" 199#$% Sketching the History of Statistical Mechanics and Thermodynamics

(From about 1575 to 198 !

8 Hy&er'eff (et)ork

History * +hilo * +hysics * ,log - Sources. /inks. (otes 0

1deas of atomism. that heat is a mode of motion Anti)ithin bodies and that &ressure is the result of quity such motion. are all floating around2 Hero of 3le4andria (see also here! )rites 1st Pneumatics. an in5estigation on atmos&heric air. cent summari6ing a great deal of )hat )as kno)n at AD the time on sy&hons. &um&s. the effects of heat on li7uids. and engine designs2 3l$,a7ilani (d 1 18! said to ha5e introduced 9th atomism to the Muslim 9alam (&erha&s cent influencing /eibni6!2 The loss of &ermanent magnetism )hen 11th materials are sub:ected to high tem&eratures cent kno)n in ;hina2 The aeoli&ile of Hero /e5i ben 3braham (1%<#$1815! includes a short 13th &assage noting that heat is a form of motion (for cent both light and matter! in his )ork. Liwyat Hen2 F ;ommandine translates Hero of 3le4andria=s 1575 Pneumatics into /atin (translated earlier in 15<7 into 1talian by 3leotti!2 Santorre Santorio (see here also! (15#1$1#8#! is kno)n to ha5e been using an early thermosco&e and also )rites Commentariar in artem 1612 medicinalem Galeni2 Santorre )rites to >alileo >alilei (15#<$1#<%! including sketches of his de5ice. to )hich >alileo re&lies that it )as an in5ention of his2 The &riority remains unclear2 Thermosco&es of Santorio are sensiti5e enough 1615 to detect near$by body heat and candles2 'ohannes 5an Helmont defines ?gas? (the 1620 Flemish )ord for chaos! for air$like substances2 >alileo &oints out that sim&le &um&s can only raise )ater about 8% feet. though this had been 1638 common kno)ledge to &um& makers of the time2 Ferdinand 11. >rand @uke of Tuscany. in5ents a thermometer using li7uid in a glass tube )ith 1641 one end sealed. a slight im&ro5ement to >alileo=s thermosco&e2 A5angelista Torricelli (1# 8$1#<7! in5ents the 1643 barometer. also &roducing the first &artial

5acuum2 BenC @escartes= (159#$1#5 ! treatise Principa Philosophiae &ublished in 3msterdam2 The )ork e4tends effords to formulate a fully 1644 mathematico$mechanical model of the )orld. including conce&ts of nonlocality. the absence of any 5acuum and his 5orte4 model of atoms2 >illes +ersonne de Bober5al (1# %$1#75! &erformed an oft$7uoted e4&eriment on air &ressure )hereby a car&=s s)im$bladder is 1647 &artially remo5ed. s7uee6ed of almost all air and tied shut2 The car& is then &laced in a Torricellian 5acuum and the bladder is obser5ed to e4&and2 Florin +errier e4&erimentally sho)s that the height achie5ed by mercury in a barometer 1648 decreased as one scaled a mountain. a theoretical &rediction of his brother$in$la). ,laise +ascal. and also kno)n as the +uy de @Dme e4&eriment2 ca (Coffee begins to be important to and catch on 1650 in Europe.) 'ean +ec7uet=s (1#%%$1#7<! book on &sychology &o&ulari6es the Bober5al e4&eriment (Anglish translation in 1#58!2 He also introduces the term 1651 ?elater? as the tendency of air to e4&and. and theori6es that air on the earth=s surface is com&ressed by the )eight of the atmos&heric air2 Etto 5on >uericke=s (1# %$8#! e4&eriment )ith t)o iron hemis&heres held together by a strong &artial 5acuum being strong enough to resist the 1654 &ull of a train of horses on either side2 Ferdinand 11 in5ents the sealed thermometer2 Bobert ,oyle (1#%7$91! &ublishes New E periments Physio!"echanicall# touching the $pring of the %ir# and its Effects2 Ene e4&eriment clearly sho)s the de&endency on Torricelli=s 5acuum on ambient air &ressure2 3lso &resented are discussions of both +ec7uet=s 1660 idea of air modelled by coiled$u& )ool$like or s&ring$like atoms ()hich )as &referred by ,oyle! and of @escartes= idea of )hirling Bobert ,oyle &articles )hich re&ell one another at short distances2

1n res&onse to ,oyle=s ideas. Franciscus /inus (1595$1#75! &ro&oses a theory )hereby a 5acuum is e4&lained by the creation of an in5isible collection of thread$like ?funiculus.? )hich stri5e to hold nearby ob:ects together2 Bichard To)nley (1#%8$17 7! and Henry +o)er=s (1#%8$1##8! e4&eriments establishing the +F la) for e4&ansion (the so$called ?,oyle=s /a)? or ?Marriotte=s /a)?!2 ,oyle adds an a&&endi4 to his 1## )ork. res&onding to the criticisms of /inus and Thomas Hobbes. &resenting im&ro5ed 1661 e4&erimental results and gi5ing a 5ersion of )hat is no) kno)n as ?,oyle=s /a)? for the case of com&ression2 ,oyle=s ?@efense of the @octrine touching the 1662 S&ring and Geight of the 3ir2? ,laise +ascal (1#%8$1##%! )rites &n the E'uilibrium of Li'uids (&ublished &osthumously! suggesting that &ressure is transmitted e7ually in all directions in a fluid 1663 (later kno)n as ?+ascal=s la)?!. &robably disco5ered around 1#<82 +o)er=s book E perimental Philosophy. &ublishing early results on the +F la)2 'ohann 'oachim ,echer=s $ubterranean Physics. a tract on alchemy and e4&erimental results on minerals. introduces the idea that a ?terra 1669 &ingus? (oily earth! causes fire2 (This idea is later &icked u& to form the &hlogiston theory of heat2! ,oyle disco5ers that )hen acid interacts )ith 1670 certain metals a flammable gas is &roduced. kno)n no) as Hydrogen2 ;hristiaan Huygens (1#%9$95! builds a motor 1673 dri5en by the e4&losion of gun&o)der2 'ohn Mayo) suggests that air may consist of t)o different gases from e4&eriments done on 1674 mice and candles. re&orted in his (i)e "edico! Physical *reatises2 1676 AdmC Mariotte (H1#% $1#8<! inde&endently finds relationshi& bet)een &ressure and 5olume. in his )ork &n the Nature of %ir2 (9no)n as ?Mariotte=s la)? in France. and ?,oyle=s la)?

else)here2! Mariotte=s *he "otion of +ater and &ther 1685 (luids &ublished (&osthumously!2 @enis +a&in (1#<7$171%! uses steam &ressure to 1690 mo5e a &iston for the first time2 >eorg Arnts Stahl introduces the idea of 1697 &hlogiston as the agent of burning and rusting2 >uillaume 3montons e4tra&olates the idea of absolute 6ero from the obser5ation that e7ual dro&s in tem&erature &roduce e7ual dro&s in &ressure. and since &ressure cannot become negati5e. there must be a lo)er limit to 1702 tem&erature2 Ele ;hristensen BImer de5ises a tem&erature scale based on the t)o &henomena of the boiling &oint of )ater and the tem&erature at )hich sno) begins to form2 Francis Hauksbee sho)s that sound needs air for 1705 &ro&agation2 1712 Thomas (e)comen=s steam engine2 >abriel Fahrenheit=s mercury thermometer 1714 introducing his tem&erature scale2 (see notes! 'akob Hermann (1#78$1788! &ro&oses the first definite measure of the heat of molecular motion in his )ork on rational mechanics. Phoronomia2 1716 He &ostulates that (in modern lingo! &ressure is &ro&ortional to density and to the s7uare of the a5erage 5elocity of the &articles of motion2 Stahl=s (oundations of ,ogmatic and 1723 E perimental Chemistry &o&ulari6es &hlogiston 'akob Hermann and the ideas of 'ohann ,echer2 Hermann ,oerhaa5e &ro&oses that heat is a fluid 1724 of some sort2 /eonhard Auler (17 7$1788!. e4tending 'ohann ,ernoulli=s )ork on @escartes= 5orte4 cosmology. models air )ith tightly$s&aced. s&inning s&heres2 He formulate an e7uation of 1729 state relating humidity. &ressure. density and 5elocity. finding the To)nley$+o)er$,oyle la) as an a&&ro4imation2 He calculates air molecules to be about <77 mJs at mean conditions. and that this is about the s&eed of sound2 'ohann 'uncker=s Conspectus of Chemistry 1730 systematically e4&ands &hlogiston theory2

@aniel ,ernoulli (17 $178%!. in a treatise on hydrodynamics )orked out in the &eriod from 17%8 to 1788. gi5es a deri5ation of the gas la)s from a billiard ball model. deri5es the ,oyle$ Mariotte relation and used conser5ation of mechanical energy to sho) that as tem&erature 1733 changes the &ressure )ill change &ro&ortionally to the s7uare of the &article 5elocities2 This te4t marks the first truly statistical treatment of kinetic theory2 3 significantly u&dated edition of the te4t is &ublished in 17882 The &a&er is all but forgotten until 18592 >eorge Martine establishes that the 5olume of @aniel ,ernoulli 1739 an ob:ect is not &ro&ortional to the amount of heat it has2 3nders ;elsius (17 1$17<<! &ublishes ?Ebser5ations on t)o &ersistent degrees on a thermometer.? basing his scale on the free6ing 1742 &oint (1 degrees! and boiling &oints ( degrees! of )ater2 (The system is reoriented in 17<5 by ;arl /innaeus. a2k2a2 ;arl 5on /innC2! Mikhail Fasilie5ich /omonosso5 &ublishes a 1744 &a&er on the causes of heat and cold. stating that heat is a form of motion2 (also. ;arl 5on /innC. 17 7$1778! reorients 1744 ;elsius=s scale2 /omonoso5 formulates la)s of conser5ation of energy and mass2 Through about 17# . he &erforms a number of theoretical in5estigations 1748 about molecular structures. s&eculating on the effects of translation. 5ibration. and rotations of such molecules2 Gilliam ;ullen=s %n Essay on the Cold 1756 Produced by E)aporating (luids and some &ther "eans of Producing Cold2 Bud:er >iuse&&e ,osko5ic (1711$1787! &ublishes *heoria Philosophiae Naturalis. the first attem&t to use (e)ton=s la)s to account for all &hysical &henomena as the interaction of 1758 &oint &article acting at a distance2 Molecules are modeled as sub:ected to intermolecular forces )hich are attracti5e nearby but re&ulsi5e at greater distances2 His efforts. ho)e5er. are too 5aguely )orked out to base a theory on2 1761 'ose&h ,lack (17%8$1799! finds that )hen melting ice. heat can be absorbed )ithout

changing tem&erature2 'ames Gatt in5ents his steam engine. )hich is 1765 o5er si4 times more effecti5e than (e)comen=s2 'ohan ;arl Gilcke calculates the latent heat of 1772 ice2 Gilcke comes u& )ith the conce&t of s&ecific 1781 heats2 /a5oisier establishes an early 5ersion of the conser5ation of matter through his finding of 1782 constancy of )eight before and after chemical reactions2 /a5oisier=s )ork. -eflections on Phlogiston. on 1783 the )eaknesses of &hlogiston theory )ith res&ect+hlogiston Theory to combustion2 (H1## =s to H179 =s! 1786 /a5oisier and /a&lace=s )ork "emoir on Heat2 9inetic Heat Theory 'ackues$3le4andre ;harles determines that at a (H171# to H17# =s! gi5en tem&erature change. different gases (then H181# to &resent! 1787 e4&and the same amount (kno)n as ?;harles=s ;aloric Heat Theory la)?!2 (H178 =s to H18# =s! /a5oisier=s book Elementary *reatise on Ga5e Theory of Heat 1789 Chemistry. containing the la) of mass (H188 =s to H18# =s! conser5ation2 Statistical Mechanics Bichard 9ir)an (H1788$181%!. &re5iously a (H185 =s to &resent! staunch defender of &hlogiston theory. concedes (,ernoulli e4ce&ted! that the e4&erimental e5idence says other)ise2 Kuantum Statistics (H19 =s to &resent! +ierre +rC5ost=s theory of heat and radiation e4change. stating that cold is the absence of 1791 heat. hot bodies radiate continually and that a lack of radiation indicates e7uilibrium )ith surroundings tem&erature2 'eremias Bichter (17#%$18 7! founds stoichiometry. the &rinci&le of fi4ed chemical reactions2 ;annon$boring e4&eriments of ,en:amin Thom&son (;ount Bumford! (1758$181<! demonstrating the con5ersion of )ork into heat 1798 in his )ork En'uiry Concerning the $ource of Heat which is E cited by (riction. sho)ing also that additional )eight of an ob:ect due to heating (a &rediction of caloric theory! )as not detected2 1799 1ce$rubbing e4&eriments of Hum&hrey @a5y (1778$18%9! demonstrating the con5ersion of )ork into heat. and suggesting that an indefinite amount of heat could be generated from a body

()hereas caloric theory se5erely limits its a5ailable amount!2 'ose&h$/ouis +roust formulates that elements in a com&ound al)ays combine in definite mass ratios (?+roust=s /a)?!2 Gilliam Herschel (179%$1871! &ublishes ?3n in5estigation of the &o)ers of &rismatic colours to heat and illuminate ob:ects? in5estigating the 1800 effects of different )a5elengths of light on a thermometer. finding light :ust beyond the red to be the hottest2 'ohann Bitter disco5ers ultra5iolet radiation )hile doing )ork )ith sil5er chloride2 1801 'ohn @alton (17##$18<<! finds that t)o gases in the same region &roduce the same &ressure as if they occu&ied the region alone. kno)n as the la) of &artial &ressures2 'ose&h$/ouis >ay$/ussac (1778$185 ! finds 1802 that. at a gi5en &ressure. the change in 5olume is &ro&ortional to the change in tem&erature2 @alton formulates his atomic theory of matter. stating that chemicals are formed by integer numbers of atoms. by studying the )eights of chemicals and reactants2 ;laude$/ouis ,erthollet demonstrates that 1803 reaction rates de&end on both the amount of substances &resent as )ell as their affinities in his )ork Essay on $tatic Chemistry2 Gilliam Henry finds that a gas=s mass )hen dissol5ed in a li7uid is &ro&ortional to the &ressure (later kno)n as ?Henry=s la)?!2 'ohn /eslie (17##$188%! )rites %n E perimental .n'uiry into the Nature and 1804 Propagation of Heat. sho)ing that light and radiated heat ha5e similar &ro&erties2 +ierre$Simon /a&lace (17<9$18%7! formulates 1805 his theory of ca&illary forces based on his studies of molecular forces in li7uids2 Thomas Loung (1778$18%9! formulates a &recursor to the modern formulation of energy. 1806 mathematically associating it )ith m)/ (t)ice +ierre$Simon /a&lace the modern ?kinetic energy?!2

Loung=s $ystem of Chemistry contains the first &ublished account of @alton=s ideas on atomic theory2 'ean ,a&tiste 'ose&h Fourier (17#8$188 ! com&letes his &n the Propagation of Heat in 1807 $olid 0odies. introducing many mathematical no5elties. including his series e4&ansion techni7ues2 (@ec 81st! >ay$/ussac states that gases 1808 chemically combine in e4act &ro&ortions of 5olume2 SimCon$@enis +oisson (1781$18< ! de5elo&s his mathematical theory of heat. based on the )ork of Fourier2 3mede5 35ogadro (177#$185#! hy&othesi6es that the ?number of integral molecules in any gases is -2220 al)ays &ro&ortional to the 5olumes?. and that the ratio of the masses of 1811 molecules is &ro&ortional to the ratio of gas densities at e7ual tem&erature and &ressure (later becoming ?35ogadro=s la)?!2 'Mns 'akob ,er6elius states that electrical and 'ean Fourier chemical forces are one and the same and that atoms are electrically charged. in his )ork *heory of Chemical Proportions and the Chemical %ction of Electricity2 @a5y )rites Elements of Chemical Philosophy. including a hy&othesis that in addition to the 5ibrational and undulatory motion of solids. gasses as )ell e4hibit rotational motion about an a4is2 1812 @elaroche and ,Crard=s measurements of s&ecific heats at atmos&heric &ressure of a large number of gasses2 Their measurements agreed )ith /a&lace=s &redictions and remained a cornerstone for caloric theory2 'ohn Hera&ath (179 $18#8! )rites. ?En the &hysical &ro&erties of gases.? essentially 1816 &ro&osing the same theory. but de5elo&ed inde&endently. as that of @aniel ,ernoulli2 +ierre$/ouis @ulong and 3lC4is ThCrNse +etit 1819 (1791$18% ! find constant s&ecific heat at

constant &ressure for metals o5er )ide range of tem&eratures. finding that the &roduct of the s&ecific heat and the atomic mass remains constant (kno)n as the ?/a) of @ulong and +etit?!2 Hera&ath &ublishes. ?3 mathematical in5estigation into the causes. la)s. and &rinci&al &haenomena of heat. gases. gra5itation. etc.? in the %nnals of Philos. He e4&lained in outline ho) kinetic theory could gi5e accounts of sound &ro&agation. &hase changes and diffusion2 The &a&er is all but ignored due to re:ection by the 1821 Boyal Society of /ondon. and Hum&hry @a5y in &articular2 Thomas 'ohann Seebeck disco5ers a &rocess by )hich heat is con5erted into electricity in the :unction of some metals. kno)n as theormoelectricity2 Fourier=s essay %nalytic *heory of Heat is &ublished. furthering his techni7ues of analysis2 ;harles ;agniard de la Tour. in li7uification e4&eriments. finds that both tem&erature and &ressure must be a&&ro&riately controlled. and disco5ers )hat is no) kno) as the critical &oint of a substance2 Sadi ;arnot (179#$188%! &ublishes ?Beflections on the Moti5e +o)er of Fire.? introducing the ideal gas cycle analysis. sho)ing that )hen heat &asses bet)een t)o bodies theormodynamic )ork ()hich he defines! is done. and &ro&oses 1824 an idea for an internal combustion engine2 1822 +ierre$Simon /a&lace (17<9$18%7! &ublishes se5eral &a&ers refining an idea of (e)ton=s that gasses are formed through re&ulsi5e interactions2 Bobert ,ro)n (1778$1858!. in5estigating the )ell$kno)n irregular motions seen of &articles sus&ended in li7uid under a microsco&e. sho)s Sadi ;arnot 1827 that such motions cannot be attributed to any 5itality of the &articles themsel5es. through studies of many organic and inorganic substances2 1829 >usta5e$>as&ard ;oriolis defines the term ?kinetic energy? in his studies &ublished as &n

the Calculation of "echanical %ction2 Thomas >raham (18 5$18#9! e4&erimentally unco5ers the la) of gas diffusion. by )hich the rate of a gas=s diffusion. s7uared. is &ro&ortional to its density2 Heinrich Friedrich Amil /en6 determines that 1833 resistence in metals increases )ith tem&erature2 ;la&eyron formulates the first 5ersion of the second la) of thermodynimcs. based on studies of steam engines2 1834 'ean$;harles$3thanase +eltier sho)s that heat can be absorbed or gi5en off )hen current is Gilliam Thomson &assed one )ay or the other across a :unction bet)een t)o different metals (kno)s as the +eltier effect!2 5on Suerman=s e4&eriments on air at reduced 1837 &ressures 5erifying ;la&&eyron=s 5ersion of ;arnot=s formulas2 'ulius Bobert Mayer (181<$1878! clearly formulates the conser5ation of energy. and that heat is a form of (mechanical! energy2 1842 Gilliam Thomson. /ord 9el5in=s (18%<$19 7! &n the 1niform "otion of Heat in Homogeneous $olid 0odies2 (through 18<8! Through a series of e4&eriments. 'ames +rescott 'oule (1818$1889! establishes the e4act relationshi& bet)een heat and mechanical The 18< =s )ere marked by the nearly )ork2 ('oule=s )ork is little read2! simultaneous and inde&endent conce&tuali6ation of the conser5ation of 'ohn 'ames Gaterston (1811$1888! energy by Mayer. 'oule. Helmholt6 and 1843 anonymously &ublishes *houghts on the "ental /ud5ig 3ugust ;olding (1815$88!2 (unctions containing in a note at the end a full and accurate account of the kinetic theory of gases and the introduction of the idea of a mean free &ath2 The )ork goes all but com&letely unread2 Gaterston submits a &a&ers on the kinetic theory of gases to the Boyal Society. )ho re:ects it2 The &a&er &recisely lays out the ideas of energy 1845 e7ui&artition and gi5es the first modern kinetic definition of tem&erature2 3 short abstract a&&ears a year later. and again in 1851. but the )ork is ignored2

'oule &ublishes ?En Matter. /i5ing Force. and Heat? in the "anchester Courier. stating the &rinci&le of the conser5ation of energy and gi5ing the con5ersion from heat to kinetic energy2 Hermann /ud)ig Ferdinand 5on Helmholt6 (18%1$9<! &ublishes his &n the Conser)ation of Energy. e4tending ;arnot=s &rinc&le of the 1847 =im&ossibility of unlimited mo5ing force= (kinetic energy! to a mathematical formulation of the =&rinci&le of conser5ation of li5ing force= (5is 5i5a J kinetic energy!2 (1nde&endent of 'oule=s &ublications2! 'ohn Gilliam @ra&er finds that all substances begin to glo) around 5%5O;. starting in the red and e5entually becoming )hite2 'ames 'oule 'oule reads a &a&er using Hera&ath=s kinetic theory2 The &a&er contains the first numerical results from the kinetic theory2 ((ot &ublished until 1851. and not )ell kno)n until ;lausius=s reference to it in 18572! 1848 Gilliam 'ohn Mac7uorn Bankine=s (18% $187%! researches into mechanics and heat (mainly through 1855!2 9el5in de5elo&=s a scale of absolute tem&erature (no) kno)n as the ?9el5in? scale! based on the theory of ;arnot2 'ames Thomson (18%%$189%!. using ;arnot=s theories. &redicts the lo)er of the free6ing &oint of )ater under high &ressures2

1849

9el5in. in s&eaking of ;arnot=s theory. coins the term ?thermodynamics2? 'ohn Herschel (179%$1871! &ublishes (anonymously. though generally kno)n! an article on Kuetelet=s )ork in statistics. introducing much of the continental )ork on 1850 statistics to ,ritish scientists2 Budolf ;lausius (18%%$88! gi5es a 5erbal formulation of the second la). for )hich there is Hermann 5on Helmholt6 no mechanism )hose only function is the

transfer of heat2 9el5in inde&endently redisco5ers the idea of absolute 6ero (1<9 years after 3montons!. e4tra&olating from ;harles= la) that it must be 1851 about $%78O;. and suggesting that the energy of the molecules )ould tend to 6ero2 He also deri5es the second la) of thermodynamics using ;arnot=s ideas2 Henri$Fictor Begnault (181 $1878! sho)s that gas beha5ior doesn=t 7uite follo) ,oyle=s la) at lo) tem&eratures and e4tra&olates a 5alue of $%78O; for absolute 6ero2 1852 'oule and 9el5in sho) that e4&anding gases become cooler in the &rocess. the latter gi5ing the first general statement of the &rinci&le of the ?uni5ersal tendency to)ard dissi&ation of energy2? Hendrik Boo6eboom e4&erimentally determines the &hase la). later deri5ed mathematically by >ibbs2

1854

;lausius &ro&oses the function dKJT as a )ay to com&are heat flo)s )ith heat con5ersions2 1855 Bankine=s &utlines of the $cience of Energetics. 9arl 9rMnig (18%%$79! )rites a &a&er suggesting that gas molecules in e7uilibrium tra5el in straight lines until they collide )ith something. &ublished in Poggendorfs %nnalen der Physi22 Budolf ;lausius 1856 Ghereas the efforts of ,ernoulli. Auler. Hera&ath. Hermann and 'oule )ere largely ignored. 9arl 9rMnig=s efforts )ere )idely read. though not constituting an ad5ance in kinetic theory2 ;lausius &ublishes a &a&er on a mathematical kinetic theory. e4&laining e5a&oration and 1857 establishing heat as energy distributed statistically among &articles2 ;lausius introduces the idea of the mean free 1858 &ath of a &article in )orking out a kinetic theory of diffusion2

'ames ;lerk Ma4)ell (1881$79! reads a &a&er on kinetic theory. &rinted in 18# as ?1llustrations of the @ynamical Theory of >ases.? using random 5elocity distributions for gases. and sho)ing 5iscosity to be inde&endent of tem&erature2 The &a&er is originally intended to sho) internal inconsistencies in the kinetic theory. but through its rigor it greatly refined the theory and &ro5ided ne) insights2 1859 >usta5 Bobert 9irchhoff (18%<$1887! deri5es from the second la) of thermodynamics that ob:ects cannot be distinguished by their thermal radiation at a gi5en uniform tem&erature. one must also use reflected light2 ,ernoulli=s &a&er re&ublished due to rene)ed interest in kinetic theory2 (Hera&ath henceforth goes into obscurity2! Michael Faraday=s &a&er ?+ressure Melting Affect? describing the lo)ering of the free6ing &oint of )ater using &ressure2 Ma4)ell sho)s a discre&ancy bet)een the 'ames ;lerk Ma4)ell &rediction by kinetic theory of the s&ecific heat 1860 of diatomic gases and e4&eriment2 ((ot to be resol5ed satisfactorally until the early stages of 7uantum theory2! This &a&er is the first of four )orks on kinetic theory by Ma4)ell. bringing a ne) le5el of rigour and so&histication to the theory2 Thomas 3ndre)s (1818$1885!. in a series of e4&eriments )ith ;E % through 18#9. finds that at lo) tem&eratures ,oyle=s la) breaks do)n. and there are regions on a +F chart )here. for a gi5en isotherm. changes in 5olume &roduce no 1861 change in &ressure2 This region is recogni6ed to be the li7uid$5a&our e7uilibrial state2 He rigorously finds the critical &oint and tri&le &oint2 9irchhoff formulates the notion of a blackbody2 'ohn Tyndall=s (18% $1898! Heat as a mode of "otion. &o&ulari6ing Ma4)ell=s ideas on heat2 3ndre)s sho)s that. contrary to e4&ectations.

1863

abo5e a substance=s critical &oint it may be continuous changed from gas to li7uid and 5ice 5ersa through 5ariations of tem&erature and &ressure2 ;lausius &ublishes "echanical *heory of Heat. the first treatise on thermodynamics2 Fol % &ublish in =#9. dealing )ith a&&lications to 1864 electricity2 3 second edition. &ublished as a te4tbook. )as finished in =752 Anglish translation in 18#7 (Fol 1 only!. and French in 18#8 (both 5olumes!2 ;lausius uses ;arnot=s techni7ues to deri5e ?entro&y? (and sho)s the t)o la)s of thermodynamics e4&ressible in the same )ays as the older caloric theory!. a term coined for the 7uantity defined early by him. dKJT2 1n a &ublic s&eech entitled ?The entro&y of the uni5erse tends to a ma4imum.? he sho)s ho) thermodynamics seem to im&ly an e5entual heat 1865 death for the uni5erse2 'osef /oschmidt=s (18%1$95! &oints out that Ma4)ell=s conclusion that the &ro&ortionality of the mean free &ath to FJ(d% could be used to estimate the si6e of an atom2 Gith further considerations. he estimates the si6e of an air molecule to be about 1 $7 cm. about < times too large. but the best estimate to date2 Ma4)ell models interatomic forces by a in5erse 1866 fifth$&o)er la). though only as an interim solution2 Ma4)ell &ublishes his ma:or )ork on kinetic theory. &n the ,ynamical *heory of Gases. 1867 9el5in=s &n 3orte !%toms.

(S&urred on by Ma4)ell=s )ork. serious debates on the statistical inter&retation of irre5ersibility begin2! /ud)ig ,olt6mann=s (18<<$19 #! e4tends Ma4)ell=s distribution la) to include e4ternal 1868 forces2 1n the case of gra5ity. he )orked through the distribution of densities and &ressures and that thermal e7uilibrium )as maintained2 Ma4)ell. hel&ing out + > Tait. )ho )as 1871 drafting an te4tbook on thermodynamics. comes /ud)ig ,olt6mann

u& )ith his &arabol of the daemon to conce&tually e4&lain heat statistics2 ,olt6mann suggests that one may deri5e the &robabilistic &icture from the kinetic one by heuristically assuming that all microstates must be reali6ed in a system before returning to a s&ecific microstate. and thus measured 5alues should a5erage the effects of such states2 (9no)n as the ?ergodic theorem.? and so named by Ahrenfest in 19112! 'ames Thomson suggests that e5en belo) the critical &oint. a substance may smoothly transition bet)een gas and li7uid from considerations of e4&erimental data on &ressure and 5olume2 1n a 1 $&age &a&er entitled. ?Further Studies of the Thermal A7uilibrium of >as Molecules.? ,olt6mann=s deri5es his trans&ort e7uation (P$ Theorem!. sho)ing e4&licitly that isolated systems must al)ays e5ol5e in such a )ay that 1872 entro&y increases2 He introduces a number of mathematical inno5ations. including a techni7ue of discreti6ing the allo)ed energy le5els for a molecule. and allo)ing this energy bin to go to 6ero2 /ittle read at first. the &a&er later meets )ith )ide$s&read o&&osition2 'osiah Gillard >ibbs (1889$19 8! &ublishes Graphical "ethods in the *hermodynimcs of (luids and % "ethod of Geometrical -epresentation of the *hermodynamic Properties of $ubstances by "eans of $urfaces. introducing many ne) gra&hical techni7ues2 From 1878 to 1878 he &ublishes a series of im&ortant articles in the *ransactions of the Connecticut %cademy of %rts and $ciences# 1873 )idely influencing scientists in the QS and in Auro&e2 'ohannes @iderik 5an der Gaals (1887$19%8!. in doctoral dissertation. gi5es the first correct a&&ro4imation for the effects of a non$5anishing ratio of molecule diameter to a5erage distance by assuming long$range attracti5e and short$ range re&ulsi5e forces. a&&lying this to the case 'osiah >ibbs

of gases at high densities2 Qsing his ?e7uation of state.? he gi5es the first successful attem&t to e4&lain a (gas$li7uid! &hase transition2 The theory both accounted for 3ndre)s=s critical &oint &henomena and confirmed 'ames Thomson=s hy&othesis2 9el5in &oints out that the irre5ersibility of ,olt6mann=s kinetic theory seems to contradict the underlying classical la)s of &hysics 1874 remaining time$in5ariant (the so$called ?re5ersibility &arado4.? sometimes attributed to /oschmidt!2 >ibbs &ublishes the first &art of &n the E'uilibrium of Heterogeneous $ubstances (the %nd &art in 1878!2 The )orks deal )ith chemical reactions. &hase e7uilibrium and the use of free 1876 energy2 (9arl +aul >ottfried 5on /inde builds the first &ractical refrigerator using li7uid ammonia2! ,olt6mann formulates a statistical mechanical 5ersion of the second la) of thermodynamics in the &a&er. ?En the Belation ,et)een the Second /a) of the Mechanical Theory of Heat and the +robability ;alculus )ith Bes&ect to the Theorems on Thermal A7uilibrium?2 There he formulates that the entro&y of a system is &ro&ortional to the log of the &hase s&ace 1877 5olume occu&ied by the macrostate of the system. $ 4 2 ln 5. making use of his mathematical inno5ation of using finite areas of &hase s&ace2 /i7uification of o4ygen achie5ed. after nearly one hundred years of trying. by /ouis +aul ;ailletet (188%$1918! (on @ec %nd! and Baoul +ierre +ictet (18<#$19%9! (on @ec %%nd!2 'osef Ste&han (1885$1898! determines that the amount of radiation gi5en off by a body through 1879 heating is &ro&ortional to the fourth &o)er of its tem&erature (kno)n as the ?Ste&han$,olt6mann la)?!. -6 4 7*8. ,olt6mann (18<<$19 #! succeeds in theoretically deri5ing the radiation la) found by 1884 Ste&han. sho)ing that a mechanical &ressure and energy density must be associated )ith the

radiation in order to satistfy the second la)2 >ibbs coins the term ?statistical mechanics? for the kinetic theory=s treatment of thermodynamic issues2 /odge &romotes the idea that mechanical energy can be locali6ed and flo). as ins&ired by the )ork a year earlier by +oynting in electromagnetic theory2 1885 'ohann 'akob ,almer (18%5$1898! finds a formula for describing the four s&ectral )a5elengths then kno)n for hydrogren as found by Rngstrom2 'ules Henri +oincarC (185<$191%! deri5es his recurrence theorem. )hereby a system )ith fi4ed total and 5olume )ill e5entually return 1889 arbitrarily closely to any gi5en state2 >ibbs= last )ork. Elementary Principles in $tatistical "echanics2 Ad)ard +arnell ;ul5er)ell (1855$1981! &oints out the a&&arent contradiction bet)een ,olt6mann=s H$theorem and the irre5ersibility of 1890 the micromechanical &rocesses on )hich it is based. suggesting that some kind of irre5ersible &rocess takes &lace at this micro le5el. &erha&s in connection )ith the ether2 Gilhelm ;arl Gerner Etto Frit6 Fran6 Gien (18#<$19%8! e4&erimentally finds that the )a5elength of ma4imum radiation of thermal 1893 body is &ro&ortional to the in5erse of its tem&erature (kno)n as ?Gien=s la)?! using an o5en )ith a small hole as an a&&ro4imation to a theoretical black$body2 S H ,urbury &oints out that the H$theorem relies on the uncorrelated nature of molecular interactions. but that this may not be 5alid after an indi5idual collision. and hence not in general 5alid )ithout some e4ternal randomi6ing 1894 element2 ,olt6mann calls this the hy&othesis of molecular disorder. s&ecifically referring to the lo) &robabilitiy of t)o molecules colliding t)ice )ithin any significant time frame. but mentioning that this )ould become an issue for gases at high densities2

+ierre ;urie (1859$19 #!. in his doctoral dissertation. defined both ferro$. dia$. and &aramagnetism. sho)ing that ferromagnets lose their magnetic &ro&erties as their tem&erature is increased. e5entually losing it com&letely abo5e a certain tem&erature s&ecific to that material 1895 (the ?;urie &oint?!2 He suggests that diamagnetism is an atomic &ro&erty. )hile the other t)o are &ro&erties of bulk matter2 Gilhelm BMntgen (18<5$19%8! disco5ers a ne) &enetrating kind of radiation. dubbed S$rays2 Arnst Termelo (1871$1958!. starting )ith the &ostulate that the second la) is true. tries to sho) the inherent contradictions of the &urely mechanical basis of statistical mechanics. making use of +oincarC=s result on recurrence (his ?recurrence &arado4?!2 1896 Gien &ro&oses an e4&licit form for the black body distribution la). U V WX8e4&Y$ZXJT[. )hich fits the e4isting data2 3ntoine Henri ,ec7uerel (185%$19 8! disco5ers radioacti5ity in fluorescent materials2 'ose&h 'ohn Thomson (185#$19< ! demonstrates that cathode rays )ere electrically 1897 charged &article streams. kno) shortly thereafter as electrons2 ,olt6mann &ublishes his Lectures on Gas 1898 *heory2 Etto /ummer (18# $19%5! and Arnst +ringsheim com&lete the first accurate measurements of the s&ectral radiancy of blackbodies. sho)ing the breakdo)n of Gien=s la) at high tem&eratures and lo) fre7uencies2 1899 Amile Hilaire 3magat &ublishes *he Laws of Gases of e4tensi5e e4&eriments )ith gases under 5ery high &ressures2 Ma4 +lanck

'' Thomson and +hili&& /enard (18#%$19<7! begin e4&erimental in5estigations of &hotoelectric radiation2 9el5in &ro&oses a modification to Gein=s la) of +lanck=s 19 analysis did not. at the 1900 the form U H X%e4&Y$ZXJT[2 time. im&ly any ne) la) about the

Ma4 9arl Arnst /ud)ig +lanck (1858$19<7!. studying blackbody radiation and follo)ing ,olt6mann=s techni7ues of di5iding the energy continuum into cells. &ro&oses fi4ing cell si6es to be &ro&ortional to oscillator fre7uency. and in so doing deri5es the correct radiation s&ectrum for blackbodies2 +lanck &ro&oses the constant. h (+lanck=s constant!. as a 7uantum of action in &hase s&ace2 >ibbs &ublishes Elementary Principles in $tatistical "echanics. his treatise on the sub:ect. deri5ing common thermodynamic &ro&erties from &article statistics. gi5ing his full account of 1902 ensemble theory and their relationshi&s (including the so$called ?>ibbs &arado4.? though there )as nothing &arado4ical about it at the time!2 Marian 5on Smolucho)ski and 3lbert Ainstein microstructure of matter. nor )as there (1879$1955! inde&endently in5estigate any reason to belie5e that e4tra&olation of ,ro)nian motion. the motion of 5ery small the Bayleigh$'eans la) signalled any &articles sus&ended in li7uid2 This is sho)n to failure of classical methods2 be an obser5able effect of the fluctuations of statistical mechanical mo5ement. des&ite &roducing no net effect on a5erage2 Ainstein &ublishes a &a&er on the &hotoelectric effect. basing his analysis on an analog of the statistical mechanical a&&roach for classical 1905 electromagnetic fields modelled as 7uanta of light2 +aul /ange5in (187%$19<#! de5elo&es a more satisfactory theory of &ara$ and diamagnetism. a&&lying statistical mechanics to gases of molecules )ith &ermanent di&ole moments. also e4&laining the in5erse tem&erature de&endence of &aramagnetic susce&tibility. though later sho)n by ,ohr to be inconsistent )ith statistical mechanics obeying classical mechanics2

Galther (ernst (18#<$19<1! formulates his ?heat theorem.? stating that in the limit of absolute 6ero tem&erature. both the entro&y change and the heat ca&acity go to 6ero 1906 (subse7uently recogni6ed as the Third la) of thermodynamics!2 +ierre Geiss (18#5$19< ! creates general theory of &aramagnetic to ferromagnetic transitions2 3ndrei 3ndreye5ich Marko5 (185#$19%%! de5elo&s his theory of linked &robabilities2 Ainstein &ublishes a &a&er on the s&ecific heats of solids. deri5ing the la) of @ulong$+etit from atomic oscillators confined to 7uanti6ed 1907 energies. )orking out )ell )ith the recent theorem of (ernst2 +ierre Geiss e4&lains ferromagnetism by )ay of small domains of magnetic &olari6ation )ithin a 3lbert Ainstein material2 'ean$,a&tiste +errin calculates the a&&ro4imate si6e of a )ater molecule in e4&erimental tests of Ainstein=s )ork on ,ro)nian motion. further con5incing many of the atomic hy&othesis2 1908 +lanck begins formulating deri5ations of the black$body la) starting )ith an assum&tion of energy 7uanti6ation2 '' Thomson solidifies his ?&lum$&udding? model of the atom2 ;onstantin ;arathCodory &ublishes a &urely mathematical and a4iomatic account of thermodynamics2 1909 Ainstein corrects the blackbody deri5ation of +lanck. )hich )as technically only 5alid for hX\\kT2 'ean +errin e4&erimentally sho)s that the theoretical &redictions of Ainstein=s calculations 1910 on ,ro)nian motion are in agreement. becoming for many the best e4tant &roof of the e4istence of atoms2 Arnst Butherford (1871$1987! &ro&oses the 1911 nuclear model of the atom2

+lanck=s first &a&er e4&licitly 7uanti6ing the allo)ed radiation of oscillators in a blackbody2 3rnold Sommerfeld (18#8$1951! notes that elementary regions of &hase s&ace should be related to +lanck=s constant2 Etto Sackur (188 $191<! suggests the need for an absolute definition of entro&y. in order that 7uantum systems be taken into account (suggesting that &hase s&ace be di5ided into cells of 5olume h8!2 /adisla) (atanson &ro&oses that +lanck=s la) is the result of the indistinguishability of states of light 7uanta2 (iels Henrik @a5id ,ohr (1885$19#%! defends his dissertation and begins constructing atomic models )hich try to forge a connection )ith +lanck=s constant as a fundamental constant of 7uanti6ation2 Heike 9amerlingh Ennes (1858$19%#! e4&erimentally finds that mercury )ill become su&erconducti5e )hen cooled 5ery close to absolute 6ero and also disco5ers su&erfluidity2 +aul (188 $1988! and Tatiana 3fanass:e)a Ahrenfest (187#$19#<! &ublish a )ork gi5ing a detailed criticism of the ensemble theories in statistical mechanics2 (ernst=s e4&eriments )ith many substances. sho)s s&ecific heats going to 6ero at absolute 6ero in general. &ro5iding strong su&&ort for the ne) 7uantum theories2 +oincarC &ro5es that one can in5ert the +lanck distribution 5ia a Fourier transform and deduce that black$body radiation im&lies a 7uanti6ation of energy states2 Sackur and H Tetrode inde&endently sol5e ,olt6mann=s /a) to obtain S V (k ln-(%UmkT!(8J%!FJ(h80 ] (5J%!(k

1912

sho)ing a need for 7uanti6ation in classical gas la)s2 3rtur Bosenthal (1887$1959! and Michel +lancherel (1885$19#7! &ro5e that the ergodic hy&othesis is not 5iable for any dynamical system (o&ening the )ay to the 7uasi$ergodic hy&othesis and certain theorems in ergodic theory!2 1913 +aul Ahrenfest sho)s ho) to estimate rotational effects of a diatomic gas on s&ecific heat by re&lacing integrals )ith sums o5er discrete contributions from 7uanti6ed states2 The )ork is later refined by A Holm (1918! and by +lanck (1915!2 ,ohr=s article. ?En the ;onstitution of 3toms and Molecules2? Bobert 3ndre)s Millikan (18#8$1958!. in e4&eriments )ith the &hotoelectric effect. both confirms the theoretical )ork of Ainstein and confirms the 5alue of +lanck=s constant inde&endent of )ork done )ith blackbodies2 Ainstein &roduces a deri5ation of the black$body radiation distribution )ith the assum&tion of both s&ontaneous as )ell as stimulated emission of radiation by matter2 (ernst &redicts a state of degeneration can be reached for any gas at a lo) enough 1916 tem&erature. through e4tensions of his thermodynamic theory2 Sydney ;ha&man (1888$197 ! and @a5id Anskog (188<$19<7! de5elo& )ays to sol5e the Ma4)ell$,olt6mann trons&ort e7uations for a general class of inter$molecular force la)s2 >ilbert (e)ton /e)is (1875$19<#! de5ises a theory of molecular bonding based on atoms consisting of a series of concentric cubes. the edges of )hich may share electrons )ith other atoms2 (The idea is &o&ulari6ed. starting in 1919. by 1r5ing /angmuir (1881$1957!2! 1917 3rthur Stanley Addington (188%$19<<!

&ublishes a &a&er on radiati5e e7uilibrium. suggesting that the ioni6ation of atoms in stars2 Meghnad Saha (1898$195#! )rites. ?1oni6ation in the solar chromos&here.? analy6ing s&ectral lines of stars as atomic dissociation in the chromos&here. )here lo)er &ressures o5erride the lo)er tem&eratures of a star. also (in a second &a&er! &redicting that lo)er$tem&erature sun$s&ots )ill sho) lines of rubidium and 1920 cesium (an effect detected in 19%% by H ( Bussell!2 Gilhelm /en6 (1888$1957! models crystals by a lattice of di&olar atoms )hich feel nearest$ neighbor interactions. obtaining the ;urie la) for magneti6ation and suggestions its a&&lications to ferromagnetism2 /ouis Fictor +ierre Baymond duc de ,roglie (189%$1987! a&&lies Sackur=s techni7ue of 7uanti6ing &hase s&ace to deri5e the Gien distribution la) for energy density^ du V (8UhJc8! e4&($hXJkT! X8 dX 1922 ;harles @ar)in (1887$19#%! and Bal&h Ho)ard Fo)ler (1889$19<<! &ublish ?En the &artition of energy.? de5elo&ing a ne) a&&roach to e5aluating statistical &robabilities using com&le4 analysis and the method of stee&est descent2 /e)is=s *hermodynamics and the (ree Energy of Chemical $ubstances. bringing 1923 thermodynamics in closer contact )ith chemistry2 ('une! Satyendranath ,ose (189<$197<! sends Ainstein a co&y of his &a&er. containing a ne) deri5ation of +lanck=s radiation la) based &urely on &hoton statistics. after it )as re:ected by Philosophical "aga9ine2 Ainstein translates it into >erman and submits it to the :eitschrift f;r Physi2 for him )ith a recommendation2 1924 Ainstein &resents a &a&er sho)ing that in the Satyendranath ,ose limit of high tem&eratures. a gas of indistinguishable ,ose &articles a&&roaches the characteristics of a ,olt6mann gas2 de ,roglie )rites t)o &a&ers in the Comptes

rendus of the +aris 3cademy elaborating on a fundamental &rinci&le of )a5e$&article duality2 The )orks mature into his 19%5 doctoral thesis2 Ma4 ,orn (188%$197 !. Gerner 9arl Heisenberg (19 1$197#!. and +ascual 'ordan formulate 7uantum mechanics based on the mathematics of matri4 algebra2 Ainstein. citing )orks by ,ose and de ,roglie. suggests that the analogy bet)een 7uantum gases and molecular gases are com&lete. and that both &hotons and molecules ha5e both &article and )a5e characteristics2 He also &oints out that molecules at lo) tem&eratures cannot be considered inde&endent entities. e5en in the absence of intermolecular forces. and )ill form a 7uantum condensate2 Samuel 3 >oudsmit=s (19 %$1979! hy&othesis an e4tra degree of freedom to electrons termed ?s&in? due to the mathematical similarity to 1925 classical s&in2 /ater. )ith >eorge Augene Qhlenbeck (19 $1988!. half$integer 7uantum numbers are introduced in the theory of the hydrogen atom2 Golfgang +auli (19 $1958! formulates the e4clusion &rinci&le for the electron. accounting for a number of chemical &ro&erties in atoms and molecules2 +lanck de5ises a ne) deri5ation of thermodynamic formulas for ,olt6mann gases using the formulations. 6 V e4&($_JkT!. T V 6( J (` Arnst 1sing (19 $!. follo)ing the in5estigations of /en6. &ublishes a &a&er dealing )ith magnetic models 5ia di&olar atomic interactions2 ,orn introduces into 7uantum mechanics his &robability inter&retation of interactions2 1926 Anrico Fermi (19 1$195<! deri5es the statistical &ro&erties of gases )hich obey the +auli e4clusion &rinci&le2 +aul @irac

Ar)in Budolf 'osef 3le4ander SchrMdinger (1887$19#1! de5elo&es a second formulation of 7uantum theory in terms of )a5e mechanics inde&endently2 +aul 3drien Maurice @irac (19 %$198<! relates the symmetry of 7uantum mechanical )a5e functions to the statistics of ,ose. Ainstein and Fermi2 He also deri5es the +lanck distribution from first &rinci&les2 Addington=s *he .nternal Constitution of the $tars. relating the radiation &ressure of stars to their luminosity2 Fo)ler sho)s that some of the &ro&erties of )hite d)arf stars could be accounted for by treating them as (Fermi! 7uantum degenerate gases. being an early e4am&le of 7uantum statistics e4&laining the &ro&erties of large macrosco&ic ob:ects2 Bobert Hutchings >oddard launches the first rocket. using li7uid fuel and reaching a height of 18< feet and # miles &er hour2 'ohn 5on (eumann (19 8$1957! formulates a fully 7uantum mechanical generali6ation of statistical mechanics2 ,ohr &ronounces his notion of com&limentarity in 7uantum theory2 Heisenberg formulates the uncertainty &rinci&le of 7uantum mechanics2 1927 @irac and +auli inde&endently &ro&ose to model metals )ith molecules obeying Fermi$@irac statistics2 +auli e4&lains the &aramagnetic susce&tibility of metals using electron s&in and the e4clusion &rinci&le2 Gillem Hendrik 9eesom (187#$195#! and M Golfke find discontinuities in se5eral &ro&erties of helium at 5ery lo) tem&eratures and suggest

that it may be due to a &hase change. calling them helium 1 and 112 Galter Heitler (19 <$! and Frit6 /ondon (19 $ 195<! a&&ly Heisenberg=s resonance theory to the co5alent molecular bond bet)een t)o hydrogen atoms. sho)ing stability to a function of electron s&ins. and arguing against the stability of such helium bonds2 Sommerfeld treats electrons in metals as a degenerate Fermi gas using the ne) techni7ues of 7uantum theory2 @irac comes u& )ith a relati5istic 7uantum mechanical )a5e e7uation for the electron2 Feli4 ,loch (19 5$! suggests a theory of metals based on electrons layered &eriodic &ositi5e 1928 &otentials )hich can sustain small dis&lacements )hich lead to resistance 5ia scattering of electrons by the lattice 5ibrations2 'ohn ;larke Slater (19 $197#! is the first to study the 7uantum mechanical treatment of the molecular formation of rare gases (helium!2 /inus +auling (19 1$! a&&lies the Heitler$ /ondon treatment to chemical bonds2 Admund ;lifton Stoner (1899$19#8!. using (s&ecial! relati5istic formulas for electron energies. suggests that beyond a certain density in stars the out)ard degenerate gas &ressure )ould no longer sustain itself against the in)ard 1929 gra5itational attraction (though he did not 'ohn 5on (eumann s&eculate about )hat )ould then ha&&en!2 Slater formulates a multi$electron )a5e function )hich can generally satisfy the +auli e4clusion &rinci&le2 @isco5ery of the lambda &oint of helium at 1930 )hich it becomes a su&erfluid (so$named in 19<1! at %2%O92 >eorge @a5id ,irkhoff (188<$19<<! &ro5es the general ergodic theoreom2 1931 +auling &ublishes his )ork on chemical bonds.

&ro5ing the stability of such bonds2 3leksandr Lako5le5ich 9hinchin (189<$1959!. 1932 in )ork through 198<. founds the modern study of stationary random &rocesses2 Galther Meissner (188%$197<! and B Echsenfeld re&ort that metals cooled belo) their 1933 su&erconducting tem&eratures in a magnetic field com&letely e4&el all lines of magnetic induction. becoming a &erfect diamagnet2 Gilliam /a)rence ,ragg (189 $1971! and Gilliams formulates an 1sing model for &aramagnetic to ferromagnetic transitions2 1934 ;ornelius 'acobus >orter (19 7$198 ! and Hendrik ,ruygt >erhard ;asimir (19 9$! form an analysis of the e4&ulsion of magnetic fields in su&erconducting metals in a magnetic field2 Gilliam Francis >iau7ue achie5es a tem&erature of only 21O9 for helium using a magnetic tra& to slo) the motion of the molecules2 /e5 @a5ido5ich /andau (19 8$19#8! &ublishes his &henomenological mean$field treatment for &hase transitions2 Subrahmanyan ;handrasekhar (191 $1995! deri5es the ma4imum mass formula for a degenerate Fermi gas2 1935 Frit6 Golfgang /ondon (19 $195<! and brother Hein6 /ondon )ork on a su&erconducti5ity theory of macrosco&ic ob:ects using classical electrodynamical theory and some additional assum&tions2 /e5 /andau Hans ,ethe (19 #$! im&ro5es on ,ragg$ Gilliams theory by adding short$range atomic interactions2 Ad)ard 3rmand >uggenhaim (19 1$! de5elo&s a theory of li7uid solutions using nearest$ neighbor rules. into )hat is no) callod the ?7uasi$chemical? (K;! method2 'ose&h Ad)ard Mayer (19 <$! (see links! and 1936 Sally F Harrison (1918$!. along )ith Maria >oe&&ert$Mayer (19 #$197%!. initiate the

modern theory of gas condensation. in )ork through 1988. by use of ?cluster integrals? re&resenting the interactions of many molecules to find the 5irial coefficients of intermolecular forces2 +eter /eonido5ich 9a&it6a (189<$a! determines that helium 11 has a 5iscosity of about 15 times smaller than helium 1 and terms the &henomena ?su&erfluidity2? 3t almost the same time. 'ohn Frank 3llen (19 8$! and 3 @ 1937 Miscner disco5er the same effect inde&endently (&ublishing 19 days later!2 'ohn Ad)ard /eonard$'ones (189<$195<! and 3 F @e5onshire formulate (through =89! the ?#$1% &otential? for intermolecular forces2 ;laude Al)ood Shannon (191#$! &ublishes % $ymbolic %nalysis of -elay and $witching Circuits. instigating the study of information theory and gi5ing a systematic )ay of 1938 mathematically treating noise2 /ondon=s theoretical )ork on li7uid helium and ,ose$Ainstein condensation2 G ;onyer Herring calculates bulk &ro&erties of 1939 materials from 7uantum &rinci&les. s&ecifically ;laude Shannon e4&laining ho) beryllium acts as a metal2 Fo)ler and >uggenheim e4tend the K; method. 1940 a&&lying it to models )hich take into account longer$range interactions2 /ars Ensager (19 8$197#! (also see links! gi5es his solution to the t)o$dimensional /en6$1sing model. sho)ing that a &hase transition )ill 1942 occur2 ?-10t is the first e act solution of a nontri5ial &roblem in statistical mechanics. in )hich inter&article forces are taken into account )ithout a&&ro4imation? (S> ,rush!2 A5genni Mikhailo5ich /ifshit6 (1915$1985! sho)s that ?second$sound? )a5es in su&erfluids 1944 can be detected as tem&erature de5iations2 The effect is e4&erimentally confirmed shortly there after by F +eshko52 (ikolai (ikolae5ich ,ogolyubo5 (19 9$! )rites his Problems of ,ynamical *heory in $tatistical 1946 Physics2 He )orks on a generali6ation of the ,olt6mann e7uation. using the time$re5ersal

in5ariant /iou5ille e7uation. further clarifying the internal structure of statistical mechanics2 9hinchin refines ,olt6mann=s theorem to read that. as a function of the si6e of an ensembles. the time a5erage of a system becomes arbitrary close to the canonical a5erage2 Bichard 3 Egg. 'r suggests that &airs of electrons beha5e as bosons. and that su&erconducti5ity may be thought of as a ,ose$ Ainstein condensate2 (The idea is ignored until about 195<2! Shannon=s ma:or &ublication on information 1948 theory and symbolic logic. % "athematical *heory of Communication2 Herbert FrMlich (19 5$! suggests that &honon interactions bet)een electrons may be the basis 1950 of an e4&lanation of su&erconducti5ity. gi5ing one of the first uses of 7uantum field theory to statistical mechanics2 Bichard +hilli&s Feynman (1918$1988! begins his )ork on the theory of su&erconducting 1953 helium using his &ath$integral a&&roach. further clarifying ho) &re5ious theoretical attem&ts ha5e )orked andJor failed2 Ar)in Gilhelm Mueller=s (1911$1977! field ion microsco&e is the first instrument to allo) imaging of indi5idual atoms2 G (oll &ro5es that by taking the a&&ro&riate &hase a5erages. any molecular system modelled by statistical mechanics can be sho)n to satisfy e4actly the e7ui5alent field e7uations for a continuous material. thus theoretically sho)ing the e7ui5alence of the t)o a&&roaches2 /eon ;oo&er (198 $!. 'ohn ,ardeen (19 8$! and 'ohn Bobert Schrieffer (1981$! form a many$ 1956 electron theory of su&erconduction )hich gi5es good agreement )ith e4&eriment and &roduces the Meissner effect2 9hinchin=s book. "athematical (oundations of .nformation *heory2 1957 ,erni 'ulian 3lder (19%5$! and Thomas A5erett Gain)right (19%7$! com&utationally disco5er 1955

the hard$s&here &hase transition2 >eorge 3llen ,aker. 'r (198%$! found a method of determining the singularities at the critical 1961 &oint 5ia series e4&ansions of /en6$1sing models2 ,en:amin Gidom=s (19%7$! )ork on surface 1965 tension theory using a modified 5an der Gaals theory2 3lder and Gain)right disco5er 5orte4 diffusion 1968 in li7uids2 9enneth Gilson (198#$!. e4tending earlier )ork by /eo 9adanoff (in 19##!. a&&lies the 1971 techni7ue of the renormali6ation grou& to study of scaling la)s for &hase transition theory2 Michel Allis Fisher (1981$! and Gidom sho) that the /en6$1sing model generali6ed to arbitrary dimensions dis&lay a continuous 1972 transition bet)een classical and non$classical la)s. )here correlation lengths tend to)ard infinity at critical &oints2 Heinrich Bohrer and >erd ,innig de5elo& the 1980 scanning tunnelling microsco&e. allo)ing for imaging of atoms embedded on surfaces2 Sources: ,rush. Ste&hen >. Statistical +hysics and the 3tomic Theory of Matter From ,oyle and (e)ton to /andau and Ensager (out of &rint! ,unch. ,ryan b Hellemans. 3le4ander. The Timetables of Science Aisberg. B and Besnick. B. Kuantum +hysics. %nd ed. 1985 Flamm. @ieter. ?History and outlook of statistical &hysics.? &hysicsJ98 8 5. < March. 1998 Flamm. @ieter. ?/ud)ig ,olt6mann $ 3 +ioneer of Modern +hysics.? &hysicsJ971 7. 7 Ectober. 1997 9uhn. Thomas S. ,lack$,ody Theory and the Kuantum @iscontinuity. 189<$191% Mendo6a. A. ?3 Sketch for a History of Aarly thermodynamics.? Physics *oday. February 19#1. & 8% Mendo6a. A. ?3 Sketch for a History of the 9inetic Theory of >ases.? Physics *oday. March 19#1 Mendelssohn. 9. The Kuest for 3bsolute Tero (out of &rint! Moore. Galter. SchrMdinger^ /ife and Thought Truesdell. ;. Assays in the History of Mechanics (out of &rint! 3nd the great MacTutor History of Mathematics 3rchi5e Links: The +neumatics of Hero of 3le4andria +aul ;harles)orth=s History of Science &ages ;hris Hillman=s Antro&y in the +hysical Sciences ,iogra&hies of chemists and some &hysicists a5ailable at the History of ;hemistry &age 3bout Tem&erature by +ro:ect Skymath

Fahrenheit=s +a&er of 17%< The Erigin of the ;elsius Tem&erature Scale Ga5e Mechanics^ /ouis de ,roglie The /ars Ensager 3rchi5e Begister of 'ose&h Mayer=s +a&ers otes: Gould like to get into more history of &robability theory as it a&&lied to these histories2

(eed to read more )orks by Mr Truesdell (the abo5e book is great!2 Filling out more &re$17th century material )ould really enhance the &ers&ecti5e of the timeline2 ;ertain mathematico$conce&tual issues e5entually ha5e to be dealt )ith2 1f there=s anything that you feel should be address. or addressed more fully. or if there are references )hich you=d like to suggest 1 look into. &lease feel free to email the author at hy&er:effcmac2com2