Thermodynamic study on reaction path of Hg(Ⅱ) with S(Ⅱ) in solution

The mercury sulfidation experiments were conducted in the pH range from 1 to 13.The results show that Hg(Ⅱ) reacted with equimolar S(Ⅱ) has the lowest remained Hg(Ⅱ) concentration(9.7 μg/L) at pH 1.0 and the highest remained concentration(940.8 μg/L) at pH 13.0.Meanwhile,the changes of pH values were monitored exactly,which reveal that solution pH values change when mixing the same pH value solutions of HgCl2 and Na2S.In order to explain the phenomena and determine the reaction paths of Hg(Ⅱ) reacting with S(Ⅱ) in the solution,the concerned thermodynamics was studied.Species of S(Ⅱ)-H2O system and Hg(Ⅱ)-H2O system at different pH values were calculated,and then the species distribution diagrams of S(Ⅱ)-H2O system,Hg(Ⅱ)-H2O system and Hg(Ⅱ)-Cl--OH--H2O system were drawn.Combining the experimental data and thermodynamic calculation,the mechanism of Hg(Ⅱ) reacting with S(Ⅱ) was deduced.The results indicate that different species of S(Ⅱ) and Hg(Ⅱ) have the diverse reaction paths to form HgS precipitate at different pH values and the standard Gibbs free energies change(△r GmΘ)of those equations are also calculated,which can provide a guidance for mercury-containing wastewater treatment with Na2S.     

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.     

Enantioselective extraction of mandelic acid enantiomers based on chiral ligand exchange

Based on the chiral ligand exchange, the distribution behavior of mandelic acid enantiomers, and the partition of Cu^2 at different pH values were studied in a water/alcohol two-phase system containing Cu^2 and N-ndodecyl-L-proline(A). The influences of the solvent sort, the pH value, the concentrations of Cu^2 and chiral ligand on the partition coefficient(K) and separation factor(α) were discussed. The experimental results show that the A formed has more stable ternary complex with D-mandelic acid enantiomer than with L-mandelic acid enantiomer. There is an important influence of the pH value on K and a. When the pH values are less than 3.5, the formation of binary complexes is thermodynamically unfavourable. K and a become maximum when pH values are above 3.5 and the molar ratio of the chiral ligand to Cu^2 is 2:1.     

Electrochemical performance of nano-scale β-Ni（OH） 2 prepared at different transformations of pH value

The influence of transforming pH values on the electrochemical performance of nano-scale Ni （OH）2 was analyzed. The measurement results of XRD indicate that the nano-scale Ni （OH） 2 prepared at different transformations of pH value is β （ Ⅱ ）-phase with different crystal lattice parameters. Cyclic voltammograms （CV） and electrochemical impedance spectroscopy（EIS） measurement results show that transformations of pH value affect the proton diffusion coefficient （D） and charge-transfer resistance （Re,） of the material. The simulation of.cell experiment shows that the sample prepared at a pH of 10. 1 exhibits the maximum specific capacity （327.8 mAh/g） and higher discharge platform, the discharge performance of electrodes depends on both D and Rct, so the kinetics characteristics that electrodes reaction is controlled by both mass-transfer step and charge- transfer step are put forward.     

Optimization for Hydroforming Loading Paths of Parallel Multi-branch Tubes Based on Grey System Theory

According to characteristic of hydroforming of parallel multi-branch tubes, multi-objective problems were transformed to single objective problem of relational grade comparison by grey system theory. Two different objectives were selected, according to the principle that process parameters were optimal which of grey relational grade were maximum, the optimal loading parameters under different objective condition were obtained, and loading paths were optimized. The results indicated that parallel multi-branch tubes hydroformed under loading paths optimized by grey system theory could meet with the requirement that objective was optimal. And the optimal loading paths under different objectives were different, and the appropriate objective should be selected according to forming characteristic.     

Electrical conductivity of Cu/（10NiO-NiFe2O4） cermet inert anode for aluminum electrolysis

Cu/(10NiO-NiFe2O4) cermets containing mass fractions of Cu of 5%, 10%, 15% and 20% were prepared, and their electrical conductivities were measured at different temperatures. The effects of temperature and content of metal Cu on the electrical conductivity were investigated especially. The results indicate that the metallic phase Cu distributes evenly in 10NiO-NiFe2O4 ceramic matrix. The mechanism of electrical conductivity of Cu/(10NiO-NiFe2O4) cermets obeys the rule of electrical mechanism of semiconductor, the electrical conductivity for cermet containing 5% Cu increases from 2.70 to 20.41 S/cm with temperature increasing from 200 to 900 ℃. The change trend of electrical conductivity with temperature is similar with each other and it increases with increasing temperature and content of metal Cu. At 960 ℃, the electrical conductivity of cermet increases from 2.88 to 82.65 S/cm with the content of metal Cu increasing from 0 to 20%.     

Wind tunnel test on aerodynamic effect of wind barriers on train-bridge system

To investigate the aerodynamic effect of wind barriers on a high-speed train-bridge system,a sectional model test was conducted in a closed-circuit-type wind tunnel.Several different cases,including with and without barriers,with different barrier heights and porosity rates,and with different train arrangements on the bridge were taken into consideration;in addition,the aerodynamic coefficients of the train-bridge system were measured.It is found that the side force and rolling moment coefficients of the vehicle are efficiently reduced by a single-side wind barrier,but for the bridge deck these values are increased.The height and porosity rate of the barrier are two important factors that influence the windbreak effect.Train arrangement on the bridge will considerably influence the aerodynamic properties of the train-bridge system.The side force and rolling moment coefficients of the vehicle at the windward side are larger than at the leeward side.     

Effect of Na_3AlF_6 Addition and Surface Modification of SiCp on the Microstructure and Mechanical Properties of SiCp/Al Composites

Al-matrix composites reinforced with 56.5 vol% SiC were prepared by powder metallurgy with different amounts of additives and surface modifications of SiC_p. The crystalline phase, morphology, elements on the surface of SiC_p and the interface between SiC_p and Al were characterized by XRD, SEM, EDS and EPMA. The results show that it is favorable for the reaction between TiO_2-C on the surface of SiC_p and Al at the SiC_p-Al interface at 1 050 ℃. Besides, the process of Na_3 AlF_6 melting, dissolving and then contacting with Al_2 O_3 formed the NaF-AlF_3-Al_2 O_3 system, which generated OAlF2-, promoting the dessolution of Al_2 O_3 film on the surface of Al powder. Na_3 AlF_6 meets the needs of chemical reaction in TiO_2-C-Al system at the SiC_pAl interface in the way of offering more molten Al. After 0.75 wt% Na_3 AlF_6 was added into raw materials, the whole TiO_2-C film and most SiO_2 film were destroyed and the interfacial bonding between SiC_p and Al was keeping good, in which no obvious void and crack were observed. Meanwhile, no brittle Al_4 C_3 phase formed in the system. At this time, the flexure strength and density of samples presented optimal values, reaching up to 106.5 MPa and 90.77% respectively.     

Equilibrium and kinetics of adsorption of Ca（ II ） ions onto KCTS and HKCTS

The adsorption of Ca(Ⅱ) ions from aqueous solution by chitosan α-ketoglutaric acid(KCTS) and hydroxamated chitosan α-ketoglutaric acid(HKCTS) was studied in a batch adsorption system.The Langmuir and Freundlich adsorption models were applied to describing the equilibrium isotherms,and isotherm constants were determined.The kinetics of the adsorption with respect to the initial Ca(Ⅱ) ions concentration,temperature and pH was investigated.The pseudo-first-order and second-order kinetic models were used to des...     

Effect of Cl~- Concentration on the Corrosion Behavior of 16Mn Steel in Saturated H_2S/CO_2 Solution

The corrosion behavior of 16Mn steel was studied in saturated H_2S or H_2S/CO_2 solutions containing different Cl~-concentrations at 80℃.The microstructure and chemical composition of the corrosion products were investigated through scanning electron microscopy,energy-dispersive X-ray spectroscopy,EPMA,and X-ray diffraction.Results showed that the corrosion rate decreased with increasing Cl~-concentration in saturated H_2S or H_2S/CO_2 solution at pH 4.Conversely,the corrosion rate increased with increasing Cl~-concentration in saturated H_2S solution at pH 6.The relative H~+concentration decreased because of the increase of Cl~-concentration at pH 4,and Cl~-acted as a catalyst in the corrosive medium at pH 6 because the net H~+concentration decreased obviously compared with the condition at pH4.Cl~-promoted the formation of Fe-deficient iron sulfide at pH 4,and the opposite effect was observed in the nearly neutral solution.The corrosion rate increased firstly with increasing Cl~-concentration and then decreased in the saturated H_2S/CO_2solution at pH 6.The corrosion products were mainly composed of two kinds of iron sulfide.Sulfide FeS_(1-x) was a kind of tetragonal crystal,whereas the other was the hexagonal/monoclinic iron sulfide Fe_(1-x)S.The corrosion film that was mainly composed of FeS_(1-x) did not confer a protective effect on the base metal.The atomic ratio of Fe/S was more than 1 for FeS_(1-x).The appearance of sulfide FeS_(1-x) resembled a square block or small,needlelike,flocculent particles.The atomic ratio of Fe/S was less than 1 for Fe_(1-x)S,and the corrosion film mainly composed of Fe_(1-x)S conferred some protective property on the base metal.The sulfide FeS_(1-x) exhibited a long claviform morphology with a hexagonal or quadrilateral cross-sectional shape.     

Thermodynamic equilibrium of bismuth hydrometallurgy in chloride and nitrate solutions

Simultaneous equilibrium was applied to the thermodynamic analysis and calculation of Bi( Ⅲ )-X(Cl- ,NO3- )-H2O systems, based on which the diagrams of the logarithm of equilibrium concentration of Bi( Ⅲ ) of series precipitation vs pH value of these two systems at 25 ℃ were obtained, and the pH ranges of the stable zones of various precipitations were analyzed and determined. In Bi( Ⅲ )-Cl -H2O system, the variations of c0 (Bi3 ) and c0 (Cl-) have little effect on the equilibria of Bi(OH)3-solution and BiOOH-solution, but has great influence on the equilibrium of BiOCl-solution. However, in Bi( Ⅲ )-NO3-H2O system, the variations of c0 (Bi3 ) and C0 (NO3-)have little effect on equilibria of Bi(OH)3-solution, BiOOH-solution and Bi2O3-solution. When pH value is high,Bi2O3 is the thermodynamic stable phase, its stable zone is the widest, almost including the stable zones of BiOCl or BiONO3, Bi(OH)3 and BiOOH. Bi(OH)3 cannot be obtained from Bi( Ⅲ )-Cl--H2O system, even strong alkaline media. Bi2O3 can be obtained from the solution directly, and highly pure BiOCl or BiONO3 can also be obtained through strictly controlling pH value.     

Electrical conductivity of （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts

The effects of contents of AlF3 and Al2O3, and temperature on electrical conductivity of （Na3AlF6-40%K3AlF6）- AlF3-Al2O3 were studied by continuously varying cell censtant （CVCC） technique. The results show that the conductivities of melts increase with the increase of temperature, but by different extents. Every increasing 10 ℃ results in an increase of 1.85 × 10^-2, 1.86× 10^-2, 1.89 × 10^-2 and 2.20 × 10^-2 S/cm in conductivity for the （Na3AlF6-40%K3AlF6）-AlF3 melts containing 0%, 20%, 24%, and 30% AlF3, respectively. An increase of every 10 ℃ in temperature results an increase about 1.89× 10^-2, 1.94 × 10^-2, 1.95 × 10^-2, 1.99× 10^-2 and 2.10× 10^-2 S/cm for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts containing 0%, 1%, 2%, 3% and 4% Al2O3, respectively. The activation energy of conductance was calculated based on Arrhenius equation. Every increasing 1% of AlF3 results in a decrease of 0.019 and 0.020 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3 melts at 900 and 1 000 ℃, respectively. Every increase of 1% Al2O3 results in a decrease of 0.07 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts. The activation energy of conductance increases with the increase in content of AlF3 and Al2O3.     

Thermal Hydrolysis Synthesis and Characterization of Monoclinic Metahewettite CaV_6O_(16)·3H_2O

Monoclinic metahewettite CaV 6 O 16 ·3H 2 O has been fabricated via thermal hydrolysis of calcium vanadate(Ca 10 V 6 O 25). High purity calcium vanadate precipitate, featuring column structure with surface area of 8.61 m2/g, can be obtained by reacting sodium orthovanadate(Na 3 VO 4) with calcium oxide at 90 ℃ for 2 h. By acidifi cation of calcium vanadate in hot water at pH of 1.0-3.0, the monoclinic metahewettite crystals with uniform particle distribution, layered structure and nonporous structure can be fabricated. With the well crystallized layered structure, CaV 6 O 16 ·3H 2 O may be a potential cathode material for secondary batteries as well as super capacitor materials.     

Electrochemical behaviors of gold and its associated elements in various complex agent solutions

1　INTRODUCTIONGoldisquitestableanddifficulttodissolveinacommonmineralacid .However ,becausethereisadelectroniclayerunfilledingoldatomicstructure ,goldcanbecombinedwithmanychemicalagentstoformstablecomplexions,causingthepotentialofgoldinasolutiontodecreaseandgoldtodissolveinthesolutioneasily .Basedonthisprinciple ,cyanideisanefficientlixiviatingagentofgold ,andhasbeenwidelyusedtoextractgoldfrom primaryandsecondaryresources .However ,itisthemosttoxicandnotbeneficialtoen vironmentprotection…     

Microstructures and Electrical Properties of Bi_(0.5)-(Na_(1-x-y)K_xLi_y)_(0.5)TiO_3 Lead-free Piezoelectric Ceramics

The microstructures and electrical properties of Bi0.5(Na1-x-yKxLiy)0.5TiO3 lead-free piezoelectric ceramics were studied.These ceramics were prepared by conventional ceramic technique.XRD analysis reveals that the ceramics possess almost pure perovskite phase when y≤0.2.The SEM results show that,with more amounts of Li+,the crystalline grain growing speed is accelerated,and the sintering temperature can effectively be decreased.The measurements of piezoelectric properties indicate that the ceramics with relatively low amount of Li+ and high amount of K+ have comparatively large piezoelectricity.The dielectric measurements show that the ceramics have properties like relaxor ferroelectrics and diffuse phase transition(DPT) at Td and Tc,respectively.The results of ferroelectric measurements reveal the system has relatively higher remanent polarization Pr(27.6 μC/cm2) and lower coercive field Ec(37.5 kV/cm).     

Electrochemical behavior of K3Fe（CN）6 in water-in-oil microemulsion

A water-in-oil (W/O) microemulsion composed of Triton X-100, n-hexanol, n-hexane and water solution with hydrochloric acid was prepared. K₃Fe(CN)₆ was added in as a water-soluble electroactive probe, and its electrochemical behavior was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that the H⁺ concentration of the water phase has a great effect on the conductivity of the W/O microemulsion, and hence influences the electrochemical behavior of K₃Fe(CN)₆. When the pH value of water phase is about 7, the electrical conductivity of the W/O microemulsion is only 1.2×10⁻⁶ S/cm, and K₃Fe(CN)₆ almost cannot react at the glassy carbon electrode. But when the H⁺ concentration is more than 3 mol/L, the W/O microemulsion has a good electrical conductivity and K₃Fe(CN)₆ shows good electrochemical performance in it. The results of CV and EIS studies indicate that the electrochemical behavior of Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ in the W/O microemulsion is different from that in the aqueous solution. This may be due to the unique liquid structure of the W/O microemulsion and the unique mass transfer in the W/O microemulsion. Foundation item: Projects(20673036, J0830415) supported by the National Natural Science Foundation of China; Projects(05JT1026, 2007JT2013) supported by the Science Technology Project of Hunan Province, China     

Sorption of Pb(II) from aqueous solution by konjac glucomannan beads

Konjac glucomannan beads have been investigated as metal biosorbent for Pb(II) from aqueous solu-tions. The effect of contact time, solution pH, initial metal concentration, and desorption were studied in batch experiments at 20℃±2℃. Maximum mental sorption was found to occur at initial pH 4.0―5.5. Kinetic studies revealed that the initial uptake was rapid and equilibrium was established in 3 h and that the data followed the prseudo-second order reaction. The equilibrium sorption data at initial pH 4.0 were described by the Langmuir and Freundlich isotherm models; however, Langmuir isotherm model has been found to provide the best correlation. The highest value of Langmuir maximum uptake (qmax) was found to be 105.71 mg·g-1. Similar Freundlich empirical constant (KF) was obtained to be 1.98 for lead. Adsorption-complexation may be involved in the sorption process of lead. Desorption experi- ments showed evidence that after two contacts neither HCl nor EDTA solutions were able to desorb lead from the konjac glucomannan beads, but the desorbtion efficacy of HCl solution was higher than EDTA solution. The results obtained show that konjac glucomannan beads may be used for the treat-ment of wastewater contaminated with lead.     

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)     

Effect of catalyst on structure of （PEO）8LiClO4-SiO2 composite polymer electrolyte films

（PEO）8LiClO4-SiO2 composite polymer electrolytes（CPEs） were prepared by in-situ reaction, in which ethyl-orthosilicate （TEOS） was catalyzed by HCl and NH3·H2O, respectively. The ionic conductivity, the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra, contact angle method and TEM. The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10^-5 and 1.1×10^-5 S/cm respectively at 30 ℃. The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2, and influences the surface energy and conductivity of CPE films directly. Meanwhile, the ionic conductivity is related to the surface energy.