Thermodynamics of the Young Equation

The extensive use of the Young equation (Eq. X-18) reflects its general acceptance. Curiously, however, the equation has never been verified experimentally since surface tensions of solids are rather difficult to measure. While Fowkes and Sawyer [140] claimed verification for liquids on a fluorocarbon polymer, it is not clear that their assumptions are valid. Nucleation studies indicate that the interfacial tension between a solid and its liquid is appreciable (see Section K-3) and may not be ignored. Indirect experimental tests involve comparing the variation of the contact angle with solute concentration with separate adsorption studies [173]. 

The microscopic complexity of the contact angle is illustrated in Fig. X-14, which shows the edge of a solidified drop of glass—note the foot that spreads out from the drop. Ruckenstein [176] discusses some aspects of this, and de Gennes [87] has explained the independence of the spreading rate on the nature of the substrate as due to a precursor film present also surrounding a nonspread- 

Bikerman [182] criticized the derivation of Eq. X-18 out of concern for die ignored vertical component of On soft surfaces a circular ridge is raised at the periphery of a drop (see Ref. 67) on harder solids there is no visible effect, but the stress is there. It has been suggested that the contact angle is determined by the balance of surface stresses rather than one of surface free energies, the two not necessarily being the same for a 

The integral A/, while expressible in terms of surface free energy differences, is defined independently of such individual quantities. A contact angle situation may thus be viewed as a consequence of the ability of two states to coexist bulk liquid and thin film. 

Koopal and co-workers [186] have extended this thermodynamic analysis to investigate the competitive wetting of a solid by two relatively immiscible liquids. They illustrate the tendency of silica to be preferentially wet by water over octane, a phenomenon of importance in oil reservoirs. 

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