The Third Principle of thermodynamics and the zero-point entropy of glasses: History and new developments

Thermodynamic properties of amorphous solids: The electrochemical approach

“…It is predicted by classical thermodynamics, that for equilibrium systems at T → 0, according to the usually cited Planck's postulate [20] we should expect for this difference a value of ΔS 0 = 0. However for non-equilibrium systems (as glasses typically are known to be), it is to be expected that ΔS 0 > 0, again according to Planck (see [20], p.280-281 and also [21,22]). In this second statement Planck (citing Simon's experimental findings [6]) refers to both multi-component and single-component systems in non-equilibrium.…”

“…A survey of theoretical expectations on this essential problem of zeropoint entropy in glasses, as they follow from the standpoint of both classical thermodynamics and in the framework of the thermodynamics of non-equilibrium systems may be found in refs. [4,8,9,22]. Differing views on this problem are expressed in refs.…”

“…[23][24][25]; a cross-section through the publications and ideas of different authors on the significance of entropy in glasses, as they have been expressed in a recent conference is summarized in the respective Proceedings Volume of the JNCS [26], edited by Wondraczek and Conradt. In this volume (especially in the introductory paper [22] and in recent publications like [8,22,[27][28][29]) different argumentations of the statement may be found, that for non-equilibrium systems in general theory predicts and that experiment shows in particular for glasses frozenin entropy differences glass/crystal ΔS g = ΔS o > 0, remaining practically constant from glass-transition temperatures, T g, down to the zero-point of temperatures, T → 0.…”

“…We see in this respect a new and non-exploited possibility in the electrochemical measurements discussed here: they indicate a new way in the determining the values of both the ΔH g -and the ΔS g -differences. The significance of new sources of experimental evidence in this respect has been already outlined in recent literature [22,23,27,28], mainly in considering application to glass solubility experimentation results, as they are presented in refs. [13][14][15]22].…”

“…[22] that the partly or fully degenerated electron gas in metallic glasses and crystals has to be similar in its properties in the liquid, the vitreous and the crystalline forms of the same substance. The electron gas follows quantum statistics and thus (as also shown in [22]) the electronic properties of glasses do not display the freezing-in effects, caused by the stiffened configurational structure of glass, and those of its structural entities, governed by classical Boltzmann statistics. This imposes, as discussed here in Section 4, specific properties on the glass/ crystal contact potential.…”