HETP Curve The HETP curve is a graph relating the variance per unit length of a column to the linear velocity of the mobile phase. The variance per unit length of a column, for a specific solute, can be calculated as the ratio of the column length to the column efficiency. For an LC column the mobile phase velocity can be taken as the ratio of the column length to the retention time of an unretained solute of sufficient size so that it can not enter any pores of the support or stationary phase (e.g. a dispersion of silica smoke). The linear velocity in a GC column can be determined by dividing the column exit flow rate by the column cross-sectional area. However, in GC, the linear velocity calculated in this way must also be corrected for the compressibility of the gas. The relationship between the variance per unit length of the column and the linear mobile phase velocity is given by the HETP equation which takes the form of a hyperbolic function. This hyperbolic function may contain three or four individual expressions depending on whether it is for a packed column or for a capillary column. The HETP curve shows a minimum at a particular velocity, which is called the optimum velocity. It follows, that at the optimum mobile phase velocity, the column will provide a maximum number of theoretical plates.

Free book pdf downloads

Author: RPW Scott Book:Dispersion in Chromatography Columns
Section:Dispersion   Van-Deemter-Equation

nbsp; The HETP curve is the result of a curve fitting procedure to the experimental points shown. The column was 25 cm long, 9 mm in diameter and packed with 8.5 micron (nominal 10 micron) Partisil silica gel. The mobile phase was a solution of 4.8%w/v ethyl acetate in n-decane. The hyperbolic form of the curve is confirmed, the minimum is clearly indicated and the fit of the points to the curve is good. From the curve fitting procedure the values of the Van Deemter constants could be determined and the separate contributions to the curve from the multipath dispersion, longitudinal dispersion and the resistance to mass transfer calculated and included in the figure. It is seen that the major contribution to dispersion at the optimum velocity (where the value of (H) is a minimum) is the multipath effect. Only at much lower velocities, does the longitudinal diffusion effect become significant.

Dispersion   Van-Deemter-Equation

Author: RPW Scott Book:Dispersion in Chromatography Columns
Section:Dispersion   Van-Deemter-Equation

where, A=2ldp, B=2gDm and   Equation (33) is a hyperbolic function which has a minimum value of (H) for a particular value of (u). Thus, a maximum efficiency will obtained at a particular linear mobile phase velocity. An example of an HETP curve obtained in practice showing this hyperbolic relationship is given in figure 11.     Figure 11. HETP Curve for Hexamethylbenzene

Dispersion   Van-Deemter-Equation

Author: RPW Scott Book:Dispersion in Chromatography Columns
Section:Dispersion   Golay-Equation

;                                                                  (54) Where,   and           The form of the HETP curve for a capillary column is the same as that for a packed column and exhibits a minimum value for (H) at an optimum velocity. Differentiating equation (54) with respect to (u),               Thus, when      H = Hmin,    then,                      and thus,    &

Dispersion   Golay-Equation

Author: RPW Scott Book:Dispersion in Chromatography Columns
Section:Dispersion   Alternative-Equations   Huber

The form of the HETP curve that is produced by the Huber equation is shown in figure 15.      Figure 15.H versus U Curves for the Huber Equation It is seen that the composite curve obtained from the Huber equation is indeed similar to that obtained from that of Van Deemter but the individual contributions to the overall variance are different. The contributions from the resistance to mass transfer in the mobile phase and longitudinal diffusion are common to both equations. However, the (A

Dispersion   Alternative-Equations   Huber

Author: RPW Scott Book:Dispersion in Chromatography Columns
Section:Dispersion   Compressibility-Effects-GC

Figure 9. HETP Curves for the Same Column and Solute Using the Average Mobile Phase Velocity and the Exit Velocity   The two curves are clearly quite different and, if the results are to be fitted to the HETP equation, only the data obtained using the exit velocity  will give meaningful values for the exclusive dispersion processes. This problem is further emphasized in the graphs shown in figure 10. In figure 10, the individual contributions from the different dispersion processes are obtained by deconvoluting the HETP curve obtained using the average velocity data

Dispersion   Compressibility-Effects-GC

Author: RPW Scott Book:Dispersion in Chromatography Columns
Section:Dispersion   Alternative-Equations   Huber

takes place between the particles. Huber's equation implies (but, in fact, was not explicitly stated by the authors) that the mixing effect between the particles (that reduces the magnitude of the resistance to mass transfer in the mobile phase) does not commence until the mobile phase velocity approaches the optimum velocity (as defined by the Van Deemter equation). Furthermore, it is not complete until the mobile phase velocity is well above the optimum velocity. Thus, the shape of the HETP/u curve will be a little different from that predicted by the Van Deemter equation

Dispersion   Alternative-Equations   Huber

 
 
 

Journal of Chromatographic Science

Query

    Text Only