THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.     

ZSM-5沸石膜的吸附表征

The framework and thickness of synthesized ZSM-5 membranes were characterized using static and dynamic adsorption methods. It is shown that the adsorptive properties of the membranes are the same as ZSM-5 zeolite, the average thickness of the membranes was 13 μm calculated from the adsorptive ability, which matched very well with the result measured by scanning electron micrograph. The results also shown that zeolite membranes have greated adsorptive ability than zeolite powders. The high Si/Al rate zeolite membranes have selective ability on ethanol/water, and this interpreted the separation of ethanol-water mixtures with the membranes.     

A theoretical form of the Martin-Hou equation of state

A new equation of state is derived from the Barker-Henderson hard-sphere perturbation theory. It has the form similar to the Martin-Hou equation of state. The numerical values of the characteristic constants in the equation can be calculated by the method of Martin and Hou. The equation can be used to predict P-V-T properties accurately for fluids when the critical parameters (T_c, P_c and V_c) and one point on the vapor pressure cure are given. By using the functional relationships between the characteristic constants and the microscopic parameters, the molecular microscopic parameters of the substance can be obtained.     

自溶液中的吸附 VII: 硅胶自环己烷中吸附醇,酮和酯

The adsorption isotherms of some monofunctional alcohols, ketones and esters from cyclohexane onto silica gel have been determined at 30`C and 10`C. The silica gel used bad a BET area of 417 m2/g and an average pore radius of 45A. The concentrations of free and associated hydroxyls on the silica gel were 1.4 and 4.1/100A^2 respectively. The adsorption order is cyclohexanol>n-octyl alcohol>cyclohexanone>methyl isobutyl ketone>n-propyl acetate=n-amyl acetate. The adsorption decreases with increasing temperature as normal. Except at very low concentrations, the isotherms can be represented by the Langmuir equation. The limiting adsorption, nms, on the silica gel does not accord with the stoichiometric ratio (1:1) between the free surface hydroxyl groups of the adsorbent and the adsorbate. In addition to surface conditions and the functional group of the adsorbate, it seems that the limiting adsorption is also controlled by the other factors, including temperature, solvent, and, sometimes the chain length of the adsorbate. The standard free energy (ΔG0) and standard enthalpy (ΔH0) of the adsorbates in adsorptien processes have been determined from the Langmuir parameters. The results indicate that the absolute value of ΔH0 is higher than that of ΔG0 (in other words, standard entropy ΔS0 is negative), as in the case of the adsorption of gases. Since there is practically no difference in ΔG0 or ΔH0 of adsorption between alcohols or esters, it is suggested that in dilute solution only the polar groups take part in adsorption, and the hydrocarben chains remain in solution during the adsorption process. For ketones, the absolute values of ΔG0 and ΔH0 are somewhat lower for methyl isobutyl ketone than that for cyclohexanone. A possible explanation is that in the adsorbed state the isobutyl chain of the methyl isobutyl ketone may somewhat close to the surface and thus decreases the adsorption and changes the ΔG0 and ΔH0.     

NATURE OF THE A AND THE F MATRIX IN THE CALCULATION OF FORCE CONSTANTS OF MOLECULAR VIBRATION

In this paper,calculations of force constants of molecular vibrations are carried out by using Wilson GF matrix method.In the determination of force constants from frequencies and factorization of Gmatrix,an ordering relationship of A matrix(may be n dimensional) relative to L matrix was found according to the ordering of symmetry coordinates.With the help of inverse unitary transformation,a general method to calculate Ft from constants Fs was established.The additivity of Fr depending on the symmetry block was determined to be true.All the force constants in non-planar and planar of urea,thiourea and sclenouroa molecules were calculated by using the general va-leine force field.The calculated values of frequencies were com-pairec with other data given in the literature,and it was shown that the present calculation is in good agreement with the experimental     

STUDY ON THE ADSORPTION OF PHENOL BY CHITOSAN FROM AQUEOUS SOLUTION

The effects of pH, initial concentration and temperature on the adsorption of phenol by chitosan were investigated in this paper. The isothermal data was applied to Langmuir linear and the Freundlich linear isotherm equation, and the thermodynamic parameters （AH, AG, AS） were calculated according to the values of binding Langmuir constant, KL. Results indicated that the adsorption between chitosan and phenol was significantly physical in nature, the negative ΔH constant at lower temperature confirmed that more phenol was adsorbed by chitosan at lower temperature. The kinetics of the sorption process of phenol on chitosan was investigated using the pseudo-first order and pseudo-second order kinetics, and results showed that the second order equation model provided the best correlation with the experimental results.     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

四苯硼钠在活性炭表面吸附过程的疏水相互作用

In this paper, the adsorption characteristics of sodium tetraphenylborate(NaBPh4) on activated carbon at 298.2,303.2,308.2,313..2 and 323.2 K was studied.The results show that the adsorption isotherm of NaBPh4 on activated carbon at different temperatures could be described using Langrnuir equation. Furthermore, the standard Gibbs energy, enthalpy, entropy and hydrophobic interaction Gibbs energy for the adsorption of NaBPh4 on activated carbon were studied, and the result shows that the hydrophobic interaction of BPh4^- ion plays the most important role for the transfer of NaBPh4 from water to activated carbon surface.     

Prediction of the Conductance of Strong Electrolytes and the Calculation of the Ionization Constant of Weak Electrolytes in a Dilute Solution by a New Equation

In order to predict the conductance for dilute 1-1 valent electrolyte solutions,a new conductance equation was proposed based on the Onsager and Onsagar-Fuoss-Chen conductance equation.It has only one parameter A,which can be obtained directly from the data of ionic limiting molar conductivity Λ∞m,and its expression is very simple.The new equation has been verified by the experimental molar conductivities of some single strong electrolyte and mixed electrolyte solutions at 298.15 K reported in literatures.The results are in good agreement with the experimental data.Meanwhile the ionization constants of some weak electrolyte solutions were calculated by a modified equation of this new equation,and it was also found that the calculation results are in good agreement with the data in the literature.     

EFFECT OF HYPERCROSSLINKED RESINS SURFACE CHEMISTRY ON THE ADSORPTION OF PHENOL FROM AQUEOUS SOLUTION

Two hypercrosslinked resins with similar physical characters but different surface chemistry were synthesized and used to remove phenol from aqueous solutions. The FTIR spectra, elemental analysis and the Boehm titration were used to characterize the chemical properties of the resins. The adsorption experiments were carried out using the bottle-point technique, and the effects of the surface chemistry on the adsorption were discussed. The adsorption data fit well with the Freundlich model, indicating the heterogeneity of the resins surface. It could be seen from the experimental results that the adsorption capacity increased with the increase in the total surface concentration of oxygen-containing groups. The pH dependence and the effects of ionic strength were also discussed. The kinetic adsorption data fit well with the pseudo-second order model, and the results showed that the surface oxygen-containing groups have little effect on the adsorption rate.     

垮越临界温度的分子筛吸附: 微孔体积填充理论的适用性

用高真空重量法测定了NaX分子筛对不同吸附质NH3, H2O, C2H5OH等的吸附等温线, 用微孔体积填充理论对吸附等温线进行非线性拟合, 得到满意结果。表明该理论不但可扩展到以静电场为主的吸附体系, 还可适用于吸附温度高于吸附质临界温度的吸附体系。计算结果表明, NaX吸附不同吸附质测得的极限空腔体积基本相同, 且与结构分析得到的空腔体积一致, 进一步表明微孔体积填充理论对该体系的适用性。计算了各种吸附质的极限吸附量, 以及某填充度下的蚊分吸附热随着温度的变化趋势。可为固体吸附式制冷系统的设计与制造提供理论依据及有关掺数。     

Application of quasi-equilibrated thermodesorption of hexane and cyclohexane for characterization of porosity of zeolites and ordered mesoporous silicas

Quasi equilibrated temperature programmed desorption and adsorption (QE-TPDA) of hexane and cyclohexane was applied for characterization of zeolites 5A, ZSM-5, 13X, Y, NaMOR and ordered mesoporous silicas MCM-41, MCM-41/TMB, SBA-15 and HMS. Similar QE-TPDA profiles of hexane and cyclohexane with a single desorption maximum were observed for the wide pore zeolites. No adsorption of cyclohexane for zeolite 5A and a single desorption maximum for ZSM-5 were found, while two-step desorption profiles of hexane were observed for these zeolites. Similar values of the adsorption enthalpy and entropy of hexane and cyclohexane were obtained by fitting the Langmuir model functions for the zeolites X and Y. For NaMOR and ZSM-5 larger differences in these parameters were found. A single desorption peak found at low temperatures in the QE-TPDA profiles of hexane and cyclohexane for the studied silicas was attributed to the multilayered adsorption on their mesopore surface. The adsorption isobars calculated from the thermodesorption profiles were fitted with the BET function. This way values of the specific surface area and the adsorption heat were calculated. Additionally values of the initial heat of adsorption were found by fitting the Henry’s law to the high-temperature sections of the linearized isobars. The largest deviations from the BET and Henry functions and the largest values of the adsorption heats found for SBA-15 indicated the greatest heterogeneity of the adsorption sites on its surface.     

固-液界面上的吸附膜

利用Gibbs吸附公式处理了硅胶自四氯化碳和环己烷中吸附脂肪醇、环己醇、苯甲醛、苯甲醚、乙酸丙酯的实验结果,得到吸附膜的表面压(π)和分子面积(A)的关系曲线,这些曲线均可用描述不溶物液态扩张膜的Smith方程描述。文中对所得结果给出了初步的解释。     

AlPO4-11分子筛的吸附热力学性质

AlPO_4-n系列分子筛是八十年代初由美国联合碳化物公司开发的一类新型分子筛,据报导到目前为止已经合成出20种不同型号结构的AlPO_4分子筛。经X-射线多晶和单晶衍射结构分析,部分AlPO_4分子筛的结构已搞清楚,AlPO_4-11结构也已经测定,它具有十元环一维孔道,孔口大小为0.67nm×0.40nm的分子筛。     

Analysis of the Micropore Structure of Various Microporous Materials from Nitrogen Adsorption at 77 K

The micropore structure of four microporous materials (two zeolites, ZSM-5 and Y-82; an activated carbon and an alumina pillared clay) and their binary physical mixtures (50-50 wt%) have been examined by nitrogen adsorption at 77 K. Various micropore sizes have been considered from the stages on the micropore filling mechanism in the microporous materials. The application of the Dubinin-Astakhov (DA) equation to characterize and obtain the adsorption potential distributions of the microporous materials is presented.     

Characterization of the porous structure of carbon adsorbents with a wide size distribution of micropores

Our study using the nonlocal density functional theory (NDFT) showed that active coals might have a bidisperse microporous structure. The binomial equation of the theory of volume filling of micropores (TVFM) approximates well the nitrogen adsorption isotherms at relative pressures from 1 × 10⁻⁴ to 0.2. The dominant micropore sizes calculated in terms of the characteristic adsorption energy lie in the region of the maximum of the size distribution of micropores calculated by the NDFT method. The tentative micropore sizes can be determined from the modified second term of the TVFM equation. The Henry and BET equations describe very limited regions of the nitrogen adsorption isotherm on microporous active coals.     

比表面积和孔径分布测定与计算方法的改进

本文比较了BET多层吸附模型, Pickett有限层吸附模型以及Dubinin微孔填充模型, 并在此基础上, 假定多层吸附和微孔填充两种过程同时发生, 导出一个修正的吸附方程式, 并说明修正后的方程具有较大的适用性和准确性, 在孔径分布的测定中, 用H2替代He作为载气, 大大降低测定成本, 应用微机实现数据运算过程微机化和结果的图谱化, 大大缩短处理时间。     

High-resolution sorption studies of argon and nitrogen on large crystals of microporous zeolite ZSM-5

Summary High resolution adsorption (HRADS) with argon and nitrogen at 77 K were performed on large crystals of zeolite ZSM-5 using a novel volumetric device. Multi-step isotherms for both adsorptives could be observed for the first time. The micropore filling was followed by low temperature microcalorimetry. Exothermic heats of adsorption were found to be correlated with steps in the adsorption isotherms. Based on results from atom-atom potential energy calculations (AAP) as well as from independent model building it is shown that 24 kinetic adsorbate molecules can be situated in a ZSM-5 unit cell. Localized adsorption is presented as possible filling mechanisms. Experimental results are reasonably interpreted assuming primary filling of narrow channels and secondary adsorption in the wider channel intersections. At least for nitrogen there is evidence for a transition of fluid-like to a solid-like adsorbate phase.Compared to argon, Henry's constants and the initial isosteric heat of adsorption indicate a stronger adsorption of nitrogen which is thought to be due to additional interactions of the nitrogen quadrupole moment with the zeolite framework.

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Sorptionsuntersuchungen zur Hochauflösung von Argon und Stickstoff an großen Kristallen von mikroporösem Zeolit ZSM-5

     

The sorption isotherms of oleic, linoleic, and linolenic acids from solutions in cyclohexane and heptane on magnetite

The adsorption-desorption isotherms of oleic, linoleic, and linolenic acids from solutions in cyclohexane and heptane on the surface of magnetite were obtained by the equilibrium adsorption method. The adsorption of fatty acids was described in terms of the theory of volume filling of micropores. This theory was used to calculate the limiting adsorption values, characteristic energy, and volume of the pore space. In solutions in cyclohexane, the adsorption-desorption isotherm of oleic acid was situated above the isotherms of linoleic and linolenic acids. The situation was opposite with adsorption from heptane. The conclusion was drawn that the limiting adsorption and characteristic energy values increased from linolenic to oleic acid in adsorption from cyclohexane and decreased from linolenic to oleic acid in adsorption from heptane. The adsorption-desorption isotherms exhibited hystereses. Original Russian Text ? V.V. Korolev, O.V. Balmasova, A.G. Ramazanova, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 6, pp. 1156–1160.     

ZSM-5沸石催化剂外表面的化学修饰

通过离子改性、水热处理、表面毒化及预积炭等方法均可提高ZSM-5沸石的择形催化性能.上述方法在改变沸石孔道结构时也明显地改变了沸石的表面酸性质.近年来,采用化学修饰的方法对沸石表面和孔口进行调变的研究已有一些报导.杨儒等用硅烷或SiCl_4等进行气相硅烷化,除缩小孔口尺寸外,还产生了骨架脱铝补硅作用,导致表面酸性质发生变化.王清遐等用正硅酸乙醇浸渍(ZSM-5沸石,随着硅的载入量增加,催化剂酸量和反应活性均降低,而对位选择性增加.Murakami用正硅酸甲