Van Deemter

An alternative form of this equation is the van Deemter equation... 

Plot of the height of a theoretical plate as a function of mobile-phase velocity using the van Deemter equation. The contributions to the terms A B/u, and Cu also are shown. 

There is some disagreement on the correct equation for describing the relationship between plate height and mobile-phase velocity. In addition to the van Deemter equation (equation 12.28), another equation is that proposed by Hawkes... 

Equation 16-183 is qualitatively the same as the van Deemter equation [van Deemter and Zuiderweg, Chem. Eng. Sci., 5, 271 (1956)] and is equivalent to other empiric reduced HETP expressions such as the Knox equation [Knox,y. Chromatogi Set., 15, 352 (1977)]. 

It appears that the equation introduced by Van Deemter is still the simplest and the most reliable for use in general column design. Nevertheless, all the equations helped to further understand the processes that occur in the column. In particular, in addition to describing dispersion, the Kennedy and Knox equation can also be employed to assess the efficiency of the packing procedure used in the preparation of a chromatography column. 

The silica dispersion showed the smallest retention volume. It should be noted, however, that the authors reported that the silica dispersion required sonicating for 5 hours before the silica was sufficiently dispersed to be used as "pseudo-solute". The retention volume of the silica dispersion gave the value of the kinetic dead volume, /.e., the volume of the moving portion of the mobile phase. It is clear that the difference between the retention volume of sodium nitroprusside and that of the silica dispersion is very small, and so the sodium nitroprusside can be used to measure the kinetic dead volume of a packed column. From such data, the mean kinetic linear velocity and the kinetic capacity ratio can be calculated for use with the Van Deemter equation [12] or the Golay equation [13]. 

The dispersion of a solute band in a packed column was originally treated comprehensively by Van Deemter et al. [4] who postulated that there were four first-order effect, spreading processes that were responsible for peak dispersion. These the authors designated as multi-path dispersion, longitudinal diffusion, resistance to mass transfer in the mobile phase and resistance to mass transfer in the stationary phase. Van Deemter derived an expression for the variance contribution of each dispersion process to the overall variance per unit length of the column. Consequently, as the individual dispersion processes can be assumed to be random and non-interacting, the total variance per unit length of the column was obtained from a sum of the individual variance contributions. 

Equation (5), however, would apply only to a perfectly packed column so Van Deemter introduced a constant (2X) to account for the inhomogeneity of real packing (for ideal packing (X) would take the value of 0.5). Consequently, his expression for the multi-path contribution to the total variance per unit length for the column (Hm) is... 

Equation (11) accurately describes longitudinal diffusion in a capillary column where there is no impediment to the flow from particles of packing. In a packed column, however, the mobile phase swirls around the particles. This tends to increase the effective diffusivity of the solute. Van Deemter introduced a constant (y) to account... 

The concept of the "fudge factor" was introduced by Golay to describe such constants as (X), (y), (co) and (q) used by Van Deemter, Giddings and others in the... 

The first alternative HETP equation to be developed was that of Giddings in 1961 [1] of which the Van Deemter equation appeared to be a special case. Giddings did not develop his equation because the Van Deemter equation did not fit experimental data. 

It is seen that when u E, equation (1) reduces to the Van Deemter equation. 

When u E, this interstitial mixing effect was considered complete, and the resistance to mass transfer in the mobile phase between the particles becomes very small and the equation again reduces to the Van Deemter equation. However, under these circumstances, the C term in the Van Deemter equation now only describes the resistance to mass transfer in the mobile phase contained in the pores of the particles and, thus, would constitute an additional resistance to mass transfer in the stationary (static mobile) phase. It will be shown later that there is experimental evidence to support this. It is possible, and likely, that this was the rationale that explains why Van Deemter et al. did not include a resistance to mass transfer term for the mobile phase in their original form of the equation. 

The composite curve from the Huber equation is 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 stationary phase and... 

The curves represent a plot of log (h ) (reduced plate height) against log (v) (reduced velocity) for two very different columns. The lower the curve, the better the column is packed (the lower the minimum reduced plate height). At low velocities, the (B) term (longitudinal diffusion) dominates, and at high velocities the (C) term (resistance to mass transfer in the stationary phase) dominates, as in the Van Deemter equation. The best column efficiency is achieved when the minimum is about 2 particle diameters and thus, log (h ) is about 0.35. The optimum reduced velocity is in the range of 3 to 5 cm/sec., that is log (v) takes values between 0.3 and 0.5. The Knox... 

It is seen that the HETP equation, as derived by Van Deemter, now applies only to a point distance (x) from the inlet of the column. Now, it has already been shown that... 

It is now seen that only the resistance to the mass transfer term for the stationary phase is position dependent. All the other terms can be used as developed by Van Deemter, providing the diffusivities are measured at the outlet pressure (atmospheric) and the velocity is that measured at the column exit. 

A number of HETP equations were developed other than that of Van Deemter. Giddings developed an alternative form that eliminated the condition predicted by the Van Deemter equation that there was a finite dispersion at zero velocity. However, the Giddings equation reduced to the Van Deemter equation at velocities approaching the optimum velocity. Due to extra-column dispersion, the magnitude of which was originally unknown, experimental data were found not to fit the Van Deemter... 

In the next chapter, experimental data supporting the Van Deemter equation will be described and discussed. Only data that has been acquired with equipment that has been specifically designed to eliminate, or reduce to an insignificant level, the dispersion sources described in this chapter can be used reliably for such a purpose. 

The results obtained were probably as accurate and precise as any available and, consequently, were unique at the time of publication and probably unique even today. Data were reported for different columns, different mobile phases, packings of different particle size and for different solutes. Consequently, such data can be used in many ways to evaluate existing equations and also any developed in the future. For this reason, the full data are reproduced in Tables 1 and 2 in Appendix 1. It should be noted that in the curve fitting procedure, the true linear velocity calculated using the retention time of the totally excluded solute was employed. An example of an HETP curve obtained for benzyl acetate using 4.86%v/v ethyl acetate in hexane as the mobile phase and fitted to the Van Deemter equation is shown in Figure 1. 

Examination of the data given in Table 2 shows a rational fit of the experimental data to the equations of Van Deemter, Giddings and Knox. Both the Huber and Horvath equations, however, gave alternating positive and negative values for the constant (D)... 

Stating the Van Deemter and Knox equations in the explicit form, the Van Deemter equation is... 

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