homomeric （N--H…O） and unusually cyclic tetrameric heteromeric （O-H…O） hydrogen-bonds. It is noted that there exist unusually linear metal-water chains comprised of tetrameric units linked by vertexes sharing cobalt centers through hydrogen-bonding. TG-DTG curves illustrated that thermal decomposition was completed by two steps, one is the loss of two terminal water molecules in the range of 156--234℃, and the other is the pyrolysis of HnicO ligand in the range of 234--730 ℃. The standard molar enthalpy of formation of the complex was determined to be （-1845.43± 2.77） kJ·mol^-1 by a rotary-bomb combustion calorimeter.     

氯化镧与甘氨酸配位反应的热化学研究

The reaction enthalpy of coordination reaction of lanthanum chloride with Glycine is determined by solution calorimetry in an isoperibel reaction calorimeter. The calormetric solvent is the solution of hydrochloric acid (2 mol·L- 1), a new thermochemical cycle is designed. According to the results, the following date:()(298.2 K)=- 4.310 kJ·mol- 1()(La(Gly)3Cl3· 5H2O, s, 298.2 K)=- 4222.93 kJ·mol- 1 were obtained.     

Der Chemische Transport ternärer intermetallischer Phasen in den Systemen Cr/Co/Ge und Co/Ta/Ge

Chemical Vapor Transport of Intermetallic Systems. 11 Chemical Vapor Transport of Ternary Intermetallic Phases in the Systems Cr/Co/Ge and Co/Ta/Ge By means of chemical vapor transport using iodine as transport agent it is possible to prepare a number of ternary intermetallic compounds in the system Co/Cr/Ge as single crystals. The transport behaviour in this ternary system is related to that in the binary systems. Some informations are given about transport phenomena in the systems Co/Cr and Co/Ta/Ge.     

The structure and thermochemistry of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1) and some related compounds

Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol⁻¹, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol⁻¹) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol⁻¹) adjusted from DSC measurements at the melting temperature (1, (T _fus, 357.7 K, 16.9 ± 1.3 kJ mol⁻¹)); 2, (T _fus, 383.3 K, 10.9 ± 0.1) kJ mol⁻¹) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol⁻¹) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol⁻¹) and 7-heptadecanone ((94.5 ± 1.8) kJ mol⁻¹) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T _fus, 312.7 K, 18.4 ± 0.5) kJ mol⁻¹) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound 1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone.     

NH-acides Verhalten von Imidazol beim thermischen Abbau seiner Bis-Addukte von Übergangsmetall-1,3-diketonaten

NH-acidic Behaviour of Imidazole in the Course of the Thermal Degradation of its Bis(adducts) with Transition Metal 1,3-Diketonates The behaviour of complexes of the type M(O? O)₂(HIm)₂ (O? O = 1,3-diketonate, HIm = imidazole, M = Co, Ni, Cu) in the course of the thermal degradation is different. In the case of M(acac)₂(HIm)₂ in the first step acetylacetone is split off. By proton transfer from imidazole to the acetylacetonato ligands the bis(imidazolates) M(Im)₂ are formed, which, at higher temperatures eliminate both imidazolyl residues, probably as 1H, 1H′-(2,2′)-bisimidazolyl. The thermal degradation of M(bzac)₂(HIm)₂ or M(dbm)₂(HIm)₂ (Hbzac = benzoylacetone, Hdbm dibenzoylmethane) starts with the partial elimination of imidazole. The intermediates M(bzac)(Im) or M(dbm)(Im) are obtained, and the final product of thermal degradation is the metal oxide. The main reasons for the different thermal behaviour of the complexes M(O? O)₂(HIm)₂ are differences in the volatility of the 1,3-diketones and probably in the molecular structures.     

硝酸镝与丙氨酸配位反应的热化学研究

采用新型的具有恒温环境的反应热量计 ,以 2mol L的HCl作溶剂 ,分别测定了 [Dy(NO3) 3·6H2 O +4Ala]和Dy(Ala) 4(NO3) 3·H2 O在 2 5℃时的溶解焓。通过设计的热化学循环得到六水硝酸镝与丙氨酸配位反应的反应焓ΔrHmθ=30 .638kJ mol,并计算出配合物Dy(Ala) 4(NO3) 3·H2 O在 2 98.1 5K时的标准生成焓ΔfHmθ=-3833.8kJ mo     

盐卤硼酸盐化学 ⅩⅤ.2MgO·B_2O_3.MgCl_2·14H_2O和MgO.2B_2O_3·9H_2O的热化学研究

合成氯柱硼镁石(2MgO·2B_2O_3·MgCl_2·14H_2O)和章氏硼镁石(MgO·2B_2O_3·9H_2O),用恒定温度环境反应热量计测定溶解热和反应热的基础上,运用热化学循环原理计算得到这两种硼酸盐的标准生成焓。     

Crystal Structures of Ni(II) and Co(II) cis-Octahedral Complexes with 3-Imidazoline Nitroxide

NiL₂Bipy·1.5EtOH, CoL₂Bipy·1.5EtOH, and CoL₂Phen·0.5EtOH mixed-ligand complexes with a fixed cis` position of paramagnetic ligands (L = 4-(3',3',3'-trifluoro-2'-oxopropylidene)-2,2,5,5-tetramethyl-3-imidazolidine-1-oxyl) have been synthesized and studied by X-ray crystallography.     

三元素氢氧化物中镍钴锰含量的测定

采用仪器分析方法和化学分析方法相结合测定三元前驱体Ni0.33Co0.33Mn0.33(OH)2中镍、钴、锰主含量,分别采用电感耦合等离子体原子发射光谱(ICP-AES)内标法测定镍、钴、锰的摩尔比例,EDTA滴定法测定镍、钴、锰的摩尔总量,计算得到各元素的含量。通过优化实验条件,进行了准确度和精密度实验,加标回收率为99.2%~101%,相对标准偏差小于0.65%。方法准确、快速,已用于实际的检测工作中。     

Dampfdruckmessungen und Protonenresonanzuntersuchung an Hydriden der intermetallischen Phasen Ti2(Ni,Co) und Ti2(Ni,Fe)

NMR and hydrogen equilibrium pressure measurements were performed on hydrides of the intermetallic compounds Ti₂(Ni, Co) and Ti₂(Ni, Fe). The following values of enthalpy H and entropy S for the formation of the hydrides of the intermetallic phases Ti₂Co and Ti₂Ni were found: H(Ti₂CoH _y )=–47.6 kJ/mol H₂, H(Ti₂NiH _y )=–53.7 kJ/mol H₂; S(Ti₂CoH _y )=–119.8 J/(K·mol H₂), S(Ti₂NiH _y )=–127.5 J/(K·mol H₂). By substitution of Ni or Co by Fe, the values of H and S of the corresponding quaternary hydrides become less negative. An interpretation of the experimental results is tried by the model ofShaltiel and coworkers.Proton diffusion was investigated in a series of the intermetallic hydrides Ti₂(Ni, Co)H _x and Ti₂(Ni, Fe)H _x . The diffusion rate is lowered by increased Ni/Fe substitution. Substitution of Ni by Co scarcely effects the hopping process. The activation energies were found to be smaller for the Ti₂Ni-hydrides compared with the Ti₂Co-hydrides.

Herrn Prof. Dr.H. Nowotny zum 70. Geburtstag gewidmet.     

四苯硼酸盐的热化学研究——Ⅱ.一价四苯硼酸盐的标准生成焓

本文用自行建立的精密溶解层热装(?)测定了298.15K时,NH_4BPh_4、KBPH_4、RbBPh_4、CsBPh_4、TlBPh_4、AgBPh_4和HgPh_2七种沉淀反应的反应焓,由此计算了一价四苯硼酸盐的标准生成焓、熵及吉布斯自由能.     

Über die Verdampfungsthermodynamik und die Bildungsenthalpien von CaSe,SrSe und BaSe

On the Thermodynamics of Vaporization and the Enthalpies of Formation of CaSe, SrSe and BaSe The congruent vaporization of the solid compounds CaSe, SrSe and BaSe of stoichiometric composition was studied over the temperature ranges 1832?2138 K, 1862?2122 K and 1860?2158 K, respectively, by the Knudsen effusion weight-loss method. Using enthalpy and entropy data from the literature for gaseous M, MSe, Se₂ and Se (M = Ca, Sr, Ba) and estimated data for the standard entropies and enthalpy functions of solid MSe, it can be shown that within the given temperature ranges CaSe and SrSe vaporize predominatly to the atomic species, while in case of BaSe the mode of vaporization to the atoms and to the molecular species BaSe are of about equal importance. The Se₂-content of the gas phase is very small in all cases. The following second and third law enthalpies and entropies (indices II and III respectively) were derived for the vaporization to the gaseous elements: see “Inhaltsübersicht”. The following standard enthalpies of formation of MSe(s) were derived from the third law enthalpies (in kJ · mol^?1): CaSe: ?445 ± 44; SrSe: ?451 ± 42; BaSe: ?467 ± 44.     

Cs2CuCl4标准生成焓的热化学研究

用自行研制的具备恒定温度环境的新型反应热量计，以０．０１ｍｏｌ．Ｌ＾－１Ｈ２ＳＯ４溶液为量热溶剂，分别测定了（２ＣｓＣｌ（ｓ）＋ＣｕＣｌ２．２Ｈ２Ｏ（ｓ）和ＣｓＣｕＣｌ４的溶解焓，根据Ｈｅｓｓ定律设计了一个热化学循环，求出了Ｃｓ２ＣｕＣｌ４的标准生成焓，推荐其值为     

Wasserstoffaufnahme und magnetisches Verhalten der intermetallischen Phasen Ti2(Ni,Co) und Ti2(Ni,Fe)

Hydrogen absorption by the intermetallic compounds Ti₂(Ni,Co) and Ti₂(Ni,Fe) with Ti₂Ni-structure (O _h ⁷ -Fd3m) is accompanied by an increase of the volume of the unit cell without any structural change, while the maximum value of absorbed hydrogen is practically independent of the alloy composition. By taking up hydrogen, the intermetallic compounds, showingPauli spin paramagnetism with complex temperature dependence, become either temperature independent paramagnetic [hydrides of Ti₂(Ni,Co)] or strongly temperature dependent paramagnetic, following a modifiedCurie-Weiss-Law [hydrides of Ti₂(Ni,Fe)], respectively.

Herrn Prof. Dr.H. Bittner zum 60. Geburtstag gewidmet.     

四苯硼酸盐的热化学研究——Ⅱ.一价四苯硼酸盐的标准生成焓

本文用自行建立的精密溶解层热装置测定了298.15K时,NH₄BPh₄、KBPH₄、RbBPh₄、CsBPh₄、TlBPh₄、AgBPh₄和HgPh₂七种沉淀反应的反应焓,由此计算了一价四苯硼酸盐的标准生成焓、熵及吉布斯自由能.     

复盐Zn2HIO6• 1.25H2O的热化学研究

由于高碘酸盐及其复盐晶体具有优良的电学性能和抗腐蚀性能,在分析上也很有应用价值［１］三元相高碘酸盐－高碘酸－水系统早在６０年代就引起了人们的兴趣,Ｄｒａｔｏｖｓｋｙ等人对它进行了大量的研究［２－５］．八十年代Ｎａｂａｒ等人用新的方法合成了几种新的高碘...