Chromatographic determination of the thermodynamic adsorption characteristics of saturated tricyclic hydrocarbon isomers using capillary columns with graphitized carbon black

Summary Due to their high efficiency capillary columns packed with graphitized thermal carbon black (GTCB) permit to realize high selectivity in the chromatographic separation of isomers on the flat surface of this adsorbent. However, the increase in the efficiency is connected to a considerable increase of the pressure drop across the column which hinders the determination of the thermo-dynamic adsorption characteristics. The optimum conditions for the preparation of such columns designed both for analytical purposes and for thermodynamic measurements of the individual isomers have been established. The retention volumes for small (zero) sample size (Henry constants for adsorption on GTCB) of six isomers of tricyclo(8,4,0,0^2,7)tetradecane (perhydrophenanthrene), seven isomers of tricyclo-(7,4,0,0^2,6)tridecane (1,2-cyclopentanodecalin) and six isomers of tricyclo(7,3,0,0^2,6)dodecane have been determined. The Henry constants increase with the flattening of the isomeric molecules in these hydrocarbon series. A qualitative procedure of identification of the isomers on the basis of optimum orientation of their molecules on a flat surface has been considered.     

多微孔活性炭的制备及对二甲苯的吸附研究

研究了以木质活性炭颗粒为原料,通过KOH再活化的方法制备多微孔活性炭的方法。考察了活性炭和KOH的最佳质量比例,并通过低温氮吸附、SEM、XRD等手段表征了样品的比表面、孔结构、孔分布、颗粒形貌和晶体结构;通过对含间二甲苯50mg.L-1的气流的吸附实验表征了所制备活性炭的二甲苯去除能力,实验结果表明,经过KOH再活化显著调高了样品的间二甲苯吸附容量,这很可能和样品中发达的微孔结构有关。     

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.     

多微孔活性炭的制备及对二甲苯的吸附研究

研究了以木质活性炭颗粒为原料, 通过KOH再活化的方法制备多微孔活性炭的方法。考察了活性炭和KOH的最佳质量比例, 并通过低温氮吸附、SEM、XRD等手段表征了样品的比表面、孔结构、孔分布、颗粒形貌和晶体结构;通过对含间二甲苯50 mg·L^-1的气流的吸附实验表征了所制备活性炭的二甲苯去除能力, 实验结果表明, 经过KOH再活化显著调高了样品的间二甲苯吸附容量, 这很可能和样品中发达的微孔结构有关。     

Retention of diphenyls,terphenyls, phenylalkanes and fluorene on graphitized thermal carbon black

Summary This paper defines values of retention volumes for zero surface coverage (Henry's constant) at different temperatures, retention indices and variations of the internal energy (differential heats of adsorption) of diphenyl and its alkyl derivatives, terphenyls, diphenylmethane, triphenylmethane, diphenylethanes and fluorene on graphitized thermal carbon black (GTCB). Adsorption on GTCB takes place in accordance with the geometry of these molecules, the strongest adsorption being observed for para-terphenyl with least inhibited internal rotation of the molecule, while the weakest adsorption occurs for 2,6,2,6-tetramethyldiphenyl with the most inhibited internal rotation of the molecules. The flat molecules of fluorene are adsorbed on GTCB more readily than the nonflat molecules of diphenylmethane.     

Molecular statistical calculations of the adsorption of proline and its hydroxy derivatives on graphitized thermal carbon black

The thermodynamic characteristics of adsorption of proline and its hydroxy derivatives on the surface of graphitized thermal carbon black (GTCB) were calculated. The arrangement of hydroxyl groups in the amino acid molecule was shown to influence their adsorption on GTCB. The influence of internal rotation angles in proline and its hydroxy derivative molecules on their adsorption on GTCB was studied.     

A study of adsorption of some bicyclo [2.2.1] heptane derivatives on graphitized thermal carbon black

Retention volumes at zero sample size (Henry's constants of adsorption equilibrium), Kovats' indices and the changes in differential molar internal energy and entropy upon adsorption are found for bicyclo[2.2.1] heptane (norbornane), six isomeric dimethylnorbornanes and 7,7′-bisnorbornane by gas adsorption chromatography on packed columns with GTCB. A molecular statistical calculation of the thermodynamic characteristics of adsorption is carried out and the results are compared with experimental data.     

Experimental and molecular statistical study of alkyladamantane adsorption on graphitized thermal carbon black

Experimental measurements and molecular statistics methods were used to calculate thermodynamic characteristics of adsorption (TCA) of alkyladamantanes of different structure on the surface of hydrogen-treated graphitized thermal carbon black (GTCB) Carbopack C HT. High selectivity of separation of isomeric alkyladamantanes on GTCB is due to specific features of their geometry and electronic structure. The influence of the spatial structure of adsorbates on the TCA was established. Special attention was given to analysis of the heat capacities of adsorption. The best agreement between the experimental TCA and those calculated by the molecular statistics methods is achieved when the “cage effect“ in the adamantane ring is taken into account. The corresponding corrections are introduced into the parameters of the atom-atomic potential function of pair intermolecular interaction of the Me groups with the carbon atoms of the basal face of graphite, which are localized in the nodal positions of the lattice. The critical parameters for a large group of alkyladamantanes were calculated in terms of the additive group Lydersen method. A set of various topological indices used further for constructing structure-retention correlations on GTCB was obtained.     

Adsorption of dyes on activated carbon and graphitic thermal carbon black

The adsorption of a basic dye (Methylene Blue; MB) and an acidic dye (Acid Orange; AO) has been studied on three activated carbons (ACs; FAS, SKD, and BAU) significantly differing in their porous structures and surface concentrations of ion-exchange groups and on graphitic thermal carbon black (GTCB). The effective specific surface area of FAS, SKD, and BAU determined by dye adsorption is, respectively, 60, 50, and 40% of the BET nitrogen adsorption surface area. The MB uptake on ACs and GTCB increases with rising pH, while the AO uptake decreases. Addition of an electrolyte (0.3 M NaCl) virtually does not effect the adsorption of dyes on ACs and GTCB. It is suggested that hydrophobic interactions, and not ionic ones, are the major contributors to the adsorption of dyes on ACs.     

Gas chromatographic investigation of adsorption equilibria on graphitized thermal carbon black

Summary Retention volumes and heats of adsorption at low surface coverages of graphitized thermal carbon black (GTCB) for C₆–C₁₄ aromatic hydrocarbons have been determined. The dependence of heats of adsorption of these molecules on their structure and the number of carbon atoms in the molecule have been investigated. Substitution in the ring in methylbenzenes is not equivalent to the lengthening of the side-chain in the isomers of n-alkylbenzenes and gives rise to a much greater increase in the retention volumes and heats of adsorption.     

Molecular Modeling in Chromatoscopy as a New Tool in the Structure Elucidation of Novel Isomers by GC/MS

The importance of gas–solid chromatography on graphitized thermal carbon black (GTCB) as a source of additional data for the positive structural elucidation of novel isomers by gas chromatography–mass spectrometry is discussed. The retention parameters of isomers being investigated were calculated by Kiselev's method (chromatoscopy) to predict the order of their separation on a column packed with GTCB. To extend the possibilities of this method and to improve the accuracy of a prediction of retention parameters, the molecular mechanics was used for the optimization of hypothetical molecular models of isomers required for these calculations. As a test mixture 11 isomers of perhydroanthracene and perhydrophenanthrene were consedered. The predicted elution order from the column packed with GTCB of these isomers, calculated on the basis of molecular models optimized by molecular mechanics appeared to be close to the experiment, whereas the result obtained by a conventional approach appeared to fail. Molecular modeling in chromatoscopy was used for the structural elucidation of novel isomers of perhydroxanthene (PHX) and perhydro-4-thia-s-indacene (PHTI), which were found by GC–MS in reaction mixtures. The evidence for this assignment-based on the obtained GC and MS data, is discussed.     

Die Retention von Indan- und Inden-Kohlenwasserstoffen auf graphitiertem thermischen Ruß

Zusammenfassung Es werden die Werte der Retentionsvolumina, der Retentionsindices und andere thermodynamische Adsorptionscharakteristiken von zehn Indan- und Inden-Kohlenwasserstoffen mit 9–11 Kohlenstoffatomen auf graphitiertem thermischem Ruß (GTR) bestimmt. Es wurde festgestellt, daß auf GTR die Kohlenwasserstoffe der Inden-Reihe am stärksten adsorbiert werden und am schwächsten cis-Hydrandan, was mit den Besonderheiten der geometrischen Struktur dieser Verbindungen zusammenhängt. Es wird die Möglichkeit der Anwendung von GTR für die vollständige Trennung der cis- und trans-Isomeren von Hydrindan gezeigt.

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Retention of indan and indan-type hydrocarbons on graphitized thermal carbon black

Summary The retention volumes, retention indices and other thermodynamic values characteristic of the adsorption of ten indan-hydrocarbons having 9–11 carbon atoms were determined on graphitized thermal carbon black (GTCB). It is shown that GTCB adsorbs strongest the hydrocarbons of the indan series and weakest cis hydrindan. This is related to the peculiarities of the geometric structure of the compounds. The possibility of the application of GTCB for the complete separation of cis and trans hydrindan is shown.

     

Cobalt(II) and cobalt(III) coordination polymers constructed from flexible bis-imidazole and polycarboxyl co-ligands: syntheses,crystal structures and properties

Two metal coordination polymers, namely {[Co(1,3-BIP)(OBA)]·0.5H₂O}_n (SNUT-1) and [Co₂(µ-η¹:η¹-O₂)(1,3-BIP)₂(PMA)]_n (SNUT-2), where 1,3-BIP?=?1,3-bis(imidazol)propane, H₂OBA?=?4,4′-oxybis(benzoate) and H₄PMA?=?benzene-1,2,4,5-tetracarboxylic acid, were prepared by hydrothermal methods. Single-crystal X-ray analysis revealed that the structure of SNUT-1 consists of a 3D?→?3D twofold interpenetrating network that can be described as a 4-connected uninodal net with (6⁵·8) topology. The structure of SNUT-2 consists of a 3D framework which can be described as a (4,5)-connected binodal net with (4²·6³·8⁴·10) (3³·4²·5) topology. The gas adsorption properties of SNUT-1 and photocatalytic activity of SNUT-2 for the degradation of Rhodamine B have been explored.

     

Applications of cationic gemini surfactant in preparing multi-walled carbon nanotube contained nanofluids

Stable homogeneous nanofluids of multi-walled carbon nanotubes (MWNTs) were prepared by using gemini cationic surfactant trimethylene-1,3-bis (dodecyldimethyl ammonium bromide), abbreviated as 12-3-12,2Br⁻¹, as dispersing agents. Zeta potential and FT-IR measurements were employed to investigate the adsorption mechanism of 12-3-12,2Br⁻¹ on MWNTs. The interactions between MWNTs and 12-3-12,2Br⁻¹ through hydrophobic segments cause hydrophilic MWNT-suspended medium interfaces with high positive charges, which enables the nanofluids to be stable for long periods. At relatively low temperatures the superfluous surfactant molecules form stable layer or column micelles, making an increase in the viscosity of nanofluids. Only 0.6 wt% gemini surfactant was used to obtain 0.5 wt% MWNT dispersions. The dispersions show no MWNTs precipitation for at least 5 weeks.     

On the synthesis of siloxanes. XXIV. Nucleophilic substitution reactions of 2-functional 1,3-dioxa-2-4,7-trisilacylcloheptanes and 1,3-dioxa-2,4,8-trisilacyclooctanes

2-Hydrogen-1,3-dioxa-2,4,7-trisilacycloheptanes and 2-hydrogen-1,3-dioxa-2,4,8-trisiacyclooctanes, each as a mixture of three configurational isomers, were synthesized and halogenated with chlorine and bromine in the presence of pyridine. The stereochemical course of the halogenation reactions was studied by gas chromatography. 2-Chloro-2,4,7-trimethyl-4,7-bis(trimethyl-siloxy)-1,3-dioxa-2,4,7-trisiacycloheptanes and 2-chloro-2,4,7-trimethyl-4,7-diphenyl-1,3-dioxa-2,4,7-trisilacycloheptanes reacted with alcohols in the presence of pyridine, triethylamine, or 2,6-dimethylpyridine. Gas chromatography, and¹H NMR and²⁹Si NMR spectroscopy were used to investigate the stereochemistry of these substitution reactions. It has been found that all reactions proceed with retention of configuration and that the differences of the relative reactivities of the configurational isomers were distinctly smaller than those observed for reactions of the configurations isomers of functional cyclotrisiloxanes.     

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO₂ from flue gas or natural gas. Here, a typical metal-organic framework HKUST-1(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO₂ adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO₂ storage capacity of HKUST-1 doped with moderate quantities of Li⁺, Na⁺ and K⁺, individually, was greater than that of unmodified HKUST-1. The highest CO₂ adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST-1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO₂ than those of N₂. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO₂ after 10 cycles.     

Chemical structure and surface activity

Surface tension measurements on aqueous solutions of 2-alkyl-2-methyl-1,3-dioxolanes, 2-alkyl-4-methyl-1,3-dioxolanes, and 2-alkyl-1,3-dioxanes at a temperature of 293.2 K are presented. The surface tension isotherms obtained were used to calculate some adsorption parameters, i. e. the efficiency of surface tension reduction, pC₂₅, surface excess concentration, , and surface area,A, per molecule in the adsorption layer. The Temkin adsorption isotherm equation was used to calculate standard free energy of adsorption, G ⁰ _=0.5 . The increments for a methylene group in the alkyl chain, G ^o [–CH₂–], and for the residual part of the molecule, G ^o [W], were also determined.The results obtained show that: (i) an increase in alkyl chain length at the C-2 carbon atom of the ring by one methylene unit brings about a marked increase in surface activity; (ii) the introduction of a methyl group into the 1,3-dioxolane ring (i. e., at C-2 or C-4 atom) has a weaker effect on surface activity of alkyl-substituted 1,3-dioxolanes, and (iii) the contribution of the 5- and 6-membered 1,3-dioxacyclane rings to a total surface activity of, respectively, 2-alkyl-1,3-dioxolanes and 2-alkyl-1,3-dioxanes is similar.     

An experimental and theoretical investigation on adsorption properties of some diphenolic Schiff bases as corrosion inhibitors at acidic solution/mild steel interface

The effect of novel synthesized three Schiff bases, namely, 1,3-bis[2-(2-hydroxy benzylidenamino) phenoxy] propane (P1), 1,3-bis[2-(5-chloro-2-hydroxybenzylidenamino) phenoxy] propane (P2), and 1,3-bis[2-(5-bromo-2-hydroxybenzylidenamino) phenoxy] propane (P3), on the corrosion of mild steel in 0.1 M HCl was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy methods. Polarization measurements suggest that P1 acts as mixed type inhibitor while P2 and P3 behave as mainly cathodic inhibitors for acidic corrosion of steel. All electrochemical measurements show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that inhibitive actions of inhibitors were mainly due to adsorption on steel surface. Adsorption of these inhibitors follows Temkin adsorption isotherm. The correlation between the adsorption ability of inhibitors and their molecular structures has been investigated using quantum chemical parameters obtained by MNDO semi-empirical method. Calculated quantum chemical parameters indicate that Schiff bases adsorbed on steel surface by chemical mechanism.     

Alkylation of 1,2,3-benzotriazole with iodomethyl ketones

Solvent-free reactions of 1,2,3-benzotriazole with 1-iodopropan-2-one and 1,3-diiodopropan-2-one in the absence of a catalyst involved alkylation of the heteroring at the N¹ atom and subsequent quaternization at the N³ atom with formation of 1,3-bis(2-oxopropyl)-1H-1,2,3-benzotriazolium triiodide which is a new conducting ionic liquid. The reaction of 1,2,3-benzotriazole with 1,3-diiodopropan-2-one was accompanied by reductive deiodination of the iodomethyl groups in the initial ketone with hydrogen iodide liberated by N¹-alkylation. Triiodide ion readily exchanges for nitrate ion by the action of AgNO₃ to produce 1,3-bis(2-oxopropyl)-1H-1,2,3-benzotriazolium nitrate. The reaction of 1,2,3-benzotriazole with 2-iodo-1-phenylethan-1-one in melt resulted in the formation of 1,3-bis(2-oxo-2-phenylethyl)-1H-1,2,3-benzotriazolium triiodide.