Silica-gel surface

Content of chemisorbed and physisorbed water on a silica gel surface ... 

Interaction of periodate with immobilized on the silica gel surface QAS - trinonyloctadecylammonium chloride has been studied. The optimal conditions of periodate sorption have been investigated. Interference of main components of sea water has been examined. 16500-fold excess of Ck, 11000-fold excess of Na+, 380-fold excess of K+, 420-fold excess of Ca +, 500-fold excess of Mg +, 60-fold excess of HC03, 20-fold excess of B03, 280-fold excess of SO do not interfere with the determination of periodate. 

Consider the bi-layer adsorption of strongly polar solvent (B) (e.g., ethyl acetate) from a solution in a dispersive solvent (A) (e.g., n-heptane) onto a silica gel surface, as depicted in Figure 6. 

Let the concentration of solvent (B) in equilibrium with the silica gel surface be (c) g/ml. Let a fraction (a) of the surface be covered with a mono-layer of the polar solvent (B) and, of that fraction (a), let a fraction ( 3) be covered by a second layer of the polar solvent (B). The number of molecules striking and adhering to the surface covered with a mono-layer of polar solvent (A) and that covered with a mono-layer of solvent (B) per unit time will be (n ) and be (n") respectively. Furthermore, let the number of molecules of solvent (A) leaving the mono-layer surface and the bi-layer surface per unit time be ni and 2 respectively. Now, under conditions of equilibrium,... 

Kagel (29) found that whereas pyridine is hydrogen bonded to a silica gel surface 2-chloropyridine is not, the spectrum of 2-chloropyridine adsorbed on silica gel being identical with that of the liquid, and concluded that steric hindrance probably prevents hydrogen bond formation in this case. 

Nevertheless, silica gel is the material of choice for the production of the vast majority of LC stationary phases. Due to the reactive character of the hydroxyl groups on the surface of silica gel, various organic groups can be bonded to the surface using standard silicon chemistry. Consequently, the silica gel surface can be modified to encompass the complete range of interactive properties necessary for LC ranging from the highly polar to almost completely dispersive. 

Solute Interactions with the Silica Gel Surface (Mobile Phase n-Heptane/Chloroform)... 

There are basically two types of interaction that can take place between a solute and the silica gel surface. Firstly, the solute molecule can interact with the adsorbed solvent layer and rest on the surface of... 

Solute/Solvent Interactions with a Silica Gel Surface... 

The identification of bi-layer adsorption of polar solvents on the surface of silica gel arose from some work by Scott and Kucera (5) who measured the adsorption isotherms of the some polar solvents, ethyl acetate, isopropanol and tetrahydrofuran from n-heptane solutions onto silica gel. The authors found that the experimental results for the more polar solvents did not fit the simple mono-layer adsorption equation and, as a consequence, the possibility of bi-layer adsorption on the silica gel surface was examined. 

In contrast, the mono-layer of methanol is built up much more slowly and is not complete until the concentration of methanol in the aqueous mixture is about 35%w/v. The behavior of methanol on the reverse phase is reminiscent of the adsorption of chloroform on the strongly polar silica gel surface. The complementary nature of the silica gel surface and that of the reverse phase is clearly apparent. It is also clear that strongly dispersive solvents might form bi-layers on the reverse phase surface just as polar solutes form bi-layers on the highly polar surface of silica gel. In fact, to date there has been no experimental evidence furnished that would support the formation of bi-layers on the surface of reverse phases, although their formation is likely and such evidence may well be forthcoming in the future. 

Solutes will interact with the reverse phase surface in much the same way as they do with the silica gel surface. There will be basically two forms of interaction, by sorption and by displacement. Sorption interaction has been experimentally confirmed by Scott and Kucera (10) by measuring the adsorption isotherm of acetophenone on the reverse phase RP18 from a 40%w/v acetonitrile mixture in water. The authors noted that there was no change in the acetonitrile concentration, as the solute was adsorbed. Displacement interactions, although certain to occur, do not appear to have been experimentally demonstrated to date. 

The silica gel surface is extremely polar and, as a result, must often be deactivated with a polar solvent such as ethyl acetate, propanol or even methanol. The bulk solvent is usually an n-alkane such as n-heptane and the moderators (the name given to the deactivating agents) are usually added at concentrations ranging from 0.5 to 5% v/v. Silica gel is very effective for separating polarizable materials such as the aromatic hydrocarbons, nitro hydrocarbons (aliphatic and aromatic), aliphatic ethers, aromatic esters, etc. When separating polarizable substances as opposed to substances with permanent dipoles, mixtures of an aliphatic hydrocarbon with a chlorinated hydrocarbon such as chlorobutane or methylene dichloride are often used as the mobile... 

Reversed-phase PLC precoated plates are based on silica gel matrices with chemical modifications in such a manner that the accessible polar, hydrophilic silanol groups at the silica gel surface are replaced by nonpolar, hydrophobic alkyl chains via silicon-carbon bonds. For preparative purposes, up to now only PLC precoated RP plates with C-18 modification are available. This abbreviation is often also designated as RP-18, meaning that an octadecyl alkyl chain is chemically bonded to the silica gel surface. 

Silica gel. Silica gel is a porous amorphous form of silica (Si02) and is manufactured by acid treatment of sodium silicate solution and then dried. The silica gel surface has an affinity for water and organic material. It is primarily used to dehydrate gases and liquids. 

Gardner 45) has observed the spectrum of Cl atoms adsorbed on a silica-gel surface at 77°K. The experimental results indicate that the orbital degeneracy of the 3p atomic orbital has been removed as a result of the electrostatic interaction with the surface. From the occupancy of the atomic orbitals one would predict that gx >011 — 2.00 and indeed the experimental g values are = 2.012 with g = 2.003. The hyperfine coupling indicates that the impaired electron is highly localized in the 3p orbitals. 

Methyl radicals formed on a silica gel surface are apparently less mobile and less stable than on porous glass (56, 57). The spectral intensity is noticeably reduced if the samples are heated to —130° for 5 min. The line shape is not symmetric, and the linewidth is a function of the nuclear spin quantum number. Hence, the amplitude of the derivative spectrum does not follow the binomial distribution 1 3 3 1 which would be expected for a rapidly tumbling molecule. A quantitative comparison of the spectrum with that predicted by relaxation theory has indicated a tumbling frequency of 2 X 107 and 1.3 X 107 sec-1 for CHr and CD3-, respectively (57). 

Small pore silica gel surface, drying stages of, 23 69-71... 

Interestingly, the ratio of the /i,y-adduct to the y,d-adduct formed from 2-cyclo-hexenone and allene also changed in favor of the latter on a silica gel surface [44]. 

Figure 8.2. Fluorescence emission and excitation spectra of a strongly scattering sample as detected in forward (Ff) and backward (Fb) direction. (Pyrene adsorbed on silica gel, surface loading cpyr = 5.5-10-7 mol g l, spec, surface area cisiiica = 500 m2 g ),...

Sindorf, D.W. and Maciel, G.E., Silicon-29 nuclear magnetic resonance study of hydroxyl sites on dehydrated silica gel surfaces, using silylation as a probe, J. Phys. Chem.,%1, 5516, 1983. 

Gab, S Saravanja, V., and Korte, F. Irradiation studies of aldrin and chlordene adsorbed on a silica gel surface. Bull. Environ. 

In the case of amines the type of interaction shown in Figure 15.9 may occur. The shorter the alkyl chain length on the silica gel surface the more likely it is that adsorption also plays a part in the extraction. It is possible to buy highly endcapped reverse-phase silica gels where most of the residual silanols have been blocked but it may be better to take advantage of the mixed lipophilic and adsorptive properties of reverse phases which have not been endcapped. 

Further insight into molecular binding to the solid surface is possible from a determination of the surface area occupied by each molecule in a mono-layer. In a detailed study of the adsorption of a range of substances on silica gel (surface area 200 m2/g), Weis and coworkers9 found that a relatively small number of polynuclear aromatic substances occupied all available binding sites, indicating that the molecules are oriented parallel to the solid surface to... 

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