对物理化学中的“热力学”的分析

物理化学中的“热力学”是相当抽象而充满逻辑性的科学知识，学生在理解和掌握的过程中普遍感到难度较大。怎样完成物理化学中的“热力学”教学，是每一位物理化学教师必须切实解决的问题，文章对物理化学中热力学涉及到的基本概念，以及热力学第一定律、热力学第二定律、热力学第三定律以及第零定律等内容进行了系统的分析，为教师帮助学生从本质上认识“热力学”知识，真正掌握“热力学”知识提供了参考。

试论物理化学课程思政元素的挖掘--以“热力学三大定律”的教学为例

近年来,在物理化学的教育领域中思政育人受到广泛重视,合理开展思政育人工作是培养学生良好思想素养和综合素质的重要举措,为探索出培养物理化学专业学生思想素养的措施,该文将“热力学三大定律”的教学作为案例,提出几点物理化学课程思政元素的挖掘建议,在全面挖掘课程中的思政育人元素同时,创建全面性、全过程与全员性的思政协同育人发展模式,拓展物理化学课程中的思政教育功能,在培养学生专业能力的同时不断提升学生的思想道德素质,为培育国家需要的物理化学综合性人才提供帮助。

Molecular simulation study of the microstructures and properties of pyridinium ionic liquid[HPy][BF_(4)]mixed with acetonitrile

The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this work.The following properties were determined:density,self-diffusion coefficient,excess molar volume,and radial distribution function.The results show that with an increase in the mole fraction of[HPy][BF_(4)],the self-diffusion coefficient decreases.Additionally,the excess molar volume initially decreases,reaches a minimum,and then increases.The rules of radial distribution functions(RDFs)of characteristic atoms are different.With increasing the mole fraction of[HPy][BF_(4)],the first peak of the RDFs of HA1-F decreases,while that of CT6-CT6 rises at first and then decreases.This indicates that the solvent molecules affect the polar and non-polar regions of[HPy][BF_(4)]differently.

Synergistic extraction and separation of valuable elements from high-alumina fly ash with carbochlorination method

A novel process was proposed for synergistic extraction and separation of valuable elements from high-alumina fly ash.A thermodynamic analysis revealed that to achieve effective carbochlorination,it is crucial to conduct carbochlorination of the fly ash within the temperature range from 700 to 1000℃.The experimental results demonstrated that under the optimal conditions,the carbochlorination efficiency for Al,Si,Ca,Ti,and Mg exceeded 81.18%,67.62%,58.87%,82.15%,and 59.53%,respectively.The XRD patterns indicated that Al and Si in the mullite phase(Al_(6)Si_(2)O_(13))were chlorinated during the carbochlorination process,resulting in the formation of mullite mesophases(Al_(4.75)Si_(1.25)O_(9.63) and Al_(1.83)Si_(1.08)O_(4.85)).After the carbochlorination process,Al was accumulated as AlCl_(3) in the condenser,while SiCl_(4) and TiCl_(4) were enriched in the exhaust gas,and CaCl_(2),MgCl_(2),and unreacted oxides remained in the residue for further recycling.

Effects of Fluorescent Pair on the Kinetics of DNA Strand Displacement Reaction

Fluorescent labels are widely used in the characterizations of DNA-based reaction network operations.We systematically studied the effects of commonly used fluorescent pairs on thermal stabilities of signal-substrate duplex and the strand displacement kinetics.It is demonstrated that the modifications of duplex with fluorescent pairs stabilize DNA duplex by up to 3.5℃,and the kinetics of DNA strand displacement circuit is also evidently slowed down.These results highlight the importance of fluorescent pairs towards the kinetic modulation in designing nucleic acid probes and complex DNA dynamic circuits.

Thermodynamic simulation of stepwise precipitation of NH_(4)VO_(3)and NaHCO_(3)from carbonating Na_(3)VO_(4)solution

Thermodynamic simulation was conducted to design a new process of stepwise precipitating NH_(4)VO_(3)and NaHCO_(3)from regulating the CO_(2)carbonation of Na_(3)VO_(4)solution.Firstly,a new V(V)speciation model for the aqueous solution containing vanadate and carbonate is established by using the Bromley-Zemaitis activity coefficient model.Subsequently,thermodynamic equilibrium calculations are conducted to clarify the behavior of vanadium,carbon,sodium,and impurity species in atmospheric or high-pressure carbonation.To ensure the purity and recovery of vanadium products,Na_(3)VO_(4)solution is initially carbonated to the pH of 9.3-9.4,followed by precipitating NH_(4)VO_(3)by adding(NH_(4))_(2)CO_(3).After vanadium precipitation,the solution is deeply carbonated to the final pH of 7.3-7.5 to precipitate NaHCO_(3),and the remaining solution is recycled to dissolve Na_(3)VO_(4)crystals.Finally,verification experiments demonstrate that 99.1%of vanadium and 91.4%of sodium in the solution are recovered in the form of NH_(4)VO_(3)and NaHCO_(3),respectively.

Distribution behavior of valuable elements in oxygen-enriched top-blown smelting process of waste printed circuit boards

Oxygen-enriched top-blown smelting is a promising technology for processing waste printed circuit boards(WPCBs).The distribution behavior of valuable elements in WPCBs during smelting was investigated by varying the oxygen-enriched concentration,oxygen volume,CaO/SiO_(2)(mass ratio),and Fe/SiO_(2)(mass ratio).The optimal operating conditions were obtained by implementing a one-factor-at-a-time method.X-ray diffractometer,scanning electron microscopy−energy dispersive spectrometer,and inductive coupled plasma-atomic emission spectroscopy methods were utilized to detect the chemical composition,occurrence state as well as elemental contents of alloy and slag.It is found that the elements of Cu,Sn and Ni are mainly accumulated in the alloy while Fe is mainly oxidized into the slag.The direct yields of Cu,Sn and Ni are 90.18%,85.32%and 81.10%under the optimal conditions of temperature 1250℃,oxygen-enriched concentration 30%,oxygen volume 24 L,CaO/SiO_(2) mass ratio 0.55,and Fe/SiO_(2) mass ratio 1.05.The results show that the valuable metals are mainly lost in the slag through mechanical entrainment.

Mechanical Properties and Thermal Shock Resistance of SrAl_(2)Si_(2)O_(8) Reinforced BN Ceramic Composites

Hexagonal boron nitride(h-BN)ceramics have become exceptional materials for heat-resistant components in hypersonic vehicles,owing to their superior thermal stability and excellent dielectric properties.However,their densification during sintering still poses challenges for researchers,and their mechanical properties are rather unsatisfactory.In this study,SrAl_(2)Si_(2)O_(8)(SAS),with low melting point and high strength,was introduced into the h-BN ceramics to facilitate the sintering and reinforce the strength and toughness.Then,BN-SAS ceramic composites were fabricated via hot press sintering using h-BN,SrCO_(3),Al_(2)O_(3),and SiO_(2) as raw materials,and effects of sintering pressure on their microstructure,mechanical property,and thermal property were investigated.The thermal shock resistance of BN-SAS ceramic composites was evaluated.Results show that phases of as-preparedBN-SAS ceramic composites are h-BN and h-SrAl_(2)Si_(2)O_(8).With the increase of sintering pressure,the composites’densities increase,and the mechanical properties shew a rising trend followed by a slight decline.At a sintering pressure of 20 MPa,their bending strength and fracture toughness are(138±4)MPa and(1.84±0.05)MPa·m^(1/2),respectively.Composites sintered at 10 MPa exhibit a low coefficient of thermal expansion,with an average of 2.96×10^(-6) K^(-1) in the temperature range from 200 to 1200℃.The BN-SAS ceramic composites prepared at 20 MPa display higher thermal conductivity from 12.42 to 28.42 W·m^(-1)·K^(-1) within the temperature range from room temperature to 1000℃.Notably,BN-SAS composites exhibit remarkable thermal shock resistance,with residual bending strength peaking and subsequently declining sharply under a thermal shock temperature difference ranging from 600 to 1400℃.The maximum residual bending strength is recorded at a temperature difference of 800℃,with a residual strength retention rate of 101%.As the thermal shock temperature difference increase,the degree of oxidation on the ceramic surface and cracks due to thermal stress are also increased gradually.

Aging Characteristics of Lithium-Ion Battery Under Fast Charging Based on Electrochemical-thermalmechanical Coupling Model

The aging characteristics of lithium-ion battery(LIB)under fast charging is investigated based on an electrochemical-thermal-mechanical(ETM)coupling model.Firstly,the ETM coupling model is established by COMSOL Multiphysics.Subsequently,a long cycle test was conducted to explore the aging characteristics of LIB.Specifically,the effects of charging(C)rate and cycle number on battery aging are analyzed in terms of nonuniform distribution of solid electrolyte interface(SEI),SEI formation,thermal stability and stress characteristics.The results indicate that the increases in C rate and cycling led to an increase in the degree of nonuniform distribution of SEI,and thus a consequent increase in the capacity loss due to the SEI formation.Meanwhile,the increases in C rate and cycle number also led to an increase in the heat generation and a decrease in the heat dissipation rate of the battery,respectively,which result in a decrease in the thermal stability of the electrode materials.In addition,the von Mises stress of the positive electrode material is higher than that of the negative electrode material as the cycling proceeds,with the positive electrode material exhibiting tensile deformation and the negative electrode material exhibiting compressive deformation.The available lithium ion concentration of the positive electrode is lower than that of the negative electrode,proving that the tensile-type fracture occurring in the positive material under long cycling dominated the capacity loss process.The aforementioned studies are helpful for researchers to further explore the aging behavior of LIB under fast charging and take corresponding preventive measures.

Temperature-feedback two-photon-responsive metal-organic frameworks for efficient photothermal therapy

The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.

Effect of thermo-mechanical treatment on microstructure and mechanical properties of wire-arc additively manufactured Al-Cu alloy

Wire-arc additive manufacture(WAAM)has great potential for manufacturing of Al-Cu components.However,inferior mechanical properties of WAAM deposited material restrict its industrial application.Inter-layer cold rolling and thermo-mechanical heat treatment(T8)with pre-stretching deformation between solution and aging treatment were adopted in this study.Their effects on hardness,mechanical properties and microstructure were analyzed and compared to the conventional heat treatment(T6).The results show that cold rolling increases the hardness and strengths,which further increase with T8 treatment.The ultimate tensile strength(UTS)of 513 MPa and yield stress(YS)of 413 MPa can be obtained in the inter-layer cold-rolled sample with T8 treatment,which is much higher than that in the as-deposited samples.The cold-rolled samples show higher elongation than that of as-deposited ones due to significant elimination of porosity in cold rolling;while both the T6 and T8 treatments decrease the elongation.The cold rolling and pre-stretching deformation both contribute to the formation of dense and dispersive precipitatedθ′phases,which inhibits the dislocation movement and enhances the strengths;as a result,T8 treatment shows better strengthening effect than the T6 treatment.The strengthening mechanism was analyzed and it was mainly related to work hardening and precipitation strengthening.

Temperature-Induced Unfolding Pathway of Staphylococcal Enterotoxin B:Insights from Circular Dichroism and Molecular Dynamics Simulation

In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the relationship between the experimental and simulation results were explored.Our computational findings on the secondary structure of SEB showed that at room temperature,the CD spectroscopic results were highly consistent with the MD results.Moreover,under heating conditions,the changing trends of helix,sheet and random coil obtained by CD spectral fitting were highly consistent with those obtained by MD.In order to gain a deeper understanding of the thermal stability mechanism of SEB,the MD trajectories were analyzed in terms of root mean square deviation(RMSD),secondary structure assignment(SSA),radius of gyration(R_(g)),free energy surfaces(FES),solvent-accessible surface area(SASA),hydrogen bonds and salt bridges.The results showed that at low heating temperature,domain Ⅰ without loops(omitting the mobile loop region)mainly relied on hydrophobic interaction to maintain its thermal stability,whereas the thermal stability of domain Ⅱ was mainly controlled by salt bridges and hydrogen bonds.Under high heating temperature conditions,the hydrophobic interactions in domain Ⅰ without loops were destroyed and the secondary structure was almost completely lost,while domain Ⅱ could still rely on salt bridges as molecular staples to barely maintain the stability of the secondary structure.These results help us to understand the thermodynamic and kinetic mechanisms that maintain the thermal stability of SEB at the molecular level,and provide a direction for establishing safer and more effective food sterilization processes.

Thermodynamics and kinetics of adsorption of molybdenum blue with D301 ion exchange resin

The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the adsorption characteristic of D301 for molybdenum blue fits well with the Freundlich adsorption isotherm equation.In the adsorption process of D301 for molybdenum blue,both the enthalpy change ΔH and entropy change ΔS are positive,while the free energy change ΔG is negative when temperatures are in the range of 303-333 K.It is indicated that the adsorption is a spontaneous and endothermic process,and the elevated temperatures benefit to the adsorption.Kinetic studies show that the kinetic data are well described by double driving-force model,and the adsorption rate of molybdenum blue on D301 is controlled by the intraparticle diffusion during the adsorption process.The total kinetic equation is determined.

Thermodynamic study on phosphorus removal from tungstate solution via magnesium salt precipitation method

The thermodynamic equilibrium diagrams of Mg2＋- 3-4PO - ＋4NH -H2O system at 298 K were established based on the thermodynamic calculation. From the diagram, the thermodynamic conditions for removing phosphorus from the tungstate solution by magnesium salt precipitation were obtained. The results show that when the concentration of total magnesium increases from 0.01 mol/L to 1.0 mol/L, the optimal pH for the phosphorus removal by magnesium phosphate decreases from 9.8 to 8.8. The residual concentration of total phosphorus almost keeps the level of 4.0×10-6 mol/L in the system. MgHPO4, Mg3（PO4）2 and the mixture of Mg3（PO4）2 and Mg（OH）2 are stabilized in these system, respectively. However, increasing the total concentration of magnesium has little effect on phosphorus removal by magnesium ammonium phosphate, while it is helpful for phosphorus removal by increasing the total ammonia concentration. The calculated results demonstrate that the residual concentration of total phosphorus can decrease to 5.0×10-7 mol/L as the total concentration of ammonia reaches 5.0 mol/L and the optimal pH value is 9-10. Finally, verification experiments were conducted with home-made ammonium tungstate solution containing 50 g/L WO3 and 13 g/L P. The results show that when the dosage of MgCl2 is 1.1 times of the theoretical amount, the optimum pH for removing phosphorus is 9.5, which matches with the results of the theoretical calculation exactly.

Thermodynamics of removing impurities from crude lead by vacuum distillation refining

A novel technique was developed to remove impurities from crude lead by vacuum distillation.The thermodynamics on vacuum distillation refining process of crude lead was studied by means of saturated vapor pressure of main components of crude lead,separation coefficients and vapor-liquid equilibrium composition of Pb-i（i stands for an impurity） system at different temperatures.The behaviors of impurities in the vacuum distillation refining process were investigated.The results show that the vacuum distillation should be taken to obtain lead from crude lead,in which Zn,As and partial Sb are volatilized at lower temperature of 923-1023 K.Lead is distilled from the residue containing Cu,Sn,Ag and Bi at higher temperature of 1323-1423 K,but the impurity Bi is also volatilized along with lead and cannot be separated from lead.

Boron removal in purifying metallurgical grade silicon by CaO-SiO_2 slag refining

Boron removal from metallurgical grade silicon （MG-Si） using a calcium silicate slag was studied. The results show that it is impossible basically to remove boron using a pure SiO2 refining. The oxidizing ability of CaO-SiO2 slag for boron removal was characterized by establishing the thermodynamic relationship between the distribution coefficient of boron （LB） and the activities of SiO2 and CaO. The experimental results show that the distribution coefficient and the removal efficiency of boron are greatly improved with the increase of CaO proportion in the slag. The maximal value of LB reaches 1.57 with a slag composition of 60%CaO-40%SiO2 （mass fraction）. The boron content in the refined silicon is reduced from 18×10^-6 to 1.8×10^-6 using slag refining at 1600 ℃ for 3 h with a CaO-SiO2/MG-Si ratio of 2.5, and the removal efficiency of boron reaches 90%.

Thermodynamic behavior and morphology of impurities in metallurgical grade silicon in process of O_2 blowing

Gas blowing is a valid method to remove the impurities from metallurgical grade silicon（MG-Si） melt.The thermodynamic behavior of impurities Fe,Al,Ca,Ti,Cu,C,B and P in MG-Si was studied in the process of O2 blowing.The removal efficiencies of impurities in MG-Si were investigated using O2 blowing in ladle.It is found that the removal efficiencies are higher than 90% for Ca and Al and nearly 50% for B and Ti.The morphology of inclusions was analyzed and the phases Al3Ni,NiSi2 and Al3Ni were confirmed in MG-Si by X-ray diffraction.It was found that SiB4 exists in Si？B binary system.The chemical composition of inclusions in MG-Si before and after refining was analyzed by SEM-EDS.It is found that the amount of white inclusion reduces for the removal of most Al and Ca in the forms of molten slag inclusion and the contents of Fe,Ni and Mn in inclusion increase for their inertia in silicon melt with O2 blowing.

Removal of phosphorus from metallurgical grade silicon by Ar-H_2O gas mixtures

The removal of phosphorus in metallurgical grade silicon （MG-Si） by water vapor carried with high purity argon was examined. The effect of the nozzle types, refining time, refining temperature, refining gas temperature and refining gas flow rate on the phosphorus removed was investigated by the self-designed gas blowing device. The optimal refining conditions are nozzle type of holes at bottom and side, refining time of 3 h, refining temperature of 1793 K, refining gas temperature of 373 K, refining gas flow rate of 2 L/min. Under these optimal conditions, the phosphorus content in MG-Si is reduced from 94×10^-6 initially to 11×10-6 （mass fraction）, which indicates that gas blowing refining is very effective to remove phosphorus in MG-Si.

Thermodynamic calculation of high zinc-containing Al-Zn-Mg-Cu alloy

Phase fraction and solidification path of high Zn-containing Al-Zn-Mg-Cu series aluminum alloy were calculated by calculation of phase diagram （CALPHAD） method. Microstructure and phases of Al-9.2Zn-1.7Mg-2.3Cu alloy were studied by X-ray diffraction （XRD）, differential scanning calorimetry （DSC） and scanning electron microscopy （SEM）. The calculation results show that η（MgZn2） phase is influenced by Zn and Mg. Mass fractions of η（MgZn2） in Al-xZn-1.7Mg-2.3Cu are 10.0%, 9.8% and 9.2% for x=9.6, 9.4, 8.8 （mass fraction, %）, respectively. The intervals of Mg composition were achieved for θ（Al2Cu）＋η（MgZn2）, S（Al2CuMg）＋η（MgZn2） and θ（Al2Cu）＋S（Al2CuMg）＋η（MgZn2） phase regions. Al3Zr, α（Al）, Al13Fe4, η（MgZn2）, α-AlFeSi, Al7Cu2Fe, θ（Al2Cu）, Al5Cu2MgsSi6 precipitate in sequence by no-equilibrium calculation. The SEM and XRD analyses reveal that α（Al）, η（MgZn2）, Mg（Al,Cu,Zn）2, θ（Al2Cu） and Al7Cu2Fe phases are discovered in Al-9.2Zn-1.7Mg-2.3Cu alloy. The thermodynamic calculation can be used to predict the major phases present in experiment.