Solids by Mercury Displacement Method

A helium-mercury displacement method is sometimes used to check the pore volume obtained from the adsorption-desorption isotherm at the saturation pressure (Ries, Van Nordstrand, Johnson, and Bauer-meister, 50). The helium measurement which gives the solid volume and solid density is obtained by means of a miniature isotherm type apparatus. This part of the determination is essentially the same as that described by Smith and Howard (58) and Schumb and Rittner (55). Mercury displacement yields the pellet volume and pellet density and is measured volumetrically by means of a mercury buret attached directly to the same sample bulb in which the helium measurement is performed. The difference between the pellet volume and the solid volume is obviously the pore volume. 

The particle density is the weight of a unit volume of solid, including the pores and cracks (Mahajan and Walker, 1978). The particle density can be determined by any of three methods (1) mercury displacement (Gan et al., 1972) (2) gas flow (Ergun, 1951) and (3) silanization (Ettinger and Zhupakhina, 1960). 

A more accurate procedure is the helium-mercury method. The volume of helium displaced by a sample of catalyst is measured then the helium is removed, and the volume of mercury displaced is measured. Since mercury will not fill the pores of most catalysts at atmospheric pressure, the difference in volumes gives the pore volume of the catalyst sample. The volume of helium displaced is a measure of the volume occupied by the solid material. From this and the weight of the sample, the density of the solid phase, P5, can be obtained. Then the void fraction, or porosity, of the particle, p, may be calculated from the equation... 

Various methods are available for determining the density of a phase, many of them based on the measurement of the mass of a fixed volume or on a buoyancy technique. Three examples are shown in Fig. 2.4 on the next page. Similar apparatus may be used for gases. The density of a solid may be determined from the volume of a nonreacting liquid (e.g., mercury) displaced by a known mass of the solid, or from the loss of weight due to buoyancy when the solid is suspended by a thread in a liquid of known density. 

Here the volume is the sum of the solid, closed pores, and accessible pores within the particle. It is essentially the volume of the particle, but should not be found by measuring dimensions. A displacement pychometer is used but with a fluid that does not penetrate the interior pores of the pellet. One approach is to fill these pores with the fluid prior to displacement, for example, with methanol. A more satisfactory method is to use mercury,... 

In other cases, the method of removal depends upon the nature of the product, e.g. gases may be (1) vented from the reactor, possibly via a slight reduction In pressure (2) displaced from the electrolyte via inert gas sparging (3) segregated via a solid polymer electrolyte (section 5.2) or recirculated via a gas-liquid separator. Liquid products may be (1) separated by flotation or settlement if they are immiscible and have a markedly different density to the electrolyte or (2) emulsified by mixing, then swept out of the reactor. Solid products can be separated via (I) flotation or settlement (2) fluidization or tangential shear to remove them from the reactor (3) solvent extraction or incorporation into a mercury phase, e.g. amalgamation of metals. 

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