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[[File:Savery-engine.jpg|225px|right|thumb|The 1698 '''Savery Engine''' – the world's first commercially-useful [[steam engine]]: built by [[Thomas Savery]]]]
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{{thermodynamics|cTopic=History and Culture}}
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]] in much of [[science]] and [[technology]], its history is finely woven with the developments of [[classical mechanics]], [[quantum mechanics]], [[magnetism]], and [[chemical kinetics]], to more distant applied fields such as [[meteorology]], [[information theory]], and [[biology]] ([[physiology]]), and to [[technology|technological]] developments such as the [[steam engine]], [[internal combustion engine]], [[cryogenics]] and [[electricity generation]]. The development of thermodynamics both drove and was driven by [[atomic theory]]. It also, albeit in a subtle manner, motivated new directions in [[probability]] and [[statistics]]; see, for example, the [[timeline of thermodynamics]].
 
==History==
{{See also|Timeline of thermodynamics}}
 
===Contributions from ancient and medieval times===
{{See also|History of heat|Vacuum}}
 
The ancients viewed [[heat]] as that related to [[fire]]. In 3000 BC, the [[ancient Egypt]]ians viewed heat as related to origin mythologies.<ref name="Griffith">{{cite journal | author = J. Gwyn Griffiths | year = 1955 | title = The Orders of Gods in Greece and Egypt (According to Herodotus) | journal = The Journal of Hellenic Studies | volume = 75 | pages = 21–23 | doi = 10.2307/629164 | jstor=629164}}</ref> 
In the [[western philosophy|Western philosophical]] tradition, after much debate about the primal element among earlier [[pre-Socratic philosophy|pre-Socratic philosopher]]s, [[Empedocles]] proposed a four-element theory, in which all substances derive from [[earth (classical element)|earth]], [[water (classical element)|water]], [[air (classical element)|air]], and [[fire (classical element)|fire]]. The Empedoclean element of fire is perhaps the principal ancestor of later concepts such as [[phlogiston]] and [[caloric theory|caloric]]. Around 500 BC, the [[Greek philosophy|Greek philosopher]] [[Heraclitus]] became famous as the "flux and fire" philosopher for his proverbial utterance: "All things are flowing." Heraclitus argued that the three [[classical elements|principal elements]] in nature were fire, earth, and water.
[[File:Thermally Agitated Molecule.gif|266px|thumb|left|'''Heating''' a body, such as a segment of [[protein]] [[alpha helix]] (above), tends to cause its atoms to vibrate more, and to expand or change [[Phase (matter)|phase]], if heating is continued; an axiom of nature noted by [[Herman Boerhaave]] in the in 1700s.]]
 
[[Atomism]] is a central part of today's relationship between thermodynamics and statistical mechanics. Ancient thinkers such as [[Leucippus]] and [[Democritus]], and later the [[Epicureans]], by advancing atomism, laid the foundations for the later [[atomic theory]]. Until experimental proof of [[atoms]] was later provided in the 20th century, the atomic theory was driven largely by philosophical considerations and scientific intuition. Consequently, ancient philosophers used atomic theory to reach conclusions that today may be viewed as immature: for example, Democritus gives a vague atomistic description of the soul, namely that it is "built from thin, smooth, and round atoms, similar to those of fire".
 
The 5th century BC, Greek philosopher [[Parmenides]], in his only known work, a poem conventionally titled ''On Nature'', uses verbal reasoning to postulate that a void, essentially what is now known as a [[vacuum]], in nature could not occur. This view was supported by the arguments of [[Aristotle]], but was criticized by [[Leucippus]] and [[Hero of Alexandria]].  From antiquity to the Middle Ages various arguments were put forward to prove or disapprove the existence of a vacuum and several attempts were made to construct a vacuum but all proved unsuccessful.
 
The European scientists [[Cornelius Drebbel]], [[Robert Fludd]], [[Galileo Galilei]] and [[Santorio Santorio]] in the 16th and 17th centuries were able to gauge the relative "[[coldness]]" or "[[hotness]]" of air, using a rudimentary air [[thermometer]] (or [[thermoscope]]). This may have been influenced by an earlier device which could expand and contract the air constructed by [[Philo of Byzantium]] and [[Hero of Alexandria]].
 
Around 1600, the English philosopher and scientist [[Francis Bacon]] surmised: "Heat itself, its essence and quiddity is motion and nothing else."  In 1643, [[Galileo Galilei]], while generally accepting the 'sucking' explanation of ''horror vacui'' proposed by Aristotle, believed that nature’s vacuum-abhorrence is limited.  Pumps operating in mines had already proven that nature would only fill a vacuum with water up to a height of ~30 feet.  Knowing this curious fact, Galileo encouraged his former pupil [[Evangelista Torricelli]] to investigate these supposed limitations.  Torricelli did not believe that vacuum-abhorrence (''[[Horror vacui]]'') in the sense of Aristotle's 'sucking' perspective, was responsible for raising the water.  Rather, he reasoned, it was the result of the pressure  exerted on the liquid by the surrounding air.
 
To prove this theory, he filled a long glass tube (sealed at one end) with mercury and upended it into a dish also containing mercury.  Only a portion of the tube emptied (as shown adjacent); ~30&nbsp;inches of the liquid remained.  As the mercury emptied, and a [[vacuum]] was created at the top of the tube.  This, the first man-made vacuum, effectively disproved Aristotle’s 'sucking' theory and affirmed the existence of vacuums in nature.  The gravitational force on the heavy element that is Mercury prevented it from filling the vacuum.  Nature may abhor a vacuum, but gravity does not care.
 
=== Transition from chemistry to thermochemistry ===
{{See also|History of chemistry}}
[[File:Ice-calorimeter.jpg|150px|right|thumb|The world’s first '''ice-calorimeter''', used in the winter of 1782-83, by [[Antoine Lavoisier]] and [[Pierre-Simon Laplace]], to determine the [[heat]] evolved in various [[chemical change]]s; calculations which were based on [[Joseph Black]]’s prior discovery of [[latent heat]].  These experiments mark the foundation of [[thermochemistry]].{{Citation needed|date=April 2012}}]]
The theory of phlogiston arose in the 17th century, late in the period of alchemy. Its replacement by [[caloric theory]] in the 18th century is one of the historical markers of the transition from alchemy to chemistry.  Phlogiston was a hypothetical substance that was presumed to be liberated from combustible substances during [[combustion|burning]], and from [[metal]]s during the process of [[rusting]].  Caloric, like phlogiston, was also presumed to be the "substance" of heat that would flow from a hotter body to a cooler body, thus warming it.
 
The first substantial experimental challenges to caloric theory arose in [[Benjamin Thompson|Rumford]]'s 1798 work, when he showed that boring [[cast iron]] [[cannon]]s produced great amounts of heat which he ascribed to [[friction]], and his work was among the first to undermine the caloric theory. The development of the [[steam engine]] also focused attention on [[calorimetry]] and the amount of heat produced from different types of [[coal]]. The first quantitative research on the heat changes during chemical reactions was initiated by [[Lavoisier]] using an [[ice]] [[calorimeter]] following research by [[Joseph Black]] on the [[latent heat]] of water.
 
More quantitative studies by [[James Prescott Joule]] in 1843 onwards provided soundly reproducible phenomena, and helped to place the subject of thermodynamics on a solid footing. [[William Thomson, 1st Baron Kelvin|William Thomson]], for example, was still trying to explain Joule's observations within a caloric framework as late as 1850. The utility and explanatory power of [[kinetic theory]], however, soon started to displace caloric and it was largely obsolete by the end of the 19th century. [[Joseph Black]] and [[Lavoisier]] made important contributions in the precise measurement of heat changes using the [[calorimeter]], a subject which became known as [[thermochemistry]].
 
=== Phenomenological thermodynamics ===
[[File:Robert Boyle 0001.jpg|thumb|150px|left|Robert Boyle. 1627-1691]]
*[[Boyle's law]] (1662)
*[[Charles's law]] was first published by [[Joseph Louis Gay-Lussac]] in 1802, but he referenced unpublished work by [[Jacques Charles]] from around 1787. The relationship had been anticipated by the work of [[Guillaume Amontons]] in 1702.
*[[Gay-Lussac's law]] (1802)
 
===Birth of thermodynamics as science===
At its origins, thermodynamics was the study of [[engines]].  A precursor of the engine was designed by the German scientist [[Otto von Guericke]] who, in 1650, designed and built the world's first [[vacuum pump]] and created the world's first ever [[vacuum]] known as the [[Magdeburg hemispheres]].  He was driven to make a vacuum in order to disprove [[Aristotle]]'s long-held supposition that [[Horror vacui (physics)|'Nature abhors a vacuum']].
 
Shortly thereafter, 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. Using this pump, Boyle and Hooke noticed the pressure-volume correlation: P.V=constant. In that time, air was assumed to be a system of motionless particles, and not interpreted as a system of moving molecules. The concept of thermal motion came two centuries later.  Therefore Boyle's publication in 1660 speaks about a mechanical concept: the air spring.<ref>New Experiments physico-mechanicall, Touching the Spring of the Air and its Effects (1660). [http://www.imss.fi.it/vuoto/eboyle.html]</ref> Later, after the invention of the thermometer, the property temperature could be quantified. This tool gave [[Gay-Lussac]] the opportunity to derive his law, which led shortly later to the [[ideal gas law]].  But, already before the establishment of the ideal gas law, an associate of Boyle's named [[Denis Papin]] built in 1679 a bone digester, which is a closed vessel with a tightly fitting lid that confines steam until a high pressure is generated.
 
Later designs implemented a steam release valve to keep the machine from exploding.  By watching the valve rhythmically move up and down, Papin conceived of the idea of a piston and 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. Although these early engines were crude and inefficient, they attracted the attention of the leading scientists of the time. One such scientist was [[Nicolas Léonard Sadi Carnot|Sadi Carnot]], the “father of thermodynamics”, who in 1824 published ''“[[Reflections on the Motive Power of Fire]]”,'' a discourse on heat, power, and engine efficiency.  This marks the start of thermodynamics as a modern science.
 
[[File:Maquina vapor Watt ETSIIM.jpg|right|thumb|300px|A [[Watt steam engine]], the [[steam engine]] that propelled the Industrial Revolution in Britain and the world]]
 
Hence, prior to 1698 and the invention of the [[steam engine|Savery Engine]], horses were used to power pulleys, attached to buckets, which lifted water out of flooded salt mines in England. In the years to follow, more variations of steam engines were built, such as the [[newcomen steam engine|Newcomen Engine]], and later the [[watt steam engine|Watt Engine]]. In time, these early engines would eventually be utilized in place of horses.  Thus, each engine began to be associated with a certain amount of "horse power" depending upon how many horses it had replaced. The main problem with these first engines was that they were slow and clumsy, converting less than 2% of the input [[fuel]] into useful work.  In other words, large quantities of coal (or wood) had to be burned to yield only a small fraction of work output.  Hence the need for a new science of engine [[dynamics (mechanics)|dynamics]] was born.
 
[[File:Carnot2.jpg|150px|left|thumb|Sadi Carnot (1796-1832): the "father" of thermodynamics]]
Most cite [[Nicolas Léonard Sadi Carnot|Sadi Carnot’s]] [http://www.thermohistory.com/carnot.pdf 1824 paper] ''Reflections on the Motive Power of Fire'' as the starting point for thermodynamics as a modern science.  Carnot defined "motive power" to be the expression of the ''useful effect'' that a motor is capable of producing.  Herein, Carnot introduced us to the first modern day definition of "[[Mechanical work|work]]": ''weight lifted through a height''.  The desire to understand, via formulation, this ''useful effect'' in relation to "work" is at the core of all modern day thermodynamics.
 
In 1843, [[James Joule]] experimentally found the [[mechanical equivalent of heat]]. In 1845, Joule reported his best-known experiment, involving the use of a falling weight to spin a paddle-wheel in a barrel of water, which allowed him to estimate a mechanical equivalent of heat of 819&nbsp;ft·lbf/Btu (4.41 J/cal). This led to the theory of conservation of energy and explained why heat can do a work.<ref>[http://www.juliantrubin.com/bigten/mechanical_equivalent_of_heat.html James Prescott Joule: The Discovery of the Mechanical Equivalent of Heat]</ref>
 
The name "thermodynamics," however, did not arrive until 1849, when the British mathematician and physicist [[William Thomson, 1st Baron Kelvin|William Thomson]] (Lord Kelvin) coined the term ''thermodynamics'' in a paper on the efficiency of steam engines.
 
In 1850, the famed mathematical physicist [[Rudolf Clausius]] defined the term entropy '''''S''''' to be the heat lost or turned into waste, stemming from the Greek word ''entrepein'' meaning ''to turn''.
 
<!--  Commented out because image was deleted: [[File:Baron Kelvin.jpg|thumb|right|Lord Kelvin {{Deletable image-caption|date=May 2012}}]] -->
In association with Clausius, in 1871, a Scottish mathematician and physicist [[James Clerk Maxwell]] formulated a new branch of thermodynamics called ''Statistical Thermodynamics'', which functions to analyze large numbers of particles at [[thermodynamic equilibrium|equilibrium]], i.e., systems where no changes are occurring, such that only their average properties as temperature '''''T''''', pressure '''''P''''', and volume '''''V''''' become important.
 
Soon thereafter, in 1875, the Austrian physicist [[Ludwig Boltzmann]] formulated a precise connection between entropy '''''S''''' and molecular motion:
 
:<math>S=k\log W  \,</math>
 
being defined in terms of the number of possible states [W] such motion could occupy, where k is the [[Boltzmann's constant]]. 
 
The following year, 1876, was a seminal point in the development of human thought.  During this essential period, chemical engineer [[Willard Gibbs]], the first person in America to be awarded a PhD in engineering (Yale), published an obscure 300-page paper titled: ''On the Equilibrium of Heterogeneous Substances'', wherein he formulated one grand equality, the [[Gibbs free energy]] equation, which gives a measure the amount of "useful work" attainable in reacting systems.  Gibbs also originated the concept we now know as [[enthalpy]] '''''H''''', calling it "a heat function for constant pressure".<ref>{{cite book|last=Laidler|first1=Keith|authorlink=Keith J. Laidler|title=The World of Physical Chemistry|publisher=Oxford University Press|year=1995|page=110}}</ref> 
The modern word ''enthalpy'' would be coined many years later by [[Heike Kamerlingh Onnes]],<ref>{{cite journal |doi=10.1021/ed079p697 |last=Howard|first=Irmgard |year=2002|title=H Is for Enthalpy, Thanks to Heike Kamerlingh Onnes and Alfred W. Porter|journal=Journal of Chemical Education|publisher=ACS Publications|volume=79|issue=6|pages=697|url=http://pubs.acs.org/doi/abs/10.1021/ed079p697|bibcode = 2002JChEd..79..697H }}</ref>
who based it on the Greek word ''enthalpein'' meaning ''to warm''.
 
Building on these foundations, those as [[Lars Onsager]], [[Erwin Schrödinger]], and [[Ilya Prigogine]], and others, functioned to bring these engine "concepts" into the thoroughfare of almost every modern-day branch of science.
 
=== Kinetic theory ===
{{main|Kinetic theory}}
 
The idea that [[heat]] is a form of [[Motion (physics)|motion]] is perhaps an ancient one and is certainly discussed by [[Francis Bacon]] in 1620 in his ''Novum Organum''. The first written scientific reflection on the microscopic nature of heat is probably to be found in a work by [[Mikhail Lomonosov]], in which he wrote:
 
:"(..) movement should not be denied based on the fact it is not seen. Who would deny that the leaves of trees move when rustled by a wind, despite it being unobservable from large distances? Just as in this case motion remains hidden due to perspective, it remains hidden in warm bodies due to the extremely small sizes of the moving particles. In both cases, the viewing angle is so small that neither the object nor their movement can be seen."
 
During the same years, [[Daniel Bernoulli]] published his book ''Hydrodynamics'' (1738), in which he derived an equation for the pressure of a gas considering the collisions of its atoms with the walls of a container. He proves that this pressure is two thirds the average kinetic energy of the gas in a unit volume. Bernoulli's ideas, however, made little impact on the dominant caloric culture. Bernoulli made a connection with [[Gottfried Leibniz]]'s ''[[vis viva]]'' principle, an early formulation of the principle of [[conservation of energy]], and the two theories became intimately entwined throughout their history. Though Benjamin Thompson suggested that heat was a form of motion as a result of his experiments in 1798, no attempt was made to reconcile theoretical and experimental approaches, and it is unlikely that he was thinking of the ''vis viva'' principle.
 
[[John Herapath]] later independently formulated a kinetic theory in 1820, but mistakenly associated temperature with [[momentum]] rather than ''vis viva'' or [[kinetic energy]]. His work ultimately failed [[peer review]] and was neglected. [[John James Waterston]] in 1843 provided a largely accurate account, again independently, but his work received the same reception, failing peer review even from someone as well-disposed to the kinetic principle as Davy.
 
Further progress in kinetic theory started only in the middle of the 19th century, with the works of [[Rudolf Clausius]], [[James Clerk Maxwell]], and [[Ludwig Boltzmann]]. In his 1857 work ''On the nature of the motion called heat'', Clausius for the first time clearly states that heat is the average kinetic energy of molecules. This interested Maxwell, who in 1859 derived the momentum distribution later named after him. Boltzmann subsequently generalized his distribution for the case of gases in external fields.
 
Boltzmann is perhaps the most significant contributor to kinetic theory, as he introduced many of the fundamental concepts in the theory. Besides the [[Maxwell-Boltzmann distribution]] mentioned above, he also associated the kinetic energy of particles with their [[degrees of freedom (physics and chemistry)|degrees of freedom]]. The [[Boltzmann equation]] for the distribution function of a gas in non-equilibrium states is still the most effective equation for studying transport phenomena in gases and metals. By introducing the concept of [[Statistical mechanics|thermodynamic probability]] as the number of microstates corresponding to the current macrostate, he showed that its logarithm is proportional to entropy.
 
== Branches of ==
The following list gives a rough outline as to when the major branches of thermodynamics came into inception:
 
* [[Thermochemistry]] - 1780s
* [[Classical thermodynamics]] - 1824
* [[Chemical thermodynamics]] - 1876
* [[Statistical mechanics]] - c. 1880s
* [[Equilibrium thermodynamics]]
* Engineering thermodynamics
* Chemical engineering thermodynamics - c. 1940s
* [[Non-equilibrium thermodynamics]] - 1941
* Small systems thermodynamics - 1960s
* [[Biological thermodynamics]] - 1957
* Ecosystem thermodynamics - 1959
* Relativistic thermodynamics - 1965
* [[Quantum thermodynamics]] - 1968
* [[Black hole thermodynamics]] - c. 1970s
* Geological thermodynamics - c. 1970s
* Biological evolution thermodynamics - 1978
* Geochemical thermodynamics - c. 1980s
* [[Atmospheric thermodynamics]] - c. 1980s
* Natural systems thermodynamics - 1990s
* Supramolecular thermodynamics - 1990s
* Earthquake thermodynamics - 2000
* Drug-receptor thermodynamics - 2001
* Pharmaceutical systems thermodynamics – 2002
 
Ideas from thermodynamics have also been applied in other fields, for example:
* [[Thermoeconomics]] - c. 1970s
 
== Entropy and the second law ==
{{Main|History of entropy}}
Even though he was working with the caloric theory, [[Nicolas Léonard Sadi Carnot|Sadi Carnot]] in 1824 suggested that some of the caloric available for generating useful work is lost in any real process. In March 1851, while grappling to come to terms with the work of [[James Prescott Joule]], [[Lord Kelvin]] started to speculate that there was an inevitable loss of useful heat in all processes. The idea was framed even more dramatically by [[Hermann von Helmholtz]] in 1854, giving birth to the spectre of the [[heat death of the universe]].
 
In 1854, [[William John Macquorn Rankine]] started to make use in calculation of what he called his ''thermodynamic function''. This has subsequently been shown to be identical to the concept of [[entropy]] formulated by [[Rudolf Clausius]] in 1865. Clausius used the concept to develop his classic statement of the [[second law of thermodynamics]] the same year.
 
== Heat transfer ==
{{Main|Heat transfer}}
 
The phenomenon of [[heat conduction]] is immediately grasped in everyday life. In 1701, Sir [[Isaac Newton]] published his [[Heat transfer#Newton's law of cooling|law of cooling]]. However, in the 17th century, it came to be believed that all materials had an identical conductivity and that differences in sensation arose from their different [[heat capacity|heat capacities]].
 
Suggestions that this might not be the case came from the new science of [[electricity]] in which it was easily apparent that some materials were good electrical conductors while others were effective insulators. [[Jan Ingen-Housz]] in 1785-9 made some of the earliest measurements, as did Benjamin Thompson during the same period.
 
The fact that warm air rises and the importance of the phenomenon to meteorology was first realised by [[Edmund Halley]] in 1686. Sir [[John Leslie (physicist)|John Leslie]] observed that the cooling effect of a stream of air increased with its [[speed]], in 1804.
 
[[Carl Wilhelm Scheele]] distinguished heat transfer by [[thermal radiation]] (radiant heat) from that by convection and conduction in 1777. In 1791, [[Pierre Prévost]] showed that all bodies radiate heat, no matter how hot or cold they are. In 1804, Leslie observed that a matt black surface radiates heat more effectively than a polished surface, suggesting the importance of [[black body radiation]]. Though it had become to be suspected even from Scheele's work, in 1831 [[Macedonio Melloni]] demonstrated that black body radiation could be [[reflection (physics)|reflected]], [[refraction|refracted]] and [[polarisation (waves)|polarised]] in the same way as [[light]].
 
[[James Clerk Maxwell]]'s 1862 insight that both light and radiant heat were forms of [[electromagnetic wave]] led to the start of the [[quantitative property|quantitative]] analysis of thermal radiation. In 1879, [[Jožef Stefan]] observed that the total [[radiant flux]] from a blackbody is proportional to the fourth power of its temperature and stated the [[Stefan–Boltzmann law]]. The law was derived theoretically by [[Ludwig Boltzmann]] in 1884.
 
== Cryogenics ==
 
In 1702 [[Guillaume Amontons]] introduced the concept of [[absolute zero]] based on observations of [[gas]]es. In 1810, Sir John Leslie froze water to ice artificially. The idea of absolute zero was generalised in 1848 by Lord Kelvin. In 1906, [[Walther Nernst]] stated the [[third law of thermodynamics]].
 
== See also ==
* [[Conservation of energy#Historical development|Conservation of energy: Historical development]]
* [[History of Chemistry]]
* [[History of Physics]]
* [[Maxwell's thermodynamic surface]]
* [[Timeline of thermodynamics, statistical mechanics, and random processes]]
* [[Thermodynamics]]
* [[Timeline of heat engine technology]]
* [[Timeline of low-temperature technology]]
 
==References==
<references />
 
== Further reading ==
* {{cite book | author=Cardwell, D.S.L. | title=From Watt to Clausius: The Rise of Thermodynamics in the Early Industrial Age | publisher=Heinemann | location=London | year=1971 | isbn=0-435-54150-1}}
* {{cite book | author=Leff, H.S. & Rex, A.F. (eds) | title=Maxwell's Demon: Entropy, Information and Computing | publisher=Adam Hilger | location=Bristol | year=1990 | isbn=0-7503-0057-4}}
 
== External links ==
*[http://history.hyperjeff.net/statmech History of Statistical Mechanics and Thermodynamics] - Timeline (1575 to 1980) @ Hyperjeff.net
*[http://www.mhtl.uwaterloo.ca/courses/me354/history.html History of Thermodynamics] - University of Waterloo
*[http://www.wolframscience.com/reference/notes/1019b Thermodynamic History Notes] - WolframScience.com
*[http://www.nuc.berkeley.edu/courses/classes/E-115/Slides/A_Brief_History_of_Thermodynamics.pdf Brief History of Thermodynamics] - Berkeley [PDF]
*[http://thermodynamicstudy.net/history.html History of Thermodynamics] - ThermodynamicStudy.net
*[http://che.konyang.ac.kr/COURSE/thermo/history/therm_his.html Historical Background of Thermodynamics] - Carnegie-Mellon University
*[http://www.nt.ntnu.no/users/haugwarb/Presentations/History%20of%20Thermodynamics/ History of Thermodynamics] - In Pictures
 
{{DEFAULTSORT:History Of Thermodynamics}}
[[Category:History of thermodynamics| ]]

Latest revision as of 15:49, 29 April 2014

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