Elution isotherm

Under such circumstances the temperature can be programmed up to the maximum stable temperature for the solutes and any remaining solutes in the column must then be eluted isothermally. This situation can often occur in the separation of substances... 

Therefore the elution isotherm should be very similar to the one that results from a static gravimetric measurement. This is shown in Figure 2. ... 

Figure 2. Comparison of grav.-static measured isotherms and IGC elution isotherm for alumina...

For example, suppose that we are using a 10-m column with a linear velocity of 33 cm/s at 50°C, and that peak 1 elutes isothermally in 10 min, with a retention factor (k) of... 

It was found that the benzene, toluene, mesitylene, durene and hexamethylbenzene tricarbonyl chromium could best be separated and quantitatively determined in mixtures by use of temperature programming with the flame ionization detector. Figure 204 illustrates the separation achieved. It can be seen that the resolution is excellent, and that the retention times of the early components are far enough removed from the tail of the solvent peak that measurements from the original base line are possible in each case. Under isothermal conditions (135°C) using flame ionization, the benzene tricarbonyl--chromium and toluene tricarbonylchromium peaks eluted on the tail of the benzene peaks and the retention time of the hexamethylbenzene tricarbonylchromium was 32.6 minutes. This peak was also considerably broader and flatter when eluted isothermally. For this determination therefore, programmed temperature operation is the most efficient means of analysis not only is the resolution improved, but also the total time of analysis is reduced to 15 minutes. 

Temperature-risiag elution fractionation (tref) is a technique for obtaining fractions based on short-chain branch content versus molecular weight (96). On account of the more than four days of sample preparation required, stepwise isothermal segregation (97) and solvated thermal analysis fractionation (98) techniques usiag variatioas of differeatial scanning calorimetry (dsc) techniques have been developed. 

Two variations of the technique exists isocratic elution, when the mobile phase composition is kept constant, and gradient elution, when the mobile phase composition is varied during the separation. Isocratic elution is often the method of choice for analysis and in process apphcations when the retention characteristics of the solutes to be separated are similar and not dramaticallv sensitive to vei y small changes in operating conditions. Isocratic elution is also generally practical for systems where the equilibrium isotherm is linear or nearly hnear. In all cases, isocratic elution results in a dilution of the separated produces. 

Isocratic Elution In the simplest case, feed with concentration cf is apphed to the column for a time tp followed by the pure carrier fluid. Under trace conditions, for a hnear isotherm with external mass-transfer control, the linear driving force approximation or reaction kinetics (see Table 16-12), solution of Eq. (16-146) gives the following expression for the dimensionless solute concentration at the column outlet ... 

BBT solution on unmodified sorbents of different nature was studied. Silica gel Merck 60 (SG) was chosen for further investigations. BBT immobilization on SG was realized by adsoi ption from chloroform-hexane solution (1 10) in batch mode. The isotherm of BBT adsoi ption can be referred to H3-type. Interaction of Co(II), Cu(II), Cd(II), Ni(II), Zn(II) ions with immobilized BBT has been studied in batch mode as a function of pH of solution, time of phase contact and concentration of metals in solution. In the presence of sodium citrate absorbance (at X = 620 nm) of immobilized BBT grows with the increase of Cd(II) concentration in solution. No interference was observed from Zn(II), Pb(II), Cu(II), Ni(II), Co(II) and macrocomponents of natural waters. This was assumed as a basis of soi ption-spectroscopic and visual test determination of Cd(II). Heavy metals eluted from BBT-SG easily and quantitatively with a small volume of HNO -ethanol mixture. This became a basis of soi ption-atomic-absoi ption determination of the total concentration of heavy metals in natural objects. 

Unless there are solutes that are very strongly retained, and the maximum operating temperature of the system is reached without all the solutes being eluted, there is usually no need for a final isothermal period of any significant length. There is, however, one exception where a final isothermal period is helpful, and that is for mixtures that contain thermally labile materials. 

The simplest mode of IGC is the infinite dilution mode , effected when the adsorbing species is present at very low concentration in a non-adsorbing carrier gas. Under such conditions, the adsorption may be assumed to be sub-monolayer, and if one assumes in addition that the surface is energetically homogeneous with respect to the adsorption (often an acceptable assumption for dispersion-force-only adsorbates), the isotherm will be linear (Henry s Law), i.e. the amount adsorbed will be linearly dependent on the partial saturation of the gas. The proportionality factor is the adsorption equilibrium constant, which is the ratio of the volume of gas adsorbed per unit area of solid to its relative saturation in the carrier. The quantity measured experimentally is the relative retention volume, Vn, for a gas sample injected into the column. It is the volume of carrier gas required to completely elute the sample, relative to the amount required to elute a non-adsorbing probe, i.e. 

The ability of a GC column to theoretically separate a multitude of components is normally defined by the capacity of the column. Component boiling point will be an initial property that determines relative component retention. Superimposed on this primary consideration is then the phase selectivity, which allows solutes of similar boiling point or volatility to be differentiated. In GC X GC, capacity is now defined in terms of the separation space available (11). As shown below, this space is an area determined by (a) the time of the modulation period (defined further below), which corresponds to an elution property on the second column, and (b) the elution time on the first column. In the normal experiment, the fast elution on the second column is conducted almost instantaneously, so will be essentially carried out under isothermal conditions, although the oven is temperature programmed. Thus, compounds will have an approximately constant peak width in the first dimension, but their widths in the second dimension will depend on how long they take to elute on the second column (isothermal conditions mean that later-eluting peaks on 2D are broader). In addition, peaks will have a variance (distribution) in each dimension depending on... 

So far, it has been assumed that elution is independent of analyte load or the presence of multiple components in a mixture. If this condition holds, then the analyte concentration in the mobile phase is directly proportional to the concentration in the stationary phase, no matter what the concentration is. Experimentally, this could be determined by incubating various concentrations of an analyte with a fixed amount of stationary phase and measuring the amount adsorbed. A plot of the concentration of analyte in the mobile phase on the x-axis vs. that in the stationary phase on the y-axis would be linear, and such a plot is called a "linear isotherm". A convex isotherm implies that tailing would be expected, and a concave isotherm implies that fronting is expected. 

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