The effects of shape on the interaction of colloidal particles

TLDR: In this article, it was shown that colloids in general are apt to exhibit considerable deviations from Raoult's law and that crystalline phases retaining a fair proportion of solvent may separate from concentrated solutions.

Abstract: Introdzution. The shapes of colloidal particles are often reasonably compact, so that no diameter greatly exceeds the cube root of the volume of the particle. On the other hand, we know many coiloids whose particles are greatly extended into sheets (bentonite), rods (tobacco virus), or flexible chains (myosin, various Iinear polymers). In some instances, a t least, solutions of such highly anisometric particles are known to exhibit remarkably great deviations from Raoult’s law, even to the extent that an anisotropic phase may separate from a solution in which the particles themselves occupy but one or two per cent of the total volume (tobacco virus, bentonite). We shall show in what follows how such results may arise from electrostatic repulsion between highly anisometric particles. Most colloids in aqueous solution owe their stability more or less to electric charges, so that each particle will repel others before they come into actual contact, and effectively claim for itself a greater volume than what it actuaily occupies. Thus, we can understand that colloids in general are apt to exhibit considerable deviations from Raoult’s law and that crystalline phases retaining a fair proportion of solvent may separate from concentrated solutions. However, if we tentatively increase the known size of the particles by the known range of the electric forces and multiply the resulting volume by four in order to compute the effective van der Waal’s co-volume, we have not nearly enough to explain why a solution of 2 per cent tobacco virus in 0.005 normal NaCZ forms two phases.