Packed columns HETP equation

Effect of Mobile Phase Compressibility On the HETP Equation for a Packed GC Column... 

Thus, the complete HETP equation for a packed GC column that takes into account the compressibility of the carrier gas will be... 

Equation (15) gives the variance per unit length of a GC column in terms of the outlet pressure (atmospheric) the outlet velocity and physical and physicochemical properties of the column, packing, and phases and is independent of the inlet pressure. However, equation (13) is the recommended form for HETP measurements as the inlet pressure of a column is usually known, and is the less complex form of the HETP expression. 

Katz et al. [1] also examined the effect of particle diameter on resistance to mass transfer constant (C). They employed columns packed with 3.2 im, 4.4 p,m, 7.8 pm, and 17.5 pm, and obtained HETP curves for the solute benzyl acetate in 4.3%w/w of ethyl acetate in n-heptane on each column. The data were curve fitted to the Van Deemter equation and the values for the A, B and C terms for all four columns extracted. A graph relating the value of the (C) term with the square of the particle diameter is shown in Figure 8. 

The Van Deemter equation remained the established equation for describing the peak dispersion that took place in a packed column until about 1961. However, when experimental data that was measured at high linear mobile phase velocities was fitted to the Van Deemter equation it was found that there was often very poor agreement. In retrospect, this poor agreement between theory and experiment was probably due more to the presence of experimental artifacts, such as those caused by extra column dispersion, large detector sensor and detector electronic time constants etc. than the inadequacies of th Van Deemter equation. Nevertheless, it was this poor agreement between theory and experiment, that provoked a number of workers in the field to develop alternative HETP equations in the hope that a more exact relationship between HETP and linear mobile phase velocity could be obtained that would be compatible with experimental data. 

The identification of the pertinent HETP equation must, therefore, be arrived at from the results of a sequential series of experiments. Firstly, all the equations must be fitted to a series of (H) and (u) data sets and those equations that give positive and real values for the constants of the equations identified. The explicit form of those equations that satisfy the preliminary data, must then be tested against a series of data sets that have been obtained from different chromatographic systems. Such systems might involve columns packed with different size particles or employ mobile phases or solutes having different but known physical properties. 

The rate theory examines the kinetics of exchange that takes place in a chromatographic system and identifies the factors that control band dispersion. The first explicit height equivalent to a theoretical plate (HETP) equation was developed by Van Deemter et al. in 1956 [1] for a packed gas chromatography (GC) column. Van Deemter et al. considered that four spreading processes were responsible for peak dispersion, namely multi-path dispersion, longitudinal diffusion, resistance to mass transfer in the mobile phase, and resistance to mass transfer in the stationary phase. 

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. 

Strigle [94] proposed this term to better describe the performance of a packed column at or near the previously described loading point. Kister [93] evaluated the limited published data and proposed using the MOC at 95% of the flood point. The flood point can be estimated by Equation 9-20 or from the plots in References 90 and 93. The data are reported to be within 15-20% of the prediction [93]. See Figure 9-22 for the identification of MOC on the HETP vs. Cg chart For more accurate information... 

The conceptual idea of a theoretical plate can be used in SEC to measure column efficiency and to compare the performance of packed coluians. For column comparisons it is usually measured with small molecules, such as toluene, acetone or benzyl alcohol, which can explore all of the pores of the packing (K jc - 1). Plate counts measured in this way produce HETP values lower than the actual values measured with monodisperse polymers and proteins. The plate count in this case can be expressed by equation (4.40)... 

As with distillation, the correlation for overall tray efficiency for absorbers, given in Equation 10.7, should only be used to derive a first estimate of the actual number of trays. More elaborate and reliable methods are available, but these require much more information on tray type and geometry and physical properties. If the column is to be packed, then the height of the packing is determined from Equation 9.64. As with distillation, the height equivalent of a theoretical plate (HETP) can vary... 

Ellis(36) presented the following dimensionally consistent equation for the HETP (Zt) of packed columns using 25 and 50 mm Raschig rings ... 

A column having a smaller HETP value is a good column because diffusion inside the column is small, resulting in better separation. The HETP value is given by the Van Deemter equation, which describes the peak broadening of packed columns through which a non-compressible solvent is moving. 

---