~ \ ~ r i I ~ , ~ w . ] THE JOURNAL OE' THE SOCIETY OV UHEMI(3A.L INDUSTRY. 327 --

A cosvEKiEsrr L;OI~II OF i)is*rmrbTIox IL~SK

w,\'rms, ASD FOIC OI~TAISISG WATEB FIIEI.: FOB THE IESJ'IbIA'l'lON OF AM3IONIA IS

FIIOJI OIIGASIC BIAT'I'!CII. 1 l Y J. 11. CllI.K:JI.\S, .\.II.C.SC., F.I.C.

Is the estiiiiiition of "free " nntl '' ullruiiiiiioid" uniiiioiiiu iii w t e r considcriilile tlitliciilty iii freeing tlic iipIiiinitiin frniii niniiioiiiii gns is cxpcriciicccl. 'Hiis is not +o grcd if it retort lie used no the tliutillutor. Ihit evcii iii this ewe, in the ntliqitntioii of the neck of the retort it is iiccessiiry tliiit tlic nteitin C O ~ C I into coiitnct with riildicr-joints, unless the retort is siiinll ; aiiice, if lurgc retorts me used, it is nccts- riiry to ilntw ont tlic iieck so cis to lit iiito tlie inner coiiilenscr tube, or II qieciiilly liirgo conileiiser tulle riiust be i i a a l . Tlin ulilinrtitus thcii is roiiicrliiit cunibcrsomc.

If ii corked lliisk be iiscil iii place of it retort. the steuiii couics iiilo direct contiict with tlic cork, iiiid with tlic iiiiijoritp of corks tlie siipply of aniinoniit iippenr csliiiost- lew. hnulgsts aell know the value of 11 cork wliicli is nof IL source of iiniinoiiiu i i i tlic iibovc olierntions.

Ily einploying n distilliitiou Iliiak into tlie neck of wliicli is fusctl it side tubc Bttcd with it light, hollow, glir.zs stopper, d l the above objcctioiis iirc done iiwuy with. 'J'lie stopper, when wettctl, is perfectly stcnin-proof, even if tlic gritirliiig is iiiiliflcrcnt. Tlie side tube pnssx sevcr;il inches tloan the iiiner conileiiser tube, wliicli is of jiist siitliciciit diaincter to iiclniit it, iiiid 50 the riililicr-joiiit is obvi:itcrl, perfect coiitlciisiitioii oeciirriiig ritlioiit crciipe of stciirii.

The writer or rciigeiit iiiiiy IN uiltlccl without clisturbiiig tlie uppiinitcia Iry siiiiply fiikiiig out iiiid rcliluciiig tile s tnlqicr.

I t will bc ~iecii tliiit Iiy implogitig l u r p tlusks, wntcr free froni orgniiic niiittcr cuii be conveniently prcpnrecl iii this II~llIunttus.

.-xculs----

A SIJII'LI< bIlC'l'lIO1) 01'' CAl~ l l~ l~ . l ' l ' lS (3 A I)lfLl VlCltlSG I'lI'kX'l'l~.

11T I'ILOYtSSUlt l'Il.\SIi t!l.LIWlX, USC., f .1 .U.

'I'IIE fohviiig will lie foiiiiil to be 'it siiiiplc iind iiccurnte wily of cstiiiintiirg the cupcity of it pipettr, no stop cocks or ntlirr iiilditioiiiil iipp:ir.t!iis liciiig iicetleil.

'l'lic cleitii iinil dry 1i;pettc is Iirst provided with iiii iirniiigciiieiit for closi~ig tliu tlclivcriiig eiid SO tlint it rang lie weighed while it contniiis wtcr .

' I l i a iirrnngcineiit is cllcctctl by slipping :t strip of rulilwr 4 in. loiig mid + in. wille Over the lower ciiil of the pipette, tlicii drnwiiig up the free eiitls on opposite sides iiiitlcr slight tension iiud biiitling tlieiii tightly with copper wire. Tlie riiblier iiow forins iiii elastic loop, with wliicli tlic end of t!ic pipctte niuy bc closet1 ut plensure. An iiidiit. riilrher riiig cut ucross unswcrs rtdniirubly for this strip.

111 tlic 1irocc.zs of cnlilirutioii tlic rubber loop is tlrnw usido ni id tlic pipcttc fillet1 by siictiori. Thc pipette ia itlloivctl to eiupty wid clriiin for liulf it iniuute, i i i i t l tlic eiid Iieiiiq at once closed 1iy the rubtcr bnnd, is weiglied at oiiec IXstilletl wiiter l i t 15.5' C. is iiow iiitrotlucc!il into tlic iippei eiid of the pipette liy iiieuiis of 11 fiiic wiisli-bottle jet, iiiiti! tne griiduittioii is reitclicd. 'l'lic pipetto is now weiglieti iigitiii. Tlic iiicrcuse iii weight sl:ould lie cipiit1 to tlic weigh1 of tlic rcgiatewd iiuinbcr of cc. nt 15.5OC. Slioiiltl this 1101 tic so, a little wuter iniiy be iitltlcd or tuken urviiy Iiy iiieniis of it piece of gliiss tiibc tlruwn out iiito it wleiitler ciipillury.

Iliiving iiiljiisteil tlic weight of wiitcr NO i i w to correslioiii with tlie rcgistereil vnlliiiic, tlic griitliiiitioii is tlieii iiiiiile ii the i isiiti l iiiiitiiicr.

)Iv DUJIAS' 3lETIIOI) OF l.:STI~IA'I'Ih'C NITROGEN 1s OIIC.\XIC U01)IXS.

11: tlic methods ciiiployetl to clctcrminc tlic quuiititg of iitrogcii iii orgnnic coinpoiinds tlicrc is not onc iiinre eroiired, niicl justly, tlinn tlint of the iibsolutc iiietliocl of hinins. Tliia process eiitnila more Iiihoiir, und tnkcs more iiuc tlinn uny other, Iiut this is coinpensnted for by tlic fititli vliicli ciin be plitccd in tlic results obtuined by it.

Dr. I~'niiiklniit1 (liliil. Tmna. rol. cxlvii. p. 5'3) in hi* :Iiissicnl reseurchcs '' On tlie Sulistitution of Nitrogeii for hrbon i n Orgiiiiic Compounds," experienced coiiriilcntlrle litliciilty i i i estinintiirg tlic iiitrogen iii tlic siibstitiitioii ,roducta. Ile cniployctl Simpson's iiiotliliciitioii of I)iiuiitx' iictlind niid found it iiiipossible to obtuiii the resulting gnx 'rec froiu coiisirlernblc qunutitiew of nitric oxide, iiltliougli :lie giis wiis i n i i t h to stream over IS iiiches of copper. To h t u i i i the iibsoliite voluiiies of nitrogen nntl nitric oridc, n ;:is-uniilysiy iippunitiis Iintl to be eiiiployctl. M y cxIierieiicc with tbc nbsolutc iiicthotl prorea tlint the

;ns obtiiiiictl iiiviiriiibly coiituiiis iiii nplireciiible quiiiitity of iiitric oxide, aatl tlint the iinrouiit is iiot iniiclt iiiflueiiecd by lie presciicc of the i isii i i l coppr in the coiiibiifition tirlic.

iiibstiiiiccs, cscc~it ivlicrc it i s otlicrtvisc stiitetl, w r e iiot imitlc to provc this, but were siiiqily piirts of uii itii:tlytic;il Iirores.*. 'The comliustioii tube wis tillctl iis in I ~ N I I S ' inctliod 5

however, :lie bic:irhiiute of sotla w i s dispcnsetl with, us u Sprt:ngcl Iii i i i ip \viis in 1111 c~iscs eiiiplogctl to obtiiin it

viicuuin i i i i t l to collect the rcsultiiig gums wlicn the CON- 1rii.itioii WILY coiiiplctctl.

l'lic copper osidc eiiiploycil wiis Irreiiiirctl froiu coppcr wire cut i n lciigtbs of nbout 5 iiiiii., niid tlic copper WIIS n roll of colilicr gauze 3 in. long, cnclosctl in a picce of sheet copper 1 this siie ositliacvl i i i i t 1 rctluccil by liydrycii prior to

Tlic tiiiir tiikcii to liuru tlic estriicts nientioiictl wts iii no cnse I C K ~ t h i n tlireo hours, iind tlic reiuniiiiiig boilien tiiliuliitetl, being iiiorc tlilliciilt to burn, took itboiit four hours. iirsciiiouu ncitl iuixctl with the copper oxid?, ns iidvisctl by Strcckcr, tlitl iiot liiivo iiny iiifliience in accelerating tlie coinlustion. A pw-ncitilysis nplinniturt wis eiiiplogct1 iii nll cnjes to tlctcriniiic the nbsolutc voliiincs of iiitrogeii iind nitric oxitlc iii tlic resulting CW wliicli wns collccted over potiisli. 'l'lic total voluiiic of p i s WILY first dctcrniinctl, nntl nftcr tlie ittlilitioir of i in execs of osggcii iii the presciice of potiidi, tlic CXCCSB of oxggcn \vus reiiioved by n few d r o p of pyrognllin. 'The rcsidunl gtw, being nitrogen, \vns thcii dcteriiiiiied, nnd the dilrcreiicc lietween this qiiiintity and tliiit of the origitiiil p s gitvc the nitric oxide prcseiit, which m a nbaorbed us nitric peroxide 11y the ~lOIilS11.

111 'l'iible 1. is sliowii the iiiiisimuiii, iiiiniiiiuni, iwi1 iiveriige pcrccntiigcs of nitric osidc in thc resulting gnu ivllcll COppCr WIII iiscil iii the coiiibriatioii tube :--.

I I Y J A M K . 4 O'?)I:Ll.I\..\S, X.I.C., Y.C.8.

, * 1 Iic cstiiiiatioirs of n i t rop i i n the iiiitlrriiieiitioireil

use.

*28 THE JOURNAL OF TEE SOOIETP OF UBEBlIUAL INDUSTRY. CAW1 W. 1 8 ~ .

12

11

n 17

111

.&

ti

Thcse iiuiiibcrs, to wliicli iiiiiiiy iiiorc obtiiiiicd froiii similnr bodica coiiltl be iitlilecl, show that with 'iill t l ic siibstnnccr buriicd, cvcii tlioiigli tlicrc \vus colqicr in tlic cornbuwtion tiibe, nitric oxide wns present iii the gus.

I hitoc Iiud coiiaidernlilc cspcricncc with 1)r. lh i ik l i t i id 's mctliod of ilctcrininiiig orgiuiic curlion itnd iiitrogcii in wiitcr rcsiducs iiiid Iiitvc iicvcr olitirincd II giis that did not coiitiiiii iiitric ositle rrltltougli coliiicr \vits iilwiiys usccl.

It occurred to iiic, u s iiiy csprriciicc Iirovcil tlic iuvnriiiblc prcsciicc of uitric ositlc i i t tlic gus, wliicl! l i i d to Iic cstiniutcd, iii 1111 ciu'cs, tliiit tlic copper iiiiglit lie ilisciirdcd uiitl it liliig of iislicstiis .sulistitiiterl. This docs iirviiy with tlic tctlioiis proccsw of ImIiiiriiig, by rctliiciiig with Iiytlrogcii, the ositliscil eoppcr, i t i id it will l ie seen froiii 'l'itlilc 11. thiit not much iiiorc nitric oxide is foiiiid i n the gns t h i s obtiiiiictl.

'I'.\iirx 11.

Ikvr... .................... 1hrIq.v. .................... a m ....................... Alcoholic crlrnt~t or 1xirlv.v. Aldoliolir crtriitit olmnlt...

Iiuioliililo rcsidiiu of Ir114c.v

Iiiwliililu resltlue of in:rIt (Rniiiis).

(gniiiis).

Sumlxr 1)ct~niii. Illltllllla.

Sulistonces. or

___ I

............ - ............

In order to diow tliut tlie iiitric oxide wts iiot diic to tlic siibstuncerr bciiig buriicd iiiidcr n rc~hiccd prwsiirc, us is the cuse whcn ii Sprcngel piimp \vus iiscd, 1 iiiiidc i i few dctcriniiiittioiis by breiilciiig tlic viiciiuin before Iirocccdiiip with tlic coinbiistioii of the siilistniicc. J\ loriger coiiibustioii tube tlinn i is i i id WIM ciii~iIuyc11. Alioiit 0.3 griii. of cniic siigw wns phcctl iit the clorctl ciitl of tlie tiibc, wliicii wits t l ici i filled with the coppcr osiilc i i i i t l tlic siilistitiicc, iiftcr whioli IL iniicli lnrgcr cliiiiiitity of colilicr ositlc wiis ~iliicccl tliiiii iisiiiil. \Vlieii tlic virciiiiiii wi ts foriiictl, tlircc to foiir iiiclica of tlic froiit of tlic tiilic were Iiaitctl to rctliicss iiiiil tlieii the ciiil coiitiiiiiiiig h e ciiiio siigiir. r\s soon IIX tlie viiciiuiii wiis lirolccii by tlic ciirboiiic iiitliyi1riih tho eonilius- tioii WIN proceded with iii tlic i isii i i l uiitiiiicr. l?oiir clctcr- niiiiiitioiiw of nitrogcii in ninlt ivcrc iiiutlc in this wiy , two without copper in tlic tulic. one with copper, iiud oiic with 11 coil of silver foil iiir;tcntI of copper. The i e d t i n g giiscs cniitiiiiiccl the following perceiitngcs of iiiiric oxide oii tlic 11itii1 giis iiicnsiirct1:-

I'cr CUllt. Ko.l,witiio~~t m~i~~~i~. , , , , . . . . . . . , . . . R ' I I No. 2, ................. Il.65 So. :I, with cnplicr ................... !i'W No. .+, with silver .................... R'.l!t

TCVO i1ctcritiiiiutioiis tif iiitrogcii i i i uric 'itcitl were iiiritle witlioiit ciiiployiiig colqier ; iii oiic tlie viiciiiiiii WUN tirokeii 11y ciriie wgitr:iiid tlic followiiig iirc the iiiiiiilicrs olitiiiiict1:- __ .... - __ . __ -. .... - -. - .- ... .........

I liitvo aliPcrrctl tliiit iii tho tlctcriiiiiiiitioiis of ciirlioii iiiitl liyclrojyi iii Iiodius coiitiiiiiiiig IiitroRcii, cwlicciitlly wlicii thu rii l istii i iccn \vcrc IiiiriiciI i i i uxygcii, tktt tho wiitur iii tlic

:Iiloriile of citlciiiiii tiilic tiwtctl wid itiid Iiiid an ucid rcnctioii vlictlicr copper or silver iviis ii.sci1 in tlic combiistion tiilic. l'liis shows tlie prcrciicc of nitric pcrosido iii the p i s which nuat bc nlisorbcd h i tlic pohwh linlbs, iinil coiiscqiicntly iicrcicws the ciirlinii iiiiiiilier. I)r. Ihmklitnd, in tho work ilrciitly iiiciitioiietl, oliscrvetl 'tliitt his ciirlioii results werc iigli, i r i i t l iIrccrilictl this to tlic foriiiiitioii of potiirsic iiitritc. :Fntiikliiiiil's lfspcriiiiciitnl llcuc:irclics, 2:E.)

'L'hc cliiitiititics of tlie siilistitiiccs Iiuriictl nre iiot given icrc, nor tlie iiiiioiiiits of tlic g i w s olitiiiiied ; Iiowcvcr, the otiil girs niciisiirctl iii iiiiy cnw \viis iiot inorc tlisii O * ( r 4 griii. in11 not less tliiiii (1.008 griii.

111 coiicliisioii, iiiy cxlicriciicc OF the dctcriiiiiiittioii ot iiitrogcn liy this Iirocccs s l i o ~ s tliiit copper ciin bc disliciised with, iintl iis there is iiliviiy:~ iiitric osiiia in the gita tlic iiiwt tcciinitc results iire obtiiiiietl Iiy iiiciisiiriiig tlic qiiiintity of iiitric oxide i i i i r l iiitrogcii in tlic giis by incniis of it #t+ initlysis niipirutiis.

111' J. II. C O I X J I A S , ,\.lLC.SC., Y.I.C., AS11 -1. I). l ~ l t , \ S l ~ K l t .

Is the voliiiiictric estiniiitioii of ciilciiiiii pliospliit~c Iiy iiiciiiis of iiruiiiuin ?;oliitioii, it in rtiitetl liy soiiic iiiitlioritics tliiit to obtiiiii correct results ciilciiiiii Iiliospliittc iii ~i lacc of sotliuni pliospliiitc i i i i ist Iic iisecl for rtiiiidar~li~iitioii.

l'o iisccrtiiiii the rclutivc iicciirucy of tlic two i i ic t l io t l~ tIic wnir iiniiiiiiiii snliitioii iv i i * itiiiii~1ir11i~ct~, tirstIy, tiy iiicii i is of sotliun: Iiytlrogeii ~ihnspliiitc solutioii, i i i i t l secontlly liy iiiciiiis of ciilciiiiii pliospliir~c soliitioii.

'l'lic iiictliotl cinploycyctl i i i i i l l tlic ilctcriiiinut,ioiis wiis tlic follo\viiig : A solutioii of iiriiiiiiiiii iiitrutc, iircviously iuisett with sotliiiiii ucetutc, \viis riiii into ilii iicctic iicitl solutioii nf tlic plio~pliiitc, ulso Iircvioiialy iuircd with sotliiiin IICCIIIIC. 'Wit titnitiaii x i i s Iicrforiiizd at 80- C.

l'lic ciicl of tlic process wits iiidicutcd wlicii i i drop of tlic liquid gitvc i t fuiiit Iirorrii coloiinitioii with II drop of potiissiiiiii fcrrocytiiitlc.

It sliould lie iiotctl tliiit iiii iipiircciiiblc qiiuiitity of fret! iicetic iiciil returds tlic foriiiittioii of tlic colour coitriJcnrlily, tlicreforc 11s littlo free acid ns possible \vns used.

Tlte fiodiiiin phospliutc, Si1~111~0,. 13 1I2O. iixc~l WILS twice crptitllisctl itiitl dried bctwccii filtcrqiiqicr. I t \vus iiiiiilyscd it i icl foiiiid to coiitiiiii 19.60 iicr ceiit. of 1 1 ~ ) ~

iiguiiist 19*H:I per cciit. by tlicory, this cliffcrciice liciiig proliiilily ilnc to tlic Iircmicc of II little iiioistiirc.

l'lic piire ciilciiiai pliospliiite w:is Iircliitrcd by the ridtlitioii of i t solutioii bf Nii211L'0, to iiii iilkriliiic solution of CitCI,. the lnttcr Iiciiig kcjit i n csccss. 'l'ho iirccipitete its \virsliccI i i i i c l fiuiilly dried iii tlic steiiiii oveii. I t is stiitcd tliiit this prccipitittc viiries i n coiiqiositioii. 'l'lirec snniples wcrc Iircpit'd by tlic iibovc uictlioc!. 'l'lic l'..O, Iirccipitutetl witli iiiiiiiioiiiuiii iuoIyIitIitte iiiii~ tIic prcc;pitiite tlinrolvctl iii iiiiiiuoiiiii, iiiid re-~irccipitittcd liy iiicuiis of iiiugiicsiit iiiistiirc i i i i t l wciglicil us JIg,l',O,

Tho pcrcciitiige of P20J iii the nlicciiuciis wcrc .tti*93, JR.86, 49.59, wherciis CIL$+J~ coiitiiins 45'82.

Siiicc theso niiiiibcrs ritricd grcutly, niiotlier liiiiiipIo of citlciuiii pliospliuta i w s Iirepirrcd by irdtliiig iiii iilkitliiie aoliitioii of Xi~lll 'O, to II sohitioil of CitCI,. l'liie tiuiiiplc I ~ U W iiiiirlyscd by the iiictliod iiiciitioiicd irliovu i i i i t l foiiii11 to coiituiii Xi.18 ~ i c r cciit. ll,Ofi.

A wtiiiidiirtl soliitioii of ciilciiiiii ~iliowpliiitu WUN iiest lire- iinrctl, cxitniiiiiig ? griiiw. of I'&), per l i t ru , i.a. :,{) oc. - 1) ' 1 grin. PcOi,.