CHRONOABSORPTOMETRY FOR THE DETERMINATION OF KINETIC PARAMETERS OF ELECTRON TRANSFER REACTIONS USING LONG-OPTICAL-PATH ELECTROCHEMICAL CELL

A single potential step chronoabsorptometric method for the determination of ki- netic parameters of simple quasi-reversible reactions is described.It is verified by determining the kinetic parameters for the electroreduction of ferricyanide.A long-optical-path electro- chemical cell with a plug-in electrode is used.The thickness of solution layer is 0.55 mm

Determination of Kinetic Parameters and Metal Ions in Urea-Urease System Based on the Biochemical Reaction Heat Induced Laser Beam Deflection

A new analytical method for the determination of urea-urease system based on biochemical reaction heat induced laser beam deflection is presented in this paper. With the method, the Michaelis constant (K-m) of urease and apparent inhibition constant (K-i) of some metal ion inhibitors were measured respectively. This method was also used for the quantitative determination of metal ions with satisfactory result.

Comparisons on methods for identifying accident black spots using vehicle kinetic parameters collected from road experiments

Identification of accident black spots has gained tremendous popularity among road agencies and safety specialists for evaluating and subsequently enhancing road traffic safety.However,there is still limited understanding of the internal relationship between black spots and microscopic vehicle kinetic parameters.To address this gap,this paper describes a project that was undertaken using the real-time tire force data(kinetic response)obtained from road experiments on Wenli Expressway.First,factor analysis was applied to extracted three independent indicators(power-braking,handling stability,and ride comfort)from seven original kinetic indicators with multiple collinearities.Afterward,the main indicators were given vehicle kinetic meaning by analyzing the characteristics of original indicators associated with them.A compelling correlation was established among kinetic parameters,vehicle running qualities,and accident risk.Additionally,an integrated evaluation framework was established to identify accident black spots based on applying ordered logit models and PLS-entropy-TOPSIS approaches.The recognition results exhibited that the overall recognition accuracy obtained by the latter was found to be comparable to that achieved using the previous one.The compound evaluation model proposed in this paper has been proven to present many advantages for black spot identification.It is evidently clear from the findings that the vehicle kinetic parameters have significant correlations with road accident risk.This paper could provide some insightful knowledge for identifying and preventing the black spots from ameliorating traffic safety.

Thermoluminescence glow curve analysis and kinetic parameters of Dy-doped BaSi_(2)O_(5)phosphor

In this paper,Dy^(3+)incorporated BaSi_(2)O_(5)phosphors were synthesized by gel co mbustion method and characterized by X-ray diffraction(XRD).The effects of various heating rate s on thermoluminescence(TL)kinetics and glow peak temperatures of Dy^(3+)incorporated BaSi_(2)O_(5)phosphors exposed toβirradiation at room temperature were investigated.The glow curves of the phosphor exposed toβ-irradiation(0.1-100 Gy)consist of four main peaks located at 87,130,271,and 327℃and exhibit a good linearity between 0.1 and100 Gy.Three experimental techniques including variable heating rate(VHR),repeated initial rise(RIR),peak shape(PS)and computerized glow curve deconvolution(CGCD)were employed to determine TL kinetic parameters.Our findings indicate that the TL glow peaks of the phosphor obey first-order kinetics.Analysis of the main dosimetric peaks through the techniques mentio ned above indicates that activation energies(E)and pre-exponential factor(s)are in the range of 0.80-1.50 eV and 1.15×10^(8)-3.28×10^(13)s^(-1).Additionally,it is found that the temperature of the glow peaks shifts toward the higher temperatures and the TL intensity smoothly decreases as the heating rate increases.The effect on the TL intensities and glow peak temperatu res of the heating rate is discussed in terms of thermal quenching.

Thermochemical Aspects of Activated Ammonium Perchlorates with Superior Thermal Stability,Decomposition Enthalpy,Propagation Index,and Decomposition Kinetic Parameters

Ammonium perchlorate(AP)includes oxidizing and reducing elements on the same molecule.AP can act as an efficient oxidizer and mono-propellant as well.In this study,AP experienced crystallographic phase change from orthorhombic centrosymmetric to non-centrosymmetric under controlled isothermal heat treatment.XRD diffractograms confirmed this crystallographic phase change.The thermal behaviour of activated AP had been investigated using DSC.Activated AP demonstrated high chemical stability with an increase in endothermic phase transition enthalpy by 170%.The enthalpy of the subsequent two main exothermic decomposition reactions was increased by 250%.Whereas AP demonstrated total decomposition enthalpy of 733 J/g,activated AP showed 2614 J/g.Activated AP can secure self-sustained response at a high rate.Propagation index(combustion enthalpy/ignition temperature)was employed to assess self-sustained reaction propagation.Activated AP demonstrated high propagation index of 8.7 compared with 2.5 for un-activated AP.Primary decomposition kinetic parameters had investigated using Kissinger and KAS methods.Activated AP showed an increase in activation energy by 89%using the Kissinger method;kinetic parameters using the KAS method were in good agreement with the Kissinger method.It can have concluded that AP with novel kinetic decomposition parameters for enhanced safety storage and high combustion characteristics has evolved.

Multi-time scale identification of key kinetic processes for lithium-ion batteries considering variable characteristic frequency

The electrification of vehicles puts forward higher requirements for the power management efficiency of integrated battery management systems as the primary or sole energy supply.In this paper,an efficient adaptive multi-time scale identification strategy is proposed to achieve high-fidelity modeling of complex kinetic processes inside the battery.More specifically,a second-order equivalent circuit model network considering variable characteristic frequency is constructed based on the high-frequency,medium-high-frequency,and low-frequency characteristics of the key kinetic processes.Then,two coupled sub-filters are developed based on forgetting factor recursive least squares and extended Kalman filtering methods and decoupled by the corresponding time-scale information.The coupled iterative calculation of the two sub-filter modules at different time scales is realized by the voltage response of the kinetic diffusion process.In addition,the driver of the low-frequency subalgorithm with the state of charge variation amount as the kernel is designed to realize the adaptive identification of the kinetic diffusion process parameters.Finally,the concept of dynamical parameter entropy is introduced and advocated to verify the physical meaning of the kinetic parameters.The experimental results under three operating conditions show that the mean absolute error and root-mean-square error metrics of the proposed strategy for voltage tracking can be limited to 13 and 16 mV,respectively.Additionally,from the entropy calculation results,the proposed method can reduce the dispersion of parameter identification results by a maximum of 40.72%and 70.05%,respectively,compared with the traditional fixed characteristic frequency algorithms.The proposed method paves the way for the subsequent development of adaptive state estimators and efficient embedded applications.

Non-linear relationship between combustion kinetic parameters and coal quality

Combustion kinetic parameters(i.e.,activation energy and frequency factor) of coal have been proven to relate closely to coal properties;however,the quantitative relationship between them still requires further study.This paper adopts a support vector regression machine(SVR) to generate the models of the non-linear relationship between combustion kinetic parameters and coal quality.Kinetic analyses on the thermo-gravimetry(TG) data of 80 coal samples were performed to prepare training data and testing data for the SVR.The models developed were used in the estimation of the combustion kinetic parameters of ten testing samples.The predicted results showed that the root mean square errors(RMSEs) were 2.571 for the activation energy and 0.565 for the frequency factor in logarithmic form,respectively.TG curves defined by predicted kinetic parameters were fitted to the experimental data with a high degree of precision.

Gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification

The gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification were investigated.One kind of lignite and three kinds of bituminous coals were used as the samples,and their coal ranks follow the ascending order:XB<KL<ZJ<GD.As characterized by the comprehensive gasification index,the gasification reactivity of coal chars follows the descending order:XB>KL>ZJ>GD.Through systematically analyzing factors affecting gasification reactivity,it was ascertained that the gasification reactivity is mostly determined by the carbonaceous structure.The gasification reactivity is inversely proportional to the coal rank,and the higher the coal rank,the lower the gasification reactivity.A new kinetic model was proposed to calculate the kinetic parameters,in which the reaction order was considered as an unknown kinetic parameter.The reaction order n follows the ascending order:XB<KL<ZJ<GD,which are n=1.00,n=1.34,n=1.83,and n=2.63,respectively.It is proved that the reaction order is proportional to the coal rank,and the higher the coal rank,the higher the reaction order.

Kinetics and Thermodynamic Parameters of the CopperExchange on Na-montmorillonite Clay Mineral inSelected Solvents

The kinetics of Cu ion exchange on Na-montmorillonite clay mineral has been investigated at three temperatures, in three solvents: H2O, ethylene glycol and glycerol. Solvent effects on the reaction rate have been discussed. The thermodynamic activation parameters were calculated and discussed in terms of solvation effects. The determined isokinetic temperature indicates that the reaction is enthalpy controlled where the interaction between solvent and clay surface plays an important role. A reaction mechanism which describes the solvent effect on the rate of Cu ion exchange is proposed.

A new kinetic model for direct CO2 hydrogenation to higher hydrocarbons on a precipitated iron catalyst:Effect of catalyst particle size

The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with various particle sizes was studied in a well mixed, continuous spinning basket reactor. The iron catalysts promoted with copper and potassium were prepared via precipitation technique in various alcohol/water mixtures to achieve a series of catalyst particle sizes between 38 and 14 nm. A new kinetic model for direct COhydrogenation was developed with combination of kinetic model for FTS reaction and RWGS equilibrium condition. For estimate of structure sensitivity of indirect COhydrogenation to higher hydrocarbons, the kinetic parameters of developed model are evaluated for a series of iron catalysts with various particle sizes. For kinetic study a wide range of syngas conversions have been obtained by varying experimental conditions. The results show that the new developed model fits favorably with experimental data. The values of activation energies for indirect COhydrogenation reaction are fall within the narrow range of 23–16 kJ/mol.

Reduction behavior and kinetics of vanadium–titanium sinters under high potential oxygen enriched pulverized coal injection

In this work, the reduction behavior of vanadium–titanium sinters was studied under five different sets of conditions of pulverized coal injection with oxygen enrichment. The modified random pore model was established to analyze the reduction kinetics. The results show that the reduction rate of sinters was accelerated by an increase of CO and H2contents. Meanwhile, with the increase in CO and H2contents, the increasing range of the medium reduction index (MRE) of sinters decreased. The increasing oxygen enrichment ratio played a diminishing role in improving the reduction behavior of the sinters. The reducing process kinetic parameters were solved using the modified random role model. The results indicated that, with increasing oxygen enrichment, the contents of CO and H2in the reducing gas increased. The reduction activation energy of the sinters decreased to between 20.4 and 23.2 kJ/mol. ? 2017, The Author(s).

Influence of ammonium sulfate on the corrosion behavior of AZ31 magnesium alloy in chloride environment

Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is studied.Effect of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an evolution from localized corrosion to uniform corrosion.Acceleration effect of NH_(4)^(+)can be attributed to that(i)NH_(4)^(+)dissolves the inner MgO and hinders the precipitation of Mg(OH)_(2) and(ii)the buffering ability of NH_(4)^(+)provides H+,enhances the hydrogen evolution,and expedites the corrosion process.The latter is demonstrated as the dominant factor with the results in unbuffered and buffered environments.The severe corrosion and hydrogen process in NH_(4)^(+)-containing solution results in a high Hads coverage and yields an inductive loop within the low frequency.Meanwhile,SO_(4)^(2−)is helpful in generating cracked but partially protective corrosion products,while Cl−could broaden the corrosion area beneath the corrosion product.

Growth Kinetics Study of a Bacterial Consortium Producing Biosurfactants,Constructed with Six Strains Isolated from an Oily Sludge

We investigated the ability of a bacterial community constructed with six strains isolated from an oily sludge, to utilize diesel oil at high concentrations. The consortium was able to grow at concentrations up to 84 g diesel oil/L and had produced biosurfactants during its active growth phase;these compounds, in their crude form, reduced the surface tension of distilled water from 72 mN/m to 31 mN/m, with a corresponding Critical Micelle Concentration value γCMC = 81 mg/L. The plot of specific growth rates obtained from the growth curves versus initial concentrations was found to fit adequately the experimental data by the Andrews inhibitory model, which resulted in the following kinetic constants: μmax = 0.535d-1 ± 0.063, KS = 18.68 g/L ± 3.59 and KI = 29.02 g/L ± 4.96, reflecting the slow biodegradation rate. At 25.2 g diesel oil/L, close to the optimal concentration S* = 23.28 g/L ± 4.23, the consortium metabolized diesel oil faster than each strain did individually, suggesting that the process was stimulated by a synergistic interaction between the members of the consortium.

Dose-Dependence of Trap Parameters of OSL Decay from Al_(2)O_(3):C

Optically Stimulated Luminescence (OSL) trap parameters can only be reliably determined through the detailed analy- sis of OSL decay curves. In this study the kinetic parameters of a blue-light stimulated luminescence (BLS) decay curve from Al2O3:C sample irradiated at 0.1, 0.15, 0.2, 0.4 and 0.6 Gy beta doses were obtained using the same basic methods with some modifications applied and also by using our suggestion: Active-OSL Approximation (AOSL). The results were compared with those of other studies on the trap parameters of Al2O3:C material.

Kinetics studies of nano-structured iron catalyst in Fischer-Tropsch synthesis

Kinetic parameters of nano-structured iron catalyst in Fischer-Tropsch synthesis （FTS） were studied in a wide range of synthesis gas conversions and compared with conventional catalyst.The conventional Fe/Cu/La catalyst was prepared by co-precipitation of Fe and Cu nitrates in aqueous media and Fe/Cu/La nanostructure catalyst was prepared by co-precipitation in a water-in-oil micro-emulsion.Nano-structured iron catalyst shows higher FTS activity.Kinetic results indicated that in FTS rate expression,the rate constant （k） increased and adsorption parameter （b） decreased by decreasing the catalyst particle size from conventional to nano-structured.Since increasing in the rate constant and decreasing in the adsorption parameter affected the FTS rate in parallel direction,the particle size of catalyst showed complicated effects on kinetic parameters of FTS reaction.

Effect of acid-associated mechanical pretreatment on the hydrolysis behavior of pine sawdust in subcritical water

The effects of sulfuric acid-associated mechanical pretreatment on the hydrolysis behavior of pine sawdust were investigated in this study.Sulfuric acid could act as an acidic catalyst to depolymerize holocellulose through cleavage of the glycosidic bonds,the dissociation energies of which were supplied by the impact of a ball on pine sawdust,during milling.The destruction of glycosidic and hydrogen bonds in pine sawdust resulted in a decrease of crystallinity and an increase of water solubility.The sulfuric acid could promote the hydrolysis of holocellulose and its hydrolysis products.It also destroyed the chemical linkages between holocellulose and lignin during ball milling.The cleavage of chemical linkages with holocellulose made lignin more difficult to hydrolyze in subcritical water,and higher activation energy was needed to hydrolyze pretreated pine sawdust at higher reaction temperatures.It also led to the formation of glucose char and aromatic-linked polymer char from the hydrolysis products of holocellulose.

Numerical Simulation for Hydrodynamic Characteristics of A Bionic Flapping Hydrofoil

In order to study the propulsion mechanism of the bionic flapping hydrofoil （BFH）, a 2-DoF （heave and pitch） motion model is formulated. The hydrodynamic performance of BFH with a series of kinematical parameters is explored via numerical simulation based on FLUENT. The calculated result is compared with the experimental value of MIT and that by the panel method. Moreover, the effect of inlet velocity, the angle of attack, the heave amplitude, the pitch amplitude , the phase difference, the heave biased angle, the pitch biased angle and the oscillating frequency are investigated. The study is useful for guiding the design of bionic underwater vehicle based on flapping propulsion. It is indicated that the optimal parameters combination is v = 0.5 m/s, Ф0 = 40°, θ0 = 30°, ψ = 90°, Фbias = 0°, θbias= 0° and f=0.5Hz.

A Study of Estimating the Safe Storage Life, Self-accelerating Decomposition Temperature and Critical Temperature of Thermal Explosion of Double-base Propellant Using Isothermal and Non-isothermal Decomposition Behaviours

A method of estimating the safe storage life （τ）, self-accelerating decomposition temperature （TsADT） and critical temperature of thermal explosion （Tb） of double-base propellant using isothermal and non-isothermal decomposition behaviours is presented. For double-base propellant composed of 56±1wt% of nitrocellulose （NC）, 27±0.5wt% of nitroglycerine （NG）, 8.15±0.15wt% of dinitrotoluene （DNT）, 2.5±0.1wt% of methyl centralite, 5.0±0.15wt% of catalyst and 1.0±0.1wt% of other, the values of r of 49.4 years at 40℃, of TSAOT of 151.35℃ and of Tb of 163.01℃ were obtained.

The Thermal Decomposition of Calcium Carbonate

The thermogravimetry(TG) and derivative thermogravimetry(DTG) curves of the thermal decomposition reaction of calcium carbonate have been measured at five different heating rates. The kinetic parameters and the reaction mechanism of the reaction were evaluated from analysis of the TG and DTG curves by using the Ozawa method, the combined integral and differential methods and the reduced equations derived by us.

Comparative Studies of Substrate and Inhibitor Specificity of Glutathione S-Transferases in Six Tissues of Oxya chinensis(Thunberg)(Orthoptera:Acrididae)

Specific activity, substrate specificity, and kinetic parameters （Km and Vmax） of glutathione S-transferases （GSTs） towards three substrates, 1-chloro-2,4-dinitrobenzene （CDNB）, 1,2-dichloro-4-nitrobenzene （DCNB）, and p-nitrobenzene chloride （pNBC） were investigated in six tissues （foregut, midgut, hindgut, fat body, hemolymph, and muscle） of Oxya chinensis. In addition, the inhibition in vitro （ethacrynic acid, and Cibacron Blue 3GA） of Oxya chinensis in the six tissues was also investigated. Glutathione S-transferase activity was detected in all the six tissues examined. The rank order of GST activities towards CDNB was fat body 〉 midgut 〉 hindgut 〉 muscle 〉 foregut 〉 hemolymph both in females and males. Glutathione S-transferase activities in the fat body in females and males were 1.3- to 10.4-fold and 1.1- to 10.0- fold higher than those in the other tissues. The rank order of GST activities towards the other substrates changed slightly. From these results, it was inferred that GSTs in the fat body and midgut played important roles in detoxifying xenobiotics including insecticides and plant allelochemicals in O. chinensis. In the three substrates examined, CDNB seemed to be the best substrate, followed by pNBC and DCNB. The kinetic parameters of GSTs were different among the six tissues. This suggested that GSTs in different tissues have various affinities and catalytic efficiency to substrates. In vitro inhibition study showed that the median inhibition concentration （IC50） values of the two inhibitors to GSTs from the six tissues were different. The results suggested that the two inhibitors have different inhibition potency to GSTs from the different tissues. The observed changes in kinetic parameters and inhibition in vitro among the six tissues of the insect might suggest that the number and structure of isoenzymes and their rate of expression varied for the different tissues.