Introduction[edit]

Historically, thermodynamics arose from the study of two distinct kinds of transfer of energy,
as heat and as work, and the relation of those to the system's macroscopic variables of volume,
pressure and temperature.[13][14] As it developed, thermodynamics began also to study transfers of
matter.
The plain term 'thermodynamics' refers to a macroscopic description of bodies and processes.
[15]

Reference to atomic constitution is foreign to classical thermodynamics. [16] The qualified term

'statistical thermodynamics' refers to descriptions of bodies and processes in terms of the atomic or
other microscopic constitution of matter, using statistical and probabilistic reasoning.
Thermodynamic equilibrium is one of the most important concepts for thermodynamics.[17] The
temperature of a thermodynamic system is well defined, and is perhaps the most characteristic
quantity of thermodynamics. As the systems and processes of interest are taken further from
thermodynamic equilibrium, their exact thermodynamical study becomes more difficult. Relatively
simple approximate calculations, however, using the variables of equilibrium thermodynamics, are of
much practical value. Many important practical engineering cases, as in heat engines or
refrigerators, can be approximated as systems consisting of many subsystems at different
temperatures and pressures. If a physical process is too fast, the equilibrium thermodynamic
variables, for example temperature, may not be well enough defined to provide a useful
approximation.
Central to thermodynamic analysis are the definitions of the system, which is of interest, and of
its surroundings.[8][18] The surroundings of a thermodynamic system consist of physical devices and of
other thermodynamic systems that can interact with it. An example of a thermodynamic surrounding
is a heat bath, which is held at a prescribed temperature, regardless of how much heat might be
drawn from it.
There are four fundamental kinds of physical entities in thermodynamics, states of a system, walls of
a system,[19][20][21][22][23] thermodynamic processes of a system, andthermodynamic operations. This
allows two 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. In this way, a thermodynamic system
is a macroscopic physical object, explicitly specified in terms of macroscopic physical and chemical
variables that describe its macroscopic properties. The macroscopic state variables of
thermodynamics have been recognized in the course of empirical work in physics and chemistry.
[9]

Always associated with the material that constitutes a system, its working substance, are the walls

that delimit the system, and connect it with its surroundings. The state variables chosen for the
system should be appropriate for the natures of the walls and surroundings. [24]

A thermodynamic operation is an artificial physical manipulation that changes the definition of a

system or its surroundings. Usually it is a change of the permeability or some other feature of a wall
of the system,[25] that allows energy (as heat or work) or matter (mass) to be exchanged with the
environment. For example, the partition between two thermodynamic systems can be removed 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 with the laws of thermodynamics. Besides 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.
[26]

A cyclic process is a cyclic sequence of thermodynamic operations and processes that can be

repeated indefinitely often without changing the final state of the system.
For thermodynamics and statistical thermodynamics to apply to a physical system, it is necessary
that its internal atomic mechanisms fall into one of two classes:

those so rapid that, in the time frame of the process of interest, the atomic states rapidly
bring system to its own state of internal thermodynamic equilibrium; and

those so slow that, in the time frame of the process of interest, they leave the system
unchanged.[27][28]

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 quickly bring the system near enough to thermodynamic equilibrium. "When
intermediate rates are present, thermodynamics and statistical mechanics cannot be
applied."[27] Such 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 subject.
For example, classical thermodynamics is characterized by its study of materials that have equations
of state or characteristic equations. They express equilibrium relations between macroscopic
mechanical variables and temperature and internal energy. They express the constitutive
peculiarities of the material of the system. A classical material can usually be described by a function
that makes pressure dependent on volume and temperature, the resulting pressure being
established much more rapidly than any imposed change of volume or temperature. [29][30][31][32]
The present article takes a gradual approach to the subject, starting with a focus on cyclic processes
and thermodynamic equilibrium, and then gradually beginning to further consider non-equilibrium
systems.

Thermodynamic facts can often be explained by viewing macroscopic objects as assemblies of very
many microscopic or atomic objects that obey Hamiltonian dynamics.[8][33][34]The microscopic or atomic
objects exist in species, the objects of each species being all alike. Because of this likeness,
statistical methods can be used to account for the macroscopic properties of the thermodynamic
system in terms of the properties of the microscopic species. Such explanation is called statistical
thermodynamics; also often it is referred to by the term 'statistical mechanics', though this term can
have a wider meaning, referring to 'microscopic objects', such as economic quantities, that do not
obey Hamiltonian dynamics.[33]