Retention time and boiling point relationship problems

What is Retention Time? Chromatography Today

retention time and boiling point relationship problems

of a coal-derived liquid based on the correlation between points. In a previous paper24, converting g.c. retention time into boiling point, the boiling point distributions of aromatic this problem, the use and validity of aromatic hydrocarbon. This article explores what happens when temperature fluctuates and how that can affect a compounds retention time when working with gas. If two solutes have similar boiling points, however, then a separation is possible only if An important problem with all liquid stationary phases is their .. standard and determine the relationship between the peak area for p-xylene, Because a compound's retention times on two identical columns are not.

The temperature of the column does not have to be above the boiling point because every compound has a non-zero vapor pressure at any given temperature, even solids.

That is the reason why we can smell compounds like camphor 0. However, their vapor pressures are low compared to liquids i. The polarity of components versus the polarity of stationary phase on column If the polarity of the stationary phase and compound are similar, the retention time increases because the compound interacts stronger with the stationary phase.

retention time and boiling point relationship problems

As a result, polar compounds have long retention times on polar stationary phases and shorter retention times on non-polar columns using the same temperature. Chiral stationary phases that are based on amino acid derivatives, cyclodextrins and chiral silanes are capable of separating enantiomers because one enantiomer interacts slightly stronger than the other one with the stationary phase, often due to steric effects or other very specific interactions.

For instance, a modified -cyclodextrin column is used in the determination of the enantiomeric excess in the chiral epoxidation experiment Chem 30CL. Column temperature A excessively high column temperature results in very short retention time but also in a very poor separation because all components mainly stay in the gas phase.

However, in order for the separation to occur the components need to be able to interact with the stationary phase. If the compound does not interact with the stationary phase, the retention time will decrease. At the same time, the quality of the separation deteriorates, because the differences in retention times are not as pronounced anymore. The best separations are usually observed for temperature gradients, because the differences in polarity and in boiling points are used here.

Carrier gas flow rate A high flow rate reduces retention times, but a poor separation would be observed as well. Like above, the components have very little time to interact with the stationary phase and are just being pushed through the column. Column length A longer column generally improves the separation. The trade-off is that the retention time increases proportionally to the column length and a significant peak broadening will be observed as well because of increased longitudinal diffusion inside the column.

One has to keep in mind that the gas molecules are not only traveling in one direction but also sideways and backwards.

Gas Chromatography Theory

This broadening is inversely proportional to the flow rate. Broadening is also observed because of the finite rate of mass transfer between the phases and because the molecules are taking different paths through the column.

Amount of material injected Ideally, the peaks in the chromatogram display a symmetric shape Gaussian curve. If too much of the sample is injected, the peaks show a significant tailing, which causes a poorer separation. Most detectors are relatively sensitive and do not need a lot of material in order to produce a detectable signal. The splitless mode will only be used if the sample is extremely low in concentration in terms of the analyte. Conclusion High temperatures and high flow rates decrease the retention time, but also deteriorate the quality of the separation.

Which detectors are used? The process should be reversed if low boiling compounds i. The sample should never be injected in neat form! The GC samples cannot contain any solids. Sample introduction manual injection The sample solution is introduced through the injection port, using a micro-liter syringe.

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The injection port is very hot in order to allow for the solvent and the compounds evaporate instantaneously. The syringe has to be cleaned thoroughly before it is used. To load the syringe, the plunger is slowly pulled to draw the sample from the solution. If the plunger is drawn too fast, a lot of air will be drawn into the syringe as well, which makes it necessary to start over. The loaded syringe taken out of the sample solution, and the plunger then pulled a little more to suck the liquid out of the needle.

This way, the sample solution is not in the needle anymore.

retention time and boiling point relationship problems

The syringe is brought to the injection port and the needle pushed through the septum. Then, quickly and smoothly the plunger is pushed down to inject the sample. Afterwards, the syringe needle is pulled out of the septum and the injection port. Care has to be taken to avoid the bending of the plunger by applying too much force during the injection.

A bent plunger causes leaks in the syringe and makes it difficult to draw the solution afterwards. After the injection, the syringe should be immediately rinsed with a low boiling solvent.

retention time and boiling point relationship problems

This also avoids the build-up of a residue on the inside of the upper part of the syringe, which is very difficult to remove. Only in cases of a very low concentration sample the splitless mode is used. The injection port is usually heated to oC. The column temperature has to be above the dew points of the compounds to prevent condensation in the column.

The temperature of the oven can be kept constant isothermalor gradually be changed gradient. The second method often provides a better result due to the fact that the differences in boiling points can additionally be used to separate the compounds. The separation is greatly improved, the peaks are less broad, and the higher boiling components leave the column much earlier see example discussed above.

One reason for this measure is to avoid condensation of water in the detector. To ensure an acceptable lifetime of the column, the column should not be. The absorbent may decomposes or boil out and deposit in the detector. This would destroy the column and the detector at the same time. Every column has a tag attached that states its composition and operation temperatures.