Exploration of Higher Vocational Food Specialty of Inorganic and Analytical Chemistry Teaching Reform under the Background of Information Technology

Inorganic and analytical chemistry is an important professional basic courses in higher vocational of food specialty. With the extensive application of Intemet technology, we analyzed the problems which appeared in ＂Inorganic and Analytical Chemistry＂ and described some reform measures on the course in this paper.

MY WORK IN MOLECULAR SIEVE CHEMISTRY AND INORGANIC SYNTHE-SIS

After my graduation as a chemistry major from Shanghai Jiaotong University in 1952. I was assigned to work at the People’s University of Northeast China (the predecessor of today’s Jilin University) in Changchun City, serving as a teaching assistant.I)uring my career on campus.I have lectured on a dozen courses on inorganic chemistry,general chemistry,analytic chemistry. rare-element chemistry, complex chemistry. inorganic synthesis,solid-state chemistry

Thermochemistry on coordination behavior of samaric chloride hydrate with diethylammonium diethyldithiocarbamate

The complex of samaric chloride lower hydrate with diethylammoniumdiethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2atmosphere. The title complex was identified as Et_2NH_2[Sm(S_2CNEt_2)_4] by chemical and elementalanalyses, the bonding characteristics of which was characterized by IR. The enthalpies of solutionof samaric chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change ofliquid-phase reaction of formation for Et_2NH_2[Sm(S_2CNEt_2)_4] at different temperatures weredetermined by mi-crocalorimetry. On the basis of experimental and calculated results, threethermodynamic parameters (the activation enthalpy, the activation entropy, and the activation freeenergy), the rate constant, and three kinetic parameters (the apparent activation energy, thepre-exponential constant, and the reaction order) of liquid phase reaction of formation wereobtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by athermochemical cycle.

Conductivity of K_(10)H_3[Dy(SiW_4Mo_7O_(39))_2] Treated by Chemistry-Heated Diffusion of Sm and Gd Permeation

Chemistry-heated diffused permeation was used to treat POMs. ICP, IR, TG-DTA, XPS were used to characterize K_(10)H_3[Dy(SiW_4Mo_7O_(39))_2] and the sample. The result show that Sm and Gd can be permeated into the body of this sample, chemical bonds forming between Sm and other components and the conductivity of K_(10)H_3[Dy(SiW_4Mo_7O_(39))_2] improves by 0 9356×10~4 times.

Synthesis and crystal structure of an organic-inorganic complex [Cu(DMF)_3(H_2O)_2]_2[SiMo_(12)O_(40)]·2H_2O

The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu（DMF）3（H2O）212[SiMo12O40].2H2O （DMF = N, N-dimethyl formamide） is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper（I/） centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.

Electroless deposition of Cu on multiwalled carbon nanotubes

Copper has been deposited on the surface of multiwailed carbon nanombes （MWNTs） and inside MWNTs by electroless deposition. The as-prepared Cu-MWNT composite materials have been characterized by X-ray diffractometer （XRD）, transmission electron microscopy （TEM）, and electrochemical measurement. XRD analyses showed that Cu was a face-centered cubic （fcc） structure. The average size of Cu was calculated by Scherrer＇s formula from XRD data, and it was 11 nm. TEM revealed that Cu grains on the surface of MWNTs were uniform with the sizes of about 30-60 nm. The electrochemical measurement indicated that Cu-MWNT composite materials possessed fine electron conductivity.

Separation of indium (Ⅲ), gallium (Ⅲ), and zinc (Ⅱ) with Levextrel resin containing di(2-ethylhexyl) phosphoric acid (CL-P204): Part I. Selection of separation conditions

A kind of Levextrel resin separation process was developed for separation ofindium (III), gallium (III), and zinc (II) from aqueous sulfate solution with Levextrel resincontaining di(2-ethylhexyl) phosphoric acid (CL-P 204). The aim of the research is to collectpreliminary results for a pilot-scale production. Properties of adsorbing indium (III), gallium(III), and zinc (II) from sulfate solution with the Levextrel resin were first studied by batchoperation and column operation. The optimum pH, adsorption capacities and concentrations ofstripping agents for indium (III), gallium (III) were tested. The separation order of indium (III),gallium (III), and zinc (II) from sulfate solution with CL-P 204 Levextrel resin was found thatindium (III) could be first separated by adsorbing at the acidity of 1.0 mol/L whereas gallium (III)and zinc (II) could not, and they were adsorbed together by adsorbing at pH =2.8, then separatedfrom each other by stripping with 0.1 and 0.5 mol/L hydrochloric acid, respectively. The recoveriesof three metal ions were all higher than 99 percent. The cyclic properties of this resin are well.

Synthesis and Characterization of A Polynuclear Yttrium Trifluoroethoxide and Its Activity for Oligomerization of Phenyl Isocyanate

A polynuclear yttrium trifluoroethoxide was synthesized and its activity for the oligomerization of phenyl isocyanate was tested. Reaction of anhydrous YC13 with CF3CH2ONa in a 1 ： 3 molar ratio in THF at room temperature, after workup, gave complex 1 as colorless crystals. The composition of complex 1 is [Y（OCH2CF3）3]6ONa2（THF）12, which was identified by elemental analysis and ^1H NMR. Further X-ray structure determination reveals that complex 1 is a polynuclear ion pair compound, [Y6（μ6-O）（OCH2CF3）18]^2- [Na（THF）6]2＋ （1）. The crystal data of complex 1 are trigonal, P-3 space group, a = 1.78440（14） nm, b = 1.78440（14） nm, c = 1.27395（12） nm, γ= 120°, V=3.5129（5） nm^3, Z = 1, Dc = 1.607 mg·m^-3, μ = 2.591 mm^- 1（Mo Ka）, F（000） = 1710, R = 0.067, wR = 0. 182. Preliminary results demonstrated that complex 1 is a highly effective catalyst for the oligomerization of phenyl isocyanate.

Crystal structure and properties of terbium o-methylbenzoate complex with 1,10-phenanthroline [Tb(o-CH_3C_6H_4COO)_3(C_(12)H_8N_2)]_2

A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen(where o-MBA = o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solutionand its crystal structure was determined by X-ray diffraction. The crystal of the complexTb(o-MBA)_3phen belongs to triclinic crystal system and P1 (#2) space group. The crystal data are asfollows: a = 1.4371(4) nm, b = 1.7387(2) nm, c = 1.3109(2) nm, α = 96.37(1)°, β = 107.21(2)°,γ= 82.78(2)°, Ⅴ= 3.094(1) nm^3, Z= 2, M_r = 1489.12, D_c= 1.598 g·cm^(-3), μ = 2.330 mm^(-1)and F(000) = 1488.00. The final R and R_w are 0.038 and 0.047 for 8668 [Ⅰ > 2σ(Ⅰ)] uniquereflections, respectively. In the complex each Tb^(3+) ion is eight-coordinated by one1,10-phenanthroline molecule, one bidentate carboxylate group and four bridging carboxylate groups.The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and thebridging bidentate. Excitation and luminescence data observed at room temperature show that thetitle complex emits strong green fluorescence under ultraviolet light. The results of thermalanalysis indicate that the complex Tb(o-MBA)_3phen is quite stable to heat.

Synthesis and Characterization of the First Dinuclear Europium(Ⅱ) Complex Supported by Carbon-Bridged Biphenolate Ligand

Anhydrous EuCl3 reacted with sodium carbon-bridged biphenolate LNa2[ L = 2,2＇-methylene bis（6-tert-butyl-4- methyl-phenoxo ] in a 1 ： 1 molar ratio in THF in the presence of HMPA （HMPA = hexamethylphosphoric triamide）, then the product formed in situ was reduced by Na-K alloy to generate the divalent carbon-bridged biphenolate europium complex [ LEu （HMPA） 2 ] 2 （THF） 4 （ 1 ） in a good isolated yield. Complex 1 was fully characterized by elemental analysis, NMR and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P2 1/c space group, a=1.6521（3） nm, b=2.8274（3） nm, c=1.2074（2） nm, β=111.723（6）°, V=5.2393（14） nm^3, Z=2, Dc= 1.259 mg·m^-3, μ = 1.304 mm^-1, F（000） = 2092, R = 0.0815, wR = 0. 1723. Complex 1 is a dimer with two Eu - O bridges. The coordination geometry of each europium atom can be best described as a distorted trigonal bipyramid.

Interaction between Ternary Rare Earth Complexes of Cinnamic Acid and Phenanthroline with DNA by Spectroscopy

The interaction of ternary complexes [RE(phen)(cin)_3(H_2O)](RE= Nd (III),Ce(III),Eu(III))with calf thymus DNA was investigated by electronic absorption spectroscopy, ethidium bromide(EB)-DNA quenching fluorescent spectra and resonance light scattering. All experimental results indicate that the three complexes bind to DNA by the electrostatic mode and the intercalative mode. It is predicted that these complexes show high anticancer activity or other biologic activity.

Thermokinetics of Liquid-Liquid Reaction of Dy(NO_3)_3 with Histidine

The thermokinetics of liquid liquid reaction of dysprosium nitrate with histidine were studied using a microcalorimeter. 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, three kinetic parameters (the activation energy, the pre exponential constant and the reaction order) were obtained. On the basis of thermodynamics and kinetics, the formation reaction of the complex was discussed.

Synthesis of GdF_3 from the Gd_2O_3-NH_4HF_2 system

GdF3 was synthesized with Gd2O3 and NH4HF2 under atmospheric pressure and vacuum. The effects of pressure,temperature,and reactant ratio on the reaction process were investigated. A new mechanism for the synthesis of GdF3 was proposed. Powdered Gd2O3 started to react with NH4HF2 at low temperature,and the products were GdNH4F4,NH4F,NH3,and H2O. GdNH4F4 decomposed to GdF3 and NH4F after further high-temperature treatment,accompanying the volatilization and decomposition of NH4F. The whole process could be divided into three steps： synthesis,decomposition,and deamination. The initial and final reaction temperatures decreased under vacuum condition. An optimized process for the preparation of GdF3 was obtained： synthesis under atmospheric pressure at low temperature and decomposition and deamination under vacuum at high temperature.

Paraffin wax as a diluent for extraction and separation of trivalent gallium, indium, and thallium with 2,6-bis-(l'-phenyl-3'-methyl-5'-oxopyrazole-4') pyridineacyl

A method is proposed for the extraction and separation of trivalent gallium,indium and thallium from their corresponding aqueous solutions at 65 deg C with 2,6-bis-(1'-phenyl-3'-methyl-5'-oxopyrazole-4') pyridineacyl (H_2PMBPP or H_2A) using molten paraffinwax as a diluent. The values of pH_(1/2) for extraction of gallium, indium and thallium are2.62,4.32 and 4.93, respectively. Gallium can he extracted by H_2PMBPP at a lower acid medium. Theeffect of solvent and the composition of the extracted species are reported. And the thermodynamicdata of the extraction are also obtained.

Fabrication of gold nanoparticles with different morphologies in HEPES buffer

Gold nanoparticles with different morphologies, such as spindle, octahedron, and decahedron were obtained by using different molar ratios of HAuCl4/HEPES in the presence and absence of surfactants at room temperature.These nanoparticles were characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, high-resolution transmission electron microscopy（HRTEM）, scanning electron microcopy（SEM）, energy-dispersive X-rays analysis（EDX）, and selected area electron diffraction（SAED）.The kinetics of the formation of gold nanoparticles in HEPES buffer was studied by UV-visible spectrophotometer.The formation of gold nanoparticles was strongly dependent on the concentration of HEPES and pH value.The surfactants play a crucial role in the size and shape controlled synthesis of gold nanoparticles.

Synthesis,Characterization and Luminescent Properties of Complexes of Rare Earth Nitrates with Tris{2-[N-(pyridine-methanoyl)amino]ethyl} amine

A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(where Ln=La, Nd, Eu, Tb, Y) were characterized by elemental analysis, IR spectra, thermal analysis, 1 H NMR spectra, molar conductivity and luminescent spectra. All the complexes are stable in air and their conductances in acetonitrile solution lie in the range of 142～150 S·cm 2·mol -1 , indicating 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the C=O groups take part in coordination to the metal ions. The thermal behaviour of Eu complex shows that the weight losses at 75～120 ℃ and 120～210 ℃ correspond to the loss of four lattice water molecules and that of two coordinated water molecules, respectively. The luminescent spectra of the complexes of Eu(Ⅲ) and Tb(Ⅲ) were investigated in methanol.

Synthesis and Characterization of Li_(1+2x+3y)Al_xSc_yZn_yTi_(2-x-2y)Si_xP_(3-x)O_(12)

Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.

Syntheses and crystal structures of rare earth (Nd, Gd) 1-D chain com-plexes with N-p-tolylsulfonyl-β-alanine

Two rare earth complexes of Ts-β-AlaH with the formula of [Ln2（H2O）4（Ts-β-AlaH）6]n·4nH2O （where Ln = Nd（1）, Gd（2）; Ts-β-AlaH = N-p-tolylsulfonyl-β-Alanine） have been synthesized and characterized by elemental analysis, IR and X-ray diffraction. The results show that the two complexes are isostructural. They crystallize in a monoclinic system with P21/n space group. Crystal data for 1： a = 0.95149（19） nm, b = 1.9012（4） nm, c = 2.2863（5） nm, β= 100.37（3）°, Z= 4, De= 1.509 mg/cm^3, F（000） = 1880, R1= 0.0560, wR2= 0.1564 [I 〉 2σ（/）]; for 2： a = 0.9495（2） nm, b = 1.9037（4） nm, c = 2.2987（5） nm, β= 99.87（3）°, Z = 4, Dc= 1.541 mg/cm^3, F（000） = 1916, R1= 0.0515, wR2= 0.1566 [I〉2σ（I）]. The two complexes are one-dimensional chains and the coordination number of the Nd^3＋ or Gd^3＋ ion is nine.

Synthesis, Characterization, and Reactivity of Amine Bis(phenolato) Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.

Non-isothermal kinetics of the first-stage decomposition reaction of the complex of samarium p-methoxybenzoate with 1,10-phenanthroline

The complex of [Sm（p-MOBA）3phen]2 （p-MOBA, p-methoxybenzoate; phen,1 10-phenanthroline） was prepared and characterized by elemental analysis, IR, and UV spectroscopy. The thermal decomposition of the [Sm（p-MOBA）sphen]2 complex and its kinetics were studied under a static air atmosphere by TG-DTG methods. The intermediate and residue for each decomposition stage were identified from the TG curve. The kinetic parameters and mecha- nisms of the first decomposition stage were obtained from the analysis of the TG-DTG curves by a new method of processing the data of thermal analysis kinetics. The lifetime equation at a mass loss of 10% was deduced as lnr= - 30.6795 ＋ 21034.56/Tby isothermal thermogravimelric analysis.