Thermodynamics is a branch of physics that deals with heat, work, and temperature, and

their relation to energy, entropy, and the physical properties of matter and radiation. The
behavior of these quantities is governed by the four laws of thermodynamics which convey a
quantitative description using measurable macroscopic physical quantities, but may be
explained in terms of microscopic constituents by statistical mechanics. Thermodynamics
applies to a wide variety of topics in science and engineering, especially physical
chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other
complex fields such as meteorology.

Historically, thermodynamics developed out of a desire to increase the efficiency of

early steam engines, particularly through the work of French physicist Sadi Carnot (1824)
who believed that engine efficiency was the key that could help France win the Napoleonic
Wars.[1] Scots-Irish physicist Lord Kelvin was the first to formulate a concise definition of
thermodynamics in 1854[2] which stated, "Thermo-dynamics is the subject of the relation of
heat to forces acting between contiguous parts of bodies, and the relation of heat to electrical
agency." German physicist and mathematician Rudolf Clausius restated Carnot's principle
known as the Carnot cycle and gave to the theory of heat a truer and sounder basis. His most
important paper, "On the Moving Force of Heat",[3] published in 1850, first stated the second
law of thermodynamics. In 1865 he introduced the concept of entropy. In 1870 he introduced
the virial theorem, which applied to heat.[4]

The initial application of thermodynamics to mechanical heat engines was quickly extended
to the study of chemical compounds and chemical reactions. Chemical
thermodynamics studies the nature of the role of entropy in the process of chemical
reactions and has provided the bulk of expansion and knowledge of the field. Other
formulations of thermodynamics emerged. Statistical thermodynamics, or statistical
mechanics, concerns itself with statistical predictions of the collective motion of particles
from their microscopic behavior. In 1909, Constantin Carathéodory presented a purely
mathematical approach in an axiomatic formulation, a description often referred to
as geometrical thermodynamics.

Introduction

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 transferred between
physical systems as heat, as work, and with transfer of matter.[5] 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.[6]

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.[7][8]

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.

History
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.[9]

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 Anglo-Irish 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.[10] 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 Watt was 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.[11] 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.[12]

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.[13] 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.

Clausius, who first stated the basic ideas of the second law in his paper "On the Moving
Force of Heat",[3] published in 1850, and is called "one of the founding fathers of
thermodynamics",[14] introduced the concept of entropy in 1865.

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,[15] 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.[16] Also Pierre
Duhem in the 19th century wrote about chemical thermodynamics.[17] During the early 20th
century, chemists such as Gilbert N. Lewis, Merle Randall,[18] and E. A.
Guggenheim[19][20] applied the mathematical methods of Gibbs to the analysis of chemical
processes.

Etymology

Thermodynamics has an intricate etymology.[21]

By a surface-level analysis, the word consists of two parts that can be traced back to Ancient
Greek. Firstly, thermo- ("of heat"; used in words such as thermometer) can be traced back to
the root θέρμη therme, meaning "heat". Secondly, the word dynamics ("science of force [or
power]")[22] can be traced back to the root δύναμις dynamis, meaning "power".[23]

In 1849, the adjective thermo-dynamic is used by William Thomson.[24][25]

In 1854, the noun thermo-dynamics is used by Thomson and William Rankine to represent
the science of generalized heat engines.[25][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,[12] however, Joule never used that
term, but used instead the term perfect thermo-dynamic engine in reference to Thomson's
1849[24] phraseology.[21]

Branches of thermodynamics

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

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
Statistical mechanics, also known as 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

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. The primary objective of chemical thermodynamics is determining the
spontaneity of a given transformation.[26]

Equilibrium thermodynamics

Equilibrium thermodynamics is the study of transfers of matter and energy in systems or

bodies that, by agencies in their surroundings, can be driven from one state of thermodynamic
equilibrium to another. The term 'thermodynamic equilibrium' indicates a state of balance, in
which all macroscopic flows are zero; in the case of the simplest systems or bodies, their
intensive properties are homogeneous, and their pressures are perpendicular to their
boundaries. 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

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.[27] Many natural systems still today remain
beyond the scope of currently known macroscopic thermodynamic methods.

Laws of thermodynamics

Main article: Laws of thermodynamics

Annotated color version of the original

1824 Carnot heat engine showing the hot body (boiler), working body (system, steam), and
cold body (water), the letters labeled according to the stopping points in Carnot cycle.

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

The zeroth law of thermodynamics states: 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 whether 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.[28] The law
provides an empirical definition of temperature, and justification for the construction of
practical thermometers.

The zeroth law was not initially recognized as a separate 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 already, and found common acceptance in the physics
community before the importance of the zeroth law for the definition of temperature was
realized. As it was impractical to renumber the other laws, it was named the zeroth law.

First law

Opening a bottle of sparkling wine (high-speed photography). The

sudden drop of pressure causes a huge drop of temperature. The moisture in the air freezes,
creating a smoke of tiny ice crystals.[29][30][31]

The first law of thermodynamics states: In a process without transfer of matter, the change

in internal energy, , of a thermodynamic system is equal to the energy gained as

heat, , less the thermodynamic work, , done by the system on its surroundings.[32][nb
1]

where denotes the change in the internal energy of a closed system (for which heat
or work through the system boundary are possible, but matter transfer is not

possible), denotes the quantity of energy supplied to the system as heat,

and denotes the amount of thermodynamic work done by the system on its
surroundings. An equivalent statement is that perpetual motion machines of the first kind

are impossible; work done by a system on its surrounding requires that the system's

internal energy decrease or be consumed, so that the amount of internal energy lost

by that work must be resupplied as heat by an external energy source or as work by

an external machine acting on the system (so that is recovered) to make the system
work continuously.

For processes that include transfer of matter, a further statement is needed: With due
account of the respective fiducial reference states of the systems, when two systems,
which may be of different chemical compositions, initially separated only by an
impermeable wall, and otherwise isolated, are combined into a new system by the
thermodynamic operation of removal of the wall, then

where U0 denotes the internal energy of the combined system, and U1 and U2 denote
the internal energies of the respective separated systems.

Adapted for thermodynamics, this law is an expression of the principle

of conservation of energy, which states that energy can be transformed (changed from
one form to another), but cannot be created or destroyed.[33]

Internal energy is a principal property of the thermodynamic state, while heat and
work are modes of energy transfer by which a process may change this state. A
change of internal energy of a system may be achieved by any combination of heat
added or removed and work performed on or by the system. As a function of state,
the internal energy does not depend on the manner, or on the path through
intermediate steps, by which the system arrived at its state.

Second law
A traditional version of the second law of thermodynamics states: Heat does not
spontaneously flow from a colder body to a hotter body.

The second law refers to a system of matter and radiation, initially with
inhomogeneities in temperature, pressure, chemical potential, and other intensive
properties, that are due to internal 'constraints', or impermeable rigid walls, within it,
or to externally imposed forces. The law observes that, when the system is isolated
from the outside world and from those forces, there is a definite thermodynamic
quantity, its entropy, that increases as the constraints are removed, eventually
reaching a maximum value at thermodynamic equilibrium, when the inhomogeneities
practically vanish. For systems that are initially far from thermodynamic equilibrium,
though several have been proposed, there is known no general physical principle that
determines the rates of approach to thermodynamic equilibrium, and thermodynamics
does not deal with such rates. The many versions of the second law all express the
general irreversibility of the transitions involved in systems approaching
thermodynamic equilibrium.

In macroscopic thermodynamics, the second law is a basic observation applicable to

any actual thermodynamic process; in statistical thermodynamics, the second law is
postulated to be a consequence of molecular chaos.

Third law

The third law of thermodynamics states: As the temperature of a system approaches

absolute zero, all processes cease and the entropy of the system approaches a
minimum value.

This 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 include "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 achieve, is
−273.15 °C (degrees Celsius), or −459.67 °F (degrees Fahrenheit), or 0 K (kelvin), or
0° R (degrees Rankine).

System models

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 or notional, but
serve to confine the system to a finite volume. Segments of the boundary are often
described as walls; they have respective defined 'permeabilities'. Transfers of energy
as work, or as heat, or of matter, between the system and the surroundings, take place
through the walls, according to their respective permeabilities.

Matter or energy that pass across the boundary so as to effect a change in the internal
energy of the system need to be accounted for in the energy balance equation. The
volume contained by the walls can be the region surrounding a single atom resonating
energy, such as Max Planck defined in 1900; it can be a body of steam or air in
a steam engine, such as Sadi Carnot defined in 1824. The system could also be just
one nuclide (i.e. a system of quarks) as hypothesized in quantum thermodynamics.
When a looser viewpoint is adopted, and the requirement of thermodynamic
equilibrium is dropped, the system can be the body of a tropical cyclone, such
as Kerry Emanuel theorized in 1986 in the field of atmospheric 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.