Mercury porisimetry

Many adsorbents, particularly the amorphous adsorbents, are characterized by their pore size distribution. The distribution of small pores is usually determined by analysis, using one of several available methods, of a cryogenic nitrogen adsorption isotherm, although other probe molecules are also used. The distribution of large pores is usually determined by mercury porisimetry [Gregg and Sing, gen. refs.]. 

Determination of Pore Size Distributions. The shape and range of a GPC calibration curve are, in part, a reflection of the pore size distribution (PSD) of the column packing material. A consideration of the nature of PSDs for the ULTRASTYRAGEL columns to be used in this work is therefore appropriate. The classical techniques for the measurement of PSDs are mercury porisimetry and capillary condensation. The equipment required to perform these measurements is expensive to own and maintain and the experiments are tedious. In addition, it is not clear that these methods can be effectively applied to swellable gels such as the styrene-divinylbenzene copolymer used in ULTRASTYRAGEL columns. Both of the classical techniques are applied to dry solids, but a significant portion of the pore structure of the gel is collapsed in this state. For this reason, it would be desirable to find a way to determine the PSD from measurements taken on gels in the swollen state in which they are normally used, e.g. a conventional packed GPC column. 

Dullien et. al. [55-57] examined salt particles embedded in a matrix of Wood s metal using the principles of quantitative stereology. They then leached out the salt particles and examined the matrix using mercury porisimetry. Poor agreement was obtained and this they attribute to the mercury porosimetry being controlled by neck diameter. Nicholson... 

Pore sixe distribution data obtained from gas desorption (Barret et al. 1951) and mercury porisimetry experiments together with a knowledge of adsorbate molecular size thus enables the mode of diffusive transport to be ascertained. It should be noted that both molecular and Knudsen diffusion may occur in the same porous medium when the porous medium contains both macropores and micropores (revealed from an analysis of a bimodal pore size distribution curve). Unconstrained molecular diffusion. Dm, and Knudsen diffusion, Dk, coefficients are subsequently calculated from formulae derived from transport properties of fluids (gaseous and liquid) and the kinetic theory of gases. The molecular diffusivity for a binary gas mixture of A and B is evaluated from the Chapman-Enskog theory (Chapman and Cowling 1951) equation... 

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