A Kinetic Study of Ozone and Nitric Oxides in Dielectric Barrier Discharges for O_2/NO_x Mixtures

A simple model is described to simulate kinetic processes in dielectric barrier dis-charges for O2/NOx mixtures. A threshold of ozone production found experimentally is confirmedby the calculations of this modeling, and the underiying chemical reaction mechanisms are dis-cussed. It is also found that the effects of diffusion processes in the period of the lifetime of Oatoms are not important to microdischarge channels with a large radius, i.e. larger than l50 μm.

Kinetic Study of Cementation of Copper on Zinc Metal in Ethanol-Water Mixtures

The cementation reaction of copper on zinc metal in solutions of different concentrations ofcopper sulphate, at 25℃, has been studied and it is found to be a first order reaction. Moreover,the rates of this reaction at 0.15 mol'L-1 copper sulphate solution have been measured in a varietyof ethanol-water media at temperatures from 20℃ to 40℃. The correlation between the masstransfer coefficient and the dielectric constant has been investigated. Also, the thermodynamicparameters of activation have been calculated. The isokinetic relationship reveals the existenceof compensation effect, where the solute-solvent interactions play an important role.

Thermal Decomposition Behavior and Kinetic Study of Jamadoba Coal and Its Density Separated Macerals: A Non-Isothermal Approach

This kinetic study focuses on determining the thermal gravimetric profile of a particular grade of Indian sub-bituminous coal. A thermogravimetric analyzer (TGA-1000) was employed to investigate the thermal behavior and extract the kinetic parameters of Jamadoba coal and its corresponding density separated macerals. The weight loss was measured in air atmosphere. The coal samples used in this study were obtained from Jamadoba mines, Jharkhand. Samples of 35 mg and 200 μm mean size were subjected to synthetic air atmospheres (21% O2). Heating rates of 2, 5 and 7°C/min were applied until the temperature reached 1400°C, which was kept constant until burnout. Low heating rate was preferred so that devolatilization occurs prior to ignition and combustion. Derivative thermogravimetry (DTG) analysis method was applied to measure the weight changes and rates of weight loss used for calculating the kinetic parameters. The activation energy (Ea) and pre-exponential factor were obtained from model-free methods by applying non-isothermal thermogravimetry analysis.

The kinetic study for reduction of NO by CO over cobalt tetraphenylporphyrin supported on titanium dioxide

The catalytic reduction of nitric oxide by carbon monoxide over cobalt tetraphenylporphyrin supported on titanium dioxide (Co-TPP/TiO2) has been investigated. Co-TPP/TiO2 pretreated by evacuation at 270℃ exhibited a remarkable activity. The kinetic equation for the reduction of nitric oxide by carbon monoxide in the reaction temperature ranging from 80 to 150℃ (v=kPNO 0.56Pco 0.41) suggested that the reaction can be assumed to occur via a surface reaction of the Langmuir-Hinshelwood model between nitric oxide and carbon monoxide adsorbed on the central metal ion of Co-TPP. Experimental results indicated that the reduction of nitric oxide and formation of molecular nitrogen took place simultaneously during initial stage of the reaction. The apparent activation energy was calculated to be 30.8 kJ/mol.

A kinetic study of the electron-transfer in the reaction of tribenzylchlorotin with[CoW_(12)O_(40)]^(5-)

A kinetic study of the electron-transfer in the reaction of tribenzylchlorotin with potassium 12-tungsto cobalt （Ⅲ） ate ion, Ks[CoW12O40], abbreviated as Co（III）W, has been performed in different solvents. The studies were carried out in methanol, ethanol, acetonitrile and acetic acid/water. The rate constants, reaction rates and activation parameters were calculated. Our findings show that the rate of disappearance of the Co（Ⅲ） is pseudo-first order. The kinetic data is strongly affected by used solvents. The maximum and minimum rate constants were achieved in the ethanol and acetic acid/water （70/30） as a solvent, respectively. In all of the used solvents, negative value of activation entropies was observed, but negative activation enthalpies are observed in methanol, ethanol and acetonitrile. The reaction rate is increased with increase of Co（Ⅲ） concentration. ？2009 Fatemeh E Bamoharram. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

KINETIC STUDY ON PHOTOISOMERIZATION OF AN AZO-CONTAINING POLYMER AT THE AIR-WATER INTERFACE USING A IANGMUIR TROUGH

Photoisomerization of a new polymer: monoesters of polymaleic acid containing naphthalene-azo-anthraquinone groups in side chains at the air-water interface of a Langmuir trough wan detected by recording the development of surface pressure with time. This process wan found to be a first-order reaction and complete within several minutes.

KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER-BOUND CIS-DICARBONYLRHODIUM COMPLEX

The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed.

THE DISMUTATION OF SUPEROXIDE ANION BY COPPER(Ⅱ)COMPLEX OF 1,4,7,10-TETRAAZACYCLOTRIDECANE-11,13-DIONE—A KINETIC STUDY BY MEANS OF PULSE RADIOLYSIS

The dismutation kinetics of superoxide anion by copper complex of 1,4,7,10-tetranza- cyctotridecane-11,13-dione was studied by pulse radiolysis.The dismutation rate constants at various pH and concentration of complex were obtained.

KINETIC STUDY ON THE EXTRACTION OF PALLADIUM(Ⅱ) WITH BIS(2-ETHYLHEXYL)SULFIDE

The effects of concentration, temperature, stirring rate and specific interfacial area on the extraction of Pd (Ⅱ) with bis(2--ethylhexyl) sulfide (DEHS) were studied by the use of a constant interracial area cell. The results support an interracial chemical reaction regime.

Kinetic Study of Thermal Polymerization Reactions between Diazide and Different Diynes

The reaction kinetics between diazide（4,4＇-biphenyl dibenzyl azide） and different diynes（dipropargyl bisphenol A and 1,3-diethynylbenzene） were studied by means of differential scanning calorimetry（DSC） and nuclear magnetic resonance spectroscopy（~1H-NMR）.DSC was adopted to analyze the reactions under bulk polymerization condition,while ~1H-NMR for solution reaction polymerization was conducted.The apparent activation energies（E_α） calculated by Kissinger＇s method were 77.96,81.24 k J/mol,which were confirmed by Friedman＇s method,and 65.45,69.36 k J/mol by ~1H-NMR for dispropargyl bisphenol A/4,4＇-biphenyl dibenzyl azide and 1,3-diethynylbenzene/4,4＇-biphenyl dibenzyl azide,respectively.The polymerizations between the diazide and diynes were first-order reactions based on calculation from both DSC and ~1H-NMR.The results showed that the reaction between dipropargyl bisphenol A and 4,4＇-biphenyl dibenzyl azide was easier than that between 1,3-diethynylbenzene and 4,4＇-biphenyl dibenzyl azide,verifying that the reactivity of aliphatic alkyne was higher than that of aromatic alkyne.

One step sintering of homogenized bauxite raw material and kinetic study

A one-step sintering process of bauxite raw material from direct mining was completed, and the kinetics of this process was analyzed thoroughly. The results show that the sintering kinetics of bauxite raw material exhibits the liquid-phase sintering behavior. A small portion of impurities existed in the raw material act as a liquid phase. After X-ray diffraction analyses, scanning electron microscopy observations, and kinetics calculations, sintering temperature and heating duration were determined as the two major factors contributing to the sintering process and densification of bauxite ore. An elevated heating temperature and longer duration favor the densification process. The major obstacle for the densification of bauxite material is attributed to the formation of the enclosed blowhole during liquid-phase sintering.

Study on metal recovery process and kinetics of oxidative leaching from spent LiFePO_(4)Li-batteries

A green environmental protection and enhanced leaching process was proposed to recover all elements from spent lithium iron phosphate(LiFePO_(4))lithium batteries.In order to reduce the influence of Al impurity in the recovery process,NaOH was used to remove impurity.After impurity removal,the spent LiFePO_(4)cathode material was used as raw material under the H2SO4 system,and the pressure oxidation leaching process was adopted to achieve the preferential leaching of lithium.The E-pH diagram of the Fe ePeAleH_(2)O system can determine the stable region of each element in the recovery process of spent LiFePO_(4)Li-batteries.Under the optimal conditions(500 r·min^(-1),15 h,363.15 K,0.4 MPa,the liquidesolid ratio was 4:1 ml·g^(-1)and the acidematerial ratio was 0.29),the leaching rate of Li was 99.24%,Fe,Al,and Ti were 0.10%,2.07%,and 0.03%,respectively.The Fe and P were precipitated and recovered as FePO_(4)·2H_(2)O.The kinetic analysis shows that the process of high-pressure acid leaching of spent LiFePO_(4)materials depends on the surface chemical reaction.Through the life cycle assessment(LCA)of the spent LiFePO_(4)whole recovery process,eight midpoint impact categories were selected to assess the impact of recovery process.The results can provide basic environmental information on production process for recycling industry.

Simultaneous removal of NO_(x)and chlorobenzene on V_(2)O_(5)/TiO_(2)granular catalyst:Kinetic study and performance prediction

The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology,which is still in the initial stage and facing many challenges.We developed a V_(2)O_(5)/TiO_(2)granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene(i.e.,an important precursor of dioxins).The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability.Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited,the reaction order of each reaction was not considerably affected,and the pseudo-first-order reaction kinetics was still followed.The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants(i.e.,NO and dioxins)emission control.

Identification and Kinetics Study on the Transformation of Mevinolin in Acidic Alcohol Solution by High-performance Liquid Chromatography with Photodiode Array Detector or Mass Spectrometry

Mevinolin is one of the earlier statin drugs which is effective for the treatment of hypercholesterolemia, as an inhibitor of the HMG-CoA reductase. The transformations of mevinolin in acidic alcohol（ such as ethanol, methanol and isopropanol） solutions caused by solvent effects were revealed in the present article. The solvates, that is, mevinolinic methyl ester, mevinolinic ethyl ester and mevinolinic isopropyl ester, were identified by LC/PDA and LC/MS. The kinetics parameters of the transformations caused by solvent effects, such as the observed rate constant of mevinolin （kobs）, the maximum concentration（ Cmax ）, and its corresponding maximum time（ t time for the acid form to reach the maximum concentration） of mevinolinic acid, are discussed. The influencing factors, such as the kind of solvents, the acidic concentration, the initial mevinolin concentration, and the water content as well as temperature were investigated. Two kinds of comparative reactions, hydrolysis and alcoholysis, of mevinolin in solution were studied. This detailed study on the kinetics of mevinolin transformations is valuable and meaningful for the purification, preparation, injection manufacturing, extraction, storage, etc. , of mevinolin or other similar compounds. This work provides useful information for the quality control of mevinolin and mevinolin-like drugs as well.

Enhanced carbon dioxide adsorption performance and kinetic study of K and Al co-doped Li4SiO4

Herein, we report the effects of doped K and Al on the carbon dioxide （CO2） adsorption performance of the Li4SiO4-based adsorbents. The CO2 adsorption capacity of 0.8 wt% K and 1.5 wt% AI doped Li4SiO4 is ～2.2 times and ～1.3 times higher than that of the pristine Li4SiO4 at 500 and 600℃, respectively. The kinetic study further indicated that the reaction rates of the lithium diffusion process is greatly improved by K and AI doping, and the lithium diffusion rate of 0.8 wt% K and 1.5 wt% AI doped Li4SiO4 is ～2 times higher than that of the pristine Li4SiO4 at 575-650 ℃. K and AI doping increases the adsorption capacity of Li4SiO4-based adsorbents, and widens its effective adsorption temperature range

Kinetic Study of MOCVD Ⅲ-Ⅴ Quaternary Antimonides

The kinetics of MOCVD GaInAsSb and AlGaAsSb was studied by the growth rate as a function of growth temperature and partial pressure of Ⅲ and Ⅴ MO species. The diffusion theory was used to explain the mass transport processes in MOCVD Ⅲ Ⅴ quaternary antimonides. On the basis of the discussion about their growth kinetics and epilayer properties, the good quality multi epilayers of these two quaternary antimonides and their photodetectors and arrays with wavelength of 1.8～2.3 μm and detectivities of D *>10 9 cm Hz 1/2 W -1 were obtained.

Kinetics study of CO_(2) absorption in potassium carbonate solution promoted by diethylenetriamine

In this work,characterization and kinetics of CO2 absorption in potassium carbonate(K_(2)CO_(3))solution promoted by diethylenetriamine(DETA)were investigated.Kinetics measurements were performed using a stirred cell reactor in the temperature range of 303.15–323.15 K and total concentration up to 2.5 kmol m3.The density,viscosity,physical solubility,CO_(2) diffusivity and absorption rate of CO_(2) in the solution were determined.The reaction kinetics between CO_(2) and K2CO3þDETA solution were examined.Pseudo-first order kinetic constants were also predicted by zwitterion mechanism.It was revealed that the addition of small amounts of DETA to K_(2)CO_(3) results in a significant enhancement in CO_(2) absorption rate.The reaction order and activation energy were found to be 1.6 and 35.6 kJ mol1,respectively.In terms of reaction rate constant,DETA showed a better performance compared to the other promoters such as MEA,EAE,proline,arginine,taurine,histidine and alanine.

Study on the epoxidation of olefins with H_(2)O_(2)catalyzed by biquaternary ammonium phosphotungstic acid

Selective epoxidation of olefins is an important field in chemical industry.In this work,we developed a new phosphotungstic acid catalyst{[(C_8H_(17))(CH_(3))_(2)N]_(2)(CH_(2))_(3)}_(1.5){PO_(4)[WO(O_(2))_(2)]_(4)}with long carbon chain and biquaternary ammonium cation.Cyclohexene could be epoxidized to cyclohexene oxide in 96.3%conversion and 98.2%selectivity.The catalyst type,solvent type,catalyst loading,initial molar ratio,temperature,cycle performance and substrate extensibility were studied and optimized,the kinetic parameters about overall reaction and unit reaction were also calculated.Dynamic light scattering analysis was carried out to explain the different catalytic performance between catalysts with different carbon chain length.This novel catalyst and the corresponding dynamics and mechanism study could probably help the industrial application on the epoxidation of cyclohexene with H_(2)O_(2).

Kinetic study on the ligand exchange reactions between bis(alkylxanthato)palladium(II)and bis(N,N-dialkyldithiocarbamato)palladium(II)by high-performance liquid chromatography

The rate constants and equilibrium constants of ligand exchange reactions between his (alkylxanthato)palladium(Ⅱ),Pd(S_2COR)_2(R=Am,n-Hex,Bz),and bis(N,N-dialkyldithiocarbamato) palladium(Ⅱ),Pd(S_2CNR_2)_2(K=Et,n-Pr,n-Bu),in chloroform solution have been determined in a temperature range of 20—50°C by means of high-performance liquid chromatography.It was found that both the forward and reverse reactions are of second order.All of the equilibrium constants K determined are 10.3±1.0,much greater than the value(K=4)calculated statistically which indicates that the ternary complexes are more stable than the binary complexes.The experimental results revealed that the reaction rate decreases with the increase in the size of R and R^1 groups and the latter are more remarkable,consistent with the deduction of steric effect.The activation parameters of the reactions have been calculated.In reaction series(11)and(12)(in the text)the isokinetic tempera- tures B=390±8K and β=346±15 K have been observed respectively.A plausiblemechanism in- volving an eight-membered ring intermediate has been proposed on the basis of experimental results.

DSC STUDY OF MARTENSITIC TRANSFORMATION KINETICS IN A Cu－Zn－Al－Mn－Ni SHAPE MEMORY ALLOY

The kinetics of the reversible martensitic transformation in a Cu-Zn-Al-Mn-Ni shape memory alloy has been studied by means of differential scanning calorimetry.The apparent activation energy has been calculated and the kinetic equations of positive and adverse martensitic transformation have been established with the variations of temperature and time.