Adsorption of Pb^2＋ on macroporous weak acid adsorbent resin from aqueous solutions： Batch and column studies

The adsorption properties of a novel macroporous weak acid resin (D152) for Pb²⁺ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb²⁺ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb²⁺ adsorbed on D152 resin can be eluted with 0.05 mol/L HCl quantitatively. The adsorption rate constants determined under various temperatures are k _{288 K}=2.22×10⁻⁵ s^t-1, k _{298 K}=2.51×10⁻⁵ s⁻¹, and k _{308 K}= 2.95×10⁻⁵ s⁻¹, respectively. The apparent activation energy, E _a is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are ΔH ^Θ=13.3 kJ/mol, ΔS ^Θ=119 J/(mol·K), and ΔG ^Θ 298 K =−22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb²⁺ follows Langmuir model. Foundation item: Project(2008F70059) supported by the Scientific and Technological Research Planning of Zhejiang Province, China     

Synthesis of 1,4-benzenedicarbonyl thiourea resins and their adsorption properties for Ag（I）

Several 1,4-benzenedicarbonyl thiourea resins (BTR) were synthesized through interfacial polymerization between 1,4-benzenedicarbonyl diisothiocyanate and polyamine. Their structures were confirmed by FT-IR. The adsorption properties (including the effect of adsorption time, pH, initial concentrations and temperature) of BTR-1, BTR-2 and BTR-3 for Ag(I) were investigated by batch tests. The results show that the adsorption equilibria of BTR-1, BTR-2, BTR-3 for Ag(I) are achieved after about 10 h. Their equilibrium adsorption capacities are 7.11, 6.75 and 6.23, respectively, and the adsorption process accords with G. E. Boyd equation and Langmuir adsorption isotherm as well. The adsorption capacities increase with the increase of pH (the highest uptake values are observed at pH being about 6–7). The thermodynamic parameters of BTR-1 were calculated. The results show that ΔH ^Θ; and ΔS ^Θ are 6 958.8 J/mol and 64.28 J/(mol·K), respectively, and ΔG ^Θ at 20, 30, 40 and 50 °C are −11.79, −12.52, −13.16 and −13.8 kJ/mol, respectively. The silver-loaded resins can be quantitatively eluted by a solution containing 6% thiourea in 1 mol/L HNO₃.     

Preparation of calcium phosphate coating on pure titanium substrate by electrodeposition method

The influences of pH value, electrolyte temperature and loading time on depositing calcium phosphate coating on pure titanium substrate by electrodeposition process were investigated. The process was carried out with an electrochemical work-station supplying a direct current power at potential of -0.8V (vs SCE). The electrolyte consists of 7 mmol·L-1 CaCl2·2H2O, 3 mmol·L-1 Ca(H2PO4)2·H2O and 2.5% H2O2. NaOH and HCl solutions were used to adjust pH value. The deposited samples were characterized by X-ray diffraction and scanning electron microscope. The comparison of the deposits obtained at lower and higher pH values demonstrates that the crystallization process at the interface is favoured by high pH value. With temperature increasing, the deposited hydroxyapatite is occasionally of plate-like shape, and the width and the length of the deposited calcium phosphates at 65 ℃ are larger than those at 55 ℃. Therefore, it is confirmed that the morphology and microstructure of electrochemically deposited calcium phosphates can be regulated. Additionally, the coating formed in electrolyte with H2O2 additive is homogeneous and the evolution of H2 bubble can be eliminated.     

Thermochemical Study of Mixed Ligand Complexes of Rare Earths with Glycine and L-alanine

In order to obtain the standard molar enthalpies of formation of Rare-Earth amino acid coordination compounds, precise isothermal solution-reaction calorimetric method was used. The value of Δ_rH _m ^Θ of two coordination reactions was determined at T=298.2 K. From the experimental results and other auxiliary values, the standard molar enthalpies of formation of Ln(Gly)_5/2(Ala)_3/2(ClO₄)₃·H₂O(s) [Ln=La, Yb] at T=298.2 K were obtained. The values of them is to be Δ_rH _m ^Θ [La(Gly)_5/2(Ala)_3/2(ClO₄)₃·H₂O(s)]=−3545.45 kJ/mol and Δ_rH _m ^Θ [Yb(Gly)_5/2(Ala)_3/2)(ClO₄)₃·H₂O(s)]=−3793.81 kJ/mol, respectively. QU Jing-nian: Born in 1954 Funded by the Teaching and Research Award Program for Outstanding Young Professors in High Education Institute, Ministry of Education, P. R. China     

Synthesis and characterization of arsenate antimonic acid AAAc(1 : 1)

The AAAc(1 : 1) was synthesized in water by As₂O₃ and Sb₂O₃ with molar ratio of 1 : 1. AAAc(1 : 1) was characterized by Raman, IR, TG/DTG, DSC, XPS and XRD. The results show that there are four peaks to v _s of As-OH, As-O-Sb, Sb-OH and Sb-O-Sb in Raman spectra of AAAc(1 : 1) at 100 – 1 000 cm⁻¹. The solution of AAAc(1 : 1) was also titrated with KOH solution. The titration results show that AAAc(1 : 1) is a hexabasic acid with dissociation constants of k ₁=3.62 × 10⁻², k ₂=3.05 × 10⁻³, k ₃=6.43 × 10⁻⁶, k ₄ =9.78 × 10⁻⁸, k ₅=1.32 × 10⁻¹¹, k ₆=3.87 × 10⁻¹². AAAc(1 : 1) has a good solubility and stability in water, its solid obtained by free volatilizing water from its solution under air at ambient temperature is amorphous. Chemical and thermal analysis show that the composition of AAAc(1 : 1) is As₂O₅ · Sb₂O₅ · 8H₂O in air at 25 °C. AAAc(1 : 1) has the structure of AsO(OH)₂-OH-Sb(OH)₄-O-Sb(OH)₄-OH-AsO(OH)₂ or As(OH)₃-O-Sb(OH)₄-O-Sb(OH)₄-O-As(OH)₃ (isomerism) through experimental determination and geometry optimization. Foundation item: Project(50274075) supported by the National Natural Science Foundation of China     

Preparation of ITO nano-powders by hydrothermal-calcining process

1 INTRODUCTIONSn-doped In2O3(ITO) is one kind of n-typesemiconductor material[1].It has excellent electro-optical properties , such as electrical conductivityand high transparency under visible light[2],andiswidely used in electronic , transparent electrode ,solar cells and electro-irradiance , especially inscreen display[3 ,4].Recently nearly half of the met-al indium has been used to prepare ITO materialsin the developed countries[5], such as Japan, A-merica ,France and so on.So the…     

Spectra and DNA-binding properties of two novel mixed-ligand complexes containing organosulfonate

Two novel mixed-ligand complexes, [M(phen)₂(ans)₂]·H₂O (M = Cd(II) 1, Zn(II) 2; phen is 1, 10-phenanthroline, and ans is 4-aminonaphthalene-1-sulfonate), were obtained from the reaction of 1, 10-phenanthroline, sodium 4-aminonaphthalene-1-sulfonate tetrahydrate and acetate in mixed solvents. Interaction of the complexes with calf thymus DNA (ctDNA) were investigated using UV-vis absorption spectra, luminescence titrations, steady-state emission quenching by [Fe(CN)₆]⁴⁻, DNA competitive binding with ethidium bromide (EB) and viscosity measurements. The experimental results indicate that there exist two interaction modes between the complexes and DNA, namely the electrostatic interaction and intercalation, with the binding constants of 1.82 × 10⁵ M⁻¹ for 1 and 4.78 × 10⁴ M⁻¹ for 2 in buffer of 50 mM NaCl and 5 mM Tris-HCl (pH 7.0). Funded by Key Project of the National Natural Science Foundation of China (No. 60537050)     

Flow stress behavior of Cu13Zn alloy deformed at elevated temperature

Ｃｏｎｓｔｉｔｕｔｉｖｅｍｏｄｅｌｉｓａｍａｔｈｅｍａｔｉｃａｌｒｅｐｒｅｓｅｎｔａｔｉｏｎｏｆｔｈｅｄｅｆｏｒｍａｔｉｏｎｒｅｓｐｏｎｓｅｏｆａｍａｔｅｒｉａｌｔｏｅｘｔｅｒｎａｌｌｙａｐ ｐｌｉｅｄｌｏａｄｉｎｇ ,ｉｎｃｌｕｄｉｎｇｅｎｖｉｒｏｎｍｅｎｔａｌｆａｃｔｏｒｓ .Ｔｈｅｐｒｅ ｃｉｓｅｋｎｏｗｌｅｄｇｅｏｆｔｈｅｃｏｎｓｔｉｔｕｔｉｖｅｂｅｈａｖｉｏｒｏｆｔｈｅｍａｔｅｒｉａｌｉｓｔｈｅｆｏｕｎｄａｔｉｏｎｏｆｎｕｍｅｒｉｃａｌｓｉｍｕｌａｔｉｏｎｔｅｃｈｎｏｌｏｇｙｏｆｍａｔｅｒｉ…     

The synergistic mechanism of solvent extraction of gold in HCI media with TOA and TOPO

The mechanism of synergistic extraction of gold in HCl media was researched with tri-n-octyl amine(TOA) and tri-n-octyl phospine oxide(TOPO). It was determined that the composition of synergistic extract is (TOAHTOPO) AuCl₄; the constant of synergistic extracting equilibrium is 10^9.20; and the synergistic reaction is exothermic with − 17.187 kJ/K· mol of ΔH ₂₉₈. The extraction mechanism was also studied by the IR-spectra and UV-spectra. It is found that the extraction mechanism belongs to ion-association type. Synopsis of the first author Yang Tianzu, professor, born in April 1958, majoring in the metallurgy of precious metals and coordination chemistry in hydrometallurgy.     

Ethylene Polymerization by a Novel Dinuclear Heter-oligated Titanium Complex with the Ligand of （Salicylaldiminato） （β-enaminoketonato）

The condensation of acetylacetone （CH3COCH2COCH3） with benzdine （H2N-C6H4-C6H4-NH2） yielded diimine ligand 1 [HOC（Me）C（H）（Me）C=N（p-C6H4）（C6H4-p）N= C（Me）C（H）C（Me）OH）], which was converted into sodium salts. And then the sodium salts reacted with monosalicylaldiminato titanium complex 2{[3,5-di-But′2-（O）C6H2CHN（PH）]TiCl3（THF）} in dried dichloromethane to give a new benzdine-bridged binuclear complex 3{[3,5-di-Bu′-2-（O）C6H2CHN（PH）]2 [OC（Me）C（H）（Me）C=N（p-C6H4）-（C6H4-p）N=C（Me）C（H） C（Me）]Ti2Cl4}. The complex 3 was characterized by ^1HNMR and elemental analysis. In the presence of MAO（methylaluminoxane）, the complex 3 in toluene was effective to catalyze polymerization, affording moderately high catalytic activity 1.93 × 10^5 g PE/（mol.Ti.h）]and high molecular weight polyethylene [5.63× 10^5 g/moll. The high temperature gel permeation chromatography （GPC） curve of polyethylene obtained revealed a single peak, but the molecular weight distribution （MWD = 3.21） is obviously broader than that of the similar mononuclear titanium complex. The melting points of the obtained polyethylene reaches 138 ℃, indicating that the polyethylene is of high crystallinity.     

Physical simulation of hot deformation of TiAI based alloy

In order to establish a model between the grain size and the process parameters, the hot deformation behaviors of Ti-49.5Al alloy was investigated by isothermal compressive tests at temperatures ranging from 800 to 1 100 ℃ with strain rates of 10^-3-10^-1 s^-1. Within this range, the deformation behavior obeys the power law relationship, which can be described using the kinetic rate equation. The stress exponent, n, has a value of about 5.0, and the apparent activation energy is about 320 J/mol, which fits well with the value estimated in previous investigations. The results show that, the dependence of flow stress on the recrystallized grain size can be expressed by the equation: σ = K1 drex^-0.56. The relationship between the deformed microstructure and the process control parameter can be expressed by the formula: lgdrex= -0.281 1gZ 3.908 1.     

Investigation on the surface active sites variation of mineral dusts

Ｔｈｅｇｒｏｕｐｏｆｎａｔｕｒａｌｍｉｎｅｒａｌｄｕｓｔｓｒｅｌａｔｅｓｔｏｔｈｅｉｒｂｉｏｌｏｇｉｃａｌａｃｔｉｖｉｔｙａｎｄｃｏｎｔｒｏｌｓｔｈｅｉｒｆｅａｔｕｒｅａｎｄｃｏｎｔｒｉｂｕｔｉｏｎｏｆｓｕｒｆａｃｅａｃｔｉｖｅｓｉｔｅｓａｎｄｉｎｆｌｕ ｅｎｃｅｓｏｎｔｈｅｐｒｏｃｅｓｓｏｆｔｈｅｉｒｓｕｒｆａｃｅ/ｃｅｌｌｐｈｙｃｏ ｃｈｅｍｉｓｔｒｙ[1] .1　ＥｘｐｅｒｉｍｅｎｔａｌＴｈｅｓａｍｐｌｅｓｕｓｅｄｉｎｅｘｐｅｒｉｍｅｎｔａｌｗｅｒｅｆｉ ｂｒｏｕｓｂｒｕｃｉｔｅｆｒｏｍｔｈｅｓｏｕ…     

Simultaneous determination of adenine, uridine and adenosine in cordyceps sinensis and its substitutes by LC／ESI-MS

A simple, sensitive and reproducible high performance liquid chromatography-mass spectrometry coupled with electrospray ionization method for simultaneous separation and determination of adenine, adenosine and uridine was developed. The analytical column is a 2.0 mm× 150 mm Shimadzu VP-ODS column and volume fraction of the mobile phase is 86.5 %water, 12.0%methanol and 1.5%formic acid. 2-chloroadenosine was used as internal standard. Selective ion monitoring mode and selective ion monitoring ions at ratio of mass to electric charge of 136 for adenine, 268 for adenosine and 267 for uridine were chosen for quantitative analysis of the three active components. The results show that the regression equations and linear range are Y=0. 062X 0. 005 and 2.0 - 140.0μg · mL 1for adenine, Y=0. 049X 0. 004 and 4. 0 - 115.0 μg · mL-1 for uridine, Y=0. 154X 0. 014 and 1.0 - 125.0 μg · mL 1 for adenosine. The limits of detection are 0.6 μg · mL 1 for adenine, 1.0μg · mL-1 for uri dine and 0.2 μg · mL 1 for adenosine.The recoveries of the three constituents are from 96.6% to 103.2%.     

Study on the isothermal oxidation behavior in air of Ti3AlC2 sintered by hot pressing

The isothermal oxidation behavior at 900–1300°C for 20 h in air of bulk Ti₃AlC₂ with 2.8 wt% TiC sintered by means of hot pressing was investigated in the work. The isothermal oxidation behavior generally followed a parabolic rate law. The parabolic rate constants increased from 1.39×10⁻¹⁰ kg²·m⁻⁴·s⁻¹ at 900°C to 5.56×10⁻⁹ kg²·m⁻⁴·s⁻¹ at 1300°C. The calculated activation energy was 136.45 kJ/mol. It was demonstrated that Ti₃AlC₂ had excellent oxidation resistance due to the continuous, dense and adhesive protect scales consisted of a mass of α-Al₂O₃ and a little of TiO₂ and/or Al₂TiO₅. In principle, the oxide scale was grown by the inward diffusion of O²⁻ and the outward diffusion of Ti⁴⁺ and Al³⁺. The rapid outward diffusion of cations usually resulted in the formation of cracks, gaps, and holes.     

Critical driving force for martensitic transformation fcc (γ)→hcp(ε) in Fe-Mn-Si shape memory alloys

By the application of Chou's new geometry model and the available data from binary Fe-Mn, Fe-Si and Mn-Si systems, as well as SGTE DATA for lattice stability parameters of three elements from Dinsdale, the Gibbs free energy as a function of temperature of the fcc(γ) and hep(ε) phases in the Fe-Mn-Si system is reevaluated. The relationship between the Neel temperature of the γ phase and concentration of constituents in mole fraction, is fitted and verified by the experimental results. The critical driving force for the martensitic transformation fcc (γ)→ hep (ε), △ G_C~(γ→ε), defined as the free energy difference between γ and ε phases at M_s of various alloys can also be obtained with a known M_s. It is found that the driving force varies with the composition of alloys, e. g. △ G_C~(γ→ε) = - 100.99 J/mol in Fe-27.0Mn-6.0Si and △ G_C~(γ→ε) = - 122.11 J/mol in Fe-26.9Mn-3.37Si. The compositional dependence of critical driving force accorded with the expression formulated by Hsu of the     

Adsorption of D113 resin for dysprosium(III)

The adsorption behavior and mechanism of D113 resin for Dy(III) was investigated by using the method of resin adsorption. Experimental results show that the optimum medium pH of adsorption of D113 resin for Dy³⁺ is pH=6.00 in the HAc-NaAc medium. The static adsorption capacity of D113 resin for Dy³⁺ is 292.7 mg·g⁻¹. The optimum eluant is 0.5 mol·L⁻¹ HCl. The adsorption rate constant is k ₂₉₈=6.8×10⁻⁶s⁻¹. The apparent activation energy of D113 resin for Dy(III) is 14.79 kJ·mol⁻¹. The adsorption behavior of D113 resin for Dy(III) obeys the Freundlich isotherm. The adsorption parameters of thermodynamic are ΔH=14.48 kJ·mol⁻¹, ΔS=54.69 J·mol⁻¹·K⁻¹, ΔG=−1.82 kJ·mol⁻¹.The adsorption mechanism of D113 resin for Dy³⁺ was confirmed by chemical analysis and IR spectra. Funded by the Natural Science Foundation of Zhejiang Province (No.201027), Foundation of Zhejiang Provincial Education Bureau (No.20040551) and Zhoushan Science Technology Bureau (No.04114)     

Experiments and reaction characteristics of liquid phase simultaneous removal of SO<Subscript>2</Subscript> and NO

Experiments of simultaneous removal of SO₂ and NO from simulated flue gas, using NaClO₂ solution as the absorbent, were carried out in a self-designed bubble reactor, and high simultaneous removal efficiencies of SO₂ and NO were obtained under the optimal experimental conditions. The mechanism of simultaneous removal based on NaClO₂ acid solutions was proposed by analyzing the removal products. Possibility and limitation of the desulfurization and denitrification using NaClO₂ acid solutions were calculated by thermodynamic methods. Experimental results of reaction kinetics for simultaneous desulfurization and denitrification indicated that the oxidation-absorption processes of SO₂ and NO were divided into two zones, namely the fast and slow reaction zones. In the slow reaction zones both were zero order reactions, and in the fast reaction zones, the reaction order, rate constant and activation energy of SO₂ reaction with absorbent were 1.4, 1.22 (mol·L⁻¹)^−0.4·s⁻¹ and 66.25 kJ·mol⁻¹, respectively, and 2, 3.15×10³ (mol·L⁻¹) ⁻¹·s⁻¹, and 42.50 kJ·mol⁻¹ for NO reaction, respectively. Supported by the National High-Tech Research and Development Program of China (“863” Project) (Grant No. 2007AA061803)     

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine system with high plating rate

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine (THPED) chelating agent was researched comprehensively. The results indicate that plating rate decreases with the increase of concentration for THPED, CuSO₄ · 5H₂O and HCHO, pH value and bath temperature. The additive of K₄[Fe(CN)₆] · 3H₂O, 2, 2′-dipyridyl and polyethylene glycol(PEG) decrease plating rate and K₄[Fe(CN)₆] · 3H₂O has a bad effect on deposits quality, but 2, 2′-dipyridyl and PEG make deposits quality improve greatly. Low concentration of 2-mercaptobenzothiozole (2-MBT) increases plating rate and improves deposits quality, but decreases plating rate and worsens deposits quality when 2-MBT reaches 5 mg/L. The optimal conditions of this electroless copper plating process are that the concentration of THPED, HCHO, CuSO₄ · 5H₂O, PEG, 2, 2′-dipyridyl and 2-MBT are 16.8 g/L, 16.0 mL/L, 13.3 g/L, 0.5 g/L, 5.0 mg/L and 2.0 mg/L, respectively, pH value is 12.75, bath temperature is 30 °C. Plating rate reaches 9.54 μm/h plating for 30 min in the bath. The SEM images demonstrate that the surface of copper film is smooth and the crystal is fine. Foundation item: Project supported by Hubei Daye Nonferrous Metal Corporation of China     

Characterization and Electrochemical Properties of LiMn2O4 Thin Films Prepared by Solution Deposition

1 IntroductionThin-filmlithium-ion batteries have attracted greatattention of researchfor possible use inimplantable medi-cal devices , CMOS-based integrated circuits ,radio fre-quency (RF) identification tags for inventory control andanti-theft protection[1],etc. Li Mn2O4thin films , aspromising cathode materials for thin-filmlithium-ion bat-teries, have been prepared by a few methods such aspulsedlaser deposition[2 ,3],electrospraying[4-9],RF mag-netron sputtering[10], laser ablation[11]…     

Direct rapid determination of traces of sulfide in environment samples

An improved ethylene blue method for determination of sulfide is developed. It has been adapted to a direct determination of sulfide by both common spectrophotometric method and total differential spectrophotometric method. In common spectrophotometric method, the calibration curve is A=1.69ρ+0.006 and the correlation coefficient is 0.9994.The apparent molar absorptivity is 5.42×104 L*mol-1*cm-1 and calibration curve is liner when ρ is in the range of 0-0.9 mg*L-1. In total differential spectrophotometric method, the calibration curve is A=9.25ρ+0.004 and the correlation coefficient is 0.9996. The apparent molar absorptivity is 2.96×105 L*mol-1*cm-1and calibration curve is liner when ρ is in the range of 0-0.10 mg*L-1. The sensitivity of this method is increased significantly compared with the former ethylene blue method. The speed of reaction is also faster than the former one. The limit of detection is found to be 1.0 ng*mL-1 by both common spectrophotometric method and total differential spectrophotometric method. Ten replicate analyses of a sample solution containing 100 ng*mL-1sulfide give a relative standard deviation of 1.8%. The effects of various cations and anions on the determination of sulfide are studied and procedures for removal of interference is described. The method is used for the determination of sulfide in environment samples with satisfactory results.