History

of Thermodynamics

The history of thermodynamics has always seemed to me to be not only one of the most interesting but one of the most dramatic episodes to be found in the story of the intellectual progress of the human mind. Starting in an investigation of a purely practical problem of engineering economics, it has grown into a body of doctrine of profound philosophical significance, with consequences which permeate the thinking of men on many subjects, from those with the most practical use to the problems of cosmology. Throughout its development it has had to struggle with misconceptions arising from imperfections in our apprehensions of the nature of heat and of the structure of matter. The men who have raised the edifice and who form a considerable part of Gibbs' intellectual ancestry have been men of interesting and most diverse character and experience and were drawn from many professions -- the military, the engineering, and the medical as well as that of teaching. No other branch of physics except that of electricity has exerted so profound an influence on the thought of mankind or extended that influence over so vast a domain. From early age to modern science: As a science, thermodynamics was formulated in the 18th and 19th centuries. At that time it concentrated on investigating the transformation of different 1

forms of energy. Thermodynamics was then formulated as a science about temperature, heat, and also interconvertibility of heat and work into each other. The term was derived from the Greek "terme" (heat), and "dynamics", (force,power, or work). The history of thermodynamics started with G. Galilei (1597) who introduced the concept of temperature and invented one of the first thermometers. It was G. Black (1770) who was the first to use the term "thermodynamics". In 1772 G. Wilke introduced the unit of measuring the amount of heat, a calorie. It was W. Thompson (1854) who introduced the term "thermodynamics" into conventional use. With expansion of the knowledge base in this field, thermodynamics started to include specialty areas, and accordingly the subject of thermodynamics as a science has become formulated in various topics listed below.

In the 20th century, thermodynamics became a basic independent division of Theoretical Physics dealing with the study of general properties of physical systems under equilibrium, as well as common regularities taking place while attaining equilibrium. Thermodynamics is divided into phenomenological and statistical thermodynamics.
y

Phenomenological (classical) Thermodynamics proceeds from experimentally established principles and operates with the recognized data on the properties of physical bodies.

Statistical Thermodynamics is based on representations of the molecular 2

(atomic) structure of physical bodies. Its tools are statistical methods and the mathematical apparatus of probability theory. Non-equilibrium Thermodynamics. The first considerations of thermodynamic analysis of non-equilibrium processes were proposed by W. Thompson in 1854; however, it was developed as a separate branch of science only in the 20th century based on the works of G. Meissner, I. Prigogine, and S. DeGroot.
y

Non-equilibrium thermodynamics focuses on studying processes in their development not having yet reached equilibrium, and on the quantitative study of non-equilibrium processesin particular the rate of the processes as dependent on the ambient conditions, and of the direction of said processes.

The Axiomatic method of Thermodynamics, devised by a Greek theoretical physicist S. Caratheodory (1909), makes it possible to derive all the postulates of thermodynamics from several initial axioms.

Chemical Thermodynamics studies the dependence of thermodynamic properties of substances on their composition, structure, and existence conditions. The objects of its study are chemical reactions, heat absorption and heat release processes taking place at chemical reactions (Thermochemistry), the rate of chemical reactions (Chemical Kinetics), first- and second-order Phase Transitions, Adsorption and Absorption, chemical and physical equilibrium, Solutions, andElectrochemical processes.

Engineering Thermodynamics, which developed as an area of specialty within 3

the engineering field in the 20th century, deals with the interrelationship between heat and work. The object of its study is the use of the Laws of thermodynamics in engineering of thermal processes, namely, developing the theory of heat engines and plants; investigating into the process of transforming heat energy into mechanical or electrical power; analyzing thermodynamic cycles as applied to power plants and heat power plants; designing refrigeration plants and gas liquefaction plants; and investigating the processes ofheat exchange and the heat engineering properties of substances. Thermodynamics is the only physical theory of a general nature of which I am convinced that it will never be overthrown. Albert Einstein

Heat and Work

As its name implies thermodynamics is the science underlying heat and work. Theseterms have been known since early times, but energy, which brings them together,was not recognised and formally defined until well into the 19th century. The potential for converting heat to work was known in ancient times. There is a famous drawing of a machine invented by Hero of Alexandria, a first century mathematician, in which the steam emerging from vents of a heated vessel makes thevessel rotate. Leonardo da Vinci drew a design for a steam driven canon. The firstcommercial advances were made in the late 17th century when several devices weretested for raising water from mines by steam pressure, and in the 4

early 18th centuryThomas Newcomen invented a safe and efficient pump based on the vacuumproduced by condensing steam. James Watt deduced that too much energy was usedin Newcomens pumps by raising the temperature of the chamber after each steamcondensation, and he and Mathew Boulton made an improved steam engine in which the steam chamber was kept at an elevated temperature throughout the operation, with condensation occurring in a separate low temperature chamber. Steam producedmechanical power was being extensively used for manufacture and locomotion from the beginning of the 19th century. The scientific underpinning of steam-powered engineering had two major hurdles to overcome. The first of these was to understand the nature of heat, and the second was the recognition that heat and work are different manifestations of a wider concept,which we call energy.The modern view that heat is a manifestation of the motion of the atoms and molecules that make up matter was supported by many philosophers and scientists in the 17th century. Most notably, Franc is Bacon wrote in 1620 the very essence ofheat, or the substantial self of heat, is motion and nothing else. It is rather surprisingtherefore that the alternative idea that heat was a fluid lasted for many years. Itsorigins probably go back to the Greek idea that fire was one of the four elements(with earth, air and water). Even Robert Boyle, a champion of the so-calledmechanical philosophy that matter consists of particles in motion, proposed that theincrease in the weight of metals after they were heated in air was due to theircombination with the materials of fire.The first quantitative measurements of heat by calorimetry were made by 5

JosephBlack on melting and vaporization. His researches appeared in a book Lectures onthe elements of chemistry, published after his death in 1803. However, Blackhimself assumed that heat was a substance by adopting the view that when a materialis heated some heat matter is added to it, and when it is cooled that matter is takenaway. He concluded that it was this matter that led to the expansion of bodies whenheated. Although we now reject the heat as a fluid model, some of its language is stillwith us as we talk about heat flowing from hotter to colder bodies.The word calorique (caloric) was introduced by Guyton de Morveau in 1787, andadopted by Lavoisier, who, in his Traite elementaire de chemie (1789), listed italong with 23 authentic elements, to represent the imponderable fluid of heat. Byplacing it amongst his elements Lavoisier implied that it could not be created ordestroyed, it just moved from one body to another. This assumption was finallyoverturned by the famous canon boring experiments of Benjamin Thompson, later tobe Count Rumford. In 1798 he observed that the amount of heat produced by frictionin boring a canon was greater for a blunt instrument than it was for a sharpinstrument. Moreover, the quantity of heat and the quantity of borings were roughlyin inverse proportions. He also established that the shavings had the same weight andheat capacity as the original metal. He concluded that heat was not a fluid beingreleased from the material but was a result of the conversion of mechanical work intoheat; he even made a roughestimate of the mechanical equivalent of heat.

*Rumfords experiments were carried out on a specially constructed brass canon 6

barrel, which was insulated against loss of heat, and he used a blunt drill bit. The front of the barrel was immersed in a tank full of water. He wrote :.. at 2 hours and30 minutes it actually boiled.

Energy and the first law:

Reasonably accurate values for the mechanical equivalent of heat were first obtainedby James Prescott Joule around 1843. He examined the heat produced by bothelectrical and mechanical means, and was convinced that the various forms of energycould be converted one into another. By measuring the heat produced in water by apaddle wheel he deduced that 772 foot-pounds of mechanical work was equivalent tothe heat required to raise one pound of water by 1oF. In modern units this wouldmake 1cal=4.15J, the current value being 1cal=4.184J. Joule deduced the mechanical equivalent of heat by both electrical andmechanical means. However, the rise in temperature produced by his famous paddlewheel experiment is very small, and a modern attempt at Cambridge failed toreproduce his result; but Joule claimed to be able to detect 1/200 of a degree Fahrenheit on his thermometer. One joule of energy is that required to raise a pound of water by 9 inches, or to raise its temperature by 0.001F

The equivalence of all forms of energy also received support from biological studies.Lavoisier and Laplace had shown that the ratio of heat evolved to the quantity ofcarbon dioxide produced was roughly the same 7

from a guinea pig as from the burningof a candle, and in 1842, Robert Mayer, a German physician, speculated about thelink in humans between food consumption, heat produced and work done, andconcluded that all were different manifestations of an indestructible quantity, which he called force, but meant energy. Not surprisingly Mayer and Joule later becameinvolved in a priority dispute over who first proposed the conservation of energy, butperhaps both should give way to Friedrich Mohr who wrote in 1837,Besides the fiftyfour chemical elements, there exists in nature only one agent more, and this is calledforce (he meant energy); it can under suitable conditions appear as motion, cohesion,electricity, light, heat, and magnetism. Heat is thus not a particular kind of matter, but an oscillatory motion of the smallest parts of bodies.

The work of Carnot and Clapeyron.

That thermodynamics had its foundations in engineering is most strikingly shown bythe work of Sadi Carnot, a French engineer. In his bookReflections on the MotiveForce of Fire(1824), he drew a comparison between the work that could be extractedfrom a water wheel, and that which could be obtained from a steam engine. In thefirst case the work depends on the amount of water that passes and the height throughwhich it drops, and for the second, he said that the motive force of a steam 8

enginedepends on the quantity of caloric employed and the difference in temperaturesbetween the heat source and the heat sink. He believed that heat was a fluid untilclose to his death in 1832, and perhaps he would not have arrived at his conclusionswithout it; if heat reflected mechanical motion of the atoms the analogy between awater wheel and a steam engine would be far from obvious.Carnot introduced two ideas in his analysis of heat engines, which were to play animportant part in later thermodynamic theory. The first of these was the idea of acycle, a process which occurred through several stages but which led finally back tothe same point (the same conditions of temperature, volume and pressure). The second was the idea that one could go around this cycle in a reversible manner; reversibility being a succession of slow changes such that equilibrium in the systemwas maintained at all times. Carnot deduced that the maximum amount of work thatcould be extracted from an engine was when it was operating reversibly, and theefficiency of such an engine, defined as the ratio of the work done (w), to the heatsupplied (qh), depended only on the two temperatures between which it operated. Carnots conclusions were not well known until they were taken up by Clapeyron,another engineer. He examined cycles associated with changes in pressure andvolume and represented them by pressure-volume diagrams. He deduced that the areawithin such a diagram for a complete cycle represented the work done. He developedCarnots ideas on the 9

efficiency of an engine by proving that for the ideal reversible cycle operating between a heat source providing heat qh, and a cold reservoirextracting heat (-qc), the efficiency was given by Efficiency = w/qh = (qh + qc)/qh (1) Note that by convention q is always heat added to the system so in the above equation qc is negative.

Temperature.

Temperatures began to be measured quantitatively at the beginning of the 17thcentury; Galileo is credited with the first measurements with an air thermometer,which was based on the effect of temperature on the volume of a gas. Fahrenheitinvented the mercury thermometer in 1724, and with three fixed points developed thetemperature scale that bears his name. Celsiuss scale was proposed in 1742.Several people studied the dependence of gas volume on temperature, leading to what is known as Charles law that the volume of a gas at constant pressure is proportionalto the temperature, but this is only true if a constant equal to about 273 is added to theCelsius scale. A major step forward was made in 1848 by William Thomson (laterLord Kelvin) who proposed that an absolute temperature scale could be based onCarnots theorem that the efficiency of an ideal engine depended only on thetemperatures of the hot and cold 10

reservoirs. The scale he defined, and which we now call degrees kelvin, was one for which engines operating between temperatures T andT-1, would have the same efficiency for all T. The relation between motive power and heat, as established by Carnot, is such thatquantities of heat, and intervals of temperature, are involved as the sole elements inthe expression for the amount of mechanical effort to be obtained through the agencyof heat; and since we have, independently, a definite system for the measurement ofquantities of heat, we are thus furnished with a measure for intervals according towhich absolute differences of temperature may be estimated.The characteristic property of the scale which I now propose is, that all degreeshave the same value; that is, that a unit of heat descending from a body A at thetemperature T of this scale, to a body B at the temperature T-1, would give out thesame mechanical effect, whatever the number T. This may justly be termed an absolute scale, since its characteristic is quite independent of the physical propertiesof any specific substanceIn a later paper Kelvin and Joule studied the drop in temperature of gases flowingthrough a porous plug (the Joule-Thomson effect), and showed that the work thatcould be extracted for a 1o loss of temperature was proportional to temperature if 273.7o was added to the Celsius scale, which was approximately the same 11

constant asthat deduced from Charless law; the accepted value today for the kelvin scale is273.15.

The first law.The law of the conservation of energy is the first law of thermodynamics. Such a lawhad long been proved for mechanical motion from Newtons laws, but itsgeneralisation to all forms of energy was only slowly established and several peoplehad claims to its origin. The works of Mayer and Joule have already been mentioned.William Grove published a book in 1846 On the correlation of physical forces inwhich the law is clearly stated, and Hermann Helmholtz in 1847 published Uber die Enhaltung der Kraft in which the law is dealt with very thoroughly. By the middleof the 19th century the principle of the conservation of energy was widely accepted. The second law and entropy.

The second law of thermodynamics relates to spontaneous change. It stemmed fromCarnots ideas on cycles and his analysis of how best to convert heat to work.Kelvins proposal for an absolute temperature scale was also important, but the mainadvance was made by Rudolph Clausius in 1850. He stated the second law in theform A passage of heat from a colder to a hotter body cannot take place withoutcompensation. Soon after (in 1851), Kelvin arrived at the same conclusion butexpressed the law in a different form It is impossible to devise a continuously 12

cycling engine that produces no effect other than the extraction of heat from areservoir at one temperature and the performance of an equivalent amount of work.Kelvin acknowledged the precedence of Clausius for this key law of science.In 1854 Clausius gave a detailed analysis of the Carnot cycle in which he noted thatfor an ideal engine operating reversibly, the heat received at the hot reservoir dividedby its temperature was equal to the heat given out at the cold reservoir divided by its temperature; both temperatures being in Kelvins absolute scale. Noting the negativesign for the heat given out, this can be written (qh /Tu) + (qc /Tc) = 0 (2)He further noted that if there were various temperature ranges in the cycle, all operated reversibly, then for the complete cycle one could write_ ( dq/T) = 0 (3) This puts the factor dq/T on the same footing as other quantities that are unchangedover a cycle, like volume and temperature, and indeed like the total energy, and in alater paper (1865) he introduced the symbol S, which he called entropie (entropy), bythe relationshipdS = dq/T (4) so that for a complete reversible cycle_ dS = 0 (5) * Note that in all the above equations q is the heat added in a reversible cycle. In his 1854 paper Clausius also deduced that if the cycle is not carried out reversibly then_ (dq/T) > 0 (6) and as a consequence he was later able to make his famous statement of 13

the first twolaws of thermodynamics The energy of the universe is a constant; the entropy tendstowards a maximum. It is the second law that underpins the direction forspontaneous change, and the flow of systems toequilibrium. However, it is importantto understand that when entropy is used as a measure for such changes it is the totalentropy of a system and its surroundings that is involved.Entropy and statisticsThe first suggestion that the second law of thermodynamics had a statistical basis was made by James Clerk Maxwell who noted that to violate the second law for gases intwo connected vessels one would have to put high velocity molecules in one vesseland low velocity molecules in the other, by the intervention of what became knowas Maxwells Demon (but he ignored the entropy of the demon). The preciserelationship between entropy and statistical quantities was made by LudwigBoltzmann in a series of publications beginning in 1866. His first paper was titled,On the mechanical meaning of the second law of thermodynamics, but he reached this objective only in later publications. In 1868 Boltzmann extended Maxwellskinetic theory of gases and took the important step of saying that the total energy ofthe system should be distributed amongst the individual molecules in such a mannerthat all possible combinations are equally possible. He later examined the approach to equilibrium according to two ideas, the dissipation of energy and the increase inentropy, and this lead in 1877 to one of the most famous equations of physics, S = k ln W (7)where k is Boltzmanns constant, and W is the number of 14

possible configurations ofthe molecules which are consistent with the state of the system. The form of thisequation is consistent with the fact that entropies are additive but probabilities (whichdetermine W) aremultiplicative. Note also that as W cannot be less than one, S is always positive.Boltzmann did not put the equation in precisely this form but this is how his work waslater interpreted by Planck.Thermodynamic properties of systems.We come finally to the relevance of thermodynamics to particular systems in whichone is interested, rather than the totality of the system and its surroundings. A systemmay be thermally isolated or in thermal equilibrium with its surroundings, and it may be mechanically isolated or in mechanical equilibrium; there may, for example, be changes in temperature, pressure or volume accompanying other changes to thesystem. We need to know the implications of the first two laws of thermodynamics to systems in these different situations.Several people made important contributions to the thermodynamics of systems in the 19th century, either by developing the theory themselves, or by writing some of themore obscure presentations in more understandable form. Josiah Willard Gibbs deduced most of what we know today in the 1870s, but published it using acomplicated notation in an obscure journal (Transactions of the Connecticut Journal of Arts and Science).

His work was clarified by translations into German by Ostwald 15

in 1892, and into French by le Chatelier in 1899. Two other key figures were Helmholtz, who did much the same work as Gibbs, and vant Hoff. Gibbs introduced two state functions that are important in interpreting the energies ofsystems at constant pressure and temperature. One of these H is now called theenthalpy, and the other, G called the Gibbs energy (earlier the Gibbs free energy).

Gibbs showed that changes in H were given by the heat change in aprocess, and thatthe minimum of the function G is the equilibrium condition for such a system. G alsomeasures the maximum work that can be extracted from a system at constant pressureand temperature.

It was Helmholtz who introduced the term free energy, and the function A whichcarries his name has the same role as G but for a system at constant temperature andvolume.

Vant Hoffs main contribution was to the study of equilibria, and to the connectionbetween equilibrium constants and the ratio of forward and backward rate constants.He deduced the temperature dependence of equilibrium constants in the form (d lnK )/dT = (_H/RT2) (8) and produced the equation giving the temperature dependence of rate constants

which bears Arrheniuss name. Vant Hoffs contributions to the thermodynamics ofsolutions lead to his Nobel prize in 1901, the first year of the awards. 16

The third law. Finally, we mention the development of the third law of thermodynamics. This wasstated in 1913 by Max Planck as The entropy of each pure element or substance in aperfect crystalline state is zero at absolute zero. This follows from the statisticalview of entropy, because for a perfect crystal at absolute zero there is only one wayof arranging the molecules in the lattice, and all molecules will be in their lowestenergy state. However, the third law was first formulated by Walther Nernst in 1906when it became known as the Nernst heat theorem. Nernsts contribution stemmed from the problem of deducing equilibrium constants from thermal data. The temperature dependence of the equilibrium constant depends only on enthalpydifferences, according to equation (8), but integrating to get an absolute value for Krequires one to determine a constant of integration. By examining the temperaturedependence of the free energy Nernst deduced that entropy differences (_S) mustbecome zero at absolute zero, and to be consistent with the statistical view of entropyit was decided to make the absolute values of entropies zero at absolute zero.

17

Scientist who contributes in this field:

These scientists had made tremendous contribution in the field of thermodynmics.This is not the end of the story modern scientists are working harder to improve the ideas regarding this field.

18