Table Of ContentContents of the section:
History of thermal analysis and ICTAC and CALCON societies
THERMAL SCIENCE AND ANALYSIS:
TERMS CONNOTATION, HISTORY, DEVELOPMENT, AND THE ROLE OF
PERSONALITIES
Jaroslav Šesták
Journal of Thermal Analysis and Calorimetry - 2013, DOI 10.1007/s10973-
012-2848-7
HISTORICAL ROOTS AND DEVELOPMENT OF THERMAL
ANALYSIS AND CALORIMETRY,
Jaroslav Šesták, Pavel Hubík, Jiří J Mareš
Book chapter
SOME HISTORICAL ASPECTS OF THERMAL ANALYSIS:
ORIGINS OF TERMANAL, CalCon AND ICTA
Jaroslav Šesták
TERMANAL 2005 - published in Bratislava
FROM CALORIC TO STATHMOGRAPH AND POLAROGRAPHY
Jaroslav Šesták, Jiří J Mareš
Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007)
CZECHOSLOVAK FOOTPRINTS IN THE DEVELOPMENT OF
METHODS OF THERMOMETRY, CALORIMETRY AND THERMAL
ANALYSIS
Pavel Holba, Jaroslav Šesták
Ceramics – Silikáty (Prague) 56 (2) 159-167 (2012)
JThermAnalCalorim
DOI10.1007/s10973-012-2848-7
Thermal science and analysis
Terms connotation, history, development, and the role of personalities
J. Sˇesta´k
Received:4September2012/Accepted:26November2012
(cid:2)Akade´miaiKiado´,Budapest,Hungary2012
Abstract History of thermoscopy and thermometry is principle on which temperature measurement is based and
reviewed showing the role of temperature degrees includ- evolved as a part of the development of thermal science.
ing the forgotten logarithmic scale. The importance of W
natural laws of energy, motion, least action, and thermal
efficiency is discussed. The meaning of idiomatic terms— ThermoscEope, thermometer, thermometry,
thermal physics, thermodynamics, thermostatics, thermot- and tIemperature scales
ics, and thermal analysis—is specified andrevealed within V
two parallel developed branches of thermal science. Item- EThe ancient Greek discerned the expansion of air by heat
ized 105 references with titles. long time ago. The earliest writings concerned that the
R
phenomena were the Works of Philo of Byzantium and
Keywords Thermometry (cid:2) Thermodynamics (cid:2) Heron of Alexandria (II Century B.C.). The Greeks made
R
Thermostatics (cid:2) Thermotics (cid:2) Thermal physics (cid:2) simplethermometersinthefirstcenturyBC, butthere was
Natural laws (cid:2) Temperature scales (cid:2) H.Suga (cid:2) TO.Ozawa no way to quantify heat with hot and cold still following
the Aristotelian tradition of being treated as fundamental
F
qualities of the universe. The ideas of Aristotle were
Introduction adopted by Galen (A.D. 130–200), who was the first
describing the heat and cold by a number about fifteen
A plentiful literature about thermal science [1–5] and its hundred years ago. And, the word temperature originated
precedent thermometry [6–11], as well as historic thermal from ‘‘temper,’’ after Galen determined the ‘‘complexion’’
analysis[12–21],isavailablethroughvarioussourceseasy of a person by the proportion in which four human
accessibleevenfrominternet.Therefore,wedonotwantto ‘‘qualities’’ were tempered [6–8]. It is known that by the
repeatavailablefigures,butprefermentioningsomehidden 16th Century, knowledge of the ‘‘weatherglass’’ (the other
aspects responsive to the record of accessible citations, common name for thermoscope) became widely spread
whilenotclaimingcompleteness.Allhistoryrecordsreach among educated people either due to the new edition of
back to the early concept of hotness [22] as the scientific Heron’s papers or upon the accessibility of excerpts of
Arabian alchemistic manuscripts.
One of the first modern-times considerations on active
principles(heatandcold)actingonapassivemattercanbe
DedicatedtoProf.HiroshiSugaandProf.TakeoOzawa(recently
found in the treatise published in 1563 by Italian Bernar-
passedaway),pioneersoftheadvancedthermalscienceandthe
dino Telesio (1509–1588) and perceived by Francesco
honorarychairmenoftheICTAC’15inOsaka’2012.
Patricio (1529–1597) and Giordano Bruno (1548–1600).
J.Sˇesta´k(&) Thefirstairthermoscopeappearedin1594throughGalileo
NewTechnologies—ResearchCentreoftheWestbohemian
Galilei (1564–1542), but the Englishman Robert Fludd
Region,UniversityofWestBohemiainPilsen(NTC-ZCˇU),
(1574–1651) was also regarded as one independent
Universitn´ı8,30114Plzenˇ,CzechRepublic
e-mail:[email protected] inventor around 1617. Yet, another originator was
123
J.Sˇesta´k
indicated Cornelis J. Drebbel (1572–1633) who made a of the concept of temperature are familiar and thus not
two-bulbedJ-shapedthermometerbetween1598and1622. herewith reiterated [18–22, 26].
In1626,thefactualword‘‘thermometer’’wasinitiallyused Worth of a special attention would be 1848 Thomson’s
todescribethermoscopeequippedwithascalemarkedwith approachbasedonthermalefficiencyg(originated[29,30]
eight degrees by Jean Leurechon (1591–1670) in his book byNicolasLeonardSadiCarnot(1796–1832))introducing
[23]. Shortly after, the world-known Czech educator Jan thus a logarithmic temperature scale, h, in the form of
Amos Comenius (1592–1670) inserted reflections on the dh & dT/T. After integration, it follows that h = const
1
roleofheatandcoldinnatureintohisbookwork[24]and lnT ? const ,wherebothconstantscanbedeterminedusing
2
then,in1659,publishedanotherworthnotingbook[25]on the traditionally fixed points of the melting and boiling of
the nature of heat and cold. In 1665, Christian Huygens water.Thismorenaturalscale,however,woulddramatically
(1629–1695) had a brilliant idea to use the melting and changethecustomaryconceptofthermodynamics[26,28]
boiling points of water as a standard gauge. easingtheinterpretationofthethirdlawofthermodynamics
The first quantitative thermal law expressingthe depen- replacing the traditional zero temperature by infinity (T =
dence of temperature of a cooling body (expressed in 8 -?). However, the conventional degree of freedom,
degrees)onthetimewaspublishedin1701byIsaacNewton *1/2 kT, would revolutionize to embarrassing proportion-
(1643–1727).Suchaforgottenattempttoputhightemper- ality,T * exp{(h-const )/const },etc.Ontheotherhand,
2 1
aturesonamathematicalscaledescribedathermometeron the simple interpretation of heat conduction and the cus-
thebasisofoilandcalibrateditbytaking‘‘theheatoftheair tomaryevaluationofefficiencyforsteamenginesnecessitate
inwinterwhenwaterbeginstofreeze’’as0and‘‘bloodheat’’ thetemperaturetobehavelikethepotentialofaheatedfluid
as12onthisscalewaterboilsat34.Themeltingpointsof andthetraditionallinearscale,equivalenttothecontempo-
alloysweredeterminedbyanextrapolationandlogarithmic rary Kelvin’s inWternational scale, manage to survive as the
temperature scale that was proposed for high experimental most opportune one. There can be seen various attempts
temperatures on the basis of the equation, h = 12{2(x-1)}, introducinEg so far inconvenient thermodynamics concepts
wherehwasthetemperatureinunitsoftheabovescaleand basedI,forexampleontheCarnotuseofcaloric[31,32].
xrepresentedthelogarithmictemperature[26–28]. V
One of the earliest challenges at calibration and stan- E
dardizationbetweenthermometerswasattemptedin1663by Thermal physics, thermodynamics, thermotics,
R
themembersofRoyalSocietyinLondon,whoagreedtouse and thermal analysis
one of several thermometers made by Robert H ooke
R
(1635–1703) as the standard so that the reading of others Early attempts to create a common scientific language can
could be adjusted to it. Non-Euclidean matOhematician be associated with the early work by Comenius emerging
JohannH.Lambert(1728–1777)revealedinhislessfamiliar from his effort to portray heat [25]. However, equally
F
book‘‘Pyrometria’’asmanyasnineteentemperaturescales. important was his challenge to articulate his own idea of
Differentialairthermometerwasinvented,almostsimulta- universallanguage[33]anditsrelationtotheencyclopedic
neously, by John Leslie (1766–1832) of Edinburgh and by knowledge concept of the ‘‘pansophia’’ having a profound
Benjamin Thompson, Count Rumford (1753–1814) and influence on the discussion on an exploitation of such a
consequentlyJamesClerkMaxwell(1831–1879)recognized universal language in England. Inquisitively it resulted to
that for thermometry (to be a logically closed system) it is his invitation offered by John Winthrop (1588–1649) a
necessarytoaddaconceptofthermalequilibrium. governor of Massachusetts to become a rector of a new
Daniel G. Fahrenheit (1686–1736) proposed in 1724 a US university founded by preacher John Harvard. Later,
temperature scale of 100 degrees from 0 (cid:3)F (at the tem- the Comenius younger follower Gottfried W. Leibnitz
peratureofmixtureofammoniumchloride,water,andice) (1648–1716) used his idea of ‘‘lingua catholica’’ in an
and 100 (cid:3)F at the human body temperature and invented attempt to formulate mathematical, scientific, and meta-
thefirstmercurythermometer.Ayearlater,Joseph-Nicolas physical concepts more effective. He introduced ‘‘charac-
Delisle (1688–1768) introduced an exotic scale with teristica universali’’ hopeful to create a language usable
240degrees,whichwaslater(1738)modifiedandadjusted within the framework of a universal logical calculation
to 150(cid:3)D corresponding to the melting point of water and [34, 35] or ‘‘calculus ratiocinator’’ convincingly affected
to0(cid:3)Datboilingpointofwater(240(cid:3)D = 60 (cid:3)C),andthis by Rene Descartes (1596–1650) through his correspon-
scale was being used in Russia for the whole hundred dence with Comenius [21]. Descartes [36] became
years. The story of different scales, from Fahrenheit and responsiblefortheformulationofconservationlawapplied
Celsius degrees to the now-forgotten Rankine, Rømer, to the amount of movement (momentum-mv) later cor-
Desliste, Reaumur, Lime, or Amontons scales, and the rectedbyLeibnitzas‘‘visviva’’(mv2).Ontheotherhand,
historyofthegradualscientificthenpopularunderstanding it is worth mentioning that the law of conservation was
123
Developmentandtheroleofpersonalities
foreseen by another Czech mastermind Jan Marcus Marci transfer 1822 [55] and Lars Onsager (1903–1976) [56]
(1595–1667) [37]. whiledepictingtheequationsofirreversibleprocesses(later
Anothersignificantimpacttogeneralizedunderstandingof rooting the field of extended thermodynamics [57, 58]).
nature was brought by Pierre de Fermat (1601–1655) when Sofar,theenduringtermofthermodynamicssubsiststhe
introducingtheprincipleofleasttime[38]:‘‘theNatureactsvia energetic concepts [59–63] of temperature and heat based
the easiest and the most accessible way reached within the upontheGreekword‘‘therme’’(= heat);however,itisworth
shortesttime.’’AcenturylateritwasresumedbyPierre-Louis notingthatitalsoinvolvesaGreekconcoctionforthemotive
M.deMaupertuis(1698–1759)whoin1744envisagedtheleast powerofheat,i.e.,thermodynamicsfactuallymeans‘‘heat-
actionpremisenoting[39]:‘‘whensomechangetakesplacein enginescience.’’Itisconcernedwithheatanditsrelationto
nature, the quantity of action necessary for the change is the otherformsofenergyandworkdefiningmacroscopicvari-
smallest possible.’’ The quantity of action is the product ableswhichdescribeaveragepropertiesofmaterialbodies,
obtainedbymultiplyingthemassofthebodies(m)withtheir and explains how they are related and by which laws they
velocity(v)andthedistancetravelled(k),whichinterestingly change with equilibrating [59–71]. There are many grand-
correlateswiththePlanckconstant(cid:2)h(=mvk).Itrecentlybecame fatherssuchasaUKprofessorEdwardArmandGuggenheim
thebasistoexplaintheinbornself-periodicityofmanynatural (1901–1970)[3,69].
processes[40–42].Thesefundamentallawsofmotionbecame Yet,moregeneralterms‘‘‘thermalscience‘‘or‘‘science
equallycrucialastheCarnottemperaturelimitsforthethermal ofheat’’[2]sustain for ashared studyof thermodynamics,
efficiencyofheatengines[20,29,31,32]. fluid mechanics, heat transfer, thermal investigation,
The decisive experimental studies, thanks to which tem- combustion, and thermokinetics while more restricted
perature became a clearly measurable physical quantity, terms‘‘thermalphysics’’[44,72–74]involvethecombined
contributed the formation of a contemporary discipline lan- studyofthermodW ynamics,statisticalmechanics,andkinetic
guage.Inthe1840s,athermodynamicdiscoursewasworked theories providing thus an umbrella subject which is typi-
up by Henri Victor Regnault (1810–1878) whose attitude, cally desigEned to provide a general introduction toeach of
however, turned out long after Joseph Black (1728–1799) core hIeat-related subjects.
[15,17,26,43]distinguishingbetweenthespecificheat(heat TVhereisyetanotheramoreunfamiliarterm‘‘thermotics’’
capacity) and the latent heat [19, 30]. Curiously, his less E(aliketheterm‘‘mathematics’’)stayingalsobehindthegen-
known correspondence [21] with James Watt (1736–1819, eralizedscienceofheat(andalsobasedonitsGreekorigin),
R
whoinventedsteamenginein1776)remainedunmentioned. apparentlyusedasearlyasin1837[75].In1967,American
Consequently, Pierre Simon de Laplace (1749–1827) and physical chemist Ralph Tykodi (1925) made an attempt to
R
AntoineLavoisier(1743–1794)performedin1786theirfirst revivethermotics[76,77]asanidiomwhich,hesaid,should
calorimetricmeasurements[25,44–50].Yet,afterOthedetailed beequalinusageto1946versionof‘‘energetics’’providedby
results of 1842 Regnault’s dilatometric and heat capacity the Danish physical chemist Johannes Nicolaus Brønsted
F
measurements, and together with 1824 theorem of Carnot (1879–1947)[59,60].Inthisview,thermoticssubsistather-
[29,32]andits1834interpretationbyBenoit-PauleE.Cla- malsciencecomprisedofthreesub-branches:‘‘thermo-stat-
peyron(1799–1864)itprovidedthebasisforthe1848intro- ics’’pertainingtotheordinaryclassicalequilibriumaspectsof
ducing of absolute temperature scale by William Thomson heat,‘‘thermo-dynamics’’relevanttothoseaspectsforwhich
(baron Kelvin of Larges) (1824–1907) and for the factual timevariationisimportant,and‘‘thermo-staedics’’concern-
inceptionofthermodynamic‘‘language’’[15,51–53]asanew ingtheaspectsthataretemporallysteadyorstationary.The
science, not forgetting the work of Josiah Willard Gibbs focusoflattertermmaybeseenmoresuitabletoenvelopthe
(1839–1903)[15,21,51].Literally,thisnewsciencewouldbe fieldof‘‘thermalanalysis’’[1,14–21,26,78]thetruemeaning
optimallyassociablewiththeterm‘‘thermostatics’’bywayof ofwhichwasneverappropriatelylocatedwithinthespheresof
thermallyequilibratedstatesanddevelopedthroughtheCarnot, thermalsciences[2,26,30].
Clapeyron,Clausius,and/orGibbsworkasabranchof‘‘dis- The entire term thermal analysis was coined by Gustav
sipationlesswork’’understandingofthescienceofheat[2,26]. Heinrich J.A. Tammann, (1861–1938) [79, 80], further
Complementary approach involving the concept of accreditedin[12,13]andthenparticularizedinourprevious
‘‘workless dissipation’’ comprise, however, temperature papers [2, 14, 17–19]. Seemingly the inherent thermoana-
gradients(existingeverywhereandinthermostaticconcepts lytical theory is historically based [12, 81] on equilibrated
oftenneglectedduetonecessarysimplifications)whichwas (i.e.,thermostatic)statesoftenomittingthenon-equilibrium
developed in the course of studies by Newton, Fourier, (flux)characterofitsmeasurements,whichseemsbeamost
Stokesand/orOnsagerframingthusthenewfieldof‘‘true’’ crucialsourceofinaccuracyintheexistingtheoreticevalu-
thermodynamicsinvolvingirreversibleprocesses[1–3,54]. ationofDTA(= differentialthermalanalysis)[2,13]where
Most remarkable personalities became Joseph Baptiste thermal gradients are habitually not incorporated in the
Fourier (1768–1830) while publishing the laws of heat evaluation(withfewexceptions[82–85]).
123
J.Sˇesta´k
A tribute paid to Japanese personalities: Hiroshi Suga the honor to publish joint studies [89–91] being also the
and Takeo Ozawa guarantee of the 1996 foundation of the School of Energy
Science at the Kyoto University. Both of these Japanese
The field of thermal analysis became a starting point for famous persons are accountable for the augmentation of
expanded cooperative studies under the umbrella of the thermoanalytical societies as well as the development of
InternationalConfederation(ICTA/ICTAC)[86,87]which the theory of processes carried out under non-isothermal
benefits from its over 40 years running established under conditions. Though the work of Ozawa (e.g., [92–99])
the profitable impact of many foremost personalities [88] received a wider recognition (H-index = 81, total citation
suchasthedistinguishedcelebritiesofHiroshiSuga(1930) record = 38,580 with 2,316 feedback for his best cited
and Takeo Ozawa (1932–2012) with whom the author has paper) because attentive to a more fashionable subject of
thermoanalyticalkinetics,theworkofSuga(H-index = 40,
totalcitationrecord = 5,582with316feedbackforhisbest
citedpaper)envelopedamorefundamentalsubjectofgen-
eralized behavior and characterization of noncrystalline
solids (e.g., [91, 100–105]). Their worldwide impact has
positively affected the international cooperation, which is
well illustrated by the group photos (above Figs. 1 and 2).
Weallareverygratefulfortheirfruitfulguidanceandaffable
disseminationofknowledge.
AcknowledgemenWts The results were developed within the CEN-
TEMproject,reg.no.CZ.1.05/2.1.00/03.0088thatisco-fundedfrom
theERDFwithintheOPRDIprogramoftheMinistryofEducation,
E
Youth and Sports. The author feels also indebted to his scientific
friendsI, coworkers, and uppermost thermodynamists Pavel Holba
(PilseVn),Gyo¨rgyLiptay(Budapest),Jiri.J.Maresˇ(Prague),Jirˇ´ıMa´lek
Fig.1 Thephotofromthe28thconferenceoftheJapanesesocietyon
(Pardubice),NobuyoshiKoga(Hiroshima),lateGermanK.Moiseev
calorimetryandthermalanalysis(JSCTA)inTokyo(WasedaUniver- E
(Jekateˇrinburg),IngoMu¨ller(Berlin),lateTooruAtake(Tokyo),late
sity,1992)shows(fromleft)M.Taniguchi(Japan),lateC.J.Keattch
(UK),lateR.Otsuka(Japan),S.St.J.Warne(Australia,formerICTAR IvoProks(Bratislava),Vladim´ırSˇatava(Prague),PeterSˇimon(Bra-
president),H.Suga(Japan),J.Sˇesta´k(Czechoslovakia),andH.Tanaka tislava), late Bernhard Wunderlich (Knoxville), Harumi Yokokawa
(Tsukuba),andShmuelYariv(Jerusalem).Theauthor,however,was
(Japan).TheregularJSCTAconferencesstartedinOsaka1964under
R disappointedthatthistributelecturewassuspendedbytheconference
theorganizationofProf.S.Sekiwhobecamethefirstpresidentwhenthe
secretary (Riko Ozao) out from the Commemorate Special Session
JSCTA was officially established in 1973. Since thenO, the JSCTA
(creditingtheconferencehonorarychairmen)togeneralsessiononly.
journal NETSU SOKUTEI has been published periodically and the
Sino-JapaneseconferencesrepetitivelyorganizedtoFo
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21 Historical roots and development of thermal
analysis and calorimetry
Jaroslav Šesták1, Pavel Hubík2, Jiří J. Mareš2
1New Technology Research Centre, University of West Bohemia, Univerzitní 8, CZ-30614
Plzeň, Czech Republic
2Institute of Physics ASCR, v.v.i., Cukrovarnická 10, 162 00 Praha 6, Czech Republic
e-mail: [email protected]
21.1 Historical aspects of thermal studies, origins of caloric
Apparently, the first person which used a thought experiment of continuous heat-
ing and cooling of an illustrative body was curiously the Czech thinker and Bo-
hemian educator [1], latter refugee Johann Amos Comenius (Jan Amos Komenský,
1592-1670) when trying to envisage the properties of substances. In his “Physicae
Synopsis”, which he finished in 1629 and published first in Leipzig in 1633, he
showed the importance of hotness and coldness in all natural processes. Heat (or
better fire) is considered as the cause of all motions of things. The expansion of
substances and the increasing the space they occupy is caused by their dilution with
heat. By the influence of cold the substance gains in density and shrinks: the con-
densation of vapor to liquid water is given as an example. Comenius also deter-
mined, though very inaccurately, the volume increase in the gas phase caused by the
evaporation of a unit volume of liquid water. In Amsterdam in 1659 he published a
focal but rather unfamiliar treatise on the principles of heat and cold [2], which
was probably inspired by the works of the Italian philosopher Bernardino Tele-
sius. The third chapter of this Comenius' book was devoted to the description of
the influence of temperature changes on the properties of substances. The aim and
principles of thermal analysis were literally given in the first paragraph of this
chapter: citing the English translation [3-5]: "In order to observe clearly the effects
of heat and cold, we must take a visible object and observe its changes occurring
during its heating and subsequent cooling so that the effects of heat and cold be-
come apparent to our senses." In the following 19 paragraphs of this chapter Com-
enius gave a rather systematic description (and also a partially correct interpreta-
tion) of the effects of continuous heating and cooling of water and air, and also
stressed the reversibility of processes such as, for example, evaporation and con-
densation, etc., anticipating somehow the concept of latent heat. Comenius con-
cludes this chapter as follows: "All shows therefore that both heat and cold are a
motion, which had to be proved." In the following chapter Comenius described
2
and almost correctly explained the function of a thermoscope (‘vitrum caldarium’)
and introduced his own qualitative scale with three degrees of heat above and three
degrees of cold below the ambient temperature launching thus a concept of “calor-
ic”.
Nonetheless, it is difficult to trace [1,3-6] and thus hard to say if it was possible
(though likely) to disseminate the Comenius idea of caloric from Amsterdam
(when he mostly lived and also died) to Scotland where a century later a new sub-
stance, or better a matter of fire, likewise called caloric (or caloricum), was tho-
roughly introduced by Joseph Black (1728-1799) [7] and his student Irvine. Un-
fortunately, Black published almost nothing in his own lifetime [5,8] and his atti-
tude was mostly reconstructed from contemporary comments and essays published
after his death.
Caloric [1,7,9-11] was originally seen as an imponderable element with its own
properties. It was assumed, e.g., that caloric creeps between the constituent parts
of a substance causing its expansion. Black also supposed that heat (caloric) was
absorbed by a body during melting or vaporization, simply because at the melting
or boiling points sudden changes took place in the ability of the body to accumu-
late heat (~1761). In this connection, he introduced the term ‘latent heat’ which
meant the absorption of heat as the consequence of the change of state. Irvine ac-
counted that the relative quantities of heat contained in equal weights of different
substances at any given temperature (i.e., their ‘absolute heats’) were proportional
to their ‘capacities’ at that temperature and it is worth noting that the term ‘capaci-
ty’ was used by both Black and later also Irvine to indicate specific heats [7,9-11].
Black’s elegant explanation of latent heat to the young James Watts (1736-
1819) became the source of the invention of the businesslike steam engine as well
as the inspiration for the first research in theory related to the novel domain of
thermochemistry, which searched for general laws that linked heat, with changes
of state. In 1822, Jean-Baptiste Joseph Fourier (1768-1830) published an influen-
tial book on the analytical theory of heat [12], in which he developed methods for
integration of partial differential equations, describing diffusion of the heat sub-
stance. Based on the yet inconsistent law of conservation of caloric, Siméon D.
Poisson (1823) derived a correct and experimentally verifiable equation describ-
ing the relationship between the pressure and volume of an ideal gas undergoing
adiabatic changes. Benjamin Thompson (Count Rumford, 1753-1814) presented
qualitative arguments for such a fluid theory of heat with which he succeeded to
evaluate the mechanical equivalent of heat [11,13]. This theory, however, was not
accepted until the later approval by Julius Robert Mayer (1814-1878) and, in par-
ticular, by James Prescott Joule (1818-1889), who also applied Rumford’s theory
to the transformation of electrical work.
In the year 1826 Nicolas Clement (1779-1842) [11] coined the unit of heat as
amount of caloric, necessary for heating 1 g of liquid water by one degree centi-
grade. Though the expected temperature changes due to “thickened caloric” did
not experimentally occur (cf. measurements in “Torricelli’s vacuum” over mer-
cury by Gay-Lussac) and in spite of that Thompson (1798) showed that the heat
3
could be produced by friction ad infinitum, the caloric theory survived many de-
feats and its mathematical scheme is in fact applied for the description of heat
flow until today. The above customary unit was called ‘calorie’ (cal) or ‘small
calorie’, whereas a ‘large calorie’ corresponded to the later ‘kilocalorie’ (kcal).
The word “calorie” was more widely introduced into the vocabulary of academic
physicists and chemists by Favre and Silbermann [14] in 1852. The expression of
one kilocalorie as 427 kilogram-meters was given by Mayer in the year 1845.
We should add that caloric differed from the foregoing concept of phlogiston
because, beside else, it could be measured with an apparatus called a calorimeter,
however, it is not clear who was the first using such an instrument. If we follow
the studies of Brush [8], Mackenzie [15] and Thenard [16] they assigned it to
Wilcke. It, however, contradicts to the opinion presented in the study by McKie
and Heathcote [17] who consider it just a legend and assume that the priority of
familiarity of ice calorimeter belongs to Laplace who was most likely the ac-
knowledged inventor and first true user of this instrument (likely as early as in
1782). In fact, Lavoisier and Laplace entitled the first chapter of their famous
“Mémoire sur la Chaleur” (Paris 1783) as “Presentation of a new means for mea-
suring heat” (without referring Black because of his poor paper evidence). Report
of Black’s employment of the calorimeter seems to appear firstly almost a century
later in the Jamin’s Course of Physics [1].
21.2 Underlying features of thermal physics interpreted within
the caloric theory
In the light of work of senior Lazare Carnot (1753-1823) on mechanical engines
[11], Sadi Carnot (1796-1832) co-opted his ideas of equilibrium, infinitesimal
changes and imaginatively replicated them for caloric (in the illustrative the case
of water fall from a higher level to a lower one in a water mill). He was thinking
about writing a book about the properties of heat engines applying caloric hypo-
thesis generally accepted in that time within broad scientific circles [18-20]. In-
stead, he wrote a slim book of mere 118 pages, published in 200 copies only,
which he entitled as the “Reflections on the motive power of fire and on machines
fitted to develop that power” (1824) [21], which was based on his earlier outline
dealing with the derivation of an equation suitable for the calculation of motive
power performed by a water steam [11]. He discussed comprehensively under
what conditions it is possible to obtain useful work (“motive power”) from a heat
reservoir and how it is possible to realize a reversible process accompanied with
heat transfer. Sadi also explained that a reversibly working heat engine furnished
with two different working agents had to have the same efficiency related to the
temperature difference, only. Among other notable achievements [14,22-27] there
was the determination of the difference between the specific heats of gases meas-
ured at constant pressure and volume. He found that the difference was the same
