rties of the system.

It may be
ctions of
ime. Such
measured

admitted that on repeated measurement of those conjugate intensive fun

state, they are found to have slightly different values from time to t
variability is regarded as due to internal fluctuations. The different
values average to their nominal values.

If the system is truly macroscopic as postulated by classical thermodynamics, th

en the fluctuations are too small to detect macroscopically. This is called the
thermodynamic limit. In effect, the molecular nature of matter and the quantal n
ature of momentum transfer have vanished from sight, too small to see.
If the system is repeatedly subdivided, eventually a system is produced that is
small enough to exhibit obvious fluctuations. This is a mesoscopic level of inve
stigation. The fluctuations are then directly dependent on the natures of the va
rious walls of the system. The precise choice of independent state variables is
then important. At this stage, statistical features of the laws of thermodynamic
s become apparent.
If the mesoscopic system is further repeatedly divided, eventually a microscopic
system is produced. Then the molecular character of matter and the quantal natu
re of momentum transfer become important in the processes of fluctuation. One ha
s left the realm of classical or macroscopic thermodynamics, and one needs quant
um statistical mechanics. The fluctuations can become relatively dominant, and q
uestions of measurement become important.
The statement that 'the system is its own internal thermodynamic equilibrium' ma
y be taken to mean that 'indefinitely many such measurements have been taken fro
m time to time, with no trend in time in the various measured values'. Thus the
statement, that 'a system is in its own internal thermodynamic equilibrium, with
stated nominal values of its functions of state conjugate to its specifying sta
te variables', is far far more informative than a statement that 'a set of singl
e simultaneous measurements of those functions of state have those same values'.
This is because the single measurements might have been made during a slight fl
uctuation, away from another set of nominal values of those conjugate intensive
functions of state, that is due to unknown and different constitutive properties
. A single measurement cannot tell whether that might be so, unless there is als
o knowledge of the nominal values that belong to the equilibrium state.
Thermal equilibrium[edit]
Main article: Thermal equilibrium
An explicit distinction between 'thermal equilibrium' and 'thermodynamic equilib
rium' is made by B. C. Eu. He considers two systems in thermal contact, one a th
ermometer, the other a system in which there are occurring several irreversible
processes, entailing non-zero fluxes; the two systems are separated by a wall pe
rmeable only to heat. He considers the case in which, over the time scale of int
erest, it happens that both the thermometer reading and the irreversible process
es are steady. Then there is thermal equilibrium without thermodynamic equilibri
um. Eu proposes consequently that the zeroth law of thermodynamics can be consid
ered to apply even when thermodynamic equilibrium is not present; also he propos
es that if changes are occurring so fast that a steady temperature cannot be def
ined, then "it is no longer possible to describe the process by means of a therm
odynamic formalism. In other words, thermodynamics has no meaning for such a pro
cess."[51] This illustrates the importance for thermodynamics of the concept of
temperature.
Thermal equilibrium is achieved when two systems in thermal contact with each ot
her cease to have a net exchange of energy. It follows that if two systems are i
n thermal equilibrium, then their temperatures are the same.[52]

Thermal equilibrium occurs when a system's macroscopic thermal observables have

ceased to change with time. For example, an ideal gas whose distribution functio
n has stabilised to a specific Maxwell Boltzmann distribution would be in thermal
equilibrium. This outcome allows a single temperature and pressure to be attribu
ted to the whole system. For an isolated body, it is quite possible for mechanic
al equilibrium to be reached before thermal equilibrium is reached, but eventual
ly, all aspects of equilibrium, including thermal equilibrium, are necessary for
thermodynamic equilibrium.[53]
Non-equilibrium[edit]
Main article: Non-equilibrium thermodynamics
A system's internal state of thermodynamic equilibrium should be distinguished f
rom a "stationary state" in which thermodynamic parameters are unchanging in tim
e but the system is not isolated, so that there are, into and out of the system,
non-zero macroscopic fluxes which are constant in time.[54]
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with sys
tems that are not in thermodynamic equilibrium. Most systems found in nature are
not in thermodynamic equilibrium because they are changing or can be triggered
to change over time, and are continuously and discontinuously subject to flux of
matter and energy to and from other systems. The thermodynamic study of non-equ
ilibrium systems requires more general concepts than are dealt with by equilibri
um thermodynamics. Many natural systems still today remain beyond the scope of c
urrently known macroscopic thermodynamic methods.
General references[edit]