A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring sp...A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring speed on vanadium and chromium extraction were studied. The results suggest that the reaction temperature and KOH-to-ore mass ratio are more influential factors for the extraction of vanadium and chromium. Under the optimal reaction conditions （temperature 180 °C, initial KOH-to-ore mass ratio 4：1, stirring speed 700 r/min, gas flow 1 L/min, and reaction time 300 min）, vanadium and chromium extraction rates can reach up to 95% and 90%, respectively. Kinetics analysis results show that the decomposing process of vanadium slag in KOH sub-molten salt can be well interpreted by the shrinking core model under internal diffusion control. The apparent activation energies for vanadium and chromium are 40.54 and 50.27 kJ/mol, respectively.展开更多
The overall reaction was determined on the basis of the dissociation constant of TBA and the ratio of the ligand to the rare earth ion in the complex.The rate law,rate constants and acitivition energies for the reacti...The overall reaction was determined on the basis of the dissociation constant of TBA and the ratio of the ligand to the rare earth ion in the complex.The rate law,rate constants and acitivition energies for the reaction of La^(3+),Gd^(3+)and Ho^(3+)with TBA were studied.It is shown in the study that prerequisites for performing differential rate analysis for binary rare earths with TBA are that the pseudo-first-order parallel reaction mechanism should be conformed with,no multinuclear complex would be formed and the co-coloration effects could be neglected.展开更多
The kinetic behaviours of the substitution reaction of rare earth-PHA with CyDTA were studied systemati- cally.The relationship between the rate constant and atomic number was discussed.The rate differentiation val- u...The kinetic behaviours of the substitution reaction of rare earth-PHA with CyDTA were studied systemati- cally.The relationship between the rate constant and atomic number was discussed.The rate differentiation val- ue R_d(R_d=lgk_(z+n)-lgk_z)was proposed to evaluate the possibility of differential kinetic analysis.The R_d value between the neighbouring lanthanide ions first increases and then decreases along with increasing atomic number, so that the middle and heavy rare earth mixture(such as Sm-Gd and Gd-Y)are ideal systems for the differential rate kinetic analysis.展开更多
The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This p...The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry （ DSC ） , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.展开更多
The large accumulation of coal gangue,a common industrial solid waste,causes severe environmental problems,and green development strategies are required to transform this waste into high-value-added products.In this s...The large accumulation of coal gangue,a common industrial solid waste,causes severe environmental problems,and green development strategies are required to transform this waste into high-value-added products.In this study,low-cost ceramsites adsorbents were prepared from waste gangue,silt coal,and peanut shells and applied to remove the organic dye methylene blue from wastewater.We investigated the microstructure of ceramsites and the effects of the sintering atmosphere,sintering temperature,and solution pH on their adsorption performance.The ceramsites sintered at 800℃under a nitrogen atmosphere exhibited the largest three-dimensional-interconnected hierarchical porous structure among the prepared ceramsites;further,it exhibited the highest methylene blue adsorption performance,with an adsorption capacity of 0.954 mg·g^(−1),adsorption efficiency of over 95%,and adsorption equilibrium time of 1 h at a solution pH of 9.The removal efficiency remained greater than 75%after five adsorption cycles.The adsorption kinetics data were analyzed using various models,including the pseudosecond-order kinetic model and Langmuir equation,and the adsorption was attributed to electrostatic interactions between the dyes and ceramsites,n-interactions,and hydrogen bonds.The prepared coal gangue ceramsites exhibited excellent adsorption capacities,removal rates,and cyclic stabilities,demonstrating their promising application prospects for the comprehensive utilization of solid waste and for wastewater treatment.展开更多
In the conversion of methane and propane under high temperature and pressure,the ignition delay time(IDT)is a key parameter to consider for designing an inherently safe process.In this study,the IDT characteristics of...In the conversion of methane and propane under high temperature and pressure,the ignition delay time(IDT)is a key parameter to consider for designing an inherently safe process.In this study,the IDT characteristics of methane and propane(700–1000 K,10–20 bar)were studied experimentally and using kinetic modeling tools at stoichiometric fuel-tooxygen ratios.All the experiments were conducted through insentropic compression.The reliable experimental data were obtained by using the adiabatic core hypothesis,which can be used to generate and validate the detailed chemical kinetics model.The IDTs of methane and propane were recorded by a rapid compression machine(RCM)and compared to the predicted values obtained by the NUIGMech 3.0 mechanism.To test the applicability of NUIGMech 3.0 under different reaction conditions,the influence of temperature in the range of 700–1000 K(and the influence of pressure in the range of 10–20 bar)on the IDT was studied.The results showed that NUIGMech 3.0 could reasonably reproduce the experimentally determined IDT under the wide range of conditions studied.The constant volume chemical kinetics model was used to reveal the effect of temperature on the elementary reaction,and the negative temperature coefficient(NTC)behavior of propane was also observed at 20 bar.The experimental data can serve as a reference for the correction and application of kinetic data,as well as provide a theoretical basis for the safe conversion of low-carbon hydrocarbon chemicals.展开更多
The effects of long-term moisture changes on the migration,release,and bioavailability of selenium in soil are complex.Due to the lack of effective monitoring methods for precise quantification,its dynamic behavior is...The effects of long-term moisture changes on the migration,release,and bioavailability of selenium in soil are complex.Due to the lack of effective monitoring methods for precise quantification,its dynamic behavior is still unclear.Based on the DGT(Diffusive Gradients in Thin-films)technology,this study sets up three moisture control scenarios:continuous wet,wet-dry alternating,and continuous dry,and carries out a 6-month soil moisture control experiment.In the experiment,the DGT device collected the diffusion gradient data of soil selenium under different scenarios,and analyzed the migration characteristics of selenium in combination with the adsorption isotherm.Meanwhile,the release rate,migration coefficient,and bioavailability parameters of selenium are calculated by fitting the first-order kinetic model,further verifying the reliability and applicability of the DGT data.The experimental results demonstrate that under continuous wet conditions,the release rate of soil selenium reaches 1.85µg·cm^(-2)·h^(-1),with a migration coefficient of 0.012 cm^(2)·h^(-1)and a bioavailability parameter of 0.74;under wet-dry alternating conditions,they are 1.42µg·cm^(-2)·h^(-1),0.01 cm^(2)·h^(-1),and 0.68,respectively;under continuous dry conditions,the release rate of soil selenium is the smallest,at 0.88µg·cm^(-2)·h^(-1),with a migration coefficient of 0.004 cm^(-2)·h^(-1)and a bioavailability parameter of 0.5.The results of this experiment reveal the dynamic behavior of soil selenium under different moisture conditions and reflect the high efficiency of DGT technology in dynamic monitoring and quantitative analysis of soil selenium behavior,providing a scientific basis for the optimal management of rhizosphere soil selenium.展开更多
Electrocatalysis has been investigated as a promising strategy to utilize green electricity to produce renewable fuels,valuable chemicals,and treat pollutants.Electrode kinetic analysis is a potent technique in interr...Electrocatalysis has been investigated as a promising strategy to utilize green electricity to produce renewable fuels,valuable chemicals,and treat pollutants.Electrode kinetic analysis is a potent technique in interrogating reaction mechanisms and evaluating the electrocatalysts.Electron transfer(ET)and proton‐coupled electron transfer(PCET)processes are widely present in reaction networks of electrocatalysis.pH dependence of the kinetics is frequently employed to evaluate whether an elementary step involves proton participation,which is determined by both the reversibility and the specific reactants of electrode reactions.In this article,we discuss the pH dependence of two widely used formulations of the Butler–Volmer kinetics for a model PCET step and highlight a potential pitfall in kinetic analysis.This work aims to provide guiding principles for distinguishing ET and PCET steps via kinetic measurements in electrolytes in a broad range pH values.展开更多
This study prepared a class of RDX-based composite microspheres(RAF)containing ADN and FKM2602.The reaction kinetics of RAF composite microspheres were effectively improved by maintaining the system's high energy ...This study prepared a class of RDX-based composite microspheres(RAF)containing ADN and FKM2602.The reaction kinetics of RAF composite microspheres were effectively improved by maintaining the system's high energy and safety performance.In the close packing state,when the heating rate is rapid,the thermal stability of RAF composite microspheres is better than that of RDX;the close packing state will reduce the degree of freedom of RDX and ADN reaction but will increase the degree of freedom of RAF composite microsphere reaction.The thermal conductivity of RAF composite microspheres is close to that of RDX.In the ignition experiment,the flame of RAF composite microspheres can be maintained without the external heat source.Regarding safety,the H50of RAF composite microspheres was 274.04%higher than that of RDX.The detonation velocity of RAF composite microspheres is slightly higher than that of raw material RDX.Overall,these findings highlight the effectiveness of ADN in enhancing the reaction kinetics of RDX-based composites.展开更多
In the present study, we studied the inhibitory effects of chelidonine and rutaecarpin on porcine pancreatic a-amylase （PPA） catalyzed hydrolysis using 2-chloro-4-nitrophenyl-4-O-β-D-galactopyranosylmaltoside （Gal...In the present study, we studied the inhibitory effects of chelidonine and rutaecarpin on porcine pancreatic a-amylase （PPA） catalyzed hydrolysis using 2-chloro-4-nitrophenyl-4-O-β-D-galactopyranosylmaltoside （Gal-G2-α-CNP）. We, for the first time, provided kinetic report and detailed inhibitory effects of both compounds on PPA. Lineweaver-Burk plot revealed that the inhibition was a mixed-noncompetitive type, and only one molecule of inhibitor bound to the enzyme or to the enzyme-substrate complex. Kinetic constants calculated from secondary plots were in millimole range. Dissociation constants of enzyme-inhibitor complex （KEI） were 0.9 mM and 3.5 mM, respectively. Moreover, dissociation constants of enzyme-inhibitor-substrate complex （KESI） were 0.04 mM and 0.31 mM, respectively. These data indicated that the inhibition was more inclined to competitive to Gal-G2-α-CNP hydrolysis. Further molecular docking study manifested that hydrogen bonding formed between acarbose and aspartic acid （Asp300）, histidine （His305） and glycine （Gly3-6）, while hydrogen bonding was observed between chelidonine and glutamic acid （Glu233）, lysine （Lys200） and His305. In addition, rutaecarpine had only one hydrogen bond with Lys200. Our data indicated that chelidonine and rutaecarpine were two promising drug candidates, and chelidonine possessed stronger inhibitory effect compared with rutaecarpine.展开更多
Many electrochemical energy storage devices,such as batteries,supercapacitors,and metal ion capacitors,rely on effective and inexpensive electrode materials.Herein,we have developed highly active nitrogen-doped porous...Many electrochemical energy storage devices,such as batteries,supercapacitors,and metal ion capacitors,rely on effective and inexpensive electrode materials.Herein,we have developed highly active nitrogen-doped porous carbon nanofoams(NPCNs-600-N)for sodium-ion capacitors(SICs).NPCNs-600-N have a highly porous framework,extended interlayer spacing(0.41 nm),and lots of surface functional groups.Accordingly,NPCNs-600-N achieves a high reversible capacity(301 mAh·g^(-1)at 0.05 A·g^(-1)),superior rate capability(112 mAh·g^(-1)at 5.00 A·g^(-1)),and ultra-stable cyclability.The excellent rate and cycling performance originate from the abundant active sites and porous architecture of NPCNs-600-N.Further-more,SICs device is constructed by employing the NPCNs-600-N as the battery-like anode and commercial superconductive carbon black as the capacitive cathode,which delivers high energy/power densities of 92 Wh·kg^(-1)/15984 W·kg^(-1)with a remarkable cyclability(93%reten-tion over 5000 cycles at 1.00 A·g^(-1)).The methodology of the work enables the simultaneous tuning of the porous architectures and surface function groups of carbon for high-performance SICs.展开更多
Biodegradation has become a popular alternative remediation technology for its economic and ecological advantages. An aerobic bacterium （strain ZW） capable of degrading α-pinene was isolated from a biofilter by a s...Biodegradation has become a popular alternative remediation technology for its economic and ecological advantages. An aerobic bacterium （strain ZW） capable of degrading α-pinene was isolated from a biofilter by a selective enrichment. Based on the 16S rRNA gene analysis and physiochemical properties, this strain was identified as Pseudomonas veronii. Under the optimized condition achieved by the response surface methodology （RSM）, as well as pH 6.82, temperature 26.3℃ and NaC1 concentration 1.36%, almost 100% α-pinene could be removed within 45 hr. Enzymatic biodegradation by the crude intracellular enzyme could be described well by the Michaelis-Menten model in which the maximum degradation rate Vraax and the half-saturation constant Km were calculated to be 0.431 mmol/（L.min） and 0.169 mmol/L, respectively. Activity assay of catechol suggested that the strain ZW possessed a catechol- 1,2-dioxygenase and could decompose benzene-ring through ortho ring cleavage. Based on the identified intermediates by GC/MS, a new metabolic pathway was proposed, in which the final metabolites were some simpler organic and inorganic compounds. The present work demonstrated that the strain ZW would have a great application prospect for the remediation of α-pinene-contaminated environment.展开更多
A novel variable displacement compressor (VDC) for automotive air conditioner (AAC) is introduced, which inherits the advantages of common wobble plate type VDC. It has fewer parts and makes less noise, and instead of...A novel variable displacement compressor (VDC) for automotive air conditioner (AAC) is introduced, which inherits the advantages of common wobble plate type VDC. It has fewer parts and makes less noise, and instead of pneumatic valve the displacement is controlled by electronic control valve. In order to know the control mechanism well and get a good control effect, a mathematical model for the variable displacement mechanism is developed according to the geometrical and kinematical information of the compressor. Using the model, the effect of relevant parameters on variable displace control is estimated. It is helpful to make the optimum decision in the flow control of AAC. As the novel displacement control device, the structure and control rule of electronic control valve is introduced. It can get better effect than the conventional pneumatic valves. And by using this new electronic control device, the optimum systemic control of AAC is available.展开更多
The photodegradation of gaseous dichloromethane （DCM） by a vacuum ultraviolet （VUV） light in a spiral reactor was investigated with different reaction media and initial concentrations. Through the combination of d...The photodegradation of gaseous dichloromethane （DCM） by a vacuum ultraviolet （VUV） light in a spiral reactor was investigated with different reaction media and initial concentrations. Through the combination of direct photolysis, O3 oxidation and HO. oxidation, DCM was ultimately mineralized into inorganic compounds （such as HC1, CO2, H20, etc.） in the air with relative humidity （RH） of 75%-85%. During the photodegradation process, some small organic acids （including formic acid, acetic acid） were also detected and the intermediates were more soluble than DCM, providing a possibility for its combination with subsequent biodegradation. Based on the detected intermediates and the confirmed radicals, a photodegradation pathway of DCM by VUV was proposed. With RH 75%- 80% air as the reaction medium, the DCM removal followed the second-order kinetic model at inlet concentration of 100-1000 mg/m3. Kinetic analysis showed that the reaction media affected the kinetic constants of DCM conversion by a large extent, and RH 80% air could cause a much lower half-life for its conversion. Such results supported the possibility that VUV photodegradation could be used not only for the mineralization of DCM but also as a pretreatment before biodegradation.展开更多
The influence of different pre-oxidation temperatures and pre-oxidation degrees on the reduction and fluidization behaviors of magnetite-based iron ore was investigated in a hydrogen-induced fluidized bed.The raw magn...The influence of different pre-oxidation temperatures and pre-oxidation degrees on the reduction and fluidization behaviors of magnetite-based iron ore was investigated in a hydrogen-induced fluidized bed.The raw magnetite-based iron ore was pre-oxidized at 800 and1000℃ for a certain time to reach a partly oxidation and deeply oxidation state.The structure and morphology of the reduced particles were analyzed via optical microscope and scanning electron microscopy(SEM).The reaction kinetic mechanism was determined based on the double-logarithm analysis.The results indicate that the materials with higher oxidation temperature and wider particle size range show better fluidization behaviors.The lower oxidation temperature is more beneficial for the reduction rate,especially in the later reduction stage.The pre-oxidation degree shows no obvious influence on the fluidization and reduction behaviors.Based on the kinetic analysis,the reduction progress can be divided into three stages.The reduction mechanism was discussed combing the surface morphology and phase structure.展开更多
Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energ...Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.展开更多
To get fiber motion in condensing zone of compact spinning,velocity of this area is achieved by simulation,and then a bead-elastic rod fiber model is established.Based on simulation and dynamic analysis on this zone,g...To get fiber motion in condensing zone of compact spinning,velocity of this area is achieved by simulation,and then a bead-elastic rod fiber model is established.Based on simulation and dynamic analysis on this zone,governing equations are constructed and Runge-Kutta approach is used.Lastly,trajectories of fibers are calculated by specially designed Matlab procedure according to the principles mentioned above.Results show that fiber motions at different initial positions are different;X-axis velocity component makes fibers gathering on sides of suction slot;Y-axis airflow gets fibers gradually close and then stick to the surface of lattice apron.Fiber motions also reflect that the compact spinning process in condensing zone can be divided into three parts:fast convergence zone,adjustment convergence zone,and steady convergence zone.展开更多
At 0.12 mmol/L γ-glutamyl p-nitroaniline(GGPNA),an improved integrated method was developed for kinetic analysis of γ-glutamyltransferase(GGT) reaction process and the integration with the classical initial rate met...At 0.12 mmol/L γ-glutamyl p-nitroaniline(GGPNA),an improved integrated method was developed for kinetic analysis of γ-glutamyltransferase(GGT) reaction process and the integration with the classical initial rate method to measure serum GGT.For the improved integrated method,an integrated rate equation,which used the predictor variable of reaction time and considered inhibitions by both GGPNA and products,was nonlinearly fit to GGT reaction processes.For the integration strategy,classical initial rates were estimated when GGPNA consumption percentages were below 50%;otherwise,maximal reaction rates of GGT were estimated by the improved integrated method and converted into initial rates according to the differential rate equation at 0.11 mmol/L GGPNA.The inte-gration strategy was validated using optimized GGT kinetic parameters and 10-s intervals to record reaction curves within 8.0 min.By the integration strategy,there was a linear response from 0.9 to 32.0 U/L GGT,coefficients of variation were below 3.5%for GGT from 8.0 to 32.0 U/L(n=5) ,and GGT activities in clinical sera responded linearly to their classical initial rates at 2.00 mmol/L GGPNA with an expected slope.Therefore,the integration strategy was successful in measuring GGT at 0.12 mmol/L GGPNA.展开更多
A novel thermal-assisted ultra-violet(UV) photocatalysis digestion method for the determination of total phosphorus(TP) in water samples was introduced in this work. The photocatalytic experiments for TP digestion wer...A novel thermal-assisted ultra-violet(UV) photocatalysis digestion method for the determination of total phosphorus(TP) in water samples was introduced in this work. The photocatalytic experiments for TP digestion were conducted using a 365 nm wavelength UV light and Ti O2 particles as the photocatalyst. Sodium tripolyphosphate and sodium glycerophosphate were used as the typical components of TP and the digested samples were then determined by spectrophotometry after phosphomolybdenum blue reaction. The effects of operational parameters such as reaction time and temperature were studied for the digestion of TP and the kinetic analysis of two typical components was performed in this paper. The pseudo-first-order rate constants k of two phosphorus compounds at different temperatures were obtained and the Arrhenius equation was employed to explain the effect of temperature on rate constant k. Compared with the conventional thermal digestion method for TP detection, it was found that the temperature was decreased from 120 °C to 60 °C with same conversion rate and time in this thermal-assisted UV digestion method, which enabled the digestion process work at normal pressure. Compared with the individual ultra-violet(UV) photocatalysis process, the digestion time was also decreased from several hours to half an hour using the thermal-assisted UV digestion method. This method will not lead to secondary pollution since no oxidant was needed in the thermal-assisted UV photocatalysis digestion process, which made it more compatible with electrochemical detection of TP.展开更多
The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied ...The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied were analyzed by mechanism-function method. The results indicate that three carbon species adopt different oxidation mechanisms due to their different structures. The oxidation of carbon nanotubes with cylindrical structure follows contracting volume reaction mechanism [R3 mechanism, 1- (1- α)^1/3 = kt], indicating that the oxidation of carbon nanotubes takes place from the ends to the center. For graphite with planar sandwich structure, the oxidation starts at the edges initially and gradually moves toward the center, which corresponds to contracting area phase boundary reaction mechanism [R2 mechanism, 1 - (1 - α)^1/2 = kt]. The oxidation of C60 with spherical structure, however, is complex and apparently cannot be illustrated with a single kinetic model. The values of apparent activation energy obtained by the mechanism-function method are (145 ± 5) kJ·mol^-1 for carbon nanotubes and (193 ± 7) kJ·mol^-1 for graphite, respectively, while the value of apparent activation energy for C60 determined using Kissinger method is 91 kJ·mol^-1。展开更多
基金Project(2013CB632605)supported by the National Basic Research Development Program of ChinaProjects(51274178,51274179)supported by the National Natural Science Foundation of China
文摘A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring speed on vanadium and chromium extraction were studied. The results suggest that the reaction temperature and KOH-to-ore mass ratio are more influential factors for the extraction of vanadium and chromium. Under the optimal reaction conditions （temperature 180 °C, initial KOH-to-ore mass ratio 4：1, stirring speed 700 r/min, gas flow 1 L/min, and reaction time 300 min）, vanadium and chromium extraction rates can reach up to 95% and 90%, respectively. Kinetics analysis results show that the decomposing process of vanadium slag in KOH sub-molten salt can be well interpreted by the shrinking core model under internal diffusion control. The apparent activation energies for vanadium and chromium are 40.54 and 50.27 kJ/mol, respectively.
基金The Project was supported by the National Natural Science Foundation of China
文摘The overall reaction was determined on the basis of the dissociation constant of TBA and the ratio of the ligand to the rare earth ion in the complex.The rate law,rate constants and acitivition energies for the reaction of La^(3+),Gd^(3+)and Ho^(3+)with TBA were studied.It is shown in the study that prerequisites for performing differential rate analysis for binary rare earths with TBA are that the pseudo-first-order parallel reaction mechanism should be conformed with,no multinuclear complex would be formed and the co-coloration effects could be neglected.
文摘The kinetic behaviours of the substitution reaction of rare earth-PHA with CyDTA were studied systemati- cally.The relationship between the rate constant and atomic number was discussed.The rate differentiation val- ue R_d(R_d=lgk_(z+n)-lgk_z)was proposed to evaluate the possibility of differential kinetic analysis.The R_d value between the neighbouring lanthanide ions first increases and then decreases along with increasing atomic number, so that the middle and heavy rare earth mixture(such as Sm-Gd and Gd-Y)are ideal systems for the differential rate kinetic analysis.
文摘The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry （ DSC ） , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.
基金supported by the Natural Science Foundation of China under Grant(No.52172099)the Provincial Joint Fund of Shaanxi(2021JLM-28).
文摘The large accumulation of coal gangue,a common industrial solid waste,causes severe environmental problems,and green development strategies are required to transform this waste into high-value-added products.In this study,low-cost ceramsites adsorbents were prepared from waste gangue,silt coal,and peanut shells and applied to remove the organic dye methylene blue from wastewater.We investigated the microstructure of ceramsites and the effects of the sintering atmosphere,sintering temperature,and solution pH on their adsorption performance.The ceramsites sintered at 800℃under a nitrogen atmosphere exhibited the largest three-dimensional-interconnected hierarchical porous structure among the prepared ceramsites;further,it exhibited the highest methylene blue adsorption performance,with an adsorption capacity of 0.954 mg·g^(−1),adsorption efficiency of over 95%,and adsorption equilibrium time of 1 h at a solution pH of 9.The removal efficiency remained greater than 75%after five adsorption cycles.The adsorption kinetics data were analyzed using various models,including the pseudosecond-order kinetic model and Langmuir equation,and the adsorption was attributed to electrostatic interactions between the dyes and ceramsites,n-interactions,and hydrogen bonds.The prepared coal gangue ceramsites exhibited excellent adsorption capacities,removal rates,and cyclic stabilities,demonstrating their promising application prospects for the comprehensive utilization of solid waste and for wastewater treatment.
基金supported by the National Natural Science Foundation of China [Grant No. 22278452]the SINOPEC Research Institute of Safety Engineering for financially supporting this project。
文摘In the conversion of methane and propane under high temperature and pressure,the ignition delay time(IDT)is a key parameter to consider for designing an inherently safe process.In this study,the IDT characteristics of methane and propane(700–1000 K,10–20 bar)were studied experimentally and using kinetic modeling tools at stoichiometric fuel-tooxygen ratios.All the experiments were conducted through insentropic compression.The reliable experimental data were obtained by using the adiabatic core hypothesis,which can be used to generate and validate the detailed chemical kinetics model.The IDTs of methane and propane were recorded by a rapid compression machine(RCM)and compared to the predicted values obtained by the NUIGMech 3.0 mechanism.To test the applicability of NUIGMech 3.0 under different reaction conditions,the influence of temperature in the range of 700–1000 K(and the influence of pressure in the range of 10–20 bar)on the IDT was studied.The results showed that NUIGMech 3.0 could reasonably reproduce the experimentally determined IDT under the wide range of conditions studied.The constant volume chemical kinetics model was used to reveal the effect of temperature on the elementary reaction,and the negative temperature coefficient(NTC)behavior of propane was also observed at 20 bar.The experimental data can serve as a reference for the correction and application of kinetic data,as well as provide a theoretical basis for the safe conversion of low-carbon hydrocarbon chemicals.
文摘The effects of long-term moisture changes on the migration,release,and bioavailability of selenium in soil are complex.Due to the lack of effective monitoring methods for precise quantification,its dynamic behavior is still unclear.Based on the DGT(Diffusive Gradients in Thin-films)technology,this study sets up three moisture control scenarios:continuous wet,wet-dry alternating,and continuous dry,and carries out a 6-month soil moisture control experiment.In the experiment,the DGT device collected the diffusion gradient data of soil selenium under different scenarios,and analyzed the migration characteristics of selenium in combination with the adsorption isotherm.Meanwhile,the release rate,migration coefficient,and bioavailability parameters of selenium are calculated by fitting the first-order kinetic model,further verifying the reliability and applicability of the DGT data.The experimental results demonstrate that under continuous wet conditions,the release rate of soil selenium reaches 1.85µg·cm^(-2)·h^(-1),with a migration coefficient of 0.012 cm^(2)·h^(-1)and a bioavailability parameter of 0.74;under wet-dry alternating conditions,they are 1.42µg·cm^(-2)·h^(-1),0.01 cm^(2)·h^(-1),and 0.68,respectively;under continuous dry conditions,the release rate of soil selenium is the smallest,at 0.88µg·cm^(-2)·h^(-1),with a migration coefficient of 0.004 cm^(-2)·h^(-1)and a bioavailability parameter of 0.5.The results of this experiment reveal the dynamic behavior of soil selenium under different moisture conditions and reflect the high efficiency of DGT technology in dynamic monitoring and quantitative analysis of soil selenium behavior,providing a scientific basis for the optimal management of rhizosphere soil selenium.
基金supported by the Beijing Natural Science Foundation Key Research Program(Grant Z240026)the Beijing National Laboratory for Molecular Sciences.
文摘Electrocatalysis has been investigated as a promising strategy to utilize green electricity to produce renewable fuels,valuable chemicals,and treat pollutants.Electrode kinetic analysis is a potent technique in interrogating reaction mechanisms and evaluating the electrocatalysts.Electron transfer(ET)and proton‐coupled electron transfer(PCET)processes are widely present in reaction networks of electrocatalysis.pH dependence of the kinetics is frequently employed to evaluate whether an elementary step involves proton participation,which is determined by both the reversibility and the specific reactants of electrode reactions.In this article,we discuss the pH dependence of two widely used formulations of the Butler–Volmer kinetics for a model PCET step and highlight a potential pitfall in kinetic analysis.This work aims to provide guiding principles for distinguishing ET and PCET steps via kinetic measurements in electrolytes in a broad range pH values.
基金supported by the Natural Science Foundation of Shanxi Province(Grant No.202203021221120)The Open Fund of MCRI-Shannxi Laboratory of Energetic Materials(Grant No.204-J-2024-2622)。
文摘This study prepared a class of RDX-based composite microspheres(RAF)containing ADN and FKM2602.The reaction kinetics of RAF composite microspheres were effectively improved by maintaining the system's high energy and safety performance.In the close packing state,when the heating rate is rapid,the thermal stability of RAF composite microspheres is better than that of RDX;the close packing state will reduce the degree of freedom of RDX and ADN reaction but will increase the degree of freedom of RAF composite microsphere reaction.The thermal conductivity of RAF composite microspheres is close to that of RDX.In the ignition experiment,the flame of RAF composite microspheres can be maintained without the external heat source.Regarding safety,the H50of RAF composite microspheres was 274.04%higher than that of RDX.The detonation velocity of RAF composite microspheres is slightly higher than that of raw material RDX.Overall,these findings highlight the effectiveness of ADN in enhancing the reaction kinetics of RDX-based composites.
基金State Key Laboratory of Natural and Biomimetic Drugs 2013 Funded Project "Establishment and Application an Online Natural Medicines System with Efficient Separation,Structural Identification and Activity Detection"
文摘In the present study, we studied the inhibitory effects of chelidonine and rutaecarpin on porcine pancreatic a-amylase （PPA） catalyzed hydrolysis using 2-chloro-4-nitrophenyl-4-O-β-D-galactopyranosylmaltoside （Gal-G2-α-CNP）. We, for the first time, provided kinetic report and detailed inhibitory effects of both compounds on PPA. Lineweaver-Burk plot revealed that the inhibition was a mixed-noncompetitive type, and only one molecule of inhibitor bound to the enzyme or to the enzyme-substrate complex. Kinetic constants calculated from secondary plots were in millimole range. Dissociation constants of enzyme-inhibitor complex （KEI） were 0.9 mM and 3.5 mM, respectively. Moreover, dissociation constants of enzyme-inhibitor-substrate complex （KESI） were 0.04 mM and 0.31 mM, respectively. These data indicated that the inhibition was more inclined to competitive to Gal-G2-α-CNP hydrolysis. Further molecular docking study manifested that hydrogen bonding formed between acarbose and aspartic acid （Asp300）, histidine （His305） and glycine （Gly3-6）, while hydrogen bonding was observed between chelidonine and glutamic acid （Glu233）, lysine （Lys200） and His305. In addition, rutaecarpine had only one hydrogen bond with Lys200. Our data indicated that chelidonine and rutaecarpine were two promising drug candidates, and chelidonine possessed stronger inhibitory effect compared with rutaecarpine.
基金financially supported by the Natural Science Foundation of Jiangsu Province (No. BK20170549)the National Natural Science Foundation of China (Nos. 21706103 and 22075109)+2 种基金Nanjing Tech University Research Start-Up Fund (No. 38274017111)Zhongyan Jilantai Chlor-Alkali Chemical Co., Ltd (No. FZ2019-RWS-027)the Open Fund of the Key Laboratory of Fine Chemical Application Technology of Luzhou (No. HYJH-2101-B)
文摘Many electrochemical energy storage devices,such as batteries,supercapacitors,and metal ion capacitors,rely on effective and inexpensive electrode materials.Herein,we have developed highly active nitrogen-doped porous carbon nanofoams(NPCNs-600-N)for sodium-ion capacitors(SICs).NPCNs-600-N have a highly porous framework,extended interlayer spacing(0.41 nm),and lots of surface functional groups.Accordingly,NPCNs-600-N achieves a high reversible capacity(301 mAh·g^(-1)at 0.05 A·g^(-1)),superior rate capability(112 mAh·g^(-1)at 5.00 A·g^(-1)),and ultra-stable cyclability.The excellent rate and cycling performance originate from the abundant active sites and porous architecture of NPCNs-600-N.Further-more,SICs device is constructed by employing the NPCNs-600-N as the battery-like anode and commercial superconductive carbon black as the capacitive cathode,which delivers high energy/power densities of 92 Wh·kg^(-1)/15984 W·kg^(-1)with a remarkable cyclability(93%reten-tion over 5000 cycles at 1.00 A·g^(-1)).The methodology of the work enables the simultaneous tuning of the porous architectures and surface function groups of carbon for high-performance SICs.
基金supported by the National Natural Science Foundation of China (No. 51178431)the International S&T Cooperation Program of China (No.2011DFA92660)+1 种基金the Key Project of Science and Technology Department of Zhejiang Province (No. 2011C13023)Zhejiang Provincial Funds for Distinguished Young Scientists (No. R5090230)
文摘Biodegradation has become a popular alternative remediation technology for its economic and ecological advantages. An aerobic bacterium （strain ZW） capable of degrading α-pinene was isolated from a biofilter by a selective enrichment. Based on the 16S rRNA gene analysis and physiochemical properties, this strain was identified as Pseudomonas veronii. Under the optimized condition achieved by the response surface methodology （RSM）, as well as pH 6.82, temperature 26.3℃ and NaC1 concentration 1.36%, almost 100% α-pinene could be removed within 45 hr. Enzymatic biodegradation by the crude intracellular enzyme could be described well by the Michaelis-Menten model in which the maximum degradation rate Vraax and the half-saturation constant Km were calculated to be 0.431 mmol/（L.min） and 0.169 mmol/L, respectively. Activity assay of catechol suggested that the strain ZW possessed a catechol- 1,2-dioxygenase and could decompose benzene-ring through ortho ring cleavage. Based on the identified intermediates by GC/MS, a new metabolic pathway was proposed, in which the final metabolites were some simpler organic and inorganic compounds. The present work demonstrated that the strain ZW would have a great application prospect for the remediation of α-pinene-contaminated environment.
文摘A novel variable displacement compressor (VDC) for automotive air conditioner (AAC) is introduced, which inherits the advantages of common wobble plate type VDC. It has fewer parts and makes less noise, and instead of pneumatic valve the displacement is controlled by electronic control valve. In order to know the control mechanism well and get a good control effect, a mathematical model for the variable displacement mechanism is developed according to the geometrical and kinematical information of the compressor. Using the model, the effect of relevant parameters on variable displace control is estimated. It is helpful to make the optimum decision in the flow control of AAC. As the novel displacement control device, the structure and control rule of electronic control valve is introduced. It can get better effect than the conventional pneumatic valves. And by using this new electronic control device, the optimum systemic control of AAC is available.
基金supported by the National Natural Science Foundation of China (No. 20976165,21207115)the Ph.D.Programs Foundation of Ministry of Education of China(No. 20093317110003)the Zhejiang Provincial Funds for Distinguished Young Scientists (No. R5090230)
文摘The photodegradation of gaseous dichloromethane （DCM） by a vacuum ultraviolet （VUV） light in a spiral reactor was investigated with different reaction media and initial concentrations. Through the combination of direct photolysis, O3 oxidation and HO. oxidation, DCM was ultimately mineralized into inorganic compounds （such as HC1, CO2, H20, etc.） in the air with relative humidity （RH） of 75%-85%. During the photodegradation process, some small organic acids （including formic acid, acetic acid） were also detected and the intermediates were more soluble than DCM, providing a possibility for its combination with subsequent biodegradation. Based on the detected intermediates and the confirmed radicals, a photodegradation pathway of DCM by VUV was proposed. With RH 75%- 80% air as the reaction medium, the DCM removal followed the second-order kinetic model at inlet concentration of 100-1000 mg/m3. Kinetic analysis showed that the reaction media affected the kinetic constants of DCM conversion by a large extent, and RH 80% air could cause a much lower half-life for its conversion. Such results supported the possibility that VUV photodegradation could be used not only for the mineralization of DCM but also as a pretreatment before biodegradation.
基金the funding support of K1-MET GmbH,metallurgical competence centerthe financial support from the program of China Scholarship Council(No.201908420284)。
文摘The influence of different pre-oxidation temperatures and pre-oxidation degrees on the reduction and fluidization behaviors of magnetite-based iron ore was investigated in a hydrogen-induced fluidized bed.The raw magnetite-based iron ore was pre-oxidized at 800 and1000℃ for a certain time to reach a partly oxidation and deeply oxidation state.The structure and morphology of the reduced particles were analyzed via optical microscope and scanning electron microscopy(SEM).The reaction kinetic mechanism was determined based on the double-logarithm analysis.The results indicate that the materials with higher oxidation temperature and wider particle size range show better fluidization behaviors.The lower oxidation temperature is more beneficial for the reduction rate,especially in the later reduction stage.The pre-oxidation degree shows no obvious influence on the fluidization and reduction behaviors.Based on the kinetic analysis,the reduction progress can be divided into three stages.The reduction mechanism was discussed combing the surface morphology and phase structure.
基金Project supported by the National Basic Research Program(973 Program,2012CBA01205)。
文摘Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.
文摘To get fiber motion in condensing zone of compact spinning,velocity of this area is achieved by simulation,and then a bead-elastic rod fiber model is established.Based on simulation and dynamic analysis on this zone,governing equations are constructed and Runge-Kutta approach is used.Lastly,trajectories of fibers are calculated by specially designed Matlab procedure according to the principles mentioned above.Results show that fiber motions at different initial positions are different;X-axis velocity component makes fibers gathering on sides of suction slot;Y-axis airflow gets fibers gradually close and then stick to the surface of lattice apron.Fiber motions also reflect that the compact spinning process in condensing zone can be divided into three parts:fast convergence zone,adjustment convergence zone,and steady convergence zone.
基金Project supported by the National Natural Science Foundation of China (No.30200266)the Program for New Century Excellent Talents in University of Ministry of Education of China(No.NCET-09-928)
文摘At 0.12 mmol/L γ-glutamyl p-nitroaniline(GGPNA),an improved integrated method was developed for kinetic analysis of γ-glutamyltransferase(GGT) reaction process and the integration with the classical initial rate method to measure serum GGT.For the improved integrated method,an integrated rate equation,which used the predictor variable of reaction time and considered inhibitions by both GGPNA and products,was nonlinearly fit to GGT reaction processes.For the integration strategy,classical initial rates were estimated when GGPNA consumption percentages were below 50%;otherwise,maximal reaction rates of GGT were estimated by the improved integrated method and converted into initial rates according to the differential rate equation at 0.11 mmol/L GGPNA.The inte-gration strategy was validated using optimized GGT kinetic parameters and 10-s intervals to record reaction curves within 8.0 min.By the integration strategy,there was a linear response from 0.9 to 32.0 U/L GGT,coefficients of variation were below 3.5%for GGT from 8.0 to 32.0 U/L(n=5) ,and GGT activities in clinical sera responded linearly to their classical initial rates at 2.00 mmol/L GGPNA with an expected slope.Therefore,the integration strategy was successful in measuring GGT at 0.12 mmol/L GGPNA.
基金Supported by the National Natural Science Foundation(61372053)the National High Technology Research and Development Program(2012AA040506)
文摘A novel thermal-assisted ultra-violet(UV) photocatalysis digestion method for the determination of total phosphorus(TP) in water samples was introduced in this work. The photocatalytic experiments for TP digestion were conducted using a 365 nm wavelength UV light and Ti O2 particles as the photocatalyst. Sodium tripolyphosphate and sodium glycerophosphate were used as the typical components of TP and the digested samples were then determined by spectrophotometry after phosphomolybdenum blue reaction. The effects of operational parameters such as reaction time and temperature were studied for the digestion of TP and the kinetic analysis of two typical components was performed in this paper. The pseudo-first-order rate constants k of two phosphorus compounds at different temperatures were obtained and the Arrhenius equation was employed to explain the effect of temperature on rate constant k. Compared with the conventional thermal digestion method for TP detection, it was found that the temperature was decreased from 120 °C to 60 °C with same conversion rate and time in this thermal-assisted UV digestion method, which enabled the digestion process work at normal pressure. Compared with the individual ultra-violet(UV) photocatalysis process, the digestion time was also decreased from several hours to half an hour using the thermal-assisted UV digestion method. This method will not lead to secondary pollution since no oxidant was needed in the thermal-assisted UV photocatalysis digestion process, which made it more compatible with electrochemical detection of TP.
基金Supported by the Natural Science Foundation of Zhejiang Province (No. 500105).
文摘The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied were analyzed by mechanism-function method. The results indicate that three carbon species adopt different oxidation mechanisms due to their different structures. The oxidation of carbon nanotubes with cylindrical structure follows contracting volume reaction mechanism [R3 mechanism, 1- (1- α)^1/3 = kt], indicating that the oxidation of carbon nanotubes takes place from the ends to the center. For graphite with planar sandwich structure, the oxidation starts at the edges initially and gradually moves toward the center, which corresponds to contracting area phase boundary reaction mechanism [R2 mechanism, 1 - (1 - α)^1/2 = kt]. The oxidation of C60 with spherical structure, however, is complex and apparently cannot be illustrated with a single kinetic model. The values of apparent activation energy obtained by the mechanism-function method are (145 ± 5) kJ·mol^-1 for carbon nanotubes and (193 ± 7) kJ·mol^-1 for graphite, respectively, while the value of apparent activation energy for C60 determined using Kissinger method is 91 kJ·mol^-1。
