HDC

At least two catalytic processes have been used to purify halogenated streams. Both utilize fluidized beds of probably noimoble metal catalyst particles. One has been estimated to oxidize >9000 t/yr of chlorinated wastes from a vinyl chloride monomer plant (45). Several companies have commercialized catalysts which are reported to resist deactivation from a wider range of halogens. These newer catalysts may allow the required operating temperatures to be reduced, and stiU convert over 95% of the halocarbon, such as trichlorethylene, from an exhaust stream. Conversions of C-1 chlorocarbons utilizing an Englehardt HDC catalyst are shown in Figure 8. For this system, as the number of chlorine atoms increases, the temperatures required for destmction decreases. 

As noted, hdc U calciilated in terms of equivalent clear liquid. Actu-ahy, the liquid in the downcomer may be aerated and ac tual backup is... 

GPC has many uses and is a powerful analysis technique for acrylate polymers. With care in selecting solvents and stationary phases, one finds that many polymers can be analyzed successfully. Opportunities always exist to use analytical GPC columns in nonstandard ways (semiprep, HDC, pseudo-ElPLC combined with GPC ) to the benefit of the analyst, but the analyst must always be keenly aware of which mode of operation is dominating when practicing such nonroutine analyses. 

Hydrodynamic chromatography (HdC) is a relatively new technique, especially in molecular weight separation. It was first investigated in 1969 by DiMarzio and Guttman (1,2) and was called separation by flow (3,4). Small started calling it hydrodynamic chromatography in 1974 (5). The application of this technique was first concerned with the separation of particle size. Prud homme applied it to the molecular weight separation of macromolecules in 1982 (6). 

The instrumentation of HdC, including a pump, an injector, a column (set), a detector, and a recorder or computer, is very similar to size exclusion chromatography SEC). The essence of this technique is the column. There are two types of HdC columns open microcapillary tubes and a nonporous gel-packed column. This chapter emphasizes column technology and selection and the applications of this technique on the molecular weight analysis of macromolecules. 

Although the early studies on HdC were done using packed columns, the basic principles of HdC are easily explained by considering the transport of spherical... 

Figure 22.2 shows the relation of molecular size to the retention time in HdC. However, the correlation of molecular weight to the retention time is needed to apply the technique. Consider all polymer radii to be represented by the general equation... 

HdC separation also occurs in the interstices of a packed column, although the configuration of channels is not as simple as a microcapillary tube. The... 

Most of the PCHdC columns are packed with nonporous spherical gels, except the work done by Mori et al. (20), in which the HdC column was packed with 0.9- to 1.4-/rm glass rods. 

The nonporous spherical gels for PCHdC are often specially prepared for research purposes. However, nonporous polystyrene/divinylbenzene beads. Solid Bead, can be obtained in various particle sizes from Jordi Associates, Inc. (Bellingham, MA). Columns packed with these gels can be used for HdC of the polymers that are currently analyzed using polystyrene/divinylbenzene SEC columns. Fumed silica nanospheres are offered by Cabot (Tuscola, IL) (17), and nonporous silica (NPS) microspheres are offered by Micra Scientific, Inc. (Northbrook, IL). These nonporous silica gels may also be used for HdC. 

As in SEC, the surface chemistry of the HdC gels should be similar to that of the mobile phase and the solute. Otherwise, the retention time may increase as with the nonsize exclusion effects. However, the tolerance of PCHdC for a poorer mobile phase is better than SEC. The polymer size under 0 conditions has been studied using PCHdC (19). 

Fig. 22.11. Because the HdC separation does not involve the stagnant mohile-phase transfer, the HdC peaks are significantly narrower than the SEC peaks. The HdC separation in columns with large-pore gels will not he obvious because its separation range will overlap and mix with the SEC separation.

The HdC calibration curves of different particle sizes, as shown in Fig. 22.12 (30), are similar to the calibration curves of different pore size columns the separation ranges of MW due to hydrodynamic chromatography depend on particle size. The larger the particle size, the higher the MW ranges. Stegeman et al. (30) proposed that a smooth calibration curve may be achieved by proper ratio of the particle diameter to the pore diameter. 

FIGURE 22.12 Theoretical HdC/SEC calibration graphs for different particle diameters. Pore diameter = 10 nm particle diameters dotted line, S /xm dashed line, 3 /xm solid line, I /xm. (Reprinted from J. Chromatogr., 550, 728, Copyright 1991, with permission from Elsevier Science.)... 

The comparison among these techniques is tabulated in Table 22.1. In summary, HdC is a separation technique with low selectivity however, the efficiency can be very high. Especially in PCHdC, high analysis speed can be achieved over a wide MW range. ThFFF performs best for the separation of high MW samples. SEC has an intermediate selectivity between FldC and ThFFF. Practicality makes SEC the most suitable method for the common MW range of synthetic polymers. SEC is by far the most commonly used technique for molecular weight distribution determinations. However, HdC is better for the fast analysis purpose. 

Another advantage of HdC is its generosity in terms of mobile-phase selection. The polymer size and solution properties of a polymer can be studied using HdC, especially OTHdC, in almost any solvent. In SEC, by comparison, the packing material and mobile phase have to be selected to prevent the nonsize exclusion effect. Because the instrumentation of HdC is similar to SEC, and the packing material and columns have become available commercially, this technique will gain in popularity. 

Another area of rapid growth for particle separation has been that of Field-Flow Fractionation (FFF) originally developed by Giddings (12,13>1 1 ) (see also papers in this symposium series). Like HDC, the separation in field-flow fractionation (FFF) results from the combination of force field interactions and the convected motion of the particles, rather than a partitioning between phases. In FFF the force field is applied externally while in HDC it results from internal, interactions. 

This paper will be limited to a discussion of our packed column studies in which we have addressed attention to questions regarding, (a) the role of ionic strength and surfactant effects on both HDC and porous packed column behavior, (b) the effects of pore size and pore size distribution on resolution, and (c) the effects of the light scattering characteristics of polystyrene on signal resolution and particle size distribution determination. 

Calculations for Rp as a function of the relevant experimental parameters (eluant ionic species concentration-including surfactant, packing diameter, eluant flow rate) and particle physical and electrochemical properties (Hamaker constant and surface potential) show good agreement with published data (l8,19) Of particiilar interest is the calculation which shows that at very low ionic concentration the separation factor becomes independent of the particle Hamaker constant. This result indicates the feasibility of xmiversal calibration based on well characterized latices such as the monodisperse polystyrenes. In the following section we present some recent results obtained with our HDC system using several, monodisperse standards and various surfactant conditions. 

Complete recoveries are essential for the calculation of accurate particle size distributions from HDC data. In Small s work (O NaCl was used to increase the ionic strength of the eluant phase, however, quantitative results were not reported for any of the recoveries, especially at high ionic strengths, other than the statement that no latexes of 338 nm or 35T nm diameter were eluted at 0.1T6 M. In our case using SLS only in the mobile... 

As noted before, the whole spectrum of particle sizes between 38 and 357 nm is encompassed with a AV of U.O ml or about 6% of the total column void volume. This low capacity of the HDC system is counterbalanced by its excellent resolution both of itself and in comparison to porous packing systems. The latter point is addressed in the next section. 

The experimental set-up used for porous chromatography is virtually identical, to that used for HDC as described elsewhere (i6,1T). The use of stainless steel columns for the LEG work required 3l6 stainless steel column end-fittings and l/l6 O.D. capillary tubing. 

Figure 3, HDC universal calibration curve (eluant ionic strength L29rriM. AM A monodisperse lattices (O) polystyrene polyvinyl chloride ( ) poly (styrene-...

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