Influence of calcination temperature on surface acidity of the solid superacid of sulfated alumina

The acidity of sulfated alumina catalysts was studied by analyzing DTG and heat of Ar adsorption together with the isomerization of pentane. The initial acid sites were Brönsted-type, and converted into Lewis-type upon increasing the pretreatment temperature. The heat of Ar adsorption of the most active sulfated alumina was 18.9 kJ mol^–1, this value being a little smaller than that of sulfated zirconia (23.6 kJ mol^–1).This revised version was published online in December 2005 with corrections to the Cover Date.     

CO气体分子在金属氧化物SrO(001)表面吸附和脱附机理

研究了高纯度金属氧化物SrO粉末表面吸附C¹⁸O后在程序升温热脱附过程中的脱附反应规律,讨论了CO气体分子在SrO(100)表面吸附和脱附之间的关系及机理.SrO吸附C¹⁸O后,在升温过程中可通过氧的同位素交换生成C¹⁶O而脱附,同时伴随少量C¹⁸O的直接脱附,并与C¹⁶O具有相近的脱附活化能.C¹⁶O的脱附量随C¹⁸O气体暴露量增加而增加,但当气体覆盖度超过一定值后,脱附量趋于定值.脱附峰值温度随气体暴露量的增加而下降.     

乙炔、丙烯在多种分子筛上的吸附和脱附性质

在80℃下研究了ZSM5、13X、Y、MOR、5A、SAPO34等多种分子筛和常见载体上乙炔和丙烯的吸附和脱附性能。结果表明,乙炔和丙烯在SiO2、γ-Al2O3上不吸附,而与分子筛存在较强的相互作用。对于同类型的分子筛,两者的饱和吸附量均随分子筛硅铝比的增大而减小。在同一种分子筛上,以摩尔计的丙烯吸附量均明显高于乙炔。在80℃改性β分子筛上乙炔和丙烯饱和吸附量可分别达到0.11mmol/g和4.89mmol/g,该结果明显高于文献报道的结果。     

Adsorption and desorption of macromolecules on solid surfaces studied by on-line size exclusion chromatography 2. Preferential adsorption and exchange processes

Preferential and exchange adsorption of polymers differing in molar mass and/or chemical nature under dynamic conditions were investigated using on-line size-exclusion chromatography (SEC). The sample investigated dissolved in an appropriate solvent was injected into a small adsorption–desorption column packed with nonporous silica. A nonadsorbed or desorbed fraction of the polymer was directed into an SEC column for determination of both the amount and the molecular characteristics. This approach is in many aspects superior to other techniques for studies of polymer adsorption onto solid surfaces due to its low sample and time consumption. At a low degree of surface coverage, adsorption and desorption of macromolecules were rapid and were affected by the rate of supply of macromolecules to the adsorbent surface. The exchange between macromolecules at the stage of surface saturation was found to depend on the mean molar masses of preadsorbed and displacing polymer species and possibly also on the chain flexibility of the macromolecules. It was shown that the preferential adsorption driven by the chain-length difference upon saturation of the adsorbent surface was more noticeable if the preadsorbed macromolecules were smaller. Received: 7 April 1999 Accepted in revised form: 21 July 1999     

迎头色谱程序升温脱附快速测定吸附热新方法

在Ｐｏｌａｎｙｉ吸附势理论基础上，结合程序升温脱附曲线的测定，建立了一个快速测定吸附热的新方法，详细讨论了该方法的原理，通过微机采样和数据处理，测定一条吸附热与覆盖度的曲线仅需１ｈ左右。     

Adsorption enthalpy and desorption enthalpy during displacement of adsorbate to solvent in a liquid-solid system

The adsorption heat of the stoichiometric displacement process for the adsorption of a solute in a liquid-solid system was investigated. On the basis of the SDM-A and the rule of the additivity of energy, an expression which describes the dependence of the adsorption enthalpy on the nature and concentration of the solute, and on the solvent and adsorbent, was derived. The adsorption heat determined for the solute with the traditional method can be divided into two independent fractions, relating to the adsorption of the solute and to the desorption of the solvent. Experimental data on both isotherms from the literatures and precise calorimetry were used to test the adsorption heat and its fractions computed quantitatively via the equations presented in this study, and a satisfactory degree of conformity between them was obtained. Supported by the Natural Science Foundation of Shaanxi Province in China.     

Adsorption and mobility of molecules of water and organic compounds in carbon adsorbents

The mobility of molecules of water and fluorine-containing organic compounds adsorbed in a mixture on active carbons has been studied by the NMR pulsed field gradient technique (¹H and¹⁹F resonances). Samples with various H₂O/C₆F₆ and H₂O/C₂Cl₃F₃ ratios have been examined. The mobility of components at total fill factors > 0.8 has been shown to decrease in comparison with the adsorption of pure substances while the diffusion activation energy increases. The results are interpreted on the basis of adsorption mechanisms of water and organic compounds on active carbons.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 56–61, January, 1993.In conclusion the authors would like to express their thanks to the German Research Society for the financial support of this work.     

Water desorption isotherms of cellulose-acetate membranes

 The water desorption isotherms are determined in three cellulose acetate membranes with different acetyl content as a function of p/p ₀ at 10–40 °C. The partition coefficients (adsorbed water over water pressure) show a minimum at p/p ₀=0.5–0.6. This indicates a two energy mechanism. The agreement of our results with the BET adsorption isotherms only till p/p ₀<0.3 shows that a two energy adsorption mechanism is valid only for small water contents, probably one hydrate layer and a second more liquid-like water layer. At large p/p ₀, the adsorbed water becomes more and more liquid like by polarization of the hydrogen bonds. The heat of desorption is larger than the vaporization heat of water ΔH _vap(H₂O). It decreases with increasing water content asymptotically to ΔH _vap(H₂O). The cause may be a larger van der Waals interaction of the hydrate layer due to coordination numbers larger than 4.4 as in liquid water. Additionally, we found a hole adsorption process by sorbing unpolar solvents. The water and methonal adsorption are 100 times larger due to a swelling mechanism depending on the number of acetyl groups in the membranes. The amounts of n-alcohols sorbed decrease with their chain length. Received: 25 April 1997 Accepted: 10 June 1997     

腐植酸对砷的吸附作用研究

腐植酸中含有大量的极性基团,对金属离子有较强的吸附性能。运用氢化物-原子荧光光谱法,以泥炭腐植酸为原料,研究了腐植酸对砷(V)离子的吸附作用和腐植酸吸附剂中砷的回收,并得出了最佳的吸附和脱附条件。实验考察了酸度、时间分别对吸附和脱附的影响。结果表明,泥炭腐植酸对砷吸附的最佳模型为Freundlich吸附方程,当溶液成中性时腐植酸对砷的吸附量较大且趋于平稳。砷的浓度为1μg/mL,溶液的pH值为7,吸附时间控制在55min时,吸附效果最佳,最大吸附率为85.49%。脱附的最佳条件为:pH值14,脱附时间20min。     

Adsorption and desorption of tributyltin in sediments of San Diego Bay and Pearl Harbor

Adsorption and desorption of butyltin compounds from sediment under simulated estuarine conditions depends upon the characteristics of the sediment including grain size distribution, percentage of organic carbon, clay mineralogy and aqueous butyltin concentration in the overlying water column. Sediments from Pearl Harbor, Hawaii, USA, primarily consisting of calcium carbonate mud and 18–28% organic carbon by weight, have generally abundant adsorption sites and display tributyltin partition coefficients (K_p) ranging from 1000 to 5000 μg kg^?1 per μdm^?3. Adsorption and desorption of butyltin from San Diego Bay, California, USA, sediments is linearly dependent upon the characteristics of each sediment and the range in K_p values is from approximately 20 to 2500 μg kg^?1 per μg dm^?3. Sandy, low-organic carbon sediments have low K_p while fine-grained, relatively organic-rich sediments have high K_p values. Similarly, samples containing significant amounts of high cation exchange capacity (CEC) clay minerals have relatively higher adsorption potentials than those consisting of low CEC minerals.     

Enthalpy of Adsorption and Isotherms for Adsorption of Naphthenic Acid onto Clays

The enthalpies of adsorption and the isotherms for adsorption of naphthenic acid onto Na-montmorillonite, Na-kaolinite, and Na-illite were studied by means of calorimetry and the static method at 298.15 K. The results show that the enthalpies of adsorption and saturated adsorption amounts of naphthenic acid on different clays change in the order Na-montmorillonite > Na-illite > Na-kaolinite. The interaction between naphthenic acid and clays is discussed.     

Adsorption isotherm for a solid electrode: The link between the differential surface tension and capacitance curves

Investigation of thermodynamically equilibrium single-component adsorption from a liquid solution on a solid electrode with allowance made for elastic deformation of its surface is continued. A full electrocapillarity equation is derived from thermodynamics equations for an interphase layer in the absence of irreversible processes. Thermodynamic aspects of the Shuttleworth equation are discussed and the equation is compared with two-dimensional Murnaghan formulas for elastic isotropic media. An adsorption isotherm equation and compatibility equations that had been derived previously are examined in a special case where the derivative of a surface concentration with respect to depends solely on (=()) and a rigorous solution of these is obtained for a deformed electrode ( 0). The effect of and dimensionless electrode potential on the extreme (at an infinitely high adsorbate concentration) value of is studied. The model of two parallel capacitors is considered in detail for a general case. Owing to the use of capacitance curves for an elastically stretched electrode, a formula that expresses the differential surface tension of a nondeformed electrode through such curves is derived for the first time ever.To the memory of my motherTranslated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 20–34.Original Russian Text Copyright © 2005 by Podgaetskii.     

高灵敏宽温区吸附热测定装置的建立

 描述了一个适于气／固体系的宽温区、高灵敏的微分吸附热测定装置．在该装置中，吸附放热由Setaram公司热流式微量热量计测定，吸附量由MKS公司电容式压力传感器测定．此外，设计、制作了可在高真空和宽温区内进行吸附热测定的试样池以及对高活泼金属催化剂进行预处理的试样处理池．用标准物质对热量计进行了标定．为验证该装置对吸附热测定的可靠性，测定了H2在Pt／SiO2和γ－Mo2N上的吸附热，所得结果与文献值一致．数据的误差分析结果表明，吸附热测定的相对误差在4％以内．     

Correlation and Calculation of Multicomponent Adsorption Equilibria Data Using a Generalized Adsorption Isotherm

Enhanced by the need for reliable and accurate data of multicomponent gas adsorption equilibria on porous solids like activated carbons or zeolites, a new method to measure and correlate coadsorption equilibria has been developed. This method is a combination of gravimetric or volumetric measurements of the total load of pure or multicomponent adsorbates (Staudt, 1994; Gregg and Sing, 1982) and a correlation and calculation procedure using a new adsorption isotherm (AI) (Keller, 1990). This AI is thermodynamically consistent and describes adsorbates with fractal dimension for single- or multicomponent systems and load dependent adsorption energies. This method allows calculation of partial loads of multicomponent coadsorption equilibria from pure component data and the total loads of the mixture adsorption equilibria. This will be demonstrated for binary and ternary adsorption equilibria of CH₄, C₂H₄ and C₂H₆ on activated carbon (Reich et al., 1980).     

A new method for characterizing solid surface acidity - an infrared spectroscopic method using probe molecules such as N2 and rare gases

A new infrared-spectroscopic method to characterize acid sites of zeolites using small and weakly basic molecules such as diatomic and monoatomic molecules is reviewed. It has been revealed that N2 is an effective probe molecule to characterize both Brønsted acidity and Lewis acidity of H-form zeolites. The characteristics of the N 2 probe are discussed in detail in comparison with the CO probe. O2 and rare gases have also been applied to monitor the strong acid sites in the H-form zeolites. Further, the studies of the adsorption of water on H-form zeolites are shortly reviewed: a recent IR study of the H₂ ¹⁸O adsorption on H-ZSM-5 has given direct experimental evidence that the main feature of the observed IR bands is due to the hydrogen-bonded adsorption of water on the Brønsted acid sites.     

Laser desorption/ionization techniques in the characterization of high molecular weight oil fractions. Part 1: asphaltenes

The molecular weight distribution of the asphaltene fractions of two types of crude oils from two different Italian fields (samples 1 and 2) was investigated. The analytical tools used to perform these analyses were matrix assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) mass spectrometry. After observing that the use of the matrix (as well as the addition of Ag+) did not improve the quality of the data compared to that obtained in LDI conditions, all further measurements were performed with the latter technique. Operating under usual conditions of laser power and delay time, a very low resolution was observed, showing only macroscopic differences between the two samples in the molecular weight distribution of the different components. An accurate study on the possible reasons of this undesirable behavior indicates that it can originate from space charge phenomena occurring either in the ion source region or during the flight. A valid parameterization of the delay time and the laser power allowed higher quality spectra to be obtained. Surface-enhanced laser desorption ionization (SELDI) measurements were also performed using normal phase (silica) as the sample holder surface. Under these conditions, better results are obtained, proving that the sample-surface interaction is important to achieve, by means of laser irradiation, a homogeneous set of product ions. Both asphaltene samples were fractionated in five subfractions by gel-permeation chromatography (GPC) to obtain a better separation of the molecular weight distributions; the related spectra confirmed these findings. By using different approaches, relevant and reproducible differences between the asphaltene fractions of the two oil samples were observed.     

Adsorption properties of low-silica zeolite ZK-5

Water vapor, methanol, and argon adsorption isotherms, as well as the heat of adsorption of ammonia, methanol, and carbon dioxide have been determined on zeolite types A, ZK-4, and ZK-5. The results are explained by the distribution and the bond lengths of cations in the zeolite crystal lattice. It was shown that the exchange of 10–15% of the Na⁺ ions with Li⁺ in zeolite ZK-5 leads to a deformation of the 8-membered ring impeding the diffusion of adsorbed molecules. Cations contained in the 8-membered ZK-5 zeolite ring are bound more strongly to the framework, than in zeolite NaA, resulting in their smaller adsorption capacity.I. V. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, 199164 St. Petersburg, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2494–2500, November, 1992.     

Temperature effect on the adsorption and desorption processes in retinoic acid crystals: An electrical conductivity study

Using electrical conductivity as a probe, the effect of crystal temperature on the process of adsorption and desorption of some chemical vapours on retinoic acid semiconductor has been investigated. It has been observed that a three-stage adsorption process in a sample at low temperature changes over to a two-stage process at higher temperature. Measures of activation energies of adsorption and desorption at different stages have been estimated from kinetic data analysis by using a modified Roginsky-Zeldovich equation.     

Determining moisture absorption/desorption properties of commercial membranes by thermogravimetry (TG)

A series of different commercial membranes were characterized by their moisture absorption and desorption properties under controlled humidity and temperature conditions. This work was made possible by combining the features of a constant humidity conditioning chamber with those of a thermogravimetric (TG) apparatus. These two modules were interconnected by tubing, rotameters, an atmosphere-recycling microbellows pump and switching valves. Under programmed heating and isothermal conditions reproducible data were obtained in terms of weight-gain or weight-lossvs. time and pore size. Evaluation of the resulting TG curves allowed us to report reasonable differences in the materials, some of which had been previously surface-modified by the manufacturer.     

Characterization of the acidic properties of zeolites by means of temperature-programmed desorption (TPD) of ammonia

Desorption energy distributions were calculated for temperature-programmed desorption (TPD) of ammonia from H zeolites of different type by means of regularization. This method does not require any limiting assumptions about the distribution function. It could be shown that the desorption energy distributions obtained are nearly independent of the experimental conditions and therefore they should represent a suitable measure for the distribution of the strength of acidic sites. The calculated desorption energy distributions for the ammonia desorption from the isolated bridging SiOHAl groups of H zeolites of different type significantly differ from each other in shape. The increase of the desorption energy of the main range of the distribution functions correlates well with the increase of the average acid strength of the SiOHAl groups with decreasing Al content of the zeolites.