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  • 1
    ISSN: 1572-8838
    Keywords: adsorption ; dye photooxidation ; titanium dioxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A two-part study was undertaken to examine the feasibility of combining a batch-recirculated photoreactor with a hollow-fibre membrane based ultrafiltration unit for heterogeneous photocatalysis applications. Methylene Blue (MB) and titanium dioxide (Degussa, P-25) were used as the test substrate and photocatalyst respectively for this study. This paper, which forms Part I of this study, describes the influence of MB concentration, recirculation flow rate, TiO2 dose, solution volume in the reservoir and solution pH on the photocatalytic reaction rate. The dark adsorption of MB on the TiO2 particle surface was also analysed. The combination of the reservoir and the annular reaction vessel could be modelled as a continuous flow stirred tank in series with a plug-flow reactor. This model predicts that the reaction rate should increase with a decrease of solution volume in the reservoir, both in the low and high substrate concentration regimes of the Langmuir–Hinshelwood kinetics formalism. This prediction was borne out by the experimental data for the low concentration regime. Part II of this series will describe experiments and modelling of the UF unit, and the operation of the combined system, respectively.
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  • 2
    ISSN: 1572-8838
    Keywords: acidic media ; adsorption ; corrosion inhibitors ; electrochemical impedance spectroscopy ; mild steel ; triazoles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A new class of corrosion inhibitors, namely, 3,5-bis(n-hydroxyphenyl)-4-amino-1,2,4-triazoles and 3,5-bis(n-aminophenyl)-4-amino-1,2,4-triazoles which have been labelled n-HPAT and n-APAT has been synthesized. The influence of aminotriazoles on the corrosion of mild steel in 1m HCl has been studied using weight loss and electrochemical impedance spectroscopy. Results obtained show that these compounds are very good anodic inhibitors. The adsorption of these aminotriazoles is found to obey Langmuir adsorption isotherm.
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  • 3
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    Adsorption 1 (1995), S. 103-112 
    ISSN: 1572-8757
    Keywords: adsorption ; mixtures ; activity coefficients ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Experimental and simulated data for adsorption of gas mixtures on energetically heterogeneous surfaces like activated carbon and zeolites exhibit negative deviations from ideality. The deviations are large in some cases, with activity coefficients at infinite dilution equal to 0.1 or less. Similar molecules form ideal mixtures, but molecules of different size or polarity are nonideal. Equations for bulk liquid mixtures (Wilson, Margules, etc.) do not apply to isobars for adsorbed mixtures. A two-constant equation for activity coefficients as a function of composition and spreading pressure is in good agreement with theory, simulation, and experiment.
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  • 4
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    Adsorption 5 (1999), S. 183-192 
    ISSN: 1572-8757
    Keywords: adsorption ; activated carbon ; neural network ; ideal adsorption solution theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Three neural network models were used for prediction of adsorption equilibria of binary vapour mixtures on an activated carbon. The predictions were compared both with published experimental data and calculated values from the Ideal Adsorption Solution (IAS) model. The neural network was trained using both binary and single component experimental adsorption data. Even for a limited number of data points (about 60) the network models were capable of approximating experimental data very precisely.
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  • 5
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    Adsorption 5 (1999), S. 261-278 
    ISSN: 1572-8757
    Keywords: adsorption ; concentrated systems ; pressure transients ; flow transients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A study of the occurrence of large pressure and flow transients when a strongly adsorbed gas is fed to a column which is initially loaded with a lightly adsorbed gas is presented here. Under certain conditions, these transients can cause premature breakthrough and change the shape of the breakthrough curve. This will result in improper estimation of adsorption parameters by the dynamic column loading method and lower apparent adsorption capacity in a full scale unit. A data acquisition system was used to record the pressure and flow transients. An isothermal PDE model developed to study these transients agreed reasonably well with the nonisothermal experimental results. The PDE model predicts that pressure and flow transients will occur during step and pulse~tests conducted to obtain adsorption and mass transfer parameters by the chromatographic method. For instance, lower adsorption capacity will be realized during step tests due to lowering in column pressure. Oscillations were observed when columns are connected in series. The PDE model also predicts these oscillations. Simulations indicate that the extent of oscillations is dependent on the dead volume between columns.
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  • 6
    ISSN: 1572-879X
    Keywords: methane ; adsorption ; hydroxyl groups ; H-D exchange reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Infrared investigations on the interaction of methane with silica, aluminas (η,γ and α) and HZSM-5 zeolite have been carried out. At low temperature (173 K), methane adsorption was observed over these oxides and HZSM-5 zeolite. Our findings featured that the infrared inactiveΝ 1 band (2917 cm−1) of a gaseous methane molecule became active and shifted to lower frequencies (2900 and 2890 cm−1) when it adsorbed on the surfaces of these adsorbents. Our results also demonstrate that hydroxyl groups played a very important role in methane adsorption over the acidic oxides and the HZSM-5 zeolite. When interaction between the hydroxyl groups and methane took place, the band shift of the hydroxyl groups varied with different oxides. The strength of the interaction decreased according to the following sequence, Si-OH-Al〉Al-OH〉Si-OH, which is in accordance with the order of their acidities. At higher temperatures, methane interacted quite differently with various oxides and HZSM-5 zeolite. It has been observed that the hydroxyl groups of silica, γ-alumina and HZSM-5 zeolite could exchange with CD4 at temperatures higher than 773K, while those on η-alumina could exchange at a temperature as low as 573 K. Another interesting observation was the formation of formate species over Al2O3 (both η and γ) at temperatures higher than 473 K. The formate species would decompose to CO2, or produce carbonate at much higher temperatures. Formation of formate species was not observed over silica and HZSM-5 under similar conditions, α-Al2O3 did not adsorb or react with methane in any case.
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  • 7
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 8
    ISSN: 1572-879X
    Keywords: adsorption ; adsorption isotherms ; dinitrogen ; FTIR spectroscopy ; geminal species ; NaY ; nitrogen ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption of N2 on NaY zeolites at 85 K and equilibrium pressures higher than 1 kPa results in the formation of geminal dinitrogen complexes characterized by an IR band at 2333.5 cm−1 (2255.4 cm−1 after adsorption of 15N2). With decreasing equilibrium pressure the complexes tend to loose one N2 ligand, thus forming linear species characterized by an IR band at 2336.8 cm−1 (2258.7 cm−1 after adsorption of 15N2). All species disappear completely after evacuation. Co-adsorption of N2 and CO revealed that the dinitrogen complexes are formed on Na+ cations. The changes in the concentrations of the linear and geminal N2 species with the changes in the equilibrium pressure are excellently described by equations of adsorption isotherms proposed earlier for mono- and di-carbonyls.
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  • 9
    ISSN: 1572-879X
    Keywords: hydrogen ; copper ; activation energy ; adsorption ; sticking probability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The coverage-dependent sticking probabilities of molecular hydrogen on polycrystalline copper supported on alumina have been determined in the temperature range 213–273 K by analysis of the hydrogen frontal adsorption line shape. In this temperature range the initial sticking probabilities increase from 8× 10−13 (213 K) to 1.3× 10−10 (273 K). The overall activation energy to adsorption has been found to be 42 kJ mol−1. The application of reactive frontal chromatography for the measurement of hydrogen sticking probabilities on copper is a novel variant of the N2O reactive frontal chromatographic method, developed for the measurement of copper surface areas. Its use here shows that reactive frontal chromatography may be applied generally to any adsorbate/adsorbent system involving activated adsorption and low sticking probabilities.
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  • 10
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    Catalysis letters 60 (1999), S. 1-9 
    ISSN: 1572-879X
    Keywords: microcalorimetry ; IR ; platinum ; gold ; ethylene ; CO ; adsorption ; quantum chemical calculations ; DFT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethylene adsorption on a Pt/Au/SiO2 catalyst (2 wt% Pt; Au/Pt atomic ratio of 10) was studied using adsorption microcalorimetry and FTIR spectroscopy. Ethylene adsorption at 300 K on Pt/Au/SiO2 produced π‐bonded, di‐σ‐bonded, and ethylidyne species with an initial heat of 140 kJ/mol, compared to a heat of 157 kJ/mol for Pt/SiO2 on which only ethylidyne species formed. At 203 and 263 K, ethylene adsorbed on Pt as well as on Au surface atoms for the Pt/Au/SiO2 catalyst. Quantum chemical, DFT calculations indicate that Au exerts a significantly smaller electronic effect on Pt than does addition of Sn to Pt.
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  • 11
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    Catalysis letters 61 (1999), S. 7-13 
    ISSN: 1572-879X
    Keywords: sum‐frequency spectroscopy ; Pt(111) ; carbon monoxide ; adsorption ; far‐infrared ; free‐electron laser
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Sum‐frequency spectroscopy (SFS) was used in an attempt to detect the platinum–carbon vibration of CO adsorbed on Pt(111). The international free‐electron laser FELIX at the FOM Institute, Rijnhuizen, provided the required tunable far‐infrared (19–23 µm) source, while complementary measurements in the C–O stretch region (4.7–5.1 µm) were performed at the University of Oxford with a conventional nanosecond laser system. Ordered Pt(111) surfaces were prepared by the H2/O2 flame annealing approach and CO monolayers were produced by exposure of the Pt crystal to gaseous CO in a flow reactor. The monolayers were characterized by sum‐frequency (SF) measurements of the v C-O vibrational frequency. The CO adsorbed primarily in the terminal (atop) configuration, with a v C-O frequency of around 2078 cm−1. In the far‐IR region, the non‐resonant background from the Pt substrate could readily be detected by SFS, but there was no evidence for the v Pt-CO mode. Direct laser‐induced desorption and thermal desorption of CO are unlikely under the experimental conditions. It is therefore probable that the intrinsic cross‐section of the Pt–CO mode is too low for easy detection by SFS. The implications for the use of SFS to detect metal–adsorbate vibrational modes are discussed in light of these findings.
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  • 12
    ISSN: 1572-879X
    Keywords: Fe‐ZSM‐5 ; carbon monoxide ; FTIR spectroscopy ; nitrates ; nitrogen monoxide ; selective catalytic reduction ; adsorption ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption of NO on Fe‐ZSM‐5 leads to formation of Fen+–NO (n = 2 or 3) species (1880 cm-1), Fe2+(NO)2 complexes (1920 and 1835 cm-1) and NO+ (2133 cm-1). Water strongly suppresses the formation of NO+ and Fen+(NO)2 and more slightly the formation of Fen+ –NO. Introduction of oxygen to NO converts the nitrosyls into surface nitrates (1620 and 1575 cm-1) and this process is almost unaffected by water. The nitrates are thermally stable up to ca. 300°C, but readily interact with propane at 200°C, thus forming surface C–H–N–O deposit (bands in the 1700–1300 cm-1 region). Here again, water does not hinder the process. The C–H–N–O deposit is relatively inert (it does not interact with NO or NO + O2 at ambient temperature) but, at temperatures higher than 250 °C, it is decomposed to NCO- species (bands at 2215 (Fe–NCO) and 2256 cm-1 (Al–NCO)). In the presence of water, however, the Fe–NCO species only are formed. At ambient temperature the NCO- species are inert towards NO and O2, but easily react with a NO + O2 mixture. The mechanism of the selective catalytic reduction of nitrogen oxides on Fe‐ZSM‐5 and the effect of water on the process are discussed.
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  • 13
    ISSN: 1572-8757
    Keywords: adsorption ; molecular simulation ; activated carbon ; surface oxygen ; alkaloids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The influence of the density and the type of surface oxygen on the adsorption of berberine alkaloid onto activated carbon was investigated using the molecular dynamics simulation method in vacuum. The carbon surface consisted of a basal plane of graphite and surface oxygen groups which were bonded on the graphite plane in a regular square array with various densities. Two types of surface oxygen groups, =O and —OH, were employed. The simulation results showed that the berberine alkaloids were favorable to be adsorbed on the negative charged carbon surfaces. It was indicated that the vdw attraction of the carbon surface to the alkaloid molecule dominates the adsorption only at the lower surface density of oxygen. It is also indicated that a good adsorptive selectivity for a certain berberine alkaloid can be obtained by controlling the density of surface oxygen. The adsorption simulation of berberine alkaloids onto activated carbon in the presence of water was also carried out by using a dome-shape molecular model for presenting the alkaloid/water/carbon system. It was found that the adsorption of berberine alkaloids on the activated carbon which has a higher density of surface oxygen was strongly inhibited by the presence of water.
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  • 14
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 15
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    Adsorption 5 (1999), S. 159-167 
    ISSN: 1572-8757
    Keywords: impedance spectroscopy ; uptake curve ; adsorption ; polarization of adsorbate ; dielectric properties of adsorbed phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Physisorption equilibria of gases on inert porous solids like activated carbon or molecular sieves can be characterized by measuring the (frequency dependent) capacitance of a capacitor filled with a sample adsorbent. This quantity strongly depends not only on the physico-chemical structure of the empty adsorbent in vacuum, but also on the permanent or induced dipole moments of the molecules adsorbed and of the fluid phase. Consequently, it should be possible to determine the excess mass being adsorbed on the internal surface of a highly porous solid by measurements of the dielectric constant. The aim of this work is to show for various pure gases and adsorbents that the change of the capacitance of an adsorption system depends on the adsorbed mass. Therefore, this effect can be used to characterize porous solids and their adsorbates and, for example, to check the state or the quality of industrial adsorbents during a process on site if calibration measurements have been taken (Staudt et al., 1994, 1998).
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  • 16
    ISSN: 1572-8757
    Keywords: zeolites ; polar compounds ; adsorption ; adsorption isotherms ; equilibrium ; liquid phase ; breakthrough curves ; acetonitrile ; acrylonitrile ; dioxane ; ZSM-5 ; MCM-22 ; Na-X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The liquid phase removal of low concentrations of polar compounds (acetonitrile, acrylonitrile and dioxane) from toluene by adsorption on zeolites reveals very high selectivity factors. Kinetic selectivity factors as high as 16,100 are observed. The selection of the zeolites (MFI, MWW and FAU type) allowed the study of the effects of varying aluminum content, the presence and absence of acidic centers and varying pore volumes. To assess the relative effectiveness of each adsorbent, both equilibrium and continuous flow, pseudo equilibrium, breakthrough experiments were conducted. The continuous flow experiments were carried out at 25 and 75°C. The zeolites H-ZSM-5, H-MCM-22 and Na-X are highly effective in removing the polar compounds from toluene to a concentration level down to less than 20 ppm (detection limit). The results obtained with the equilibrium batch experiments are confirmed by the continuous flow breakthrough experiments.
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  • 17
    ISSN: 1572-8773
    Keywords: adsorption ; complexes ; Trichoderma harzianum ; IIb metals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Fungi are capable of accumulating metals and, in soil, such accumulation may influence metal speciation and transport. The interactions between a common soil fungus, Trichoderma harzianum, and IIb elements were studied in the present investigation. The accumulation of the metals zinc, cadmium and mercury by starved and non-starved mycelium at different pH was determined by a batch technique using radioactive tracers; uptake of the metals was found to be large, with respective distribution coefficients of about 103.5, 102.5 and 104.0 for zinc, cadmium and mercury, respectively. Metal accumulation by a starved system was largely independent of pH in the range 3–9, where in a non-starved system an increased accumulation of zinc (at 10− m) was observed at low pH (3–5). Potentiometric titrations performed on the two systems revealed significant differences in acid capacities, i.e. values close to zero for the starved system and 500–800 meq kg− for the non-starved system. The maximum metal uptake was at least 50 mmol kg− at pH 6.5 (calculated from adsorption isotherms). The present findings suggests that in the non-starved system a metabolite is produced and then released when the pH is within a certain range.
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  • 18
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    Catalysis letters 20 (1993), S. 133-139 
    ISSN: 1572-879X
    Keywords: NO ; N2 ; reduction ; transition metal oxide ; micropore ; activated carbon ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Activated carbon fibers (ACFs) were modified with various kinds of transition metal hydroxides. The surface modified ACFs were characterized by EXAFS. The NO reduction over the surface modified ACFs, which is not poisoned by SO2, was examined. Almost all NO (80%) was converted to N2 at 473 Kover α-FeOOH-dispersed ACF.
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  • 19
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    Journal of thermal analysis and calorimetry 55 (1999), S. 1011-1020 
    ISSN: 1572-8943
    Keywords: adsorption ; adsorption calorimetry ; microporous carbon ; porosity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The fundamental empirical relationships that correlate the adsorption energy with physicochemical parameters of adsorbates are discussed. Based on the experimental data of the adsorption enthalpy of different organic adsorbates on microporous activated carbons some new correlations between adsorption enthalpy and entropy at zero surface coverage and physicochemical parameters of adsorbed molecules are proposed. It is shown that they can be applied for the calculation of carbon porosity. The influence of carbon surface oxidation on its energetic heterogeneity is also discussed.
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  • 20
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    Journal of thermal analysis and calorimetry 57 (1999), S. 643-651 
    ISSN: 1572-8943
    Keywords: adsorption ; heat capacity ; solid-liquidinterface ; solid monolayer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Heat capacity measurements have been made to investigate the formation of two solid monolayers each of n-pentane, n-heptane and n-dodecane adsorbed on graphite, one at submonolayer coverages and the other coexisting with the liquid. At submonolayer coverages the monolayers are found to melt respectively at 99.8, 151.6, and 217.3 K, well below the bulk melting points. The monolayers coexisting with the liquid melted at 205.6 for heptane and at 287.8 K for dodecane, whereas no evidence was obtained for pentane on the formation of such solid monolayer above the bulk melting point. The order persisting in the liquid near the interface depends upon the length of the molecules. The dodecane monolayers showed another transitions below the melting points both at submonolayer and multilayer coverages.
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  • 21
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    Journal of thermal analysis and calorimetry 56 (1999), S. 323-330 
    ISSN: 1572-8943
    Keywords: adsorption ; balance ; gravimetry ; sorption ; thermoporometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of surface structure investigations involving the use of thermoporometry and gas-sorptometry on porous glass, silica and a zeolite were compared. The most frequent and the mean pore width were found to be in accordance, but major differences in specific surface were observed. These two measuring methods complement each other, because with gas adsorption a dry sample is investigated, while with thermoporometry a sample immersed in a liquid is investigated. The probe molecules (nitrogen or noble gas and water or benzene, respectively) differ in size. The features of the two methods are discussed.
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  • 22
    ISSN: 1572-8943
    Keywords: adsorption ; calorimetry ; derivative enthalpy ; prediction ; selectivity ; single xylene ; xylene mixture ; zeolite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The derivative enthalpies of adsorption of m-xylene and p-xylene onto the NaY and BaY zeolites were measured at 150°C, then compared with those obtained at 25°C, and finally used to predict the selectivity of adsorption of xylene mixtures. Significant differences were observed as the temperature was elevated: for the NaY zeolite, the adsorbate-adsorbate interactions became prevalent, in contrast with the BaY zeolite, between zeolite and derivative interactions were stronger. The difference between the adsorption derivative enthalpies of the two xylenes displayed an abrupt variation from 2 molec. α−1 for both zeolites, the filling from which selectivity towards m-xylene for the NaY zeolite and towards p-xylene for the BaY zeolite appeared. The preferentially adsorbed xylene was closely connected with the sense of this difference, which changed with the zeolite.
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  • 23
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    Journal of thermal analysis and calorimetry 58 (1999), S. 67-76 
    ISSN: 1572-8943
    Keywords: adsorption ; DRIFT spectroscopy ; elemental analysis ; γ-aminopropyl-trimethoxysilane ; thermogravimetric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A comparative method based on thermogravimetry is applied in order to characterise chemically functionalised surfaces. The mass loss of silica modified with γ-aminopropyl-trimethoxysilane (γ-APS) adsorbed from a range of solvents is interpreted by considering the physically adsorbed water, the silanol groups and the organic solvent. DRIFT spectroscopy is used to analyse the binding structure and adsorption mechanism. The mass loss calculated from thermogravimetric analysis is found to be in agreement with the values obtained by classical elemental analysis. Thermogravimetric analysis is found to be a quick and reproducible method, which only requires a few milligram sample. The amount adsorbed seems to be primarily dependent on the solvation of the γ-aminopropyl-trimethoxysilane by the solvent. A good solvent prevents adsorption as shown when comparing the magnitude of the mass loss with the difference between the solubility parameters of the γ-APS and the solvents. Ethanol seems to influence the structure of the adsorbed γ-aminopropyl-trimethoxysilane film.
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  • 24
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    Topics in catalysis 9 (1999), S. 225-234 
    ISSN: 1572-9028
    Keywords: large pore zeolites ; alkylaromatics ; computations ; adsorption ; diffusion characteristics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Alkylation of aromatics over solid acid catalysts such as zeolites, has emerged in the recent past as a viable alternative to conventional Friedel–Crafts alkylation over environmentally hostile catalysts. We studied the diffusion behaviour of ethylbenzene (EB), isobutylbenzene (IBB), o-, m- and p-isobutylethylbenzene (IBEB) in various zeolites such as offretite (OFF), cancrinite (CAN), ZSM-12 (MTW) and ZSM-18 (MEI) by computational procedures. The periodic variations of interaction energy between the molecules and zeolite framework in the calculated diffusion energy profiles are used to predict the energy barrier for diffusion. We analyzed the results to understand the product selectivity in the formation of IBEB in the transalkylation/disproportionation reaction between IBB and EB. The results indicated that the zeolites with channel-like pores are more suitable than those with cage-like pores to achieve better selectivity. The zeolites with channels whose diameters are close to the dimensions of the molecules and those which do not have intersecting channels are better selective catalysts. The efficiency of shape selective production of p-IBEB in these zeolites will be in the order MEI 〈 OFF ∼ MTW 〈 CAN as predicted from their diffusion energy barriers. The detailed analysis of the configurations of the molecules in the most favourable and unfavourable adsorption location, indicate that the p-IBEB has favourable interaction energy in all the four zeolites with different pore architecture, compared to o- and m-IBEB except for MEI. It could be concluded that the pore architecture plays a dominant role in controlling the adsorption and diffusion characteristics of these molecules. The actual values of interaction energy themselves are indication of their adsorption behaviour inside the pores of the zeolite.
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  • 25
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    Topics in catalysis 9 (1999), S. 235-250 
    ISSN: 1572-9028
    Keywords: Ziegler–Natta ; density functional theory ; adsorption ; polymerisation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Total energy pseudopotential calculations have been used to examine the adsorption of TiCl4 at both the 110 and 100 surfaces of magnesium chloride. Titanium(IV) chloride is found to bind most strongly on the 100 surface resulting in the formation of a complex with approximately trigonal bipyramidal coordination of titanium, which will dissociate to form TiCl 3 + and Cl− with an energy of 127.7 kJ mol−1. Cluster calculations indicate that this site only weakly binds ethene, but does catalyse the formation of C–C bonds with an activation energy consistent with experimental estimates.
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  • 26
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    Topics in catalysis 9 (1999), S. 123-133 
    ISSN: 1572-9028
    Keywords: NO/Pd ; adsorption ; clusters ; DFT
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction of NO with Pd clusters has been studied by means of the LCGTO-DF method. Metal cluster models (up to 13 atoms) with different size and geometry have been used to describe the atop, bridge and three-fold sites. The use of different model core potentials to increase the size of the cluster model treated and to save computational time has been discussed. The binding energies of N(1s), 4σ, 5σ and 1π electrons are calculated and compared directly to the experimental XPS and UPS data available. The NO is tilted with respect to the surface normal axis when adsorbed on top and bridge sites by about 52.6 and 46.7 degrees, respectively. On the two types of three-fold sites (hcp and fcc) the NO remains upright. The bending angle is very sensitive to the cluster size and affects the binding energies of N(1s), 4σ, 5σ and 1π orbitals. The NO adsorption energies on the different adsorption sites have been estimated using different cluster models. The vibrational frequencies have been calculated in the harmonic approximation and they are in reasonable agreement with the available experimental values. The cluster model approach is discussed in terms of its reliability to determine the adsorption energies and the favored site of adsorption.
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  • 27
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    Russian chemical bulletin 42 (1993), S. 427-431 
    ISSN: 1573-9171
    Keywords: zeolites ; adsorption ; methanol ; IR spectra
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Calorimetry and IR spectroscopy were used to study the adsorption of methanol on faujasites and mordenites with different Si/Al ratios. It was shown that the disturbance of the OH bonds in CH3OH weakens and the heat of adsorption decreases as the cation content in the zeolites decreases. The protic acid sites in decationized mordenite form strong hydrogen bonds with the adsorbed molecules.
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  • 28
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    Russian chemical bulletin 42 (1993), S. 1313-1315 
    ISSN: 1573-9171
    Keywords: adsorption ; gas chromatography ; carbon sorbents, carbon black ; molar volume ; adsorption isotherm
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The adsorption isotherms of benzene,n-hexane, cyclohexane, and 1,2-dibromo-1,1,2,2-tetrafluoroethane on a nonporous carbon adsorbent, carbon black, were calculated from the results of a gas-chromatographic experiment at 373 K. A general equation of adsorption isotherm for vapors of organic substances on nonporous sorbents that was proposed earlier is shown to be valid in the range of relative pressures,p/p s, of 10−7–1 and temperatures of 293–373 K.
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  • 29
    ISSN: 1573-9171
    Keywords: zeolite-like aluminophosphates ; adsorption ; methanol ; IR spectra
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Electrostatic properties of zeolite-like aluminophosphates are intermediate between those of zeolites and zeolite-like silica modifications. The adsorption measurements and IR spectroscopic investigations of the framework vibrations demonstrate that the number of the adsorption complexes of CH3OH with Al atoms increases in the following order: AlPO4-5 〈 AlPO4-17 ≪ AlPO4-18. The OH vibrations of methanol molecules in the first coordination sphere of the Al atoms are reflected in the IR spectra as an absorption band at 3200 cm−1, which is not observed for the adsorption of CH3OH on zeolites.
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  • 30
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    Russian chemical bulletin 44 (1995), S. 2073-2078 
    ISSN: 1573-9171
    Keywords: scanning force microscopy ; adsorption ; molecular films
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption of residual impurities from liquid media on various substrates was studied by scanning force microscopy. A new express method for controlling the purity of liquids was suggested.
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  • 31
    ISSN: 1573-9171
    Keywords: photocatalyst ; adsorption ; surfactant ; kinetics ; colloid ; cadmium sulfide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photoreduction of Methyl Orange dye (MOr) by sodium sulfide was studied under steady-state photolysis (λ = 365 nm). The reaction was sensitized by the CdS colloid with the characteristic ∼5-nm particle size. The quantum yield of the reaction is independent of the light intensity when the latter is less than 5 mW cm−2. The form of the dependence of the initial quantum yield of the reaction on [MOr] coincides qualitatively with the adsorption isotherm of the dye on the CdS surface. The reaction kinetics under steady-state irradiation were analyzed. The kinetics in solution as a whole are shown to be adequate to those on a single colloidal particle. On the basis of the experimental data, two types of surfaces of the colloidal particles are suggested (“open” and “covered” with macromolecules of a colloid stabilizer), which significantly differ in the rate at which they establish an adsorption-desorption equilibrium with the solution.
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  • 32
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    Russian chemical bulletin 44 (1995), S. 416-418 
    ISSN: 1573-9171
    Keywords: adsorption ; interface ; dispersion interactions ; inert gases ; methane ; graphite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new approach to the estimation of the extent of the inhomogeneous region during the adsorption of a gas on a planar or slightly curved solid surface is developed. Relationships are derived that enable the corresponding calculations to be made for the case of dispersion interactions of gases with solids. Numerical estimations of the extent of the inhomogeneous region for graphite-helium (neon, argon, krypton, xenon, and methane) systems as a function of temperature are presented.
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  • 33
    ISSN: 1573-4986
    Keywords: lectin receptor binding ; adsorption ; integrated optics ; lipid membrane incorporation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A novel integrated optical technique is used to monitor the kinetics of incorporation of glycophorin A (GPA) from solution into a planar dimyristoylphosphatidylcholine-cholesterol bilayer membrane, and the subsequent binding of wheat germ agglutinin (WGA) to the membrane-incorporated GPA. The technique significantly improves the attainable accuracy of kinetic measurements. The number of bound molecules can be determined to a precision of ca ± 80 mol µm−2. Our results show that GPA incorporates spontaneously into the bilayer. Binding of WGA to GPA is optimal in the presence of human serum albumin, and can be reversed byN-acetyl-d-glucosamine. The kinetics of the binding are consistent with the presence of two classes of kinetically distinguishable binding sites with association rates of 2.0×104 and 9.6×102 M−1 s−1, and dissociation rates of 2.7×10−3 s−1 and 〈10−5 s−1, respectively. A stoichiometry of 4 WGA monomers per GPA monomer was determined as characteristic of the overall binding interaction.
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  • 34
    ISSN: 1573-4854
    Keywords: relative permeability ; pore structure characterisation ; adsorption
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A novel design for the application of a simplified experimental procedure, capable of providing satisfactory relative permeability data for porous media at low relative pressures, is presented. The technique avoids the two-component mixing complications as well as the problems arising from the sample macroscopic inhomogeneity. The latter has been reduced with the aid of a variable pressure compaction procedure. Thus, it becomes easier to utilise the powerful relative permeability technique for the characterisation of the structure of porous solids. Emphasis is given to the combination of the relative permeability data obtained with an analytical approach based on Effective Medium Theory for the calculation of pore connectivity.
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  • 35
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    Journal of porous materials 2 (1995), S. 191-199 
    ISSN: 1573-4854
    Keywords: adsorption ; analysis of pore structure ; estimation from sorption pore shape ; from ad-de-sorption surface area ; calculations from sorption
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interpretation of pore dimensions based on physical ad-desorption analyses is central to the characterization of pore network structure. Several approaches have been proposed and are commonly employed in the analysis of physical adsorption and/or desorption to deduce the dimensions of the porous network. These approaches assume either theoretical (e.g., BET, the Halsey equation as interpreted by Pierce et al., or the more recent analyses of microporosity) or “standard” isotherms as model(s) for the sequential calculations required in estimating the pore network dimensions. Subsequent representation of the pore dimensions and the relationship between these distributions in dimension and other experimental parameters (such as catalytic activity, adsorptivity or transport); thus, depend explicitly on the model employed in the analyses. Each instrument currently available for the measurement of porous solid structure by sorption employs the same specific models for the relationship between the volume ad-desorbed and the dimensions of the porous network that is being characterized. This paper analyzes the interpretation of porous dimensions based on the sequential calculations required in the analyses. A new approach is proposed which is based on a modification to current practices reflecting Halsey's original theory for the thickness of the adsorbed layer (as a function of P/P 0). Further, the calculations of the incremental changes in the exposed surface area are discussed as they relate to pore network structure. A method is proposed to infer the differences in pore shape. Sorption data are analyzed by these new approaches, and these analyses will be compared with those approaches currently employed. Analyses based on these modified approaches provide a dramatically more consistent interpretation of the sorption data and the corresponding pore network structures.
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  • 36
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    Pharmaceutical research 12 (1995), S. 715-719 
    ISSN: 1573-904X
    Keywords: salbutamol base drug ; oleic acid ; propellant ; metered-dose inhaler ; stability ; adsorption
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The distribution of oleic acid between Salbutamol base drug and the solvent in metered-dose inhalers (MDI's) has been investigated. The equilibrium surfactant concentration in the drug dispersions has been determined using a colorimetric method. The samples examined contained Salbutamol base drug particles and oleic acid dispersed in different propellant blends of freon 11 and 12. The maximum equilibrium concentration observed depended on the propellant blend used. The propellant blend and the distribution of the surfactant affected the dispersion stability. The effect of the surfactant is illustrated by the adsorption isotherm for oleic acid onto the Salbutamol particles. The results are correlated with zeta-potentials and particle size measurements made on similar systems in order to characterize the properties of surfactant stabilized MDI's.
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  • 37
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    Colloid & polymer science 271 (1993), S. 56-62 
    ISSN: 1435-1536
    Keywords: Alumina ; phosphate ester dispersants ; flow calorimetry ; adsorption
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interaction of two commercially available phosphate ester dispersants with calcined alumina has been investigated using the techniques of flow calorimetry and electrophoresis. Flow calorimetric experiments have shown that these dispersants chemically interact with the surface of calcined alumina. The electrical charging of alumina particles in an iso-octane solution containing a phosphate ester indicates that an acid-base interaction mechanism is operative in this system.
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  • 38
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    Colloid & polymer science 271 (1993), S. 236-240 
    ISSN: 1435-1536
    Keywords: PVC plastisol ; adsorption ; plastification
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The significant phenomenological analogy between physical adsorption from liquid solutions on microporous adsorbents and plastification of PVC has been observed. This justified the use of the solution analog of the adsorption isotherm equations of the theory of volume filling of micropores as being adequate to describe the process of plastification of PVC by the composition of plasticizer and modifying agent. The qualitative agreement between isotherm predicted by model and experimental data allowed to formulate the mechanism of the process of interest.
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  • 39
    ISSN: 1435-1536
    Keywords: Cotton fibers ; dye ; adsorption ; calorimetry ; zeta potential ; fluorescence ; degree of whiteness
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fluorescent whitening agents (FWA) are used to improve the whiteness of cellulose fabrics. It is well known but not completely understood that the fluorescence decreases (chemical and physical mechanisms of distinguishing) above a certain FWA concentrationc crit. This reduction of fluorescence correlates very well with the alteration of the adsorption process studied by calorimetry and zeta potential measurements. The results obtained by these methods indicate that the adsorption mechanism is different at concentrations below and abovec crit. The reduction of the intensity of fluorescence, the degree of whiteness and the zeta potential are caused by the adsorption of a second layer of fluorescent whitening agents. This second layer reduces the zeta potential due to a shielding effect and reduces the whiteness and fluorescence by a bathochromic shift of the reflection curves. The final effect is a reduction of the total reflection.
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  • 40
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    Colloid & polymer science 271 (1993), S. 1157-1164 
    ISSN: 1435-1536
    Keywords: Polymer emulsion ; albumin ; fibrinogen ; protein ; adsorption ; surface hydrophilicity ; surface heterogeneity ; microsphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The competitive adsorption of bovine fibrinogen (BFb) and bovine serum albumin onto polymer microspheres from the mixture solution was examined under various protein-to-microsphere ratios using various homopolymer microspheres and poly(2-hydroxyethyl methacrylate)/polystyrene composite microspheres having heterogeneous surface structures consisting of both hydrophilic and hydrophobic parts. They were produced by emulsifier-free (seeded) emulsion polymerizations. The selective adsorption of BFb was not observed for the homopolymer microspheres, but observed for the composite polymer microspheres having optimum compositions.
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  • 41
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    Colloid & polymer science 271 (1993), S. 709-713 
    ISSN: 1435-1536
    Keywords: Water glass ; silica gel ; argon ; adsorption ; microporous
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Surface characterization of silica gels prepared at different gelation pH from water glass and sulphuric acid were made by argon adsorption at 77 K using continuous volumetric method. While microporous silica gels prepared in the pH range of 1–3 had BET surface areas of 504–571 m2 g−1, total pore volumes of 0.26–0.31 cm3 g−1 and micropore volumes of 0.16–0.23 cm3 g−1, mesoporous silica gels prepared in the pH range of 3.36–0.65 had BET surface areas of 374–530 m2 g−1 and pore volumes of 0.61–0.79 cm3 g−1.
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  • 42
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    Colloid & polymer science 271 (1993), S. 307-309 
    ISSN: 1435-1536
    Keywords: Silica ; TiO2 ; adsorption ; ionic surfactant ; surface modified
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Colloidal silica and titanium dioxide were surface-modified by chemisorption of octadecyl dimethylmethoxy silane. The surface density of these alkyl silane groups was adjusted to less than 7% of the available surface hydroxyls, leaving the adsorbents hydrophilic and electrically charged in aqueous solution. Ionic surfactants (tetradecylpyridinium chloride and sodium lauryl sulfate) are adsorbed onto the surface-modified silica and titanium dioxide from aqueous solution, even in the case where the surface of the adsorbents exhibits the same sign of electrical charge as the surfactant ionic head groups. According to the adsorption model of Gu the chemiadsorbed alkyl chains are supposed to serve as anchors for small surface aggregates of the ionic surfactants.
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  • 43
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    Colloid & polymer science 273 (1995), S. 787-792 
    ISSN: 1435-1536
    Keywords: Zeolite ; modification ; surfactant ; adsorption
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Adsorption characteristics of anion-, cation- and nonion-type surfactants and phenol from their aqueous solution on Na-Y zeolites modified by SiCl4 treatment and NA-ZSM-5 zeolites with several Si/Al ratios were measured. Surfactants used were sodium dodecylbenzenesulfonte (DBS), laurylpyridinium chloride (LPC), polyoxyethylenenonylphenylether (POENPE) and phenol. Adsorption of surfactants was enhanced by SiCl4 treatment of Na-Y, which indicates an important role of the hydrophilic-hydrophobic character in the adsorption. Adsorption isotherms were in general of Langmuir type and adsorbed amount depended on the Al/(Si+Al) or Si/Al ratio of zeolite frameworks. In case of DBS adsorption of Na-ZSM-5 series, adsorption occurred only on the outer surface due to steric hindrance. LPC adsorption abilities were observed on even hydrophilic zeolites and were ascribed to ion exchange effect. In case of phenol adsorption on hydrophobic Na-Y, the adsorption isotherm was of Type V according to BDDT classification.
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  • 44
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    Colloid & polymer science 273 (1995), S. 817-821 
    ISSN: 1435-1536
    Keywords: Composite particle ; temperature-sensitive ; biomolecules ; adsorption ; surface
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Temperature-sensitive composite polymer particles were prepared by seeded emulsion copolymerization of dimethylaminoethyl methacrylate and ethylene glycol dimethacrylate with 0.17 μm-sized monodispersed polystyrene seed particles. The adsorption and desorption behaviors of low molecular weight cationic emulsifier as well as albumin were examined to determine the variation of surface properties as a function of temperature below and above 35°C.
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  • 45
    ISSN: 1573-515X
    Keywords: adsorption ; bacterial dissimilatory sulfate reduction ; dry deposition ; forested catchment ; Lake Gårdsjön ; isotopes ; oxidation of sulfur ; sulfate ; sulfur ; Sweden
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A small catchment on the Swedish West Coast has been studied over four years to determine S dynamics by using S isotope ratios. A Norway spruce dominated forest covers the catchment, and small peat areas occur in the lower parts of the catchment. The runoff δ34SSO4 values varied both during the year, and from year to year. Over the period from February 1990 to December 1993, the δ34SSO4 values ranged from −1‰ to +11‰. Over the same period, the throughfall δ34SSO4 values ranged from +1‰ to +15‰. There was no correlation (r2 = 0.01; Pr(F) = 0.57) between δ34SSO4 values in throughfall and runoff. Since the only input of S to the catchment is atmospheric deposition, the long-term runoff S mass flux is controlled by the deposition. Therefore, processes in the catchment are responsible for the variation in the runoff δ34SSO4 values. During periods with 34SSO4 enriched runoff, bacterial dissimilatory SO42- reduction occurs in the catchment. After very dry periods, oxidation of this reduced S, which is 32S-enriched, can be traced in runoff. Previous studies of the catchment have not been able to distinguish between: 1) oxidation of reduced S and dry deposition, and 2) reduction and adsorption. From the current study, it can be concluded that adsorption and dry deposition cannot cause the observed variation in runoff δ34SSO4.
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  • 46
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    Colloid & polymer science 271 (1993), S. 799-801 
    ISSN: 1435-1536
    Keywords: Surfactant ; adsorption ; surface-micelle ; BET equation
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract 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.
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  • 47
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    Colloid & polymer science 273 (1995), S. 1028-1032 
    ISSN: 1435-1536
    Keywords: Hydrolyzed polyacrylamide ; hematite ; adsorption ; kinetics
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The adsorption measurements of hydrolyzed polyacrylamide (HPAM) onto hematite suspension are carried out to study the dynamics of the polymer adsorption onto the suspension particles and to investigate the mode of the polymer adsorption. The polymer is found to show much affinity for the adsorption because of the opposite charges possessed by the polymeric flocculant and the suspension particles. Various adsorption parameters such as adsorption coefficient, the rate constants for the adsorption and desorption, are evaluated with the help of a recently proposed kinetic scheme. It is found that the extent of adsorption and the adsorption rate are adequately affected by increasing the pH of the suspension while, unexpectedly, the adsorption is found to show only a marginal increase on addition of Na2SO4. Both the amount of the adsorbed polymer and the adsorption rate are also found to increase with the degree of hydrolysis of the polyelectrolyte.
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  • 48
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    Journal of thermal analysis and calorimetry 55 (1999), S. 441-448 
    ISSN: 1572-8943
    Keywords: adsorption ; capillary condensation ; gravimetric method ; McBain microbalance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The isotherms of adsorption-desorption of the vapour of benzene, cyclohexene and n-hexane on different porous silica gels were measured gravimetrically. For all the adsorbates, the amount of vapour condensed in the adsorbent pores is significantly greater than the amount adsorbed. The isotherms of all the adsorbates are linear in a wide range of relative pressures.
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  • 49
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    Journal of thermal analysis and calorimetry 55 (1999), S. 581-599 
    ISSN: 1572-8943
    Keywords: adsorption ; desorption ; humidity ; hysteresis ; isotherm ; kinetic curve ; temperature test
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The CISORP Water Sorption Analyser has been used to characterise a selection of solid samples at relative humidities from 0 to 100% and at ambient pressure. The analysis reveals many interesting features about the samples and shows the scope of the equipment. Hysteresis due to porosity and differences in the physical properties of similar chemical samples show up clearly in isotherm curves. Kinetic curves reveal features such as the level of stability of dehydrated food products, changes in the hydration states of salts, and the effect of adding powdered excipient on the water sorption behaviour of a pharmaceutical compound. Kinetic curves were also used to compare the water sorption behaviour of two types of wood found inside a pine cone, and to determine equilibrium moisture sorption by calculation. It was shown that many samples take up moisture irreversibly under the experimental conditions such as amorphous sucrose and other freeze-dried samples, as well as unstable crystalline forms of compounds. Wet samples such as soaked brick and archaeological wood from a well dry out irreversibly even at 100% RH. Recording isotherms at different temperatures allows the calculation of enthalpies of water sorption. If these are compared with the enthalpy of water condensation the two processes can be compared quantitatively.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1453-1459 
    ISSN: 1572-8943
    Keywords: activated carbon ; adsorption ; calorimetry ; gravimetry ; hydrocarbon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption isotherms of n-butane on a granulated activated carbon were measured by two different but complementary experimental methods: calorimetry and gravimetry. Adsorption heats were determined in different ways. For the system studied, the experimental results prove that the adsorbent offers a homogeneous site distribution. Besides, there can be differences between the adsorption heat values which might come from the way they are obtained (by calculation or direct measurements).
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  • 51
    ISSN: 1573-515X
    Keywords: adsorption ; bacterial dissimilatory sulfate reduction ; dry deposition ; forested catchment ; Lake Gårdsjön ; isotopes ; oxidation of sulfur ; sulfate ; sulfur ; Sweden
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A small catchment on the Swedish West Coast has been studied over four years to determine S dynamics by using S isotope ratios. A Norway spruce dominated forest covers the catchment, and small peat areas occur in the lower parts of the catchment. The runoff $$\delta ^{34} S_{SO_4 } $$ values varied both during the year, and from year to year. Over the period from February 1990 to December 1993, the $$\delta ^{34} S_{SO_4 } $$ values ranged from — 1%. to +11%. Over the same period, the throughfall $$\delta ^{34} S_{SO_4 } $$ values ranged from +1%. to +15%. There was no correlation (r 2= 0.01; Pr(F)=0.57) between $$\delta ^{34} S_{SO_4 } $$ values in throughfall and runoff. Since the only input of S to the catchment is atmospheric deposition, the long-term runoff S mass flux is controlled by the deposition. Therefore, processes in the catchment are responsible for the variation in the runoff $$\delta ^{34} S_{SO_4 } $$ values. During periods with $$\delta ^{34} S_{SO_4 } $$ enriched runoff, bacterial dissimilatory SO 4 2− reduction occurs in the catchment. After very dry periods, oxidation of this reduced S, which is32S-enriched, can be traced in runoff. Previous studies of the catchment have not been able to distinguish between: 1) oxidation of reduced S and dry deposition, and 2) reduction and adsorption. From the current study, it can be concluded that adsorption and dry deposition cannot cause the observed variation in runoff $$\delta ^{34} S_{SO_4 } $$ .
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  • 52
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    Journal of porous materials 1 (1995), S. 139-153 
    ISSN: 1573-4854
    Keywords: microporous ; sol-gel ; silica ; pore size ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Gas physisorption is a generally used technique for the characterization of porous solids. Microporous solids, however, need a different approach compared to mesoporous solids due to enhanced adsorption in pores of molecular dimensions. Therefore, conventional theories and models can not be used. The application of physisorption for microporous solids, and the interpretation of the isotherms is elucidated. Some models presented in literature for pore size assessment in the micropore range are discussed. Based on a number of criteria, the Horváth-Kawazoe model, modified for cylindrical pore geometry, is selected. N2 adsorption measurments on zeolites were performed to calibrate the method and to show the applicability and physical justification. Typical data obtained from experiments on non-supported microporous silica membrane top-layers show that the pore size distribution of these materials is bimodal, with a strong maximum at an effective diameter of 0.5 nm, and a weaker maximum at 0.75 nm.
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  • 53
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    Journal of porous materials 1 (1995), S. 75-84 
    ISSN: 1573-4854
    Keywords: carbon ; silica ; xerogel ; aerogel ; composite ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract High surface area carbon-silica xerogels and aerogels were prepared by adding various amounts of activated carbon particles during gelation of tetramethyoxysilane (TMOS). Surface areas and pore structure of the gels were determined by nitrogen and water adsorption and desorption measurements. Carbon increased the surface area of silica gel and the carbon-silica gel composites were found to be hydrophobic. The pore structure of xerogel composites was dominated by carbon whereas that of aerogel composites was apparently controlled by silica component.
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  • 54
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    Journal of porous materials 1 (1995), S. 55-67 
    ISSN: 1573-4854
    Keywords: zeolite ; porous material ; adsorption ; desiccant ; natural gas ; dehumidification ; gas-fired cooling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This study was aimed at modifying the pore structure and surface chemistry of a zeolite to achieve an ideal material for gas-fired dehumidifying and cooling system application. Zeolite Y was chemically modified with various amounts of ethylenediaminetetraacetic acid (H4EDTA) corresponding to H4EDTA/Al (zeolite) molar ratio, X=0.5, 0.6, 0.75, 0.9 and 1.0 under reflux condition to achieve various degrees of dealumination. Sample treated with X=0.5 remained highly crystalline, but crystallinity of the samples decreased as the X increased. Although the sample treated with X=0.9 was x-ray amorphous, SEM micrographs indicated that the original crystal morphology was largely preserved. Chemical analysis and 29Si showed a progressive extraction of Al and Na with increased X. 27Al MASNMR indicated that AlIV was the only Al species up to X=0.75, whereas the x-ray amorphous phase (X=0.9) exhibited three peaks at 60, 52 and 38 ppm indicating the distortion of and change in AlIV coordination. Adsorption analyses using H2O, N2 or Ar as probe molecules indicated that the X-ray amorphous product remained essentially microporous having a broad micropore size distribution and a reduced hydrophilicity. Consequently, water adsorption isotherm changed from an extreme Type I to a moderate Type I. The moderate Type I isotherm with water is the key for its suitability as a desiccant in gas-fired dehumidifying and cooling system. These materials are also potentially useful in solar heating and cooling applications.
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  • 55
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    Journal of porous materials 2 (1995), S. 19-23 
    ISSN: 1573-4854
    Keywords: carbon molecular sieve ; adsorption ; micropore size distribution ; molecular probe ; DR equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Nitrogen adsorption at 77 K is the most common technique for defining the surface area and pore volume of a porous material. However it is not adequate to assess the microporosity of carbon molecular sieves (CMS), because of activated diffusion effects. In this paper, a molecular probe technique was used to defining the pore size of CMS materials. Adsorption of gases (vapors) with different molecular sizes, were measured by a gravimetric method using a spring balance. The amount adsorbed at room temperature was recorded over a 24-h period. The following molecular probes were chosen: CO2 (0.33 nm), C2H6 (0.4 nm), n-C4H10 (0.43 nm), i-C5H112 (0.5 nm), and CCl4 (0.6 nm). The micropore volumes were estimated by the Dubinin-Raduhkevich (DR) equation. Assuming that the diameters of the micropores are larger than those of the adsorbed molecules, the micropore volume distribution of each sample was estimated. The results demonstrated that the main pore size of the studied CMSs are less than 0.5 nm. One of the samples had a narrow pore size distribution in the range of 0.33–0.43 nm, which is the critical pore size for kinetic separation of oxygen from nitrogen. It is concluded that the molecular probe technique is an effective mean to assess the CMS adsorbents structure, which is not currently possible using conventional approaches with a single adsorbate, such as nitrogen or argon.
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  • 56
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    Journal of porous materials 2 (1995), S. 9-17 
    ISSN: 1573-4854
    Keywords: adsorption ; isotherm ; characterization ; modeling ; simulation ; pore size ; density functional theory ; argon ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The formalism of (nonlocal) density functional theory provides an attractive way to describe the physical adsorption process at the fluid-solid interface. It provides numerical results of analytic precision in a small fraction of the time required by a simulation technique. In particular, the ability to model adsorption in a pore space of slit-like or cylindrical geometry has led to useful methods for extracting pore size distribution information from experimental adsorption isotherms. However, critical comparisons of experimental isotherms with the isotherms predicted by density functional theory have shown important differences when using the usual prescription for the nonlocal free energy density functional. It is clear that these differences would affect the accuracy of such pore size information. We show in this paper how a small modification to the mean field computation of the intermolecular attractive potential results in excellent agreement with experiment for the systems studied.
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  • 57
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    Pharmaceutical research 12 (1995), S. 1025-1030 
    ISSN: 1573-904X
    Keywords: isothermal microcalorimetry ; adsorption ; wetting ; powders ; lactose ; batch variability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. This study describes the development of a microcalorimetric flow cell which allows powder surface energetics to be probed my means of measuring their interaction with water vapour. Methods. A flow cell has been constructed and tested in an isothermal microcalorimeter to assess the interaction between water vapour and powder surfaces. The cell was constructed to mix two separate air streams (0% and 100% relative humidity respectively) to create any humidity at a standard flow rate. The powder sample was equilibrated in dry air and then exposed to sequential increments in humidity. Results. Adsorption isotherms were constructed from the cumulative heat as a function of humidity. It was possible to differentiate between different samples of α-lactose monohydrate (which appeared identical by contact angle determination). It was also possible to measure adsorption to two different alkyl p-hydroxybenzoates which were hydrophobic and of low surface area. Conclusions. This technique offers a very sensitive and versatile method of obtaining a reliable indication of powder surface energetics and as such is a major advance in the field.
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  • 58
    ISSN: 1573-1421
    Keywords: thorium ; scavenging ; adsorption ; irreversibility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Thorium(IV) sorption onto hematite (α-Fe2O3) was examined as a function of pH and ionic strength. Sorption behaved Langmuirian over an eleven order of magnitude range in adsorption densities, Γ: 10−12 to 10−1 moles Th sorbed per mole hematite sites, indicating that the overall free energy of Th adsorption is independent of adsorption density. Modeling of Th sorption was conducted with the Triple Layer Model of Davis and Leckie; reactions considered included solution-phase hydroxy and carbonato complexes of thorium, and carbonate/hematite surface complexes. The entire Th sorption isotherm can be modeled with a single surface complex formation reaction $$ \equiv Fe - OH + Th^{4 + } \mathop = \limits^{*K_{Th}^{int} } \equiv Fe - OTh^{3 + } + H^ + $$ Inverse modeling of pH-fractional Th adsorption data yielded a value of *K Th int of 21.2. The relatively large value of the surface complex formation constant is required for hematite surface sites to effectively compete against solution-phase hydroxide and carbonate ions at high system pHs. Insensitivity of fractional thorium sorption to changes in ionic strength suggests the formation of inner-sphere surface complexes. Sorption and desorption rate experiments showed: (1) Th sorption onto hematite suspended in a simple electrolyte solution is rapid with equilibrium attained within a few minutes; (2) sorption is irreversible on the time scale of the experiments (4 days). Coagulation and sedimentation experiments demonstrate the utility of Th isotopes asin situ ‘coagulometers’: even at relatively low particle concentrations (e.g., 5 ppm), Th acts as a surrogate for particle mass transfer.
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  • 59
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    Journal of inclusion phenomena and macrocyclic chemistry 15 (1993), S. 105-119 
    ISSN: 1573-1111
    Keywords: FT-IR spectroscopy ; FT-Raman spectroscopy ; clays ; sepiolite ; bentonite ; hectorite ; saponite ; 4,4′-bipyridyl ; adsorption ; XRD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The adsorption of 4,4′-bipyridyl by natural sepiolite and smectite group clay minerals (bentonite, hectorite and saponite) from Anatolia (Turkey) has been studied using vibrational spectroscopy. Investigation of Fourier-transform infrared and Fourier-transform Raman spectra of adsorbed 4,4′-bipyridyl indicate the presence of chemisorbed species. However, any evidence for the generation of anionic species on the surface of the phyllosilicates has not been detected. It is proposed that the adsorbed bipyridyl molecules on sepiolite are centrosymmetric and H-bonded to the surface hydroxyls through both the nitrogen lone pairs as bidentate ligands. The adsorbed bipyridyl molecules on the smectite group clays are coordinated to exchangeable cations both directly and also indirectly through water as monodentate ligands. XRD patterns of the clays studied are also recorded.
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  • 60
    ISSN: 1573-2746
    Keywords: contact angle transition ; wetting ; interfacial energy ; solid pb-Ni/graphite system ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The wetting of Pb-Ni crystals on graphite has been observed at 558 K in a Scanning Auger Microprobe. Samples were prepared so as to produce 10 μm crystals of Pb with Ni contents increasing from 0 to 0.3 wt% along one axis of the graphite substrate. In the low Ni region, the contact angle was found to decrease slowly from 119° to 98° with increasing Ni content. In the region of high Ni content, a constant contact angle of 83° was measured. In between, crystals with contact angles of 98° and 83° were observed to coexist, near the limit of solubility of Ni in Pb, indicating the presence of a first order transition in contact angle. The continuous decrease in contact angle, in the low Ni region, is due to Ni adsorption at the Pb-graphite interface, which leads to a decrease in interfacial energy. The constant contact angle in the high Ni region is associated with the precipitation of a Ni-rich phase. Various hypotheses are advanced to account for the first order transition in contact angle as a function of Ni concentration.
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    Russian chemical bulletin 44 (1995), S. 2064-2067 
    ISSN: 1573-9171
    Keywords: carbon adsorbents ; X-ray diffraction ; microcrystallites ; micropores ; adsorption ; water vapor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A correlation of adsorption and X-ray data for a series of both initial and modified active carbons (AC) was performed. The AC were modified by thermal treatment and progressive activation. A linear correlation between the sizes of crystallites and micropore widths of AC was established. It was shown that the adsorption of water vapor results in an increase in the parameterL aof crystallites of active carbons.
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  • 62
    ISSN: 1573-9171
    Keywords: adsorption ; adsorption volume ; excess adsorption ; adsorption isotherm ; equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method for the determination of adsorption space volume has been proposed, which is applicable to adsorbents with an arbitrary porous structure, including nonporous adsorbents with open surfaces. The method is based on the use of an experimental excess adsorption isotherm measured over a wide range of pressures in the equilibrium gaseous phase (as a rule up to 100–150 MPa) and the absolute adsorption isotherm equation with unspecified parameters in the most general form, given by statistical physics. The method has been tested for a number of adsorption systems, and it has been found that the result was always unambiguous, correct, and stable in the sense of input data.
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    Russian chemical bulletin 44 (1995), S. 1525-1527 
    ISSN: 1573-9171
    Keywords: adsorption ; carbon fiber ; macroporous glasses ; protein ; thin-layer inorganic sorbents ; titanium hydroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption of bovine serum albumin by macroporous glasses and fiber sorbents was studied. Differences in the mechanism of protein Sorption by sorbents depending on the chemical nature of the surface and the texture of the initial matrix were found. Optimum conditions for protein immobilization on thin-layer sorbents were determined. The reversibility of protein adsorption was studied by the radioactive indicator technique. The extent of reversibility of protein adsorption by thin-layer titanium hydroxide coatings was shown to depend significantly on the texture of the initial matrix.
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