Experiments on the Transmission of the Vapour of Acids through an Hot Earthen Tube, andFurther Observations Relating to Phlogiston. By the Rev. Joseph Priestley, L L. D. F. R. S.Author(s): Joseph PriestleyReviewed work(s):Source: Philosophical Transactions of the Royal Society of London, Vol. 79 (1789), pp. 289-299Published by:Stable URL: http://www.jstor.org/stable/106698 .Accessed: 04/11/2011 14:04

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XXIII. Experiments on zbe lRranJ^nif on of zbe Vapour of Scids throvg;D an ho earzben Czgbe, andftgrther ObJerqJations relating to PhlogiJ?on. By he Rev. Jofeph PrieIlley, LL.D. F R. St

Read July 2, x789.

I N my late experimetlts on the phlogiJ?ication of J9irit oJr nzZra by heat it appeared, that wher] pure air was expelled from

what is called dephlogifl:icated fpirit of liere, the remaotlder was left phlogifticated. This I find abutldalltly coIafirlned by repeating the experiments in a different manner atad OI1 a larger fcale; and I have applied the fame procefs to other acids alld liquors of a differellt kind. lFrom theCe it will appear, that oil of vitriol and fpirit of nitre, in their moR dephlogiRicated ftatet confiR of a proper faturation of the acids with phlo- giRotl, fo that what we have called the phlo, iJ?icvzion of them, ought rather to have been called their Japer-phlog#cdtion.

I l)egan with treating a quatltity of oil of vitriol as I had done the fpirit of nitre, viz. expofing it to heat ill a glafs tule, hermetically Nealed, and llearIv exllauRed; alld the refult was f1tnilar to tllat of the experiment witll the nitrous acid, with refpeE to the expultion of air from it, though the phlogi{tica- tioil not appearitlg by atly cllange of colo?rs I did not ill this metllod afcertain that circum0anceX The particulars svere -as follol7vs.

After tlle acid had been made to boil fome time, a denfe white vapour appeared ill- quick tBOtiOIl At a diRallce above vlne

acid:,

Dr. PRIESTLEY'S EDncperitnents 29o acid, alld though, oll withdravvillg tne fire, that vapour difap- peared, it iItalltly re-appeared on renewing tlle heat. \7Vhetl tlle tul)e ssTas cool, I opetled it ut der svater, aald a quantity of air rulhed outX though the acid had been made to botl viow lently wtlile it was clofitlg, fo that there could not have been rnuch air itl the tulze. This air, svllich muIR therefore have l)eell generated ill the tlslbeX was a little svorfe tllatu commo airX lDeitlg of tile Ilalldard of 1.Is when the latter ras I.04. I repeated t}

on the Vapaur oJ Acidst t9I lezoo), I colleEtee3 19dw. 6gr. of the volatile acid, of the fpecific gravity of 340 atld 130 os. meafures of dephlogilli cated atr- of the pureIt kitld viz. of the Ratadard of o. I 5.

It is eafy in this mallller to colleA a great qualltity of de- phlogi{ticated air; lzut the principal objeAiols to the procefs is, that after ufing a few titness the eartilell tubes becotne teIlder, and too eafily break efpecially in heating or coolitlg. It is alSo difiicult to lute the retort contailling tlle acid aIld t}e earthen tube. The air produced in tllis manner is filled with the denfeR w}aite cloud imagilaable.

Going through the falme procefs with fpirit of nitre, the refult was in all refpeds fornilar, but much more IEriking, the produEioll of both dephlogifticatecl air and phlogifl:icated acid vapour being prodigiou{ly quicker, and more abundant. Ex- pending 5 oz. 8 dw. 6gr. of fpirit of llitre, I colleAed 600 OZ. meafilres of very pure dephlogiRicated air, being of the Rall- dard of 0.2. I alfo colleEed I 0z 7 dw. t4gr. of a greetlii acid of 1litre7 which emitted copious red fumes. All the appa- ratus beyotld the hot tube was Elled witll the delafeR red vapourw and the svater of the trough itl which the air was received sras fo much ill-pregnated Wittl it, that the fmell was vsery firoIng; and il: fpontalueoufly yielded 1litrous air feveral days, juI} as rater does wllen ilnpregnated with nitrous vapour. PerceivZ ing the emiffiloll of air from the water, after it had ftood fome t;ne, I Elled a jar containillg 30 oz. meafures with it, and svitlaout ally heat it yiclded tsvo oz. meafures of tlle firotage{t

* -

nltrous atr. Takiglg the fpecific gravity of the acid t)efore aIad after this

diRillatioll the former was to the latter as J47I to II82 Whell the ^ reight of the air produced in this experilnetltX alld- tllat of the liquor di{lilleds is conlpared s^tith that of the acid

7 beforb

M93 Dr. PRIFSTI E?S Encteriments before diRillatiotl, it will appear, that there mtlll have been a great lofs of acid vapotlr, wElich was either retained ill the snrater of the trougll or eScaped through it.

I do laot fee that tlzefe experimellts can l)e explained, buton the fuloSpofitioll that tlat moR dephlogiRicat-ecl til of vitriol aald fpirit of nitle are, in a proper fenfe, Iaturated with phlogiRon; atld t:hat vvlletl part of the acidifvilag pritlciple iJ expelled in the fc)rm of tEle air, the relnaillder is filperfaturated with it

To try *hetEzer the acid, thus fuperfaturated zvith phlo g;0(ll, wtas collvelt:ible itltO pure air by this procefs, I heated tlle liquor colledcd after the diRillation of the oil of vitriol, that iss water impregtlated svith vitriolic acid airl atld made tlle vapour pars through the hc)t ttlbe, but lwo air catne froln it; alld strhell colleEted a fecond time, it was not at all diffieretlt frotn what it had beell before. The fpecific gravity was alfo the fame.

lt is evident, thowever, though this procefs-does tot {hew it, that the volatile vitriolic acid coIltains the proper elemerlt of dephlogiRicated air; fillce by meltlng iron in vitriolic acid air, a quantity of fixed air (which is compofed of inflammable and dephlogifticated air) is produced. lVIelting rirotl in 9

on zho Mapour of Acid30 29 deplllogifticated air. The qualltity of tile liquor expetwec was alout z ozg meafures. It lllay, however, be prefutneds that this ftnall quantity of air came fiotn fome of tlle acid which efcaped the &iOtl of the fire ill the former procefsX Tv- deed its coming at the 1a1} otily may be confldered as a proof of tllis as all the more volatile acid, which catne over firI}> yielded no air.

I futlzitted a quallt;ty offfzriZ of J*vlt to both tlatSe pro cefles viz. expofitlg it to a boiling heat in glaEs tubes, lzer- xnetically fealeds alld making the vapour pafs through a red llot earthen tubeX l)ut 1a0 air v^7as produced in either cafee Ill the former caSe9 the vater ruIl

y94 Dr. I>IES'rLEYsS Ex.ter4>lents formed; whereasX in the other caf-C it 5vaS coIntnEtllicated to tlae zvater ill the worm-tub.

I1w o1le of the proseies witll boiling fpirit of faltX itz a glafs tulgeX hermetically fealed I had the falne wthite vapour danc- tzg in the rniddle of tlae tul)e as itl tlle experimellt with tlle wil of sitliol; IJUt this tube bterR alld I Ilever nad the fame appe.latlce agslill, tllollgll I repeated the experiment feveral titnes for the fake of it.

The vapour of deplllogiRicated marine acid, which M. 33Ea-otLEt diScovered and with which water may be inz- pregtzated as with fixed air, being tnade to pafs tllrough the lAot eartherl tube, becatne dephlogiflcicated air as in the follow-

-

sllg exI)erlment. ; tiaving poured a quantity of fpirit of falt upon fome man-

g;alleSe in a glaSs retort, I heated it as in the preceding experi- nzents with a proper aloparatus both for rectiving the diItilled

iquor7 and the air. I foutad feventenths of the air was fixed air, arld the remainder very pure dephlogifticated. The qualz- tity I could not meafure oll account of olle of the junAures in the apparatus giving svay; but I Elo llot- imagine that quite fo mllch pure air could be got in this method as frorn the manga

eNe itSelf ill a direth proceSs. TIle liquor received in this dif- til]ation refembled firollg fpirit of falt in which manganefe had 13eell put.

t:lnhis procefs immediately fucceeding that ixl which the glafs tube, joining the earthen tube and vormitub, was left full of black matter by the diIlillation of the alkaline liquor (which will be mentioned hereafter), the blacknefs prefently vallifhed, and the tube became tranfparetlt as before. 011 this accounts hosveverX it is poffilble that I might receive lefs pure air than I Jhotlld otherwife have doneJ

3:1iRilled

oB ttg Spdar ^, He/gfio 25s :t3iRillcd vitwegat {;lI)mitted to tlais procefs yielded (l1t4 tWow

tlwirds of ^rhich was fixed air atld the reR it+flattltuable t ex pellding 2 OZ. I 9 dw. O gr. of the a.cids I got x oz. X g dssri O ; of a liquor whicil 11ad a more pullgerlt ftnell than it had before diflcillatiotl It llad alfo fome blacli matter in irg atld fvtne of the fame remaiLacd at tlle bottom of the retort when the liquor vas evaporated to drynefs. Tlle ait I received was 9s ozb mesafulFes.

Alkalitle air is cOlivertedl ifito illflainmable air ill this procefs

as svell as by tlle el>C4ric fpark, but l)y tlo means, I thltlkX iw fo great a degree. I put 2 0'. 10 dvvi o gr. of water preEty IlroIagly itr.pregnated ^rith alkalitle air illto tlle retortS aIlCi henting it fent the vapour tlarough the hot tube X svlletl I coi

ledced z oz. 3 dw. o gr. of liquorf which llad a difagreeable

etupyteumatic finell, as srrell as tEzat of a volatile alkali, and it

was quite opaque with a Slack mtter, which fubfided to tlae botrom of the vefel. Alfo the tube through shich the air

alod vapour had lJeen conveyed was left quite black, as rnen tioned above. One of the junEtures of the apparatus not havitlg beetl air-tightR I did not colled all the air7 but it came

only at tlle begintlitly of thc procefs, AIld before the tube be-

came black, or ally liquor was diRilled, alld it was all flrongly inflammable.

I thall now recite a fexv experiLnetlts of a different kttld from thote that have been mentioned abovef alld more itntnediately

relatillg to the doftrine of phLogiRon.

It is faidS by thofe W-10 do llot adMit th$ doRrine of phla- gi[5col

296 Dr. )KIES'RLEY'S Experiments it) of iron ill dephlogiIticated air, appears to mv to be very evidetlt, as well as in the procefs with Ream.

That fixed air is foutld ill the veSel ill which iron is tnelted ilu dephlogiRicated air, I obSerared before; but I Ilever took mtlctl care to aCcertain the quantity of it. This I have lately clone in many illItslllces, and in all of them fil,d it to be mllcl:l more confiderable thall can be accounted for, by fuppofing it to come fiZom plulrlbago in the very Emall quantity of iroll that I melted; fo that it muIt lleceIfarily have beeIl formed by the phlo- 2,ifiOIl fiotn the iron, and the pure air in the veXel, at the fame time tllat the iroll lDecame fillery cindel by izlbibing w^ater from the air; and I hav-e thewn, that by far the greateIt part of tlle svoiglat of tllis air is water. tl>he experimeIlts were made with a very good- burning lells, of fixteen inches diameter, with svElicll A4r. PAREER tas generoufly furIlifled me; and by 1l1eSI1S of it I catl I10W make thefe exper;tnents, whicll require a gleat degree of heat, svitll much nore eafe aIld certailaty than t: could do lesote

In 6-X oz. mearures of cleplilogiRicated air I melted turnings of malleal)le iron till there retnai1zed olaly I 3 OZ. meafure, and of tilis 3 7 0zv meafure svas hxed air. Ill 6 oz. meafures of EleplllogiRicated airX of tl

on thfe Vapot oJC Acirls. S 9 7 had been about Ex grains. I repeated tl-we experiawetst Witil the fame refult.

When tlle dephlogi{licated air is molXe imptlare, fille quarltity of fixed air vill always be leSs in proportiotl. Thtlsv laviIg melted iron in Seven outlce mearures of dephlogiflicated air of the arldard of o.6S, it was reduced to .h oz. m..; aIld of this only otle-thilzd of an outlce meafi1re was fixed air. TI-lisX how ever, is much more thatl can come from the plumbago in the ilon; ltut as the produEtion of this fixed air is by malzy aCcribed to tllis plum!ago, it may be wortll whlle to thew by computation that it is impoIElble t;hat it thould have tlAis olipMill. ECoth the qu>.Xatity of plumbago in irota (ltjd theX QURiltity Of Exed air in plumbago, are much too fmall for t6le putpofe.

From half an ounce of the pureR plumbago, I filR gotX ill a coated glaEs retort, I3 OUtRCC-lYlCarUrtS of ail^ of unich cilly tllree;oulace meafures ssrelae fiXed airS tXle .tC0L l)CWli>ag it8flalNma- ble; then ptlttialg it itltO atl eatithen ulve 3[ Lept it ful.ne hours in as great a heat as I could ploduce, (-tld >-)Ot 72 OZJs mX more; arsd of this alfo only threc XVet^d fi5acds +.tld the reR inflammable, atad the laA pcJrticutl vxras vollv- foX

But inllead of fuppofiltzg the fixecl air tI-at T got to be that whicll svas expelled from tlle plulnSlo,o Xtl tR'ld iieozS I svill fulppo{e tllat even the wlaole of^ X lis ptum'>zgo aXxU;-ded o1llv otle of the elements of the fixed air? tv;z piJlt3gizlnjllg or that which the Frellch cllemiRs call a^boie S .-5tld rIlat vlas prici ple, by its union with the dophlcp,iJfliatd ar itl tile veflelX :forms the fised airX yet on this moR utlfavourable atld itnproe lJai3le ftlppoEltion the qualltit-y will 1)e foutld to le iIlitlf-Fcient

If IOO gr of irorl CC)tlttlilla acct2t^di:tg to *VAt }3ERGNTANg O. I 2 gr. of plumbago? 7 gr. \ Evhich iRi tl io Lzlr3R ti-lat ill (Itly 6>f the prececling proceI3ts I co1lvel^t

a >g JU)r. PR IES r L$Y9S Espermenfis ct,tlloaita ollly o.ooSA gr. of plumlago; and if we fsppofe vvlth J9lr. KtItsisraNS tll?t all llutadred cubic illches of fixed air conu tclitlS 8. I 4. ts,r of telllogtfiolzs tlle fiXed ail produced in one o tlele a130Ve-r-eRt-iotled pl-oces (viz. fourfiftlls of an ounce lwlenIsIe) srcould cotltaill .O32 gr of phiogillog which is above tllree tSues tmore thtltl tlle plulnl)ngo ill the iron could furni st is nvidellt, tllerefole, t11at tlle qualatity of fixed air that I t^oulael tnuR l-lave beetl formed by plllogii[toLl from the iro ulfitillb witll tlle dephlogiAicated air iLl the vcffcl.

iIt; ^ ls:I llave infelred, from burlwitlg charcoal of copper i dephlogiRicateci alr (fice FxperimeltX Vol. VI. p. 27Z.) fixed 66lir COtlll2-S 6)f 3.45 parts of deplllogiRicated ailo arld Xb5 of pl-llogifl:oll, it rvill be fotlled, tllat four-fiftlls of atl oullce mea-

l^ure of fixed air svill cotltaill o.2l gr. of phlogiIlon,, svbich is

rnucll lalore thall 011 the fuppo&tion of Mr. KIR\0rAN.

Anothel algumellt agailllt the atltipillogiRic doEtrille may be

drawll frosll at1 expevrirnellt svlaich I made UpOIl Pru{llatl blue S if the ftnall quantity of fixed ailX that may be expelled from it

I)y heat, be cotnpared svitll the much greater quantity which is pl-oduced ssTIlelu heated in elephlogiRicated air.

PlIllctll blue is geIaerally faid to be a calx of iron fuper-

fatllrated witil pEllogi{lonv thougll of late it has been faid by -fotne tllat it laas acqtlilSed folnethitlg that is of the nature of

atl acidv From z1y experiments UpOll itj .vith a bulmilog len$ izl dephlogiflicated airs I Ihould infer, that the former hypo-

tlaefis is tlue cxcept tElat the fulfiatlce colwtains fotne fixed airs

hicla is 1lo tloubt arl acid; for mucll of the dephlogifticated air

dilblppearsX guIt as ill the pxecedillg fltnilar proceIs ^rith iron.

I threw tl-le fectls of the burtaillg letas upon 2 dw. 5 gr. of

Pruttii< b'ut lIl a weel of dephlogiRicated air, of the Ilan-

.da;d of o.s., till all tlle colour was difcharged. Beillg thels

s^7eighed,

on the V4pour of Acids. jgg xteigheds it was I dw. zgr. It1 this procefs 7+ oz. of fised air llad beell produced atad hat rerrained of the air vatcls of the Randard of og4. E-Ieatilag the lzlc)Ni7tl powder to wvlaich the Pruffi1an blue svas X edueed iL) thiS CXpCrit.ntllt in t) flaturna ble air, it iml3ibed St- c)z. m. of itg allcl becatne of a blaclv colour; but it was neither attl