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Acetic Acid per

Gilt., "011l1. 1 t tlicrcforc iippcnrs that pcriiiniignriiitc soliitioiis which Iinvc bccii previously ~vcll boiled slioiild lie tested oiicc n fortiiiglit to nsccrtniii tlic niiioiiiit of cliiingc, niid tlint the iiiiioiiiit of cliiiiigc duriiig this period will iiot cscecd tlint of csperiiiicutnl error nud iiiiiy bc iicglcctctl. Ter Cent. of Acetic i\cltl it1 lO/11 iir Retort. Acetic Acid iu l0/11 I)istilliitc. 1)istilliitc to tliut 3Ir. J. CAIITEI~ 1 1 ~1 , ~ snid tliiit lie lind Itelit soliitioiis of pcriniiiigniintc for iiiniiy uiontlis, niid Iind foiiiid the cliniigc to be very slight. h'eiirly 30 gcnrs ngo 1)r. l'crcy hnd &speriiiiciitctl upon this very subject, nud iii 3Inrcli 1SG9 lie prcpnred II Iiirgc qiiniitity of Iicriiiiiiigiiiiiitc, niitl on tliiit clntc lie obtniiicd us II iiieiiii of four cxliwiiiiciits ii stniiiliiril of 9'864 (1,000 griiiiis of soliitioii 5 3'854 griiiiis Vc). 
Tlic soliitioii wiis iigniii stiiiidnrdiscd iii hlnrcli 18G:l, n i i d thc iiienii of two esperiiiieiits gnvc ii stiiiidiiril of 9.797 (10,000 grniiis of solution = 9 . 7 9 i grniiis re), or 1111 iiltcriitioii iii 19 iuoiitlis of oiily .097 griiiii. 
1 lierc \vns no iicccssity to boil tlic soliitioii of pcruiniigniintc if piire distilled wntcr svcrc iised. , 1 .i-m 4'E30 ~ 4'75 --3'705 9 ' * 1u 3'75 63'41 3'07 j 63-59 THE RA'l'E OF DISTILLA'l'lOS OF ACE'I'IC ACID. 11Y J. A, WILSOS. 

Tm: rcsiilts of tho cspcriiiieiits coiitniiicd iii this Iinpcr were obtniiicd soiiic short tiiiie iigo, iii nii iittciiipt to npply tlic principle of rcsciirches iiindc by 11. Diiclniis, oii tlic rntc of distillntioii of vnrioiis fiitty iicids, to tlic vnliiiitioii of coiiirnerinl ncctntes. I)iicl;iiis foiiiid on distilliiig solution coiituiiiiiig vnrioiis fntty iicids, tliiit cncli ncitl possessed 11 nite of vnporisntioii peciilinr to itself, iiioreorcr, thc least volntile ncids, distillctt in the portions of distillate, coiuiiig first, wliilst iicetic iiiid foriiiic ncid Iiclinvc in tlic oppositc iiiniiiicr. IH tlic cnsc of iicctic iicid, I)iicliiiix foiiiid tlint wlieii 110 cc. of 11 liquid coiitiiiiiiiig iicctic iicid were ilistillecl iii ii retort of 090 to 300 cc., t h t 11s the tiiiic 100 cc. of tlic liquid Iind pnssetl over or l O / l l , it coiitiiiiied 79.8 per cent. of the totiil qiiiiiitity present. l!' oriiiic iicitl does not distil SO ensily, wliilst oii the 0 t h Iiand propioiiic ncid is iiiorc voliitilc, iiiitl biityric iicid ngiiiii iiiorc tlinii tlic hitter. \\'hi two or iiiorc ncids iirc presciit iii 11 licliiitl, ciicli iiiiiintniiis its own special clinrnctcristic nitc of distilliitioii. Tlic iibovc sniiiplcs of viiiegiirs giivc Iirccipitiitcs with silver iiitriitc niitl biiriiiiii cliloritlc ; oii nccoiiiit of tlic foriiicr ii little silver siilplinte iviis iidilctl. C'oiiiiiierciiil viiiegnrs :is ii riilc coiitiiiii froiii to 2.9 to 3 . 7 per cciit. solid iiiiitter, h i t they do iiot iippeiir to Iiiivc iilfcctctl tlic ilistillntioii iiiiicli. 
Tnblc :l sliows the iirlluciicc of iiciitriil siilts, soilic cliloritlc, iuid siilplintc, oii the speed of ilistillntioii, Xo. 3 liciiig iiccoiiiitctl for oii tlic pressure of npprosiiiiiitcly 6G per cciit. of Iiylriitecl wiitcr. 
'l',\ili,l~ 3. 

10'05


To

,425 07'88 (, t9 qrcc.) . 
,, coplrr (~itirc). . . Uistillntc. 

Siilplio ncettitcnliriiiiiiu:

Tiii red liquor...... 

7'2U

7'32 *. [T is iinpossilrlc to cstiiniitc the iilkiilis iii prcsciicc of siilpliitcs Iiy ordiiiitry titnitioii with nciil, :is n ccrtniii quiuitity of tlic acid is tiikcii t i p by tlic siilpliite, SO, beiiig cvolved. Morcovcr, osidisiiignpiits, siicli iis broiiiiiic or nitric ncitl, to convert siilpliitc to linlplititc, cannot, for obvious rensons, be crnploycll. 
Ilyclrogeii pcrositlc, however, :iiiswcrs the piirposc perfectly well. I t liiis no nctioii on tlic nlknlis, iiiitl coinplctcly osidiscs siilpliitcs to siilpliiitcs. l'lic inctliod tlieii is to nth1 tlic rcqiiisite qii:iiitity of tlic pcrosidc, boil iip, cool, iuid titrntc tlic till~nlis with :wit1 iii the iisii:il'wny, usiiig 111ctliyl ortinge, rrliicli is iiot nfrectcd Iiy the peroxide, ns iutlicntor. Siiicc licgiiiiiiiii* this rcscnrcli wc Iitivc foiiiid tlirit this inetliod of cstiinntion in iisc iu sonic n1Ic:ili svorks, but lidicre it Iins ncvcr yet Iiccn publiwlicd. 
Tlic effect of Iiyclrogcii pcrositlc oii vnrioiis iiiciicntorg, [is irictliyl oniiigc, litiiiiis, kc., \riis iiivestigatctl, ;tilt1 we fniiiid tll;it in tho cold iieitlicr of tliexc two iiitlicntors is iittiickctl, but on pfoloiiged boiling both arc tlecoloiiriscd. 
Scco~irlly, eslicriiiiciits w r c iiintlc to riaccrtniii wlietlier tlic siilpliitu ivyiis coiiipletcly ositliactl. A solutio~i of ulkiilitic siil~iliitcwns lioiletl i i p with tlic rcqiiisitecliiniitity of Iiytlrogcii pcrositlc iiiitl poiiretl both hot iiiitl colt1 iiito n iuisturc of iotliiie iuid stiircli, biit iii iieithcr cnsc wns tho fiiiiit blue coloiir iii tlicaliglitcst dcgrcc clisclinrgetl, sliowiiig the tibsciicc of siilpliiir diosidc. 
. pipette till tlic iiciitriil point is renciieil. Xcst the required qiiniitity of iilkiiliiic siilpliitc solutioii is ndded, iiiid boiled 111) tit oiice, but gently. 1)iiriiig tlic liitter pnrt of the boiling tlic iiiethyl orniigc is Ilenclicd. Tlic soliitioii is cooleil iiiidcr tlic tnp, n few iiiore drops of iiictliyl oniiiw ndclctl, niid the soliitioii is titrtitccl witli uoriniil ~i y t ~r o c ~i ~o z c iicict solutioii. iiotli iiietliyl oriiiigc iuitl litmus give tlic sniiic rcsiilts, but tlic feriiier sho\vs tlkc iiciitriil poitit uiore distiiictly. 
'J'lic followiiig tnlile gives tlic resiilts of scvcnil iiniilyscs :-Soliitioii I. coiisisted of 3 grins. of sodiiiiii siilpliitc nut1 7 griiis. of sotliiiiii ciirlioiiatc tlissolrcd iii 500 cc. of \niter, ctluiviilciit to -01.1 griii. of Sii2C03 iii ciicli cc. 
Soliitioii 11. coiitniiictl 9' 5 griiis. of sodiiiiu ciirboiiiite iiud 0 ' 5.griii. of sotliiiiii siilpliitc dissolved in 500 cc. of wiiter, cqiriviilctit to *018 grin. of Nii,CO, iii ciicli cc. 
Goliitioii It[. coiitniiictl 9' 5 griiis.-of sotliiiiii siilpliitc riiitl 0.6.griii. of sodiiciii ciirlioiiiitc dissolved iii 500 cc. of witcr, cqiiivnlctit to -0111 grin. of NnFO, in ciicli cc. 



  rcsiilts iiliove tire wrioiisly iii error iii two or tlircc ciise~, wid \vlictlicr tho iiicnii fiictor !6* 99 will Iic sod, encli 0110 \rill dccitle Iiiiiisclf. In tho iuiijority of cnscs tlic results coiiie wry iici~r tlioso ciilcnlatcd.3N ~i AIE'~lIO1) FOR I)IETEIIJIIXISCALKhI,IS IN iwwmcx OP surmrimcs. IIY JAS. GIIAST ASD J. 11. COIIiX, 1'II.D. 


Tiibles sliowiiig tlicsc spcciiil cliiiriicteristics iiiny lie foiiiitl iii iiiost of the works on orgiiiiic niinlysis (Alleii's Coiiiiiierciiil Orgniiic Aiinlysis, vol. 1, p. 408 ; \\'yiiter Illytli, I<ooil, p. 488), iuid I iiiiiy sny tliiit I Iinvc not bccii iililc iii fiiid i i i g other rcscnrchcs oii tlic s~iiiic siilijcct otlicr tliiiii tliosc under disciissioii. l'lic csperiiiiciits iiiiidc wcrc inostly froiii

  

ii tccliiiicul point of view, 
iiiiil, u s stiitcd ~iliovc, iiiiiiiily

  with tlic iiiteiitioii of npplyiiig tlic ~iriiiciplc to tlic coiiiiiicrciiil iissiiy of ncctiites, iicetic iicicl, iiiitl viiicgnrs. 111 iiiost of tlic text- 



books on niiiilysis tciblcs iirc giveii slioniiig tlic riitczcit wliicli ciicli licit1 distils, but iio iiiciitioii is .iuiide of tlic strciigtlis of tlic soliitioiis the nutlior cspcriiiieiitctl with. Ilowcvcr, 11s tlic proccss WIIS iiiniiily iiitciidetl for tliu dctcctioii of volntile iicids of wiiie, ivc iiiiiy rcnsoiiiibly coii- tiidcr t h y woiild lie diliite. 111 iiiy cslieriiiiciits ii 250 co. ratort wiis ciiqilqgctl iittiiclicd to 11 coiideiiser 02 iii. long iiiiil cliniiietcr of + in., niit1 tho iieclr of the retort wiis iiot surrouiitled Iiy u tloiiic, or wriippcil with lliiiiiicl, or niiy otlicr of tlie ilcvices to coiifiiie tlic hcnt iiiid thus prcvciit coiidciisntioii. I'urc sciiii-iioriiinl iilknli iviis used for tlic titrntioii, with pliciiol phtliulin ns iiidicntor. Iii Tiil~lc 1,110 cc. of tho acid of stroiigtli mcntioiicd iii coliiiiiii 1 ivcru pipcttetl iiito II 250 retort ~iiicl tlistillccl iit tho usiinl rut0 till 100 cc. lind piisscd into it griidiiiited

  

rcccivcr, tliu ninouiit of ncid iii tho distillato bciiig tlieii foilrid 1iy licntiiig with slight exec~ti of iilkiili, cooliiig, iiutl tlicii niltliiig seiiii-iioriiiiil liyilriu cliloridu till piiilc coloiir disclii~r~c~l. Tliirt sigiiifietl iiiitlcr totiil wiis olitniiicil by direct titrntioii. GIf,O, 
Pcr Lciit. "otnl. 1'013 2'287 J' 1s 10'55 ? O W .\IllOllllt of I'cr Coil. iii Xeiitixl Salt Iicr 100 cc. 93'16 93'00 83'52 99'60 8937 10'20 G griiis. pure XnCI .

  
	I,	10	,,	1,	..

,,E ~P I I ~Y .xl2soI,ioa(,.Tlic nbovc espcriiitciits ivcre cnrrictl oiit iiiost ciirefiilly, iiud iii duplicnte, iuid I wits soiiicwlint iiisiippoiiitcd iii tliciii.I ought licrc to iiiciitioii tliiit there liciiig diiiigcr iii tlistilliiig siicli n s the No. 5 strciigtli of ncitl, :in iilicliiot portion w i s takcu, so ns to liriiig it npprosiiiintcly 
to Xo, 4, uiid in:ido np to 110 cc. niid distillctl to lO/ll :IS before

  . l'dh 2 sliows tlic rcsiilts olitniiictl froiii tlircc coiiiiiicrciiil siiiiiplcs of viiiepr, with tlic iliircrciicc t1i:it tlic ligiircs iiiitler totnl nrc obtniiied by siiccessivc distillntioiis with iidtlitioii of mntcr. 



1anr.n 2. , I I - 
10'47 il2'77 10'03

  
		WI'iO
	0.75	St1'30

is tlicii t:ikcn 1iy nii

  iicciimtc .pipcttc in tlic retort, nnd 10 cc.pliosplioric ncitl ridded, tlistillctl to lO,!l1, mid. tlie qiitiiitity of ncitl iiiilic tlistillatc foiiiid 1iy titnition. IYntcr wns :iddccl to ttic rctort nftcr cooling, iuid Bistillcd to iilioiit 5 cc. successively till niiy iicitl cniiic over. I~csnlts in Tnblc 5 :-Arotata potiusiiim . . . . . . . . 


	. --		
	Coiiiiiicrcial Sdt. nccttitc sotln.	CJ I LO* I'cr Coiit Total. I 1	
			gli,O, per
			CCllt. 'ictlltll frcliii	Ermr.
			5~~~~~	. .
		G9'3S	00. 0 . 4	+ 0'81
		45'03	44-23	t 0'60
		lo*@? 50.52 ,JS.%	10'008 t o e a 1 e * m	-I . 0'015 -0'03 -0'13
		@ . ' I D 13'21	c o w 13'ZL	.t 1'83 -0'03
		12'69	12'89	-I-0'01

Tliu oxlieriiiiciits 1 iicxt iiiiidc with tliu coiiiiiicrciiil ucctiitcs ivcru coiithictctl iii tliu iisiinl iiiIiiii~cr, iii tliu siiiiiu retort, vix,, tliiit of "0 00.eiipiicity, wliicli is coiisitlei~rlrly tlic cpiitity of sir1it:incc t:ilicri \v:is nrcingccl so IIS to give 11s iiciir ns possilrlc tlic S:IIIIC :inioiiiit of volntilc wid.Tlia st:iiitl:ird inis tlint of potwsiiiiii ncctiitc, wliicli iviis iiiiidc Iiy tlissolviiig 2.5 grins. in 250 cc. of witcr.100cc.w:I'.\IIJ.€:5.I c w ~?! W%J per :cnt. Puctor. I -***. * ...... .. ,, chroma (liqiiid). . ,, (solid) ... ,) 
sarnples \vcrc dissolved in water, 11202 nddcd, ciiicl tho iiiiioiiiit of iilkiili detcriiiiiicd. Tlie rcsiilts wcrc coiiipnretl with tliosc olitiiiiicd by titnttiiig 11 kiiowii cliiniitity of tliu siiiiic sniiip1c,

  The nest point to tlecitlc ~~~i i s , wlictlier cnrboiintc or caustic nre riffcctcd by tlie Iiylrogcn pcrosidc. Differelit weighed Iiut witlioiit tlic ntltlitioii of 1 120Z, 



niitt proved tlint pcroside does not iilkct iIic cstiiiiiitioii of cnrboiinte or

  

cniist ic. Llistly, wc ciitlcnvoiirctl to fis, if possibblc, tho quiintity of Iiytlrnwii peroxide reqiiirccl 
to convert tlic wliole of tlic siilli~iicie into siitpliiit e.

  

' l h ri~ctliotl of nii:iIysis ~itloptetl is as follows : -A mcnsiircil voliiiiie of hydrogen pcroxidc is riiii into n benker together with thee or four drops of riictliyl 
omiigc. A s 11,05 is tthvtiys slightly

  ncitl, n siiiall qiuiiitity of tb w r y 



dilute soliitioii (rfiii) of SnOlI is ndtlcd by Iiicniis of 11 1 cc.

  

Iiii*gcr tliiiii tliiit iisiiii11y ciiililoyctl, wliicli is rilioiit froiii 125 to 170 cc. Tliu B I ~U U pliosphoric iieitl wiis ciiiployc~ll iiiitl
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