History of heat
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The history of thermodynamics is a fundamental strand in the
history of physics Physics is a branch of science whose primary objects of study are matter and energy. Discoveries of physics find applications throughout the natural sciences and in technology. Physics today may be divided loosely into classical physics and mode ...
, 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 heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of th ...
in much of
science Science is a systematic endeavor that Scientific method, builds and organizes knowledge in the form of Testability, testable explanations and predictions about the universe. Science may be as old as the human species, and some of the earli ...
and
technology Technology is the application of knowledge to reach practical goals in a specifiable and Reproducibility, reproducible way. The word ''technology'' may also mean the product of such an endeavor. The use of technology is widely prevalent in me ...
, its history is finely woven with the developments of
classical mechanics Classical mechanics is a physical theory describing the motion of macroscopic objects, from projectiles to parts of machinery, and astronomical objects, such as spacecraft, planets, stars, and galaxies. For objects governed by classi ...
,
quantum mechanics Quantum mechanics is a fundamental theory in physics that provides a description of the physical properties of nature at the scale of atoms and subatomic particles. It is the foundation of all quantum physics including quantum chemistr ...
, magnetism, and
chemical kinetics Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with chemical thermodynamics, which deals with the direction in ...
, to more distant applied fields such as
meteorology Meteorology is a branch of the atmospheric sciences (which include atmospheric chemistry and physics) with a major focus on weather forecasting. The study of meteorology dates back millennia, though significant progress in meteorology did no ...
, information theory, and
biology Biology is the scientific study of life. It is a natural science with a broad scope but has several unifying themes that tie it together as a single, coherent field. For instance, all organisms are made up of cells that process hereditary i ...
(
physiology Physiology (; ) is the scientific study of functions and mechanisms in a living system. As a sub-discipline of biology, physiology focuses on how organisms, organ systems, individual organs, cells, and biomolecules carry out the chemical ...
), and to
technological Technology is the application of knowledge to reach practical goals in a specifiable and reproducible way. The word ''technology'' may also mean the product of such an endeavor. The use of technology is widely prevalent in medicine, science, ...
developments such as the steam engine,
internal combustion engine An internal combustion engine (ICE or IC engine) is a heat engine in which the combustion of a fuel occurs with an oxidizer (usually air) in a combustion chamber that is an integral part of the working fluid flow circuit. In an internal c ...
,
cryogenics In physics, cryogenics is the production and behaviour of materials at very low temperatures. The 13th IIR International Congress of Refrigeration (held in Washington DC in 1971) endorsed a universal definition of “cryogenics” and “cr ...
and
electricity generation Electricity generation is the process of generating electric power from sources of primary energy. For utilities in the electric power industry, it is the stage prior to its delivery ( transmission, distribution, etc.) to end users or its s ...
. The development of thermodynamics both drove and was driven by
atomic theory Atomic theory is the scientific theory that matter is composed of particles called atoms. Atomic theory traces its origins to an ancient philosophical tradition known as atomism. According to this idea, if one were to take a lump of matter ...
. It also, albeit in a subtle manner, motivated new directions in
probability Probability is the branch of mathematics concerning numerical descriptions of how likely an event is to occur, or how likely it is that a proposition is true. The probability of an event is a number between 0 and 1, where, roughly speakin ...
and statistics; see, for example, the
timeline of thermodynamics A timeline of events in the history of thermodynamics. Before 1800 * 1650 – Otto von Guericke builds the first vacuum pump * 1660 – Robert Boyle experimentally discovers Boyle's Law, relating the pressure and volume of a gas (pu ...
.


History


Contributions from antiquity

The ancients viewed heat as that related to fire. In 3000 BC, the ancient Egyptians viewed heat as related to origin mythologies. The
ancient Indian philosophy This page lists some links to ancient philosophy, namely philosophical thought extending as far as early post-classical history (). Overview Genuine philosophical thought, depending upon original individual insights, arose in many cultures ...
including ''Vedic philosophy'' believed that five classical elements (or pancha mahā bhūta) are the basis of all cosmic creations. In the Western philosophical tradition, after much debate about the primal element among earlier
pre-Socratic philosopher Pre-Socratic philosophy, also known as early Greek philosophy, is ancient Greek philosophy before Socrates. Pre-Socratic philosophers were mostly interested in cosmology, the beginning and the substance of the universe, but the inquiries of thes ...
s,
Empedocles Empedocles (; grc-gre, Ἐμπεδοκλῆς; , 444–443 BC) was a Greek pre-Socratic philosopher and a native citizen of Akragas, a Greek city in Sicily. Empedocles' philosophy is best known for originating the cosmogonic theory of the ...
proposed a four-element theory, in which all substances derive from
earth Earth is the third planet from the Sun and the only astronomical object known to harbor life. While large volumes of water can be found throughout the Solar System, only Earth sustains liquid surface water. About 71% of Earth's surfa ...
,
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
,
air The atmosphere of Earth is the layer of gases, known collectively as air, retained by Earth's gravity that surrounds the planet and forms its planetary atmosphere. The atmosphere of Earth protects life on Earth by creating pressure allowing f ...
, and
fire Fire is the rapid oxidation of a material (the fuel) in the exothermic chemical process of combustion, releasing heat, light, and various reaction products. At a certain point in the combustion reaction, called the ignition point, flames a ...
. The Empedoclean element of fire is perhaps the principal ancestor of later concepts such as phlogin and caloric. Around 500 BC, the
Greek philosopher Ancient Greek philosophy arose in the 6th century BC, marking the end of the Greek Dark Ages. Greek philosophy continued throughout the Hellenistic period and the period in which Greece and most Greek-inhabited lands were part of the Roman Empire ...
Heraclitus Heraclitus of Ephesus (; grc-gre, Ἡράκλειτος , "Glory of Hera"; ) was an ancient Greek pre-Socratic philosopher from the city of Ephesus, which was then part of the Persian Empire. Little is known of Heraclitus's life. He wrot ...
became famous as the "flux and fire" philosopher for his proverbial utterance: "All things are flowing." Heraclitus argued that the three principal elements in nature were fire, earth, and water. In the early modern period, heat was thought to be a measurement of an invisible fluid, known as the '' caloric''. Bodies were capable of holding a certain amount of this fluid, leading to the term ''heat capacity'', named and first investigated by Scottish chemist
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 Glas ...
in the 1750s. In the 18th and 19th centuries, scientists abandoned the idea of a physical caloric, and instead understood
heat In thermodynamics, heat is defined as the form of energy crossing the boundary of a thermodynamic system by virtue of a temperature difference across the boundary. A thermodynamic system does not ''contain'' heat. Nevertheless, the term is ...
as a manifestation of a system's internal energy. Today heat is the transfer of disordered thermal energy. Nevertheless, at least in English, the term ''heat capacity'' survives. In some other languages, the term ''thermal capacity'' is preferred, and it is also sometimes used in English.
Atomism Atomism (from Greek , ''atomon'', i.e. "uncuttable, indivisible") is a natural philosophy proposing that the physical universe is composed of fundamental indivisible components known as atoms. References to the concept of atomism and its atoms ...
is a central part of today's relationship between thermodynamics and statistical mechanics. Ancient thinkers such as
Leucippus Leucippus (; el, Λεύκιππος, ''Leúkippos''; fl. 5th century BCE) is a pre-Socratic Greek philosopher who has been credited as the first philosopher to develop a theory of atomism. Leucippus' reputation, even in antiquity, was obscured ...
and
Democritus Democritus (; el, Δημόκριτος, ''Dēmókritos'', meaning "chosen of the people"; – ) was an Ancient Greek pre-Socratic philosopher from Abdera, primarily remembered today for his formulation of an atomic theory of the universe. No ...
, and later the
Epicureans Epicureanism is a system of philosophy founded around 307 BC based upon the teachings of the ancient Greek philosopher Epicurus. Epicureanism was originally a challenge to Platonism. Later its main opponent became Stoicism. Few writings by ...
, by advancing atomism, laid the foundations for the later
atomic theory Atomic theory is the scientific theory that matter is composed of particles called atoms. Atomic theory traces its origins to an ancient philosophical tradition known as atomism. According to this idea, if one were to take a lump of matter ...
. Until experimental proof of atoms was later provided in the 20th century, the atomic theory was driven largely by philosophical considerations and scientific intuition. 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 A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often di ...
, in nature could not occur. This view was supported by the arguments of
Aristotle Aristotle (; grc-gre, Ἀριστοτέλης ''Aristotélēs'', ; 384–322 BC) was a Greek philosopher and polymath during the Classical period in Ancient Greece. Taught by Plato, he was the founder of the Peripatetic school of ph ...
, but was criticized by
Leucippus Leucippus (; el, Λεύκιππος, ''Leúkippos''; fl. 5th century BCE) is a pre-Socratic Greek philosopher who has been credited as the first philosopher to develop a theory of atomism. Leucippus' reputation, even in antiquity, was obscured ...
and
Hero of Alexandria Hero of Alexandria (; grc-gre, Ἥρων ὁ Ἀλεξανδρεύς, ''Heron ho Alexandreus'', also known as Heron of Alexandria ; 60 AD) was a Greek mathematician and engineer who was active in his native city of Alexandria, Roman Egypt. He ...
. 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 Cornelis Jacobszoon Drebbel ( ) (1572 – 7 November 1633) was a Dutch engineer and inventor. He was the builder of the first operational submarine in 1620 and an innovator who contributed to the development of measurement and control systems, ...
,
Robert Fludd Robert Fludd, also known as Robertus de Fluctibus (17 January 1574 – 8 September 1637), was a prominent English Paracelsian physician with both scientific and occult interests. He is remembered as an astrologer, mathematician, cosmologis ...
,
Galileo Galilei Galileo di Vincenzo Bonaiuti de' Galilei (15 February 1564 – 8 January 1642) was an Italian astronomer, physicist and engineer, sometimes described as a polymath. Commonly referred to as Galileo, his name was pronounced (, ). He wa ...
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 A thermometer is a device that measures temperature or a temperature gradient (the degree of hotness or coldness of an object). A thermometer has two important elements: (1) a temperature sensor (e.g. the bulb of a mercury-in-glass thermometer ...
(or
thermoscope A thermoscope is a device that shows changes in temperature. A typical design is a tube in which a liquid rises and falls as the temperature changes. The modern thermometer gradually evolved from it with the addition of a scale in the early 17th c ...
). This may have been influenced by an earlier device which could expand and contract the air constructed by
Philo of Byzantium Philo of Byzantium ( el, , ''Phílōn ho Byzántios'', ca. 280 BC – ca. 220 BC), also known as Philo Mechanicus, was a Greek engineer, physicist and writer on mechanics, who lived during the latter half of the 3rd century BC. Although he was f ...
and
Hero of Alexandria Hero of Alexandria (; grc-gre, Ἥρων ὁ Ἀλεξανδρεύς, ''Heron ho Alexandreus'', also known as Heron of Alexandria ; 60 AD) was a Greek mathematician and engineer who was active in his native city of Alexandria, Roman Egypt. He ...
. Around 1600, the English philosopher and scientist
Francis Bacon Francis Bacon, 1st Viscount St Alban (; 22 January 1561 – 9 April 1626), also known as Lord Verulam, was an English philosopher and statesman who served as Attorney General and Lord Chancellor of England. Bacon led the advancement of both ...
surmised: "Heat itself, its essence and quiddity is motion and nothing else." In 1643,
Galileo Galilei Galileo di Vincenzo Bonaiuti de' Galilei (15 February 1564 – 8 January 1642) was an Italian astronomer, physicist and engineer, sometimes described as a polymath. Commonly referred to as Galileo, his name was pronounced (, ). He wa ...
, 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 Evangelista Torricelli ( , also , ; 15 October 160825 October 1647) was an Italian physicist and mathematician, and a student of Galileo. He is best known for his invention of the barometer, but is also known for his advances in optics and work ...
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; ~30 inches of the liquid remained. As the mercury emptied, and a partial
vacuum A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often di ...
was created at the top of the tube. The gravitational force on the heavy element Mercury prevented it from filling the vacuum.


Transition from chemistry to thermochemistry

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 burning, and from metals during the process of
rusting Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO(OH) ...
. 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 Rumford's 1798 work, when he showed that boring
cast iron Cast iron is a class of iron– carbon alloys with a carbon content more than 2%. Its usefulness derives from its relatively low melting temperature. The alloy constituents affect its color when fractured: white cast iron has carbide impur ...
cannon A cannon is a large- caliber gun classified as a type of artillery, which usually launches a projectile using explosive chemical propellant. Gunpowder ("black powder") was the primary propellant before the invention of smokeless powder ...
s produced great amounts of heat which he ascribed to
friction Friction is the force resisting the relative motion of solid surfaces, fluid layers, and material elements sliding against each other. There are several types of friction: *Dry friction is a force that opposes the relative lateral motion of ...
, and his work was among the first to undermine the caloric theory. The development of the steam engine also focused attention on
calorimetry In chemistry and thermodynamics, calorimetry () is the science or act of measuring changes in ''state variables'' of a body for the purpose of deriving the heat transfer associated with changes of its state due, for example, to chemical reac ...
and the amount of heat produced from different types of
coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal is formed when ...
. The first quantitative research on the heat changes during chemical reactions was initiated by Lavoisier using an ice
calorimeter A calorimeter is an object used for calorimetry, or the process of measuring the heat of chemical reactions or physical changes as well as heat capacity. Differential scanning calorimeters, isothermal micro calorimeters, titration calorimete ...
following research by
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 Glas ...
on the
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, during a constant-temperature process — usually a first-order phase transition. Latent heat can be underst ...
of water. More quantitative studies by
James Prescott Joule James Prescott Joule (; 24 December 1818 11 October 1889) was an English physicist, mathematician and brewer, born in Salford, Lancashire. Joule studied the nature of heat, and discovered its relationship to mechanical work (see energy). ...
in 1843 onwards provided soundly reproducible phenomena, and helped to place the subject of thermodynamics on a solid footing. 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 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 Glas ...
and Lavoisier made important contributions in the precise measurement of heat changes using the
calorimeter A calorimeter is an object used for calorimetry, or the process of measuring the heat of chemical reactions or physical changes as well as heat capacity. Differential scanning calorimeters, isothermal micro calorimeters, titration calorimete ...
, a subject which became known as
thermochemistry Thermochemistry is the study of the heat energy which is associated with chemical reactions and/or phase changes such as melting and boiling. A reaction may release or absorb energy, and a phase change may do the same. Thermochemistry focuses on ...
.


Phenomenological thermodynamics

*
Boyle's law Boyle's law, also referred to as the Boyle–Mariotte law, or Mariotte's law (especially in France), is an experimental gas law that describes the relationship between pressure and volume of a confined gas. Boyle's law has been stated as: The ...
(1662) *
Charles's law Charles's law (also known as the law of volumes) is an experimental gas law that describes how gases tend to expand when heated. A modern statement of Charles's law is: When the pressure on a sample of a dry gas is held constant, the Kelvin t ...
was first published by
Joseph Louis Gay-Lussac Joseph Louis Gay-Lussac (, , ; 6 December 1778 – 9 May 1850) was a French chemist and physicist. He is known mostly for his discovery that water is made of two parts hydrogen and one part oxygen (with Alexander von Humboldt), for two laws ...
in 1802, but he referenced unpublished work by
Jacques Charles Jacques Alexandre César Charles (November 12, 1746 – April 7, 1823) was a French inventor, scientist, mathematician, and balloonist. Charles wrote almost nothing about mathematics, and most of what has been credited to him was due to mistaking ...
from around 1787. The relationship had been anticipated by the work of
Guillaume Amontons Guillaume Amontons (31 August 1663 – 11 October 1705) was a French scientific instrument inventor and physicist. He was one of the pioneers in studying the problem of friction, which is the resistance to motion when bodies make contact. He is ...
in 1702. * Gay-Lussac's law (1802)


Birth of thermodynamics as a science

Irish physicist and chemist
Robert Boyle Robert Boyle (; 25 January 1627 – 31 December 1691) was an Anglo-Irish natural philosopher, chemist, physicist, alchemist and inventor. Boyle is largely regarded today as the first modern chemist, and therefore one of the founders of ...
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. 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 The ideal gas law, also called the general gas equation, is the equation of state of a hypothetical ideal gas. It is a good approximation of the behavior of many gases under many conditions, although it has several limitations. It was first stat ...
. But, already before the establishment of the ideal gas law, 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. Early ...
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 Thomas Savery (; c. 1650 – 15 May 1715) was an English inventor and engineer. He invented the first commercially used steam-powered device, a steam pump which is often referred to as the "Savery engine". Savery's steam pump was a revolutiona ...
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 Sadi Carnot, the "father of thermodynamics", who in 1824 published ''
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 physicist Sadi Carnot.full text of 1897 ed. ( Full text of 1897 edition on Wikisource ) The 118-page book's French t ...
'', a discourse on heat, power, and engine efficiency. This marks the start of thermodynamics as a modern science. Hence, prior to 1698 and the invention of the 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 Engine The atmospheric engine was invented by Thomas Newcomen in 1712, and is often referred to as the Newcomen fire engine (see below) or simply as a Newcomen engine. The engine was operated by condensing steam drawn into the cylinder, thereby creati ...
, and later the
Watt Engine The Watt steam engine design became synonymous with steam engines, and it was many years before significantly new designs began to replace the basic Watt design. The first steam engines, introduced by Thomas Newcomen in 1712, were of the "at ...
. 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 was born. Most cite Sadi Carnot's 1824 book ''
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 physicist Sadi Carnot.full text of 1897 ed. ( Full text of 1897 edition on Wikisource ) The 118-page book's French t ...
'' 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 "
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 ** Working animal, an animal t ...
": ''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 James Prescott Joule (; 24 December 1818 11 October 1889) was an English physicist, mathematician and brewer, born in Salford, Lancashire. Joule studied the nature of heat, and discovered its relationship to mechanical work (see energy). T ...
experimentally found the
mechanical equivalent of heat In the history of science, the mechanical equivalent of heat states that motion and heat are mutually interchangeable and that in every case, a given amount of work would generate the same amount of heat, provided the work done is totally convert ...
. 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 ft·lbf/Btu (4.41 J/cal). This led to the theory of conservation of energy and explained why heat can do work. In 1850, the famed mathematical physicist
Rudolf Clausius Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German physicist and mathematician and is considered one of the central founding fathers of the science of thermodynamics. By his restatement of Sadi Carnot's principle ...
coined the term "entropy" (''das Wärmegewicht'', symbolized ''S'') to denote heat lost or turned into waste. ("''Wärmegewicht''" translates literally as "heat-weight"; the corresponding English term stems from the Greek ''τρέπω'', "I turn".) The name "thermodynamics", however, did not arrive until 1854, when the British mathematician and physicist William Thomson (Lord Kelvin) coined the term ''thermo-dynamics'' in his paper ''On the Dynamical Theory of Heat''. reprinted in Hence Thermo-dynamics falls naturally into two Divisions, of which the subjects are respectively, ''the relation of heat to the forces acting between contiguous parts of bodies, and the relation of heat to electrical agency''. In association with Clausius, in 1871, the Scottish mathematician and physicist
James Clerk Maxwell James Clerk Maxwell (13 June 1831 – 5 November 1879) was a Scottish mathematician and scientist responsible for the classical theory of electromagnetic radiation, which was the first theory to describe electricity, magnetism and li ...
formulated a new branch of thermodynamics called ''Statistical Thermodynamics'', which functions to analyze large numbers of particles at 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 Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austrian physicist and philosopher. His greatest achievements were the development of statistical mechanics, and the statistical explanation of the second law of ther ...
formulated a precise connection between entropy ''S'' and molecular motion: :S=k\log W \, being defined in terms of the number of possible states ''W'' that such motion could occupy, where ''k'' is the
Boltzmann constant The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constant, ...
. The following year, 1876, chemical engineer
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 ...
published an obscure 300-page paper titled: ''On the Equilibrium of Heterogeneous Substances'', wherein he formulated one grand equality, the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature and ...
equation, which suggested a measure of the amount of "useful work" attainable in reacting systems. Gibbs also originated the concept we now know as
enthalpy Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...
''H'', calling it "a heat function for constant pressure". The modern word ''enthalpy'' would be coined many years later by
Heike Kamerlingh Onnes Heike Kamerlingh Onnes (21 September 1853 – 21 February 1926) was a Dutch physicist and Nobel laureate. He exploited the Hampson–Linde cycle to investigate how materials behave when cooled to nearly absolute zero and later to liquefy heliu ...
, who based it on the Greek word ''enthalpein'' meaning ''to warm''. Building on these foundations, those as
Lars Onsager Lars Onsager (November 27, 1903 – October 5, 1976) was a Norwegian-born American physical chemist and theoretical physicist. He held the Gibbs Professorship of Theoretical Chemistry at Yale University. He was awarded the Nobel Prize in C ...
,
Erwin Schrödinger Erwin Rudolf Josef Alexander Schrödinger (, ; ; 12 August 1887 – 4 January 1961), sometimes written as or , was a Nobel Prize-winning Austrian physicist with Irish citizenship who developed a number of fundamental results in quantum theo ...
, and Ilya Prigogine, and others, functioned to bring these engine "concepts" into the thoroughfare of almost every modern-day branch of science.


Kinetic theory

The idea that heat is a form of
motion In physics, motion is the phenomenon in which an object changes its position with respect to time. Motion is mathematically described in terms of displacement, distance, velocity, acceleration, speed and frame of reference to an observer and m ...
is perhaps an ancient one and is certainly discussed by
Francis Bacon Francis Bacon, 1st Viscount St Alban (; 22 January 1561 – 9 April 1626), also known as Lord Verulam, was an English philosopher and statesman who served as Attorney General and Lord Chancellor of England. Bacon led the advancement of both ...
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 proved 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 Gottfried Wilhelm (von) Leibniz . ( – 14 November 1716) was a German polymath active as a mathematician, philosopher, scientist and diplomat. He is one of the most prominent figures in both the history of philosophy and the history of mathem ...
's ''
vis viva ''Vis viva'' (from the Latin for "living force") is a historical term used for the first recorded description of what we now call kinetic energy in an early formulation of the principle of conservation of energy. Overview Proposed by Gottfried L ...
'' principle, an early formulation of the principle of conservation of energy, and the two theories became intimately entwined throughout their history. Though
Benjamin Thompson Sir Benjamin Thompson, Count Rumford, FRS (german: Reichsgraf von Rumford; March 26, 1753August 21, 1814) was an American-born British physicist and inventor whose challenges to established physical theory were part of the 19th-century revolut ...
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 John Herapath (30 May 1790 – 24 February 1868) was an English physicist who gave a partial account of the kinetic theory of gases in 1820 though it was neglected by the scientific community at the time. He was the cousin of William Herapath, t ...
later independently formulated a kinetic theory in 1820, but mistakenly associated temperature with momentum rather than ''vis viva'' or
kinetic energy In physics, the kinetic energy of an object is the energy that it possesses due to its motion. It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acc ...
. His work ultimately failed
peer review Peer review is the evaluation of work by one or more people with similar competencies as the producers of the work ( peers). It functions as a form of self-regulation by qualified members of a profession within the relevant field. Peer revie ...
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 Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German physicist and mathematician and is considered one of the central founding fathers of the science of thermodynamics. By his restatement of Sadi Carnot's principle ...
,
James Clerk Maxwell James Clerk Maxwell (13 June 1831 – 5 November 1879) was a Scottish mathematician and scientist responsible for the classical theory of electromagnetic radiation, which was the first theory to describe electricity, magnetism and li ...
, and
Ludwig Boltzmann Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austrian physicist and philosopher. His greatest achievements were the development of statistical mechanics, and the statistical explanation of the second law of ther ...
. 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 In physics (in particular in statistical mechanics), the Maxwell–Boltzmann distribution, or Maxwell(ian) distribution, is a particular probability distribution named after James Clerk Maxwell and Ludwig Boltzmann. It was first defined and use ...
mentioned above, he also associated the kinetic energy of particles with their degrees of freedom. The
Boltzmann equation The Boltzmann equation or Boltzmann transport equation (BTE) describes the statistical behaviour of a thermodynamic system not in a state of equilibrium, devised by Ludwig Boltzmann in 1872.Encyclopaedia of Physics (2nd Edition), R. G. Lerne ...
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 thermodynamic probability as the number of microstates corresponding to the current macrostate, he showed that its logarithm is proportional to entropy.


Branches of thermodynamics

The following list is a rough disciplinary outline of the major branches of thermodynamics and their time of inception: *
Thermochemistry Thermochemistry is the study of the heat energy which is associated with chemical reactions and/or phase changes such as melting and boiling. A reaction may release or absorb energy, and a phase change may do the same. Thermochemistry focuses on ...
– 1780s *
Classical thermodynamics Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of ther ...
– 1824 *
Chemical thermodynamics Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes of state within the confines of the laws of thermodynamics. Chemical thermodynamics involves not only laboratory measurem ...
– 1876 * Statistical mechanics – c. 1880s * Equilibrium thermodynamics * Engineering thermodynamics * Chemical engineering thermodynamics – c. 1940s *
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 ext ...
– 1941 * Small systems thermodynamics – 1960s *
Biological thermodynamics Biological thermodynamics is the quantitative study of the energy transductions that occur in or between living organisms, structures, and cells and of the nature and function of the chemical processes underlying these transductions. Biological the ...
– 1957 * Ecosystem thermodynamics – 1959 * Relativistic thermodynamics – 1965 *
Rational thermodynamics Rational thermodynamics is a school of thought in statistical thermodynamics developed in the 1960s. Its introduction is attributed to Clifford Truesdell (1919–2000), Bernard Coleman (b. 1929) and Walter Noll (1925–2017). The aim was to develo ...
– 1960s *
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 ...
– 1968 *
Black hole thermodynamics In physics, black hole thermodynamics is the area of study that seeks to reconcile the laws of thermodynamics with the existence of black hole event horizons. As the study of the statistical mechanics of black-body radiation led to the developm ...
– c. 1970s * Theory of
critical phenomena In physics, critical phenomena is the collective name associated with the physics of critical points. Most of them stem from the divergence of the correlation length, but also the dynamics slows down. Critical phenomena include scaling relatio ...
and use of
renormalization group In theoretical physics, the term renormalization group (RG) refers to a formal apparatus that allows systematic investigation of the changes of a physical system as viewed at different scales. In particle physics, it reflects the changes in the ...
theory in statistical physics – 1966-1974 * Geological thermodynamics – c. 1970s * Biological evolution thermodynamics – 1978 * Geochemical thermodynamics – c. 1980s *
Atmospheric thermodynamics Atmospheric thermodynamics is the study of heat-to-work transformations (and their reverse) that take place in the earth's atmosphere and manifest as weather or climate. Atmospheric thermodynamics use the laws of classical thermodynamics, to descr ...
– c. 1980s * Natural systems thermodynamics – 1990s * Supramolecular thermodynamics – 1990s * Earthquake thermodynamics – 2000 * Drug-receptor thermodynamics – 2001 * Pharmaceutical systems thermodynamics – 2002 Concepts of thermodynamics have also been applied in other fields, for example: *
Thermoeconomics Thermoeconomics, also referred to as biophysical economics, is a school of heterodox economics that applies the laws of statistical mechanics to economic theory. Thermoeconomics can be thought of as the statistical physics of economic value an ...
– c. 1970s


Entropy and the second law

Even though he was working with the caloric theory, 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 James Prescott Joule (; 24 December 1818 11 October 1889) was an English physicist, mathematician and brewer, born in Salford, Lancashire. Joule studied the nature of heat, and discovered its relationship to mechanical work (see energy). ...
,
Lord Kelvin William Thomson, 1st Baron Kelvin, (26 June 182417 December 1907) was a British mathematician, mathematical physicist and engineer born in Belfast. Professor of Natural Philosophy at the University of Glasgow for 53 years, he did important ...
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 Hermann Ludwig Ferdinand von Helmholtz (31 August 1821 – 8 September 1894) was a German physicist and physician who made significant contributions in several scientific fields, particularly hydrodynamic stability. The Helmholtz Associatio ...
in 1854, giving birth to the spectre of the
heat death of the universe The heat death of the universe (also known as the Big Chill or Big Freeze) is a hypothesis on the ultimate fate of the universe, which suggests the universe will evolve to a state of no thermodynamic free energy, and will therefore be un ...
. In 1854,
William John Macquorn 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 ( ...
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 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 thermodynam ...
formulated by
Rudolf Clausius Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German physicist and mathematician and is considered one of the central founding fathers of the science of thermodynamics. By his restatement of Sadi Carnot's principle ...
in 1865. Clausius used the concept to develop his classic statement of the
second law of thermodynamics The second law of thermodynamics is a physical law based on universal experience concerning heat and energy interconversions. One simple statement of the law is that heat always moves from hotter objects to colder objects (or "downhill"), unles ...
the same year.


Heat transfer

The phenomenon of heat conduction is immediately grasped in everyday life. In 1701, Sir
Isaac Newton Sir Isaac Newton (25 December 1642 – 20 March 1726/27) was an English mathematician, physicist, astronomer, alchemist, theologian, and author (described in his time as a " natural philosopher"), widely recognised as one of the grea ...
published his 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 capacities. Suggestions that this might not be the case came from the new science of
electricity Electricity is the set of physical phenomena associated with the presence and motion of matter that has a property of electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as describ ...
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 Edmond (or Edmund) Halley (; – ) was an English astronomer, mathematician and physicist. He was the second Astronomer Royal in Britain, succeeding John Flamsteed in 1720. From an observatory he constructed on Saint Helena in 1676–77, Hal ...
in 1686. Sir John Leslie observed that the cooling effect of a stream of air increased with its speed, in 1804.
Carl Wilhelm Scheele Carl Wilhelm Scheele (, ; 9 December 1742 – 21 May 1786) was a Swedish German pharmaceutical chemist. Scheele discovered oxygen (although Joseph Priestley published his findings first), and identified molybdenum, tungsten, barium, hyd ...
distinguished heat transfer by
thermal radiation Thermal radiation is electromagnetic radiation generated by the thermal motion of particles in matter. Thermal radiation is generated when heat from the movement of charges in the material (electrons and protons in common forms of matter) i ...
(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 matte 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 Macedonio Melloni (11 April 1798 – 11 August 1854) was an Italian physicist, notable for demonstrating that radiant heat has similar physical properties to those of light. Life Born at Parma, in 1824 he was appointed professor at the local Uni ...
demonstrated that black-body radiation could be reflected,
refracted In physics, refraction is the redirection of a wave as it passes from one medium to another. The redirection can be caused by the wave's change in speed or by a change in the medium. Refraction of light is the most commonly observed phenomeno ...
and polarised in the same way as light.
James Clerk Maxwell James Clerk Maxwell (13 June 1831 – 5 November 1879) was a Scottish mathematician and scientist responsible for the classical theory of electromagnetic radiation, which was the first theory to describe electricity, magnetism and li ...
's 1862 insight that both light and radiant heat were forms of
electromagnetic wave In physics, electromagnetic radiation (EMR) consists of waves of the electromagnetic (EM) field, which propagate through space and carry momentum and electromagnetic radiant energy. It includes radio waves, microwaves, infrared, (visib ...
led to the start of the quantitative analysis of thermal radiation. In 1879,
Jožef Stefan Josef Stefan ( sl, Jožef Štefan; 24 March 1835 – 7 January 1893) was an ethnic Carinthian Slovene physicist, mathematician, and poet of the Austrian Empire. Life and work Stefan was born in an outskirt village of St. Peter (Slovene: ; to ...
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 Stefan–Boltzmann law describes the power radiated from a black body in terms of its temperature. Specifically, the Stefan–Boltzmann law states that the total energy radiated per unit surface area of a black body across all wavelengths ...
. The law was derived theoretically by
Ludwig Boltzmann Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austrian physicist and philosopher. His greatest achievements were the development of statistical mechanics, and the statistical explanation of the second law of ther ...
in 1884.


Absolute zero

In 1702
Guillaume Amontons Guillaume Amontons (31 August 1663 – 11 October 1705) was a French scientific instrument inventor and physicist. He was one of the pioneers in studying the problem of friction, which is the resistance to motion when bodies make contact. He is ...
introduced the concept of absolute zero based on observations of
gas Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma). A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
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 The third law of thermodynamics states, regarding the properties of closed systems in thermodynamic equilibrium: This constant value cannot depend on any other parameters characterizing the closed system, such as pressure or applied magnetic fiel ...
.


Quantum thermodynamics

In 1900
Max Planck Max Karl Ernst Ludwig Planck (, ; 23 April 1858 – 4 October 1947) was a German theoretical physicist whose discovery of energy quanta won him the Nobel Prize in Physics in 1918. Planck made many substantial contributions to theoretical p ...
found an accurate formula for the spectrum of black-body radiation. Fitting new data required the introduction of a new constant, known as Planck's constant, the fundamental constant of modern physics. Looking at the radiation as coming from a cavity oscillator in thermal equilibrium, the formula suggested that energy in a cavity occurs only in multiples of frequency times the constant. That is, it is quantized. This avoided a divergence to which the theory would lead without the quantization.


See also

* Conservation of energy: Historical development * History of Chemistry *
History of Physics Physics is a branch of science whose primary objects of study are matter and energy. Discoveries of physics find applications throughout the natural sciences and in technology. Physics today may be divided loosely into classical physics and mode ...
*
Maxwell's thermodynamic surface Maxwell’s thermodynamic surface is an 1874 sculpture made by Scottish physicist James Clerk Maxwell (1831–1879). This model provides a three-dimensional space of the various states of a fictitious substance with water-like properties. This ...
*
Timeline of thermodynamics, statistical mechanics, and random processes A timeline of events in the history of thermodynamics. Before 1800 * 1650 – Otto von Guericke builds the first vacuum pump * 1660 – Robert Boyle experimentally discovers Boyle's Law, relating the pressure and volume of a gas (pu ...
*
Timeline of heat engine technology A timeline is a display of a list of events in chronological order. It is typically a graphic design showing a long bar labelled with dates paralleling it, and usually contemporaneous events. Timelines can use any suitable scale representi ...
*
Timeline of low-temperature technology The following is a timeline of low-temperature technology and cryogenic technology (refrigeration down to –273.15 °C, –459.67 °F or 0 K). It also lists important milestones in thermometry, thermodynamics, statistical physics and c ...
*
Timeline of thermodynamics A timeline of events in the history of thermodynamics. Before 1800 * 1650 – Otto von Guericke builds the first vacuum pump * 1660 – Robert Boyle experimentally discovers Boyle's Law, relating the pressure and volume of a gas (pu ...
*
Vacuum A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often di ...
* Philosophy of thermal and statistical physics


References


Further reading

* *


External links


History of Thermodynamics
– University of Waterloo
Thermodynamic History Notes
– WolframScience.com
Brief History of Thermodynamics
– Berkeley DF {{DEFAULTSORT:History Of Thermodynamics