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Thermodynamics is a branch of
physics Physics is the that studies , its , its and behavior through , and the related entities of and . "Physical science is that department of knowledge which relates to the order of nature, or, in other words, to the regular succession of eve ...

physics
that deals with
heat In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these ...

heat
,
work Work may refer to: * Work (human activity), intentional activity people perform to support themselves, others, or the community ** Manual labour, physical work done by humans ** House work, housework, or homemaking * Work (physics), the product of ...
, and
temperature Temperature ( ) is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy Thermal radiation in visible light can be seen on this hot metalwork. Thermal energy refers to several distinct physical concept ...

temperature
, and their relation to
energy In , energy is the that must be to a or to perform on the body, or to it. Energy is a ; the law of states that energy can be in form, but not created or destroyed. The unit of measurement in the (SI) of energy is the , which is the ...

energy
,
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

entropy
, and the physical properties of
matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, which are made up of interacting subatomic particl ...
and
radiation upThe international symbol for types and levels of ionizing radiation (radioactivity) that are unsafe for unshielded humans. Radiation, in general, exists throughout nature, such as in light and sound. In physics Physics (from grc ...

radiation
. The behavior of these quantities is governed by the four
laws of thermodynamics The laws of thermodynamics define a group of physical quantities, such as temperature Temperature is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy, present in all matter, which is the source of t ...
which convey a quantitative description using measurable macroscopic
physical quantities A physical quantity is a physical property A physical property is any property Property is a system of rights that gives people legal control of valuable things, and also refers to the valuable things themselves. Depending on the nature of t ...
, but may be explained in terms of
microscopic The microscopic scale (from , ''mikrós'', "small" and σκοπέω, ''skopéō'' "look") is the scale of objects and events smaller than those that can easily be seen by the naked eye Naked eye, also called bare eye or unaided eye, is the pr ...

microscopic
constituents by
statistical mechanics In physics Physics is the that studies , its , its and behavior through , and the related entities of and . "Physical science is that department of knowledge which relates to the order of nature, or, in other words, to the regular ...
. Thermodynamics applies to a wide variety of topics in
science Science () is a systematic enterprise that builds and organizes knowledge Knowledge is a familiarity, awareness, or understanding of someone or something, such as facts ( descriptive knowledge), skills (procedural knowledge), or objects ...

science
and
engineering Engineering is the use of scientific principles to design and build machines, structures, and other items, including bridges, tunnels, roads, vehicles, and buildings. The discipline of engineering encompasses a broad range of more specializ ...

engineering
, especially
physical chemistry Physical chemistry is the study of macroscopic The macroscopic scale is the length scale on which objects or phenomena are large enough to be visible with the naked eye, without magnifying optical instruments. It is the opposite of microscopi ...
,
biochemistry Biochemistry or biological chemistry, is the study of es within and relating to living s. A sub-discipline of both and , biochemistry may be divided into three fields: , and . Over the last decades of the 20th century, biochemistry has beco ...

biochemistry
,
chemical engineering Chemical engineering is a certain type of which deals with the study of operation and design of chemical plants as well as methods of improving production. Chemical engineers develop economical commercial processes to convert raw material into u ...
and
mechanical engineering Mechanical engineering is an engineering Engineering is the use of scientific method, scientific principles to design and build machines, structures, and other items, including bridges, tunnels, roads, vehicles, and buildings. The discip ...

mechanical engineering
, but also in other complex fields such as
meteorology Meteorology is a branch of the (which include and ), with a major focus on . The study of meteorology dates back , though significant progress in meteorology did not begin until the 18th century. The 19th century saw modest progress in the f ...
. Historically, thermodynamics developed out of a desire to increase the
efficiency Efficiency is the (often measurable) ability to avoid wasting materials, energy, efforts, money, and time in doing something or in producing a desired result. In a more general sense, it is the ability to do things well, successfully, and withou ...
of early
steam engine from Stott Park Bobbin Mill, Cumbria, England A steam engine is a heat engine In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energ ...

steam engine
s, particularly through the work of French physicist
Nicolas Léonard Sadi Carnot ''Sous-lieutenant'' Nicolas Léonard Sadi Carnot (; 1 June 1796 – 24 August 1832) was a French mechanical engineer Mechanical may refer to: Machine * Mechanical system, a system that manages the power of forces and movements to accomplish ...
(1824) who believed that engine efficiency was the key that could help France win the
Napoleonic Wars The Napoleonic Wars (1803–1815) were a series of major global conflicts pitting the French Empire#REDIRECT French Empire {{Redirect shell , {{R from ambiguous page {{R from other capitalisation ... and its allies, led by Napoleon I ...
. Scots-Irish physicist
Lord Kelvin William Thomson, 1st Baron Kelvin, (26 June 182417 December 1907) was a British mathematician A mathematician is someone who uses an extensive knowledge of mathematics Mathematics (from Ancient Greek, Greek: ) includes the study of ...
was the first to formulate a concise definition of thermodynamics in 1854 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." The initial application of thermodynamics to
mechanical heat engine In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, radiation, and physical properties of matter. The behavior of these quantities is gove ...
s was quickly extended to the study of chemical compounds and chemical reactions.
Chemical thermodynamics Chemical thermodynamics is the study of the interrelation of heat In thermodynamics, heat is energy in transfer to or from a thermodynamic system, by mechanisms other than thermodynamic work or transfer of matter. The various mechanisms o ...
studies the nature of the role of
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

entropy
in the process of
chemical reaction A chemical reaction is a process that leads to the chemical transformation of one set of chemical substance A chemical substance is a form of matter In classical physics and general chemistry, matter is any substance that has mass and t ...

chemical reaction
s and has provided the bulk of expansion and knowledge of the field.Duhem, P.M.M. (1886). ''Le Potential Thermodynamique et ses Applications'', Hermann, Paris.Guggenheim, E.A. (1933). ''Modern Thermodynamics by the Methods of J.W. Gibbs'', Methuen, London.Guggenheim, E.A. (1949/1967). ''Thermodynamics. An Advanced Treatment for Chemists and Physicists'', 1st edition 1949, 5th edition 1967, North-Holland, Amsterdam. Other formulations of thermodynamics emerged.
Statistical thermodynamics In physics Physics (from grc, φυσική (ἐπιστήμη), physikḗ (epistḗmē), knowledge of nature, from ''phýsis'' 'nature'), , is the natural science that studies matter, its Motion (physics), motion and behavior throug ...
, or statistical mechanics, concerns itself with
statistical Statistics is the discipline that concerns the collection, organization, analysis, interpretation, and presentation of data. In applying statistics to a scientific, industrial, or social problem, it is conventional to begin with a statist ...

statistical
predictions of the collective motion of particles from their microscopic behavior. In 1909,
Constantin Carathéodory Constantin Carathéodory ( el, Κωνσταντίνος Καραθεοδωρή, Konstantinos Karatheodori; 13 September 1873 – 2 February 1950) was a Greek Greek may refer to: Greece Anything of, from, or related to Greece Greece ( el, ...
presented a purely mathematical approach in an
axiomatic An axiom, postulate or assumption is a statement that is taken to be true True most commonly refers to truth Truth is the property of being in accord with fact or reality.Merriam-Webster's Online Dictionarytruth 2005 In everyday language ...
formulation, a description often referred to as ''geometrical thermodynamics''.


Introduction

A description of any thermodynamic system employs the four
laws of thermodynamics The laws of thermodynamics define a group of physical quantities, such as temperature Temperature is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy, present in all matter, which is the source of t ...
that form an axiomatic basis.
The first law ''The First Law'' is a fantasy series written by British author Joe Abercrombie. ''The First Law'' is the title of only the original trilogy in the series, but is also used to refer to the series as a whole.https://www.joeabercrombie.com/ The ful ...
specifies that energy can be transferred between physical systems as
heat In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these ...

heat
, as
work Work may refer to: * Work (human activity), intentional activity people perform to support themselves, others, or the community ** Manual labour, physical work done by humans ** House work, housework, or homemaking * Work (physics), the product of ...
, and with transfer of matter. The second law defines the existence of a quantity called
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

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. In thermodynamics, interactions between large ensembles of objects are studied and categorized. Central to this are the concepts of the thermodynamic ''
system A system is a group of Interaction, interacting or interrelated elements that act according to a set of rules to form a unified whole. A system, surrounded and influenced by its environment, is described by its boundaries, structure and purp ...
'' and its ''
surroundings Surroundings are the area around a given physical or geographical point Point or points may refer to: Places * Point, Lewis, a peninsula in the Outer Hebrides, Scotland * Point, Texas, a city in Rains County, Texas, United States * Point, the N ...
''. 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 In physics Physics (from grc, φυσική (ἐπιστήμη), physikḗ (epistḗmē), knowledge of nature, from ''phýsis'' 'nature'), , is the natural science that studies matter, its Motion (physics), motion and behavior through S ...
. Properties can be combined to express
internal energy The internal energy of a thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that ca ...
and
thermodynamic potential A thermodynamic potential (or more accurately, a thermodynamic potential energy)ISO/IEC 80000-5, Quantities an units, Part 5 - Thermodynamics, item 5-20.4 Helmholtz energy, Helmholtz functionISO/IEC 80000-5, Quantities an units, Part 5 - Thermodyn ...
s, which are useful for determining conditions for
equilibrium List of types of equilibrium, the condition of a system in which all competing influences are balanced, in a wide variety of contexts. Equilibrium may also refer to: Film and television * Equilibrium (film), ''Equilibrium'' (film), a 2002 scien ...

equilibrium
and
spontaneous process In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quanti ...

spontaneous process
es. 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 Science () is a systematic enterprise that builds and organizes knowledge Knowledge is a familiarity, awareness, or understanding of someone or something, such as facts ( descriptive knowledge), skills (procedural knowledge), or objects ...

science
and
engineering Engineering is the use of scientific principles to design and build machines, structures, and other items, including bridges, tunnels, roads, vehicles, and buildings. The discipline of engineering encompasses a broad range of more specializ ...

engineering
, such as
engine An engine or motor is a machine A machine is any physical system with ordered structural and functional properties. It may represent human-made or naturally occurring device molecular machine that uses Power (physics), power to apply For ...

engine
s,
phase transition In chemistry Chemistry is the scientific Science () is a systematic enterprise that builds and organizes knowledge Knowledge is a familiarity or awareness, of someone or something, such as facts A fact is an occurrence in ...
s,
chemical reaction A chemical reaction is a process that leads to the chemical transformation of one set of chemical substance A chemical substance is a form of matter In classical physics and general chemistry, matter is any substance that has mass and t ...

chemical reaction
s,
transport phenomena In engineering Engineering is the use of scientific principles to design and build machines, structures, and other items, including bridges, tunnels, roads, vehicles, and buildings. The discipline of engineering encompasses a broad ran ...
, and even
black hole
black hole
s. The results of thermodynamics are essential for other fields of
physics Physics is the that studies , its , its and behavior through , and the related entities of and . "Physical science is that department of knowledge which relates to the order of nature, or, in other words, to the regular succession of eve ...

physics
and for
chemistry Chemistry is the scientific Science () is a systematic enterprise that builds and organizes knowledge Knowledge is a familiarity or awareness, of someone or something, such as facts A fact is an occurrence in the real world. T ...

chemistry
,
chemical engineering Chemical engineering is a certain type of which deals with the study of operation and design of chemical plants as well as methods of improving production. Chemical engineers develop economical commercial processes to convert raw material into u ...
,
corrosion engineeringCorrosion engineering is an engineering specialty that applies scientific, technical, engineering skills, and knowledge of natural laws and physical resources to design and implement materials, structures, devices, systems, and procedures to manage c ...
,
aerospace engineering Aerospace engineering is the primary field of engineering Engineering is the use of scientific principles to design and build machines, structures, and other items, including bridges, tunnels, roads, vehicles, and buildings. The discipl ...

aerospace engineering
,
mechanical engineering Mechanical engineering is an engineering Engineering is the use of scientific method, scientific principles to design and build machines, structures, and other items, including bridges, tunnels, roads, vehicles, and buildings. The discip ...

mechanical engineering
,
cell biology Cell biology (also cellular biology or cytology) is a branch of biology Biology is the natural science that studies life and living organisms, including their anatomy, physical structure, Biochemistry, chemical processes, Molecular biolog ...
, biomedical engineering,
materials science The interdisciplinary Interdisciplinarity or interdisciplinary studies involves the combination of two or more academic disciplines into one activity (e.g., a research project). It draws knowledge from several other fields like sociology, a ...
, and
economics Economics () is a social science that studies the Production (economics), production, distribution (economics), distribution, and Consumption (economics), consumption of goods and services. Economics focuses on the behaviour and interact ...

economics
, to name a few. This article is focused mainly on classical thermodynamics which primarily studies systems in
thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic An axiom, postulate or assumption is a statement that is taken to be true True most commonly refers to truth Truth is the property of being in accord with fact or reality.Merriam-Webster's Onlin ...
.
Non-equilibrium thermodynamics Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities (non-equilibrium state variables) that represent an extr ...
is often treated as an extension of the classical treatment, but statistical mechanics has brought many advances to that field.


History

The
history of thermodynamics The history of thermodynamics is a fundamental strand in the history of physics, the history of chemistry, and the history of science in general. Owing to the relevance of thermodynamics Thermodynamics is a branch of physics that deals with ...
as a scientific discipline generally begins with
Otto von Guericke Otto von Guericke ( , , ; spelled Gericke until 1666; November 20, 1602 – May 11, 1686 Julian_calendar">nowiki/>Julian_calendar.html" ;"title="Julian_calendar.html" ;"title="nowiki/>Julian calendar">nowiki/>Julian calendar">Julian_calendar.h ...

Otto von Guericke
who, in 1650, built and designed the world's first
vacuum pump A vacuum pump is a device that draws gas Gas is one of the four fundamental states of matter In physics Physics is the natural science that studies matter, its Elementary particle, fundamental constituents, its Motion (physics), ...

vacuum pump
and demonstrated a
vacuum A vacuum is a space Space is the boundless three-dimensional Three-dimensional space (also: 3-space or, rarely, tri-dimensional space) is a geometric setting in which three values (called parameter A parameter (from the Ancient Gr ...

vacuum
using his
Magdeburg hemispheres 's sketch of Otto von Guericke's Magdeburg hemispheres experiment. The Magdeburg hemispheres are a pair of large copper hemispheres, with mating rims. They were used to demonstrate the power of atmospheric pressure Atmospheric pressure, also know ...

Magdeburg hemispheres
. Guericke was driven to make a vacuum in order to disprove
Aristotle Aristotle (; grc-gre, Ἀριστοτέλης ''Aristotélēs'', ; 384–322 BC) was a Greek philosopher A philosopher is someone who practices philosophy Philosophy (from , ) is the study of general and fundamental questio ...

Aristotle
's long-held supposition that 'nature abhors a vacuum'. Shortly after Guericke, the Anglo-Irish physicist and chemist
Robert Boyle Robert Boyle (; 25 January 1627 – 31 December 1691) was an Anglo-Irish Anglo-Irish () is a term which was more commonly used in the 19th and early 20th centuries to identify an ethnic group An ethnic group or ethnicity is a group ...

Robert Boyle
had learned of Guericke's designs and, in 1656, in coordination with English scientist
Robert Hooke Robert Hooke FRS FRS may also refer to: Government and politics * Facility Registry System, a centrally managed Environmental Protection Agency database that identifies places of environmental interest in the United States * Family Resources ...
, built an air pump. Using this pump, Boyle and Hooke noticed a correlation between
pressure Pressure (symbol: ''p'' or ''P'') is the force In physics, a force is an influence that can change the motion (physics), motion of an Physical object, object. A force can cause an object with mass to change its velocity (e.g. moving fr ...

pressure
,
temperature Temperature ( ) is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy Thermal radiation in visible light can be seen on this hot metalwork. Thermal energy refers to several distinct physical concept ...

temperature
, and
volume Volume is a scalar quantity expressing the amount Quantity or amount is a property that can exist as a multitude Multitude is a term for a group of people who cannot be classed under any other distinct category, except for their shared fact ...
. In time, Boyle's Law was formulated, which states that pressure and volume are
inversely proportional In mathematics Mathematics (from Ancient Greek, Greek: ) includes the study of such topics as quantity (number theory), mathematical structure, structure (algebra), space (geometry), and calculus, change (mathematical analysis, analysis). ...
. Then, in 1679, based on these concepts, an associate of Boyle's named
Denis Papin Denis Papin FRS (; 22 August 1647 – 26 August 1713) was a French physicist, mathematician and inventor, best known for his pioneering invention of the steam digester, the forerunner of the pressure cooker and of the steam engine fr ...

Denis Papin
built a
steam digester The steam digester (or bone digester, and also known as Papin’s digester) is a high-pressure cooker invented by French physicist Denis Papin in 1679. It is a device for extracting fats from bones in a high-pressure steam environment, which also ...
, 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 A piston is a component of reciprocating engines, reciprocating pumps, gas compressors, Hydraulic cylinder, hydraulic cylinders and pneumatic cylinders, among other similar mechanisms. It is the moving component that is contained by a cylinder ...

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 Thomas Savery (; c. 1650 – 15 May 1715) was an English inventor and engineer, born at Shilstone, a manor house A manor house was historically the main residence of the lord of the manor. The house formed the administrative centre of a ...

Thomas Savery
built the first engine, followed by
Thomas Newcomen Thomas Newcomen (; February 1664 – 5 August 1729) was an English inventor who created the atmospheric engine The atmospheric engine was invented by Thomas Newcomen Thomas Newcomen (; February 1664 – 5 August 1729) ...
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 Heat capacity or thermal capacity is a physical property A physical property is any property Property is a system of rights that gives people legal control of valuable things, and also refers to the valuable things themselves. Depending on t ...
and
latent heat Latent heat (also known as latent energy or heat of transformation) is energy released or absorbed, by a body or a thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any su ...
, which were necessary for the development of thermodynamics, were developed by Professor
Joseph Black Joseph Black (16 April 1728 – 6 December 1799) was a Scottish physicist and chemist, known for his discoveries of magnesium, latent heat, specific heat, and carbon dioxide. He was Professor of Anatomy and Chemistry at the University of Glasgo ...
at the University of Glasgow, where
James Watt James Watt (; 30 January 1736 (19 January 1736 OS) – 25 August 1819) was a Scottish Scottish usually refers to something of, from, or related to Scotland, including: *Scottish Gaelic, a Celtic Goidelic language of the Indo-European lang ...

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 from Stott Park Bobbin Mill, Cumbria, England A steam engine is a heat engine In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energ ...

steam engine
efficiency. Drawing on all the previous work led Sadi Carnot, the "father of thermodynamics", to publish ''
Reflections on the Motive Power of Fire ''Reflections on the Motive Power of Fire and on Machines Fitted to Develop that Power'' is a book published in 1824 by French people, French physicist Nicolas Léonard Sadi Carnot, Sadi Carnot.full text of 1897 ed. ( s:Reflections on the Motive P ...
'' (1824), a discourse on heat, power, energy and engine efficiency. The book outlined the basic energetic relations between the
Carnot engine A Carnot heat engine is a theoretical engine that operates on the Carnot cycle. The basic model for this engine was developed by Nicolas Léonard Sadi Carnot ''Sous-lieutenant'' Nicolas Léonard Sadi Carnot (; 1 June 1796 – 24 August 1832) ...

Carnot engine
, the
Carnot cycle
Carnot cycle
, and motive power. It marked the start of thermodynamics as a modern science. The first thermodynamic textbook was written in 1859 by
William Rankine William John Macquorn Rankine (; 5 July 1820 – 24 December 1872) was a Scottish mechanical engineer who also contributed to civil engineering, physics and mathematics. He was a founding contributor, with Rudolf Clausius and William Thomson, 1 ...
, originally trained as a physicist and a civil and mechanical engineering professor at the
University of Glasgow The University of Glasgow (abbreviated as ''Glas.'' in Post-nominal letters, post-nominals; ) is a Public university, public research university in Glasgow, Scotland. Founded by papal bull in 1451, it is the List of oldest universities in continuous ...

University of Glasgow
. The first and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the works of
William Rankine William John Macquorn Rankine (; 5 July 1820 – 24 December 1872) was a Scottish mechanical engineer who also contributed to civil engineering, physics and mathematics. He was a founding contributor, with Rudolf Clausius and William Thomson, 1 ...
,
Rudolf Clausius Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German German(s) may refer to: Common uses * of or related to Germany * Germans, Germanic ethnic group, citizens of Germany or people of German ancestry * For citize ...
, and William Thomson (Lord Kelvin). The foundations of statistical thermodynamics were set out by physicists such as
James Clerk Maxwell James Clerk Maxwell (13 June 1831 – 5 November 1879) was a Scottish mathematician A mathematician is someone who uses an extensive knowledge of mathematics Mathematics (from Greek: ) includes the study of such topics as num ...

James Clerk Maxwell
,
Ludwig Boltzmann Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austria Austria, officially the Republic of Austria, is a landlocked country in the southern part of Central Europe, located on the Eastern Alps. It is compo ...
,
Max Planck Max Karl Ernst Ludwig Planck, (; ; 23 April 1858 – 4 October 1947) was a Germans, German theoretical physicist whose discovery of quantum mechanics, energy quanta won him the Nobel Prize in Physics in 1918. Planck made many substantial co ...

Max Planck
,
Rudolf Clausius Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German German(s) may refer to: Common uses * of or related to Germany * Germans, Germanic ethnic group, citizens of Germany or people of German ancestry * For citize ...
and . During the years 1873–76 the American mathematical physicist
Josiah Willard Gibbs Josiah Willard Gibbs (; February 11, 1839 – April 28, 1903) was an American scientist who made significant theoretical contributions to physics, chemistry, and mathematics. His work on the applications of thermodynamics was instrumental in tr ...

Josiah Willard Gibbs
published a series of three papers, the most famous being ''
On the Equilibrium of Heterogeneous Substances In the history of thermodynamics, ''On the Equilibrium of Heterogeneous Substances'' is a 300-page paper written by American chemical physicist Willard Gibbs. It is one of the founding papers in thermodynamics, along with German physicist Hermann ...
'', in which he showed how thermodynamic processes, including
chemical reaction A chemical reaction is a process that leads to the chemical transformation of one set of chemical substance A chemical substance is a form of matter In classical physics and general chemistry, matter is any substance that has mass and t ...

chemical reaction
s, could be graphically analyzed, by studying the
energy In , energy is the that must be to a or to perform on the body, or to it. Energy is a ; the law of states that energy can be in form, but not created or destroyed. The unit of measurement in the (SI) of energy is the , which is the ...

energy
,
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

entropy
,
volume Volume is a scalar quantity expressing the amount Quantity or amount is a property that can exist as a multitude Multitude is a term for a group of people who cannot be classed under any other distinct category, except for their shared fact ...
,
temperature Temperature ( ) is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy Thermal radiation in visible light can be seen on this hot metalwork. Thermal energy refers to several distinct physical concept ...

temperature
and
pressure Pressure (symbol: ''p'' or ''P'') is the force In physics, a force is an influence that can change the motion (physics), motion of an Physical object, object. A force can cause an object with mass to change its velocity (e.g. moving fr ...

pressure
of the
thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, whic ...
in such a manner, one can determine if a process would occur spontaneously. Also
Pierre Duhem Pierre Maurice Marie Duhem (; 9 June 1861 – 14 September 1916) was a French theoretical physicist A physicist is a scientist A scientist is a person who conducts scientific research The scientific method is an Empirical evidence, ...

Pierre Duhem
in the 19th century wrote about chemical thermodynamics. During the early 20th century, chemists such as Gilbert N. Lewis,
Merle RandallMerle Randall (January 29, 1888 – March 17, 1950) was an American physical chemist Physical chemistry is the study of macroscopic The macroscopic scale is the length scale on which objects or phenomena are large enough to be visible with the ...
, and E. A. Guggenheim applied the mathematical methods of Gibbs to the analysis of chemical processes.


Etymology

The etymology of ''thermodynamics'' has an intricate history. 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. American
biophysicist uses protein domain dynamics on nanoscales to walk along a microtubule Microtubules are polymers of tubulin that form part of the cytoskeleton and provide structure and shape to Eukaryote, eukaryotic cells. Microtubules can grow as long as 50&n ...
Donald Haynie claims that ''thermodynamics'' was coined in 1840 from the
Greek#REDIRECT Greek Greek may refer to: Greece Anything of, from, or related to Greece Greece ( el, Ελλάδα, , ), officially the Hellenic Republic, is a country located in Southeast Europe. Its population is approximately 10.7 million as of ...
root θέρμη ''therme,'' meaning “heat”, and δύναμις ''dynamis,'' meaning “power”. Pierre Perrot claims that the term ''thermodynamics'' was coined by
James Joule James Prescott Joule (; 24 December 1818 11 October 1889) was an English physicist A physicist is a scientist A scientist is a person who conducts scientific research The scientific method is an Empirical evidence, empirical m ...

James Joule
in 1858 to designate the science of relations between heat and power, however, Joule never used that term, but used instead the term ''perfect thermo-dynamic engine'' in reference to Thomson's 1849 phraseology. 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."Kelvin, William T. (1849) "An Account of Carnot's Theory of the Motive Power of Heat – with Numerical Results Deduced from Regnault's Experiments on Steam." ''Transactions of the Edinburg Royal Society, XVI. January 2.
Scanned Copy


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 laws of thermodynamics define a group of physical quantities, such as temperature Temperature is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy, present in all matter, which is the source of t ...
. 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 In physics Physics is the that studies , its , its and behavior through , and the related entities of and . "Physical science is that department of knowledge which relates to the order of nature, or, in other words, to the regular ...
, 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 Quantum theory may refer to: Science *Quantum mechanics Quantum mechanics is a fundamental theory A theory is a reason, rational type of abstraction, abstract thinking about a phenomenon, or the results of such thinking. The process of co ...
at the microscopic level.


Chemical thermodynamics

Chemical thermodynamics Chemical thermodynamics is the study of the interrelation of heat In thermodynamics, heat is energy in transfer to or from a thermodynamic system, by mechanisms other than thermodynamic work or transfer of matter. The various mechanisms o ...
is the study of the interrelation of
energy In , energy is the that must be to a or to perform on the body, or to it. Energy is a ; the law of states that energy can be in form, but not created or destroyed. The unit of measurement in the (SI) of energy is the , which is the ...

energy
with
chemical reactions A chemical reaction is a process that leads to the chemical transformation of one set of chemical substance A chemical substance is a form of matter In classical physics and general chemistry, matter is any substance that has mass and ...

chemical reactions
or with a physical change of
state State may refer to: Arts, entertainment, and media Literature * ''State Magazine'', a monthly magazine published by the U.S. Department of State * The State (newspaper), ''The State'' (newspaper), a daily newspaper in Columbia, South Carolina, Un ...
within the confines of the
laws of thermodynamics The laws of thermodynamics define a group of physical quantities, such as temperature Temperature is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy, present in all matter, which is the source of t ...
. The primary objective of chemical thermodynamics is determining the spontaneity of a given transformation.


Equilibrium thermodynamics

Equilibrium thermodynamics Equilibrium Thermodynamics is the systematic study of transformations of matter and energy in systems in terms of a concept called thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic concept of thermodynamics Thermodynamics is a ...
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 Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities (non-equilibrium state variables) that represent an extr ...
is a branch of thermodynamics that deals with systems that are not in
thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic An axiom, postulate or assumption is a statement that is taken to be true True most commonly refers to truth Truth is the property of being in accord with fact or reality.Merriam-Webster's Onlin ...
. 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

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 The zeroth law of thermodynamics states that if two thermodynamic system A thermodynamic system is a body of matter and/or radiation, confined in space by walls, with defined permeabilities, which separate it from its surroundings. The surroundi ...

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 In mathematics Mathematics (from Ancient Greek, Greek: ) includes the study of such topics as quantity (number theory), mathematical structure, structure (algebra), space (geometry), and calculus, change (mathematical analysis, analysis). ...
on the set of
thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, whic ...
s under consideration. Systems are said to be in equilibrium if the small, random exchanges between them (e.g.
Brownian motion Brownian motion, or pedesis (from grc, πήδησις "leaping"), is the random motion of particle In the Outline of physical science, physical sciences, a particle (or corpuscule in older texts) is a small wikt:local, localized physica ...

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 Temperature ( ) is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy Thermal radiation in visible light can be seen on this hot metalwork. Thermal energy refers to several distinct physical concept ...

temperature
, it is not necessary to bring them into contact and measure any changes of their observable properties in time. 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

The
first law of thermodynamics The first law of thermodynamics is a version of the law of conservation of energy In physics Physics is the that studies , its , its and behavior through , and the related entities of and . "Physical science is that department o ...
states: ''In a process without transfer of matter, the change in
internal energy The internal energy of a thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that ca ...
,'' \Delta U'', of a
thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, whic ...
is equal to the energy gained as heat,'' Q'', less the thermodynamic work,'' W'', done by the system on its surroundings.''The sign convention (Q is heat supplied ''to'' the system as, W is work done ''by'' the system) is that of
Rudolf Clausius Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German German(s) may refer to: Common uses * of or related to Germany * Germans, Germanic ethnic group, citizens of Germany or people of German ancestry * For citize ...
. The opposite sign convention is customary in chemical thermodynamics.
:\Delta U = Q - W. 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'' :U_0 = U_1 + U_2, ''where'' ''denotes the internal energy of the combined system, and'' ''and'' ''denote the internal energies of the respective separated systems.'' Adapted for thermodynamics, this law is an expression of the principle of
conservation of energy In physics Physics is the that studies , its , its and behavior through , and the related entities of and . "Physical science is that department of knowledge which relates to the order of nature, or, in other words, to the regular s ...
, which states that energy can be transformed (changed from one form to another), but cannot be created or destroyed.Callen, H.B. (1960/1985).''Thermodynamics and an Introduction to Thermostatistics'', second edition, John Wiley & Sons, Hoboken NY, , pp. 11–13. Internal energy is a principal property of the
thermodynamic state For thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, radiation, and physical properties of matter. The behavior of these quantities is governe ...
, 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 In the Thermodynamics#Equilibrium_thermodynamics, thermodynamics of equilibrium, a state function, function of state, or point function is a function defined for a system relating several state variables or state quantities that depends only on the ...
, 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 The second law of thermodynamics establishes the concept of entropy Entropy is a scientific concept, as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term an ...
states: ''Heat does not spontaneously flow from a colder body to a hotter.'' The second law refers to a system of matter and radiation, initially with inhomogeneities in temperature, pressure, chemical potential, and other
intensive properties Physical properties A physical property is any property Property (''latin: Res Privata'') in the Abstract and concrete, abstract is what belongs to or with something, whether as an attribute or as a component of said thing. In the context of ...
, 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 Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

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
irreversibility In science, a process A process is a series or set of Action (philosophy), activities that interact to produce a result; it may occur once-only or be recurrent or periodic. Things called a process include: Business and management *Business proc ...
of such approach to 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 The third law of thermodynamics states as follows, regarding the properties of closed systems in thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic concept of thermodynamics Thermodynamics is a branch of physics that deals wit ...
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 Absolute zero is the lowest limit of the thermodynamic temperature Thermodynamic temperature is the measure of ''absolute temperature'' and is one of the principal parameters of thermodynamics. A thermodynamic temperature reading of zero deno ...
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

An important concept in thermodynamics is the
thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, whic ...
, 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 Work may refer to: * Work (human activity), intentional activity people perform to support themselves, others, or the community ** Manual labour, physical work done by humans ** House work, housework, or homemaking * Work (physics), the product of ...
, or as
heat In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these ...

heat
, or of
matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, which are made up of interacting subatomic particl ...
, 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 Max Karl Ernst Ludwig Planck, (; ; 23 April 1858 – 4 October 1947) was a Germans, German theoretical physicist whose discovery of quantum mechanics, energy quanta won him the Nobel Prize in Physics in 1918. Planck made many substantial co ...

Max Planck
defined in 1900; it can be a body of steam or air in a
steam engine from Stott Park Bobbin Mill, Cumbria, England A steam engine is a heat engine In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energ ...

steam engine
, such as Sadi Carnot defined in 1824. The system could also be just one
nuclide A nuclide (or nucleide, from nucleus ''Nucleus'' (plural nuclei) is a Latin word for the seed inside a fruit. It most often refers to: *Atomic nucleus, the very dense central region of an atom *Cell nucleus, a central organelle of a eukaryotic c ...

nuclide
(i.e. a system of
quark A quark () is a type of elementary particle In particle physics, an elementary particle or fundamental particle is a subatomic particle that is not composed of other particles. Particles currently thought to be elementary include the fundam ...

quark
s) as hypothesized in
quantum thermodynamics Quantum thermodynamics is the study of the relations between two independent physical theories: thermodynamics and quantum mechanics. The two independent theories address the physical phenomena of light and matter. In 1905, Albert Einstein argued ...
. When a looser viewpoint is adopted, and the requirement of thermodynamic equilibrium is dropped, the system can be the body of a
tropical cyclone A tropical cyclone is a rapidly rotating storm system characterized by a low-pressure center, a closed low-level atmospheric circulation Atmospheric circulation is the large-scale movement of Atmosphere of Earth, air and together with oc ...
, such as
Kerry Emanuel Kerry Andrew Emanuel (born April 21, 1955) is an American professor of meteorology currently working at the Massachusetts Institute of Technology in Cambridge, Massachusetts, Cambridge. In particular he has specialized in atmospheric convection an ...
theorized in 1986 in the field of
atmospheric thermodynamics Atmospheric thermodynamics is the study of heat In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical propertie ...
, or the
event horizon In astrophysics, an event horizon is a boundary beyond which events cannot affect an observer. The term was coined by in the 1950s. In 1784, proposed that in the vicinity of compact massive objects, gravity can be strong enough that even light ...
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: 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 State may refer to: Arts, entertainment, and media Literature * ''State Magazine'', a monthly magazine published by the U.S. Department of State * The State (newspaper), ''The State'' (newspaper), a daily newspaper in Columbia, South Carolina, Un ...
of
thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic An axiom, postulate or assumption is a statement that is taken to be true True most commonly refers to truth Truth is the property of being in accord with fact or reality.Merriam-Webster's Onlin ...
. 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

When a system is at equilibrium under a given set of conditions, it is said to be in a definite
thermodynamic state For thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, radiation, and physical properties of matter. The behavior of these quantities is governe ...
. 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 In physics Physics (from grc, φυσική (ἐπιστήμη), physikḗ (epistḗmē), knowledge of nature, from ''phýsis'' 'nature'), , is the natural science that studies matter, its Motion (physics), motion and behavior through S ...
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 Classical thermodynamics considers three main kinds of thermodynamic process: (1) changes in a system, (2) cycles in a system, and (3) flow processes. (1) A change in a system is defined by a passage from an initial to a final state of thermodyna ...
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 function, 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 variables (thermodynamics), conjugate pair. Several commonly studied thermodynamic processes are: * Adiabatic process: occurs without loss or gain of energy by
heat In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these ...

heat
* Isenthalpic process: occurs at a constant enthalpy * Isentropic process: a reversible adiabatic process, occurs at a constant
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

entropy
* Isobaric process: occurs at constant
pressure Pressure (symbol: ''p'' or ''P'') is the force In physics, a force is an influence that can change the motion (physics), motion of an Physical object, object. A force can cause an object with mass to change its velocity (e.g. moving fr ...

pressure
* Isochoric process: occurs at constant
volume Volume is a scalar quantity expressing the amount Quantity or amount is a property that can exist as a multitude Multitude is a term for a group of people who cannot be classed under any other distinct category, except for their shared fact ...
(also called isometric/isovolumetric) * Isothermal process: occurs at a constant
temperature Temperature ( ) is a physical quantity that expresses hot and cold. It is the manifestation of thermal energy Thermal radiation in visible light can be seen on this hot metalwork. Thermal energy refers to several distinct physical concept ...

temperature
* steady state, Steady state process: occurs without a change in the
internal energy The internal energy of a thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that ca ...


Instrumentation

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 A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, whic ...
. In some cases, the thermodynamic parameter is actually defined in terms of an idealized measuring instrument. For example, the zeroth law of thermodynamics, 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 Clerk Maxwell, 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. The ocean can act as temperature reservoir when used to cool power plants.


Conjugate variables

The central concept of thermodynamics is that of
energy In , energy is the that must be to a or to perform on the body, or to it. Energy is a ; the law of states that energy can be in form, but not created or destroyed. The unit of measurement in the (SI) of energy is the , which is the ...

energy
, the ability to do
work Work may refer to: * Work (human activity), intentional activity people perform to support themselves, others, or the community ** Manual labour, physical work done by humans ** House work, housework, or homemaking * Work (physics), the product of ...
. By the first law of thermodynamics, 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 (thermodynamics), Conjugate variables are pairs of thermodynamic concepts, with the first being akin to a "force" applied to some
thermodynamic system A thermodynamic system is a body of matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, whic ...
, the second being akin to the resulting "displacement," and the product of the two equaling the amount of energy transferred. The common conjugate variables are: * Pressure-
volume Volume is a scalar quantity expressing the amount Quantity or amount is a property that can exist as a multitude Multitude is a term for a group of people who cannot be classed under any other distinct category, except for their shared fact ...
(the Mechanics, mechanical parameters); * Temperature-
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

entropy
(thermal parameters); * Chemical potential-particle number (material parameters).


Potentials

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: where T is the thermodynamic temperature, temperature, S the
entropy Entropy is a scientific concept as well as a measurable physical property that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics ...

entropy
, p the
pressure Pressure (symbol: ''p'' or ''P'') is the force In physics, a force is an influence that can change the motion (physics), motion of an Physical object, object. A force can cause an object with mass to change its velocity (e.g. moving fr ...

pressure
, V the
volume Volume is a scalar quantity expressing the amount Quantity or amount is a property that can exist as a multitude Multitude is a term for a group of people who cannot be classed under any other distinct category, except for their shared fact ...
, \mu the chemical potential, N the number of particles in the system, and i 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 transformation.


Applied fields


See also

* Thermodynamic process path


Lists and timelines

* List of important publications in physics#Thermodynamics, List of important publications in thermodynamics * List of textbooks in statistical mechanics, List of textbooks on thermodynamics and statistical mechanics * List of thermal conductivities * List of thermodynamic properties * Table of thermodynamic equations * Timeline of thermodynamics


Notes


References


Further reading

* A nontechnical introduction, good on historical and interpretive matters. * * Vol. 1, pp. 55–349. * * * * 5th ed. (in Russian) * * * * * * The following titles are more technical: * * * *


External links

* *
Thermodynamics Data & Property Calculation Websites

Thermodynamics Educational Websites





Engineering Thermodynamics – A Graphical Approach

Thermodynamics and Statistical Mechanics
by Richard Fitzpatrick {{Authority control Energy Thermodynamics, Chemical engineering