Temperature, column effect sensitivity

Changes of differential pressure between the temperature control and pressure control locations are normally small compared to variations in column pressure. For this reason, the control temperature is seldom sensitive to differential pressure variations in other than low-pressure (particularly deep vacuum) services. Even then, the effects of differential pressure changes can be minimized by locating the temperature and pressure control measurement points close together. 

How then do the techniques differ For this, the terms recovery and sensitivity must be defined. For both methods, the recovery depends on the vapour pressure, the solubility and the temperature. The effects of temperature can be dealt with because it is easy to increase the vapour pressure of a compound by raising the temperature during the vaporization step. With the P T technique, the term percentage recovery is used. This is the amount of a compound which reaches the gas chromatograph for analysis relative to the amount which was originally present in the sample. If a sample contains 100 pg benzene and 90 pg reach the GC column, the percentage recovery is 90%. In the static headspace technique, a simple expression like this cannot be used because it is possible to use a large... 

Refractive index detectors. These bulk property detectors are based on the change of refractive index of the eluant from the column with respect to pure mobile phase. Although they are widely used, the refractive index detectors suffer from several disadvantages — lack of high sensitivity, lack of suitability for gradient elution, and the need for strict temperature control ( + 0.001 °C) to operate at their highest sensitivity. A pulseless pump, or a reciprocating pump equipped with a pulse dampener, must also be employed. The effect of these limitations may to some extent be overcome by the use of differential systems in which the column eluant is compared with a reference flow of pure mobile phase. The two chief types of RI detector are as follows. 

Quantitative analysis using the internal standard method. The height and area of chromatographic peaks are affected not only by the amount of sample but also by fluctuations of the carrier gas flow rate, the column and detector temperatures, etc., i.e. by variations of those factors which influence the sensitivity and response of the detector. The effect of such variations can be eliminated by use of the internal standard method in which a known amount of a reference substance is added to the sample to be analysed before injection into the column. The requirements for an effective internal standard (Section 4.5) may be summarised as follows ... 

The effect of sulfur addition on the TPR profiles for some of these catalysts is reported in Table 5. The saturation of the solid by SO2 shifts the TPR profiles to higher temperatures and a second reduction peak appears at high temperature. The maximum temperatures measured for this second high temperature peak are reported in Table 5 (column 6). The effect of sulfur addition depiends on the nature of the support, and zeolites appear less sensitive to SO2. 

Supercritical fluid chromatography is the name for all chromatographic methods in which the mobile phase is supercritical under the conditions of analysis and the solvating properties of the fluid have a measurable effect on the separation. SFC has some advantages over GC and HPLC it extends the molecular weight range of GC, thermally labile compounds can be separated at lower temperatures, compounds without chromophores can be sensitively detected, and the use of open-tubular and packed columns is feasible. SFC can be employed in both the analysis of natural pigments and synthetic dyes, however it has not been frequently applied in up-to-date analytical practice. 

Calculation of the pressure drop and flooding rate is particularly important for vacuum columns, in which the pressure may increase severalfold from the top to the bottom of the column. When a heat-sensitive liquid is distilled, the maximum temperature, and hence the pressure, at the bottom of the column is limited and hence the vapour rate must not exceed a certain value. In a vacuum column, the throughput is very low because of the high specific volume of the vapour, and the liquid reflux rate is generally so low that the liquid flow has little effect on the pressure drop. The pressure drop can be calculated by applying equation 4.15 over a differential height and integrating. Thus ... 

C-L. Scott, The Sensitivity of Selected Conventional and Heat Resistant Explosives at Low Temperatures", NOLTR 70—36 (1970), reviewed by G. Cohn, Edit in Expls- Pyrots 4(6), 1971 (The effects of temp, confinement, and column diam on the shock... 

The robustness of an analytical procedure is a measure of its capacity to remain unaffected by small but deliberate variations in the analytical procedure parameters. The robustness of the analytical procedure provides an indication of its reliability during normal use. The evaluation of robustness should be considered during development of the analytical procedure. If measurements are susceptible to variations in analytical conditions, the analytical conditions should be suitably controlled or a precautionary statement should be included in the procedure. For example, if the resolution of a critical pair of peaks was very sensitive to the percentage of organic composition in the mobile phase, that observation would have been observed during method development and should be stressed in the procedure. Common variations that are investigated for robustness include filter effect, stability of analytical solutions, extraction time during sample preparation, pH variations in the mobile-phase composition, variations in mobile-phase composition, columns, temperature effect, and flow rate. 

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