矿石及冶炼产品中元素硫的紫外分光光度法测定

用有机试剂溶出紫外分光光度法测定元素硫,国外早有报导,但国内尚未见到。本文拟定了用环已烷作为元素硫的抽取溶剂紫外分光光度法测定元素硫。试验表明,多种含硫化合物[Na_2S·H_2O,Na_2SO_3,Na_2S_2O_3·5H_2O,KCNS,(NH_2)_2CS]及金属化合物[Ca(NO_3)_2·4H_2O,Pb(NO_3)_2,Bi(NO_3)·5H_2O,     

溶胶-凝胶法制备(Ca-Zn)O-Al_2O_3-SiO_2:Eu~(3+),Bi~(3+)发光体

用溶胶-凝胶法合成无机玻璃、玻璃陶瓷和陶瓷已得到发展。本文报道利用此法低温合成(Ca-Zn)O-Al_2O_3-SiO_2:Eu~(3+),Bi~(3+)发光体的研究结果。所用原料为99.99％的Eu_2O_3、99.99％的金属铝、99.999％的金属铋及CaCO_3、ZnCO_3和Li_2CO_3(提纯)。上述原料用HNO_3(GR)溶解。将计算的摩尔比量的Si(OC_2H_5)_4、C_2H_5OH和CH_3COOH以及Ca(NO_3)_2、Al(NO_3)_3、Zn(NO_3)_2、LiNO_3、Bi(NO_3)_3和Eu(NO_3)_3溶液,在一定的pH值下,在75℃水浴中回流数小时,经水解,缩聚成凝胶。制得     

基于4-甲基-3-苯基-5-(2-吡啶基)-1,2,4-三唑的Cu(Ⅱ)、Ni(Ⅱ)和Cd(Ⅱ)配合物的合成、晶体结构及性质（英文）

4-甲基-3-苯基-5-(2-吡啶基)-1,2,4-三唑(L)分别与CuCl_2·2H_2O、Ni(NO_3)_2·6H_2O、Cu(ClO_4)_2·6H_2O和Cd(NO_3)_2·4H_2O反应合成了配合物[CuL_2Cl]Cl·H_2O(1)、[NiL_2(H_2O)_2](NO_3)_2(2)、[CuL_2(H_2O)_2](ClO_4)_2(3)和[CdL_2(NO_3)_2]·CH_3CN(4),测定了它们的X射线单晶结构,并用红外光谱、紫外光谱、荧光和热重分析进行了表征。配合物1属于正交晶系,空间群为Fddd,中心离子Cu1(Ⅱ)具有畸变的四方锥构型[CuN_4Cl]。配合物2、3和4都属于单斜晶系,空间群分别为P2_1/n,P2_1/n和P2_1/c。配合物2、3和4的中心离子Ni1(Ⅱ)、Cu1(Ⅱ)和Cd1(Ⅱ)都为畸变的八面体构型[NiN_4O_2]、[CuN_4O_2]和[CdN_4O_2]。     

一例含有八核钴簇的锗钨酸盐的合成、结构及性质

以K_8Na_2[A-α-Ge W_9O_(34)]·25H_2O,Co(NO_3)_2·6H_2O和K_2CO_3等为原料,利用常规水溶液法合成了一例基于三缺位Keggin型多金属氧簇{Ge W_9O_(34)}的高核过渡金属衍生物K_(10.5)Cs_4H_(1.5){[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}·12H_2O(1),并通过红外光谱、元素分析、热重分析和X射线单晶衍射等分析手段对其进行了表征。化合物1含有一个V型的多酸阴离子簇{[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}~(16-),该阴离子进一步通过K~+和Cs~+离子连接形成二维结构。磁学性质研究表明,化合物1中Co~(2+)离子之间主要为反铁磁性耦合。     

稀土冠醚配合物的XPS研究 Ⅰ.Ln(NO_3)_3·C_(14)H_(20)O_5和Ln(NO_3)_3·C_(20)H_(24)O_6的Ln 3d_(5/2)光电子能谱及其伴峰

X光电子能谱(XPS)已成功地应用于过渡元素配合物电子结构的研究.在以往的十多年里,也用XPS研究了稀土元素及其化合物的内壳和价带谱、混合价态谱以及伴峰现象.稀土冠醚配合物的光电子能谱未见文献报道.我们按文献方法叫合成了Ln(NO_3)_23·C_(14)H_(20)O_5(La～Sm),Ln(NO_3)_3·C_(14)H_(20)O_5·3H_2O·(CH_3)_2CO(Eu,Gd)和Ln(NO_3)_3·C_(20)H_(24)O_6(La～     

若干μ_3-氧桥三核锰(Ⅲ)Schiff碱配合物的研究

用元素分析、电导率、磁化率、热分析、红外光谱和电子光谱等方法对新合成的7种μ_3-氧桥三核锰(Ⅲ)Schiff碱配合物:Mn_3O(bzaea)_2(C_2H_3O_2)_3、Mn_3O(bzaea)_2(C_2H_3O_2)_2(NCS)、Mn_3O(bzaea)_3ClO_4·2H_2O、Mn_3O(bzaea)_2(C_2H_3O_2)_2Br、Mn_3O(bzaea)_3I·2H_2O、Mn_3O(bzaea)_2(C_2H_3O_2)_2NO_3和Mn_3O(bzaea)_2(C_2H_3O_2)_2BPh_4·3H_2O(其中bzaea~(2-)是三齿Schiff碱2-(β-羟基乙基-亚胺)-4-苯基-丁酮(4)的负二价阴离子)进行了研究,并提出了配合物的可能构型。     

一种新型稀土苯甲酸铽配合物的合成、表征及其晶体结构

本文报道一种新型稀土苯甲酸配合物,[Tb(C_7H_5O_2)_3(C_7H_6O_2)(H_2O)]_2的合成。用元素分析、DTA、TG、DTG和IR光谱对其性质进行了表征,并测定了其晶体结构。晶体属三斜晶系,空间群为P1,Z=1。晶胞参数为:a=9.148(1),b=11.460(2),c=13.506(2)A;α=112.76(1),β=91.83(1),γ=91.99(1)°;V=1303.3(4)A~3。稀土离子形成九配位的单帽正方反棱柱型配合物,稍有崎变。     

氮、硫杂冠醚稀土配合物的合成、表征和结构研究

合成和表征了3个杂冠醚配体(L1:单氮杂15C5,L_Ⅱ:单氮杂18C6,L_Ⅲ:1,7—二硫杂18C6)与稀土硝酸盐的配合物:〔Ln(NO_3)_3L_Ⅰ〕(Ln=La～Pr),[Ln-(NO_3)-3L_ Ⅱ〕(Ln=La～Pr),〔HL_Ⅱ〕~+〔Ln(NO_3)_4(OH_2)_2〕~-(Ln=Nd,Sm～Er,Yb),〔Ln(NO_3)_3.L_Ⅲ’(H_2O)](Ln=La～Nd,Sm～Er,Yb),其中L_Ⅲ’表示L_Ⅲ冠醚环上的2个硫原子在与稀土硝酸盐反应的过程中被氧化为亚砜.配合物〔HL_Ⅱ〕~+[Nd(NO_3)_4-(OH_2)_2]的晶体属单斜晶系,空间群P2_1/n,a=1.644 0(5),b=1.739 2(3),c=1.867 5(4)nm,β=107.26(2)°.Z=8,Nd~(+3)与4个二齿NO_3~-和2个水分子配位,形成长链状夹心式结构;配合物〔Er(NO_3)_3L_Ⅲ’(H_2O)〕·CH_3COCH_3的晶体为P2_1/n空间群,a=0.877 2(2),b=1.817 9(7),c=1.854 0(5)nm,β=103.50(3)°,Z=4,Er~(3+)与3个二齿NO_3~-、1个水分子及2个亚砜氧原子形成配位数为9的配合物.     

NiFe2O4磁性纳米材料的溶剂热法一步合成

以Fe(NO_3)_3·9H_2O和Ni(NO_3)_2·6H_2O为原料,在未添加任何碱性沉淀剂和高温晶化处理的条件下,通过对实验条件(包括溶剂、溶剂热温度和时间)的优化,利用溶剂热法一步制备了具有良好结晶性和超顺磁性的NiFe_2O_4磁性纳米材料。结果表明:用H_2O和EtOH-H_2O做溶剂都不利于NiFe_2O_4的生成;用EtOH做溶剂,为了获得纯度较高的NiFe_2O_4磁性纳米材料,要保证适当的溶剂热温度和时间;所得材料的磁性能与材料中磁性组分NiFe_2O_4的含量和其结晶程度有关。该制备方法最突出的优点是简单、快速、成本低、从源头消除了污染,且所得的材料磁性能优良。     

基于环状阴离子[H6W9O33]6-的担载型含钌多酸的合成、结构与表征

以Na_2WO_4·2H_2O、Ru Cl_3、二甲基亚砜(DMSO)和Sb_2O_3为原料,利用水热合成法,得到了一例基于环状阴离子[H_6W_9O_(33)]~(6-)的担载型含钌多酸Na H[H_6W_9O_(33)(Ru(DMSO)_3)_2]·4.5H_2O(1),并用X-射线单晶衍射、元素分析、红外光谱等方法对该化合物进行结构表征.结构分析表明,化合物1为六方晶系,P6_3/m空间群,其阴离子[H_6W_9O_(33)(Ru(DMSO)_3)_2]~(2-)(1a)是由两个{Ru(DMSO)3}基团分别通过3个Ru-O-W键修饰在环状多酸阴离子[H_6W_9O_(33)]~(6-)的两侧构成的.此外,两个{Ru(DMSO)_3}基团上所有氧原子都与Na~+离子配位,使得Na~+离子与[H_6W_9O_(33)(Ru(DMSO)_3)_2]~(2-)阴离子交替相连构筑成一维链状结构.     

SHG of Phenoanthrolinium Salts and Acridinium Salts

It becomes increasingly important to make second-order nonlinear optic (NLO) materials^[1-4]. N-Hydrocarbyl-o-phenoanthrolinium salt and N-hydrocarbylacridinium salt are stable to light and heat,therefore, they are expected to be used as semi-conductor laser materials with double-frequency violet-light and blue-light (750~800 nm). Their syntheses and determination of second harmonic generation (SHG) values are in the following:     

Diaryliodonium Salts Enabled Arylation,Arylocyclization, and Aryl-Migration

Our research interest focusing on synthetic methodology with diaryliodonium salts, is summarized in this account. Besides employing a dual activation strategy of C−I and ortho C−H bonds, we have introduced vicinal functional groups at ortho-positions of diaryliodonium salts, in which their unique reactivities have been explored in various processes, including arylation, diarylation, cascade annulation, benzocyclization, arylocyclization, and intramolecular aryl migration. The variety of mechanisms of these reactions that involves either transition metals, especially palladium in organometallic catalysis, or transition-metal free conditions, were discussed in the context.     

某些正盐与其酸式盐溶解度大小的讨论

一、问题的提出在条件一致的情况下,酸式盐在水中的溶解度一般比其正盐的溶解度要大.例如,KHSO4在293K时溶解度为53g/100g水,而K2SO4却只有11.1g;NaHSO4是28.6g,而Na2SO4是19.2g.然而在可溶性的碳酸盐中,酸式碳酸盐的溶解度却小于其相应的碳酸盐,如KHCO3的溶解度是33.3g,而K2CO3是111.0g;NaHCO3是9.6g,而Na2CO3是21.8g.     

环状二苯基碘盐的合成、表征与应用——综合性多步有机合成实验*

介绍了以2-碘苯胺和苯硼酸为原料,通过Suzuki偶联反应、重氮化反应、氧化反应等3步合成环状二苯基碘盐,并进一步应用于二苯并噻吩的合成。本实验涉及有机化合物的合成、结构表征以及应用,将有机化学基础理论知识、基本实验技能与学科研究热点相结合,能够有效培养学生的科学研究素养。该实验牵涉到气相质谱、核磁及熔点仪等仪器的使用,锻炼学生动手操作仪器的能力及综合实验技能,适合作为高年级学生的综合实验。     

Cyanohydridoborate Anions: Synthesis,Salts, and Low-Viscosity Ionic Liquids

High-yield syntheses up to molar scales for salts of [BH(CN)₃]⁻ ( 2 ) and [BH₂(CN)₂]⁻ ( 3 ) starting from commercially available Na[BH₄] (Na 5 ), Na[BH₃(CN)] (Na 4 ), BCl₃, (CH₃)₃SiCN, and KCN were developed. Direct conversion of Na 5 into K 2 was accomplished with (CH₃)₃SiCN and (CH₃)₃SiCl as a catalyst in an autoclave. Alternatively, Na 5 is converted into Na[BH{OC(O)R}₃] (R=alkyl) that is more reactive towards (CH₃)₃SiCN and thus provides an easy access to salts of 2 . Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et}₂] (Na 7 b ) and Na[BH(CN)₂{OC(O)Et}] (Na 8 b ). A third entry to 2 and 3 uses ether adducts of BHCl₂ or BH₂Cl such as the commercial 1,4-dioxane adducts that react with KCN and (CH₃)₃SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm] 3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm⁻¹ at 20 °C known for non-protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye-sensitized solar cells (Grätzel cells).     

Metal Salts of Dinitro‐, Trinitropyrazole,and Trinitroimidazole

The syntheses of alkali and earth alkaline dinitropyrazolate (DNP), trinitropyrazolate (TNP), and trinitroimidazolate (TNI) salts are reported. Additionally, copper trinitroimidazolate was synthesized. Their characterization by NMR spectroscopy, mass spectrometry, elemental analysis, and vibrational spectroscopy is reported as well. Crystal structures of compound Ba(DNP)₂ ( 9 ), which crystallizes with one molecule of methanol and ethyl ether as well as of compounds Sr(TNP)₂ · 3H₂O ( 12 ), Ba(TNP)₂ · 3H₂O ( 13 ), and LiTNI · 3H₂O ( 14 ) were determined. The energetic and thermal properties were measured as well. Green‐ and red‐burning pyrotechnic formulations containing barium salts 9 and 13 as well as strontium salts 8 and 12 serving as colorants are tested. Additionally, formulations using Sr(TNP)₂ · 3H₂O ( 12 ) and Ba(TNP)₂ · 3H₂O ( 13 ) as the oxidizer and colorant at the same time were examined. The formulations were investigated with regard to their combustion behavior and performances such as burn time, dominant wavelength, spectral purity, luminous intensity, and luminous efficiency. The sensitivities towards ignition stimuli and the decomposition temperatures were determined as well.     

Hydrophobic, Highly Conductive Ambient-Temperature Molten Salts

New, hydrophobic ionic liquids with low melting points (<-30 degrees C to ambient temperature) have been synthesized and investigated, based on 1,3-dialkyl imidazolium cations and hydrophobic anions. Other imidazolium molten salts with hydrophilic anions and thus water-soluble are also described. The molten salts were characterized by NMR and elemental analysis. Their density, melting point, viscosity, conductivity, refractive index, electrochemical window, thermal stability, and miscibility with water and organic solvents were determined. The influence of the alkyl substituents in 1, 2, 3, and 4(5)-positions on these properties was scrutinized. Viscosities as low as 35 cP (for 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide (bis(triflyl)amide) and trifluoroacetate) and conductivities as high as 9.6 mS/cm were obtained. Photophysical probe studies were carried out to establish more precisely the solvent properties of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide). The hydrophobic molten salts are promising solvents for electrochemical, photovoltaic, and synthetic applications.     

同时多元素萃取-原子吸收光谱法测定锂、硼、钾等无机盐中钙、镁、锰、铜、锌、镉、铁、钴、镍和铅

本文系用1-苯基-3-甲基-4-苯甲醯基吡唑啉酮-5(PMBP)/甲基异丁基甲酮(MIBK)在六次甲基四胺存在下(pH=8.9)萃取预浓缩以后,用1.5mol/LHCl-2mgLa~(3+)/ml-0.5mgNa~+/ml 进行反萃取,继用原子吸收法在 Li_2CO_3、LiBr、RbCl、Cs_2SO_4、KOH、H_3BO_3、K_2SO_4、NaNO_3、NH_4Cl、NaCl、KH_2PO_4等盐类中测定有机相中的铁,反萃液测定其它9个离子。大量的 Cl~-、NO~-_3、SO~(2-)_4、Li、Rb、Cs、B、PO~(3-)_4等没有干扰。