A description of any thermodynamic system employs the four laws of thermodynamics that form an

axiomatic basis. The first law specifies that energy can be exchanged between physical systems
as heat and work.[12] The second law defines the existence of a quantity called entropy, that
describes the direction, thermodynamically, that a system can evolve and quantifies the state of
order of a system and that can be used to quantify the useful work that can be extracted from the
system.[13]
In thermodynamics, interactions between large ensembles of objects are studied and categorized.
Central to this are the concepts of the thermodynamic system and its surroundings. A system is
composed of particles, whose average motions define its properties, and those properties are in turn
related to one another through equations of state. Properties can be combined to express internal
energy and thermodynamic potentials, which are useful for determining conditions
for equilibrium and spontaneous processes.
With these tools, thermodynamics can be used to describe how systems respond to changes in their
environment. This can be applied to a wide variety of topics in science and engineering, such
as engines, phase transitions, chemical reactions, transport phenomena, and even black holes. The
results of thermodynamics are essential for other fields of physics and for chemistry, chemical
engineering, corrosion engineering, aerospace engineering, mechanical engineering, cell
biology, biomedical engineering, materials science, and economics, to name a few.[14][15]
This article is focused mainly on classical thermodynamics which primarily studies systems
in thermodynamic equilibrium. Non-equilibrium thermodynamics is often treated as an extension of
the classical treatment, but statistical mechanics has brought many advances to that field.

The thermodynamicists representative of the original eight founding schools of thermodynamics. The schools
with the most-lasting effect in founding the modern versions of thermodynamics are the Berlin school,
particularly as established in Rudolf Clausius’s 1865 textbook The Mechanical Theory of Heat, the Vienna
school, with the statistical mechanics of Ludwig Boltzmann, and the Gibbsian school at Yale University,
American engineer Willard Gibbs' 1876 On the Equilibrium of Heterogeneous Substances launching chemical
thermodynamics.[16]

History[edit]
The history of thermodynamics as a scientific discipline generally begins with Otto von
Guericke who, in 1650, built and designed the world's first vacuum pump and demonstrated
a vacuum using his Magdeburg hemispheres. Guericke was driven to make a vacuum in order to
disprove Aristotle's long-held supposition that 'nature abhors a vacuum'. Shortly after Guericke, the
English physicist and chemist Robert Boyle had learned of Guericke's designs and, in 1656, in
coordination with English scientist Robert Hooke, built an air pump.[17]Using this pump, Boyle and
Hooke noticed a correlation between pressure, temperature, and volume. In time, Boyle's Law was
formulated, which states that pressure and volume are inversely proportional. Then, in 1679, based
on these concepts, an associate of Boyle's named Denis Papin built a steam digester, which was a
closed vessel with a tightly fitting lid that confined steam until a high pressure was generated.
Later designs implemented a steam release valve that kept the machine from exploding. By
watching the valve rhythmically move up and down, Papin conceived of the idea of a piston and a
cylinder engine. He did not, however, follow through with his design. Nevertheless, in 1697, based
on Papin's designs, engineer Thomas Savery built the first engine, followed by Thomas
Newcomen in 1712. Although these early engines were crude and inefficient, they attracted the
attention of the leading scientists of the time.
The fundamental concepts of heat capacity and latent heat, which were necessary for the
development of thermodynamics, were developed by Professor Joseph Black at the University of
Glasgow, where James Wattwas employed as an instrument maker. Black and Watt performed
experiments together, but it was Watt who conceived the idea of the external condenser which
resulted in a large increase in steam engine efficiency.[18]Drawing on all the previous work led Sadi
Carnot, the "father of thermodynamics", to publish Reflections on the Motive Power of Fire (1824), a
discourse on heat, power, energy and engine efficiency. The book outlined the basic energetic
relations between the Carnot engine, the Carnot cycle, and motive power. It marked the start of
thermodynamics as a modern science.[10]
The first thermodynamic textbook was written in 1859 by William Rankine, originally trained as a
physicist and a civil and mechanical engineering professor at the University of Glasgow.[19] The first
and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the
works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin).
The foundations of statistical thermodynamics were set out by physicists such as James Clerk
Maxwell, Ludwig Boltzmann, Max Planck, Rudolf Clausius and J. Willard Gibbs.
During the years 1873-76 the American mathematical physicist Josiah Willard Gibbs published a
series of three papers, the most famous being On the Equilibrium of Heterogeneous Substances,[3] in
which he showed how thermodynamic processes, including chemical reactions, could be graphically
analyzed, by studying the energy, entropy, volume, temperature and pressure of the thermodynamic
system in such a manner, one can determine if a process would occur spontaneously. [20] Also Pierre
Duhem in the 19th century wrote about chemical thermodynamics.[4] During the early 20th century,
chemists such as Gilbert N. Lewis, Merle Randall,[5] and E. A. Guggenheim[6][7] applied the
mathematical methods of Gibbs to the analysis of chemical processes.

Etymology[edit]
The etymology of thermodynamics has an intricate history.[21] It was first spelled in a hyphenated form
as an adjective (thermo-dynamic) and from 1854 to 1868 as the noun thermo-dynamics to represent
the science of generalized heat engines.[21]
American biophysicist Donald Haynie claims that thermodynamics was coined in 1840 from
the Greek root θέρμη therme, meaning heat and δύναμις dynamis, meaning power.[22]However, this
etymology has been cited as unlikely.[21]
Pierre Perrot claims that the term thermodynamics was coined by James Joule in 1858 to designate
the science of relations between heat and power, [10] however, Joule never used that term, but used
instead the term perfect thermo-dynamic engine in reference to Thomson's 1849[23] phraseology.[21]
By 1858, thermo-dynamics, as a functional term, was used in William Thomson's paper "An Account
of Carnot's Theory of the Motive Power of Heat."[23]

Branches of thermodynamics[edit]
The study of thermodynamical systems has developed into several related branches, each using a
different fundamental model as a theoretical or experimental basis, or applying the principles to
varying types of systems.

Classical thermodynamics[edit]
Classical thermodynamics is the description of the states of thermodynamic systems at near-
equilibrium, that uses macroscopic, measurable properties. It is used to model exchanges of energy,
work and heat based on the laws of thermodynamics. The qualifier classical reflects the fact that it
represents the first level of understanding of the subject as it developed in the 19th century and
describes the changes of a system in terms of macroscopic empirical (large scale, and measurable)
parameters. A microscopic interpretation of these concepts was later provided by the development
of statistical mechanics.

Statistical mechanics[edit]
Statistical mechanics, also called statistical thermodynamics, emerged with the development of
atomic and molecular theories in the late 19th century and early 20th century, and supplemented
classical thermodynamics with an interpretation of the microscopic interactions between individual
particles or quantum-mechanical states. This field relates the microscopic properties of individual
atoms and molecules to the macroscopic, bulk properties of materials that can be observed on the
human scale, thereby explaining classical thermodynamics as a natural result of statistics, classical
mechanics, and quantum theory at the microscopic level.
Chemical thermodynamics[edit]
Chemical thermodynamics is the study of the interrelation of energy with chemical reactions or with a
physical change of state within the confines of the laws of thermodynamics.

Equilibrium thermodynamics[edit]
Equilibrium thermodynamics is the systematic study of transfers of matter and energy in systems as
they pass from one state of thermodynamic equilibrium to another. The term 'thermodynamic
equilibrium' indicates a state of balance. In an equilibrium state there are no unbalanced potentials,
or driving forces, between macroscopically distinct parts of the system. A central aim in equilibrium
thermodynamics is: given a system in a well-defined initial equilibrium state, and given its
surroundings, and given its constitutive walls, to calculate what will be the final equilibrium state of
the system after a specified thermodynamic operation has changed its walls or surroundings.
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are not
in thermodynamic equilibrium. Most systems found in nature are not in thermodynamic equilibrium
because they are not in stationary states, and are continuously and discontinuously subject to flux of
matter and energy to and from other systems. The thermodynamic study of non-equilibrium systems
requires more general concepts than are dealt with by equilibrium thermodynamics. Many natural
systems still today remain beyond the scope of currently known macroscopic thermodynamic
methods.

Laws of thermodynamics[edit]
Main article: Laws of thermodynamics
Thermodynamics is principally based on a set of four laws which are universally valid when applied
to systems that fall within the constraints implied by each. In the various theoretical descriptions of
thermodynamics these laws may be expressed in seemingly differing forms, but the most prominent
formulations are the following:

 Zeroth law of thermodynamics: If two systems are each in thermal equilibrium with a third,
they are also in thermal equilibrium with each other.
This statement implies that thermal equilibrium is an equivalence relation on the set
of thermodynamic systems under consideration. Systems are said to be in equilibrium if the small,
random exchanges between them (e.g. Brownian motion) do not lead to a net change in energy. This
law is tacitly assumed in every measurement of temperature. Thus, if one seeks to decide if two
bodies are at the same temperature, it is not necessary to bring them into contact and measure any
changes of their observable properties in time. [24] The law provides an empirical definition of
temperature and justification for the construction of practical thermometers.
The zeroth law was not initially named as a law of thermodynamics, as its basis in thermodynamical
equilibrium was implied in the other laws. The first, second, and third laws had been explicitly stated
prior and found common acceptance in the physics community. Once the importance of the zeroth
law for the definition of temperature was realized, it was impracticable to renumber the other laws,
hence it was numbered the zeroth law.

 First law of thermodynamics: The internal energy of an isolated system is constant.

The first law of thermodynamics is an expression of the principle of conservation of energy. It states
that energy can be transformed (changed from one form to another), but cannot be created or
destroyed.[25]
The first law is usually formulated by saying that the change in the internal energy of a
closed thermodynamic system is equal to the difference between the heat supplied to the system
and the amount of work done by the system on its surroundings. It is important to note that internal
energy is a state of the system (see Thermodynamic state) whereas heat and work modify the state
of the system. In other words, a change of internal energy of a system may be achieved by any
combination of heat and work added or removed from the system as long as those total to the
change of internal energy. The manner by which a system achieves its internal energy is path
independent.

 Second law of thermodynamics: Heat cannot spontaneously flow from a colder location to a
hotter location.

The second law of thermodynamics is an expression of the universal principle of decay observable
in nature. The second law is an observation of the fact that over time, differences in temperature,
pressure, and chemical potential tend to even out in a physical system that is isolated from the
outside world. Entropy is a measure of how much this process has progressed. The entropy of an
isolated system which is not in equilibrium will tend to increase over time, approaching a maximum
value at equilibrium. However, principles guiding systems that are far from equilibrium are still
debatable. One of such principles is the maximum entropy production principle.[26][27] It states that non-
equilibrium systems behave such a way as to maximize its entropy production. [28]
In classical thermodynamics, the second law is a basic postulate applicable to any system involving
heat energy transfer; in statistical thermodynamics, the second law is a consequence of the
assumed randomness of molecular chaos. There are many versions of the second law, but they all
have the same effect, which is to explain the phenomenon of irreversibility in nature.

 Third law of thermodynamics: As a system approaches absolute zero, all processes cease
and the entropy of the system approaches a minimum value.

The third law of thermodynamics is a statistical law of nature regarding entropy and the impossibility
of reaching absolute zero of temperature. This law provides an absolute reference point for the
determination of entropy. The entropy determined relative to this point is the absolute entropy.
Alternate definitions are, "the entropy of all systems and of all states of a system is smallest at
absolute zero," or equivalently "it is impossible to reach the absolute zero of temperature by any
finite number of processes".
Absolute zero, at which all activity would stop if it were possible to happen, is −273.15 °C (degrees
Celsius), or −459.67 °F (degrees Fahrenheit), or 0 K (kelvin), or 0° R (degrees Rankine).

System models[edit]

A diagram of a generic thermodynamic system

An important concept in thermodynamics is the thermodynamic system, which is a precisely defined

region of the universe under study. Everything in the universe except the system is called
the surroundings. A system is separated from the remainder of the universe by a boundary which
may be a physical boundary or notional, but which by convention defines a finite volume. Exchanges
of work, heat, or matterbetween the system and the surroundings take place across this boundary.
In practice, the boundary of a system is simply an imaginary dotted line drawn around a volume
within which is going to be a change in the internal energy of that volume. Anything that passes
across the boundary that effects a change in the internal energy of the system needs to be
accounted for in the energy balance equation. The volume can be the region surrounding a single
atom resonating energy, such as Max Planckdefined in 1900; it can be a body of steam or air in
a steam engine, such as Sadi Carnot defined in 1824; it can be the body of a tropical cyclone, such
as Kerry Emanuel theorized in 1986 in the field of atmospheric thermodynamics; it could also be just
one nuclide (i.e. a system of quarks) as hypothesized in quantum thermodynamics, or the event
horizon of a black hole.
Boundaries are of four types: fixed, movable, real, and imaginary. For example, in an engine, a fixed
boundary means the piston is locked at its position, within which a constant volume process might
occur. If the piston is allowed to move that boundary is movable while the cylinder and cylinder head
boundaries are fixed. For closed systems, boundaries are real while for open systems boundaries
are often imaginary. In the case of a jet engine, a fixed imaginary boundary might be assumed at the
intake of the engine, fixed boundaries along the surface of the case and a second fixed imaginary
boundary across the exhaust nozzle.
Generally, thermodynamics distinguishes three classes of systems, defined in terms of what is
allowed to cross their boundaries:

Interactions of thermodynamic systems

Type of system Mass flow Work Heat

 Open

Closed

Thermally isolated

Mechanically isolated

Isolated

As time passes in an isolated system, internal differences of pressures, densities, and temperatures
tend to even out. A system in which all equalizing processes have gone to completion is said to be in
a state of thermodynamic equilibrium.
Once in thermodynamic equilibrium, a system's properties are, by definition, unchanging in time.
Systems in equilibrium are much simpler and easier to understand than are systems which are not in
equilibrium. Often, when analysing a dynamic thermodynamic process, the simplifying assumption is
made that each intermediate state in the process is at equilibrium, producing thermodynamic
processes which develop so slowly as to allow each intermediate step to be an equilibrium state and
are said to be reversible processes.

States and processes[edit]

When a system is at equilibrium under a given set of conditions, it is said to be in a
definite thermodynamic state. The state of the system can be described by a number of state
quantities that do not depend on the process by which the system arrived at its state. They are
called intensive variables or extensive variables according to how they change when the size of the
system changes. The properties of the system can be described by an equation of state which
specifies the relationship between these variables. State may be thought of as the instantaneous
quantitative description of a system with a set number of variables held constant.
A thermodynamic process may be defined as the energetic evolution of a thermodynamic system
proceeding from an initial state to a final state. It can be described by process quantities. Typically,
each thermodynamic process is distinguished from other processes in energetic character according
to what parameters, such as temperature, pressure, or volume, etc., are held fixed; Furthermore, it is
useful to group these processes into pairs, in which each variable held constant is one member of
a conjugate pair.
Several commonly studied thermodynamic processes are:

 Adiabatic process: occurs without loss or gain of energy by heat

 Isenthalpic process: occurs at a constant enthalpy

 Isentropic process: a reversible adiabatic process, occurs at a constant entropy

 Isobaric process: occurs at constant pressure

 Isochoric process: occurs at constant volume (also called isometric/isovolumetric)

 Isothermal process: occurs at a constant temperature

 Steady state process: occurs without a change in the internal energy

Instrumentation[edit]
There are two types of thermodynamic instruments, the meter and the reservoir. A thermodynamic
meter is any device which measures any parameter of a thermodynamic system. In some cases, the
thermodynamic parameter is actually defined in terms of an idealized measuring instrument. For
example, the zeroth law states that if two bodies are in thermal equilibrium with a third body, they are
also in thermal equilibrium with each other. This principle, as noted by James Maxwell in 1872,
asserts that it is possible to measure temperature. An idealized thermometer is a sample of an ideal
gas at constant pressure. From the ideal gas law pV=nRT, the volume of such a sample can be used
as an indicator of temperature; in this manner it defines temperature. Although pressure is defined
mechanically, a pressure-measuring device, called a barometer may also be constructed from a
sample of an ideal gas held at a constant temperature. A calorimeter is a device which is used to
measure and define the internal energy of a system.
A thermodynamic reservoir is a system which is so large that its state parameters are not
appreciably altered when it is brought into contact with the system of interest. When the reservoir is
brought into contact with the system, the system is brought into equilibrium with the reservoir. For
example, a pressure reservoir is a system at a particular pressure, which imposes that pressure
upon the system to which it is mechanically connected. The Earth's atmosphere is often used as a
pressure reservoir. If ocean water is used to cool a power plant, the ocean is often a temperature
reservoir in the analysis of the power plant cycle.

Conjugate variables[edit]
Main article: Conjugate variables
The central concept of thermodynamics is that of energy, the ability to do work. By the First Law, the
total energy of a system and its surroundings is conserved. Energy may be transferred into a system
by heating, compression, or addition of matter, and extracted from a system by cooling, expansion,
or extraction of matter. In mechanics, for example, energy transfer equals the product of the force
applied to a body and the resulting displacement.
Conjugate variables are pairs of thermodynamic concepts, with the first being akin to a "force"
applied to some thermodynamic system, the second being akin to the resulting "displacement," and
the product of the two equalling the amount of energy transferred. The common conjugate variables
are:

 Pressure-volume (the mechanical parameters);

 Temperature-entropy (thermal parameters);

 Chemical potential-particle number (material parameters).

Potentials[edit]
Thermodynamic potentials are different quantitative measures of the stored energy in a system.
Potentials are used to measure the energy changes in systems as they evolve from an initial state to
a final state. The potential used depends on the constraints of the system, such as constant
temperature or pressure. For example, the Helmholtz and Gibbs energies are the energies available
in a system to do useful work when the temperature and volume or the pressure and temperature
are fixed, respectively.
The five most well known potentials are:

Name Symbol Formula Natural variables

Internal energy

Helmholtz free energy

Enthalpy

Gibbs free energy

Landau Potential (Grand ,

potential)

where is the temperature, the entropy, the pressure, the volume,

the chemical potential, the number of particles in the system, and is the count of particles

types in the system.

Thermodynamic potentials can be derived from the energy balance equation applied to a
thermodynamic system. Other thermodynamic potentials can also be obtained through Legendre
transformatio