Calculation of Thermodynamic Parameters for Freundlichand Temkin Isotherm Models

Derivation of the Freundlich and Temkin isotherm models from the kinetic adsorption/desorpt ion equations was carried out to calculate their thermodynamic equilibrium constants. The calculation formulae ofthree thermodynamic parameters, the standard molar Gibbs free energy change, the standard molar enthalpy change and the standard molar entropy change, of isothermal adsorption processes for Freundlich andTemkin isotherm models were deduced according to the relationship between the thermodynamic equilibriumconstats and the temperature.

A New Competitive Adsorption Isothermal Model of Heavy Metals in Soils

A new competitive adsorption isothermal model(CAIM)was developed for the coexistent and competitive binding of heavy metals to the soil surface.This model extended the earlier adsorption isothermal models by considering more than one kind of ion adsorption on the soil surface.It was compared with the Langmuir model using different conditions, and it was found that CAIM,which was suitable for competitive ion adsorption at the soil solid-liquid surface,had more advantages than the Langmuir model.The new competitive adsorption isothermal model was used to fit the data of heavy metal(Zn and Cd)competitive adsorption by a yellow soil at two temperatures.The results showed that CAIM was appropriate for the competitive adsorption of heavy metals on the soil surface at different temperatures.The fitted parameters of CAIM had explicit physical meaning.The model allowed for the calculation of the standard molar Gibbs free energy change,the standard molar enthalpy change,and the standard molar entropy change of the competitive adsorption of the heavy metals,Zn and Cd,by the yellow soil at two temperatures using the thermodynamic equilibrium constants.

MICRO-DESCRIPTION OF THE SOLUTE-FIELD AND THE PHASE-FIELD MODEL FOR ISOTHERMAL PHASE TRANSITION IN BINARY ALLOYS

A new phase field method for two-dimensional simulations of binary alloy solidification was studied. A model basing on solute conservative in every unit was developed for solving the solute diffusion equation during solidification. Two-dimensional computations were performed for ideal solutions and Ni-Cu dendritic growth into an isothermal and highly supersaturated liquid phase.

CO_2 isothermal adsorption models of coal in the Haishiwan Coalfield

Since the capacity of CO2 adsorption of coal is a key factor in coal and CO2 outbursts,an experimental study was carried out on CO2 isothermal adsorption with high-pressure volumetry with dry coal samples from the No.2 coal seam in the Haishiwan Coalfield.Four different equations(Langmuir,BET,D-R and D-A) were used to fit the experimental data.We discuss adsorption mechanisms.The results show that the amount of CO2 adsorption increases rapidly under low relative pressure,i.e.,the ratio of equilibrium pressure and saturated vapor pressure,which indicates that molecular layer adsorption or micropore filling may occur in coal.No clear equilibrium state was observed on the isothermal adsorption curves under relative pressure(P /P0 ) ranging from 0 to 0.8.The fitted results show that the accuracy of the D-A equation is highest with n=1.Micropores are more developed in coal by comparing the BET equation with a pressure mercury injection method on the surface area.The D-A equation(n=1) provides the best fit.By comparing the calculated specific surface area of the BET equation and the mercury intrusion method,it is found that micropore adsorption of CO2 occupies a dominant position.

Features of the Excess Adsorption Isotherms of High-Pressure Methane Adsorption on Coal and Simulation Model

Four coal samples of different ranks are selected to perform the adsorption measurement of high-pressure methane（CH4）.The highest equilibrium pressure of the measurement exceeds 20 MPa. Combined with the measuring results and theoretical analyses,the reasons for the peak or the maximum adsorption capacity appearing in the excess adsorption isotherms are explained.The rules of the peak occurrence are summarized.And then,based on the features of coal pore structure,the adsorption features of high-pressure gas,the microcosmic interaction relationship of coal surface and CH4 molecule,and the coalbed methane reservoir conditions,three theoretical assumptions on the coal adsorption high-pressure CH_4 are suggested.Thereafter,on the basis of these theoretical assumptions,the Ono-Kondo lattice model is processed for simplification and deformation. Subsequently,the equations modeling the excess adsorption isotherm of high-pressure CH_4 adsorption on coal are obtained.Through the verification on the measurement data,the fitting results indicate that it is feasible to use the Ono-Kondo lattice mode to model the excess adsorption isotherm of high-pressure CH_4 adsorption on coal.

Sorption Kinetics, Isotherm and Thermodynamic Modeling of Defluoridation of Ground Water Using Natural Adsorbents

The aim of study is to investigate the removal ability of some natural adsorbents for fluoride ion from aqueous solution. The batch dynamic adsorption method was carried out at neutral pH as the functions of contact time, adsorbent dose, adsorbate concentration, temperature and effect of co-anions, which are commonly present in water. The sorption kinetics and equilibrium adsorption isotherms of fluoride on natural adsorbing materials had been investigated at afore-mentioned optimized. Equilibrium adsorption isotherms, viz., Freundlich and Langmuir isotherms were investigated. Lagergren and Morris-Weber kinetic equations were employed to find the rate constants. The negative enthalpy ΔH = -46.54 KJ·mol-1 and Gibbs free energy calculated was ΔG288-333—(2.07785, 3.08966, 4.1064, 4.90716 and 5.38036 KJ·mol-1) respectively, envisage exothermic and spontaneous nature of sorption.

Phase field modeling of multiple dendrite growth of Al-Si binary alloy under isothermal solidification

Phase field method offers the prospect of being able to perform realistic numerical experiments on dendrite growth in metallic systems.In this study,the growth process of multiple dendrites in Al-2-mole-%-Si binary alloy under isothermal solidification was simulated using phase field model.The simulation results showed the impingement of arbitrarily oriented crystals and the competitive growth among the grains during solidification.With the increase of growing time,the grains begin to coalesce and impinge the adjacent grains.When the dendrites start to impinge,the dendrite growth is obviously inhibited.

Comparative modeling of gas transport in isothermal chemical vapor infiltration process of C/SiC composites

Two comparative models taking into account of momentum, energy and mass transport coupled with chemical reaction kinetics were proposed to simulate gas transport in isothermal CVI reactor for fabrication of C/SiC composites. Convection in preform was neglected in one model where momentum transport in preform is neglected and mass transport in preform is dominated by diffusion. Whereas convection in preform was taken into account in the other model where momentum transport in preform is represented by BRINKMAN equations and mass transport in preform includes both diffusion and convection. The integrated models were solved by finite element method. The calculation results show that convection in preform have negligible effect on both velocity distribution and concentration distribution. The difference between MTS molarities in preform of the two models is less than 5×10-5, which indicates that ignorance of convection in preform is reasonable and acceptable for numerical simulation of ICVI process of C/SiC composites.

高岭土对含有Cu^(2+)和Pb^(2+)污水吸附性实验

这是一篇环境工程领域的论文。为了研究高岭土对含有Cu^(2+)和Pb^(2+)污水吸附性能的影响,开展了不同初始浓度、温度、吸附时间、高岭土掺量和pH值作用下高岭土吸附重金属离子实验,并分析了高岭土对Cu^(2+)和Pb^(2+)共同吸附实验结果。结果表明:高岭土吸附金属Pb^(2+)离子的效果要好于高岭土吸附金属Cu^(2+)离子的效果。结合实验结果和经济效益而言,在初始浓度为200 mg/L,pH值为6、温度为30℃,高岭土掺量为1.5 g,吸附时间为2.0 h时,高岭土对金属Pb^(2+)和Cu^(2+)离子的吸附效果较优,其中金属Pb^(2+)离子的吸附量分别达到了56.38、56.22、58.76、35.75、和42.42 mg/g,金属Cu^(2+)离子的吸附量45.99、47.45、47.27、25.26、22.52 mg/g。整体上,高岭土对共同吸附金属离子(Cu^(2+)、Pb^(2+))的吸附量要小于单一离子的吸附量,这是由于两个金属离子在吸附过程中会相互影响对方的吸附过程。Langmuir模型对实验曲线的拟合度要远远高于Freundlich模型对实验曲线的拟合度,这就说明了Langmuir等温吸附模型更加适用于高岭土吸附金属离子吸附量的变化规律,进而证明了高岭土吸附重金属离子属于表面吸附,被吸附的重金属离子都是相互独立存在的。

电化学方法下的聚β-环糊精吸附苯胺特征

聚β-环糊精(聚β-CD)是通过电化学合成法制备的一形状类似β-环糊精(β-CD)锥筒型的β-环糊精聚合物。苯胺是一种危害较大的环境污染物之一,聚β-CD包合吸附苯胺(An)的机制研究对今后聚β-CD去除苯胺具有重要的意义。在298.15~323.15 K的温度范围内,以电聚合法合成的聚β-CD/聚苯胺(PANI)复合材料的荷电量为吸附量,通过6种吸附等温模型(Langmuir、Freundlich、Langmuir-Freundlich、Temkin、Henry和BET)和4种动力学方程(准一级动力学、准二级动力学、颗粒内扩散及Elovich方程)的拟合,考察了聚β-CD包合吸附苯胺过程中的等温模型及其吸附动力学特征。结果显示,在此温度范围内,Langmuir-Freundlich、Temkin等温吸附模型适合描述聚环糊精对苯胺的包合吸附,说明聚β-CD包合苯胺是单分子层与多分子层吸附共存,且其吸附热与温度呈线性关系,吸附热随表面覆盖率增加而下降;准一级动力学模型更适合模拟聚β-CD包合吸附苯胺的反应过程,表明聚β-CD包合吸附苯胺以物理吸附为主,因此聚β-CD可以应用于苯胺的去除。

果胶与多酚相互作用机制及其对食品加工特性影响的研究进展

果胶和多酚共存于植物性食品体系中。除天然存在的果胶-多酚复合物外,在受到加热、高压、干燥等外力作用的食品加工过程中,两者会快速且自发地进行相互作用。果胶与多酚之间的相互作用会影响食品的理化性质和功能特性。本文总结了果胶与多酚相互作用的机制、内部和外部多重影响因素、主要的研究方法并结合Langmuir和Freundlich常见的等温吸附模型对果胶与多酚之间的吸附行为进行描述和定量表征。此外还探讨了两者相互作用对食品加工特性及多酚生物可利用性的影响,分析了该领域的研究方向和发展趋势。

初烤烟叶主脉与叶片的吸附等温线及其热力学性质研究

为探究初烤烟叶主脉与叶片在吸湿过程中所表现出的水分吸附特性,测定初烤烟叶主脉与叶片在环境温度20、25、30、35、40℃以及环境相对湿度50%、60%、70%、80%、90%下的吸湿情况,绘制初烤烟叶主脉与叶片的吸附等温线,采用5种常用的农产品吸附等温线模型对试验数据进行拟合,并在此基础上探究初烤烟叶主脉与叶片的热力学性质。结果表明,初烤烟叶主脉与叶片的吸附等温线属于Ⅲ型等温线,在环境相对湿度相同的条件下,初烤烟叶主脉与叶片的平衡含水率随环境温度的升高而降低。MHAE模型是描述初烤烟叶主脉与叶片吸附等温线的最佳模型,决定系数(R^(2))为0.99877~0.99905,平均相对百分率误差(MRE)为1.45515%~2.94968%。热力学性质研究结果表明,在平衡含水率发生变化时,初烤烟叶主脉与叶片的净等量吸附热(Q_(st))与微分吸附熵(ΔS)有相似的变化趋势,均随平衡含水率的升高而下降,且两者与温度之间都没有明显关系。在初烤烟叶主脉与叶片的水分吸附过程中,熵-焓补偿理论也同样存在并适用,并且水分吸附过程是自发的由焓所驱动的反应。综上,初烤烟叶主脉与叶片在水分吸附过程中的热力学性质较为相似,MHAE模型适合用来描述初烤烟叶主脉与叶片在温度20~40℃的吸附等温线。

含钛高炉渣制备复合吸附剂及其铬吸附性能

Cr(Ⅵ)是一种有害污染物,既污染水环境,也会对人体造成伤害。本文以工业固废含钛高炉渣为原料,通过酸浸得到浸出渣基体,经壳聚糖改性,制备一种新型GLZ-jcz/CS复合吸附剂,用来去除废水中的Cr(Ⅵ)。研究了吸附温度、废水pH、吸附剂量、Cr(Ⅵ)初始浓度、吸附时间对Cr(Ⅵ)吸附性能的影响。以Cr(Ⅵ)吸附率为评价指标,确定最优实验条件,并研究了GLZ-jcz/CS复合吸附剂的再生性能。采用扫描电子显微镜、傅里叶红外变换光谱仪、X射线光电子能谱仪、BET比表面积测试仪对GLZ-jcz/CS复合吸附剂进行表征,结合吸附动力学模型和吸附等温线模型分析,确定吸附机理。实验结果表明:当吸附温度为70℃、废水pH=4、吸附剂用量为0.13g、Cr(Ⅵ)初始浓度为50mg/L、吸附时间为2h时,吸附率达到99.8%,吸附容量可以达到67mg/g,GLZ-jcz/CS复合吸附剂经过6次洗脱,吸附率仍可达到96%以上,吸附模型符合拟二级动力学模型和Langmuir吸附等温模型。

Adsorption kinetics,isotherm,and thermodynamic studies of adsorption of pollutant from aqueous solutions onto humic acid

In the present study,humic acid was used as an adsorbent for the investigation of the adsorption kinetics,isotherms,and thermo-dynamic parameters of hexavalent chromium from aqueous solution at varying pH,temperatures,and concentrations.Adsorption isotherms and equilibrium adsorption capacities were determined by the fittings of the experimental data to three well-known iso-therm models:Langmuir,Freundlich,and Redlich-Peterson.The results showed that the Langmuir and Redlich-Peterson models appear to fit the adsorption better than did the Freundlich adsorption model for the adsorption of chromium onto humic acid.The equilibrium constants were used to calculate thermodynamic parameters such as the change of free energy,enthalpy,and entropy.The derived adsorption constants (logaL) and their temperature dependencies from Langmuir isotherm have been used to calculate the corresponding thermodynamic quantities such as the free energy of adsorption,heat,and entropy of adsorption.The thermo-dynamic data indicate that Cr (VI) adsorption onto humic acid is entropically driven and characterized by physical adsorption.

果菜秸秆生物炭吸附设施土壤硝态氮性能与机制研究

在农业生产中,过量偏施氮肥导致的硝酸盐富集是次生盐渍化、酸化等土壤障碍的重要诱因。生物炭因良好的吸附特性逐渐成为缓解盐渍化的土壤调理剂,但果菜秸秆生物炭对硝酸盐等离子的吸附研究鲜见报道。以甜椒、番茄和茄子3种果菜秸秆为原料热解制备生物炭,进行硝态氮吸附试验。通过扫描电镜(SEM)和傅里叶近红外光谱(FTIR)等技术对生物炭吸附前、后表面形貌、官能团等进行表征分析,利用吸附动力学模型和等温吸附模型等进行拟合分析,综合模型参数和形貌表征解析果菜秸秆生物炭的吸附性能和机制。研究结果表明,3种果菜秸秆生物炭对硝态氮均具有一定吸附能力,茄子秸秆生物炭吸附能力最强,最大理论平衡吸附量为114.788 mg/g,其次为番茄(29.736 mg/g)和甜椒(9.759 mg/g);茄子和甜椒秸秆生物炭吸附性能优于玉米、稻壳等大田作物秸秆生物炭,吸附过程符合准二级动力学模型,受化学键吸附、表面吸附和内扩散吸附过程的控制,番茄秸秆生物炭吸附过程符合准一级动力学模型,主要为物理吸附;FTIR分析显示,3种生物炭均含有羟基、甲基、亚甲基、羧基和羰基官能团,除此之外,甜椒和茄子秸秆生物炭还含有醚键,番茄秸秆生物炭含有醇羟基。因此,3种果菜秸秆生物炭对硝态氮均具有吸附能力,茄子秸秆生物炭吸附能力最强,受孔隙填充、官能团和络合作用等多种理化机制的影响,具有消减土壤次生盐渍化的潜力。本研究对盐渍化土壤修复和果菜秸秆资源化利用具有理论意义。

磷石膏淋滤液磷在红黏土中的迁移转化与吸附特性研究

为了探究磷石膏淋滤液磷在土壤中的迁移转化及赋存状态,文章以贵州某磷石膏堆场为研究区,通过室内物理模拟实验与土壤吸附实验,分析磷石膏淋滤液磷在红黏土中的迁移转化特征,并探讨了红黏土对磷的吸附成因。研究结果表明:不同磷石膏厚度与红黏土厚度,对磷石膏淋滤液磷的迁移有显著影响,其中磷石膏厚度越大,淋滤液中磷浓度越大,而红黏土土层厚度越大,淋滤液中磷浓度越低;磷石膏淋滤液磷在红黏土中的迁移转化过程中,其各形态之间不断发生转变,并有一部分会被红黏土所吸附,从而使磷浓度随之降低,主要存在形态为可溶磷与无机磷,占比分别为80%~94%和80%~95%,有机磷与颗粒态磷含量较小,占比分别为5%~20%和5%~16%;红黏土对磷石膏淋滤液中磷的最大吸附量为0.23mg/g,且红黏土对磷的吸附等温曲线符合Freundlich方程,相关系数R2为0.98678,吸附过程符合准二级动力学模型,相关系数R2为0.96414。

面向控制的一维非等温两相流燃料电池模型研究

经验模型不能反映电池内部复杂的物理化学耦合过程及其导致的响应迟滞,这给燃料电池系统精确控制策略的开发带来了一定困难。针对此问题,建立了面向控制的一维非等温两相流模型,考虑了流道内气体瞬态效应、电池内部水相变,研究了电流密度对气体浓度以及水热分布特性的影响,分析了运行条件和模型参数对电池输出电压的影响,探究了电流阶跃下该模型相比于集总参数模型在输出性能方面的优势。结果表明,该模型具有更好的适用性,可为燃料电池系统层面的模型优化及控制策略设计提供可靠依据。

基于本构模型的Inconel 718材料动态力学响应分析

Inconel 718常用于航空航天、汽车以及医疗设备领域,其高强度和低导热性造成大切削力和高切削温度,是一种典型的难加工材料。本文通过分离式霍普金森压杆试验得到了常温下Inconel 718的真实应力-应变曲线,通过高温硬度试验得到了该材料在不同温度下的热软化率。利用激光热导试验获取不同温度下Inconel 718的比热容和热导率,结合真实应力-应变曲线计算不同应变下的实际变形温度。利用热软化率将变温状态下的真实应力-应变曲线修正为等温状态下的应力-应变曲线,实现了应变和温度的解耦。基于Johnson-Cook和Power-Law本构模型对上述试验结果进行了拟合,结果表明,在低应变率下Power-Low本构模型的拟合精度更高,而在高应变率下Johnson-Cook本构模型的拟合精度更高。最后通过有限元仿真探究了应变、应变率、温度单独作用下,Inconel 718材料力学性能的响应机制,发现应变对应力的影响最大,温度次之,应变率对应力基本没有影响。

LF精炼过程中通电升温阶段底吹氩方式的优化

在LF(ladle furnace)精炼过程的通电升温阶段多采用双喷嘴等流喷吹的吹氩方式.本文提出一种双喷嘴差流吹氩的底吹方式,以某钢厂135 t钢包为原型设计1∶4非等温水模型实验平台,在总流量相同的情况下进行底吹比例为1∶1,2∶1和3∶1的温度均匀化实验,结果表明底吹比例为2∶1时的各监测点无量纲温差最小,均匀化效果最好.建立流动-传热耦合数学模型对实验结果进行验证,结果表明在总流量相等的情况下,底吹比例为1∶1,2∶1和3∶1时流动死区占比分别为14.1%,9.1%和9.8%,温度死区占比分别为6.2%,2.6%和0.3%,2∶1差流底吹方式在活跃流场和促进温度均匀化方面具有优势.

高性能航空复合材料用环氧树脂的固化反应动力学

针对高性能航空复合材料用环氧树脂的固化反应,采用非等温差示扫描量热仪(DSC)对其进行研究。通过模拟n级反应动力学模型,利用Kissinger方程、Arrihenius公式等以及特征温度-升温速率外推法,计算出该固化体系的表观活化能E a、指前因子A和固化反应级数n等动力学参数以及最佳固化温度。结果表明,环氧树脂的固化起始温度T i为142.40℃,固化温度T p为228.26℃,后固化温度T f为267.67℃,固化时间为32 min。