导热过程中热力学流与力的研究(一)——表象与温度场

在不可逆过程热力学原理的基础上，推导得出了过程熵产率的表达式，并且分别针对三种不同的表象求得了对应的温度和热流密度分布场。结果表明：其分布函数各不相同。

颗粒性复合材料基体破坏极限应力

若颗粒增强金属基复合材料基体和增强体结合完好,在外载作用下材料会从基体断裂,应用三相模型法确定出外应力一定时二相胞元的外加应变,进而得到基体内的细观应力场,根据损伤过程的广义热力学力计算出损伤等效应力,当损伤等效应力等于基体单向拉伸断裂应力时,计算出复合材料的基体破坏极限应力。

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.

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.

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

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

Thermodynamics and kinetics of adsorption for heavy metal ions from aqueous solutions onto surface amino-bacterial cellulose

Amino-bacterial cellulose（amino-BC） was prepared by chemical modification of bacterial cellulose（BC）.The adsorption characteristics and mechanism of amino-BC were studied.The results show that adsorption data can be fitted well by Langmuir equation and the pseudo-second order kinetics,indicating that the adsorption of amino-BC would obey monolayer molecule adsorption and the main action was chemisorption.Meanwhile,the adsorption process was studied by the Elovich equation and the intra-particle diffusion model,indicating that the absorption characteristics of metal ions on amino-BC is controlled by both film diffusion and particle diffusion.The increase of reaction temperature will accelerate the adsorbing rate because of endothermic reaction.

Modification of ACFs by chemical vapor deposition and its application for removal of methyl orange from aqueous solution

Viscose activated carbon fibers （ACFs） were characterized using specific surface area, scanning electron modified with chemical vapor deposition （CVD）. The samples were microscopy （SEM）, pore size distribution and Fourier transform infrared spectroscopy （FTIR）. Batch adsorption experiments were carried out to investigate the adsorption behavior of modified ACFs for methyl orange（MO） from its aqueous solutions. The results show that the adsorption isotherms of MO onto modified ACFs well follows the Langmuir isotherm equation. The adsorption kinetics of MO can be well described by the pseudo second-order kinetic model. The adsorption process involves the intra-particle diffusion, but is not the only rate-controlling step. Thermodynamic parameters including AG, AH and AS were calculated, suggesting that the adsorption of MO onto modified ACFs is a spontaneous, exothermic and physisorption process. FTIR result indicates that the major adsorption mechanism of modified ACFs for MO is hydrogen bond.

Iron reduction in aluminum by electroslag refining

The effect of electroslag refining on iron reduction from commercial aluminum was investigated.Cast electrodes of commercial aluminum were electroslag refined using KCl-NaCl-Na3AlF6 slag containing Na2B4O7.Experimental results indicate that the iron content decreases with increasing Na2B4O7 addition and remelting time,and the iron content decreases from 0.400% to 0.184% under 9% Na2B4O7 addition for 30 min remelting.The elastic modulus,yield strength and ultimate tensile strength commercial aluminum are improved,and the tensile elongation is increased by 43% after electroslag refining.The chemical reaction between melt and slag to form Fe2B is the main reason for iron reduction and the thermodynamic calculation of the chemical reaction theoretically accounts for the formation of Fe2B.

Thermodynamics analysis and precipitation behavior of fine carbide in K416B Ni-based superalloy with high W content during creep

The precipitation behavior of carbide in K416 B superalloy was investigated by means of creep measurement and microstructure observation. The results show that nanometer M6 C particles discontinuously precipitate in the γ matrix or along the γ/γ′ interface of the alloy during high temperature tensile creep. Thereinto, the amount of fine M6 C carbide increases as creep goes on, and the coherent interfaces of M6 C phase precipitating from the γ matrix are {100} and {111} planes. The thermodynamics analysis indicates that the solubility of element carbon in the matrix decreases when the alloy is deformed by the axial tensile stress during creep, so as to cause the carbon segregating in the regions of stress concentration and combining with carbide-forming elements M（W, Co）, which promotes the fine M6 C carbide to precipitate from the γ matrix.

Thermodynamics Properties of Oxymatrine in NaCl Solution

The enthalpies of dissolution of oxymatrine in 0.9%NaCl solution were measured using a RD496-2000 Calvet Microcalorimeter at 309.65 K under atmospheric pressure. The differen tial enthalpy and molar enthalpy of oxymatrine dissolution in the 0.9%NaCl solution of were determined. The corresponding kinetic equation that described the dissolution process was elucidated. Moreover, the half-life, molar entropy, molar enthaply, and Gibbs free energy of the dissolution process were also obtained.

Local structure of calcium silicate melts from classical molecular dynamics simulation and a newly constructed thermodynamic model

The distributions of local structural units of calcium silicate melts were quantified by means of classical molecular dynamics simulation and a newly constructed structural thermodynamic model. The distribution of five kinds of Si-O tetrahedra Qi from these two methods was compared with each other and also with the experimental Raman spectra, an excellent agreement was achieved. These not only displayed the panorama distribution of microstructural units in the whole composition range, but also proved that the thermodynamic model is suitable for the utilization as the subsequent application model of spectral experiments for the thermodynamic calculation. Meanwhile, the five refined regions mastered by different disproportionating reactions were obtained. Finally, the distributions of two kinds of connections between Qi were obtained, denoted as Qi-Ca-Qj and Qi-[Ob]-Qj, from the thermodynamic model, and a theoretical verification was given that the dominant connections for any composition are equivalent connections.

Kinetics Study on O2 Adsorption and OHad Desorption at Pt（111）, Its Implication to Oxygen Reduction Reaction Kinetics

Kinetics of dissociative O2 adsorption, OHad desorption, and oxygen reduction reaction （ORR） at Pt（111） electrode in 0.1 mol/L HClO4 has been investigated. Reversible OHad adsorption/desorption occurs at potentials from 0.6 V to 1.0 V （vs. RHE） with the exchange current density of ca. 50 mA/cm^2 at 0.8 V, the fast kinetics of OHad desorption indicates that it should not be the rate determining step for ORR. In the kineticor kinetic-mass transport mix controlled potential region, ORR current at constant potential displays slight decrease with reaction time. ORR current in the positive-going potential scan is slightly larger than that in the subsequent negative-going scan with electrode rotation speed （〉800 r/min） and slow potential scan rate （〈100 mV/s）. The open circuit potential of Pt/0.1 mol/L HClO4 interface increases promptly from 0.9 V to 1.0 V after switch from O2 free- to O2-saturated solution. The increase of open circuit potential as well as ORR current decays under potential control due to the accumulation of OHad from dissociative adsorption of O2. It indicates that at Pt（111） the net rate for O2 decomposition to OHad is slightly faster than that for OHad removal, one cannot simply use the assumption of rate determining step to discuss ORR kinetics. Instead, the ORR kinetics is determined by both the kinetics for O2 decomposition to OHad as well as the thermo-equilibrium of OHad＋H^＋＋e→←H2O.

NUMERICAL PREDICTION OF AIRCRAFT HYDRAULIC SYSTEM BASED ON THERMAL DYNAMIC ANALYSIS

A mathematical model of principal elements of the aircraft hydraulic system is presented based on the heat transfer theory. The dynamic heat transfer process of the hydraulic oil and the pump shells within an aircraft hydraulic system are analyzed by the difference method. A kind of means for the prediction to variational trends of the aircraft hydraulic system temperature is provided during operation. The numerical prediction and simulation under the operational conditions are presented for ground trial running and the decelerated operation in flight. Computational results show that there is a good coincidence between the experimental data and the numerical predictions.

Exchange Reaction Characteristics of Anion Exchange Resin for Diclofenac Sodium

Aim To study the exchange reaction characteristics of anion exchange resin for diclofenac sodium. Methods The drug-resin complexes were prepared by a batch method with diclofenac sodium as the model drug and the strong anion exchange resin (201 × 7) as the carrier. The effects of different forms (OH~ - and Cl~ - ) of the strong anion exchange resin, the particle size of the resin, and the reaction temperature on the exchange behavior were described. The exchange kinetic profiles were fitted. The related exc...

The Thermodynamics and Kinetics on the Solvent Sublation of Ni

The removal of Ni ion from an aqueous solution was carried out by solvent sublation of Ni-diacetyldioximesodium dodecylbenzensulphonic （sublate） into isopentanol. The ratio of surfactant to Ni-diacetyldioxime complex at 20：1 was most effective for the removal, with over 90% Ni ion removed from the aqueous solution within 1 h. The effects of electrolytes （e.g. NaCl）, non-hydrophobic organics （e.g. ethanol） and pH of the solution upon the process were well studied. The removal rate was enhanced by higher airflow rates but almost independent on the volume of the organic solvent floating on the top of the aqueous column. The process of solvent sublation followed first order kinetics. A characteristic parameter, the apparent activation energy of attachment of the sublate to bubbles, was estimated to be 8.99 kJ/mol. Furthermore, the simulation of a mathematical model with the experiment data on the solvent sublation of Ni-diacetyldioxime-SDS was proved to be validated.

Calculation of Vapour Pressure of Metals by Statistical-Mechanical Method With the Debye Model

Statistical expression of vapour pressure equations of metals is derived from the Debye model.The statistical distribution of T_(-p) ensemble is presented in an in-elab- orate mode and the partition function is defined.The vapour pressure of eleven metals have been calculated with the Debye equation and compared with those given by the E- instein equation and empirical equation.Comparison of results of calculation from dif- ferent methods show their evident accordance within the same orders of magnitude.

Removal of vanadate anion by calcined Mg/Al-CO_3 layered double hydroxide in aqueous solution

Mg/Al-CO3 layered double hydroxide （LDH2） with Mg（II）：Al（III） molar ratio of 2：1 was synthesized by co-precipitation method and its calcined product Mg2Al-CLDH（CLDH2） was prepared by heating Mg2Al-LDH at 773 K for 6 h. Removal of vanadate anion （ 3-4VO ） from aqueous solution on CLDH2 was studied. Batch studies were carried out to address various experimental parameters such as Mg/Al molar ratio, adsorbent dosage, initial concentration of solution, contact time and temperature. Vanadate was removed effectively at the optimized experimental conditions. The adsorption kinetics data fitted the pseudo-first-order model. Isotherms for adsorption vanadate by CLDH2 at different solution temperatures were well described using the Langmuir and Freundlich equations, and the isotherm parameters were calculated using linear regression analysis. The adsorption data fitted the langmuir model with good values of the correlation coefficient （R2〉0.999）. The negative value ofΔGΘand the positive value ofΔHΘindicate that the adsorption processes are spontaneous endothermic in nature. The mechanism of adsorption suggests that the surface adsorption is the main process.

Preparation and characterization of MWCNTs/LDHs nanohybrids for removal of Congo red from aqueous solution

The assembly of layered double hydroxides （LDHs） and multi-walled carbon nanotubes （MWCNTs） nanohybrids was prepared as MWCNTs/LDHs by co-precipitation. The synthesized nanoparticles were characterized by using XRD, FT-IR, SEM/EDX, TGA and BET. XRD and SEM studies proved that MWCNTs phases did not enter into the interlayers of LDHs, they dispersed over the LDHs surface homogeneously. BET results showed that MWCNTs/LDHs possessed hierarchically porous nanostructure with large surface area （124.974 m^2/g） and great pore volume （0.604 cm^3/g）. Batch experiments were conducted to study the adsorption efficiency of Congo red （CR）. It was worthy to note that MWCNTs/LDHs exhibited excellent adsorption performance with the maximum CR adsorption capacity of 595.8 mg/g in weak acidic environment. The adsorption kinetics and isotherm parameters can be well described by the pseudo-second-order and the Langmuir isotherm models, respectively. The thermodynamic studies indicated that the adsorption process was spontaneous and endothermic.

Recovery of rare earth element ytterbium(Ⅲ) by dried powdered biomass of spirulina: Adsorption isotherm, kinetic and thermodynamic study

The adsorption characteristics and mechanisms of spirulina powder were investigated when it was used as adsorbent to recover ytterbium(Ⅲ) from wastewater solution. Surface structure and element valence of the adsorbent were analyzed by SEM and XPS for the exploring of its adsorption mechanism for ytterbium(Ⅲ). The adsorption characteristics of ytterbium(Ⅲ) on spirulina powder was analyzed through assessing adsorption isotherm, kinetics and thermodynamic models. The adsorption isotherm data were best explained by Langmuir model, and the adsorption capacity of spirulina powder for ytterbium(Ⅲ) was 72.46 mg/g when adsorption temperature was 318 K. The kinetic experiment results showed that the pseudo-second order kinetic model can better simulate the adsorption process of spirulina powder to ytterbium(Ⅲ), indicating that the rate-controlling step was chemical adsorption. Spirulina can be an efficient and economical ytterbium(Ⅲ) recycling material, because it showed good adsorption stability and reusability from the adsorption-desorption cycle experiment results.

Adsorption behavior of Sb(Ⅲ) in single and binary Sb(Ⅲ)-Fe(Ⅱ) systems on cationic ion exchange resin: Adsorption equilibrium, kinetic and thermodynamic aspects

The present study dealt with the mechanism of competitive adsorption of Sb(Ⅲ)and Fe(Ⅱ)ions from a copper-containing aqueous solution on Purolite S957,a commercially available cationic ion-exchange adsorbent.Experiments were conducted using aqueous copper sulfate solutions containing either single or conjoint ions,using both sedentary and batch adsorption techniques to ascertain the sensitivity of the adsorption process to variation in p H,mass of resin,contact time,and temperature as well as establishing the optimal range of variables for maximum ion removal.The data from single ion adsorption tests were fitted by non-linear regression techniques to Henry,Langmuir,Freundlich,Temkin,and Dubinin–Radushkevich isotherm models.Freundlich isotherm for Sb(Ⅲ)and Freundlich and Henry models for Fe(Ⅱ)solutions best express the adsorption equilibrium data;while for binary ion electrolytes,the extended Freundlich model fitted the data satisfactorily.The kinetic model adequately describing adsorption was shown to be the pseudo-first-order,underscoring the dominant role of physical adsorption playing in the process.Thermodynamic parameters for the adsorption process reveal differences in the Sb(Ⅲ)adsorption mechanism from single ion and Sb(Ⅲ)-Fe(Ⅱ)containing electrolytes.The adsorption of Sb(Ⅲ)alone is endothermic,whereas the process becomes exothermic in the Sb(Ⅲ)-Fe(Ⅱ)system.