Louis Paul Cailletet-The Liquefaction of the Permanent Gases
Educator Indian Journal of Chemi cal Techn ology Vol. I 0. March 20m. pp. 22:l-23(i
Louis Paul Cailletet-The liquefaction of the permanent gases
1 Jaime Wi sniak ' ' Department of Chemical Engi neering. 13cn-G urion Universi ty or the cgcv. Bccr-S hcva. Israel R4 10.')
To Louis Paul Ca illetct ( l lD 1- 1913) we owe th e rea lization of th e liquefaction of perma nent gases using a free expa n sion process. A brillian t analysis of an ex perimental mishap led him to ac hieve thi s possib ility. The priority or oxygen lique faction was and continues to be a matter of disc uss ion. The life and sc ientific work or Caillctet arc descri bed toget her w ith detai ls about the priority polem ic.
4 Mankind has been interes ted in quantifying th e differ through the wai Is of th e vesse l . However, if th e I iq ence bet ween hot and cold si nee very old times. The uid evaporated into a vacuum surrounded by a freez ori gi nal apparatus, ca lled th ennoscopes, served ing mi xture th e cooling effec t could be increased in merely to show the changes in th e ten~perature of its definitely as long as the liquid exerted an appreciable surroundings. Eventually th e need arose for qu anti vapour pressure. John Leslie ( 1766-1 832) not on ly fying these observations and th e eli fferent th ermome had been able to freeze water by absorbing its vapour ters began to be developed. Astronomers built mos t of at the sa me rate it was produced ; he had also been th ese instruments, particularly for measuring low able to reach a temperature almost as low as the 1 tem peratures • Development of thermometric sca les melting point of mercury (234 K ) by evaporation of such as those of Rea umur, Fa hrenh eit and Celsius, led ether. Gay-Lussac reported that he had succccdccl in in a natural way to th e question whether th ere was a freezing mercury by evaporating wa ter in a vesse l lower I i mit to temperature, and corresponcli ngly, to surrounded by a freez ing mixture. Gay-Lussac had no the behaviour of materiaI s u ncler th ose circumsta nces. doubt that with a volatile liquid it would be pos sible While stud ying th e proper way to ca librate an ai r to obtain even lower temperatures. th ermometer Guillaume A montons ( no 1663- 1705) According to Gay-Lussac, if th e liquid ev aporated ticed that wh en the temperature was chan ged between in a perfectly dry gas in stead of a vacu um th e cool ing th e boiling point of wa ter and ambient temperature, would not be so great because th e gas press ing th e equal drops in temperature resulted in equal decreases liquid would retard th e evaporat ion process. The co ld in the pressure of th e air. From th ese res ults he con achievable had a max imum va lue corresponding to cluded that on further cooling th e air pressure would the equilibrium between th e caloric (heat) absorbed become zero at a finite temperat ure, which he es ti by th e vapour and the ca loric los t by th e air. Gay mated as - 240°C. Since the pressure of the gas could Lussac then proceeded to develop the following for not become negative, it fo llowed that th ere mu st ex ist mula describing th e degree of cold x (degrr:e dcfi"oid) a lowest tempe rature beyond which air, or any other prod uced by evaporati on: substance could not be cooled. Amontons also co n sidered that air might be a body of high volatility, ca . . . ( I ) pable of liquefacti on or even so lidifica ti on by suffi- . I . o , ctent y strong coo 1mg-·· . In 18 15 Joseph -Louis Gay-Lussac ( 1778- 1850) w here, 8. C.. H , and c are the dens ity, hea t of va made a large number of observati ons of the cooling pourization, and heat capac ity of the vapour at the 0 effect produced by the evaporati on of liquids and re temperature t in question, and P and P th e vapou r marked that under certain conditions the hea t of va pressure and the press ure, both in atm os ph eres. pouriza ti on would be eq ual to the heat transferred In th e case of wa ter th e above equation became
pO (T) = _ (I oot5~5-17.r - o . oooo625X26• ' ) *For correspondence (E-ma il : wisniak @bgumai l.bgu.ac.il ) 0 76 0 ... (2) Educator Indian J. Chem. Tec hno ! .. M:11·ch 200~
Gay-Lussac also prepared a table comparing the Antoine Laurent de Lavoisier ( 1743-17<)4) in his hook expenmental results obtain ed by wetting the bulb of E/e/1/ e/1/S oj" Chentistrv, r ub li shed in 17X9 7 La voisier the th ermometer with a cloth (wet bulb te mperature) wrote: " If the earth were sudden ly tran sported in to a with those predicted by Eq. 2 for the case of air at very cold region , the water which at present composes atmospheri c pressure. our seas, rivers, and sprin gs, and probably th e greater In a later publication5 Gay-Lussac analyzed th e number of lluids we arc acquain ted wilh, would be production of cold by th e expansion of a gas. He re converted into solid mountains and hard rocks at first alized that coolin g by evaporation was limited and diaphanous and homogeneous, like roc k crystal, but poi nted out that the minimum temperature ac hi eved which, in time, becoming mi xed with foreign and het was only - 80°C. He believed that it was possible to erogeneous substances would became opaque stones achieve lower temperatures by using the equival ence of va ri ous colours. In thi s case, the air, or at least part between coo li ng caused by th e expansion of a gas and or th e aeri form fluid s which now comrosc th e ma ss of heating ca used by compress ion. It was known th at our at mosphere, wou ld doubtlessly lose its elasticity compressin g the air to one-fifth of its original volume for wa nt of a temperature to retain it in that stal e: it increased the temperature to 300°C and Gay-Lussac would return to the liquid state of existence, and new thought that the temperature mi ght be in creased to liquids would be formed, of whose properties we can I 000°C or even 2000°C, if th e process was ra pid . I r not, at present, form the most distant idea. Sol idity, air was first compressed to five atmospheres, th en liquidity, and aeriform elasticity are only three diller allowed to cool to atmosrhcric temrerature, and fi cn t states or existence of the same matter, or three nally allowed to expand, it shou ld absorb as much rarticular modifications which almost all substances heat as was given out in its compression and its tem are susceptibl e or ass uming successi vely, and which solely depend upon the degree of te mperature to perature should be lowered by 300°C. From these re which th ey arc exposed, or. in other words, upon th e sul ts he believed that "en prenant une nwsse d'air amount of caloric wi th which th ey are penetrated". con1pri111 ee par cinquante, cent. etc .. atnwspheres, le .fi'oid produit par sa dilatation instantanee 11 'a ura Starting in th e late 1700' s many sc ientists looked point de lin1it" (if we take a mass of compressed air to for ways of reaching lo wer and lov:er temperatures 50, I 00, etc .. atmospheres, th e cold produced by its and liquefying gases. In 1799 Martinus Van Marum in stantaneous ex pansion will have no limit). In other ( 1750-1 837) and van Trovstwyk performed ex peri words, it would be possible to achieve unlimited cold ments trying to determine if th e Boyle-M ariotte's law by the ex pansion of gases. was applicable on ly to air or for all gascsx. For thi s Gay-Lussac concluded hi s paper statin g: "S 'il est purpose he chose ammonia and proceeded to com incontestable que, par Ia dilatation des gaz., on pettl press it in a system piston-cylinder. When th e pres {Jroduire un .fi'oid iflilllit e, Ia deter111ination du z.ero sure reached about seven atmospheres he noted that ahsolu de clz a feur doil para/Ire 1111 e question tout-cl although th e vo lume of the gas continued to decrease, fa it cltiiii Prique" (If it is undi sputabl e that ex pansion th e pressure did not change. Van Marum un derstood nr a gas can produce an unlimited amount of cold , that he had liquefied ammonia by a sim ple compres then the determination of the absolute zero of heat sion process without resorting to coo li ng . He al so ob must seem a complete fantasy). served th at redu ction of the gas volu me was accom Later on, Charles- Bernard Dcsormes ( I 777- 1862) panied by an in crease of the liquid vo lum e. In th e and Nicolas Clement ( 1779- 1842) argued that there same year, Louis-Bernard Guyton de Mo rv eau ( 1737- was an absolute zero and that Gay-Lttssac had shown 18 16) Iiqu e fi ed amm onia by simple cooli ng to about - what thi s temperature was. According to Gay-Lussac 50°C with a freezing mixture of calcium chl oride and the coeffici ent of expansion of gases was 1/266.66 per ice ~ while Antoine-Franc;ois Fourcroy ( 1750- 1809) degree Celsiu s, hence, Clement and Desormes argued and Louis Nicolas Vauquel in ( 1763-1 f\29) failed to that there was a limit of co ntraction at - 266.66°C, liquefy hydrogen chloride, hyd rogen su lphide, and whi ch was th e absolute ze ro('. sulphur dioxide 10 In 180 I Gaspar Mo nge ( 1746- 18 18) and Jean Franc;ois Clouet ( 175 1-1 80 I) suc Early works on the liquefaction of gases ceeded in liquefy in g sulphur di ox id e by passing a The possible effect of the low temperatures yet to stream of S02 through an U-tube submerged in a re be achieved, were described in a prophetic way by frigerant mixture of ice and salt ; they noticed that the
224 Wisni ak: Louis Paul Cailletet- T he liquefaction of th e permanent gases Educator tube fill ed up little by little with a co lourl ess and high vio lent evapo rati o n o f the liquid w ith th e corre 11 mobile Iiquid , similar to water . spo nding intense cooling and solidificati o n of th e re Thereafter, many scienti sts tri ed to liquefy gases by maining liquid into a white snow. 14 a compression process. The next important step were Thilorier studied also th e properti es of liquid C02 the results obtain ed in I R23 by Michael Faraday and found that it had a very large coefficient o f ex ( 1791-1 867), while in vesti gating the int1uence o f heat pansio n, fro m 0 to 30°C its volume in crease fro m 20 12 on chl orine hydrate He introduced hydrate crystals to 29, which was fo ur times larger th at th e expansion in one of th e extremes o f an in verted V-tube closed o n of air in th e same te mperature range. Similarl y, in the both ends and proceeded to heat th em with a water same temperature range th e vapour pressure of the bath at I oooc. Faraday noticed that the crystals first liquid increased fro m 36 to 73 atmospheres, th at is, melted and then rek ased a yell ow gas th at o n cooling one atmosphere for each degree. Liquefied C0 2 was yielded a heavy bright yell ow fluid fl oating o n top of soluble in all pro po rti ons in alcoho l, ether, naphtha, a soli d ph ase. Faraday understood th at chl orine gas turpentine, and carbo n di sulphide, and in soluble in had separated fro m the hydrate and condensed under water. its own pressure. Afterwards, it was found th at a mi xture of solid
Faraday's ex periment in fact, presented an altern a C0 2 and volatile liquids such as eth er (Thilo ri er's tive meth od fo r liquefyin g gases, in stead of generat mi xtures) were capabl e o f producin g very low tem in g the m in a separate apparatus, fo ll owed by th eir peratures (below -80°C). In 1845, Faraday combined compression with th e he lp o f pumps, of complicated th e two liquefying meth ods (cooling and compres design, operatio n, and no nfl exible, the gas was now sio n) into one by takin g advantage o f Thilo ri er's produced in an enclosed space, in in creasing amounts mi xtures to produce low temperatures. He now used a by a chemi ca I reactio n that served to generate th e regul ar U-tube submerged in a Thilori er mi xture that necessary pressure in a cooled c losed tube. all o wed reducing the temperature to - li0°C, and In the course of th e same year ( 1823), Faraday's connected to two pumps operating in seri es th at al procedure was used to lique fy hydrogen sulphide pro lowed in creasing the pressure up to 50 atmospheres. duced by th e reacti o n between hydrogen chl oride and With thi s new apparatus it was possible not onl y to iron sulphide; so2 produced by th e reacti o n between lique fy gases such as HC I, HBr, SiF4, PH1, As H1, and mercury and sulphuric acid ; nitrous oxide from th e ethylene but also to solidify others such as H2S, N20 , decompositi on of ammo nium ni trate; cyanogen, and and HCIO. He was unsuccessful to liquefy hydrogen, C02. nitrogen, oxygen, carbo n mo noxide, and, meth ane at 15 Faraday's equi pment was limited to the producti o n 50 atmospheres and - II0°C . of a very small amounts of liquefied gas; in 1834 a By mid-nineteenth century, all but six of th e known very smart modi ficati o n by Charl es Sainte-Ange gases had been liquefi ed, and temperatures below 170 Thilori er all owed increasin g substanti all y the amo unt K had been achi eved by evaporating a Thilorier mix 13 of Ii quefied gas, parti cul arl y Iiqu id C0 2 . T hi lo ri er' s ture o f solid C0 2 and di eth yl ethe r. The six re maining apparatus was composed o f two large vessels con gases (oxygen, nit rogen, carbo n mo noxide, nit rous nected by a tube. T he firs t vessel, built of copper lined oxide, methane, and hydrogen) were call ed pern wnenl with lead, was used as th e reactor. This vessel hung gases and beli eved to be no n-condensabl e. He lium fro m two pi vots so that it could be osci ll ated to in was not considered th en because this gas was d iscov crease the mi xing of the reagents (fo r example, sul ered o nl y in 1869 w hile observin g the sun and identi phuri c acid and sodium bicarbonate). T he reactio n fi ed by a bright yellow line in a spectrum analysis or produced large amounts of gas, w ith the correspond the sun ' s coro na. Ramsay discovered the first deposits ing increase o r the pressure in side th e vessel. No liq in th e earth in a sample of pitchblende. a dark rock uefaction took pl ace on account of the temperature containing radium and uranium. in crease, which took pl ace due to the heat of reactio n. George Aime ( 18 10 - 1846) tri ed, w itho ut success, A valve was now opened o n th e top of the vessel and to liquefy oxygen and nitrogen by immersin g recipi the gas was a ll owed to flow in to the second vessel, ents containing air in the sea, to a depth correspo nd 16 held at room temperatu re, where liquefacti o n now ing to more than 200 atmospheres . In 1844 Johann took place. Opening of a valve located o n top of the August Natterer ( 182 1- 1900) succeeded in producing second vessel released th e pressure and resulted in a large quantities of liq uid nitrous oxides but later on he
225 Educator Indian J. Chc: m. Tech no!.. M ;udl 2003
failed to liquefy air by compress ing it to press ures It took th e experiments or Andrews IO understand 17 2122 bet wee n 1300 to 28 00 atmospheres th e rea so n of th e failure . 18 In 1850 Victor Reg nault ( 18 10- 1878) made ex Thomas A ndrews ( 18 13- 1885) stud ied th e behav te nsi ve measurements of th e velocity of sound in dif iour of gases under high press ures and different tem ferent gases and of th e heat absorbed during th e ex peratures and was able to formulate the co ncep t or p~ul s i o n of th e gas through an orifice in a ves se l, coex istence of th e vapou r-liquid equ ilibrium an d th e through ca pillaries, and when th e gas was suddenly constancy o f temperatu re during a phase change (An stopped . In so me of his experiments on th e discharge drew's isotherms). A ndrews demonstrated that for of a gas th rough a capi llary tube he observed a small every gas th ere ex ists a temperature (ca lled th e criti cooling effect but dismi ssed th em as ex perimental cal te111 perature) above which it was imposs ible to errors. Two yea rs later, James Presco tt Joul e ( 1818- condense th e gas, no matter how hi gh a pressure was 188t)) and William Thomson ( 1824-1907, Lord Kel- applied. For thi s purpose he used C02 partly becau se v1n. ) I') wou IIc report th e sam e re sult and understand its or the facility with wh ich it can be prod uce d in a pure significa nce (th e Joule-Thomso n effect). state (by th e act ion o f boiling sulphuric ~tc id over Based on his findinQs on th e behav iour of the com- marble, and dried by pa ss ing through sulphuric acid) 0 press 1·b 1·l 1· ty o ,·. gases R ~egnau I 1 prec ,.Je ted '- , as was later and its critica l temperature being 31 °C. Prev ious ex 1 demonstrated. that application of insufficient pressure perimenters x had shown that C0 2 deviated se nsibly was th e onl y obstac le for th e liquefa cti on of oxygen from Boy le's la w. even at temperatures well above an d nitrogen. Also. th at if hydrogen was cooled, it th e criti ca l one.
would show enough compressi bi I i ty to he I iqucfied. Andrews found that on partl y liqucl'ying C02 by On December 24, 1877. Regnault sa t for the las t time press ure all1ne, and rai sing simultan eously the tem in a sess ion o f th e Academic. he was alread y ve ry ill peratu re to 8R °F, th e surface of demarcation between ~ llld would cli e a few weeks later. On that opportunity th e liquid and gas pha ses disappeared grad ually. AI Dumas read Ca illetct's communica ti on on th e lique tem perature above gg oc th ere was no apparent lique fac ti on of oxygen (mentioned below). A week later, facti on of th e gas, on ly one phase was visible, even al 21 Ca illetet announced that he had also succeeded in liq press ures as hi gh as 400 atmospheres . He usee! the uefying nitrogen. co nce pt of critical temperature to di stingu ish between Joule and Thomson performed a se ri es o f ex peri a vapour and a gas, a distinction that was ba sed previ ments of throttling air at pressures up to 4. 11 atm and ously on th e boi ling point. a clearly arbitrary clcfini temperatures up to 171 °F through a pipe blocked at ti on. Andrews proposed calling v<~ p ou r any gas that one end by a piece of calf-skin lea th er and found was at a temperature be low th e critica l one, and gas if " there is a final cooling effect prod uce d by air rushing it was above this tempera ture. According to hi s defi th rough a sma ll aperture at an y temperature up 170° F, nition a vapou r could be changed into a liquid by a and that th e amount of thi s th ermal cffect decreases as simple increase in pressure and the two phases cou ld th e temperature is increased". Not only thai, thei r re coex ist in equilibrium. sults indica ted that in th e ca se of sa turated stea m the Another important ex perimental res ult was that th e density va lues used by Reg nault were lower by a fac gaseou s and liquid forms o f matter could be tran s 1 tor 1.01 9 from the rea l ones 'J. fanned into one another by a seri es or continuous and 21 It was found empiricall/ 3 that th e Jou le-Thomson unbroken changes . In 1873 th e cont inuity o f th e gas cooling effec t 6.T was proportional lo th e press ure and liquid state wou ld be th e subject o f Johann es Did erik van der Waals' ( 18 37 -1923) doctoral th es is (Over drop !J.P and in verse ly proportional to th e square of 2 de continuYteit va n de gas-en vloe istoftoestand ) ' . the abso lu te temperature T, according to following eq uation, In what follows we desc ribe the I i l'e and works of Louis Paul Cailletet ( 1832- 1931 ), th e fi rst to show that permanent gases could be liq uefi ed, and th e ,j 273 )" . .. (3) 6.T = 116.. l T events that accompanied this achievement.
where 11 is a constant characteri stic for each gas ( for Louis Paul Cailletct <.ur 11 = 0.276), T is in kel vin s, and P is in atmos Louis Paul Cailletet (Fig. I ) w as born in Chatillon pheres. sur-Sei ne, Core- d-Or, France, on September 2 1, 18:12 .
226 Wisniak: Loui s P
227 Educator Indian J. Chcm. Techno !. . M;1rch 200.1
rooms and chl orophyll plants. He analyzed th e ashes furnace. To prove hi s point he cast th e liquid melt in of a piece of tree on which mu shroo ms grew and water-jacketed molds made of metal to avoid th e found that th e larges t majority of th e minerals had prese nce of humidity . A nalysis of th e gases released been absorbed by th e latter. T o him, this fact ex indicated that instead of water it was a mi xture of hy- 1 1 plained why a tree subject to th e act ion of cryptoga ms c1 r ogen, n1tro. gen, anc I canonI dI. OX .IC I e ·lll ·· . de teri orated seri ously. In addition he found th at sili Cailletet did also work on th e permeability of dif con th at co nst ituted about 70% of th e weight of fern s ferent gases, particular ly hydrogen, oxygen, and car and graminae, was not prese nt in mu shrooms. The bon monoxide, and usc hi s res ults to ex plain the fail as hes of th e latter were poor in ca lcium ox ide and ures that occurred during th e tempering of inco m magnesium oxide, but ve ry ri ch in alkali and phos pl etely forged pi eces of iron of large dimensions and phoric acid. also during ce mentation. In th e latter case . he found th at the pulls contained hydrogen and ca rbon mon Metallurgy ox ide and that th ey accumulated in th ose areas where 12 13 Operat ors of blast furnaces we re aware th at they th e meta l sponge was incompletely forged . had to do th eir work ca refully to avoid ex pl os ions. It was kn own that metals like iron . platinum and Similarly, it was kn own that mec hanical work of cast aluminum hardly ama lga mated with mercury. A l iron might res ult in its ca tching fire. A series of acci th ough the sa me phenomenon was observed if mer dents of thi s nature in his factory moved Ca illetet to cury was replaced by a dry ama lgam of sod ium or study th eir origin. ammonia, add ition of water res ulted in amal ga mati on Jacq ues Joseph Ebelmen ( 18 14- 1852) an d other and rel ease of hydrogen gas. Cailletet performed an chemists had occupied th emse lves with th e analys is of ingeni ous experiment to demonst rate that amal gama the gases produced in th e blast furnace, by aspirating ti on took place together with hydrogen release: He them with a long iron tube containing an intern al por used an electroly tic ce ll that had a shee t of iron, plati ce lain tube, and under conditions that re sulted in th eir num, or aluminum as th e negati ve electrode and a coo ling. Ca illetet rejected th eir res ults bec au se on layer of mercury under an elec trolyti c hath made of coo ling the dissoc iating compounds recombined acid or basic water. Dropping th e metal sheet into th e aga in, as predicted by th e dissoc iation ph enomena mercury res ulted in th e immediate arpariti on of hy discovered by Sai nt -Ciai re De vi lie. In ord er to avoid drogen bubbles and thi s was enough to obtain amal thi s problem Cail letet designed hi s equipment to sa m ga mation. When a few drops of a lead or copper sa lt ple the gases from th e midst of th e furnace (o perating were added to th e elec trolyte hydrogen generati on at a te mperature we ll above th e fu sion point of plati stopped and th e metal used as negati c pole was un num) followed by sudden cooling (q uenching). His abl e to ama lga mat e. res ults indicated that th e gas co mpos ition was sub Cailletet used this procedure to produce amal gams stan tially different from that reported by Ebelmen and of the metal s known to amal ga mate with difficulty others: Carbon diox ide and other tlammable gases and to stu dy their properti es. He re marked that th e such as hydrogen, ca rbon monoxide were prese nt in amal gam of mercury and aluminum was unu sual in its ve ry small amounts. The gas mi xture was opaq ue be ab 1.l .1t y to d eco mpose pure wa ter·~ . cau se it carried a large amount of finely di vided ca r 2 1 bon in suspen sion that required a long time to settle ' . Liquefaction of gases It was a well-known fact that when using cas t iron The most important resea rches of Cai llete t are re for fabri cating molded pi eces th e melt released co m lated to the behav iour of gases under press ure and bustible gases while it so lidified. The large amounts th eir liquefac ti on, particularly oxygen. Between the of gas released required speci al preca utions to avoid end of 1877 and the beginning of 1878 Ca illetet lique an explos ion. Many th eo ri es had been proposed to try fi ed all the gases co nsidered permanent. to explain th e ori gin of th e gases disso lved in th e cast In hi s first work he st udied the val idity of Mari and in molten steel s. In foundries it was believed that otte's law (idea l gas) at hi gh press ures, using a piece the gases ori ginated from th e decomposition of the of equipment which was a prototype of th e one he water occ luded in th e molding ea rth by th e metal at would use later to liquefy gases35 H is fi rst res ults in hi gh temperat ure. Cail letet believed that th e gases dicated that at high press ure hydroge n and air did not were ac tually furnace gases th at had di sso lved in the behave idea lly, the compressi bi I ity of hydrogen de liquid metal, before it's being discharged from the creased regu larl y with increased press ure, while th at
22R Wi sniak: Louis Paul Cai ll etet- The lique facti on of the permane nt gases Educator of air first increased to a maximum value at about 80 atm and then it decreased more rapidly than that of hydrogen. Further work with nitrogen indicated th at thi s gas did al so not behave ideall y and that its com pressibility presented a maximum va lu e at I5 °C and about 92 atm'r'. He then used hi s equipment to liquefy carbon di ox ide under temperature and pressure conditions not reported by other in ves ti gators. Cailletet found that liquid C02 wa s colourless and very mobile, did not conduct electricity, and th at electricity produced a burst of brilliant induction spark s, in the midst of a very vo latile liquid. Liquid C02 was not attacked by sodium . did not di ssolve sulphur or ph osphorus but mi xed with eth er in all proportions. Iodine gave it a violet tint. Cailletet thought that sin ce C02 and water had a similar structure th ey wo uld di ssolve the same sa lts. Contrary to hi s expectati ons liquid C02 did not disso lve NaCI , Na2S04 , or CaCI 2. Liquid C02 di s solved partially in water; the less dense layer bein g Fig. !- Lou is Pau l Caill etet ( 183 1- 1913) (By permissio n of Ed gar Fahs Smith Coll ecti o n. Un iversity of Pcnnsylva.nia Library). C0/ 7 Next, Cai ll etct studi ed th en th e co mpressi bi Iity of lene, an incident took pl ace: Before th e liquefacti on acetylene at hi gh pressures and found th at the gas be pressure could be reached th e apparatus sprang a leak ha ved according to the law of Mariotte (i deal gas)'g and the compressed gas escaped. The sudden re lease Caill etet built hi s equipment essentiall y along th e of th e gas resulted in a considerable drop in tempera same lin es as th ose used by Andrews for hi s experi ture and appearance of a thick mi st (brouillard epais) . ments with C02 (Fig. I). The central pi ece was an At first, Cailletet thought that hi s gas was impure and inv ert ed probe (TT), opened at its bottom and con what he had seen was condensation of humidity. nected to a hydrauli c pump through a layer of mer Cailletet had now th e brilli ant idea of repeating hi s cury (tube TU). The upper part of the probe was fu sed experiment using a sample of very pure acetylene to a thick capillary tube containing th e gas to be provided by Marcel in Berth elot ( 1827- 1907) and studi ed. The capillary was in side a liquid bath (P) agai n observed the formation of mi st. Cai!letet under contai nin g water or a refrigeratin g mixture, as desired. stood th at the liquefaction had been achieved by the The bath was made of glass and was surrounded by a intense coolin g produced by the sudden release of bell jar (C) th at offered protec ti on in case of a burst. press ure and that he had now in hi s hands a new tech The ca pillary was subj ected on th e outside to atmos nique for gas liquefacti on. ph eri c pressure and on th e in side to an internal pres Cai ll elet observed that compression of acetylene. sure that determined liquefacti on. The pro be was initially at I8°C, to a pressure of 83 at m, res ulted in subj ected to th e sa me pressure, in side and out. The th e formation of many drops drippi ng on the walls of glass constructi on permitted observation of what was the vessel. Reduction of th e pressure by several at happening in side th e capillary ". mosph eres resulted in vapouri zati on of the vessel and Prev ious to building hi s eq uipment, Caill etet had the tube bein g filled with a fin e mist. d eve Iope d the necessary anc.ii I ary elements·W-4" - . Fo r The liquid acetylene obtained was colourl ess. example, he studi ed the res istance of glass tubes to hi ghly mobil e, and apparently very refrin gent. It was rupture''1 and th e building of manometers for th e li ghter than the water and di ssolved in a large propor 0 1 measurement of hi gh press ur es~ -~ . tion into it. It dissolved paraffin and greases. Cooling Acetylene was chosen first because it had been the liquid to 0°C in the presence of water and lin seed suggested that at room temperature a pressure of oil produced a white snowy substance, which decom 38 about 600 atm might be sufficient to liquefy it . In posed rapidly on sli ght heating or lowering of th e October 1877, during a routine verification of acety- pressure, generating a large amount of gas bubbles.
229 Educator Indian J. Chcm. Tcchnol.. March 200]
Caill etet determined th e following pressures and at 7°C, a sudden release of the pressure produced a 8 temperatures at whi ch acetylene was liquefied -' : mist simil ar to th e one observed with carbon dioxide: for thi s reason he believed he would be abl e to liquefy t°C atm meth ane. This publication carri ed a comment by Ber thelot about the importance of Cai ll etet' s findings 4X because so far it had been impossible to liqu efy gases 2.5 .'iO that beha ved accordin g to Mariote's law . Berthelot 10 63 menti oned that in th e las t years Andrews had shown IR R:l that the reason fo r the failure was that every vapour 2.'i 94 had a criti cal temperature, above wh ich the vapour 31 103 could not be transformed into li qui d, no matter how Compari son of the above va lues with those re much a pressure was applied to it. 4 According to Berthelot, Caill etet's experiences ported by Din ' for the liquid-vapour saturation dome of acety lene shows th at Caill etet reported th e condi showed th at th e criti cal point of nit rogen dioxide was 0 tions upstream the throttling process and not th ose of between 8 and - II C. He also be lieved that Ca il the vapour-liquid equilibrium. letet's procedure wou ld soon lead to the liquefaction Caill etet used th e sa me eq uipmen t to liquefy eth of oxygen and carbon monox ide. ane, and found that at 4°C the required pressure was Liquefaction of oxygen about 46 atm, that is , sl ightl y larger th an that required Liquefaction of oxygen represen ts a sensa ti onal for acetylene. scientifi c accomplishment th at was ac hieved in 1877 Caill etet closed hi s paper with th e remark that hi s almost simultaneously by Cai ll etet and Rao ul Pictet liquefaction equipment was very simple and easy to ( 1846- 1929) usin g completely different experimental operate and th at he intended to test it with oth er gases. techniques. This ac hi evemen t was also accompanied In Caill etet's experimen t the discharge (expansion) (a nd continuous to be) by much discussion regarding of the gas may be considered adiabatic. hence, as priority to th e discovery. suming as a first approx imati on ideal behaviour, it is Caill etet and Pi ctet' s resu lts we re com muni cated to possibl e to calcu late the final temperature with th e th e Academic des Sciences by the Pe rm anent Secre re lation tary, Jean Baptiste Andre Dumas ( 1800- 1884) during th e session held on December 24, 1877, and appear in .. . (4) Co111p1 . Ren(/ti , 85, 12 12. 1877 . It is important to give a detailed account of thi s where i and f indicate th e initi al and final conditi on, particul ar session in order to understand th e reasons respecti ve ly. According to Eq. (4) th e fin al tempera of th e pri ority polemic that followed the announce ture depends on the va lu e of y , th at is, on the gas in ment. questi on. y is about 1.67 for monatomic gases and Dumas opened th e session reading the prophetic wo rds of Lavoisier, written alm ost one-hu ndred years about 1.40 for diatomic gases lik e H2, 0 2• N2, CO, and 0. before, regarding th e new liquids that could be pro Ass uming I 03 atm and 304. 1S K as init ial condi duced by liquefaction (see above). tions, a drop to atmospheric pressure correspond s to a Cai ll etet' s note "De Ia Condens(/( ion de I' Oxygene fina l temperature of about 8 1 K. The cooling effect is et de I'Oxyde de Carbone" was read immediately due to th e external work done by th e gas in expanding thereafter"'5 In it Caill etet reported that if oxygen or agai nst th e downstream press ure. The actual cooling carbon monoxide were put in his apparatus"'" (b ioxide. wi ll be less because of th e cooling effect of the wa ll s REF) at 300 atm and cooled to -29°C with boiling of the vessel, and heat losses to the environment. sulphur dioxide, both gases remain ed as such. If the In a following pub li cation Cailletet reported th at he gases were th en released suddenly they wou ld cool, had used hi s eq ui pment to li quefy nitrogen dioxide at accordin g to Poi sson ' formula, to a temperature :woo 0 104 atm and - II C. At to 8°C N02 remain ed in ihe below th e initial, and immediately an intense tnist 4 gaseous state at pressures up 270 atm "'. He also ob (brouill ard intense) woul d be seen, caused by th e liq served th at when methane was compressed to 180 atm uefacti on and perhaps the solidification of oxygen or
230 Wisniak: Louis Paul Caill etet- The liquefaction of the pe rmanent gases Educator ca rbon monoxide. The same phenomenon was ob served when th e gas was carbon di oxide, nitrous ox ide. and nitrogen di ox ide. This mi st was produced when compressed oxygen was released after it had cooled to room temperature. Caill etet indi cated that he had demonstrated this fact during experi ences he had performed on Sunday, December 16. in the chemi stry laboratory of the Ecole Nor/1/al Superieure, in th e presence of various in vestigators and professors, some of th em members of the Academic. Caill etet added that to authenticate th at oxygen or ca rbon monoxide were in th e liquid or solid state it was enough to perform an opti cal tes t. which unfortu nat ely was easier to say than to do because of the shape and thic kness of the tubes in hi s ap paratus. Several certain chemi cal reactions had all owed him to bear out that oxygen had not transformed into ozone during the compression . Caill etet fini shed hi s report indi catin g that he had app li ed the same operatin g co nditi ons to hyd rogen wi th out observin g the presence of mi st and that he intended to apply th em to try to liquefy nitrogen. 46 Afte rwards, Mr. de Loynes , th e Pari s representa 1 tive of the firm Raoul Pictet & Co., read the telegram Fi g. 2- Sche mc or Cai lletet"s equipmcnt ' sent by Pictet and received on December 22 at 8 PM , L is a flask made of forged iron, capable of sus reportin g the liquefaction of oxygen in the following taining a pressure of 500 atmospheres, used to gener words: "Oxvgene !iqtu!{ie aujord'!tui sous 320 atn ws ate pure oxygen by heatin g potassium chl orate with a p!t ere.\ et - 140 de _fi-oid par ocide su/p!tureux et car heat source. The quantity of salt added to th e fla sk !Jonique accmtples''. The telegram had been followed determines th e oxygen pressure achieved. The gas by a document describ in g in detail the eq uipment and thus produced accumulates in the internal tube of H, proced ure utili zed for ach iev in g th e condensation maintained at - 140°C. After several hours of opera (Fig. :?.) . ti on oxygen achieves the conditi ons of 320 atmos Q and R are double-effect aspiration pumps. R op pheres and - 140°C. erates on liqui d anhydrous sulphur dioxide contain ed Opening the cock at N results in a strong expansion in tu be Cat - 65 °C. The gaseous S02 generated in C is of the compressed and cold oxygen and a large part of directed to the condenser D, operating with refriger it liquefies and fi ll s the tube M. ated water, where it liquefies at - 25 °C and about 2.75 After de Loyens' words, Dumas read a letter sent atmospheres. The diameter of pipe k is sma ll enough on December 2 by Caill etet to Sainte-Claire Dev ill e to produce the req uired backpressure to condense that th e latter had deposited th e nex t day in th e hands soc of the Secretary of the Academic, in a scaled enve Simila rl y, pumps R operated on liquid C02 con lope, which he now proceeded to open and read: "I tained in th e annular space H, held at th e proper pres hasten to in form you, and you first without losing a sure to evaporate the liquid at - 140°C. The gaseous moment that I ha ve liquefied this day both carbonic C02 produced is direc ted to th e condenser K sur ox ide and oxygen. I am perhaps wrong in sayi ng li q rounded by a tu be contain in g liquid S02 at -65°C and uefied, because th e temperature I obtained by evapo 5 atmospheres. The diameter of pipe d is sn:all rating sulphurous acid. is at -29°C and under 200 at enough to produce th e required backpressure to con mospheres pressure. I did not see any liquid. but a fo g dense C02. The liquid C02 return s to H through the so dense that I was able to in fer the presence of a va connector k. pour very close to its point of liquefaction. I have
231 Educator Indi an J. Chem. Tc:chnol. . March ~003
written today to Mr. Deleuil to ask him for some pro toxide of nitrogen. by means of which I shall doubt lessly be able to see carbonic and oxygen flow . P.S . I have just carried an experiment. whi ch sati s fies me completely. I have compressed hydrogen to 300 atmospheres, and after cooling it down to - 28°C, I ex panded it suddenl y. There was no trace or mi st in the tube. My gases (CO and 0 ) are. therefore. cer tainly at the point of liquefaction , as thi s mi st is only produced by vapours close to liquefaction. The fore casts of M. Berthelot are completely ve rifi ed". After Dumas finished reading Cailletet's letter Sainte-Claire Dev ill e rose to add more details. He said that on Sunday December 16. Cai ll etet had repeated his ex peri ences on th e condensation of oxygen at the laboratory of the Ecole Nonnale and that th ey had success full y duplicated the results he had reported in his previou s not e. Cailletet had not wish to publi sh them because he was a candidate to th e positi on of Correspondant of th e Academic, positi on that he was awarded on the session of December 17, an d he did Fig. 3- Sch..: mc of Pi clc!· s equi pmc: r11 13 not want that the di sc uss ion of hi s merits for th e posi ti on included a pi ece of work that its res ult s and not Loui s Pasteur ( 1822- 1895). and Charl es -Adolph e been repeated in front of appropriate judges. He did WUrt z ( 18 17- 1884). not wa nt to publish such an important achievement A year later after the presentati on at th e Academic, exactl y on th e day of his election. Fortunately. on De Pi ctet publi shed an ex tensive memoir giving many cember 3, Sainte-Claire Dev ill e had put the letter, details about hi s equipment and th e re~ ult s of th e nu pro perly sealed, in th e hands of th e Permanent Secre merous experi ences he had d o n e ~ 7 . tary. For th ese reasons Sainte-Claire Dev ill e believed that the priority of th e discovery belonged to Cailletet. The polemic about priority He al so added that the remarkable work of Pictet had Although th e proceedings of th e session of the hardly been qu oted; hi s operating procedure being Academic des Sciences indicate that Cailletet reported compl etely different from th at of Caill etet. th e liquefa ction of oxygen ahead of Pictet. th ere has Afterwards, several members ex pressed th ei r views been much argument about how well do th ey present that both methods were proof that oxygen had been the facts as th ey really took occurred. lique fi ed or solidified. Jules Jamin ( 18 18-1 886) indi Kurti 48 did a thorough study of all th e documents cated that the real confirmation of th e actual state related to th e proceedings of th e Academic and fou nd would be the ability to maintain liquid oxygen at it s several discrepancies. For example. Dumas om itt ed boiling tem perature, as had been done with li quid ni part of the letter that de Loynes, had sent to justify hi s trous ox ide; or at the solid state, as had been done employer claims. In th e paragraphs omitted, de Loy with carbon dioxide. nes indicated that Pictet's was well-known for manu For th eir in vestigations on th e liquefaction of oxy fac turing so2 anh ydrous, a criti cal element fo r gen Cailletet and Pi ctet recei ved th e Davy Medal from achieving the liquefaction of oxygen in both Cail the Royal Society of London (November 1878) and letet's and Pi ctet's procedures . In addition, Sainte the Prix Lacaze from the Acade111ie des Sciences Claire De vill e had ex plained that th e reason why he ( 1883). The selecti on committee members were Ber had not reported before to the Academic th e res ults thelot, Auguste Cahours ( 181 3-1 89 1), Michel Eugene achieved by Cailletet was that the latte r was a candi · Chevreul ( 17R6-1889, Henri Debray ( 1827-1888), date to membership and did not want that thi s impor Jean Baptiste Andre Dumas ( 1800-1884), Edmond tant achievement be part of the argument, before it Fremy ( 18 14-1894 ), Charles Friedel ( 18 32-1 899), had been endorsed by competent judges. According to
232 Wisniak : Loui s Pau l Cai ll etet-T he li quefaction of the permanent gases Educator
Kurti, th ere is nothing in Cailletet's letter indicating th e letter sent on December 5, 1880, by Ulrich th at he did not want his results to be known by the DUhring to the Permanent Secretary (Dumas) of th e Academi e before the electi on. Kurti went to archi ves Academie des Science, requesting that th e Academy of the Academi e, located the ori gin al letter and on publish an attached document entitled Reclamation de reading it found th at when reading it to th e Academi e la loi des temperatures d'ebullitioll correspondents Dumas had cut three paragraphs fro m the o ri ginal. In (Ciai m regarding th e law of corresponding boi Ii ng the mi ssing materi al it is c learl y stated th at Cailletet points). Ulrich pointed o ut that on th e session held by thought th at hi s preliminary results would help him the Academi e February 23, 1880. Sain te-C lai re achi eve membership. Devill e had read a communicati o n by Paul de Mode Kurt raises the questi on: " Why did Sainte-C laire sir regarding a compari son between th e temperatu res Deville in sist on Caill etet's pri ority over Pi ctet. Was it at whi ch pure components exerted th e same vapour chauvini sm - France versus Switzerl and?" pressure. De Modesir's communicati on was pu bli shed 8 enaroc I1 e 4'! rat. ses ot h er arguments based o n pho- in Compte.\· Rendu, 18RO, 90, 360-367. Ulrich tocopi es of the criti cal documents present in the ar Di.ihring pointed o ut th at hi s fa th er had already pub chi ves of the Academi e: (a) According to Sainte li shed the law "di scovered" by de Modesir in essen C laire-Devill e he deposited Cailletet's letter o f De tiall y the same terms and using th e same vapour pres cember 2, on December 3, in a sealed envelope, in th e sure measurements made by Regnault. More than that, hands of the Secretary of th e Academi e. There is no hi s father had not only publi shed th e law and ex record in th e Acade mi e (as existed for other similar pl ained it th eoreti call y, he had also suggested its letters) that thi s letter was deli vered, (b) Sainte-C laire practi cal applicati ons and its re lation to th e che mi cal Deville claimed th at Cailletet was candidate as corre structu re of the molecul es. Di.ihring's book reports spondant for th e electi o n held on December 17 . Cail that the Academi e published onl y an extract of Ul letet's name does not appear in the li st of candidates rich's letter ( Comptes Relldu, volume 91 ) under th e th at was posted in the session held o n December I 0, title Reclamation de priorite au suject de la loi des as was th e usual procedure, (c) th e most curi ous fact temperatures d' ebullition correspondents. Exu-ait is that th e letter that was supposed to be received o n d'une lettre de M. U. Diihrillg. The way th at the December 3, was actu all y received o n December 2, original letter was reduced in length caused another (d) the post-script in Cailletet's letter to Sainte-Claire bl ast of Di.ihring again st th e scienti fic establi shment 50 Devill e (deli vered o n December 23), was dated De and its journals . cember 2, and hence it was not possible th at the post script was deli vered on December 3, and fin all y (e) It Liquefaction of other gases is clear that in the letter from Sainte-C laire-Deville to In th e same year that he liquefied oxygen ( 1877) Dumas th e date has been corrected. Cailletet reported th at he had been abl e to lique fy ni 5 1 Benaroche is not sure if all th ese inconsistencies trogen, and air, and probabl y hydrogen . To liquefy represent a chain of cleri cal errors or other moti ves. nitrogen he first compressed th e dry gas to about 200 In thi s context we can menti on the accusati ons of atm at l 3°C ; after a sudden release of the pressure the pl agiari sm that Karl DUhring ( 1833- 192 1) made fo rmati on of large liquid drops was observed, which against Paul de Mondesir in hi s book Neue Grundge disappeared in contact with th e wall s of the vessel, setze m r Rationalle11. Physik und Chemie ("Funda fo rming a sort of liquid column alo ng the axis of the mental Laws of Physics and C hemi stry"), published tu be. The total pheno meno n lasted for abo ut three in two volumes. The second volume closes with a seconds. On December 30. 1877, he repeated the ex two-page statement entitled "About Pl agiari sm of th e peri ence at -29°C, in th e presence of several me mbers first volume of Fundamental Laws of Physics and of th e Academi e, amo ng th em Jean-Baptiste Boussin Chemi stry". In it DUhring makes a bitter attack on gault ( 1802-1 887). several peopl e he accuses of copyi ng his ideas about Cailletet used the same techniq ue to liquefy air, ab the corresponding temperatures of boil ing liquids. In solutely dry and free of C0 2 and commented th at thus parti cul ar he singles o ut Winke lmann for th e papers Lavoisier's prophetic words had been confi rmed: pro he publi shed in Allnalell der Physik and de Modesir ducti o n of substances with new and un known pro per for the paper he publ ished in Comptes Re11. du. In the ties. He also remarked th at hydrogen had always be mi ddle of th e second volume th ere is also a copy of ing considered the most non-condensabl e gas because
233 Educator Indian J. Chcm. Tcchn ol. . March 20()]
or its low density and mecha ni ca l properties almost when the liquid passed into gas, at temperatures above identi ca l to those of ideal gases . Anyhow, he per th e critical one. According to Cai lletet ancl Haut e fo rmed his experiments of sudden expansi on from feuille th e disappearance of the meni SC US Wa S llOt 280 at m, in the presence of Berthelot. Sainte-Claire necessarily sy nchronous with the al tai nment of the Deville, and Eleuthere Mascart ( 1837- 1908), and all critical temperature. had had th e experi ence of observi ng a ve ry fine and Cai lletet and Bordet54 discovered tha t when phos light mist, suspended in all th e mass of th e gas, that phine WaS co mpressed in th e presence of Watel· it disappeared very fast. would liquefy and lloat on top of th e water layer. If In a following work. Ca illetet was able to liquefy th e press ure was suddenl y released a white crystalline eth y lene under various press ure and temperature con body would form that would di sap pear i f th e press ure ditions 5~ . For exa mple, at I 0°C th e pressure required was reduced further. The formation and decomposi was 60 atm while at I °C it was 45 atm. From hi s ti on of th e crystal occurred at fi xed press ures ancl man y meas urement s he es timated th e critical tem temperatures: for exa mple at 2.2°C ~llld 2.8 atmos pera ture of ethy lene to be about I 3°C (ac tual ly 282.4 pheres. and 20.0°C and I 5. 1 atmospheres. The cri ti cal K ) in compari son with 3 1° C for ca rbon dioxide. In a temperature of form ati on (congruen t point) was 28°C. footnote he indicated that determination of th e critica l Ca illetet and Bordet believed that the crystals were tem perature was difficult because it va ri ed strongly co mposed of phosphine hydrate, although they were with small amounts of impurities. unable to determine its compos ition. The low value of ethylene's cri ti ca l temperature They repeated th e experi ence with oth er wet gases sugges ted Ca illetet th e poss ibility of using boiling and found similar resu lts. For ex ample, th e compres ethylene in stead of boiling nitrous ox ide (N 0 , Tc = 2 sion of equal volumes of wet C02 and phosphine re 309.6 K ) to achieve lower temperatures. He repeated generated a white crystalline solid, without leav ing a hi s experiments on th e liquefa ct ion of oxygen using gaseous res idue th at was ass umed to be a mixture of this time liquid eth ylene at - 105°C as th e coldest th e hydrates of th e two gases. Hydrogen sulphide also so urce, in stead of liquid Nc. O at - 88°C and found that co mbined w ith water y ielding a hydrate having a th ere were substanti al eli rrerences between the two critica l temperature of 29°C. liquids. With Nc. O, th e free expansion produced onl y a Cailletet and Mathias55 des igned a very simple ap thin mist of very short life while w ith liquid eth y lene paratus made ou t of glass to meas ure the density or a definite amount of liquid oxygen was produced th at th e vapour and liquid phas es of a pure co mpound as it boiled vigorously for a long period of time. Cailletet approaches its critical point. A plot of their experi remarked th at liquid eth y lene was not on ly capab le of mental res ults of th e dens ity for N::> O, eth y lene, and prod ucing lower temperatures , it also had the advan C0 , showed that the mean densi ry of both phases tage of being transparent, in con trast with liquid C0 2 2 decreased linearl y with th e temperature and that the and liquid Nc.O, which were opaque. st rai ght line drawn through the middle point of the 5 Ca illetet and Hautefeuille ' did so me interes ting chords went through th e critical point. They suggested work on th e behaviour of gases nea r their critica l employing this fact to determine th e critica l tempera point. Small temperatures chan ges around th e critical ture and den sity of a gas, usi ng measu rements be low point gave place to observable striat ion and undula the critical point. tions and th e question was if the liquefied gas was This finding is known today as th e Ca illetet co lou rl ess, had a colour, or cou ld a colour be added M at hias rule. Mathematically arti ficially. Ca illetet and Hautefeu ille found that al th ough it was very easy to co lou r liquid C0 by addi 2 Pavcra gc = 0.5 (pl. + P c; ) = (/- bT ... (5) ti on of either iod ine or ozone, th ese we re not appro priate because iodine attacked mercury and th e prop where pL and pG are th e densi ti es of the liquid and ert ies of ozone mad e observat ions of th e ph enomena gas phase, respecti ve ly. Applying Eq . (5) to the va l occurring nea r the critical point difficult. After trying ues T = 0 and T = Tc we get a = 0.5p, and many so lutes they concluded th at the best one was blue oi l of galbanum ( ote I ). A small drop of th e oil PL = Pc = Pc, where P, is th e density of the so lid was enough to colour th e gas w ith a light blue tint. phase at 0 K and Pc the density at the critical point. The co lourati on allowed th e changes that took pl ace Hence,
234 Wisniak: Louis Paul Cnilletet- The liquefaction o f the permane nt gases Educator
T I 0 Fourcroy A & Vauquelin N. Ann Chi 111 . 29 ( 17')9) 28 I ... (6) P~. + Pc; = P, - (p, - 2pr ) T I I Monge G & Clouet J F, Ann Chilli. 2 ( 180 I ) 74 c 12 Fa raday M . Trans No\'(/ I Soc. 13 ( 1823) I (JO
Epilogue 13 C l;tud e G. Air Liquide. Orvgc~ n e. A=ore. DurHld. l'aris. 1909 The ex isten ce of liquid oxygen ha ve a picturesque 14 Thilorier C, An11 Ch in1 , 60 ( 1835) 427 56 angle in Jonathan Swift's book "Gulliver's Travels" l .'i Farnday M. Phil Tmns, 13'i ( 1845) l.'i.'i 57 and in Jules Verne's book " Le Doe teur Ox" (REF). 16 Aime G. Ann Chi111 . 8 ( 1843) 27.'i In chapter V of "A Voyage to Balnibarbi", Lemuel 17 Netterer J 0. Ann Chin1 . 62 ( 1844) 132 Gulliver describes hi s visit to the Grand Academy of 18 Regnault R. Relarion des E.rperiences. in three vo lu mes . Lagado and th e projects its sc ientists are engaged: "I Pari s. 1847- 1870. also published w ith th e s;une pa gination had hitherto see n only one side of th e Academy, th e as Menwires de /'!\cade111ie des Sciences. 2 1. 1847). 1-7(17: other be ing appropriated to the advancers of specula 26 ( 1862), 3-928: 37( I ) ( 18(18). 3-575: 37(2) ( 1870). 'i79- tive learning, of whom I shall say so mething when I 96R The obse rvation in question appears in volume 37(2) ha ve mentioned one illustrious perso n more, who is 593. ca lled among them ' th e universal artist' . He told us 19 Joule J P & Thomson W. fJhil Mag. 141. 4 (I 852) 48 I ·he had been thirty years employing his thoughts for 20 Regnault R. Me111 Acwl Sci. 37(2) ( I X70) :179 the i mprovemcnt of human I i fe'. He had two large 2 1 A ndrews T . Phil Trans. l.'i9 ( 1869) 575 roo ms full of wonderful curios ities, and fifty men at 22 Andrews T. Phil Tmns. 166 ( 1876) 421 work. So me were cond ensing air into a dry tan gible 23 Wisniak J. Che111 Er/fl('o(()r JOnlineJ . 5 (2000) 1-l'): S 1-+3- substa nce, by extracting th e nitre, and letting th e 4 17 1 (00) 03386-3 aqueous or fluid particles percolate ... " 24 Ca illetet L. Co111p1 Rendu. 65 ( 1867) 322 In " Le Doctcur Ox" Doctor Ox and hi s assistant 25 Ca i lletct L. Con1p1 Rendu. 73 ( 187 1) 681 Ygene co me to the small quiet community of 26 Ca illc:tct L. 73 ( I X7 1) 1476 Quiquendone located in Flanders. He promi ses to Cm11p1 Rendu. light thi s town with a network of oxyhydri c gas pipes. 27 Cailletct L. Co111p1 Rendu. 82 ( I X76) 120.'i During the construction of this network, th e quiet 28 Bert P. Co111pr Rcndu. 70 ( I X7 1) 33X. 73 ( 187 1) 1444 co mmunity becomes quite excitable, to the point 29 Cailletet L. Cmnpr l? endu. 62 ( 1866) 891 where th ey arc ready to go to war against a nei ghbor 30 Ca i lletet L, ConJfJI l? endu. 60 ( 1865) 344 ing co mmunity. But what is the cause of this cha nge 31 Ca i lletct L. Co111p1 Rendu. 61 ( I X65) x.'iO in th e nature of the good people of Quiquend one? 32 Ctilletet L , Colllfll Rendu. 5R ( 1864) 327 Perhaps it is so mething in th e air, but only Doc tor Ox and hi s assistant Ygene know for sure. 33 Cailletct L. Co111p1 l?endu. 58 ( 1864) 1057 34 C~1i l let e t L. Co111pr l?endu. 44 ( 1857) 1250 References 3.'i Cai lletct L. Co111p1 Rendu. 70 ( I X71) I 13 1
Wisniak J. Cl1enJ f:'c/uwror (Online (. .'i(2): Sl430-4 17 1 (00) 36 Ca illetet L. Colllfll Rendu. XX ( 1879) 6 1 0237 1X (2000) 37 Cai llete t L. Co111p1 l? endu. 75 ( 1872) 1271 2 Amontons G. 1/isr Acari Rovale Sci. 200 ( 1703) 38 Cailletet L. Co111p1 l?endu. 85 ( 1877) 851 3 Amontons G. Hisr Awd Noyole Sci. I 19 ( 1704) 39 Ca i lletet L. Cmupr l?endu. 7R ( I 874) 411 4 Gay-Lussac J. An11 Chi111 Phvs. 21 ( 1822) 82 . In a footn ote to 40 Ca illetct L. Co 111p1 Rendu. 83 ( 1876) 12 11 the paper Gay-Lussac indicates that it is an abs tract of a memoir he read to th e Ac;Hie mie on M;trch (J. I X l .'i (In 4 1 Ca illetet L. Cm11p1 l? endu. 84 ( 1877) 82 rrench) 42 Ca illctet L. Conrpr Rendu. 94 ( I R82) 623 .'i Ga y-L ussac J. A1111 Chin1 Phv.1, 9 ( 18 18) 30.'i 43 Din F, Thennod\'1/(/1/ Jic Fun cr ions of' Cases. Vol 2 (l)utter- 6 C lement N & Deso rmes C B. J Phvs. 89 ( 18 19) 32 1 worths. London). 19.'i6. 77 7 Lavoisier A. Ele111 enrs oj' Che111isrry. Great Books of th e 44 Ca illetct L. Co111p1 l? endu. 85 ( 1877) 1016 Western World (W . Benton. Pub lisher. Encyclopedia Britan 4.'i Cai lletet L. Co 111pr l? e/1(111. X5 ( 1877) 12 13 ni ca. Chi cago). 1952. 16 (originally published in French in 1789) 46 De Loyncs. Co111p1 Rendu. 85 ( 1877) 121 4 8 va n Marum M & va n Trovstwyk P. Ann Phvs. I ( 1799) 145 47 Pi ctct R. Ann Cl1i111. 13 ( 1878) 145 9 Guyton de Morveau L. Ann Chi111 . 29 ( 1799) 290 48 Kurti N. Crvogenics. I X ( 1978) 451
235 Educator Indian J. Chem. T ec hn o!. . March 200]
49 Benaroche S. Arch Sci. 38 ( 1985) 225 56 Swift J, Gullive r'.\· Tra vels (Penguin. London ). 1938 (Thi s book was first published in 1726) .~0 Wisni ak J. .I Phase Equil. 22 (200 1) 616 57 Vern e J. Le Docteur Ox (Doctor Ox) Hetze l. Paris. 18!l3 51 Cai lletet L. Co111p1 Rendu, 85 ( 1877) 1270 52 C:J illetet L. Co111p1 Rendu. 94 ( I S82) 1224 Notes 5:1 C 1illetet L & 1-l autefeuille P. Co111p1 Rendu. 92 ( IRS I ) 840 I . Ga lbanum is a resinous oil th at was import ed from the Middle Ea st and used for medicinal purposes and incense offerings. It 54 Ca illetet L & Borde! L. Co111p1 Rendu. 95 ( I 882) 58 also mentioned in th e Bible. Exodus :10::14 under the name of 55 Cailletet L & M at hi :J s E. Crn npl Rendu. I 02 ( 1886) 1202 che f!Jonah .