Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol

The reaction of a typical unsaturated alcohol, 3-methyl-3-buten-1-ol （MBO331）, with Cl atoms, was investigated for the first time. The reaction was investigated using discharged flow-tube coupled with electron impact mass spectrometer. The experiments were performed over the temperature range of 248 K-298 K and at pressure of 1 torr in He as the bath gas. The obtained kinetic data were used to derive the Arrhenius expression： k1 = （3.47 ± 1.21） × 10^-11 exp[（ 599 ±69）/7] cm^3 molecule^-1 s^-1. Finally, atmospheric lifetimes of the MBO331 with respect to OH radicals, NO3 radicals and CI atoms have been calculated and the atmospheric implications are considered briefly.     

Uptake of gas-phase alkylamines by sulfuric acid

Recent field and experimental studies have suggested that acid-base reactions of alkylamines may play an important role in secondary aerosol formation. We investigated the heterogeneous chemistry of ethylamine (EA), diethylamine (DEA) and triethylamine (TEA) on liquid H2SO4 (1 wt%–80 wt%). Irreversible reactive uptakes were observed for all three alkylamines. The reactive uptake coefficients (γ ) of alkylamines increased with the acid concentration, and the γ value for DEA appeared to increase slightly faster than that of EA and TEA. The potential roles in secondary aerosol formation of different alkylamines are briefly discussed.     

3－甲基－3－丁烯－1－醇溴代的新方法

以亚磷酸三苯酯的二溴化物替代三溴化磷作为溴代试剂，成功地进行了３－甲基－３－丁烯－１－醇的溴代．反应容易控制，重复性好，后处理简便，产率有了明显的提高．指出了三溴化磷作为溴代试剂进行３－甲基－３－丁烯－１－醇的溴代的不适之处．所得溴代产物结构得到１ＨＮＭＲ波谱的证实．     

UV/visible spectroscopic analysis of CO<Superscript>3+</Superscript> and CO<Superscript>2+</Superscript> during the dissolution of cobalt from mixed Co-Cu oxidized ores

The leaching of cobalt from four-mixed Co-Cu oxidized ores containing cobalt at levels ranging from 0.5wt% to 34wt% was studied and the results has been reported. Conventional dissolution of these oxidized Co-Cu ores with diluted H₂SO₄ and SO₂ as a reducing agent resulted in a substantial improvement in the solution based recovery of cobalt. UV/visible spectroscopic analysis of the leached solutions indicated that the increased cobalt content in the solution was a result of flushing the acidified cobalt leaching solution with SO₂. Furthermore, UV/visible spectroscopy confirmed that as SO₂ was flushed into the acidified leaching solution, Co³⁺ bearing minerals were reduced to the readily soluble Co²⁺ bearing minerals, and this resulted in the increase of total cobalt in the collected solution. The mechanism of the reduction of Co³⁺ to Co²⁺ bearing minerals when SO₂ is flushed during the leaching of mixed Co-Cu oxidized ores, including the stability trends of Co³⁺, Co²⁺, and Cu²⁺ complexes, as shown by their UV/visible spectra, are also discussed.     

硼稀土共渗钛合金的耐蚀性研究

采用不需保护性气氛的固体粉末法对Ti6Al4V(TC4)合金表面进行稀土与硼共渗,并对硼稀土共渗TC4钛合金、单渗硼TC4钛合金及未经渗硼处理的TC4钛合金基体,分别在35%NaCl和5%H2SO4(质量分数)溶液介质中进行了腐蚀实验.X射线衍射分析表明,TC4表面渗层由TiB2和TiB组成.扫描电镜观察表明,外层的TiB2具有平坦的生长前沿,而内层TiB为锯齿状形貌;其中外层的TiB2内部存在少量针孔,分析认为是Ce原子与B原子共渗时产生的Kirkendall效应所致.Tafel极化曲线分析结果表明,在35%NaCl和5%H2SO4溶液介质中,各样品的耐蚀性大小排序为单渗硼TC4钛合金>硼稀土共渗TC4钛合金>未经渗硼处理的TC4钛合金.     

Alternative beneficiation of tantalite and removal of radioactive oxides from Ethiopian Kenticha pegmatite-spodumene ores

The beneficiation methods for Ethiopian Kenticha pegmatite-spodumene ores were assessed through mineralogical and quantitative analyses with X-ray diffraction (XRD) and energy-dispersive X-ray fluorescence (EDXRF). The tantalite in the upper zone of the Kenticha pegmatite-spodumene deposit is 58.7wt% higher than that in the inner zone. XRD analysis revealed that the upper zone is dominated by manganocolumbite, whereas the inner zone is predominantly tantalite-Mn. Repeated cleaning and beneficiation of the upper-zone ore resulted in concentrate compositions of 57.34wt% of Ta₂O₅ and 5.41wt% of Nb₂O₅. Washing the tantalite concentrates using 1vol% KOH and 1 M H₂SO₄ led to the removal of thorium and uranium radioactive oxides from the concentrate. The findings of this study suggest that the beneficiation and alkaline washing of Kenticha pegmatite-spodumene ores produce a high-grade export-quality tantalite concentrate with negligible radioactive oxides.     

玻璃粉对混凝土酸侵蚀性能的影响

采用试验方法,研究了玻璃粉替代胶凝材料在不同掺量(0、5%、8%、15%)时对混凝土抗压强度和耐酸侵蚀性的影响。对比了各个试样在5%H2SO4溶液和5%CH3COOH溶液中腐蚀28 d后的质量亏损和抗压强度损失,并采用SEM分析了试样腐蚀后的表面形貌。结果表明,玻璃粉有利于提高混凝土的耐H2SO4和CH3COOH侵蚀性,耐CH3COOH侵蚀差于耐H2SO4腐蚀,H2SO4侵蚀后的试样表面形成了大量石膏,CH3COOH侵蚀后试样表面疏松并出现了大量孔洞和裂纹。当玻璃粉掺量为8%时,试样的耐H2SO4和CH3COOH侵蚀性最佳。     

Temperature effect on the corrosion and passivation characterization of Ni<Subscript>82.3</Subscript>Cr<Subscript>7</Subscript>Fe<Subscript>3</Subscript>Si<Subscript>4.5</Subscript>B<Subscript>3.2</Subscript> alloy in acidic media

The effects of temperature on corrosion and the electrochemical behavior of Ni_82.3Cr₇Fe₃Si_4.5B_3.2 glassy alloy in HCl, H₂SO₄, and H₃PO₄ acids were studied using AC and DC techniques. Impedance data reveal that the susceptibility to localized corrosion increases with increasing temperature. Potentiodynamic polarization curves reveal that the bulk glassy alloy is spontaneously passivated at all the investigated temperature in H₂SO₄ and H₃PO₄ solutions. A localized corrosion effect in HCl solution is clearly observed. The apparent activation energies in the regions of Tafel, active, and passive, as well as the enthalpies and entropies of the dissolution process were determined and discussed. The high apparent activation energy (E_a) value for H₃PO₄ solution in Tafel region is explained by the low aggressivity of PO₄3- ions.     

Voltammetric studies on free radicals of lower fatty alcohols

In this work, both generation and reduction processes of the a -radicals of lower fatty alcohols were studied by voltammetry in lower fatty alcohols/peroxydisul- fate/phosphate buffer system. Experimental results showed that such three reactions were successively completed at negative potential on mercury electrode surface: (ⅰ) sulfate radical anion SO₄^.- was generated electrochemically from one-electron reduction of peroxydisulfate ion S₂O₆^2-, (ⅱ) the SO₄^.-oxidized lower fatty alcohols to the corresponding a -radicals and (ⅲ) the a -radicals were reduced in one-electron and one-proton addition to produce their own reduction waves. The apparent free energy ΔrGm of the a -radicals of lower straight-chain fatty alcohols such as methanol, ethanol, propanol, butanol and pentanol obtained were 107.09, 116.74, 122.53, 126.39 and 129.28 kJ·mol/L, respectively. The proposed method is more simple and convenient than the current approaches based on the radical-chain reaction for studying alcohol oxidation.     

Characteristics of electric double layer in different aqueous electrolyte solutions for supercapacitors

Aiming to find suitable electrolytes for electric double layer capacitor (EDLC),the relationship between the formation velocity of electric double layer and the specific capacitance in different electrolyte (H 2 SO 4,KOH,KCl,NH 4 Cl,and LiOH) solutions was investigated by cyclic voltammetry and AC impedance with varying frequency and potential,which was also analyzed based on Stern model and Gouy-Chapman diffusion layer model.It shows that the capacitance is positively correlated with the formation velocity of the electric double layers,which is affected by the type of ions applied,the concentration of the electrolyte solution,and the potential and frequencies as well.The electrolyte solutions of 6 mol/L KOH and 4 mol/L H 2 SO 4 provide the largest capacitance,reaching 214 and 186 μF/cm 2,respectively.Both 6 mol/L KOH and 4 mol/L H 2 SO 4 solutions are suitable electrolytes for EDLC applications using Pt as electrodes.     

Effects of the hierarchical pyrolysis polyaniline on reversible hydrogen storage of LiBH4

In this work,LiBH_4–20 wt%PP composite was prepared by ball-milling with as-synthesized hierarchical pyrolysis polyaniline(PP)and LiBH_4,and the hydrogen sorption performance as well as catalytic mechanism of the composite was studied.It is found that the onset desorption temperature of the composite decreases to 75°C,almost 235°C lower than that of the milled LiBH_4.Moreover,the composite could release 4.1 wt%H_2and rehydrogenate a total of 4.4 wt%H_2when the temperature raiseds up to 400°C,showing an outstanding reversibility,which even 3.9 wt%H_2can be kept after five cycles.Through scanning electron microscopy(SEM)observation and X-ray diffraction(XRD)analysis,we found that the PP surface forms some nanoholes after hydrogenation-dehydrogenation cycles,which leads to the confinement of some LiBH_4in the PP nanoporous structure,therefore,the hydrogen sorption kinetics and reversibility are significantly enhanced.In addition,we also found the oxygenic groups of the PP can react with LiBH_4forming LiBO_2and Li_3BO_3,where the containing Li–B–O bonds loaded in the porous structure of the PP catalyze the hydrogenation reaction of LiBH_4.     

Development of high volume rice husk ash alumino silicate composites

The development of high volume rice husk ash (RHA) alumino silicate composites (ASC) was studied. RHA was used as the source of silica and aluminium in the ASC. The mass ratios of RHA:Al(OH)3 of 70:30 to 99:1 were tested. The results indicate that the obtained ASC mortars are not stable and disintegrate in water. Boric acid was introduced to the mixture to overcome this problem. Stable ASC mortars with high RHA:Al(OH)₃ mass ratios of 90:10 to 97.5:2.5 were obtained with the use of boric acid and 115℃ curing. The compressive strength of the mortar of 20 MPa was gained. The immersion test indicates that high volume RHA ASC mortars show good resistance in 3vol% H₂SO₄ solution, but is slightly less durable in 5wt% MgSO₄ solution.     

冷凝液硫含量对SUS444铁素体不锈钢腐蚀行为的影响

利用冷凝液浸蚀-高温氧化循环腐蚀法模拟汽车排气系统内部服役环境,借助失重分析、腐蚀形貌观察及腐蚀产物分析,研究了SUS444不锈钢在不同硫含量的冷凝液中的腐蚀行为。结果表明,随着腐蚀循环次数的增加,不锈钢表面不断沉积的FeSO_4·7H_2O、Fe(NH_4)(SO_4)_2及Fe_4(SO_4)_5(OH)_2·18H_2O等硫酸盐物质加速了不锈钢的腐蚀进程,其点蚀深度及腐蚀速率均随冷凝液中硫含量的升高而增加。     

金属离子对钢在没食子酸/硫酸介质中的腐蚀行为研究

 用失重法研究了4种金属离子(Na⁺,Zn²⁺,Cu²⁺,Fe³⁺)在0.5 mol/L H₂SO₄以及500 mg/L没食子酸+0.5 mol/L H₂SO₄介质中在20℃对冷轧钢腐蚀行为的影响.结果表明:Cu²⁺对钢的腐蚀起抑制作用;而其余3种金属离子(Na⁺,Zn²⁺,Fe³⁺)对钢的腐蚀起加速作用.在相同条件下,冷轧钢在0.5 mol/L H₂SO₄溶液中的腐蚀速率顺序为:Cu²⁺2++3+;而在500 mg/L没食子酸+0.5 mol/L H₂SO₄介质中,腐蚀速率顺序为:Cu²⁺2+3++.     

Effect of modifying agents on the hydrophobicity and yield of zinc borate synthesized by zinc oxide

The aim of this study was to synthesize zinc borate using zinc oxide, reference boric acid, and reference zinc borate (reference ZB) as the seed, and to investigate the effects of modifying agents and reaction parameters on the hydrophobicity and yield, respectively. The reaction parameters include reaction time (1–5 h), reactant ratio (H₃BO₃/ZnO by mass: 2–5), seed ratio (seed crystal/(H₃BO₃+ZnO) by mass: 0–2wt%), reaction temperature (50–120℃), cooling temperature (10–80℃), and stirring rate (400–700 r/min); the modifying agents involve propylene glycol (PG, 0–6wt%), kerosene (1wt%–6wt%), and oleic acid (OA, 1wt%–6wt%) with solvents (isopropyl alcohol (IPA), ethanol, and methanol). The results of reaction yield obtained from either magnetically or mechanically stirred systems were compared. Zinc borate produced was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and contact angle tests to identify the hydrophobicity. In conclusion, zinc borate is synthesized successfully under the optimized reaction conditions, and the different modifying agents with various solvents affect the hydrophobicity of zinc borate.     

超声波下酸化碘酸钾和亚硫酸钠反应的反应速率研究

分别测定在有超声波作用和在无超声波作用条件下 ,酸化碘酸钾 (KIO3 )和亚硫酸钠 (Na2 SO3 )反应的反应速率方程式及活化能 ,从而研究该反应的机理以及超声波在该反应中的作用 ,并确定反应的最佳条件。实验得出 ,超声波对该反应有一定的促进作用 ,但是这种促进作用只提高反应的速率常数和降低反应的活化能 ,并没有改变反应机理。在超声波功率为 30 0W时 ,反应的速率方程表示式为 :v =k·c1 0 9(KIO3 ) ·c1 0 0 (Na2 SO3 )·c1 0 8(H+ ) ,其中 :k =95 0 (mol-1·L) 2 ·s-1,活化能为 17 35kJ·mol-1。实验还得出 ,在温度为2 98K时 ,当KIO3 与Na2 SO3 的初始浓度比为 2∶5 ,H+ 的初始浓度为 0 0 4 2 8mol·L-1,超声功率为 30 0W时 ,反应速率为最快 ,即v =4 31× 10 -4mol·L-1·s-1)。     

Effect of surfactant on the catalyzed oxidation of 2,6-dimethylphenol by rhus vernicifera laccase

Rhus vernicifera laccase-catalyzed oxidation of 2,6-dimethylphenol (DMP) was studied in the presence of 12 surfactant (Sf). C₁₆H₃₃N⁺ (CH₃)₃ Br⁻ (CTAB) etc 5 cationic Sf and C₁₂H₂₃SO₄Na (SDS) etc 3 anionic Sf can promote the reaction in the different extent. The promotion of CTAB is the largest among them. The affected factors of the reaction—concentration of CTAB and DMP, pH, temperature, laccase quantity and reaction kinetics are inverstigated further. The nonionic Sf-Tween-20, Tween-60, Tween-80 and Triton X-100 have not promotion to the reaction. Ji Licai: born in 1945, Associate professor     

Physical chemistry mechanisms of CDR system in sulphide mineral flotation

The flotation tests, zeta potential measurements, and Fourier transform infrared spectroscopy (FTIR) analysis on galena, sphalerite, and pyrite were studied in a collecting-depressing-reactivating (CDR) system. In this system, sulphide minerals were first collected and activated by the collector, and then depressed strongly by Ca(OH)₂ in a strong alkaline solution. Finally, they were reactivated by H₂SO₄. The flotation tests of pure minerals showed that in the Ca(OH)₂ depressing process sulphide minerals had similar flotation characteristics because they had already been influenced by the collector. Hence, the flotability differences between them were reduced. However, in the H₂SO₄ reactivating process considerable differences in the flotability between galena and sphalerite/pyrite were produced. That is to say, galena was relatively easy to be reactivated by H₂SO₄, but sphalerite and pyrite were not reactivated at pH > 11. The zeta potentials of sulfide minerals measured by the Zeta Plus presented irreversible characteristics on the change of pH values. The results of the FTIR spectra analysis indicated that the collectors already adsorbed on the mineral surface were removed partially by Ca(OH)₂.     

Dehydrogenation and reaction pathway of Perovskite-Type NH4Ca(BH4)3

Perovskite-type borohydride, NH_4Ca(BH_4)_3, is considered as a promising hydrogen storage material due to its high gravimetric hydrogen capacity(15.7 wt%). In this work, the dehydrogenation performance and reaction pathway of NH_4Ca(BH_4)_3 have been systematically investigated. It is found that the initial decomposition temperature is only 65 °C, suggesting a low thermodynamic stability of NH4Ca(BH4)3. The desorption kinetics conducted by differential scanning calorimetry(DSC) indicates that the activation energy of decomposition is about 226.1 k J/mol. The dehydrogenation pathway of NH_4Ca(BH_4)_3 characterized by fourier-transform infrared spectroscopy(FTIR) and solid-state nuclear magnetic resonance(NMR) shows a stepwise decomposition process,in which the initial dehydrogenation is due to destabilization of H~+ in NH4 and H-in BH4 followed by the subsequent dehydrogenation steps arising from the decomposition of homologous NH_3BH_3 and the final decomposition of Ca(BH_4)_2 at a high temperature, respectively.     

Dielectric properties of porous SiC/Si_3N_4 ceramics by polysilazane immersion-pyrolysis

The SiC nanotubes were synthesized on porous Si_3N_4 matrix by polysilazane immersion-pyrolysis. The β-SiC and free C contents increased with the increasing dipping times, which cause some clear vibration and loss peaks of the dielectric constant patterns emerged at around 12.9 GHz and 14.7 GHz in the samples of 20 wt% and 30 wt%benzoic acid, respectively. The reflectivity of the obtained ceramics were -7 dB ～-10 dB from the frequency of 8 GHz–18 GHz, which means that the amount of 80%–90% electromagnetic wave could be attenuated. The ceramics containing 40 wt% benzoic acid showed the high loss, low reflectivity and a wide absorbing band,indicating the high absorbing efficiency and good dielectric properties.