水合氯化镧与二乙氨基荒酸二乙铵配合行为的热化学

在干燥氮气气氛下，以无水乙醇为溶剂，制备了低水合氯化镧与二乙氨基荒酸 二乙铵（D-DDC）的配合物，确定其组成为Et_2NH_2[La(S_2CNEt_2)_4]。用微量热 法测定了298.15 K下水合氯化镧和D-DDC在无水乙醇中的溶解焓和不同温度下二乙 氨基荒酸镧液相生成反应的焓变。在实验和计算基础上，得到了液相生成反应的热 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（表现活化能 、频率因子和反应基数），通过合理的热化学循环，求得了标题固相反应的焓变。     

Thermochemical Study of Coordination of Holmium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of holmium chloride hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized via mixing their solutions in absolute alcohol under a dry N2 atmosphere. The elemental and chemical analyses show that the complex has the general formula Et2NH2[Ho(S2CNEt2)4]. It was also characterized by IR spectroscopy. The enthalpies of the dissolution of holmium chloride hydrate and D-DDC in absolute alcohol at 298.15 K o and the enthalpy changes of liquid-phase reactions of the formation of Et2NH2[Ho(S2CNEt2)4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of the liquid-phase reaction of the complex formation were obtained, The enthalpy change of the solid-phase complex formation reaction at 298.15 K was calculated by means of a thermochemical cycle.     

Coordination behavior of erbium chloride hydrate with diethylammonium diethyldithiocarbamate

The complex of erbium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) has been synthesized conveniently in absolute alcohol and dry N₂ atmosphere. The title complex was identified as Et₂NH₂[Er(S₂CNEt₂)₄] by chemical and elemental analyses, the bonding characteristics of which was characterized by IR. The enthalpies of solution of erbium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et₂NH₂[Er(S₂CNEt₂)₄] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase Chemistry and Thermochemstry on Coordination Behavior of Zinc Chloride with Leucine

The solubility property of the ZnCl2-Leu-H2O(Leu=L-a-leucine) system at 298.15K in the whole concentration range was investigatey by the semimicro-phase equilibrium method.The corresponding solubility diagram and refractive index diagram were constructed.The results indicated that there was one complex formed in this system.namely,Zn(Leu)Cl2.The complex is congruently soluble in water.Based on Phase equilibrium data,the complex was prepared.Its composition and properties were characterized by chemical analysis,elemental analysis,IR spectra,and TG-DTG.The thermochemical properties of coordination reaction of zinc chloride with L-a-leucine were investigated by a microcalorimeter.The enthalpies of solution of L-a-leucine in water and its zinc complex at infinite dilution and the enthalpy change of solid-liquid reaction wrer determined at 298.15K.The enthalpy change of soild phase reaction and the standard enthalpy of formation of zinc complex were claculated.On the basis of experimental and calculated results,three thermodynamic parameters(the activation enthalpy,the activation entropy and the activation free energy),the rate constant and three kinetic parameters(the activation energy,the preexponential constant and the reaction order) of the reaction,and the standard enthalpy of formation of Zn(Leu)^2 (aq) were obtained.The results showed that the title reaction took place easily at studied temperature.     

Et2NH2[Nd(S2CNEt2)4]的晶体结构和生成反应焓变

在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化钕与二乙氨基荒酸二乙铵(D-DDC)配合物,确定其组成为Et2NH2[Nd(S2CNEt2)4].单晶结构分析表明,配合物中4个二乙氨基荒酸根各通过2个硫原子与钕离子成键形成八配位十二面体阴离子,并与二乙铵阳离子形成缔合型分子.晶体属单斜晶系,空间群P21/n,a=1.37517(14)nm,b=2.1146(2)nm,c=1.44641(15)nm,β=102.028(2)°,Z=4.用微量热法测定了298.15K下水合氯化钕和D-DDC在无水乙醇中的溶解焓及二乙氨基荒酸钕液相生成反应焓变分别为(-17.89±0.096),(50.280±0.151)和(-10.116±0.065)kJ/mol,求得固相生成反应焓变.     

氯化镨对原代培养的小鼠成骨细胞增殖、分化和矿化功能的影响

采用噻唑蓝(MTT)法、碱性磷酸酶(ALP)比活性测定、油红O染色、I型胶原测定以及矿化结节染色及定量分析等方法 ,研究了不同浓度的氯化镨对原代培养的成骨细胞增殖、分化、矿化功能以及横向分化为脂肪细胞的影响。结果表明:氯化镨对成骨细胞增殖、分化、矿化功能以及横向分化为脂肪细胞的影响与作用浓度和时间密切相关,但没有呈现出时间和剂量依赖性。结果提示,氯化镨对骨代谢的影响是复杂的,其具有保护还是损害作用取决于作用浓度和时间。作用浓度和时间是影响氯化镨生物效应转变的关键因素。     

The Effect of Magnesium Chloride Hydrate on the Fire Retardation of Cellulosic Fibers

Thermal analysis was used to investigate the effect of the addition of magnesium chloride hexahydrate as a fire retardant to cellulosic fibers. The kinetics of the decomposition of the cellulosic material were first studied. The decomposition of the dry salt was also investigated and three steps disclosed. Then, the fabrics were impregnated into salt solutions of different concentrations and the loss in mass was followed by thermal analysis. The percent loss in mass was compared to that of pure cellulosic fabric at different temperatures. It was found that there is an appreciable improvement in fire retardation at a minimum percent add-on of the salt of 35%. This revised version was published online in August 2006 with corrections to the Cover Date.     

Two Praseodymium Coordination Complexes with 1,3-Phenylenediacetate:Structural Diversity Tuned by Auxiliary Ligands

Two new coordination complexes, [Pr(1,3-pda)0.5(nbca)2(H2O)2](1) and [Pr2(1,3-pda)3(2,2ˊ-bpy)2(H2O)2](2)(H2pda = 1,3-phenylenediacetic acid, Hnbca = 5-nitro [1,1ˊ-biphenyl]-3-carboxylic acid, 2,2ˊ-bpy = 2,2ˊ-bipyridine), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In 1, the nbca ligands bridge the Pr3+ ions to form a 1D chain. Moreover, these 1D chains are united together through the 1,3-pda ligands to afford a 2D layer. In contrast, due to a different auxiliary ligand, complex 2 is a 2D layer linked through only bridging deprotonated 1,3-pda. Thermal stabilities and solid fluorescence properties of 1 and 2 were also studied.     

L-亮氨酸与醋酸铜固相配位反应的热化学研究

L-亮氨酸与醋酸铜固相配位反应的热化学研究     

Thermokinetics on the reaction of formation of Dy[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

The enthalpy change of formation of the reaction of hydrous dysprosium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol at 298.15 K has been determined as (-16.12±0.05) kJ·mol-1 by a microcalor-meter. Thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), rate constant and kinetics parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of the reaction have also been calculated. The enthalpy change of the solid-phase reaction at 298.15 K has been obtained as (53.59±0.29) kJ·mol-1 by a thermochemistry cycle. The values of the enthalpy change of formation both in liquid-phase and solid-phase reaction indicated that the complex could only be synthesized in liquid-phase reaction.     

二乙基二硫代氨基甲酸钠对黄铜管的缓蚀性能研究

通过失重法、交流阻抗（EIS）以及极化曲线等测试方法,研究了在质量分数为3%NaCl溶液中二乙基二硫代氨基甲酸钠（SDDTC）对黄铜管的缓蚀行为。 失重测试结果表明,SDDTC在质量浓度为120 mg/L时具有最佳缓蚀效果,缓蚀效率达到95%。 交流阻抗的测试结果表明,黄铜电极的极化电阻R_p值最初随着浓度的增加及浸泡时间的延长而增加,在浸泡72 h以及质量浓度达到120 mg/L时达到最大值,之后随着SDDTC浓度的进一步增加和浸泡时间的延长R_p值反而有所下降。 极化曲线测试结果显示,该缓蚀剂对黄铜电极的阳极和阴极行为均具有抑制作用。     

Thermochemistry of copper(II) ion solvation in aqueous organic solvents

The integral heat effects of CuCl₂ dissolution in aqueous DMSO, aqueous ethanol and aqueous acetone solutions at 298. 15 K in the electrolyte concentration range 0.001–0.01M were measured by means of calorimetry. ΔH _sol ⁰ values were obtained by extrapolation to zero electrolyte concentration. Literature data were used to determine the thermodynamic characteristics of Cu²⁺ transfer from water to aqueous organic solvents.     

Study on Coordination Behaviour of Manganese Chloride with L-a-Histidine

The reaction thermodynamic and kinetic equations for the non-reversible reactions are established. The enthalpy change of formation reaction of manganese(II) histidine (His) complex in water has been determined by microcalorimetry, using manganese chloride with L-a-histidine at 298.15-323.15 K. The standard enthalpy of formation of Mn(His)₂ ²⁺(aq) has been calculated. On the basis of experimental and calculated results, three thermodynamics parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constants, along with three kinetic parameters (the apparent activation energies, the pre-exponential constant and the reaction order) are obtained. The results show that the reaction easily takes place over the studied temperature range. The solid complex Mn(His)₂Cl₂·4H₂O was prepared and characterized by IR and TG-DTG. This revised version was published online in August 2006 with corrections to the Cover Date.     

聚合硅酸氯化铝的研制

应用硅酸钠、氯化铝在一定条件下制成聚硅酸氯化铝 ( PASC)絮凝剂 ,并对其稳定性 ,Si O2 百分含量 ,Al/Si摩尔比等进行了研究 ,得出影响 PASC稳定性的主要因素有二 :一是溶液中的 Si O2 浓度 ,当 Si O2 的浓度在1 %左右时 ,溶液的凝胶时间在 3 0 d以上 ,而当 Si O2 浓度在 3 .0 %时 ,其絮凝时间仅为 1 0 d;二是 Al/Si摩尔比 ,最佳摩尔比约为 1 .5。对制得的 PASC进行了处理污水 (浑浊水、剩余氨水 )的条件实验 ,得出聚硅酸氯化铝对剩余氨水中 COD的去除率可达 94.1 % ,对氨氮的去除率达 93 .8% (二次絮凝 )。 PASC处理废水的适宜操作参数为 :投加量 1 3× 1 0 - 6 ,p H值为 6～ 7,高速搅拌 ( 1 3 0 0 r/min) 2 min,低速搅拌 ( 60 r/min) 1 0 min,静置沉淀 3 0 min～ 60 min。     

聚氯乙烯/炭黑导电复合体系的压阻行为

研究了聚氯乙烯/炭黑(PVC/CB)导电复合体系在单轴压力作用下的压阻行为,发现CB含量对电阻-机械响应具有显著的影响.当CB含量低于渗流阈值时,PVC/CB复合材料呈现PPC效应;而高于渗流阈值时,呈现NPC效应.在渗流阈值附近,单轴压缩可诱导NPC效应的出现,或者抑制PPC效应.     

多孔介质中甲烷水合物的生成特性的实验研究

在定容的条件下,实验研究了甲烷水合物在不同的多孔介质中的生成特性,所使用的多孔介质平均孔径为9.03,12.95,17.96与33.20 nm,其中孔径为12.95 nm的多孔介质使用了三个粒径范围,分别为0.105～0.150 mm,0.150～0.200 mm,0.300～0.450 mm;其他孔径的多孔介质的粒径...     

Reactivity Ratios of Diethyldiallylammonium Chloride with Acrylamide or Acrylic Acid

The compositions of copolymers of diethyldiallylammonium chloride (DEDAAC) with acrylamide (AM), acrylic acid (AA) or sodium acrylic acid (NaAA) at low conversion were determined by elemental analysis, and the reactivity ratios of monomers in copolymerization were obtained by Kelen-Tudos method. The results showed that the reactivity ratios rDE and rAM are 0.31 and 5.27 for DEDAAC with AM, rDE and rAA are 0.28 and 5.15 for DEDAAC with AA, and rDE and rNaAA are 0.40 and 3.97 for DEDAAC with NaAA, respectively. The copolymerizations for DEDAAC with AM, AA or NaAA are non-ideal copolymerization and the products are random copolymers.     

Development of One-Step Derivatization and Preconcentration Technique Using Weak Anion-Exchange Resin Modified with Sodium Diethyldithiocarbamate for Determination of Trace Amount of Copper(II) in Water

A new method was developed using weak anion exchange resin modified with sodium diethyldithiocarbamate (DDTC) for the derivatization and preconcentration of copper(II) in water prior to spectrophotometric determination. Several conditions affecting the extraction efficiency were investigated. Under the optimum conditions, an enrichment factor of 50 was achieved. The reaction mechanism of copper(II) and DDTC on the resin and binding experiment was studied. The detection limit is 0.6 μ g L^?1. The relative standard deviations of intra- and inter-day ranging from 2.1 to 3.6% and from 1.3 to 4.0% were obtained, respectively, and the recoveries were in the range of 95.3–99.6%.     

二乙基二烯丙基氯化铵与丙烯酰胺、丙烯酸共聚竞聚率

二乙基二烯丙基氯化铵;丙烯酰胺;丙烯酸;共聚合;竞聚率     

From a Network of Computed Reaction Enthalpies to Atom‐Based Thermochemistry (NEAT)

A simple and fast, weighted, linear least‐squares refinement protocol and code is presented for inverting the information contained in a network of quantum chemically computed 0 K reaction enthalpies. This inversion yields internally consistent 0 K enthalpies of formation for the species of the network. The refinement takes advantage of the fact that the accuracy of computed enthalpies depends strongly on the quantum‐chemical protocol employed for their determination. Different protocols suffer from different sources of error; thus, the reaction enthalpies computed by them have “random” residual errors. Since it is much more natural for quantum‐chemical energy and enthalpy results, including reaction enthalpies, to be based on the electronic ground states of the atoms and not on the historically preferred elemental states, and since these two possible protocols can be converted into each other straightforwardly, it is proposed that first‐principles thermochemistry should employ the ground electronic states of atoms. In this scheme, called atom‐based thermochemistry (AT), the enthalpy of formation of a gaseous compound corresponds simply to the total atomization energy of the species; it is always positive, and it reflects the bonding strength within the molecule. The inversion protocol developed and based on AT is termed NEAT, which represents the fact that the protocol proceeds from a network of computed reaction enthalpies toward atom‐based thermochemistry, most directly to atom‐based enthalpies of formation. After assembling a database that consisted of 361 ab initio reactions and reaction enthalpies involving 188 species, collected from 31 literature sources, the following dependable 0 K atom‐based enthalpies of formation, Δ_f${H{{{\rm AT}\hfill \atop 0\hfill}}}$ , all in kJ mol^?1, have been obtained by means of NEAT: H₂=432.07(0), CH=334.61(15), NH=327.69(25), OH=425.93(21), HF=566.13(31), CO=1072.08(28), O₂=493.51(34), CH₂=752.40(21), H₂O=918.05(20), HO₂=694.53(32), CO₂=1597.77(40), CH₃=1209.64(29), NH₃=1157.44(33), C₂H₂=1625.78(40), and CH₄=1641.68(40), in which the uncertainty values given in parentheses represent 95 % confidence intervals. The average deviation of these values from the well‐established active thermochemical tables (ATcT) values is a mere 0.25 kJ mol^?1, with a maximum deviation of 0.7 kJ mol^?1. This shows that the use of a large number of ab initio reaction enthalpies within a NEAT‐type protocol has considerable advantages over the sequential utilization of the ab initio information.