Void volume

Even if the analyte does not interact with the stationary phase, it will not appear in the detector immediately after injection. An HPLC column is filled with small particles of porous material which have a significant volume of the liquid phase between the particles and inside their porous space, so the noninteracting analyte still has to travel through this volume before it enters the detector. 

The volume of the liquid phase in the column is called void volume (Vo)-Several other names are also used in the chromatographic literature dead volume, hold-up volume, and sometimes retention volume of nonretained component. In this book we will be using term void volume.  

If a particular HPLC system provides constant and stable mobile-phase flow (F), one can convert retention volume (Vr) and void volume (Vo) into the retention time (Ir) and a void time (to). 

Void time can be interpreted as part of the total analyte retention time that the analyte actually spends in the mobile phase moving through the column, and for the rest of the retention time the analyte sits on the stationary phase surface. 

The void volume or void time is a very important parameter, and its correct determination could be critical for the interpretation of the experimental results. 

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Local average values of concentrations and partial pressures, rather chan point values, are also used in Che flux relations. However, in this case it is convenient to use interstitial local averages, based on the void volume rather than the total volume, since these are. ore closely related to the properties of bulk gases. 

Now suppose e(a) denotes the total void volume associated with pores of radii < a, per unit volume of the porous medium. This includes the contributions of any dead-end pores. Chough these are not taken into account in the distribution function f(a,ri). Then we shall write... 

Besides the solute peak, Figure 12.7 also shows a small peak eluted soon after the sample is injected into the mobile phase. This peak results from solutes that move through the column at the same rate as the mobile phase. Since these solutes do not interact with the stationary phase, they are considered nonretained. The time or volume of mobile phase required to elute nonretained components is called the column s void time, or void volume. 

Figure 9.14 Calibration curve for GPC as log M versus the retention volume Vj, showing how the location of the detector signal can be used to evaluate M. Also shown are the void volume Vy and the internal volume Vj in relation to Vj, and KVj as a fraction of Vj.

For large amounts of fillers, the maximum theoretical loading with known filler particle size distributions can be estimated. This method (8) assumes efficient packing, ie, the voids between particles are occupied by smaller particles and the voids between the smaller particles are occupied by stiH smaller particles. Thus a very wide filler psd results in a minimum void volume or maximum packing. To get from maximum packing to maximum loading, it is only necessary to express the maximum loading in terms of the minimum amount of binder that fills the interstitial voids and becomes adsorbed on the surface of the filler. 

Bulk Density. Bulk density, or the apparent density, refers to the total amount of space or volume occupied by a given mass of dry powder. It includes the volume taken up by the filler particles themselves and the void volume between the particles. A functional property of fillers in one sense, bulk density is also a key factor in the economics of shipping and storing fillers. 

Specific gravity is the most critical of the characteristics in Table 3. It is governed by ash content of the material, is the primary deterrninant of bulk density, along with particle size and shape, and is related to specific heat and other thermal properties. Specific gravity governs the porosity or fractional void volume of the waste material, ie. 

Rapid heating of either borax decahydrate or pentahydrate causes the crystal to dissolve before significant dehydration, and at about 140°C, puffing occurs from rapid vaporisation of water to form particles having as high as 90% void volume and very low bulk density (78). 

Stmcture is usually measured by a void volume test such as the absorption of dibutyl phthalate (DBPA) (15), or by bulk density measurements of the carbon black under compression. In order to eliminate the effects of pelletizing conditions the DBPA test has been modified to use a sample that has been precompressed at a pressure of 165 MPa (24,000 psi) and then broken up four successive times (24M4) (16). This procedure causes some aggregate breakdown and is claimed to more closely approximate the actual breakdown that occurs duting mbber mixing. 

With closely screened material, the percentage of voids (usually 37 percent) is independent of particle size. With unscreened particles showing a wide variation in size, the void volume is decreaseci irregularity in gas flow results. 

Fig. 12-88. Curve A shows the calculated surface based on an assumed 50 percent void volume and cubical-shaped particles. The B set of cui ves applies to such unscreened irregularly shaped particles as are usually encountered in practice.

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