Retention times isothermal

Note that the initial slope of the adsorption isotherm can be easily obtained from the knowledge of the retention time associated to a small injection performed on a column, as this retention time is given by t = t icj where... 

Knowing the experimental retention times, the previous equation allows the calculation of experimental concentration on the solid phase. Parameters of adsorption isotherms, can then be determined by fitting experimental and calculated concentrations. 

In Table 10.2, this correlation is shown, comparing solid phase concentration calculated from the retention times of the fronts, and using the adsorption isotherm equation. 

The peak symmetry, resolution, and detector response are directly dependent on the concentration of the sample. As the concentration of a sample increases, the retention time, separation, and peak symmetry generally decrease. These phenomena are due to isotherm nonlinearity. The detector response may also be nonlinear above or below certain concentrations. In some cases, small amounts of a dilute component are irreversibly adsorbed to the column, leading to reduced recovery. Above some concentration, the response of any detector will cease to be linear. The UV-VIS is one of the most linear detectors, generally exhibiting at least three decades of linearity, while RI, electrochemical, and fluorimetric detectors have a markedly narrower range of linearity. 

The spray paint can was inverted and a small amount of product was dispensed into a 20 mL glass headspace vial. The vial was immediately sealed and was incubated at 80°C for approximately 30 min. After this isothermal hold, a 0.5-mL portion of the headspace was injected into the GC/MS system. The GC-MS total ion chromatogram of the paint solvent mixture headspace is shown in Figure 15. Numerous solvent peaks were detected and identified via mass spectral library searching. The retention times, approximate percentages, and tentative identifications are shown in Table 8 for the solvent peaks. These peak identifications are considered tentative, as they are based solely on the library search. The mass spectral library search is often unable to differentiate with a high degree of confidence between positional isomers of branched aliphatic hydrocarbons or cycloaliphatic hydrocarbons. Therefore, the peak identifications in Table 8 may not be correct in all cases as to the exact isomer present (e.g., 1,2,3-cyclohexane versus 1,2,4-cyclohexane). However, the class of compound (cyclic versus branched versus linear aliphatic) and the total number of carbon atoms in the molecule should be correct for the majority of peaks. 

If the isothermal temperature is too low, later eluting peaks may have unacceptably long retention times, and detection limits will be poor because of excessive peak-broadening. Peak shape may also be adversely affected. 

We also vary the sample size (from 1 to 2 y ) between runs at a given P and T. This allows extrapolation of peak areas to zero sample size as shown in Figure 4. The flow rate within the column must be constant for an isotherm. We record the following parameters ambient pressure and temperature, inlet pressure, outlet pressure, column temperature, retention time for both air and water, water peak area, ambient flow rate, regulator pressure, sample sizes, detector current and temperature, injector temperature, and attenuation. 

When the amount of the sample is comparable to the adsorption capacity of the zone of the column the migrating molecules occupy, the analyte molecules compete for adsorption on the surface of the stationary phase. The molecules disturb the adsorption of other molecules, and that phenomenon is normally taken into account by nonlinear adsorption isotherms. The nonlinear adsorption isotherm arises from the fact that the equilibrium concentrations of the solute molecules in the stationary and the mobile phases are not directly proportional. The stationary phase has a finite adsorption capacity lateral interactions may arise between molecules in the adsorbed layer, and those lead to nonlinear isotherms. If we work in the concentration range where the isotherms are nonlinear, we arrive to the field of nonlinear chromatography where thermodynamics controls the peak shapes. The retention time, selectivity, plate number, peak width, and peak shape are no longer constant but depend on the sample size and several other factors. 

Equations 10.47 through 10.49 constitute the basis for the method of isotherm determination by the perturbation method. The retention time of a small injection of a solute in a column equilibrated... 

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