Impressions of irreversible Thermodynamics from Bejan

Irreversible thermodynamics illuminates the connection between thermodynamics and

transport phenomena. Transport phenomena may mean heat transport or mass transport.
Usually the laws governing the heat and mass transfer phenomena are governed by
empirical and observation based effects (just like thermodynamics laws). For example,
the Fourier law of heat conduction, Fick’s law for diffusion are all observation based.
Traditional thermodynamics is static in nature and just deals with energy accounting and
it does not go into the representation of the transport phenomena. Time does not come
into the picture except for the ideas of spontaneous and non-spontaneous processes
illustrated by the concept of entropy. The theories of transport phenomena are developed
to represent the rate processes and hence bring time into the picture. The combination of
thermodynamics and the transfer phenomena gives rise to the thermodynamic theory of
rate processes and is called irreversible thermodynamics. However, note that the concept
of equilibrium of a phase still holds and the irreversibilities are due to the transfer
between two equilibrium phases.

Irreversible thermodynamics concerns with the rates of energy and mass transfer
interactions that occur in the space between macroscopic systems that are not mutually in
equilibrium (but are in the state of local equilibrium (although the system as a whole is
not in equilibrium), themselves and even during the occurrence of the irreversible transfer
process move from one equilibrium state to another and is said to be in quasi
equilibrium).

He claims the following to be the contributions of the irreversible

thermodynamics (though it does not give any new physical insight into the relationship
between interaction rates and local thermodynamic properties of the system penetrated by
these interactions).

1. It makes a contribution in the realm of coupled transport phenomena, where two

or more transport processes coexist and influence each other. (I don’t know how
this contribution is made. The Onsager reciprocity relations are derived from
statistical mechanics. In the macroscopic irreversible thermodynamics treatment,
they are assumed to be true postulates. The connection between the expressions
derived from thermodynamics theory and the Onsagers relations is not at all clear.
Is it that the relations derived from thermodynamic theory and the Onsagers
relation are same and therefore we can gain some insight by comparing the two?)
2. The irreversible thermodynamics approach promotes a unified and analytically
compact treatment of all irreversible flow phenomena. (This has to be seen. May
be I can consider heat conduction and mass diffusion for understanding this
point).

Maintenance of uniform intensive properties throughout the system is essential for the
system to be in equilibrium and reversible (Obviously). The concepts of irreversibility
and entropy generation are associated with changes (flows) associated with intensive
property non-uniformities that can exist in the system.
Gibbs-Duhem relation specifies the number of intensive properties of the system that can
be specified independently. (Does the Gibbs-Duhem relation and the Gibbs phase rule
leads to the same conclusion regarding the number of degrees of the system?)
Considering two such equilibrium systems, we find that the discontinuities in the
intensive properties across the partition that separated the two systems are responsible for
the mass and energy interactions that cross the partition.

Assumption:

The interactions between the two systems are sufficiently slow so that during time
interval dt, the distributions of intensive properties remain uniform for each single phase
system. (This means the two systems between which the interactions take place remain in
equilibrium always. They move from one equilibrium state to another and the process is
described as quasi-static).

The changes in entropy for the two systems are written using the differential form of the
fundamental relation in entropy representation. The sum of these two changes gives the
total entropy generated in the system. This expression for the entropy generated in the
system is then rearranged so as to separate out the intensive property changes (the change
in chemical potential and the temperature between the two phases) (in other words the
driving forces) and the extensive property rates (after being divided by dt on both sides)
(N’s and U’s) (in other words flows or fluxes).

As the entropy generated can be considered to occur only at the partition (as the two
phases separated by the partition are individually at equilibrium), the expression for the
entropy generation is divided by the cross sectional area of the partition and the across
distance to make it the entropy generated per unit volume of the partition (named as the
volumetric entropy generation rate).

The same expression for entropy generation rate has been generalized for three
dimensions using the gradient stuff, which I will leave for now.

After replacing the energy flux (internal energy flux actually) by the summation of
enthalpy flux and heat flux (which are the two possible avenues for energy flux), the
driving effort and the fluxes in each term is identified. It turns out that the driving efforts
are discontinuities in “1/T’ and “mu/T”. Some sort of insight can probably be attained
here. But I am not sure.