Standard-state entropies and their impact on the potential-dependent apparent activation energy in electrocatalysis

The apparent activation energy,Eapp,is a common measure in thermal catalysis to discuss the activity and limiting steps of catalytic processes on solid-state materials.Recently,the electrocatalysis community adopted the concept of Eappand combined it with the Butler-Volmer theory.Certain observations though,such as potential-dependent fluctuations of Eapp,are yet surprising because they conflict with the proposed linear decrease in Eappwith increasing overpotential.The most common explanation for this finding refers to coverage changes upon alterations in the temperature or the applied electrode potential.In the present contribution,it is demonstrated that the modulation of surface coverages cannot entirely explain potential-dependent oscillations of Eapp,and rather the impact of entropic contributions of the transition states has been overlooked so far.In the case of a nearly constant surface coverage,these entropic contributions can be extracted by a dedicated combination of Tafel plots and temperature-dependent experiments.

Apparent activation energy for spontaneous combustion of sulfide concentrates in storage yard

In order to evaluate the spontaneous combustion hazard of sulfide concentrates in storage, three different kinds of sulfide concentrates （sulfur-rich sulfide concentrate, iron sulfide concentrate and copper sulfide concentrate） were obtained from a storage yard in Dongguashan Copper Mine, China. The reaction processes at different heating rates of 5, 10, 15, 20, and 25 ℃/min in air flow from ambient temperature to 1 000 ℃ were studied by TG-DTG-DSC analysis. By the peak temperatures of DTG curves, the whole reaction process for each sample was divided into different stages, and the corresponding apparent activation energies were calculated by the Ozawa-Flynn-Wall method. It is found that the reaction process of each sample is considerably complex; the apparent activation energy values change from 36 to 160 kJ/mol in different temperature ranges; sulfur-rich sulfide and iron sulfide concentrates have lower apparent activation energy than copper sulfide concentrate below 150 ℃; so they are more inclined to cause spontaneous combustion at ambient temperature.

Calculation of Apparent Activation Energy of Coal Oxidation at Low Temperatures by Measuring CO Yield

By analyzing previous studies on activation energy of coal oxidation at low temperatures, a theoretical calculation model of apparent activation energy is established. Yield of CO is measured by using the characteristic detector of coal oxidation at 30-90 ℃. The impact of parameters, such as airflow and particle size, on activation energies is analyzed. Finally, agreement was obtained between activation energies and the dynamic oxygen absorbed in order to test the accuracy of the model. The results show that： 1） a positive exponential relation between concentration of CO and temperature in the process of the experiment is obtained： increases are almost identical and the initial CO is low; 2） the apparent activation energies increase gradually with the sizes of particle at the same airflow, but the gradients increase at a decreasing rate; 3） the apparent activation energies increase linearly with airflow. For the five coal particles, the differences among the energies are relatively high when the airflow was low, but the differences were low when the airflow was high; 4） the optimum sizes of particle, 0.125-0.25 ram, and the optimum volume of airflow, 100 mL/min, are determined from the model; 5） the apparent activation energies decrease with an increase in oxygen absorbed. A negative exponential relation between the two is obtained,

Determination of the Apparent Activation Energy of Concrete Carbonation

Accelerated carbonation experiments about the development of carbonation rates of ordinary Portland cement concrete under different artificial climates were carried out. Six water cement ratios and six climate condition combinations of temperature and relative humidity were used. Results indicate that changes of concrete carbonation rate with environmental temperature agree the Arrhenius law well, which suggests concrete carbonation rate has obvious dependence on temperature. The higher the temperature is, the more quickly the concrete carbonates, and at the same time it is also affected by environmental relative humidity. Thereafter, the apparent activation energy Ea of concrete carbonation reaction was obtained, ranging from 16.8 to 20.6 kJ/mol corresponding 0.35-0.74 water cement ratio, and lower water cement ratio will cause the apparent activation energy increase. Concrete carbonation rates will increase 1.1-1.69 times as temperature increase every 10 ℃ at the temperature range of 10 to 60 ℃.

Apparent Activation Energy of Concrete in Early Age Determined by Adiabatic Test

The apparent activation energy of concrete in early age was determined by adiabatic temperature rise test with different initial temperatures. The influence of mineral admixtures such as fly ash, slag and silica fume on the apparent activation energy of concrete was investigated. The equivalent age that expresses the maturity of concrete was calculated to evaluate the cracking risk of concrete in structures. The results reveal that a substitution of 20% fly ash for Portland cement obviously decreases the apparent activation energy of concrete, however, a substitution of 10% silica fume for Portland cement increases the apparent activation. Finite element method analysis of a simulating concrete wall shows that the concrete containing 20% fly ash has the lowest cracking risk.

Free radicals, apparent activation energy, and functional groups during low-temperature oxidation of Jurassic coal in Northern Shaanxi

Correlations among free radicals, apparent activation energy, and functional groups during lowtemperature oxidation of Jurassic coal in Northern Shaanxi were investigated by examining three coal samples collected from the Ningtiaota, Jianxin, and Shigetai coal mines. Free radical concentrations at less than 120 ℃ were investigated by electron spin resonance experiments while the thermogravimetric experiments were conducted to analyze apparent activation energies. In addition, Fourier transform infrared spectroscopy was employed to study the spectrum of functional groups generated in coal. The results indicated that, in decreasing order, the apparent activation energies were Shigetai 〉Jianxin 〉 Ningtiaota, indicating that, from 50 to 120 ℃, the Ningtiaota coal sample most easily absorbed and reacted with oxygen while the most resistant was the Shigetai coal sample. Free radical concentrations and line heights increased with increased temperature, and the line width and Lande factor showed irregular fluctuations. Functional group variations were different among these coals, and the phenol and alcohol-associated OHs, carboxyls, and aromatic ring double bonds might have had a major impact on free radical concentrations. These results were meaningful for better consideration and management of coal oxidation at low temperatures.

Hot deformation behavior of TC11/Ti-22Al-25Nb dual-alloy in isothermal compression

The high-temperature flow behavior of TCll/Ti-22Al-25 Nb electron beam（EB） weldments was investigated by the isothermal compression tests at the temperature of 900-1060℃ and the strain rate of 0.001-10 s-（-1）.Based on the experimental data,the constitutive equation that describes the flow stress as a function of strain rate and deformation temperature is obtained.The apparent activation energy of deformation is calculated,which decreases with increasing the strain and the value is 334 kJ/mol at strain of 0.90.The efficiency of power dissipation η changes obviously with the variation of deformation conditions.Under the strain rates of 0.01,0.1 and 1 s-（-1）,the value of η increases with increasing the true strain for different deformation temperatures.While the value of η decreases with increasing the strain under the strain rates of 0.001 and 10 s-（-1）.The optimum processing condition is（t（opi）=1060℃,ε（opi）=0.1 s-（-1）） with the peak efficiency of 0.51.Under this deformation,dynamic recrystallization（DRX） is observed obviously in the microstructure of welding zone.Under the condition of 1060℃ and 0.001 s-（-1）,the deformation mechanism is dominated by dynamic recovery（DRV） and the value of η decreases sharply（η=0.02）.The flow instability is predicted to occur since the instability parameter ξ（ε）becomes negative.The hot working process can be carried out safely in the domain with the strain rate of 0.001-0.6 s-（-1） and the temperature of 900-1060℃.

Hot compression behavior and processing map of cast Mg-4Al-2Sn-Y-Nd alloy

The plastic flow behavior of a newly developed high ductility magnesium alloy, Mg-4Al-2Sn-Y-Nd, was investigated by hot compression from 200 to 400 ℃ with a strain rate of 1.5×10-3 to 7.5 s-1. The results reveal that the strain rate sensitivity factor （m） of the alloy is much lower than that of the AZ31 alloy, which implies that the alloy should be more suitable for processing at high strain rate. The constitutive relationship of the alloy deformed at elevated temperature was obtained by plotting the experimental data. The stress exponent of the alloy is 10.33, which reveals that climb-controlled dislocations creep is the dominated deformation mechanism. The processing-map technique was used to determine the practical processing window. The proper deformation temperature and strain rate of the cast alloy were determined as 350-400 ℃ and 0.01-0.03 s-1, respectively.

Kinetics of AlOOH dissolving in caustic solution studied by high-pressure DSC

Mechanism functions and kinetic parameters of AlOOH（boehmite or diaspore） dissolving in sodium hydroxide solution were researched.The mixture of boehmite or diaspore and caustic solution was scanned by high-pressure differential scanning calorimetry（DSC） instrument with heating rate of 10 ℃/min,and differential equation method was used to analyse the DSC curves,combining with iterative method and linear least square method.The most probable mechanism functions for both boehmite or diaspore and caustic solution reactions were logically selected from 30 types of non-isothermal kinetics differential equations,according to the calculated results obtained by Matlab program.The most probable differential mechanism function of boehmite dissolving in caustic solution is f（α）=1-α,which reveals the first-order reaction with apparent activation energy of 79.178 kJ/mol and the preexponential constant 1.031×108 s-1.The function,f（α）=2（1-α）3/2,can describe the dissolution of diaspore sample in sodium hydroxide solution.The calculated results of kinetic parameters are apparent activation energy of 73.858 kJ/mol,preexponential constant of 5.752×107 s-1 and reaction order of 1.5.

Kinetics study and analysis of zeolite Y destruction

A series of zeolites,including USY zeolites without sodium,Na-USY at different Na contents,La-USY with different rare earth（RE） contents and La-Na-USY with RE and Na were prepared by an ion exchange method.They were investigated to understand the activation barriers for the destruction of Y zeolite structure under hydrothermal treatment and the effect of V using the solid-state kinetic model.The results showed that the pathways for Y zeolite destruction were dealumination,desiliconization and the disappearance of La-O bonds.Zeolites were destroyed by steam through acid hydrolysis,which was accelerated by V.In addition,Na and V exerted a synergistic effect on the framework destruction,and the formation of NaOH was the rate-determining step.The presence of RE elements decreased hydrolysis and stabilized the structure of the zeolites.The interaction between V and RE destroyed zeolite structure by eliminating the stabilizing La-O[RE-OH-RE]^（5＋）bridges in the sodalite cages.

Kinetics of acid-oxygen leaching of low-sulfur Ni-Cu matte at atmospheric pressure

The leaching of low-sulfur Ni-Cu matte in acid-oxygen(CuSO4-H2SO4-O2)solution at atmospheric pressure was researched.This matte was obtained from high grade Ni-Cu matte by magnetic separation,which mainly contained Ni-Cu alloy and a small quantity of sulfides.The effects of temperature,agitation speed,oxygen flow rate,particle size,acid concentration and concentration of copper ion were studied.It is found that the matte particles are leached by shrinking core mechanism and the leaching process is electrochemically controlled.In a temperature range of 30-60℃,the surface reaction is rate-limiting step,with an apparent activation energy of 41.9 kJ/mol.But at higher temperature(70-85℃),the rate process is controlled by diffusion through the product layer,with an apparent activation energy of 7.3 kJ/mol.

Characteristics of Hydrogen Storage Alloy Mg_2Ni Produced by Hydriding Combustion Synthesis

A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.

SUPERPLASTICITY IN SiC_w/ZK60 COMPOSITE

The superplastic deformation behavior of SiCw/ZK60 composite was investigated at temperatures ranging from 573K to 723K and at initial strain rates ranging from 8.3x10-4s-1 to 8.3x10-2s-1. A maximum elongation of 200% with a m-value of 0.35 was obtained at 613K and a initial strain rate of 1.67x 10-2s-1. The apparent activation energy (98kJ/mol) approximates that for grain boundary diffusion (92kJ/mol) in magnesium. It is proposed that the dominant mechanism of superplastic deformation in the present composite is grain boundary sliding accommodated by diffusional transport, besides, interfacial sliding plays an important role in the superplastic deformation.

Effect of processing parameters on flow behaviors and microstructure during high temperature deformation of GH4586 superalloy

The apparent activation energy for deformation(Q)and strain rate sensitivity(m)of GH4586 superalloy are calculated and the variation trend is reasonably explained by the microstructure observations.Constitutive modelling of this superalloy is established and the processing maps at different strains are constructed.The results show that the Q value is in the range of 751.22−878.29 kJ/mol.At a temperature of 1060°C,strain rate of 0.001 s^(−1),and strain of 0.65,the m value of GH4586 superalloy reaches a maximum of 0.42.The optimal processing parameter of GH4586 superalloy is at a deformation temperature of 1050°C and a strain rate of 0.001 s^(−1).The domains of flow instability notably expand with increasing strain during high temperature deformation of GH4586 superalloy.

Hydration Characteristics of Sodium Sulfate Slag Cement System

The hydration characteristics by thermal analysis (DTA) were determined, and an isothermal calorimeter (IC) was used to study the pastes. The experimental results indicate: (1) The main hydration products of SSC are C-S-H (I) gel with a low Ca/Si ratio, crystalline Thomsonite-type and AFt-type phases containing certain alkali cations; (2) No phases of the AFm-type and high alkaline Ca (OH)(2) in SSC system could benefit the hydrated cements to improve its strength and durability; (3) Crystalline Thomsonite-type and AFt-type phases containing Na+ will greatly reduce free alkali and alleviate the harmness of alkali aggregate reaction (AAR) in SSC system; (4) Similar to ordinary Portland cement (OPC), the hydration process of SSC could be classified into five stage: initial, induction, acceleration, deceleration and decay; (5) Regardless of the activator used, the apparent activation energy is higher with the increased slag in cement system, and the rising temperature could promote the hydration of SSC.

Solar-heating boosted catalytic reduction of CO_(2） under full-solar spectrum

Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low efficiency due to narrow solar-spectrum utilization and sluggish heterogeneous reaction kinetics.In this work,we demonstrate that catalytic reduction of CO2 can be achieved over Au nanoparticles(NPs)deposited rutile under full solar-spectrum irradiation,boosted by solar-heating effect.We found that UV and visible light can initiate the reaction,and the heat from IR light and local surface-plasmon resonance relaxation of Au NPs can boost the reaction kinetically.The apparent activation energy is determined experimentally and is used to explain the superior catalytic activity of Au/rutile to rutile in a kinetic way.We also find the photo-thermal synergy in the Au/rutile system.We envision that this work may facilitate understanding the kinetics of CO2 reduction and developing feasible catalytic systems with full solar spectrum utilization for practical artificial photosynthesis.

Spontaneous combustion tendency of fresh and pre-oxidized sulfide ores

Three representative sulfide ore samples were collected from typical metal mines,and their corresponding pre-oxidized products were obtained under nature environment.The thermal behaviors of each sample at heating rates of 5,10,15 and 20 °C/min in air flow from ambient temperature to 800 °C were studied by simultaneous thermal analysis and the TG/DSC curves before and after the pre-oxidation were compared.By the peak temperature of DTG curves,the whole reaction process for each sample was divided into different stages,and the apparent activation energies were calculated by the Ozawa-Flynn-Wall method.The results show that the reaction process of each sample after pre-oxidation is more complex,with quicker reaction rates,fewer heat production quantities,and higher or lower ignition-points.The apparent activation energies decrease from 364.017-474.228 kJ/mol to 244.523- 333.161 kJ/mol.Therefore,sulfide ores are more susceptible to spontaneous combustion after the pre-oxidation.

Effect of sodium carbonate addition on carbothermic reduction of ilmenite concentrate

The enhanced reduction mechanism and kinetics of different Na_(2)CO_(3) additions in the carbothermic reduction of ilmenite concentrate were investigated.The reduction process was carried out at different heating rates in a thermogravimetry facility,and the kinetics was studied using the Starink method.The results indicate that Na_(2)CO_(3) addition enhanced the reduction effect as well as reduced the initial temperature of the reaction and the activation energy by increasing reactant activity in reactant form;however,it deteriorated the late-stage kinetic conditions by generating a molten phase,thereby reducing the reaction rate in the late stages of reduction.The average apparent activation energies of ilmenite concentrate with 0%,3%,and 6%Na_(2)CO_(3) are 447,289,and 430 kJ/mol,respectively.The results from kinetics parameters confirm that Na_(2)CO_(3) addition accelerated the reduction kinetics;however,excessive addition worsened the reduction kinetics.

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite（TTM） ironsand, which contains 11.41wt% TiO_2 and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence： Fe O ＋ FeTiO_3 → Fe_2 TiO_4 → FeTiO_3 → FeTi_2O_5 → TiO_2. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 k J·mol^（-1）.

Effect of Al2O3 on the viscosity of CaO-SiO2-Al2O3-MgO-Cr2O3 slags

We investigated the effect of Al2O3 content on the viscosity of CaO-SiO2-Al2O3-8wt%MgO-1wt%Cr2O3(mass ratio of CaO/SiO2 is 1.0,and Al2O3 content is 17wt%-29wt%)slags.The results show that the viscosity of the slag increases gradually with increases in the Al2O3 content in the range of 17wt%to 29wt%due to the role of Al2O3 as a network former in the polymerization of the aluminosilicate structure of the slag.With increases in the Al2O3 content from 17wt%to 29wt%,the apparent activation energy of the slags also increases from 180.85 to 210.23 kJ/mol,which is consistent with the variation in the critical temperature.The Fourier-transform infrared spectra indicate that the degree of polymerization of this slag is increased by the addition of Al2O3.The application of Iida’s model for predicting the slag viscosity in the presence of Cr2O3 indicates that the calculated viscosity values fit well with the measured values when both the temperature and Al2O3 content are at relatively low levels,i.e.,the temperature range of 1673 to 1803 K and the Al2O3 content range of 17wt%-29wt%in CaO-SiO2-Al2O3-8wt%MgO-1wt%Cr2O3 slag.