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Louis Paul Cailletet-The Liquefaction of the Permanent Gases

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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.
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