Surface-stationary phase

Gas chromatography has come into existence as an analytical method. The separation of analysed liquid or gaseous mixtures is the result of the difference in partition coefficients of their components between the gas (mobile) phase and liquid or solid surface (stationary phase). Depending on the kind of stationary phase the method is called partition or adsorption chromatography. The retention volume, defined as the volume of mobile phase causing the elution of the sample from the chromatographic column, is the value characterizing the interaction between the solute and stationary phase. 

A form of chromatography in which the stationary phase is immobilized on a flat surface. 

Analytical separations may be classified in three ways by the physical state of the mobile phase and stationary phase by the method of contact between the mobile phase and stationary phase or by the chemical or physical mechanism responsible for separating the sample s constituents. The mobile phase is usually a liquid or a gas, and the stationary phase, when present, is a solid or a liquid film coated on a solid surface. Chromatographic techniques are often named by listing the type of mobile phase, followed by the type of stationary phase. Thus, in gas-liquid chromatography the mobile phase is a gas and the stationary phase is a liquid. If only one phase is indicated, as in gas chromatography, it is assumed to be the mobile phase. 

The most widely used particulate support is diatomaceous earth, which is composed of the silica skeletons of diatoms. These particles are quite porous, with surface areas of 0.5-7.5 m /g, which provides ample contact between the mobile phase and stationary phase. When hydrolyzed, the surface of a diatomaceous earth contains silanol groups (-SiOH), providing active sites that absorb solute molecules in gas-solid chromatography. 

The stationary phase in LC is a fine granular solid such as silica gel. It can be used as such (mainly for nonpolar compounds), or the granules can be modified by a surface-bonded coating that changes (reverses) the polarity of the gel. A very small selection of stationary phases is listed in Table 35.2. 

Reversed-phase columns are used to separate polar substances. Although in LC the stationary phase is a solid, it is necessary to bear in mind that there may be a thin film of liquid (e.g water) held on its surface, and this film will modify the behavior of sample components equilibrating between the mobile and stationary phases. A textbook on LC should be consulted for deeper discussion on such aspects. 

Hydrophobic Interaction Chromatography. Hydrophobic interactions of solutes with a stationary phase result in thek adsorption on neutral or mildly hydrophobic stationary phases. The solutes are adsorbed at a high salt concentration, and then desorbed in order of increasing surface hydrophobicity, in a decreasing kosmotrope gradient. This characteristic follows the order of the lyotropic series for the anions ... 

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 the course of mixture separation, the composition and properties of both mobile phase (MP) and stationary phase (SP) are purposefully altered by means of introduction of some active components into the MP, which are absorbed by it and then sorbed by the SP (e.g. on a silica gel layer). This procedure enables a new principle of control over chromatographic process to be implemented, which enhances the selectivity of separation. As a possible way of controlling the chromatographic system s properties in TLC, the pH of the mobile phase and sorbent surface may be changed by means of partial air replacement by ammonia (a basic gaseous component) or carbon dioxide (an acidic one). 

Synthetic chiral adsorbents are usually prepared by tethering a chiral molecule to a silica surface. The attachment to the silica is through alkylsiloxy bonds. A study which demonstrates the technique reports the resolution of a number of aromatic compoimds on a 1- to 8-g scale. The adsorbent is a silica that has been derivatized with a chiral reagent. Specifically, hydroxyl groups on the silica surface are covalently boimd to a derivative of f -phenylglycine. A medium-pressure chromatography apparatus is used. The racemic mixture is passed through the column, and, when resolution is successful, the separated enantiomers are isolated as completely resolved fiactions. Scheme 2.5 shows some other examples of chiral stationary phases. 

Displacement development is only really effective if the stationary phase is a solid and the solutes are adsorbed on its surface. The sample mixture is placed on the front of the distribution system, and the individual solutes compete for the immediately available adsorption sites. Initially, all the nearby adsorbent sites will be saturated with the most strongly held component. As the sample band moves through the system the next available adsorption sites will become saturated with the next most... 

If, in LC, the mobile phase is a mixture of solvents, the pore contents will not be homogeneous. One solvent component, the one with stronger interactions with the stationary phase, will be preferentially adsorbed on the surface [10] relative to the other. Consequently, although the bulk of the contents the pores, (Vp(i)), will have... 

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