retention volumes (in chromatography) Retention measurements (and measurements of hold-up volume and peak width) may be made

in terms of times or chart distances as well as volumes. If flow and recorder speeds are constant, the volumes are directly proportional to the times and chart distances. The following definitions are drawn up in terms of volume, and it is recommended that theoretical discussion should be couched in the same terms wherever possible. Retention Volume The retention volume is the volume of mobile phase passed through the column between the injection point and the peak maximum. In liquid-chromatography, the compressibility of the mobile phase is very small, so the retention volume can be taken as the product of the time interval between the injection point and the peak maximum and the mobile phase flow rate. In gas-chromatography, however the compressibility of the mobile phase is very significant, so the corrected retention volume must be taken as the product of the time interval between the injection point and the peak maximum and the mobile phase flow rate (measured at the column exit) corrected for the compressibility of the gas. Specific Retention Volume The specific retention volume of a solute is the corrected retention volume of the solute per unit mass of stationary phase. The corrected retention volume is obtained from a column carrying a known weight of stationary phase and is measured at a carefully controlled, accurately known temperature. The corrected retention volume is taken as the difference between the solute retention volume and the dead volume. The retention volume is taken as the volume of mobile phase that passes through the column from the time of injection to the elution time of the peak maximum. The dead volume is taken as the volume of mobile phase that passes through the column from the time of injection to the elution time of the peak maximum of a completely untretained solute. If the mobile phase is a liquid, no pressure correction is usually necessary, if the mobile phase is a gas, then all measured volumes must be corrected for the compressibility of the gas. If the specific retention volume is divided by the density of the stationary phase, the corrected retention per ml of stationary phase can be calculated, the logarithm of which gives the standard energy of distribution. If the standard energy of distribution is determined over a range of temperatures, then, by plotting the corrected

retention volume per ml of stationary phase against the reciprocal of the temperature, the standard enthalpy and standard entropy of the distribution can be calculated. Retention indices are relative retention times normalised to closely eluting n-alkanes. Retention indices are system independent and long-term reproducible, even after many years and in different laboratories around the world. (2) Identifying peaks by library searches should not solely focus on mass spectral similarity, but also include retention indices in order to optimise the quality and reliablitity of library hits. Many isomeric compounds like sesquiterpene hydrocarbons can only be identified if taking both mass spectra and retention indices into account.

The retention time is the total time that a compound spends in both the mobile phase and stationary phase. Retention time is generally reported in minutes