The applicability of the Guggenheim-Anderson-de Boer adsorption isotherm equation to the determination of the texture parameters of solids with grafted surface compounds

Treatment of the data on benzene adsorption on the surfaces of silicas with grafted surface com- pounds showed that the possibilities of the Brunauer-Emmett-Teller adsorption isotherm equation were strongly limited. The three-parameter Guggenheim-Anderson-de Boer adsorption isotherm equation is suggested for use instead of the Brunauer-Emmett-Teller two-parameter equation to more reliably determine the structural characteristics of such sorbents.     

一种改进的休克尔分子轨道模型预测纯碳环分子稳定结构

从动力学和统计热力学角度介绍了BET方程中C的物理意义,分析了C的大小对吸附等温线形状的影响,推导了吸附等温线上拐点、B点位置和C大小的关系以及达到单程吸附量时C与相对压力、覆盖表面分数的关系。文章用数学方法介绍了保证C为正值的方法,解释了数据分析中的一个常见现象,还从BET方程的数学形式及物理意义探讨了C的下限。     

What is the correct form of BET isotherm for modeling liquid phase adsorption?

In this work subtleties of application of BET isotherm for liquid phase adsorption is presented. It has been shown that direct use of the classical BET equation (which was developed for gas phase adsorption) to liquid phase adsorption leads to ambiguous and erroneous results. Some cases of misuse of BET equation for liquid phase adsorption have been revisited. By close examination of the development of the classical equation, the causes of misunderstandings were elucidated and the suitable form of the BET equation for liquid phase adsorption was developed. As case studies, the classical form of the BET equation along with the correct form of the equation for liquid phase have been applied for modeling liquid phase adsorption of methyl tert-butyl ether (MTBE) on perfluorooctyl alumina, phenol on activated carbon and pentachlorophenol on carbonized bark. It has been shown that direct application of the classical BET isotherm to liquid phase adsorption results in poor and erroneous estimation of the equation parameters. For example, in aqueous phase adsorption of MTBE on perfluorooctyl alumina, the monolayer adsorption capacity of the adsorbent was calculated as 9.7 mg/g instead of 3.3 mg/g or the saturation concentration of MTBE in water was calculated as 1212 mg/L instead of 42000 mg/L.     

The effect of heat treatment on the adsorption properties of solids. II. The effect of heat treatment on the character of the adsorption isotherm

In this study the nitrogen adsorption isotherms of heat-treated zinc oxalate, sintered magnesium oxide, and some oxidised pitch resins are considered. It is shown that characterisation of the adsorption isotherm can be via the monolayer capacity, the BET constant C, or plots of the degree of coverage of the surface at various relative vapour pressures. These parameters are critically assessed and shown to be dependent upon the closeness to the manner in which the complete adsorption isotherm is described by the BET equation. In considering the complete adsorption isotherm it is considered best to characterise the adsorption data by quoting the statistical monolayer capacity and the value of C at this point on the adsorption isotherm. The adsorption isotherms are then best compared by plotting as the number of statistical layers against the relative pressure. The further characterisation by plotting the apparent variation in C or the degree of coverage of the surface against the relative pressure has a usefulness if the limitations of the method are noted.     

Determination of standard isotherms of the sorption of some vapors with cellulose

Standard isotherms of the sorption of water, methanol, and benzene vapors on cellulose using a cellulose standard are determined. The standard, namely, mesoporous cellulose with specific surface of up to 350 m2/g, is obtained by the method of exchanging water in swollen cellulose with organic solvents. A comparison of the experimental sorption isotherm with the standard isotherm makes it possible to determine the specific surface of celluloses accessible a the given sorbate and, in combination with the Brunauer-Emmett-Teller adsorption equation, to characterize their surface properties. The identity of the sorption properties of the initial and dewatered (porous) celluloses relative to active vapors is shown, which evidences the assumed mechanism of swelling as the sorbent's division into morphological structures with the formation of new surface. A comparative analysis of the sorption properties of cellulose and silica, whose nature of active sorption centers is similar (weak acid hydroxyl groups), has been made. The affinity of the standard isotherms and close values of the cross-sectional area of different sorbates on both sorbents testify the similarity in their sorption behavior. Thus, the processes of sorption with rigid and swelling sorbents can be regarded in a unified context. Therefore, the adsorption models developed for rigid sorbents can be applied to cellulose sorbents to analyze their sorption properties.     

Sulfate adsorption and surface precipitation on a volcanic ash soil (allophanic andisol)

Sulfate strongly adsorbs on metal oxides and soils with variable charges. However, its surface precipitation has not been clearly evaluated and its adsorption mechanism has been in dispute. In the present study, an allophanic andisol, a typical volcanic ash soil having both negative and positive variable charges, was used to identify the adsorption mechanism of sulfate. Sulfate adsorption isotherms were obtained by a batch method at pH values of 4, 5, 6, and 7 in a wide range of concentrations in an Na-H-SO(4)-OH system. Theoretical isotherms were applied to the measured values for the evaluation. The surface precipitation was detected by the measured adsorption isotherms, and the BET isotherm confirmed the presence of multilayer adsorption. Stronger and weaker adsorption sites were suggested by using the Langmuir isotherm for the monolayer adsorption. The adsorption energies obtained from the Langmuir equation and recent spectroscopic analysis suggested that the stronger adsorption corresponded to an inner-sphere surface complex and that the weaker adsorption corresponded to outer-sphere surface complexation. The BET and Langmuir equations showed three types of adsorption mechanisms for the sulfate adsorption on the soil.     

Second virial coefficients of adsorption isotherms of organic molecules on porous polymers

The dependence of the specific retention volumes of sorbates on their concentration in the gas phase is investigated. It is shown that the slope tangent of the dependence is related to the second coefficient of the virial expansion of adsorption isotherm. It is established that the free energy of sorbate-sorbate interactions on the surface of porous polymer sorbents is constant for all investigated molecules. An equation for calculating retention volumes at different sorbate concentrations is proposed.     

Separation of the First Adsorbed Layer from Others and Calculation of the BET Compatible Surface Area from Type II Isotherms

In the previous paper it has been proven that a BET compatible specific surface area, asc(N2, 77), can be calculated from any Type I isotherm measured below the critical temperature. In this paper it is proven that the same calculation can be performed from any Type II isotherms if the isotherm has a pure monolayer domain. In order to distinguish the mono- and multilayer adsorption the relative free energy of the surface as a function of the adsorbed amount, pir(ns), and the functions psi(pr) and psi(ns) are applied, both defined by the differential expression (ns/pr)(dpr/dns). When the multilayer adsorption becomes the dominant process then the function pir(ns) has a point of inflexion and functions psi(pr) and psi(ns) have maximum values. It has been demonstrated that in most of the Type II isotherms the mono- and multilayer domains can be separated, so the monolayer component isotherm can be calculated by the T (Tóth) equation. Therefore, it is possible to calculate the BET compatible specific surface area discussed in detail in the previous paper. It has also been proven that there are Type II isotherms which describe only multilayer adsorption; i.e., the functions psi(pr) and psi(ns) do not have maximum values. In these cases the Harkins-Jura equation should be applied. Copyright 1999 Academic Press.     

Application of thermogravimetric analysis to the evaluation of aminated solid sorbents for CO<Subscript>2</Subscript> capture

In this work a series of solid sorbents were synthesized by immobilizing liquid amines on the surface of a mesoporous alumina. The samples were chemically characterized and BET surface areas calculated from the N₂ adsorption isotherms at 77 K. The CO₂ capture performance of the sorbents and their thermal stability was studied by thermogravimetric methods. The effect of amine loading on the CO₂ capture performance of the prepared sorbents was also evaluated. Analysis of TG-DTG curves showed that thermal stabilization of the amines is significantly improved by immobilizing them on an inorganic support. Temperature-programmed CO₂ adsorption tests from 298 K up to 373 K at atmospheric pressure, proved to be a useful technique for assessing the capacity of sorbents for CO₂ capture. Alumina impregnated with diethylenetriamine presented the highest CO₂ adsorption capacities throughout the tested temperature range.     

生物质碳材料的孔道分析

生物质碳材料的孔道类型和孔径大小制约着材料有效的活性位点数量,影响材料的性能。孔道分类又是孔径分析的前提条件。因此,建立孔道分类的方法非常有意义。随着生物质碳材料的深入研究,研究者对其孔道分析的要求逐渐提高。他们用实际的吸脱附等温线与IUPAC规范中的吸脱附等温线进行匹配,来分类生物质碳材料的孔道。然而实际的吸脱附等温线具有不规则性,难以匹配IUPAC规范中的吸脱附等温线。所以,本文提出了孔隙率和比表面积占有率的孔道分类新方法。自制生物质碳材料,运用物理吸附仪和TEM (Transmission electron microscope)对其进行表征,采用BET方程（Brunauer-Emmett-Teller）、t-plot方法(Thickness-plot)、DFT方法（Non-local Density Functional Theory）、BJH（Barrett Joyner and Halenda）方法对其孔道进行分析。研究表明,采用孔隙率和比表面积占有率对其进孔道分类,可以准确的定义出微孔生物质碳材料、介孔生物质碳材料和微介孔生物质碳材料。本文用标准样品对孔隙率和比表面积占有率的孔道分类新方法进行论证,结果一致。因此,本文提出的孔隙率和比表面积占有率的孔道分类新方法准确可靠,实用性高。     

常温常压下β沸石改性吸附剂脱除噻吩类硫的研究

在合成不同硅铝比Naβ沸石的基础上，采用固相离子交换方法制备了Cu(I)、Ag(I)离子改性的β沸石系列吸附剂。样品的结晶度和BET比表面积有所降低，XRD表征结果表明，所制备的样品保持了结构的完整性，随着硅铝比的增加，Naβ样品的BET比表面积增加。Cu(I)、Ag(I)离子的引入使样品的红外骨架振动峰向低波数移动，与相同硅铝比的Naβ沸石相比，吸附剂的BET比表面积有所降低。对模型油的静态吸附结果表明,硅铝摩尔比为25时Cu(I)β吸附性能最好，模型油中硫的质量分数降到10×10－6以下，脱除率达到95％，Ag(I)β次之，脱除率达到87％。常温常压下固定床动态吸附穿透实验得到Cu(I)β、Ag(I)β的穿透硫容分别为0.144mmol/g和0.132mmol/g。     

Percus-Yevick theory of adsorption

We study adsorption of hard sphere particles on to a plane surface with a delta function adsorption potential. The calculation takes account of exclusion via the Percus-Yevick approximation. At low and intermediate bulk adsorbate densities, both type II and type III BET adsorption isotherms can be found for the surface excess density and for the monolayer surface density. The surface excess isotherm agrees with an expansion of the exact surface excess isotherm to second order in the density. We mention some biochemical ramifications of the results.     

The multi-species surface-micelle model for surfactant adsorption and the BET equations

Based on the multi-species surface micelle model, the adsorption isotherm equations are derived which are identical to the BET equations. Some of the surfactant adsorption phenomena are explained on this basis.     

Characterisation of porous silica. 2. CPG-10 (VYCOR)

Porous silica CPG-10 has been characterised by adsorption of benzene before and after modification with trimethylchlorosilane. The Brunauer–Emmet–Teller (BET) specific surface areas were determined where possible. Modification of CPG-10 reduces its adsorption for benzene and hence reduces the BET specific surface area, with the extent of reduction depending on the extent of modification. For a fully modified sample with the highest surface concentration of trimethylsilyl groups, the adsorption isotherm changes from type IV of the unmodified sample to type V. The hysteresis loop size and position are also altered. A mechanism for multilayer adsorption and capillary condensation in modified porous silica is proposed.     

NO removal of Ni-electroplated activated carbon fibers

In this study, activated carbon fibers (ACFs) were treated by a Ni-electroplating technique in order to remove nitric oxide (NO). The surface properties of the ACFs were investigated by XPS measurement. N2/77 K adsorption isotherm characteristics were determined by the BET equation. Also, NO-removal efficiency was confirmed by gas chromatography. For experimental results, Ni2p was introduced on ACFs during the Ni-electroplating technique. The nickel deposited on ACFs appeared to increase the NO removal despite the decrease in the BET specific surface areas and micropore volumes compared to nontreated ACFs. Consequently, it was found that NO conversion of ACFs was significantly improved due to the catalytic reaction of nickel deposited on ACFs.     

乙酰苯胺修饰的吸附树脂对苯酚和对氯苯酚的吸附研究

通过Friedel-Crafts后交联及化学修饰反应,合成了乙酰苯胺基修饰的超高交联吸附树脂ZH-05,通过红外光谱(IR)和比表面及孔径分析(BET)对其结构进行表征.以Amberlite XAD-4树脂作为参照,通过等温吸附实验和吸附动力学实验探讨了ZH-05树脂对水溶液中苯酚和对氯苯酚的吸附性能和机理.结果表明,与XAD-4树脂相比,ZH-05树脂对苯酚和对氯苯酚均具有更佳的吸附性能.Langmuir和Freundlich方程均能较好拟合ZH-05树脂对苯酚和对氯苯酚的吸附等温线.ZH-05树脂对苯酚和对氯苯酚的吸附以焓推动的自发物理吸附过程为主,吸附过程放热;吸附符合准一级动力学吸附方程,颗粒内扩散是吸附过程的主要控制步骤.     

Analysis of low vapor pressure region of adsorption isotherm

Summary In order to explain the low relative vapor pressure region in experimental adsorption isotherms of polar small molecules by polar adsorbents — as is the case with the protein-water system — the statistical thermodynamics of adsorption by a multi-component surface was studied on the basis of the BET model. The derived adsorption isotherm gives the same expression as the simple summation of the BET equation over all kinds of polar sites. The mathematical examination reveals a condition necessary for the approximation of the derived adsorption isotherm to the usual straight BET line. Besides, according to the present theory, it is possible to derive the number and weight averages of adsorption energy factors (C of BET theory) by the analysis of low vapor pressure region.

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Zusammenfassung Die Adsorption kleiner polarer Moleküle an polaren Adsorbentien, z. B. Wasser an Proteinen, wurde auf der Basis des BET-Modells im Bereich kleiner relativer Dampfdrücke mit den Methoden der statistischen Thermodynamik behandelt.Nach der entwickelten Theorie ist es möglich, die Anzahl und das durchschnittliche Gewicht von Adsorptionsenergiefaktoren zu ermitteln.

     

Effects of pore structure and surface chemical characteristics on the adsorption of organic vapors on titanate nanotubes

Effects of pore structure and surface chemical characteristics of titanate nanotubes (TNTs) on their adsorptive removal of organic vapors were investigated. TNTs were prepared via a hydrothermal treatment of TiO₂ powders in a 10 M NaOH solution at 150?°C for 24?h, and subsequently washed with HCl aqueous solution of different concentrations. Effects of acid washing process (or the sodium content) on the microstructures and surface chemical characteristics of TNTs were characterized with nitrogen adsorption-desorption isotherms, FTIR, and water vapor adsorption isotherms. For the adsorption experiments, gravimetric techniques were employed to determine the adsorption capacities of TNTs for four organic vapors with similar heats of vaporization (i.e., comparable heats of adsorption) but varying dipole moments and structures, including n-hexane, cyclohexane, toluene, and methyl ethyl ketone (MEK), at isothermal conditions of 20 and 25?°C. The experimental data were correlated by well-known vapor phase models including BET and GAB models. Isosteric heats of adsorption were calculated and heat curves were established. Equilibrium isotherms of organic vapors on TNTs were type II, characterizing vapor condensation to form multilayers. The specific surface area (and pore volume) and hydrophilicity of TNTs were the dominating factors for the determination of their organic vapors adsorption capacity. The GAB isotherm equation fitted the experimental data more closely than the BET equation. The heats of adsorption showed that the adsorption of organic vapors on TNTs was primarily due to physical forces and adsorbates with larger polarity might induce a stronger interaction with TNTs.