Gas chromatography is typically operated in isothermal mode for optimum separation of a mixture of compounds with a narrow boiling point range, or in temperature-programmed mode, which strives to achieve a compromise between separation efficiency and time. Temperature gradients also keep the peak widths nearly constant over a wide range of retention times, enhancing the detectability of the later eluting peaks. In this chapter, the use of negative thermal gradients for gas chromatography (NTGGC) – for the sake of simplicity, subsequently only denoted as thermal gradient-gas chromatography, TGGC – shall be discussed. (N)TGGC is achieved by producing a stationary temperature gradient along the relatively short GC column in a proprietary experimental setup that allows cooling on one end of the column and heating on the other. The sample is injected into the hot end of the GC column, and analytes move towards the colder end of the column. Along their passage through the column, they are focused by the increasingly lower temperature of the stationary phase. This leads to a focusing of the peaks as they reach the cold column end. With appropriate temperature programming, very fast (sub-minute) chromatography with excellent resolution can be achieved on short GC columns. The present contribution will both discuss the theory behind this unusual, but highly performant mode of gas chromatographic separation, and also the hardware aspects of this technique. Relevant examples will be presented which highlight both the speed and the separation power by which (N)TGGC excels in comparison with regular temperature-programmed GC.
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