The two options for sample evaporation in hot GC injectors: thermospray and band formation. optimization of conditions and injector design.

Although classical split and splitless injection is more than 30 years old, we only start to understand the vaporization process in the injector. Solvent evaporation determines much of the process and is the first obstacle to overcome. Videos recorded on devices imitating injectors showed that sample (solvent) evaporation is often a violent process which is poorly controlled and might well explain many of the puzzling quantitative results often obtained. We do not adequately take into account that two vaporization techniques are in use. Partial solvent evaporation inside the syringe needle (optimized as "hot needle injection") produces thermospray: the sample liquid is nebulized upon leaving the needle. The resulting fog is rapidly slowed and moves with the gas. Solute evaporation largely occurs from microparticles suspended in the gas phase. Empty liners are most suitable. Fast autosamplers suppress vaporization in the needle, i.e., nebulization, and shoot a band of liquid into the chamber that must be stopped by a packing or obstacles suitable to hold the liquid in place during the 0.2-5 s required for solvent evaporation. Solute evaporation largely occurs from the surfaces onto which the sample is deposited. Insights into these mechanisms help optimize conditions in a more rational manner. Methods should specify whether they were optimized and validated for injection with thermospray or band formation. The insights should also enable a significant improvement of the injector design, particularly for splitless injection.