THE STUDY ON TRE KINETICS AND MECHANISM OF THE REACTIONS OF METAL IONS WITH PnAO

The kinetics and the mechanism of the formation reactions of M(PnAO)^(2+)(M=Ni,Co,Cu)were studied with UV Spectrophotometer and Stopped Flow Spectrophotometer and a three steps mechanism was suggested.

Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH_4)_2SO_4

An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using（NH_4）_2SO_4. The optimized reaction conditions are defined as an（NH_4）_2SO_4/zinc molar ratio of 1.4：1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of（NH_4）_2SO_4/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric-differential thermal analysis was used for（NH_4）_2SO_4 and zinc mixed in a molar ratio of 1.4：1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle-Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.

Kinetic Studies on Axial Coordination Reaction of Tetraphenylporphinatocobalt（Ⅱ） Chloride

he axial coordination reactions of tetraphenylporphinatocobalt (Ⅲ) chloride(Co TPPC1) with various imidazoles RIm ( HIm . imidazole; Melm , 2-methylimida-zole) were investigated in acetone and dichloromethand solvents at different temper-atures. The reaction mechanisms were proposed and the differences between experi-mental results in the two solvents h ave been interpreted using the proposed mecha-nisms and rate equations for the first time , and the reaction scheme for the axial re-action of the metalloporphyrin has been developed. Hydrogen bonding plays an im-portant role in the reactions. The effects of various imidazoles for these reactionsand the solvents are reported. The comparison between iron and cobalt porphyrinsin the kinetics are discussed.

Kinetics and Mechanism of Adsorption of Phosphate on Fluorine-containing Calcium Silicate

The nanowires-reticulated calcium silicate with a specific surface area more than 100 m^2/g was prepared by a hydrothermalprocess using hydrated lime（Ca（OH）_2,HL）and silica containing soluble fluoride,which was a by-product of fluorine industry,and the soluble fluoride in raw silica was fixed as CaSiF_6 at the same time.The kinetic characteristics and mechanism of adsorbing phosphate by fluorine-containing calcium silicate were investigated in the experiments of phosphorus（P）removalfrom aqueous solution.The results show that the prepared fluorine-containing calcium silicate has excellent performance for adsorbing phosphate,the adsorption process appears to follow pseudo-second-order reaction kinetics and the process is mainly controlled by chemisorption.The product resulted from P adsorption is mainly composed of hydroxyapatite（HAP）and fluorapatite（FAP）,which are further used as adsorbents of heavy metalion Cd^（2＋） in aqueous solution and display excellent performance.

Reduction mechanism of high-chromium vanadium–titanium magnetite pellets by H_2–CO–CO_2 gas mixtures

The reduction of high-chromium vanadium–titanium magnetite as a typical titanomagnetite containing 0.95wt% V2O5 and 0.61wt% Cr2O3 by H2–CO–CO2 gas mixtures was investigated from 1223 to 1373 K. Both the reduction degree and reduction rate increase with increasing temperature and increasing hydrogen content. At a temperature of 1373 K, an H2/CO ratio of 5/2 by volume, and a reduction time of 40 min, the degree of reduction reaches 95%. The phase transformation during reduction is hypothesized to proceed as follows： Fe2O3 → Fe3O4 → FeO → Fe; Fe9 TiO 15 ＋ Fe2Ti3O9 → Fe2.75Ti0.25O4 → FeT iO 3 → TiO 2;（Cr0.15V0.85）2O3 → Fe2VO4; and Cr1.3Fe0.7O3 → FeC r2O4. The reduction is controlled by the mixed internal diffusion and interfacial reaction at the initial stage; however, the interfacial reaction is dominant. As the reduction proceeds, the internal diffusion becomes the controlling step.

Recent progress in production and usage of hydrogen peroxide

Hydrogen peroxide has attracted increasing interest as an environmentally benign and green oxidant that can also be used as a solar fuel in fuel cells.This review focuses on recent progress in production of hydrogen peroxide by solar-light-driven oxidation of water by dioxygen and its usage as a green oxidant and fuel.The photocatalytic production of hydrogen peroxide is made possible by combining the e^(-)and 4e-oxidation of water with the e^(-)reduction of dioxygen using solar energy.The catalytic control of the selectivity of the e^(-)vs.4e-oxidation of water is discussed together with the selectivity of the e^(-)vs.4e-reduction of dioxygen.The combination of the photocatalytic e^(-)oxidation of water and the e^(-)reduction of dioxygen provides the best efficiency because both processes afford hydrogen peroxide.The solar-light-driven hydrogen peroxide production by oxidation of water and by reduction of dioxygen is combined with the catalytic oxidation of substrates with hydrogen peroxides,in which dioxygen is used as the greenest oxidant.

Planarization mechanism of alkaline copper CMP slurry based on chemical mechanical kinetics

The planarization mechanism of alkaline copper slurry is studied in the chemical mechanical polishing （CMP） process from the perspective of chemical mechanical kinetics.Different from the international dominant acidic copper slurry,the copper slurry used in this research adopted the way of alkaline technology based on complexation. According to the passivation property of copper in alkaline conditions,the protection of copper film at the concave position on a copper pattern wafer surface can be achieved without the corrosion inhibitors such as benzotriazole（BTA）,by which the problems caused by BTA can be avoided.Through the experiments and theories research,the chemical mechanical kinetics theory of copper removal in alkaline CMP conditions was proposed. Based on the chemical mechanical kinetics theory,the planarization mechanism of alkaline copper slurry was established. In alkaline CMP conditions,the complexation reaction between chelating agent and copper ions needs to break through the reaction barrier.The kinetic energy at the concave position should be lower than the complexation reaction barrier,which is the key to achieve planarization.

Suggestion of global model for carob batch fermentation to produce bioethanol

Modelling of carob batch fermentation is established basing on mass transfer balances. The modelling treats the reaction kinetics of substrate （S）, the micro-organisms （X） and the ethanol （E）. Nine models are taken from the literature to describe specific organism growth rate and specific ethanol development rate. These models treat all types of fermentation. The Phisalapbong et al. model and the Ghose and Tyagi model show the best fit of the experimental data. This affirms that the batch fermentation of carob is conducted with substrate and/or ethanol inhibition. Some simulations and relationships （X = f（S）, E = f（S）） are obtained from the Phisalaphong et al. model. Those simulations show a lot of important and useful results of carob batch fermentation process.

Influences of different diluents on ignition delay of syngas at gas turbine conditions：A numerical study

Ignition delay of syngas is an important factor that affects stable operation of combustor and adding diluents to syngas can reduce NO_x emission.This paper used H_2O,CO_2 and N_2 as diluents and calculated ignition delay of syngas in temperature range of 900-1400 K and at pressures of 10 and 30 atm respectively.In high temperature range,comparing with N_2 dilution,adding H_2O and CO_2 can significantly inhibit autoignition of syngas because they have higher collision efficiencies in reaction H + O_2(+ M) = HO_2(+ M).As for low temperature conditions,adding H_2O can increase reactivity of syngas,especially under high pressure,because of its high collision efficiency in reaction H_2O_2(+ M) = 2OH(+ M).Comparing with different dilution rates shows that for syngas and operating conditions in this paper,adding N_2 mainly influences temperature rising process of syngas combustion,thus inhibiting reactivity of syngas.In addition,this paper calculated ignition delay of syngas at different equivalence ratios(φ= 0.5,1.0).Higher equivalence ratio(φ≤1) means that less air(especially N_2) needs to be heated,thus promoting ignition of syngas,

Redox reactions of iron and manganese oxides in complex systems

Conspectus:Redox reactions of Fe-and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments.Due to experimental and analytical challenges associated with complex environments,there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems,and most of the studies so far have only focused on simple model systems.To bridge the gap between simple model systems and complex environmental systems,it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation.In this Account,we primarily focused on(1)the oxidative reactivity of Mn-and Fe-oxides and(2)the reductive reactivity of Fe(Ⅱ)/iron oxides in comolex model systems toward contaminant degradation.The effects of common metal ions such as Mn2+,Ca2+,Ni2+,Cr3+and Cu2+,ligands such as small anionic ligands and natural organic matter(NOM),and second metal oxides such as A1,Si and Ti oxides on the redox reactivity of the systems are briefly summarized.