Die untersuchung von adsorptionsgleichgewichten auf graphitiertem thermischen ruß mittels gas-chromatographie

Zusammenfassung Auf der Oberfl?chevon graphitiertem themischen Ru? werden im Grenzgebiet kleiner Belegungen die Retentionsvolumina und Adsorptionsw?rmen der Alkane, Alkene, Alkadiene, Alkine, Cyclane,Cyclene von C₁−C₆ und Benzol bestimmt. Es werden die Abh?ngigkeiten der Adsorptionsw?rmen dieser Moleküle von ihren Polarisierbarkeiten Zhal der Kohlenstoffatome, Grad der Verzweigung und Cyclisierung, Anwesenheit von Doppelbindungen und konjugierten Bindungen untersucht.

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Gas chromatographic investigation of the adsorption equilibrium on graphitized thermal carbon black I. The henry-constants and heats of adsorption of C₁−C₆ hydrocarbons at zero coverage

Summary The retention volumes and heats of adsorption at low surface coverages of graphitized thermal carbon black for C₁−C₆ alkanes, alkenes, alkadienes, alkynes, cyclanes, cyclenes, and benzene have been determined. The dependence of heats of adsorption of these molecules on polarisability, carbon number, isomerisation and cyclisation, the presence of double bonds and conjugated bonds were investigated.

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Etude par la chromatographie en phase gazeuse de l'équilibre d'adsorption sur le noir de carbone graphitisé par voie thermique I. constante de henry et enthalpie d'adsorption des hydrocarbures en C₁ à C₆ pour les taux de recouvrement nuls

Résumé On a déterminé les volumes de retention et les enthalpies d'adsorption des molécules d'alcanes, alcènes, alcadiènes, alcynes, cyclanes, cyclènes en C_` à C₆ et du benzène sur la surface du noir de carbone graphitisé par voie thermique pour les taux de recouvrement faibles. On a aussi étudié la relation entre les enthalpies d'adsorption de ces molécules et leur polarisabilité, leur nombre d'atomes de carbone, la ramification de leur cha?ne, la cyclisation, le nombre de doubles liaisons et de doubles liaisons conjuguées.

     

Heats of n-hexane and n-heptane vapor adsorption onto polyhydroxyaluminum montmorillonite

The differential isosteric heat of the adsorption of n-hexane and n-heptane vapors on dehydrated polyhydroxyaluminum montmorillonite was determined. Using the temperature dependence of the parameters of the adsorption equilibrium, it was established that substituting sodium ions for polyhydroxyaluminum cations leads to an increase in the volume of micropores and the adsorption heat of hydrocarbons, and the curves of the adsorption heats of C₆H₁₄ and C₇H₁₆ are of an extreme nature. The appearance of the maxima is associated with the interaction between and among the adsorbate molecules and active centers, due to consolidation in the process of filling micropore volumes.     

Heats of adsorption of benzene and toluene vapors on polyhydroxyaluminum montmorillonite

Changes that occur in the surface properties and porous structure of montmorillonite when sodium ions are replaced with polyhydroxyaluminum ions are studied. It is established that thermal evacuation significantly affects the adsorption and energy properties of polyhydroxyaluminum montmorillonite (PHAM). The dependences of the differential isosteric heats of adsorption and desorption on the amount of adsorbed substance are determined from data on a series of isosteres for the sorption of benzene and toluene on dehydrated PHAMs, where the curves of the heats of sorption of C₆H₆ and C₇H₈ are of an extreme character. It is concluded that the occurrence of maxima is determined by the interaction between molecules of adsorbates and active centers (and with one another) due to packing upon the filling of the volumes of slittype micropores.     

Discussion of thermodynamic data obtained by adsorption gas chromatography of hydrocarbons on a new graphitized carbon black with a high specific surface area

Summary A new graphitized carbon black (Carbograph 5) with a specific surface area (560 m² g⁻¹) greater than those of commerically available graphitized carbons was studied by gas chromatography to determine the enthalpy, entropy, and free energy of adsorption of a series of alkanes (C₂−C₆). The adsorption properties were also investigated by considering changes in the isosteric heats and entropies of adsorption when a nonpolar stationary phase (squalane) was added to the adsorbent. The data obtained are discussed and compared with literature values for other graphitized carbon blacks.     

Distribution coefficients in the water-dodecane system and the heats of adsorption of C<Subscript>1</Subscript>-C<Subscript>8</Subscript> alcohols on silica

Distribution coefficients in the water-dodecane system and the heats of adsorption of C₁-C₈ alcohols on silica (Silochrom S-80) were determined by gas chromatography. At low temperatures, C₁-C₄ alcohols were largely distributed in the aqueous phase, and C₆-C₉ alcohols were predominantly dissolved in the organic phase; C₅ alcohols had intermediate properties. Permittivity was found to correlate with log K _d, which allowed us to predict the character of the distribution of alcohols in the water-oil system. The heats and isotherms of adsorption were determined for the alcohols studied. The heats of adsorption of alcohols on silica monotonically increased in the series under consideration. For C₅-C₈ alcohols, they exceeded the heat of adsorption of water. The isotherms of adsorption were described by the Freundlich equation.     

Retention of some phenyl-substituted and bicyclic hydrocarbons on graphitized carbon black

Summary Retention volume values for zero cample size (Henry's constants) at different temperatures, retention indices and differential adsorption heats of phenylethylene, phenylacetylene, C₉–C₁₂ phenylcyclanes, biphenylethylenes, biphenylacetylene, bicyclohexyl and bicyclohexylmethane have been determined on graphitized thermal carbon black (GTCB). The molecules of all these hydrocarbons are capable of internal rotation. The values of the thermodynamic adsorption characteristics of phenylcyclanes increase with increasing number of carbon atoms in the cycle. Bicyclohexyl is retained on GTCB considerably weaker than biphenyl while bicyclohexylmethane is retained stronger than biphenylmethane. Symmetric and nonsymmetric biphenylethylenes are retained much stronger than the corresponding biphenylethanes. Phenylethylene (styrene) and trans-biphenylethylene (trans-stilbene) are stronger retained on GTCB than phenylacetylene and biphenylacetylene (tolane), respectively. The relationship between the structure of these molecules and their retention on GTCB is discussed.     

Ethylene/ethane separation by CuCl/AC adsorbent prepared using CuCl<Subscript>2</Subscript> as a precursor

Activated carbon (AC) supported CuCl (CuCl/AC) for ethylene/ethane separation has been prepared with CuCl₂ as precursor by a solid-state dispersion method. The samples are characterized by inductively coupled plasma optical emission spectrometry, X-ray diffraction, N₂ adsorption/desorption and X-ray photoelectron spectroscopy, and investigated for ethylene (C₂H₄) and ethane (C₂H₆) adsorptions. The characterization results reveal that CuCl₂ supported on AC can be highly dispersed on the surfaces of AC support and completely converted to CuCl after activation at 543 K in N₂. The resultant adsorbent displays high ethylene adsorption capacity, high C₂H₄/C₂H₆ adsorption selectivity and excellent reversibility. The adsorption isotherms of ethylene and ethane on CuCl/AC at temperatures up to 333 K can be well fitted by the Sips models, and the corresponding isosteric heats of adsorption are calculated from the Clausius–Clapeyron equation. The value of isosteric heat of adsorption suggests that the interaction of ethylene with CuCl/AC is between physisorption and chemisorption.     

载铜活性炭吸附一氧化碳的密度泛函理论计算

应用密度泛函理论和相对论有效核势方法, 用C₁₆H₁₀, C₁₃H₉, C₁₂H₁₂原子簇模型模拟活性炭表面, 计算得到了CO在载铜活性炭上的吸附位、吸附构型和吸附能. 研究表明: 载铜活性炭吸附CO的过程, 本质上是Cu(I)通过σ-π配键与CO络合, 形成Cu—C键的过程. 载铜活性炭对CO的络合吸附能在50～60 kJ/mol之间, 远大于活性炭对CO的物理吸附能(9.15 kJ/mol), 因而络合吸附更稳定, 选择性也更高. Cu(I)选择吸附在活性炭表面的顶位和桥位, 一个Cu(I)至多可以吸附一个到两个CO分子, 但吸附一个CO比吸附两个CO稳定.     

Gaschromatographische Untersuchung der Adsorptionseigenschaften von Silicalit und ZSM-5

High silica molecular sieves (silicalite, ZSM-5) were tested as adsorbents for gas chromatographic trace analysis. Therefore the retention behaviour of low-boiling organic compounds (hydrocarbons, halogenated hydrocarbons, amines, alcohols and ethers) on these materials was investigated. The specific retention volumes at different temperatures have been determined and elution orders and peak shapes were studied. The retention data allow a simple calculation of the breakthrough volumes (dynamic adsorption capacity) and the chromatographic characterisation of the adsorbents. Both nitrogen and oxygen containing compounds could not—or at least unreproducibely—be eluated up to 300°. The elution order and the peak shape of compounds with the same number of carbon atoms but different geometric and electronic structure (e.g.n-butenes;n-hexane, cyclohexane, benzene) can be explained by the action of exclusion effects and different diffusion barriers. On the basis of calculated breakthrough volumes we conclude that silicalite should be useful in the preconcentration of both saturated C₃–C₆ hydrocarbons and C₁–C₂ chlorinated hydrocarbons from gaseous streams.     

Adsorption Properties of Thiocontaining Schungite

Chromatography–mass spectrometry and thermodesorption mass spectrometry have been employed to study mineral schungite-III, in which various thiocompounds have been detected and identified. The influence of these compounds on the adsorption activity of schungite with respect to iodine has been investigated. It has been shown that sulfur present in schungite has no effect on the results of determining its adsorption activity and does not interact with iodine; however, it can interact with amino compounds to yield sulfides. Activation energies E_a have been experimentally determined for sulfur, iodine, and dimethyl disulfide desorption from the surfaces of schungite and a model sorbent, graphitized thermal carbon black. The E_a values of these compounds have appeared to be several times lower than the heats of their adsorption on carbon black calculated by the molecular-statistical method.     

Study of structural and thermodynamic parameters of adsorption layers using density functional theory. Local density and adsorption isotherms on spherical surfaces

Local density profiles in adsorption layers of Lennard-Jones fluids on two-dimensional adsorbents with spherical geometry and isotherms of excess (Gibbs) adsorption have been calculated using the classical density functional theory (approximations with weighting coefficients). The local density profiles have been found in hydrogen adsorption layers on C₆₀, C₂₄₀, and C₅₄₀ fullerene molecules. The calculations have been performed for both subcritical and supercritical temperature ranges. It has been shown that, at a pressure of 10 MPa and a temperature of 77 K, the gravimetric (mass) hydrogen density on C₆₀ fullerene is 7.6 wt %, which is in good agreement with the results of molecular dynamics simulation and experimental data. It has also been established that the gravimetric hydrogen density on C₆₀ fullerene is higher than that on C₂₄₀ and C₅₄₀ fullerenes, being comparable with its value in a slitlike pore of a carbon adsorbent.     

Isosteric heats of adsorption of carbon dioxide on zeolite MCM-22 modified by alkali metal cations

Adsorption isotherms of carbon dioxide were measured on cation-exchanged (Li⁺, Na⁺, K⁺, Cs⁺) MCM-22 zeolite with the molar ratio of Si/Al=15 and series of Na-MCM-22 of Si/Al molar ratios varying in the range from 15 to 40 at 273, 293, 313 and 333 K. Based on the known temperature dependence of CO₂ adsorption, isosteric heats of adsorption were calculated. The obtained dependences of isosteric heats related to the amount of CO₂ adsorbed have provided detailed insight into the interaction of carbon dioxide molecule with alkali metal cations.     

The adsorption of water isotopomers on carbon adsorbents

Adsorption isotherms were measured by the gas chromatography method over the temperature range 50–80°C, and isosteric heats of adsorption of water isotopomers were calculated in the region of low coverages on two active carbons (Norit and FAS) with similar volumes of micropores (0.38 and 0.37 cm³/g) but different chemical properties of the surface (the surface of active carbon (AC) Norit is hydrophilic and that of AC FAS, hydrophobic). The isotherms on AC Norit were convex and those on AC FAS concave toward the axis of adsorption. At all equilibrium pressures, the adsorption of H₂O and D₂O on AC Norit was much higher than on AC FAS. The isotherms of adsorption of H₂O and D₂O were quite similar on both adsorbents, but the isotherms and heats of adsorption of D₂O were slightly higher than those of H₂O because of small differences in adsorbate-adsorbent and adsorbate-adsorbate interactions and the structure of adsorbate molecules. Original Russian Text ? S.N. Lanin, N.V. Kovaleva, L.A. Litvincheva, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 2, pp. 351–355.     

Distribution coefficients in the water-dodecane system and heats of adsorption of ethylene glycol monoalkyl ethers on hydrophilic and hydrophobic carriers

The distribution coefficients in the water-dodecane system and the heats of adsorption of ethylene glycol monoalkyl ethers on hydrophilic (Silochrom S-80) and hydrophobic (Apiezon L on Chromaton) carriers were determined by gas chromatography. At low concentrations and 25°C, ethers with C₁-C₄ alkyl radials predominantly occurred in the aqueous phase, whereas the amyl ether of ethylene glycol was better soluble in the organic phase. Ethers adsorbed formed monomolecular and polymolecular coatings on the hydrophobic and hydrophilic adsorbents, respectively. The heats of adsorption of ethers on the hydrophilic adsorbent were higher than the heats of adsorption on the hydrophobic adsorbent by factors of from 1.93 to 2.20.     

Study of micropores accessibility in coals and activated carbon using immersion heats with C1–C4 alkanols

Two natural coals and a sample of activated carbon were studied with respect to micropores accessibility for C1–C4 alkanols using immersion calorimetry. From the immersion enthalpies, micropores volumes were calculated according to the Stoeckli–Kraehenbuehl (SK) equation, and obtained values were compared with the surface characteristics of gas adsorption measurements. Validity of the SK equation was found to be problematic for natural coals giving micropores volumes up to three times exceeding those of the CO₂ adsorption measurements. Reason for such discrepancy is discussed, with specific interactions between coals and alkanols likewise marked swelling of coals in the presence of alkanols being recognised as possible explanation. A drop in immersion heats with branched butanols was generally observed, enabling at least semi-quantitative evaluation of the abundance of micropores with diameters below ca. 0.7 nm that are inaccessible for tert-butanol.

     

Heat of adsorption of carbon dioxyde and ethene on zeolites a exchanged with Li+, Ni2+ and Cu2+

Various contents of Li⁺, Ni²⁺ or Cu²⁺ were introduced in zeolite NaA by conventional cation exchange. Crystal damages are observed on samples having suffered the lowerpH. The heat of adsorption of CO₂ and C₂H₄ was determined by isothermal calorimetry. Very high initial heats (100–120 kJ mol^?1) are found in NaA as well as in Li⁺ exchanged samples, perhaps due to chemisorption on alkaline cations; they vanish when Ni²⁺ or Cu²⁺ replaces more than 20% of Na⁺, in like manner with Co²⁺ or ZnI²⁺. For the adsorption of C₂H₄, high initial heats are absent in the case of NaA, but gradually appear when divalent cations are introduced. Apart from these strong initial values, the heats of adsorption present a plateauvs. the adsorbed amount. Abnormal low values at the plateau are indicative of crystal damages.     

Equilibrium adsorption of <Emphasis Type="Italic">n</Emphasis>-hexane and carbon tetrachloride vapors on sodium and polyhydroxyaluminum montmorillonites

Changes in the sorption and energy characteristics of montmorillonite upon the substitution of polyhydroxyaluminum cations for exchange sodium ions are studied. Based on the temperature dependence of the equilibrium parameters of adsorption, it was found that the substitution of polyhydroxyaluminum cations for exchange ions results in an increase of micropore volume and the heat of adsorption. The curves of heats of adsorption for C₆H₁₄ and CCl₄ have extreme characters. The observed maxima are related to the interactions of adsorbate molecules with and between active sites due to their compaction during the filling of micropore volume.     

Behavior of ethylene and ethane within single-walled carbon nanotubes. 1-Adsorption and equilibrium properties

Endohedral adsorption properties of ethylene and ethane onto single-walled carbon nanotubes were investigated using a united atom (2CLJQ) and a fully atomistic (AA-OPLS) force fields, by Grand Canonical Monte Carlo and Molecular Dynamics techniques. Pure fluids were studied at room temperature, T=300 K, and in the pressure ranges 4×10⁻⁴<p<47.1 bar (C₂H₄) and 4×10⁻⁴<p<37.9 bar (C₂H₆). In the low pressure region, isotherms differ quantitatively depending on the intermolecular potential used, but show the same qualitative features. Both potentials predict that ethane is preferentially adsorbed at low pressures, and the opposite behavior was observed at high loadings. Isosteric heats of adsorption and estimates of low pressure Henry’s constants, confirmed that ethane adsorption is the thermodynamically favored process at low pressures. Binary mixtures of C₂H₄/C₂H₆ were studied under several (p,T) conditions and the corresponding selectivities towards ethane, S, were evaluated. Small values of S<4 were found in all cases studied. Nanotube geometry plays a minor role on the adsorption properties, which seem to be driven at lower pressures primarily by the larger affinity of the alkane towards the carbon surface and at higher pressures by molecular volume and packing effects. The fact that the selectivity towards ethane is similar to that found earlier on carbon slit pores and larger diameter nanotubes points to the fact that the peculiar 1-D geometry of the nanotubes provides no particular incentive for the adsorption of either species.     

In situ small angle X-ray scattering and benzene adsorption on polymer-based carbon hollow fiber membranes

The structural changes and the mechanism of benzene adsorption on microporous carbon hollow fiber membranes with different surface and pore network properties have been investigated by in situ small-angle X-ray scattering (SAXS) and benzene adsorption. Benzene adsorption measurements have been carried out in situ with SAXS alongside an adsorption/desorption isotherm cycle at 293 K with the aid of a specially constructed adsorption sample cell. In addition low-pressure C₆H₆ and high-pressure CO₂, CH₄ and N₂ adsorption isotherms have been performed. Two carbon hollow fiber membranes, both prepared by controlled pyrolysis procedures of polyimide membrane precursor, were under study. During benzene adsorption the intensity of the SAXS curves changes in a way that depends on how the pores are filled and the contrast fluctuations occur. The SAXS data have been modeled by evaluating the form factor of lamellar micropores upon filling with C₆H₆. The existence of ultra micropores within the surrounding matrix was also taken into account. The results suggest that the arrangement of the ultra micropores on the non-activated membrane is in such a way that the access of benzene to the micropores is restricted, resulting in an incomplete filling. On the other hand, the activation process generates a more accessible pore network where the micropores are completely filled.     

1,3-Dipolar addition reactions to fullerenes: the role of the local curvature of carbon surface

Structural peculiarities of fullerenes C₂₀, C₂₄, C₃₀, C₃₆, C₄₀, C₆₀, C₇₀, and C₇₆ and their adducts with 1,3-dipolarophiles (ozone and diazomethane) were investigated by the DFT method with the PBE functional. A correlation between the heats of 1,3-dipolar addition reactions and the carbon surface curvatures at reaction sites in the original fullerene molecules was found.