A New Method of Examination of Surface Films

Extract

For the quantitative examination of the behaviour of two-dimensional insoluble films on water surfaces the trough apparatus devised originally by Langmuir has been hitherto employed. With the aid of this apparatus it has been possible to demonstrate the existence of two-dimensional films in the solid, smectic, liquid and vaporous states, to observe the phenomenon of two-dimensional dimorphism, to study the conditions of phase equilibria and to measure the entropy changes associated with the process of two-dimensional fusion, vaporisation and sublimation. No very definite concept of molecular orientation has been obtained from the force area diagrams. Apart from the fact that the polar groups adhere to the surface and that the hydrocarbon chains in long chain compounds adhere to one another, our picture of all forms of films except possibly the solid and the highly attenuated or vaporous states is by no means clear and the various suggestions made as to the molecular architecture are somewhat problematical. Two other methods suggest themselves for gaining a further insight into molecular structure: optical methods on the lines outlined by Rayleigh and by Raman and measurements of the interphasic potential differences. While it may be possible in the future to develop the former into a method of precision, we have succeeded in rendering the latter as accurate as the method of the Langmuir trough. That interphasic potentials between air and liquid exist and are of not inconsiderable magnitude has long been known, although the first systematic investigations on changes in these potentials on the addition of capillary active materials to the liquid phase were made by Kenrick (Z.P.C. xix, 625,1896). The technique was considerably improved by Guyot (C.R. clix, 307, 1914, Ann. d. Phys. x, 2501, 1924) and by Frumkin (Z.P.C. cix, 34, 1924, cxi, 196, 1924, cxv, 485, 1925).