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.

Kinetics study on biomass pyrolysis for fuel gas production

Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The ki-netic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into pri-mary products ( tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.

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 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 H_(2)SO_(4) system,and the pressure oxidation leaching process was adopted to achieve the preferential leaching of lithium.The E-pH diagram of the Fe-P-Al-H_(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 liquid-solid ratio was 4:1 ml·g^(-1)and the acid-material 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.

Kinetics study on leaching of rare earth and aluminum from polishing powder waste using hydrochloric acid

In this study,a novel hydrometallurgical process consisting of hydrochloric acid three-stage countercurrent leaching and solvent extraction was proposed to recover rare earth oxide(REO)from the rare earth polishing powder waste(REPPW).The effects of HCl concentration,liquid-solid ratio(L/S ratio),temperature and time on the leaching yields of rare earths(in REO)and aluminum(in Al2O3)were studied.The result shows that the leaching yields of REO and Al2O3 are 90.96%and 43.89%respectively under the optimum leaching parameters of HCl concentration=8.00 mol/L,L/S ratio=4 mL/g,leaching temperature=353 K and leaching time=180 min.Meanwhile,the leaching kinetics of REO and Al2O3 were investigated in this study.The leaching behaviors of REO and Al2O3 follow a shrinking sphere/core model and the general leaching process is controlled by the surface chemical reaction.The leaching activation energies of REO and Al2O3 are 9.86 and 13.68 kJ/mol,respectively.The leaching yield of each substance in three-stage countercurrent leaching is improved substantially compared with single-stage leaching,with a change from 90.96%to 95.38%for REO and from 43.89%to 46.22%for Al2O3,respectively.Especially,the total concentration of REO in three-stage countercurrent leaching solution is greatly increased to above 300 g/L,and the acidity of which is decreased to ca.pH=2,which is conducive to subsequent solvent extraction directly.High purity REO(99.92%)is obtained by solvent extraction separation,oxalate precipitation and calcination.The total recovery yield of REO is 85.13%.

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin （2,3,7,8-TCDD） is an efficient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2O are introduced in detail at the method of MPWB1K/6-31＋G（d,p）//MPWB1K/6- 311＋G（3df,2p） level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus （RRKM） theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and 03 is 4.80 × 10^-20 cm3/（mole.sec） at 298 K and 760 Tort. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.

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.

THE STUDY OF THE NON-STEADY KINETICS OF THE OXYDEHYDROGENATION OF ETHANE TO ETHYLENE OVER THE CATALYST OF Mo-V-Nb/Al_2O_3 BY THE TECHNIQUE OF TEMPERATURE PROGRAMMED TRANSIENT RESPONSE AND ELECTRIC CONDUCTIVITY

In this paper, instead of with the more expensive Fourier Transform Infrared Spectrometer(FTIR) a new technique of Temperature Programmed Transient Response(TP-TR) has been used with gas chromatography. Therefore, the TP-TR will be applied more widespreadly than ever before. With the technique of TP-TR and electric conductivity, the study is on the reaction mechanism and the adsorption behavior of the reactants and products to the present catalyst Mo-V-Nb/Al_2O_3 in the reaction from ethane through oxydehydrogenation to ethylene as the product. By Range-Kutta-Gill and Margarat methods, the kinetic parameters of the reaction elementary steps (i.e. rate constants, active energies and frequency factors) have been evaluated. The mathematical treatment coincides with the experimental results.

Synthesis and Kinetics of Hydrogenated Rosin Dodecyl Ester as an Environmentally Friendly Plasticizer

The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the toxicity of phthalate esters.In this study,a new,efficient and environmentally friendly plasticizer of hydrogenated rosin dodecyl ester was prepared by an esterification reaction of hydrogenated rosin and dodecanol.The influences of different reaction conditions(including different catalysts,the catalyst concentration,the ratio of the reactants,reaction temperature,and reaction time)on the esterification yield are examined and discussed.Hydrogenated rosin dodecyl ester with 71.8%yield was synthesized under the optimized reaction conditions(1:0.8 molar ratio of rosin to dodecanol,1 mol%tetrabutyl titanate concentration,and 210℃for 6 h).The esterification reaction is a second-order reaction,and kinetic calculations showed that the activation energy is 39.77 KJ·mol^(−1).The structure of the hydrogenated rosin dodecyl ester was confirmed by FT-IR spectroscopy and^(13)C NMR spectrum.Besides,the thermal stability of target product(hydrogenated rosin dodecyl ester)was also tested by thermal gravimetric analysis(TGA),which showed a good thermal stability.

Biodegradation of Acid Anthraquinone Dye in a Facultative-aerobic Process:Kinetics and Products

The transformation of an anthraquinone dye blue 324 in a facultative-aerobic(F-A) system was investigated.Kinetic parameter study showed that higher Vmax coupled with more recalcitrant chemical oxygen demand(COD) were found in the facultative biofilm reactor(FBR) than in the aerobic reactor(AR).Results of the product analyses indicated that most of dye molecular could be facultatively broken down into simple intermediates,which would be further degraded under subsequent aerobic condition.The main metabolites in each reactor were detected by infrared(FT-IR) and high performance liquid chromatography and mass spectrometry(HPLC-MS).Comparison of the toxicities among the dye and its metabolites was conducted,surprisingly,the colorless intermediates from FBR possessed less inhibitory than original dye and the median effective luminescence concentration(EC50) in 15 min for aerobic effluent could not be detected,showing that hardly toxic products existed in the aerobic process effluent.

Improved elastase production by Bacillus sp. EL31410—further optimization and kinetics studies of culture medium for batch fermentation

An efficient culture medium producing a bacterial elastase with high yields was developed further following preliminary studies by means of response surface method. Central composite design (CCD) and response surface method-ology were applied to optimize the medium constituents. A central composite design was used to explain the combined effect of three medium constituents, viz, glucose, K2HPO4, MgSO47H2O. The strain produced more elastase in the completely optimized medium, as compared with the partially optimized medium. The fitted model of the second model, as per RSM, showed that glucose was 7.4 g/100 ml, casein 1.13 g/100 ml, corn steep flour 0.616 g/100 ml, K2HPO4 0.206 g/100 ml and MgSO47H2O 0.034 g/100 ml. The fermentation kinetics of these two culture media in the flask experiments were analyzed. It was found that the highest elastase productivity occurred at 54 hours. Higher glucose concentration had inhibitory effect on elastase production. At the same time, we observed that the glucose consumption rate was slow in the completely optimized medium, which can explain the lag period of the highest elastase production. Some metal ions and surfactant additives also affected elastase production and cell growth.

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.

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.

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).

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.