  The paper presents new thermodynamic paradigm of chemical equilibrium,
setting forth comprehensive basics of Discrete Thermodynamics of Chemical
Equilibria (DTd). Along with previous results by the author during the last
decade, this work contains also some new developments of DTd. Based on the
Onsager's constitutive equations, reformulated by the author thermodynamic
affinity and reaction extent, and Le Chatelier's principle, DTd brings forward
a notion of chemical equilibrium as a balance of internal and external
thermodynamic forces (TdF), acting against a chemical system. Basic expression
of DTd is the chemical system logistic map of thermodynamic states that ties
together energetic characteristics of chemical reaction, occurring in the
system, the system shift from "true" thermodynamic equilibrium (TdE), and
causing that shift external thermodynamic forces. Solutions to the basic map
are pitchfork bifurcation diagrams in coordinates "shift from TdE - growth
factor (or TdF)"; points, corresponding to the system thermodynamic states, are
dwelling on its branches. The diagrams feature three typical areas: true
thermodynamic equilibrium and open equilibrium along the thermodynamic branch
before the threshold of its stability, i.e. bifurcation point, and bifurcation
area with bistability and chaotic oscillations after the point. The set of
solutions makes up the chemical system domain of states. The new paradigm
complies with the correspondence principle: in isolated chemical system
external TdF vanish, and the basic map turns into traditional expression of
chemical equilibrium via thermodynamic affinity. The theory binds together
classical and contemporary thermodynamics of chemical equilibria on a unique
conceptual basis. The paper is essentially reworked and refocused version of
the earlier preprint on the DTd basics, supplemented with new results.
