氢在A、X及ZSM-5型沸石上的高压物理吸附

采用常规体积吸附装置测定了77、195、293K和7MPa的条件下氢在A、X及ZSM-5沸石上的吸附特性和吸附容量．所有的氢吸附等温线基本符合Ⅰ型等温线,但在77K,压力为2-5MPa的等温线上观察到了超临界高压吸附所特有的最大吸附量．从等温线确定了等量吸附热并讨论了其影响因素．根据骨架结构和所含阳离子类型的差异,各种沸石表现出不同的氢吸附量．其中NaX沸石在77K/4MPa下的重量储氢分数为2．55％,是该实验中所测得的最高吸附量．CaA、NaX和ZSM-5沸石的氢吸附量与其比表面积成正比,这与沸石中的可用空穴容积有关．然而NaA和KA沸石不存在这种线性关系．实验中还观察到,NaA与KA沸石间出现氢吸附量的临界值是由KA沸石中较大的阳离子堵塞效应引起的．该实验将吸附质分了的动力学直径与沸石主晶孔的有效直径之比用于判断物理吸附中的堵塞效应．     

分子间的吸引相互作用在处理实际气体行为中的影响

讨论了分子间吸引相互作用对pV-p等温线,Boyle温度的影响.     

对范德瓦耳斯等温线上存在的亚稳性质的讨论

本文用热力学理论，论证了范氏等温线上某些态的亚稳性质。     

水合金属氧化物对氟的吸附机理研究

通过碱沉淀法制备了Ce,Al,Ni,Cu的水合氧化物,研究了它们的Langmuir吸附等温线,并利用BET法通过吸附-脱附氮气测定了其比表面积,同时对其吸附氟离子前后的变化进行了IR谱图的表征.结果表明不同水合金属氧化物具有不同的比表面积,其孔径分布也不尽相同,吸附量与比表面积之间没有直接相关的正比关系.吸附等温线均符...     

一道热学题的简解

本文用等温线、绝热线概念讨论理想气体直线过程，意义清楚，方法简单。     

碳纳米纤维吸附储氢性能分析

文中综合碳纳米纤维微观结构的表征结果以及氢吸脱附等温线的实验测量结果,对碳纳米纤维的吸附储氢性能进行了综合分析,分析发现:比表面积和中孔容积均与氢吸附量成线性关系;微孔容积对材料吸附性能影响较大,微孔容积与氢吸附量成抛物线关系;氢在常温左右以及77K下的吸附等温线呈现超临界气体的吸附特征,氢在273K和353K下的吸脱附等温线也基本重合,呈现的是物理吸附的特征。实验结果还说明:常温左右,甚至是77K下,碳纳米纤维均不适合于氢的吸附储存。     

氮气在MCM-41中毛细凝聚的模拟和理论研究

采用巨正则系综 Monte Carlo 方法(GCMC)以及基于扩展基本度量理论和 MBWR 状态方程的密度泛函理论,研究了 77.4 K 时氮气在不同孔径的 MCM-41 分子筛中吸附的密度分布和吸附等温线.提出的平均场权重密度泛函理论,克服了平均场近似预测主体相热力学性质时的偏差,获得的密度分布和吸附等温线与 GCMC 分子模拟结果有着很好的一致性.     

微干涉测量技术研究液膜的楔压和液膜厚度的关系

报道了直接测定楔压等温线的方法,研究了阳离子表面活性剂ＴＴＡＢ在浓度大于ＣＭＣ时,液膜的平衡厚度与楔压的关系,以及膜表面张力与溶液表面张力之间的差别。结果显示,在低楔压时,膜厚随楔压增加而变薄,在高楔压时,随着楔压的增加,膜厚变化很小。由楔压等温线得出的膜表面张力的结果说明了一般黑膜的表面张力数值与溶液的表面张力并没有明显的差别。     

分子间的吸引相互作用对实际气体等温线的影响

对范德瓦耳斯方程吸引项修正后, 分析了两种经验状态方程的等温线, 并与范德瓦耳斯方程作了比较     

F-L模型的状态方程与退禁闭相变图象

用温度场论方法计算了F-L模型在有限温度和密度下的状态方程,分析了压强对净重子数密度的等温线.结果表明,在平均场近似下,F-L模型所给出的退禁闭相变为一级相变.     

Characterization of nanoporous carbons by combining CO2 and H2 sorption data with the Monte Carlo simulations

The Monte Carlo method in its grand ensemble variant (GCMC) is used in combination with experimental data in order to characterize microporous carbons and obtain the optimal pore size distribution (PSD). In particular, the method is applied in the case of AX-21 carbon. Adsorption isotherms of CO₂ (253 and 298 K) and H₂ (77 K) up to 20 bar have been measured, while the computed isotherms resulted from the GCMC simulations for several pore widths up to 3.0 nm. For the case of H₂ at 77 K quantum corrections were introduced with the application of the Feynman-Hibbs (FH) effective potential. The adsorption isotherms were used either individually or in a combined manner in order to deduce PSDs and their reliability was examined by the ability to predict the experimental adsorption isotherms. The combined approach was found to be capable of reproducing more accurately all the available experimental isotherms.     

The second and third virial coefficients of a two-dimensional gas

Numerical values of reduced second and third virial coefficients and their temperature derivatives are reported for a two-dimensional gas, for use in interpreting adsorption isotherms of monolayers on isoenergetic substrates. Correct values of the third virial coefficient have not been available before. Examples of earlier treatments of adsorption data are given to demonstrate that values of the higher virial coefficients are essential for adequate discussions of adsorption isotherms. When these are used the high-temperature adsorption isotherms of argon on graphitized carbon black in the monolayer region are completely described in terms of the unperturbed bulk-gas parameters.     

Dielectric and adsorption isotherms of adsorbed krypton and xenon on boron nitride

We present simultaneous measurements of adsorption isotherms and dielectric isotherms for krypton and xenon on boron nitride. Dielectric measurements give a good characterization of monolayer formation and completion, and provide new information on the dielectric properties evolution from a two-dimensional system towards the bulk.     

Application of the J-walking formalism to the test particle method: adsorption isotherms for atomic monolayers

By implementing the J-walking formalism within the test particle method, adsorption isotherms for various Lennard-Jones systems were constructed. The method decreases the uncertainties in the average thermodynamic values by approximately one order of magnitude and substantially increases the percentage insertion of the ghost particle. The adsorption isotherms showed that at low temperatures the amount of adsorbed material seems to be independent of the vapour pressure of the gas if attractive forces dominate the system. On the other hand, systems dominated by repulsive forces show the usual type B behaviour for adsorption isotherms. The equation of state is used to confirm these results.     

Investigation of the first-order metamagnetic transitions and the colossal magnetocaloric effect using a Landau expansion applied to MnAs compound

We have explored a simple Landau model to calculate magnetization isotherms considering magnetic hysteresis. The model parameters have been chosen to fit the magnetic and magnetocaloric data of MnAs compound. Experimental data show that there is a great difference between the isothermal variation of the entropy (S_T) obtained from isotherms measured increasing and decreasing magnetic field. This great difference is reproduced theoretically. From the experimental and phenomenological isotherms, we calculated the S_T. From the theoretical entropy, we also obtained S_T, which does not present the colossal peak.     

Some previously unexpected phenomena of volume recovery

We have extensively studied the nonequilibrium behavior of atactic polystyrenes in a broad range of temperatures. Depending on the conditions of the initial temperature (To) and the aging temperature (T), the shapes of isotherms plotted in the form of total fractional free volume (viz., δ) versus logarithmic aging time can be linear or nonlinear. At a T in the vicinity of T_g , the isotherms converge together. When the Tis lowered, the isotherms become increasingly nonlinear; eventually, these isotherms intersect one another at various points, forming a newly discovered crossing phenomenon. Differences in volume contraction persist throughout further aging, regardless of the equality in δ right at the moment of crossing. In a further case, the nonlinear isotherms between the two polystyrenes may be superposable by a simple δ shift, despite their substantial differences in δ. As none of these phenomena can be justified by kinetic arguments, this study seriously questions the validity of the existing kinetic theories as well as the existence of the extrapolated underlying equilibrium state.     

Adsorption of nicotine from aqueous solution onto hydrophobic zeolite type USY

The isothermal adsorption of nicotine from an aqueous solution onto zeolite type USY was investigated. The adsorption isotherms of nicotine onto the zeolite at different temperatures ranging from 298 to 322 K were determined. It was found that the adsorption isotherms can be described by the model of Freundlich adsorption isotherm. Based on the adsorption isotherms the changes of adsorption heat, free energy and entropy with adsorption degree were determined. The determined decrease of adsorption heat with adsorption degree can be explained by the presence of the adsorption centers of different energy and concentration on interface of zeolite-nicotine solution. It was found that the probability function of density distribution of the heat of adsorption (DDF) has exponential form. It was concluded that the possibility of fitting the adsorption isotherms of nicotine onto the zeolite by Freundlich adsorption isotherm was a direct consequence of that. The determined increase in entropy with the increase in adsorption degree can be explained with the change of phase state of adsorbed nicotine.