ABSTRACT
The way of analysis of thermodynamic systems, which takes into consideration systems' phase volumes, is suggested. A validity of such approach was verified by the example of studying of extrathermodynamic compensations. Several types of exact linear extrathermodynamic compensations as well as their peculiar type, which peculiarity is indefinable compensation temperature, are established. The criteria that specify these types are stated. These results are illustrated by the identified exact extrathermodynamic compensations in formation of pyrene excimers.
ABSTRACT
There are several types of the ΔH compensation. Along with well-known phenomenon of the ΔH - ΔS compensation, two more types of the ΔH - (ΔS + RΔ ln Ω) compensation are observed in some series of systems. The nature of these phenomena is connected with the behavior of phase volume of systems, Ω. The role of other thermodynamic parameters, which describe series in manifestation of this or that types of the ΔH compensation, is shown in light of molecular statistical mechanics.
ABSTRACT
A new type of extrathermodynamic relationship is presented: DeltaH = Ti[DeltaS + R Delta(ln Omega)] + beta, where Omega is the phase volume and beta is a constant. This type of relationship holds for a series of systems in the case where deltaDelta(ln Omega) is changeable. The relation between this type of correlation and linear free-energy relationships is shown. An example of the specified correlation for energy parameters of excimers forming in different dipyrenylalkanes is demonstrated.
