Surface energy, molecular measurement

This effect assumes importance only at very small radii, but it has some applications in the treatment of nucleation theory where the excess surface energy of small clusters is involved (see Section IX-2). An intrinsic difficulty with equations such as 111-20 is that the treatment, if not modelistic and hence partly empirical, assumes a continuous medium, yet the effect does not become important until curvature comparable to molecular dimensions is reached. Fisher and Israelachvili [24] measured the force due to the Laplace pressure for a pendular ring of liquid between crossed mica cylinders and concluded that for several organic liquids the effective surface tension remained unchanged... 

The interface between a solid and its vapor (or an inert gas) is discussed in this chapter from an essentially phenomenological point of view. We are interested in surface energies and free energies and in how they may be measured or estimated theoretically. The study of solid surfaces at the molecular level, through the methods of spectroscopy and diffraction, is taken up in Chapter VIII. 

Fig. 17. Adhesion energy G measured as a function of the surface density of the interfacial chains. It may noted that the strength measured in a peel test (a) is about 5 times larger than that measured using the JKR method (b). Further, a maximum exists in the value of G as function of the surface chain density. This is because of swelling effects at larger values of surface chain density. The open symbols represent the data for elastomer molecular weight Mo = 24,000 and the closed symbols represent the data for Mo = 10,000.

This section introduces the principal experimental methods used to study the dynamics of bond making/breaking at surfaces. The aim is to measure atomic/molecular adsorption, dissociation, scattering or desorption probabilities with as much experimental resolution as possible. For example, the most detailed description of dissociation of a diatomic molecule at a surface would involve measurements of the dependence of the dissociation probability (sticking coefficient) S on various experimentally controllable variables, e.g., S 0 , v, J, M, Ts). In a similar manner, detailed measurements of the associative desorption flux Df may yield Df (Ef, 6f, v, 7, M, Ts) where Ef is the produced molecular translational energy, 6f is the angle of desorption from the surface and v, J and M are the quantum numbers for the associatively desorbed molecule. Since dissociative adsorption and... 

Solids also have surface tension because molecules on the surface of a solid particle are subject to fewer attractive forces than molecules in the bulk of the solid. Measurements of the surface tension of solids (usually called the surface energy) are difficult because solids are rarely pure and smooth on the molecular scale. 

---