“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Mechanism and Kinetics Analysis of NO/SO_2/N_2/O_2 Dissociation Reactions in Non-Thermal Plasma

The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons＇ impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

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.

Thiourea crystal growth kinetics,mechanism and process optimization during cooling crystallization

In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and mechanisms governing thiourea crystals during the cooling crystallization process.The fitting results indicate that the crystal growth rate coefficient,falls within the range of 10^(-7)to 10^(-8)m·s^(-1).Moreover,with decreasing crystallization temperature,the growth process undergoes a transition from diffusion-controlled to surface reaction-controlled,with temperature primarily influencing the surface reaction process and having a limited impact on the diffusion process.Comparing the crystal growth rate,and the diffusion-limited growth rate,at different temperatures,it is observed that the crystal growth process can be broadly divided into two stages.At temperatures above 25℃,1/qd(qd is diffusion control index)approaches 1,indicating the predominance of diffusion control.Conversely,at temperatures below 25℃,1/qd increases rapidly,signifying the dominance of surface reaction control.To address these findings,process optimization was conducted.During the high-temperature phase(35-25℃),agitation was increased to reduce the limitations posed by bulk-phase diffusion in the crystallization process.In the low-temperature phase(25-15℃),agitation was reduced to minimize crystal breakage.The optimized process resulted in a thiourea crystal product with a particle size distribution predominantly ranging from 0.7 to 0.9 mm,accounting for 84%of the total.This study provides valuable insights into resolving the issue of excessive fine crystals in the thiourea crystallization process.

Growth kinetics of interfacial intermetallic compounds formed in SnPbInBiSb high entropy alloy soldered joints on Cu substrates

The growth behavior of the complex intermetallic compounds(IMCs)formed at the interface of Cu/SnPbInBiSb high entropy alloy solder joints was explored.The growth inhibition mechanism of the IMCs at the Cu/SnPbInBiSb solid−liquid reaction interface was revealed.The results showed that the growth rate of the complex IMCs obviously decreased at the Cu/SnPbInBiSb solid−liquid reaction interface.The maximum average thickness of IMCs only reached up to 1.66μm after reflowing at 200℃for 10 min.The mechanism for the slow growth of the complex IMCs was analyzed into three aspects.Firstly,the high entropy of the liquid SnPbInBiSb alloy reduced the growth rate of the complex IMCs.Secondly,the distorted lattice of complex IMCs restrained the diffusion of Cu atoms.Lastly,the higher activation energy(40.9 kJ/mol)of Cu/SnPbInBiSb solid−liquid interfacial reaction essentially impeded the growth of the complex IMCs.

Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

Catalytic Reaction Kinetics of Propylene Dimerization to 4-Methyl-1-Pentene Using Cu-K/K_(2)CO_(3) Solid Base Catalyst

The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.

Thermodynamics and kinetics of hydriding and dehydriding reactions in Mg-based hydrogen storage materials

Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.

Thermal decomposition kinetics of basic carbonate cobalt nanosheets obtained from spent Li-ion batteries:Deconvolution of overlapping complex reactions

A new non-isothermal method of kinetic analysis was employed to investigate the thermal decomposition kinetic modeling of the basic carbonate cobalt nanosheets（n-BCoC） synthesized from spent lithium-ion batteries（LIBs）. Fraser–Suzuki function was applied to deconvoluting overlapping complex processes from the overall differential thermal curves obtained under the linear heating rate conditions, followed by the kinetic analysis of the discrete processes using a new kinetic analysis method. Results showed that the decomposition of n-BCo C in air occurred through two consecutive reactions in the 136-270 ℃ temperature intervals. Decomposition started by hydroxide component（Co（OH）2） decomposition until to 65% and simultaneously carbonate phase decarbonation began. The process was continued by CO2 evolution and finally carbonate cobalt nanosheets have been produced. The reaction mechanism of the whole process can be kinetically characterized by two successive reactions： a phase boundary contracting reaction followed by an Avrami-Erofeev equation. Mechanistic information obtained by the kinetic study was in good agreement with FT-IR（Fourier transform infrared spectroscopy） and SEM（scanning electron microscopy） results.

STUDIES ON THE WITTIG REACTION(XIII): KINETICS OF THE PTC-WITTIG REACTIONS OF 2-BUTENYL METHYL-DIPHENYLPHOSPHONIUM SALT WITH SUBSTITUTED BEN2ALDEHYDES

The kinetics of PTC-Wittig reaction between substituted aromatic aldehydes and 2-butenyl methyldiphenylphosphonium salt has been studied. The low reaction constant (ρ=0. 30) implies that these PTC-Wittig reactions take place through low polar intermediate.

EFFECTS OF PARTICLE SHAPES ON THE KINETICS OF SOLID REACTIONS

In the paper, the effects of powder particle shapes on the kinetics of solid reaction (K. S. R) and errors caused by the current methods based on spherical particle models have been studied. It has been found that particle shaeps have significant effects on kinetics of the solid reaction (K. S. R). However it has now not been involved in the present kinetic equations as a factor. The ball models used by the present kinetic equation have led to great errors not only in determination of the reaction constants but also in judgement of reaction types. This is a problem that has not been much recognized and needs to be solved immediatly.

Effect of Si on growth kinetics of intermetallic compounds during reaction between solid iron and molten aluminum

The effect of Si on the growth kinetics of intermetallic compounds during the reaction of solid iron and molten aluminum was investigated with a scanning electron microscope coupled with an energy dispersive X-ray spectroscope, and hot-dip aluminized experiments. The results show that the intermetallic layer is composed of major Fe2Al5 and minor FeAl3. The Al-Fe-Si ternary phase, rl/rg, is formed in the Fe2Al5 layer. The tongue-like morphology of the Fe2Als layer becomes less distinct and disappears finally as the content of Si in aluminum bath increases. Si in the bath improves the prohibiting ability to the growth of Fe2Als and FeAl3. When the contents of Si are 0, 0.5%, 1.0%, 1.5%, 2.0% and 3.0%, the activation energies of Fe2Al5 are evaluated to be 207, 186, 169, 168, 167 and 172 kJ/mol, respectively. The reduction of the activation energy might result from the lattice distortion caused by Si atom penetrating into the Fe2Al5 phase. When Si atom occupies the vacancy site, it blocks easy diffusion path and results in the disappearance of tongue-like morphology.

Insights into kinetics and reaction mechanism of acid-catalyzed transesterification synthesis of diethyl oxalate

The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,electron accepting capacity,cations type and crystalline water)on the catalytic activity of acidic catalysts were investigated respectively.It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid(FeCl3)and a Bronsted acid(H2SO4)follows a first-order kinetic reaction process.In addition,the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism.This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis,diminishing the industrial production cost of diethyl oxalate,and developing downstream bulk or high-value-added industrial products.

Fluidized-bed chlorination thermodynamics and kinetics of Kenya natural rutile ore

Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.

Effect of montmorillonite on kinetics of polyurethane preparation reaction

The prepolymerization and curing reaction kinetics of polyurethane/montmorillonite have been studied with end group analysis and FTIR respectively. It was found that the prepolymerization and curing reaction followed the 2nd-order kinetics. But the activation energy of prepolymerization increased from 42.7 kJ/mol to 56.5 kJ/rnol after the montmorillonite was added in the reaction system, and activation energy of curing reaction decreased from 64.4 kJ/mol to 17.5 kJ/mol. 2007 Bing Liao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Thermal Behavior,Nonisothermal Decomposition Reaction Kinetics of Mixed Ester Double-base Gun Propellants

The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by thermogravimetry（TG） and differential thermogravimetry（DTG）, and differential scanning calorimetry（DSC） under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates and decomposes in the first stage, and nitrocellulose and centralite II（C2） decompose in the second stage. The mass loss, the DTG peak points, and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG. There is only one obvious exothermic peak in the DSC curves under the different pressures. With the increase in the furnace pressure, the peak temperature decreases, and the decomposition heat increases. With the increase in the content of TEGDN, the decomposition heat decreases at 0.1 MPa and rises at high pressure. The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures. The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as： dα/dt=1021.59（1-α）3e-2.60×104/T. The reaction mechanism of the process can be classified as chemical reaction. The critical temperatures of the thermal explosion（Tbe and Tbp） obtained from the onset temperature（Te） and the peak temperature（Tp） are 456.46 and 473.40 K, respectively. ΔS≠, ΔH≠, and ΔG≠ of the decomposition reaction are 163.57 J·mol^-1·K^-1, 209.54 kJ·mol^-1, and 133.55 kJ·mol^-1, respectively.

Non-isothermal reduction kinetics of titanomagnetite by hydrogen

Reduction of titanomagnetite （TTM） powders by H2-Ar gas mixtures was investigated under a non-isothermal condition by using a thermogravimetric analysis system. It was found that non-isothermal reduction of TTM proceeded via a dual-reaction mechanism. The first reaction was reduction of TTM to wustite and ilmenite, whereas the second one was reduction of wiistite and ilmenite to iron and titanium dioxide. By using a new model for the dual reactions, which was in an analytical form and incorporated different variables, such as time, temperature, particle size, and hydrogen partial pressure, rate-controlling steps for the dual reactions were obtained with the apparent activation energies calculated to be 90-98 and 115-132 kJ/mol for the first and second reactions, respectively.

Reaction mechanism and kinetics of pressurized pyrolysis of Chinese oil shale in the presence of water

A study of reaction mechanisms and chemical kinetics of pressurized pyrolysis of Chinese Liushuhe oil shale in the presence of water were conducted using an autoclave for simulating and modeling in-situ underground thermal degradation.It was found that the oil shale was first pyrolyzed to form pyrobitumen,shale oil,shale gas and residue,then the pyrobitumen was further pyrolyzed to form more shale oil,shale gas,and residue.It means that there are two consecutive and parallel reactions.With increasing temperature,the pyrobitumen yield,as intermediate,first reached a maximum,then decreased to approximately zero.The kinetics results show that both these reactions are first order.The activation energy of pyrobitumen formation from oil shale is lower than that of shale oil formation from pyrobitumen.

Estimation of kinetics parameters in Beckmann rearrangement of cyclohexanone oxime using genetic algorithm

Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+, kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.

Curing Kinetics and Properties of Epoxy Resin with 1,4-bis(2,4-diaminophenoxy)benzene

A multifunctional amine, 1,4-bis（2,4-diaminophenoxy）benzene（14 BDAPOB）, was prepared and used as a novel hardener for novolac epoxy resin（ER）. The structure of 14 BDAPOB was characterized with Fourier transform infrared（FT-IR） spectroscopy and differential scanning calorimetry（DSC）. The curing kinetics of the novolac epoxy resin/1,4-bis（2,4-diaminophenoxy）benzene（ER/14 BDAPOB） system was studied by means of non-isothermal DSC experiments at five heating rates and determined by the Kissinger, Ozawa and Crane methods. The results showed that the activation energy Ea of the ER/14 BDAPOB（74.56 kJ/mol） system was higher than that of the epoxy resin/LCA-30（ER/LCA-30, 68.85 kJ/mol）, where LCA-30 is a commercial modified diamine. The reaction order, frequency factor and the reaction rate constant at peak temperature of the two systems were calculated. The initial decomposition temperatures（Tonset） were 398.8 ℃（ER/14 BDAPOB）and 334.3 ℃（ER/LCA-30）. The tensile shear strengths were 21.63 MPa（ER/14 BDAPOB） and 21.28 MPa（ER/LCA-30）. The results showed that the two cured systems exhibited good thermal and mechanical properties.