The plain term 'thermodynamics' refers to a macroscopic description of bodies and processes.

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"Any reference to atomic constitution is foreign to classical thermodynamics."
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The qualified
term 'statistical thermodynamics' refers to descriptions of bodies and processes in terms of the
atomic constitution of matter mainly described by sets of items all ali!e so as to ha"e equal
probabilities.
Thermodynamics arose from the study of t#o distinct !inds of transfer of energy as heat and
as #or! and the relation of those to the system's macroscopic "ariables of "olume pressure and
temperature.
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Transfers of matter are also studied in thermodynamics.
Thermodynamic equilibrium is one of the most important concepts for thermodynamics.
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The
temperature of a thermodynamic system is #ell defined and is perhaps the most characteristic
quantity of thermodynamics. As the systems and processes of interest are ta!en further from
thermodynamic equilibrium their e'act thermodynamical study becomes more difficult. (elati"ely
simple appro'imate calculations ho#e"er using the "ariables of equilibrium thermodynamics are
of much practical "alue. )n many important practical cases as in heat engines or refrigerators the
systems consist of many subsystems at different temperatures and pressures. )n engineering
practice thermodynamic calculations deal effecti"ely #ith such systems pro"ided the equilibrium
thermodynamic "ariables are nearly enough #ell*defined.
+entral to thermodynamic analysis are the definitions of the system #hich is of interest and of
its surroundings.
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The surroundings of a thermodynamic system consist of physical de"ices
and of other thermodynamic systems that can interact #ith it. An e'ample of a thermodynamic
surrounding is a heat bath #hich is held at a prescribed temperature regardless of ho# much
heat might be dra#n from it.
There are four fundamental !inds of physical entities in thermodynamics states of a
system #alls of a system
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thermodynamic processes of a system and thermodynamic
operations. This allo#s t#o fundamental approaches to thermodynamic reasoning that in terms of
states of a system and that in terms of cyclic processes of a system.
A thermodynamic system can be defined in terms of its states. )n this #ay a thermodynamic
system is a macroscopic physical ob0ect e'plicitly specified in terms of macroscopic physical and
chemical "ariables that describe its macroscopic properties. The macroscopic state "ariables of
thermodynamics ha"e been recogni1ed in the course of empirical #or! in physics and chemistry.
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Al#ays associated #ith the material that constitutes a system its #or!ing substance are the
#alls that delimit the system and connect it #ith its surroundings. The state "ariables chosen for
the system should be appropriate for the natures of the #alls and surroundings.
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A thermodynamic operation is an artificial physical manipulation that changes the definition of a
system or its surroundings. 2sually it is a change of the permeability or some other feature of a
#all of the system
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that allo#s energy 3as heat or #or!4 or matter 3mass4 to be e'changed #ith
the en"ironment. 5or e'ample the partition bet#een t#o thermodynamic systems can be
remo"ed so as to produce a single system. A thermodynamic operation usually leads to a
thermodynamic process of transfer of mass or energy that changes the state of the system and
the transfer occurs in natural accord #ith the la#s of thermodynamics. 6esides thermodynamic
operations changes in the surroundings can also initiate thermodynamic processes.
A thermodynamic system can also be defined in terms of the cyclic processes that it can undergo.
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A cyclic process is a cyclic sequence of thermodynamic operations and processes that can be
repeated indefinitely often #ithout changing the final state of the system.
5or thermodynamics and statistical thermodynamics to apply to a physical system it is necessary
that its internal atomic mechanisms fall into one of t#o classes7
those so rapid that in the time frame of the process of interest the atomic states rapidly
bring system to its o#n state of internal thermodynamic equilibrium8 and
those so slo# that in the time frame of the process of interest they lea"e the system
unchanged.
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The rapid atomic mechanisms account for the internal energy of the system. They mediate the
macroscopic changes that are of interest for thermodynamics and statistical thermodynamics
because they quic!ly bring the system near enough to thermodynamic equilibrium. "9hen
intermediate rates are present thermodynamics and statistical mechanics cannot be
applied."
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:uch intermediate rate atomic processes do not bring the system near enough to
thermodynamic equilibrium in the time frame of the macroscopic process of interest. This
separation of time scales of atomic processes is a theme that recurs throughout the sub0ect.
5or e'ample classical thermodynamics is characteri1ed by its study of materials that
ha"e equations of state or characteristic equations. They e'press equilibrium relations bet#een
macroscopic mechanical "ariables and temperature and internal energy. They e'press the
constituti"e peculiarities of the material of the system. A classical material can usually be
described by a function that ma!es pressure dependent on "olume and temperature the resulting
pressure being established much more rapidly than any imposed change of "olume or
temperature.
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The present article ta!es a gradual approach to the sub0ect starting #ith a focus on cyclic
processes and thermodynamic equilibrium and then gradually beginning to further consider non*
equilibrium systems.
Thermodynamic facts can often be e'plained by "ie#ing macroscopic ob0ects as assemblies of
"ery many microscopic or atomic ob0ects that obey ;amiltonian dynamics.
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The microscopic
or atomic ob0ects e'ist in species the ob0ects of each species being all ali!e. 6ecause of this
li!eness statistical methods can be used to account for the macroscopic properties of the
thermodynamic system in terms of the properties of the microscopic species. :uch e'planation is
called statistical thermodynamics8 also often it is referred to by the term 'statistical mechanics'
though this term can ha"e a #ider meaning referring to 'microscopic ob0ects' such as economic
quantities that do not obey ;amiltonian dynamics.
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