Retention temperature program

Van Den Dool, H. and P.D. Kratz (1963), Generalization of the retention index system including linear temperature programmed gas-liquid partition chromatography . J. Chromatogr, Vol. 11, p. 463. 

Temperature programming was introduced in the early days of GC and is now a commonly practiced elution technique. It follows that the temperature programmer is an essential accessory to all contemporary gas chromatographs and also to many liquid chromatographs. The technique is used for the same reasons as flow programming, that is, to accelerate the elution rate of the late peaks that would otherwise take an inordinately long time to elute. The distribution coefficient of a solute is exponentially related to the reciprocal of the absolute temperature, and as the retention volume is directly related to the distribution coefficient, temperature will govern the elution rate of the solute. 

Furthermore, after time (tp) between (tp) and (tp+At) during a temperature program at a rate of a°C per unit time and an initial temperature of (To), the effective retention... 

It is seen that the viscosity of the gas will change significantly during a temperature program and, thus, at a constant gas mass flow rate, the inlet pressure will rise proportionally. This increase in inlet pressure will result in an increase in the inlet/outlet pressure ratio and, as a consequence, will extend the retention time and oppose the effect of any increase in temperature. It also follows that the effect of... 

Figure 5. Graphs of Retention Time of (R) 4-Benzyl-2-oxazolidinone against Temperature Program Rate for Three Different Initial Temperatures...

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... 

Halang, W. A., Langlais, R., and Kugler, E., Cubic Spline Interpolation for the Calculation of Retention Indices in Temperature-Programmed Gas-Liquid Chromatography, Ana/. Chem. 50, 1978, 1829-1832. 

Semperatuie proqcammlnq (computer simulation 55 optimization 53 preparative separations 211 programming rate 53 retention indices 178 theoretical models 54 Temperature programming LC 83 SFC 630... 

Davis, J.M. (2004). Assessment by Monte Carlo simulation of thermodynamic correlation of retention times in dual-column temperature programmed comprehensive two-dimensional gas chromatography. J. Sep. Sci. 27, 417. 

Fig. 21.14. Temperature-programmed capillary GC-MS total ion chromatograms for kerosene (upper trace) and Moth-Knox pesticide (lower trace). Note the similarity in the pattern of peaks, with the exception of the large peak in the pesticide sample (at a retention time of about 12.5 min). The mass spectrum and the retention time of this peak both corresponded to a standard of naphthalene.

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