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    Brown

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    Luis Birello

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    © All Rights Reserved
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    of 10
    COUNT RUMFORD AND THE CALORIC THEORY OF HEAT! SANBORN C, BROWN Mascachusetts Institute of Technology Tue name of Co Rumiord is found in al- most every texthook on general physics, Gen- erally, however, one only of his cannon-boring experiaients and a paraphras Professor John Tyndall's comment (1), "Ru mal, in this memoir annihilates the material theory af heat. Nothing more powerful on the subject has since been writte ‘The serious student is puzzled by the statement that a single experiment could bring about the complete downfall of the well established caloric theory, oF that ane set of cesults should credit Count Ramnford with having led the f ful attack on the accepted theary of heat of his day. The answer is, of course, niordl”s: great contemporary seputatio yeans used solely on this experiment with heat from friction, but om a long series of experiments cx- tending over a period af thirty years, which at- lacked the calorie theory from many different Points of view Rumford o of heat mor some cls rent neither the energy theory of the experiments whieh he car- ried out to prove this theory. ‘The work of Boyle. Hooke, Leibnitz, and Locke seems all to have had infiuerice on Rumford’s achievement. Rum- ford’s most famous experiment is similar in pei ciple ta one reported by Boyle, and he practically quotes Hooke in some of his descriptions of heat asa form of energy. Nevertheless. his outstanding experimental skill, his endless seareh for ways to attack the calorie theory. as well as his inter final fame as a soldier. statesman, and philos- oper. made him one of the first sucessful adver cates of our modern coneept af heat. At the end of the eighteenth century the wwe opposing theories of the nature of heat were being vigorously debated. ‘The caloric theory explained the mature of heat as a uid, and the energy theary considered it “a mode of motion.” ‘Ta appreciate Count Rumford’s preeminence as an advocate af the energy theory, ene must study the canter porary ealorte theory in detail and consider what * Supported in part by a. grant from ie American Philosophical Society. Cwiohers in parentheses indicate references at end of article. of POOCKRILSES OF THE AMERICAN FHILOSORHIIERL SOCIETY, iL 33 mal tests led Rumford to dishelieve the material éuid, expert existence of heat as Caloric was considered to be a fluid capable of penetrating all space and able to flow im and out of all substances. Caloric was self-repulsive and ‘was strongly attracted by Matter was believed to be made up of atoms held together by their mutual gravitational attraction. Each atom ‘way surrounded by an atmosphere uf caloric, whose density diminished rapidly as one recede) from the center of the atom, The height of the caloric atinasphere was a function of temperature, Most of nen phenomena of heat seemer! consistent with this material theory. A caloric explanation ard the work Rumford did to ref the caloric arguments are the subjects of this paper. THERMAL EXPANSION ‘The caloric theory supplied an to the problem of thermal expansion and con- traction, Heating a body consisted merely of adld= ing the uid to th Since the fluid occupied spa ‘expansion. On cooling, the calorie fluid was removed and uence the hody contracted, “The difference be- tween solids, liquids, and gases was considered to lie essentially in the degree of gravitational attr tion between the atoms of the substance. Wath, sinall arounts of heat, the ealoeie repulsion was: not strong and the atoms were tightly hound by strong gravitational attraction, As the tenipera: ture of a body was increased, the attraction became less as the thermal repulsion became greater. In a liquid, the caloric content was sufficiently high so that the atoms were not held ition hy the mutual gravitational attraction, In a gas, the gravitational attraction was considered inop: This theory, thereto expect the observed effeet that the expansion of a. gas was greater than i the case of a Hqnrel, which turn was greater than that of a solid Concerning the problem of thermal expansion. Count Rimford wrote as follows (2 I; seems prohable that motion is an eccential quality of matter, amt that rest is nowhere to be found in the universe... There are many appearances which seem to indicate that the constituent particles af all erative led ane to 93, 50. 4, serresumen, 1949 badies are also impressed with continual motions among themselves, and that itis these motians (which are capable of augmentation and diminution) that comstitine the heat or temperature of sensible bodies. On a superficial view of the subject, it may perhaps appear dificult to reconcile solidity, hardness, and ‘clasticity with those never-ceasing motions which we have suppased to exist among the constituent particles of all bodies. . ... No reasonable objection against this hypothesis (af the incessant motions of the con- stituent particles of all bodies), founded on a sup- position that there is not room suificient for these fotions, ean be advanced; for we have abundant reason to conclude that if there be in fnet any divisible solid particles of matter, these particles must be so extremely small, compared to the spaces they occupy. that there must be ample room for all kinds of motion among them If the motions of its constituent particles were diminished . -. it seems reasonable to conelude that their elongations would become less, and consequently that the valume of the body would be contracted, but if the motions of these partictes. were increased. we might conclude, a priors, that the volume of the body world be expanded. According to the caloric theory, when a sub- stance was cooled and the calorie Auid extracted from it, it contracted and hence became denser. It is, therefore, not surprising to find Runiford studying carefully the case of water near its freez- ing point, where its change in density is anomalous. Inhis “Account of Some New Experiments on the y Fis. 1. Apparatus used to show that water at 4 ‘sank in water at 22" F. RUMFORD AND THE CALORIC THEORY OF HEAT a7 ‘Temperature of Water at its Maximum Density,” he showed that water at 41° F. is denser than water at 32° F. by demonstrating that water at this hhigher temperature sinks in water at the lower temperature. ‘The apparatus which the Count used in this series of experiments is shown in figure 1. vessel H filled with water was brought to equi ium at 32° F. by surrounding it with ice. A tin ball # with a conically pointed end was cooled to a temperature of 42° F, and mounted as shown over the thermometer D mounted in a cork cup C. Rumford’s explanation of his results was as follows (3): T knew that the particles of ice-cold water which were thus brought into contact with the conical point would not fail to acquire some small degree of heat from the relatively warm metal, and T concluded that if the particles of water so warmed should in fact be heavier than they were before, in consequence of this small increase in temperature, they must necessarily descend in the surrounding lighter ice-cold liquid, and as the heated metallic point was placed directly over the cork eup, aed fixed immovably in that situation, [foresaw that the descending current af warns water rust nevessarily fall int that eup and at length fill it, and that the presence of this warm water in the cup would be announced by the rising of the thermometer. ‘The result of this very interesting experiment was just what I expected ; the conical metallic points had nat been in contact with the ice-cold water more than 20 seconds when the mercury in the thermometer bee and in 3 minutes it had risen three degrees In other parts of this paper, and also in a paper entitled, “An Account of a Curious Phenomenon Observed on the Glaciers of Chamouny,” Count Rumford arrived at the temperature of 41° F. as that for the maximum density of water. His pri- mary purpose in carrying out these experiments, however, is expressed in the conclusion of the paper quoted above ‘These experiments ought not to be regarded as suitable for determining with great exaciness. the temperature at which the density of water is at a. maxinyuim, but rather as proving that this temperatuce in really several degrees of the thermometric scale above that of melting ice. Count Rumford offered no explanation of this Phenomenon using the energy theory of heat. However, he apparently felt that the fact that the removal of the fluid caloric did not cause the water continuously to contract was a serious objection ‘o the material theory. 318, SANBORN CONDUCTION According to the calorie theory, conduction of heat took place heeause of the great attraction hetween walter and caloric, The less caloric a hody had, the greater was the attraction oi its tomes fi J. ‘Thus, wher heat was end of a solid bar, the atoms at the than thelr neigh- ving more, their attraction for caloric the calorie J end acquired more ealor eel to da so wail all sthstance had achieved the same that temperature the atoms of th calorie almospheres, that is, util quilibrivan was sel up Count Rumford carried! out a long series of in vestigations on the “Propagation af Heat in Vari sis Substances” (4). He studied the difference the conducting power of many substances, in ‘lifferent forms amd conditions, He showed that is observations warranted the conelusion that a single substance, the convicting power in creased with the compactness of the struct would be predicted by the caloric theory Carry he caloric theory: of comlaction to: its logical ssion, conluction thrauglt a vacutim shoul sot aceur since no attractive material particles were present. Count Rumford was the first to prove that this prediction of the caloric theary was jalse and that heat was conducted through a vac: ‘uum, In his “New Experiments upon Hear.” he describes his apparatus as follows (3) Inv the middle of a glace hody, af a peartike form | suspended 9 small mercurial thermameter fine thread of silk, in sue a manner that neither the Iuth of the thermometer, nor its tube. touched ¢ containing glass heily in ans part There wax AM opening at she bottom of the gla body, hvmaih whieh the thermometer was antrorknced : and harumetrical tube hein calderedt to the pening, the inside of the glass hoy was voided of air by means of mercury, and this opening heing afterwartls sealed hertetically. and the barametrical tithe be takes away, the thermonieter was left snsperied Vorricellian va ment being fitted to a staall stand finier that the glass hody temained in a situation, | place it i my ron the side of another enclased thermometer whiel was sit, ane ob surrounded by ved the effects produced! on i, by the variation of Heat in the atmosphere, 1 soon discovered, by the motion of the mercury in the inclosed Stermoricter. that the Heat passed through the hut it appeared! plainly. insensibility af the th Torricellian va c BROWN thermometer, that the Heat passer! with much greater dlificulty in this medium. than in common air, The calorieist’s answer to such experiments was the introduction of radiant calorie whieh was transmitted aut by the attraction of material for caloric, bat in the absence of material, hy the seli-repslsive praperty af the caloric Buid Rumford performed many and diverse experi ments to prove the passage of lreat through a vac: aim, andl comelider! (6) Phe results of the experiments performed with these instruments differed f fot at all fron tose made with the apparatus peeviosly desex ites, therefore the fact af the transmission of lien through the Torricellian vacuum was established beyond any lena bese results are sufficiently known te the lean world: now the question arises as te how these re ean be reconciled with the theory which at the present ‘tay eas ‘been adopeed: ta regard toceuleric. 1. eamst confess freely, that. however much might desire it [never could recon prclluielenppeemit nent weans iitagine how heat eam be eon ways entirely different Fron each ot municatesl RADIATION AND REFLECTION ‘The radiation of heat was known to be more influenced hy the nature and condition of the sur face oj a bot body than by the material of the body The differences in the types of surlaces for holding caloric were explained simply. A surface whieh was polished smooth was considered to have all molectles [ying in a plane, and all the molectles as close together as possible. Thus, since the sreatest animunt of mass was found at this kind of a surface, the caloric was most tightly boure andl cond he lost anly with the greatest of difficulty This defined a poor radiator lat it was & goad reflector was easily predictes!: since there already existed a tightly bound calorie surface layer. it would eepel any furtiser calorie coming upp to the dace. Good radiators are rough surfaces. This meant that for any given area.of surface, there was 2 shall amount of mass lying Sn a plane, and hence the caloric was held only by a few groups of atoms atany one place. The neighboring atoms «lid nt have the cumulative effect present when there were inare of them as neighbors. so that the calorie might escape more easily. and one obtained a good radiator, Rumford believed that this calorie picture pro= vided no explanation of the radiation of cole, which he considered to be different in kind from: that of heat, bot obeying the same laws. [1 ou OL. 24, WoL 4, 1040) assaults on the caloric theory, he describes as fol- lows (2) an experiment based on his “frigorific radiation.” Let the two opposite ends of the cylinders A and 8 [fg 2] represent the two vertical metallic disks of equal dimensions, which were preseated at the same time to the ball of the thermoscope [air thermometer] Gis ‘The disk 4 being at the temperature of 32° F., and the disk # at 112° F,, while the ball of the thermo- scope C and all other surrounding bodies were at 72", it was found that the temperature of the thermascope was not changed by the simoltaneous action of these two bodies, the one hot and the other cold. Now, as the temperature of the ball of the theemo- scope isan arithmetical mean between that of the disk 1 and that of the disk B, i is reasonable to suppose that the thermoscope receives just as much more calorie from B than it gives to it as it gives to 4 sore than it receives from it; and if that be the case in fact, jeat that the simultaneous actions of the two disks on the ball of the thermoscope (or the trafic which they carry on with it in caloric) ean neither tend to increase nor to diminish the original stock of that substance belonging ta the instrument; consequently the instrument will neither be heated nor cooled by these interchanges, but will continue in- variably at the same constant temperatu When the surface of the metallic disk 2 was black- ened by holding it over the flame of a candle, the in- tensity of its radiation at the given temperature (tha of 112") was found to be very considerably increased and when (being so blackened) it was again pre- sented to the ball of the thermoscape at the same dis- fance as in the last-mentioned experiment, and the cold disk (at the temperature of 32°) was placed ‘opposite to it at an equal distance (as represented in Fig. [2]) the thermoscope. instead of continuing to re- tain its original temperature (that of 72"), was now gradually heated. There is nothing, it is true, in that event, whieh Appears dificult to explain on the assumed (calori ples, for, if the quantity of radiant caloric temitted by the disk B be increased by blackening. its surface, the quantity received from it by the ball of the thermoscope must be increased also, and that ad- ditional quantity must, of course, tend to raise the temperature of the instrument. ut here is an cx- periment which cannot be explained on those prin ciples. “The surface of the cold disk A having been black- ‘ened as well as that of the hot disk B, when both disks (blackened) were again presented at equal distances to the ball of the thermoscope (a1 represented in fg. {2]} it was found that the original temperature of the thermoscope remained unchanged. ‘The result of this most interesting experiment Proves that the ball of the thermoscope was just as RUMFORD AND THE CALORIC THEORY OF HEAT no Fic. 2 Apparatus used to study radiation from different kinds of surfaces. much cooled by the influence of the cold blackened disk as it was heated by the hot blackened disk Now, as it was found by experiment that the in- tensity ‘of the radiation of the disk B was increased by the blackening of the surface of that disk, we must conclude that the intensity of the radiation of the disk A was likewise increased by the use of the same ‘means, but if those radiations be caloric, emitted by those bodies... how did it happen that the ball of the thermostope, instead of being more heated by the additional quantity af caloric which it received in consequence of the blackening of the disk A, was ac- tually more cooled? Te may perhaps be said by the advocates for the ‘hypothesis in question, that the blackening of the sur- face of the disk A caused a greater quantity of caloric to be sent off to it by the balls of the thermoscope. Without insisting on an explanation of the mode of am SANBORN action of the cause which is supposed to produce this effect... , 1 will content myself with just observing that as the surface of the opposite disk was also black- feed, this supposed augmentation of the quantity of calorie, emmitted by the ball of the thermoscope, ceca sioned ‘by the blackening of the surface of the hodies presented to. it, ean be of mouse in explaining the Dphenomtens im fuestion cr NGE OF STATE ‘The advocates of the calorie theory explained the process of change in state with what seemed! carefol logic, The rise in temperature of a boy meant that caloric was added to the sitbstance, ox- ng it because af the mutual repulsion of the atmospheres of the individual atoms. The addition of the heat which raised the temperature increased the caloric atmospheres around each atom. This was called “sensible” heat because it Ul be measured with a thermometer, Eventue ally the atam’s caloric atmuspheres had increased to such a point that the atons penceeded to com: Ihine with the calorie, curing into essentially «neve substance, a liquid. | This change was necessarily accompanied by a disappearance of heat from the sensible to the latent form. No heat was consid- ered lost in the process, since on cooling the caloric reverted to the sensible form. ‘Thus besides the attraction between matter and caloric, in which the caloric merely formed an at- mosphere around the atonts and moleeules, calorie could actually combine with an atom in a fashion similar to chemical combinations of the atoms themselves, the caloric losing its sensible form and ccoming latent. The “chemical” combination of an atom with ealarie produced a new eopound in. which neither the original atom nor the calor retained its identity, Tt was believed to be con pletely analogows to ordinary chemical reaction Tt took place, as do ordinary chemical reactions, only in definite proportions and ender def cirewmstances. ‘The case of vaporization seemed an additiowal cheek on the validity of the calorie theory. The requirement for a reaction to take place henween the sensible caloric orn wats a critical amount of caloric around each atom, ‘The com pression of an iron har by hammering apparently squeezed out sensible caloric, or a cylinder of gas which was compressed emitted caloric and became hotter. It seemed obvious that sensible caloric could be syueezed from a body by artifieially push- ing the atoms tugether inte a closer praximi than the mutual repulsion of their cale mospheres would allow. cat ‘Thus if one put pressure C. BROWN Trsec: same PHN, se; ‘on a substance near its boiling point, same of the sensible caloric would be lest from the substance and a higher temperature would be nec jore sufficient caloric would be available ta the sary he- atom for the vaporization reaction to cecur, ‘This Jact was amply borne out by experiment, Count Rumford’s explanation of the phenone- fot) of change of state was expressed this (2) ve not sufficient data to enable ws to of the nature of the change vebich takes ve when a solid body is melted ; but as fus casioned by heat, that is to say yerertation ich occasions expastsian, if of the 9 ‘constituent partieles af the boy, it is. ne doubt, a cer~ tain additional increase of thase molions which causes the the body to be changed. and from a solid to became a fuidl suhstanee, As long as the constitteent particles a a solid bnxly which are at the surtace of that body do not, in their mation, pass hy each other, the body must necessarily retain its furmn or shaye, however rapitl those motions or vibrations may be; but as soan as the motion of these particles is 0 augmented that they can no. longer be restrained of retained within these limits the regular distribution of the particles whieh they acquired in crystallization is gradually destroyed, and. the particles so detached from the solid mass for new and independent systems, and become a liquid substance. Whatever jay he the figures of the orbits which the particles of a Tiguid deserihe, the mean distances fof those particles fram each ather remmin pearly the soitie as when they constituted a sulic, as appears iy the small chaage af specific gravity which takes place when a solid is melted ane! becomes 5 liquid; ancl it is evident that the ad necessarily acquire, im ord form, cannot be lost, but most cantinoe to reside in the liquid, and must again make its appearance when the liquid’ changes its form and becomes a solid. It Known tat a certain quanticy site to melt a solid, which quantity disappears or mains latent in the liquid produced sn that process; and that the same quamtity of heat reappears when this liquid is congealed and becomes « soliel body. KINETIC THEORY The caloricists did not bring forth any com ing arguments to explain evaporation and sublin: ation, but one finds Rumford devoting many pages of his memoirs to discussing these changes of state. Although his language seems odd teday, one can recognize in his discussion the elementary cancepts of Kinetic theory (7) 11 seeins highly probable that many appearances which have len auteibuted 1 very different causes vo their taking the tiquid fact owing to fntense Heat existing, and pro- ng the effcets proper to it in situations where its ‘existence has not even been suspected There to suppose that it is possible for iee 10 be reduced to steam without being previously melted: and st is well known that dee cannot be meted with a lower degree of Hea! than that of 82° of Fahr- cnheit's seaie: but in the midst of winter, im the cold est cli ar when the temperature af ait of the atmosphere, as shown by the thermometer, has. been mich below 32°, ice, expoded to the air. has heen found to evagorat How can we account for this event, except that it be by supposing that some of the particles of air which accidentally come iste cantaet with the éee are se Hot, as mot only to melt he small particles of ice which they: happen to touch, ut also to eechice a part Of the generated water to st Mercury has heen aetually found ta eeRporate unt dee the mean temperature of the atmosphere. What a striking proof is this . . . that very intense Hea! may be generated, or exist where it would not rate rally be expected to be foud! And does not the evaporation af water under the mean temperature of the atmosphere afford another proof of this last fact? We ought to be on aur guard in form fan opin iow with respect to the intensity of the Heat whieh may exist in jsible insulated particles of matter of any kind that may he seattered about in a spiice, or which may float sn any Maid, where seither four feelings nor onr thermometers can possibly be sensibly affected by it. A. thermc more than indicate the mean of the atures of all those bosties or partiel happen to come into. contact neter can do no ficrent tempers of matter which it. TE it be ae ented in-air, it will indicate the mean of the temper whieh happen to touch tures of the partic at it can never gi the relative temperatures af those particles of air Count Rumford undertook careful investigations to demonstrate the existence of particle motion in a nperature, ‘These he de scribed in a paper entitled “Of the Slow Progress of the Spontaneous Mixture of Liquids” (8). His description of the part, as fol- lows! Having procured a eylitudrical wessel of elear gl Provided with a scale divided from the bation 10 inches and lines (1/12 inch], I put it on the otidile of a cellar, where the temp erature which seemed to: be tolerably constant, was 64 degrees of Fahrenheit’s » T then poured into this vessel, with die g a ayer of a samurated agueeus solution of rmuriate of soxla, 3 inches in thickness, and on to this 2 layer of rhe same thickness of distilled water, ‘This operation perfurmed in such a way that the two liquids lay. fone upon the other without being mixed, and when RUMFORD AND THE CALORIC THEORY OF HEAT an everything was at rest I Jet a large drop af the essen al oil of cloves fall into the vessel. This ail ting specifically heavier than water, amt lighter than the colation nf mariate of sada an which the water rested the drop descended throngh the layer af water; wh however, it reached the neighborhond of the stirface of the saline solution it remained there, fort little spherical ball, which maintained is pasition at rest, as though it were suspended. near the axis of the weses Alter the littl uss mentionell above four hours, T found the fittle ball had risen 3 fines, ‘The next day, at the re T feral that it had risen abeut & lines niare, andl thus it eomtinued 10 ascend about 3 lines sc days, when T yatt an end to the experi= nent. These experiments showed tat he continually, but very slowly, b ous solutions employed and the distilled water estan, pon thes Ts [thig mintere]. perks, the result of a peculiar and continu to-all liquids, caused by the instabilit rium existing antong their molecules? pixture went tween various It is itteresting to observe that whe Kinetic theory was worked ott, pointed out that the spontancens mixture of fiquids of different densities affords one of the direct experimental proois of the predictions this theory THE WEIGHT OF HEAT The expl many caloric phenomena was based on the strong attraction between caloric and matter Because of this attraction, one would ex- pect that the force between the calorie in a bady and the earth, namely the weight of calorie, should be ats ssurable quantity, One of Cosmt Rum fonl’s major investigations was an attempt to ssure this weight of heat both in its “sensible” “latent” form, This experiment is de in Rumford’s own words as isllows (10 Having provided three bottles

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