Retention volume measurements compression

If the mobile phase is a liquid, and can be considered incompressible, then the volume of the mobile phase eluted from the column, between the injection and the peak maximum, can be easily obtained from the product of the flow rate and the retention time. For more precise measurements, the volume of eluent can be directly measured volumetrically by means of a burette or other suitable volume measuring vessel that is placed at the end of the column. If the mobile phase is compressible, however, the volume of mobile phase that passes through the column, measured at the exit, will no longer represent the true retention volume, as the volume flow will increase continuously along the column as the pressure falls. This problem was solved by James and Martin [3], who derived a correction factor that allowed the actual retention volume to be calculated from the retention volume measured at the column outlet at atmospheric pressure, and a function of the inlet/outlet pressure ratio. This correction factor can be derived as follows. 

The compressibilities of solvents vary significantly from one solvent to another. The compressibility of cyclohexane is about 0.67% per thousand p.s.i. change in pressure [11] and, thus, for a column operated at 6,000 p.s.i. (mean pressure 3,000 p.s.i.), there will be an error in retention volume measurement of about 2%. In a similar manner, n-heptane has a compressibility of about 1.0% per 1,000 p.s.i. change in pressure [11] and, under similar circumstances, would give an error of about 3% in retention volume measurement. Fortunately, as already discussed in Part 1 of this book, there are other retention parameters that can be used for solute... 

An eluted solute was originally identified from its corrected retention volume which was calculated from its corrected retention time. It follows that the accuracy of the measurement depended on the measurement and constancy of the mobile phase flow rate. To eliminate the errors involved in flow rate measurement, particularly for mobile phases that were compressible, the capacity ratio of a solute (k ) was introduced. The capacity ratio of a solute is defined as the ratio of its distribution coefficient to the phase ratio (a) of the column, where... 

Liquids have relatively low compressibility compared with gases and, thus, the mobile phase velocity is sensibly constant throughout the column. As a consequence, elution volumes measured at the column exit can be used to obtain retention volume data and, unless extreme accuracy is required for special applications, there is no need for the retention volume to be corrected for pressure effects. 

The injector and the detector have dead volumes that affect the total retention volume. In gas phase chromatography, because the mobile phase is compressible, the flow rate measured at the end of the column has to be corrected by the compressibility factor J, which accounts for increased pressure at the head of the column (c.f. 2.2). 

This is largely due to the fact that retention data depend on certain factors the effects of which are difficult to eliminate completely or control and which are normally neglected. These factors are the imperfections in the gas phase and the compressibility of the stationary phase (cf., the quantities vh v , zq and 0 in eqn. 1), the finite rate of equilibration of the solute, variations in the composition of the sorbent, spurious sorption of the solute, solubility of the carrier gas in the stationary phase, etc. Hence, even relative retention volumes and/or retention indices must depend to some extent on the kind, flow-rate and absolute pressure of the carrier gas, the load of the liquid stationary phase on the support, which production batch of the stationary phase has been used and the kind of support. The absolute column pressure will obviously vary with the column length and particle size of the support. Moreover, adjusted retention data are required in all instances, which renders it necessary to measure the dead retention time. This is a crucial step in obtaining accurate retention data and presents a problem per se. 

The retention time can be taken as the product of the distance on the chart between the dead point and the peak maximum and the chart speed, using appropriate units. As in the case of the retention time, it can be more accurately measured with a stopwatch. Again, the most accurate method of measuring F for a non-compressible mobile phase, although considered antiquated, is to attach an accurate burette to the detector exit and measure the retention volume in volume units. This is an absolute method of measurement and... 

A third difference, will result from the relatively small compressibility of the mobile phase. As opposed to a gas, which is highly compressible, when measuring retention volumes, there is no need for a mobile phase pressure correction in LC, unless extremely high pressures are used. Even then, due to the small compressibility of liquids, it will be a second order effect. The effect of pressure on solute interaction with the stationary phase, however, may well be more significant. This might occur, particularly, if the stationary phase matrix on the surface of the silica is polymeric in form, and thus somewhat compressible. Indeed, small changes in selectivity have be observed [1, 2, 3], in chiral separations as the result of increased column pressure. It should be... 

Other Fiber Evaluation Methods. The extent of fiber separation (fiber openness) is an important evaluation criteria that is commonly measured by several techniques, namely ak permeabiUty, adsorbed gas volume, bulk density, and residence (compression and recovery). The adsorption and retention of kerosene is also used as a measure of fiber openness and fiber adsorption capacity (34). 

Retention is usually measured in units of time for convenience. Voliime units are more exact. Table 1.1, after suitable corrections have been applied (26). Under average chromatographic conditions liquids can be considered incompressible, but not so for gases, and in gas chromatography elution volumes are corrected to a mean column pressure by multiplying them by the gas compressibility factor, j, equation (1.2)... 

Fig. 1 Diagram depicting the dead point, dead volume, and dead time of a chromatogram. If the mobile phase is not compressible, then Vo is the total volume passed through the column between the point of injection and the peak maximum of a completely unretained peak, V is the total volume of the mobile phase in the column, V is the extra column volume of the mobile phase, is the volume of the mobile phase per theoretical plate, is the time elapsed between the time of injection and the retention time of a completely unretained peak, n is the number of theoretical plates in the column, and Q is the column flow rate measured at the exit.

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