Silica gels analysis

This chapter presents a close look at the standard silica gel analysis of a shale oil naphtha with an evaluation of its effectiveness, a description of the new method now used to quantify olefins in shale oil products, a summary of results of the hydrocarbon-type analysis using the new method for a series of three related shale oils, and a discussion of the information on olefin-type compounds which can be revealed by IR examination of whole shale oils. The paper concludes with a brief discussion of additional applications of the hydroboration of olefins to problems of interest to the petroleum analyst. 

Fig. XVII-30. Adsorption of Na on a silica gel at 77.3 K, expressed as a u-/ plot, illustrating a method for micropore analysis. (From Ref. 230.)...

This is used extensively for qualitative analysis, for it is a rapid process and requires simple apparatus. The adsorbent is usually a layer, about 0 23 mni. thick, of silica gel or alumina, with an inactive binder, e.g. calcium sulphate, to increase the strength of the layer.. A. i i slurry of the absorbent and methanol is commonly coated on glass plates (5 20 cm. or 20 x 20 cm.), but microscope... 

Mass-action model of surfactant micelle formation was used for development of the conceptual retention model in micellar liquid chromatography. The retention model is based upon the analysis of changing of the sorbat microenvironment in going from mobile phase (micellar surfactant solution, containing organic solvent-modifier) to stationary phase (the surfactant covered surface of the alkyl bonded silica gel) according to equation ... 

In this work the results of reseai ch common sorbtion-X-Ray-fluorescence analysis of Pb(II), Cd(II), Zn(II) and Mo(VI) with preconcentration on complexing chemical silica gel modified with mercaptane groups and modified with 8-hydroxyquinoline were described. The conditions and limits of determination of the X-Ray-fluorescence method in the thin lawyers ai e discussion. 

THE CONCENTRATION AND ANALYSIS OF TRACES OF NOBLE METALS USING SILICA GELS WITH GRAFTED SULFUR-CONTANING COMPOUNDS... 

Note The reagent can be employed for qualitative and quantitative analysis on silica gel and RP layers. Ammonia, amine and acid-containing mobile phases should be completely removed beforehand. Amino phases cannot be employed. The NBD-chloride reagent is not as sensitive as the DOOB reagent (qv.) on RP phases. 

After anilide 30 (1.12 g, 4.46 mmol) is hydrolized in 6 M HCl at 100 °C (by TLC analysis), toluene (5 mL) is added and then aldehyde 5 (0.74 mL, 8.92 mmol) is added dropwise at the same temperature. The reaction was stirred for 2 h and then cooled to room, temperature. The aqueous layer is removed and neutralized with aqueous NaOH to afford 31 as a crystalline solid. The crude product is purified by silica gel chromatography (hexanesiethyl acetate, 5 1) to give 31 (802 mg, 70%) as colorless crystals, mp 103 °C. 

The development of bonded phases (Section 8.2) for liquid-liquid chromatography on silica-gel columns is of major importance. For example, the widely used C-18 type permits the separation of moderately polar mixtures and is used for the analysis of pharmaceuticals, drugs and pesticides. 

The only 5//-1,3,6-triazonine system which has been reported and is fully supported by spectral data and elemental analysis is obtained by reaction of the imine 1 with chloroacetic acid and polyphosphoric acid.22 From a mixture of products, 2-chloro-6-(chloromethyl)-13-phenyl-dibenzo[e/, h [, 3,6]triazonine (2) was separated by silica-gel flash chromatography in poor yield. 

The reaction is quenched by the addition of 1.28 g (2.94 mmol) of molybdenum pentoxidc/pyridinc/UMPA, and the yellow slurry is stirred initially at OX (30 min), then for 45 min at 25 X. The mixture is added to 1 N sodium hydroxide and extracted with diethyl ether. The ethereal solution is washed with brine, dried over Na,S04 and concentrated in vacuo to give 0.705 g (100%) of an oily, light-yellow solid. Analysis of the crude aldol adduct by 1 C NMR and analytical HPLO (Waters, Radial Pak, 8 mm x 10 cm, silica gel, ethyl acetate/hexane, 15 85) indicates only one. un-diastereomer (2X3S ) accompanied by approximately 10% of the two ethyl acetate/hexane affords fine white needles yield 0.359 g (57%) mp 155.5 156.5X (a]u -92.5 (c = 0.0294, CHCfi). 

From the study of the influencing of single reactions by products and by other added substances and from the analysis of mutual influencing of reactions in coupled systems, the following conclusions can be drawn concerning adsorption of the reaction components. (1) With the exception of crotyl alcohol on the platinum-iron-silica gel catalyst, all the substances present in the coupled system, i.e. reactants, intermediate products, and final products, always adsorbed on the same sites of the catalytic surface (competitive adsorption). This nonspecificity was established also in our other studies (see Section IV.F.2) and was stated also by, for example, Smith and Prater (32), (2) The adsorption of starting reactants and the desorption of the intermediate and final products appeared in our studies always as faster, relative to the rate of chemical transformations of adsorbed substances on the surface of the catalyst. 

The thin-layer technique (CA 60, 6691) utilizes aliquots of proplnt ether extract (I) and the ether soln (II) of a known mixt. II consists of nitrates of glycerol and glycol, di-Bu or di-Et phthalates, Et or Me centralites, DNT, and diphenylamine. The chromatoplates are made of 85 15 silica gel and plaster of Paris. These plates, containing spots of I and 11, are developed with 1 1 C6H6-petroleum ether, then sprayed with specific detectors by color. The method is much quicker and easier than chemical analysis and simpler than infrared spectroscopy and column chromatography... 

An aqueous solution of HF (40%, 2eq.) was added to a solution of the substrate in MeCN at either 0°C or at ambient temperature. When the reaction was complete by t.l.c. analysis (ca. 30min), excess sodium hydrogen carbonate solution (8%) was added, and the product was extracted with ether. The product was purified by flash chromatography on silica gel. 

A solution of Pd(OAc)2 (0.05 mmol) and bis(diphenylphosphino)ethane (0.05 mmol) in acetonitrile (1 ml) was heated gently to reflux, at which time a solution of the silyl enol ether (1 mmol) and diallyl carbonate (2 mmol) in MeCN (4 ml) was added in one portion. The mixture was heated under reflux for 1-3 h, the course of reaction being monitored by t.l.c. or g.l.c. analysis. On completion, the cooled reaction solution was filtered through fluorosil. The pure a/ -unsaturated compound was isolated by column chromatography on silica gel (70-95%). 

The checkers found that a fraction, b.p. 45-71° (18 mm.), had the following spectral properties infrared (carbon tetrachloride) no absorption in the 3300-1600 cm.-1 region attributable to OH, C=0, or C=C vibrations proton magnetic resonance (chloroform-d) <5, multiplicity, number of protons, assignment 3.1-4.2 (multiplet, 4, CH—Cl, CH—O, and C//2—O), 1.0-2.5 (multiplet, 7, GH3 and 2 x C//2)-Thin layer chromatographic analysis of this fraction on silica gel plates using chloroform as eluent indicated the presence of a major component (the cis- and fraus-isomers), Rf = 0.60, and a minor unidentified component, Rf = 0.14. 

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