偶氮染料电化学氧化脱色动力学及其影响因素

以酸性红B作为模型污染物 ,研究了偶氮染料的电化学氧化脱色动力学 .考察了染料起始浓度、pH、电流密度及外加电解质 (Na2 SO4 /NaCl)对脱色过程的影响 .试验结果表明酸性红B电化学氧化脱色过程符合假一级动力学规律 ,反应物浓度对反应速率常数的影响为负一级 .酸性条件有利于酸性红B的迅速脱色 .采用NaCl作为外加电解质时 ,酸性红B的降解主要是氯离子的间接氧化作用 。

Oxidation behavior of ferrovanadium spinel particles in air:Isothermal kinetic and reaction mechanism

The oxidation behavior of ferrovanadium spinel(FeV_(2)O_(4)),synthesized via high-temperature solid-state reaction,was investigated using thermogravimetry,X-ray diffractometry,and X-ray photoelectron spectroscopy over the temperature range of 450–700℃.The results revealed that the oxidation process of FeV_(2)O_(4)can be divided into three stages with the second stage being responsible for maximum weight gain due to oxidation.Three classical methods were employed to analyze the reaction mechanisms and model functions for distinct oxidation stages.The random nucleation and subsequent growth(A_(3))kinetic model was found to be applicable to both initial and secondary stage.The third stage of oxidation was consistent with the three-dimensional diffusion,spherical symmetry(D_(3))kinetic mode.Both the model-function method and the model-free method were utilized to investigate the apparent activation energy of the oxidation reaction at each stage.It was found that the intermediates including Fe_(3)O_(4),VO_(2),V_(2)O_(3),and Fe_(2.5)V_(7.11)O_(16),played significant roles in the oxidation process prior to the final formation of FeVO_(4)and V_(2)O_(5)through oxidation of FeV_(2)O_(4).

Mechanism of high temperature oxidation of Inconel 625 superalloy with various solution and ageing heat treatment processes

The high-temperature oxidation behaviour of the Inconel 625 alloy at 950℃ was investigated after different ageing treatments.The effect of heat treatment on the oxidation behaviour of the alloy was analysed by characterizing the structure and elemental distribution before and after oxidation.The results reveal that the two ageing treatments at 650℃ for 500 h and at 750℃ for 400 h both reduced the oxidation mass gain.After oxidation at 950℃,an outer Cr_(2)O_(3) layer and inner Al_(2)O_(3) are identified as the main oxidation products.Moreover,Nb_(2)O_(5) andδ(Ni_(3)Nb)phases precipitated after oxidation.The ageing treatments cause the rapid generation of a dense Cr_(2)O_(3) layer on the surface,which prevents the diffusion of oxygen into the matrix,reduce the Al_(2)O_(3) inward growth depth,and improve the oxidation resistance of the alloy.

Effect of low curing temperature on the anticorrosion performance of composite coatings reinforced with modified Fe_(3)O_(4)

In this manuscript,the neat epoxy(EP)and functionalized Fe_(3)O_(4)(G-Fe_(3)O_(4))reinforced epoxy(G-Fe_(3)O_(4)/EP)coatings were cured under different temperatures,and the effect of the low curing temperature on the anticorrosion performance was investigated.The experimental results show that the epoxy-amine ring-open addition reaction mainly exists in the curing process,and the activation energies of the reaction for the two coatings are 55.84 and 53.29 kJ/mol,respectively.For the coatings cured at the low temperature,almost no pores could be detected on the fracture surface,but the presentence of the rough regions reflects the poor curing state.As compared with the samples cured at the high temperature,the anticorrosion performance of the coatings with the low curing temperature is worse,and the decrease rate of the anticorrosion performance is slower,because of the poor curing state and low adhesion obtained at the low temperature.

防爆型2100C过程总有机碳分析仪在水中油监测的应用

论述了2100C过程总有机碳分析仪紫外催化与化学动力氧化,载气抽提,非色散红外分析流程的工作原理和基本结构,给出了防爆区域循环冷却水中微量油泄漏连续监测的典型应用。

Preparation of α-Bi_2O_3 from bismuth powders through low-temperature oxidation

α-Bi2O3 powders were prepared from nanometer Bi powders through low-temperature oxidation at less than 873.15 K. XRD, SEM, TEM and HRTEM were used to characterize the structure and morphology of Bi powders and Bi2O3 particles. Kinetic studies on the bismuth oxidation at low-temperatures were carried out by TGA method. The results show that bismuth beads should be reunited and oxidized to become irregular Bi2O3 powders. The bismuth oxidation follows shrinking core model, and its controlling mechanism varies at different reaction time. Within 0-10 min, the kinetics is controlled by chemical reaction, after that it is controlled by O2 diffusion in the solid α-Bi2O3 layer. The apparent activation energy is determined as 55.19 kJ/mol in liquid-phase oxidation.

Oxidation kinetics of oxide film on bubble surface of aluminum foams produced by gas injection foaming process

In the range of 620？710 °C, air was blown into A356 aluminum alloy melt to produce aluminum foams. In order to study the influence of temperature on the thickness of oxide film on bubble surface, Auger electron spectroscopy （AES） was used. Based on the knowledge of corrosion science and hydrodynamics, two oxidation kinetics models of oxide film on bubble surface were established. The thicknesses of oxide films produced at different temperatures were predicted through those two models. Furthermore, the theoretical values were compared with the experimental values. The results indicate that in the range of 620？710 °C, the theoretical values of the thickness of oxide film predicted by the model including the rising process are higher than the experimental values. While, the theoretical values predicted by the model without the rising process are in good agreement with the experimental values, which shows this model objectively describes the oxidation process of oxide film on bubble surface. This work suggests that the oxidation kinetics of oxide film on bubble surface of aluminum foams produced by gas injection foaming process follows the Arrhenius equation.

Leaching kinetics of gold bearing pyrite in H_2SO_4-Fe_2(SO_4)_3 system

Gold bearing pyrite leaching was conducted in H2SO4-Fe2（SO4）3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics and mechanism were studied.When the temperature ranged between 30-75 °C,the pyrite leaching was mainly controlled by chemical reaction with positive correlation to the ferric ion concentration.The activation energy obtained from Arrhenius empirical formula is 51.39 k J/mol.The EDS and XPS analyses suggest that the oxidation of sulfur within pyrite is through a series of intermediate stages,and eventually is oxidized to sulphate accompanied with the formation of element sulfur.This indicates a thiosulfate oxidation pathway of the gold bearing pyrite oxidation in H2SO4-Fe2（SO4）3 system.

Factors Affecting Cr(Ⅲ) Oxidation by Manganese Oxides

The high oxidation ability of manganese oxides or soils was used to study effects of pH and coatingon Cr(Ⅲ) oxidation. The results indicated that Cr(Ⅲ) oxidation peaked in pH 4.0-6.5. The amount andrate of Cr(Ⅲ) being oxidized by uncoated δ-MnO2 were larger than those by Fe oxide- or CaCO3-coatedone. Inorganic Cr(Ⅲ) was more easi1y oxidized by MnO2 than organic complex Cr(Ⅲ) due to differentsurface affinities. Precipitated Cr(Ⅲ) and adsorbed Cr(Ⅲ) might be transferred onto MnO2 surface andthen oxidized to Cr(VI).

Oxidation behavior and mechanism of porous nickel-based alloy between 850 and 1000 °C

The oxidation behavior and mechanism of a porous Ni?Cr?Al?Fe alloy in the temperature range from850to1000°Cwere investigated by optical microscopy,scanning electron microscopy(SEM)and energy dispersive spectroscopy(EDS),X-raydiffraction(XRD)analyses and X-ray photoelectron spectroscopy(XPS).The results show that the oxidation kinetics at950and1000°C of this porous alloy is pseudo-parabolic type.Complex layers composed of external Cr2O3/NiCr2O4and internalα-Al2O3areformed on the surface of the oxidized porous alloys.γ?phases favor the formation of NiO/Cr2O3/NiCr2O4during the initial oxidation.Many fast diffusion paths contribute to the development of the oxide layers.The decrease of the open porosity and the permeabilitywith exposure time extending and temperature increasing can be controlled within a certain range.

Kinetics of Fe_3O_4 formation by air oxidation

The kinetics of Fe3O4 formation by air oxidation of slightly acidic suspension of Fe（OH）2 was studied. The effects of initial concentration of Fe（Ⅱ）, temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe3O4 formation is composed of two-step reaction, the first step is the formation of Fe（OH）+2 by oxidation of Fe（OH）+ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe（OH）+ and Fe（OH）+2. The oxidation reaction is zero-order with respect to the concentration of Fe（Ⅱ） and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ·mol-1.

Study on Kinetics of Iron Oxide Reduction by Hydrogen

Kinetics parameters of iron oxide reduction by hydrogen were evaluated by the isothermal method in a differential micro-packed bed. Influence of external diffusion, internal diffusion and heat transfer on the intrinsic reaction rate was investigated and the conditions free of internal and external diffusion resistance have been determined. In the experiments, in order to correctly evaluate the intrinsic kinetics parameters for reducing Fe203 to Fe3O4, the reaction temperatures were set between 440 ℃ and 490 ℃. However, in order to distinguish the reduction of Fe304 to FeO from that of FeO to Fe, the reaction temperature in the experiment was set to be greater than 570 ℃. Intrinsic kinetics of iron oxide reduction by hydrogen was established and the newly established kinetic models were validated by the experimental data.

Enhanced CO oxidation over potassium-promoted Pt/Al_2O_3 catalysts:Kinetic and infrared spectroscopic study

A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.

Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated.Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

Enhancing recovery of uranium column bioleaching by process optimization and kinetic modeling

This research aimed to enhance the column bioleaching recovery of uranium ore by Acidithiobacillus ferrooxidans.Seven factors were examined for their significance on bioleaching using a Plackett-Burman factorial design.Four significant variables([Fe2+]initial,pH,aeration rate and inoculation percent)were selected for the optimization studies.The effect of these variables on uranium bioleaching was studied using a central composite design(CCD).The optimal values of the variables for the maximum uranium bioleaching recovery(90.27±0.98)%were as follows:[Fe2+]initial=2.89g/L,aeration rate420mL/min,pH1.45and inoculation6%(v/v).[Fe2+]initial was found to be the most effective parameter.The maximum uranium recovery from the predicted models was92.01%.This value was in agreement with the actual experimental value.The analysis of bioleaching residue of uranium ore under optimum conditions confirmed the formation of K-jarosite on the surface of minerals.By using optimal conditions,uranium bioleaching recovery is increased at column and jarosite precipitation is minimized.The kinetic model showed that uranium recovery has a direct relation with ferric ion concentration.

Homology modeling and evolutionary trace analysis of superoxide dismutase from extremophile Acidithiobacillus ferrooxidans

The gene sod in Acidithiobacillusferrooxidans may play a crucial role in its tolerance to the extremely acidic, toxic and oxidative environment of bioleaching. For insight into the anti-toxic mechanism of the bacteria, a three-dimensional （3D） molecular structure of the protein encoded by this gene was built by homology modeling techniques, refined by molecular dynamics simulations, assessed by PROFILE-3D and PROSTAT programs and its key residues were further detected by evolutionary trace analysis. Through these procedures, some trace residues were identified and spatially clustered. Among them, the residues of Asn38, Glyl03 and Glul61 are randomly scattered throughout the mapped structure; interestingly, the other residues are all distinctly clustered in a subgroup near Fe atom. From these results, this gene can be confirmed at 3D level to encode the Fe-depending superoxide dismutase and subsequently play an anti-toxic role. Furthermore, the detected key residues around Fe binding site can be conjectured to be directly responsible for Fe binding and catalytic function.

Isothermal oxidation behavior of TiAl intermetallics with different oxygen contents

Isothermal oxidation behaviors of Ti-45Al-2Fe-2Mo-1Cr intermetallics with different oxygen contents were studied under the condition of 950 °C, 100 h in air, and the oxidation kinetic parameters were also evaluated. The results show that the oxidation resistance of the TiAl intermetallics is negatively related to the oxygen content, and both the mass gain and thickness of oxide scale increase with the oxygen content. The sub-surface microstructure of the oxide scales varies with the oxygen content. Z phase is observed in the sub-surface area of the low-oxygen-content alloy, while the τ2(Al2FeTi) phase is found in the medium-oxygen-content and the high-oxygen-content alloys. The deterioration of oxidation resistance is due to the enhanced internal oxidation with the increase of oxygen content. It is possible to improve the oxidation resistance by controlling the oxygen content.

Degradation of Organic Pollutants by the Advanced Oxidation Processes

A kinetic model has been developed for the degradation of organic pollutants concerning with hydroperoxide ion as the initial step for generation of hydroxyl radical and its subsequent reaction mechanisms. Rate equations were derived for depletion of ozone and pollutants in the peroxone oxidation process using ozone and hydrogen peroxide as combined oxidants. Kinetic data obtained experimentally from the hydrogen peroxide-ozone reaction and peroxone oxidation of nitrobenzene were analyzed by using the proposed rate equations.

Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor. The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined, The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determi-nation of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process. The apparent activation energy was calculated to be 32.8kJ·mol-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.