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TRAINEE muons PEG WALLIS 2mm By Ray-end Hubert John-on AWE Mitt“ w tho School of “at. 8min of Elohim State College of Agriculture and Applied 861m. in mm fulfillment of the "gunmen“ for the dag-co of man 3 $13”! Want at Chemistry 1953 DWI!“ To Doctor flier 1.0111111301- IbOlo kind help Ind efficient dis-cot on no lo mutatingly given, this than 1- mm dedicated . W W 5* 5 3.18570 10“- 3‘47535 TABLE OF CONTENTS 3 a mmMQOOOOonooaooaoooo.0..acooooooooooooooaqouoo000.00.00.00 MOM“...00......IOCOOOOOOOIOOO0.000.000.0000...OQQOOOOOOQCOOOO mWo.OOOOOOOOQOOOOOOQOC0.90.0...OIOOOOOOOODOOOOOOOIIOOOOIO Eugen“ andOOOOCooooooo00.00.0000.000.00.00.00OOOQ-QOIOOOOOO . Pmpmuon Ind truly-1' or um salmn.9000000.ocouoooc Spectrophotcutuo Studio- ot 11m Solutions.............. commawscofioooooooQ.0.0.0.00.coco-o.00¢.noose-00.0.0.0...0000000 mmm oanOOOIII000.000.00.000...IO...OOOIOOOOOOOOOOOIOOOOOC 138800-34?“ mRONCTION W10! Tho advent of titlniun Oh the inch-trill Iccnc u c Itrmtml natal bu boon” of inmuing importance in rcccnt you-c. It- no. in cm mo atriking whoa its out 1- considered. it the prclcnt mt E. 1. du Pont do Honour: and Coupon: cupplicc titaniu- nctcl having a purity of grater than 99.5 Wont. sponge lath]. mu ’7 .50 1303' pound in pound Iota, we ingot sum 1- 815.00 per pound in pound 1mm. The combination of coalition which no pounced by titaniu- Ir. until. It. night 1. interlcdiato bctwcn claim: cud iron, but nunrtholcu it but an mun-at omngth-tomight ratio (2) . That for structural upplioctim in which WII cabincd with Itrchgth in In inortInt factor, tho no or titanic: or titula- alloy- nhou a vary pro-icing future. Pcrhlpo the nut «handing physical property of tittniu :- its ruiltnncc to ccrrocivc “batman. tutu taro shown that mainly pure titanium in reactant to boiling 311cm ccctic acid, boiling 10 pcrccnt Iodiul hydroxide , in concentrated nitric acid , and rchtivcly dilut- m hydrochloric and mum-1c ccids . Thor. no mo induction. thIt a plain ti].- 1. found on titaniu by boiling nitric acid which in very rcliltlnt to turthcr ctttck by thc «id. 811% aptly tutu, con- ducted on:- c poricd or 1000 hours, hm cxhibitcd no nun. cttcct (2). In its motion- uith mu, tinnit- in quit. active. It 1-0.4in tor-I Idhcrcnt and uhtivcly ilpmublc oxide and nitride outing. at tooporotnroo up to noo° r. u m:- mpmtm- tho um diooclvoo in ito on oxide, ond I111 in tin boccoo abrittlod. Iydrogon, hunter, bohovoo Quito ditrorontly thon dooo oxygen ond nitrogon. it tnporotnroo ohovo 600° r, hydropn :- oboorhod intorotitiolly by titoninl. ‘l'ho oboorbod goo nybo ro-ovodbyhooting tho-otol ino high mot olovotod to-porotnroo (2) . loot of tho prooontodoy titoniu producod in tho Unitod Btotoo io oodo by tho mu prooooo. rho method oonoioto or rooming tho pnroot podo of titoniul totroohlorido ovoiloblo to Iotollic titoniu by nognooiu. lollwing tho roduction, tho rooultont opong mo of notol io looohod ulth diluto hydrochloric ooid to room nnroootod nonun- ood nognooiu chlorido. Tho octul rodnotion io ocoonpliohod in o uhhdonun-linod iron vooool, unda- on otnoophoro or organ. Irho inort goo io nocoooory to protoct tho um, porticnlorly that hot, tron ongon and nitrogon. It hoo boon lhO‘II thot tho proportioo of dootilo titonim oro ottootod odvorooly by I factor of up to 20 by thooo goooo diooolvod in tho notol oo ouptrod to tho ooIo onount of notollic impuritioo in tho notol (12). With tho ovoilobinty o: o oonoiotontly good quality or unm- ootol ooourod, it no thought thot o otndy or titonouo oolutiono dorivod tro- tho notol oonld ho of intoroot. It hod boon notod tilt in tho proporotion ct titohono onlroto ooh. tiono nood to rogcnoroto Holdon oilvor rodnctoro in tho otudont lohoro- torioo, tho oolutiono ooo-od to bo largely oonpcood a: num- (m) . It no dooidod to dotoroino to coat oxtont tho titoniuo no prooont in tho trinloat ototo . If it ooro prooont mtitotivoly oo titlninn (III), thio toot could ho nood to mm mm titonono rooming oolntiono . Rotoroncoo in tho litoroturo to tho opoctrophotoootrio chorootor- iotioo ct tit-moo oclntiono on very oconty. ' Thoroforo, tho pnrpooo or thio thooio io twofold: 1) to otndy tho propontion of titonouo oolntiono directly from titohin octol ond a) to invootigoto tho opootrophotouou’io proportion o: um ooluticno. \ (wo"—‘ HMORIGAL HISTORICAL In tho hydropn onlrido ocholo or quolitotivo ono-lyoio, titonim io found in tho onus-onion onltido' group, provided thot o luffioiont cuntity of otrong ooid io prcocnt to provont ito prior ivdrolyoio ond conooqnont prooipitotion. Tho oldoot nothodo or dotorninin‘g titoniuo ooro grovinotric , ond boood upon tho oooc oith fiioh totrovolont tit-him oolto voro hydrolyood ond procipitotod . Tho hydrono oxide in quontitotivoly prooipitotod ot a pH at 2.0 (13). rho odJuotnont of tho p11 at tho «lotion on con- voniontly bo nodo lith o-oniu morondo, oodiu hydroxide , oodiu oorbonoto, or our other olmino couponnd. Titanic iono oro wocipitotod by phoophoto in ocid oolntion , ot o p3 of. ohout 2. flavour, thio oothcd o: dour-inflict: hoo oooo nndooir- ohlo tootnroo . Tho procipitoto or titonic phoophoto io vory golotinono ond dirtionlt to filtor ond Iooh. In oddition tho coopooiticn of the ignitod procipitoto vorioo ococrding to tho ocid in tho oolntion tron which tho prooipitotion io nodo (S) . Cnprorron precipitotoo titanium oo o rothor wlminono , flocculont , goldon procipitoto, ovon in otrong ninorol ocid oolutiono (6) . Ferric iron io oloo prooipitotod under thooo conditiono . iooording to moi). ond Bohnoidor (a) , totrovolont titonim noy be prooipitotcd by main hydroxido tron oolntiono oontoining oluinun on! rod-tic iron by cuploxing tho lottor rith tho dicoodim nlt of ethylene dinino totrooootio laid (Veroono) . 'l'ho precipitate of the hydrono oxide of titoniul io ignited to titoninn dioxide . Volt-otric nothodo for tho dotornintion or titoniu ore dependent upon tho redo: reoctiono of the elccnt. A direct method, rewiring no prolininory reduction, lo the titre- tion or titoniun (m oith otondord cut-in (:1), doing a potentio- notricolly dotaninod oudpoint (h) . the conplete converoion of tetrovolent titonim to ito trinlent ototo requimo o powerful reductent. Biochett (l) oooompliohed thio by reducing titanic oolto oith pore electrolytic iron in o oorbon dioxide ohoophere . Be clad-ed thot toonty ocuivolonto or iron are noceooory for tho Quentitotive reduction , end thot the promo ct tori-one iron oppoored to otohilioo the oolntion ogoinot oir endotion. Liter ill the iron hod diloolvod, the titonono oolnticn cu titroted idth otondord ferric chloride, coin; pomoill thiocyonoto oo on indicotor. ' no and 901 (3) otlto thot titoninl (In) io lore reoiotent to eir oxidotion in ulhrio ooid oolntion thon in hydrochloric ocid oolntion. Syrokc-okii end 811cm (9) oooert thot ocetic cold and oononimn oolfote tore complexes with tit-nit. (III) in oqneono oolntion ohich render it looo oonoitivo to oir oxidotion. After reducing titonim in o binnith roduotor, they oonploto the procedure by titroting oith otondlrd eerie ooltoto, coin; oooetheline oo on indicotor. They cloin thot it io not nocoooory to protect the oolntion oith on inert otnoophoro during the titrotion. Jonnord (7) in o review article, refero to several nothode of pro- poring titonono oolutiono. The use of metallic oolcim, nine in sulfuric ocid oolnticno , oodiu onide , hydrogenotion noing o plotimin ootolyot, end electrolytic reduction ore diccuoood. A nothcd of mlyeing commerciol titoniun hotel hoe been reported by Thonpoon (10). The couple io diooolved in pate-cic- acid onltote tad o little sulfuric told. After complete diooolntion, the cooled nelt ie diooolvod in dilute hydrochloric ooid oolution. A preliminory reduction in ocoompliohod by nee ct oino calm, otter ohich it io paced through a Joneo rcductor. The titonono oolution io titrated under on inert otnocphcre with otondord ferric chloride . The detcninotien of .111 nounto of titonit- io boot coco-pliohod by colorimetric noono . In onlhn'ic ocid oolntion, titoniun (IV) girco on intonoe yelloo color upon the addition or hydrogen peroxide (ll). WW Roomto Hood 1. ‘ritoniuo hotel (sponge) - suppliod by E. I. do rout do Incur- odd Coupony, Incorpcrotod. 2. Potoooinn dichrt-oto - lollinchrodt Pri‘ry Stoddard grode, checked ogoinot o ouplo onppliod by the lotionol hereon of Stondordo (Huber 136). 3. Ferric chloride - Boker end Ado-eon reopnt code. i 0.1 nor-ll oolotien, node by diooclving 21.0 g. or the honhydrote in o liter of oclntion outlining 19 ll. of hydrochloric ooid, no otondordiood ococrding to the neth of Villord ond m (It). It. Corie Mani. lull.“ -- Supplied by the 0. Frederick filth CW1 Coupony, Oolnbno, Ohio. A 0.1 nor-o1 oelutien io node by diooolving 635.ctthodihydroteinolitoroi’ononomlonlmioooid. the «lotion io otondordioed opinot orooniono oxide (15) . S. Arooniono oxide «- Boker end Adonocn Fri-cry otondord undo, lot ember 0020. 6. Citric ocid - lorok roogont code. 1. Sodioo diphewlnino onlfomto .— A 0.01 oom- oolcticc' o: tho indi- actor on propel-ed (16). 8. Ferroin indioetor - A 0.025 nolor oolotion, onppliod hy the c.1rrodoricka-ithchooice10mncmuood. 9. Aulgeaotod cine ~ suppliod by the o. trederick aoith coo-idol eagerly. Properotion end Anelyoio of 'l‘itenouo Iolutiono One of the ImugOl of titeniu, noeely ito ouperior reeiotenco to ecido end other oorroeion-cenoin; egonto, in en inherent difficulty ehon the probl. of dioeolving the notel properetory to on enelyeio io eon-idored. flince tho olenont in preotioelly inporviouo to the notion ot roan moreture of eny oinglo ninu'el eoid except hydrofluoric, it no firot necoeoory to conduct oooo prolioinery quelitetivo teeto to find e oetiofoctory oodiuo in ohich to diooolvo tho couple. ' To thio end the follcving oolvento were needs 1. calm-id acid (1 part of acid to lpu-t of outer). rho ootol diooolvod roedily ot firot, but ooon port of tho Iter euporotod. At ‘ythio point titenouo oulihto oryotellieod free the oolution, and cootad tho undiooolv'od hotel to ouch en extent thot the oolrent ection of tho eoid econ ot0ppod. 2. Sulfuric acid (1.1:). rho ection of thio oolvont no approciohly olouor, but nonotholooo effective. The difficulty of oolto eryotollining from the oolution no not encountered in thio cue. 3. hydrochloric acid (1.1). the diooolving ection of thio ocid ooo ecleehot olo'er then thet of the 1:1 sulfuric eoid. b.0neperttotor-elperteulfuricecid-elperthydroehloric ecid - 0.5 port- of phoephcric eoid. ‘fhio oolrent hed the ouickoot diooolving notion upon the titenim. lo the oemplo opproeched the otego of being ocnplotoly in oolution, it hed diointogrotod into new perticloo , Ihicheorooo nolleotoboherelyvioiblooore it netforthebubhlee" of hydrogen evolved fro- thoir ourfecee. 5. Ten 3. pcteeoinl oulfete ecid -~ 5 n1. concontntod oulfurio ecid . In the oolvont the titenim oonplo initielly diooclved ouito roodily, but econ the eetion docroeood ocneidorobly, end finelly coeoed , eltogother. prhio the due to the for-etion of titenono oulfeto on the curfeco of the eipooed notel, which very effectively protected it from tho ection cf the oolvent. The feted one no light yellovohilo hot; opoo occlio; it turned ohito. not diooolvod in tutor, no blue color on inperted to the oolution, indic‘oting the oboonoo of lay trivelont titenim. It had been noted in thooe prelilinery tooto that the ooloticno reeulting free the dieoclving of titlniun in meridian; ecide were the typical blue color of triv‘elent titeninn. Accordingly, it on decided to eeoertein uhether thio feet would fernioh o neeno of determin- ing the poroontege purity of the emplo. ‘fo inure oooplote protection from eir oddetion, the opporetue in figure I too need. A io o 500 ll. nob bottle, into ohioh no ploced e eclutien of titenooo oelfete , end wee errenged thet the inert gee hobbled through tho aolotioc before nun; ito exit. 3 io e 25o o1. zleoo otopporod (otendord taper) iodine fleck, tectonic. tho mplo end tho eolvent. G ioofour inchodoptor tnbe,rithcno end otenderdteportofitinto the iodine fleet. D, o 60-1. oeperetory funnel, eee connected to the' edoptortubovithetoo-holerubborotopper. rhoruoihihgholoooo- fitted Vitho piece of right onae glue tolling, the outeido end of ‘Ihioh one connected to tho rthhcr tubing caning iron. the titenouo onlfete 10 ‘ FIGURE I DISSOL VING APPARATUS oeohbottlo. theonlypieoeofrnbbcrinthoepperetueioeocnoideroble dieteneeeloyfreotheoolution,enditiothcroforeveryenlikelythet layofthotitemoolnticneouldoonointooontutiithit. Intotho mmgloeotopeftheooperetoryfunneltnoinoortedl,eoixinch nelogroundioint. Thioleotpieoeofopperetuononecoooorytoprov'ent liquid oondenoing in the oeperetory tunnel two being opottored emnd thoeroa. thin-peturiogiooouodhythoiucrtgoohuhhlioguptmvough tho oyl‘ton. _ Toooopuete inert poeooereuoed,nitro¢eeendcubondicxido. theooeoreouppliodfreooteel cylindere. Inordertcineurethereeovol efenytroceo of oxygen proeootintho goooo,thoyvero poeood through theprelininry ocrubbingflook. imploefobcnt 0.2 g.of titeniueoeeccuntolyooighodend plaoodiotho iodine flock. thirty :1. of the oolvoet (lo .1. actor, 10 ll. eultnrie ecid, 10-1. of hydrochloric ecid, end 5 ll. of phoophoric ooid)etoictooduoodthnu¢hthoduppihgtuml,oodthaioartpo ollewodtopeeo intcthofleoh endooeepethrouhthe mend. fheoon- tentoofthefleokeoreheetedtoouietboilingenohotpleto. the emphtodiooolvingoftheooopletcokn'uebcntenholn-tcenhonrend obelf. Bincetheooightefo-ploueocepoeedoffmfeurtoeix hell pioceo of notel, the reoiotenco of titeniun to ecido of even thie «mud etc-onsthioooeflyeppereot. lolhdngcuplotooolutionofthooupleSOIl.oferenghlyO.l nor-eloolution of ferric ohlcridooaoplooodiothodrcppihg funnel, ondtheepperotuoroecyedfrcnthohotploto. fheflooefinertpoeee 12 otcppod, end noot of the ferric chloride no drovn into the flu]: by the rechlction of preeoero cooled by the cooling of the flock end ito contento . Rollover, it no emolly neceooery to remove the rubber tubing in order to elloo the complete introduction of the ferric chloride oolution. The ferric chloride no nohod into the flock with e for nfllflitero of rotor, thorohy loeving tho upper part of the opporatuo cloen end in reedinooo for nee eith enother oenplo. lo the ferric chloride oxidised the titenouo ion preeent to titenic ion, e hoevy uhite golotinoeo precipitote of titonic phoophote oloily fouled, over e period of perhepo e minute. . 'i‘ho resulting fort-cue ion produced by the oxidetion of the titeneuo ion no titrotod with 0.1000 nonol potoooiun dichroleto, doing the ocdiun colt of diphenylenine oulfonic ecid co the indicetor . the color chenge, from green to dork blue, no roodily dieeernoble, in opite of the mine precipitete of titenic phoophete preoont in the oolntion . An indicator correction of 0.05 .1. no epplied in ooch eeee. rho reoulto iurohlo I nre oelculetod eepercontpurity of tho titeniu, to follow: Percent titenin :- ml. roegent x noroelity x 0.0h790 x 1% . } to ovoid tho precipitoto of titenic phoophete ouboequont to the odditicn of ferric chloride, the effect of citric ecid, e well-m coupled.“ “out, no etudied . Inoofor to preventing totrovolent titohiuo fron precipittting in the ecid oolutiou, tho citric acid on oucceooi‘ul. An eecunt of obout 200 mg. of citric ecid no need. 13 TABLE! DERMATICH O? my 0? TEAM BI THEATIIG ' WITH STANDARD P011 some DICHRCHATE ~_ _ . d W A ‘ A “m“ ___ l i. i _ -- h- z sample “61 t K :- Titeniun . w_ " i A. 7, (m1) ' ' ' g}, Wifi, 1 0.2072 - ' 113.16 99.76 2 0.2016 1:135 99.67 a 0.2222 ' no .21: * ‘ ‘ 99.23 "c .1807 37.5? 99.5 Recover, the citric ecid foiled on ten other oonnto. The indioetor ohdpoiht too not nearly eo oherply defined eo with phoephorio acid, end oferncre oeriouo factorno thefeot thettheoitricooidoloelyree dnood the dichrooete . Oonooquontly, any titretion with the otonderd roegont no mooningleco. fhie routinely olcv ceidetion of citric ecid by dichrnotc io illuotreted in ‘feble II. mm 11 0121112103 or CHRIS ACID BI comm WIT} We: W : — A ‘ '- ”for 4 - ' L in ‘ 3 aooplo roeo. r o, not-,0, Tine (at) ‘23 mm (and _ - f p _. - (.11.. g l 5.00 0.1i2 1.99 0 2 5.00 0.53 2.01 S 3 5.00 lo 1.37 2.33 —v—» v-w fl Eoch onplo no identicel, end oonoioted of 5.00 :1. of poteeoiun diohroeeto,800ng. cfoitric ecid,25nl. ofnter,end5nl.ofeulfnrio ecid. After otending for the indicetod period of tine, $.00 ll. of tomoo mm. no oddod, 6 drop of oodiuo «phonylnino onli‘onoto indiootor, Ind tho oolution titrotod to tho notary ondpoint. Siooo tho {mono oultoto bod boon otondordiood and round to ho o‘ouy owinlont to tho potoooiu diamante, tho amount of diohruoto roduood by tho oitrio ooid my bo round by oubtrooting tho 5.00 of tomoo oulhto pipottodintothooolutiontratho ummuunmun ordi- ohrolotouood. Itiothnooppu-ontthot citrioooidiooloflyozidiood by dioh'ollto Indor tho audition! noooulry to titroto tom ion with diohruoto. In ordor to dioponoo with tho no of phoophorio ooid, ooooooory in tho titfltion of tow ion Iith diohrmoto, tho prouduro ooo Iodiflod to oouo dopoo, in thot ooroto no M on tho titrlting Mont, Iith tomin oo tho indicator. rho oupooition of tho ooid oolvont no ohongod, Iith ntor boing aboutotod for phoophorio Ioid. Honour, tho prooooo or diooolving tho ootol undo:- oo inort ot-oophoro no not oltorod, not no the oxidation of trivdont tit-hi. to totro- volont titoniul using ferric oblorido ohongod. loomoorthoompnooootthoondpoihtonditoouddoooppoorom dth littlo mine, o non Quantity of tho roduood solution to lith- drou in o coll medicino droppe- ot tho bogiming of tho titrltioo. mot tho color obngo ha rod to oolorlooo hod tom plooo, thio haunt no ooohod book into tho noin body of oolution, ond tho tint]. ondpoint notion-.11 obtoinod mm... throughout tho oooroo or thio work, ooworol loto or auto oolution um proporodood lama, accounting for tho autos-out nonolitioo in tho taming toblo. Tho noulto of tho .15 «roto titrotiono oro ito-ind in nu- In. to boron, tho rooolto u-o coloulotod to tho pox-cont purity of tho notol. um 11: DEWHG 0' P031?! G 2mm 3! THRITIIG um woman CRATE luplo Voi t I Conto Conto Titania W (5' m 1 (-1) 1, 1 1 0.18211 0.09113 1.0.22 99.60 2 0.168). 0.0910 36.35 99.87 g 0.2062 0.091;) 115.60 99.89 0.1827 0.091;) 110.29 99.61 5 0.1689 0.1083 is.» 99.15 6 0.2112 0.1083 .85 29.31 Soon-o1 titrotiono using canto ion undo um tho origin-‘1 ooid oolvoat «mining phoophorio ooid. “mu-o no no oignitioont Moron» inthourooultoihonouporoduthoolotim contoiniunophoophorio ooid. loam, moth» dittioulty, in addition to tho prooipitotion of tituio phoophoto , no tho wooipiution of corio phoophoto . Moro , ottor oooh odditioa of roogoot, outfioiont tino m to bo onoood for tho prooipitoto or oorio phoophoto to rooot . In opito ot thooo proooutioho , ootiotootory vomit-o mo obtoinod, oo Wind in toblo 1'. Boom” of tho loath o: tino noooooory to diooolvo tho oomph, it oudooidodtooooirthiolongthottinooouldboohortmdbythouoo ot‘o ootllylt. low trunnion olononto, tad wtioolorly than of tho plotim group, oxhibit tho proporty of mounting tho opood or thooo typoo of rotation! in thioh tho ovolution of hydrogon io involud. 16 TABLE 17 trauma or W8 8011111038 comm momma ACID Suplo Woi t l Coroto Goo-Ito Titania: :37” (n1) , - _1 i 1 o .2155 O .1083 kl 31:3 99 .145 2 0.1531 0.1083 29 6 99.78 3 0 .1736 0.1083 33.30 99.11? A otookoolutionofohloroplotinioooidooooodoophoflngoomon- trotion of 0.01 as. of plotinuo pox- nillilitor. Vol-ion hill nonnto orthio oolntionooao oddodto thoooid oolvontomthotho roguirod to diooolvothooooploootod. Inpnorol,thotioofloootdonbyobouto quot-tor. louver, oo my be our: tron Tohlo, Y, tho nonlto of tho do- too'oinotiono m wry omtio. It in proomod thot tho prooouoo of tho platinu- nohoo tho titonooo «lotion ouch nor-o unoitivo to do oxidotion , oinoo tho ootnol amount of tho ootolyot odcbd io not “(noiont in itoolt to man. the titlnouo ion, ouch io 61 oouroo prooont in ovonholning obundonoo Io ouporod to tho plotimn. m I mm C mm “HHS! m ACCURACY Cl’ ms DMWTIOI 0P rmm lo-plo . Ho Bropo of Omto Titania ( . Plotim (-1) 1 1 0.1829 i to .16 99.18 2 0.1818 111.13 99.65 : 0.2081; s 9.51 98 .31 0.2115 3 .32 98.85 5 .2031; 2 39.81 99.20 17 To toot tho volidity 01‘ tho ooluoo obtoinod for tho porooht purity of. tho titonixl, tho metal no doteminod using o otohdord‘nothod. In thio one the oomplo no :11de in lab oulturio ooid our! pooood through o Jonoo roduotor. the reduced oolution no cought imodiotoly in on moo of ferric chloride ond tho equivolont nount o: torreuo 1021 no titnted both 81th Itlndord potiooim dichrulto , ond Idth mum-d wrote. In “oh mo tho approprioto indicatm' no flood. Tho resulto on tobulotod in 2.81621. 2131.: V1 DBWTIOR (3 2mm 88m TEE ”HES moron -.~- u-.—_~-¢oq‘ —--—-. .~.*—N"'~‘C-_h“1ww‘ in.“ ammo—qufi-m‘mw.-. Souplo wait l “0150, 1 Quote 81.3211. Titoniu ._ S 1 0.18 9 0.1000 38.33 99.8h 2 0.18 0.1000 8.22 99 .39 i 0 .2070 o .0908 1 .39 99 .59 0.19911 0 .0908 115.76 99.82 ‘ 5 0.19011 0.1083 36.60 99.68 In oomoction oith ‘thooo Ind othor rooulto it might bo roll to indiooto tho difficulty of obtaining o roprountotive mplo or titohim . The notol uood in thio work varied in oioo fr0m mall duot-liko portioloo to lorgo ltnpo wishing oooorol grooo. rho notol 1o opong ond Quito ‘ ductilo, oo thot itno impouiblo to gum up o urg- nount lad tron thot ohoooo o roprooontotivo looplo . Gomoquontly pioooo of titonim opprozhootihg tho oioo a: o ~11 poo nro uood to ooh tho num- oolntiono. loomoo or thio orbitrory method of choosing the oomplo, it 18 cannot be positively otated thot I 317011 solution represents o homo- goneouo portion of the entire available batch or titonim. For Oflplo, tho rooulto of five detomimtiono min: the Jan“ roduotor ovorogo out to ho 99.62 poroont, ohilo thooo detomimtiono, thirtoon 121 Ill, node by diooolving the titanium directly in on inert otmoophoro, hovo on ovor-oll ovorogo or 99.61 percent. It may thereforo bo ooon thot Whilo thoro 1o dignity mong individual oomploo , the orange purity of tho botoh of notol uood 1o quite oonoiotont. Irhopromioo ohoohbythooorooultoooolodtoindiooto thotoh “11o“ oomplo of titodm notol oould bo diooolvod, um tho propor proooutiono, and bo uployod oo o otondord oolntion. To thio ond, thoroforo, o tan-1o ohlorido oolutioo no otohdordiood by reductim with otmnooo chlorido, rooonl of tho olight onooo or otmouo ion oith oorourio ohlorido , and odditioo of tho too-roan ion with otondord potlooiu' diohromlto. tho overogo of throo dotmimtiono govo tho nullity of tho torrio ohlorido oolution oo 0.1008. For tho dinoloio‘ of tho titoniuo mph, o 250 :1. tyros volu- Iotrio nook no oubotitotod for tho iodino 21m, ooimidoat oith tho oniooion of tho odoptor W. Thu tho oomph oould bo diooolvod, ond moo-cooling, dilntodtotolno,oithnooxpoourootoxvtioototho ongon oi“ tho oir. ‘ m ntor and for dilution purpoooo no trootod oo thot it oontoinod no diooolood onm. tint it no boilod, oftor ohioh oodiul bourbonoto no mm in it. than Jnot mar. boing and for 411mm, 1o no ooidifiod oith oomontrotod hydrochloric ooid, oat! briofly otirrod, oo 19 thot tho ooooping oorbon dioxldo goo ootorotod tho oolution. It no noooooory to ooidiry the ntor in ordor to prevent tho prooipitotion 01' ludrono titonouo oxide ohoh diluting tho dimlvod ouplo to voluo. Allthotino tho diooolvodooaplonooooling,ootroolotoorbon dioxldo no olloood to pooo over ito ourtooo. Onoo ot roo- toopoootm, tho oolntion no hmught mm to tho look by introduoing tho dilution ntor dirootly W the ooporotoo-y wool. Tho 11ml odJootoont no ndo with o Iodioino droppor one:- would tho Mel. The find oolution no niood throughly. After mixing, tho hmt no tillod oith tho titonooo oolution, ond titrotiono of tho otlndord ferric chloride noo conduotod. ‘l'ho imliootor out! for thooo dotoroinotiono no ton ll. of o 1.00 3. pl? liter oolution of oodiul thieoyonoto, oith tho oolor ohongo going tron rod to oolorlooo. Tho indiootor no not odded to tho titrotod oolutioh until o point obont m ortm‘oouillilitoro frolthoondpoint. Booultooro mama '11. In oooh an the nullity of tho titomuo oolutlon 1o oolothtod onobooiootthoootolboing”.6poroontporo. In 110' of tho romlto obtoinod by directly dimlvinc titonino, it in diffioillt to oxploin tho foot thot tho error involvod in tho dotonin- otiono in male on m olooyo ooptivo. At tint it no thought thot diooolvinathoonploihoryroxvolnotrio nooknightpoooihlybooot oo ootiotootory oo «linolvin; it in on iodino nook. flavour, tho titonimo contont of too onploo no dotomihod by dio- oolviug in o ryroo moo, oxidising oith torrio chloride, ond ouboomt titroting of tho owinlont mount of format produod oith otondord 21m VII USE U mucus WE A3 1 8111mm} 001.0210! o 2101, A o 2101. luplo Uoi t 1.01 2161. Error (Jh (-1” (-1) Goloolotod round torts 13:1' 7 h 1 , _ fhonoond 1 0.6380 19 .97 18 .21 0.0531 0.0527 -8 2 0.6227 19.97 3 .16 0.0518 0.0m -8 3 0.6581; , 19.91 36.91 0.05148 0.05115 .6 h 0.6186 19.97 39.39 0.0515 0.0511 *8 5 0 .0506 -6 0.611: 19.9? 39.81 0.0509 coo-Ito oolotion. "rho too voluoo round wore 99.85 am 99.60 pmont, Mustang thot tho diooolving prooooo no not ot nut. ' Anothor poooibility 1a thot tho titonouo ,IOIu‘tiOh 1- oxidiood m. boingtronotorrodtrannooktoburot. Thioootldhovo tobodohoino‘ ton-1y reproducihlo ny to oooount tor tho oonoiotonoy of tho hopuvo ' ow. Min to ohow tho rolotioo otobility or titonouo oolutiono tore oloo oondwtod. A oolution o1 titonouo ohlorido no ollond to otond toroporiodottiloinovoluootrio m,uthmottemptnadeto protoot it a... nu eunuch. on» outtioiont salmon hod boon tith- drontotillthoburot, thootoppor otthoflooknoroploood, hotno oorbon dioxido no oiroulotod throufl tho molt to dioplooo the do dnohintothonoohintho tumors-ingrown. Inthionythoootool oonditiono (ha-ins o oorioo 0: titrotiono mid pronil. rho titonono oolntioo no ollond to otond for floaty-four houro undor o oorbon dioudo otIoophoro boforo the tint Imploo mo fltMroIm. 1o indicated in Toblo VIII, the «lotion io quite otohlo for o roooonoblo length of time. In oooh cue, 19.97 :1. 0t titonouo chloride woo titrotod with otondord torrio chloride , hung thiooyonoto u indicotor. The weight 0: oeuplo no 0.6310 g. bowing o colculotod nomolity 01' 0.0529. TABLE VIII STABILITY C" 1 W8 OWE 3014071“ 1_._1 A L. ' 4* ‘r ‘4 " V P A .1_. _‘___ _2..‘ Time I101. F801. ' m1. (bro) 1@)-11 1, ill) . . . 1 1 1. 1 314.5 19.97 10.29 0 .0519 h? 19 .97 10 .05 0 .0507 57 19.97 9.82 0.0h96 72 19.97 9.10 0 .01175 It ooy ho ohooovod thot oo titohouo oolution 1o oithdrou tro- tho mok, tho ounce mo of tho oolutioh oopoood hoonoo Rooter, loom to e um oopid ouhtion of the oolntioh. In oddition, the oboolnte mount ormumnmmummmgm rote of oddition. A oioilorotndyofo titonooo oulfoto oolotionnolodo. Theronlto me very oratio, Ind uriod tron titation to titution, one: then they ooro ran ooo otter outhor. Poor titrottooo, ’mooooivoly oodo oithin rive oimtoo or the pmiooo one, dropped in mmlity than 0.0510 for the 21m, to 0.011951» the loot,“ Mann. 1!. 22 TABLE II STABILITI OF A TITANS SULFATE SOLUTION A- A- _. _—_ ._A “(513334) .11 11 lag-o . t ' 710(30o)o # 39.16 19 .97 0.0510 £23.15 19.97 0.050? .03 19.97 0.0503 110.611 19.9? 0 .0h95 T.— fir fiv— fl.— Bpootrophotcoetrio atndioo o: Titonooo Solution looouoo of tho bluo cola- or titomuo oolutiono, it no notorol to nho o opootrophotuotrio may of their proportioo. ‘ rh- 1mm and no o name out. opeotrophotmotor, lodel 00. core: collo bowing I light poth of 1.000 on. were uployod to contain the nriooo oolutiono. leoourononto wore node «or o opootrol rouge of 3:0 to 700 nilliniorono. titer no uood oo o oolvent bleak. Groph I ohowo o {wily of mo for oolutiono containing nrying nonnto of tit-nouo ouli'oto diooolwod in ono oolor onlmric ecid. It my be ohoorvod tut tho momngnlorondnooth,oiththonmmtrooooiooicnot520 nilhoiorono. in We in tho concentrotion o: titoniuo oonooo no ohift of the point 01’ mini!!- tronmittonoy. While looking thooe dotomintiono, o curiouo toot no noted. Upon otonding for o period of tine , the toonnittonoy of titonouo oolntiono W. Attirotthionothonnzttobednototorootionotooollodiol dioporoion of titanio oxide, mood by ur-ondotion of the titonono 23 com «I 2 21 E: .5qu too 82.30 83:12sz .38QO g. 11.35 $28031th E96 d>§ 00k 08 com So so». A 4 A _ a fi — _ .42 tum an.» 2225.: 62 MO.‘ _ _ :5 fit 35 222%: .oz 8.0 as 222:: .oz mod .4: «mm B: .525: .0: mo.~ .42 INK r b _ - .v .m. .N .l on 0% on Om 0k 0% Om OO‘ 3ONV11IWSNVUJ. .LNRDHEId 2t oolutiono . To diocover tho truth of thio cotter, o otreon of oxygen no ollooed to bubble through o ample or titanoue mllxote until the blue color had dinoppoored. The tromittoncy of this solution no honoured, and ' found to be 100.1 percent. It no therefore concluded thot no collodiol dioperoion of titonim (IV) oxide no formed. ’ — The com 01' this oppcrent discrepancy 54" ot present m. However, it 1o poooiblo thot titonouo and titanic oulfoto form o more deeply colored couple: thou either or the two oolto clone. Eventually olithotitononoenltetc ioeirg-ozidioed,thocouplexiodootroyed,ond oince titanic oulfoto io colorleoo, the tronmittonoy of the oolution ottlino 100 percent. Thuo there are two Opposing factors ot work. 'the complex tends to woke the oohtion tronnit loco light, while the titanic oulfoto formed by oir oxidation in colorleoo. Therefore, over o period or time, the trononittonoy o: e oolntion or titonouo ouli‘oto would decreooe to o minim. nluo, otter which it owld increoeo until ell the titonouo oultote no ‘ oxidioed. ' The deto in title I represent o couple of titonim mooe tronoe mittency end titenouo content no meooured over e period or tine. The tromittoncy no moored ot 520 millinicronog inedietely otter the oboemtion the titonouo content of the solution no dotomincd by titration with otonderd acute. Ao indicated in the toblo, the tune- nittoncy ond titonouo content both decroooo . It thno io opponent that if Irv mtitotin mooning io to be de- rived tron opectmphotonotric memento 01' titonono oolutiono, they 25 .mx WAR!” (I TRAIW! AID W3 comm G A TmlOUS MATE 301mm * _ "LA " ‘ k A l l *r A.— :_k :- 7. fl Imittlncy lg. 1'1 par M1. 71-0 (115;) r l , __ A * __1_ 0 515.5 2 .80 16 50.0 2 .78 65 .5 39 .8 2 .61 92 C5 31 no a .hS wold otmualtyhm to bond. Wuhmr mung-m diluting tho up)... land before “7 mini. sir-molt!“ on «our. to thhonduvorll mph. otmwinguomtaotuunium dutch-d, one! Wat: ot 520 Woo-om and. institute]: mar m. At the me the, a wlmtrio :10qu of their “tom content In the undo. u mutated 1:: mm: 11, plottod on 1.1.19; paper, the graphing of mummy on tho um u. ”mutation oath. ”dint. unit. inurymrlyo “night lino, Matthew W to Don": hr of tho utmou oolntiono our tho rouge of. commune Med. m Iolvurt in «on use m l: mum-la «1a. A We ma «lotion ot tit-nan chloride in: lino pruptrod Ondltudiodlnlmlhfllrtothotim manta ”lotion. The Iolunt an 1 n momma Mid. A. than in ouph m a ”lotion or titan: ohlorldo mung about the III. oomontrotton u m or um taunts, 41m:- le from it in mam. the WW uy be an in u:- ulmwum region, at tho point a: ninimm Wtunoy, 26 «20292322 0% E 828qu tom «2 .2 22 20:38 a: 22228: mo 292E 2828 q2< .32 qt 223$: 2mm: Em $2965 .92 .H Imqmo MOZ ShEmZSfi hzmotmn‘ 0% Oh Om 0k fi q _ 0m 8002 A 4 O (III) Wfl/NVJJJ :JO ”WV 83d '9W 27 ZOEDqOm DE EQZSE k0 NOZEEEWZQWC 20 2033 k0 HOMkkm 329(033 422$ Ikbzmqm><§ 8k 8m,,mf8» l+ + _ mm...) 2 I VOMNI 2 2.43 tum DESSEEE. 63 NON .N do: 3 >2 .43 mum «HS 3323:. .62 00M .2 .E 115% 0 Q) E O Q) O O) 1N3083d 1W Vii/WSN V51 28 end inthe red ”acne. A utencue chloride caution tron-1“ eon- “Wmutheredportlonottheepectmthmdoeeetim lanteeelutien,eteetm1ehteepperentemtetheeye. flu tun-italic: mm o: the tit-none chloride 00.1an hue drifted to 505 lull-intone, Iron in poeition of $20 uni-1m for e um eolfete evolution. A um chloride collation, ee antagonized from e tit-none eultlte eelutlon , mute en incl-nee to transmit”: for e care-pond- inadecreeee intimate concentration. mmtum intone 1!. mu ' 0095-31“ W name! no rm: mm W A ominous OWE 301111210! “ARM _._L __‘ - ._ w ‘4— .w j—wfi a VTfi Irena-nun” lg. 1‘1 per In. The 2 .2 24$.) l» 2 a M e 2. 0 ' 69.5 1.99 13 69.5 1.95 1:65 70.6 1.86 71 72 .8 1.72 95 75.1 1.148 It would here been profitable to carry out father etediee in different ecide. Hm, men it we ettenpted to dieeolve tit-aim 1n perchlorie told, it In dieoonred tilt the new. we mulehle, even in eelnttoee emu-etching 50 percent concentreted perchloric ecid. Attupte to dinolve the hotel in phoephorio ecid eleo proved fruit- lm,eetheeotionmextrene1yelow. A mple die-olvedineither Morhydnchlmeoidto Mmeodedeonephcephcrieecmueo 29 III than to be untenible because of the precipiteticn of titanic phoephete , «need by emanation. Illi- precipitetc formed on the aux-fees of the eolution in the Core: c9111, end darted down put the 0011 undou , mining the reading emtio Ind onrelieble . An attempt m made to transfer quickly the eoluticn to the cell in en emoephere of carbon dioxide; beuene m then tuned to float on up or the titanone eolution to protect it me tho nlr. this too proved monumental, booms the titans eolution crept up the eidoe of the cell from undernelth the benzene , Igin resulting in lit 0:1th end comment pulpit-Mm o: titanic pboIphlte . f w The beet eolvont tor ”mm tittniuu 1| monoxide ecid. Even lawn“ hydrofluoric ecid, the (Ii-earring ammndoym' libel-nice e: belt, and proceeds very wally. The realm; titencue eolution 13 neon, which open air-oddetioo become: calorie“ . DOWNSIOIB “13011131083 Rennie amou- diceclm 1n hydrochloric or mum-1c ecid to Quentitetlvely for: titenhm (III) . the tit-none ”lotion in very ”attire to lir oxidation, end in order for it to rennin in the trib- nlent cute, ongen mt be excluded m the epperetce. This 1e ceefly ucomuehed by protecting the solution filth In inert emccphere of carbon dioxide or nitrogen. The volumetric detenlinltion of the purity of I mile of timin- motel 1e thee puny seaplane, eiooe no prcldnim reduction or clunlu (It) 1- neceellry. I A The precence ct phalphoric acid in the column We the diachr- ing of titanium motel. Although phosphate tome e. precipitete with titInim (m , m precipitlte doee not conctitute In interference lath the Wat titreticn. Human (In) a detmined by oxidation no; ferric chloride end titration of the equwleat mount or iron (I!) am diclnmete or eel-etc . standard reducing eclntione of titanium (III) my he made by diuolw- mg 3 highcd ample of tittnim of known purity in e Pyrex ”metric the}: end diluting to volume . fitmen- ecluticne 1n hydrochloric ecid 'm more Itehlc than thou 1n eultnric ecid. however, even the former can not he need tit-h In new of greeter then about ten perte per W. spectrophotometric studiee ct titenou eoluticne chewed thet the onion preeent in e 3110:: ecluticn carted en epprecieble effect upon the 31 tron-hitting curve . In e wdmouorlo ecid eolution titanim (In) bed 3 point of minnow trmmittancy at 505 millimicronsg in sulfuric ecid solution the aim trenmlttunoy occurred at 520 mllllmlomm. A decree” of. the content of titenium (III) in culturic ecid colu- tion in not ecccmpanied by an increase in the trenanittenoy of the solution. In the cone of titencue eolutione 1n hydrochloric ecid, the expected situation prevails , and e decrease or titanim (III) content 1. accompanied by In increase in the tranmittancy of the solution. Heuurc- mente loading to this conclueion were once It 520 minimum. Tim eoluticne in sulfuric ecid adhere to Beet“. Lev. Mover, the color or these eolntione in not very intense, end the procedure mum not be pneticel tor Iolutiorre contldning lose the one emigre: or titanic: (:11) pa- I111fl1tcr. Another pom to be renumbered in that colorimetric neac'urementl out he rode Macintosh otter dflutihg the mp1. to value. nonetheless, the color or name (In) my be uuduthebeeiecteeclcnmtric data-nineticncftiteniu. mEEATURE CITED WWW CITED 1. W, I. x. ml. cm. 92. 195-200 (1950). c. A. 51.. M221. 2. E. I. dn Pent do Samoan-e end Cm, he” Technioel Bulletin. mumm- Haul-Sponge end Ingot. Wu, Belem-o. 3. w, I. end Del, 11. te. hp. Ind. numb Inuit" Olen, Jepen Q; “0.6:.15131) 1910). cc ‘0 25, 705‘. h. mttLa.w end Sonar, 1. Belt. 01113.10“ 2 , ssh-9h (19M). 0. A. 6, .9 5. Mullins, w. end under, 0. fiendbuch der Aalytiechen Charlie. 3133:“ :19: flatten Rheum-11mm}: . 10h. ”ringer-Vern; , Ber . 6.1‘reean1ne, W. end lender, G. Bendbnch der ammo Charlie. memento der m llebengmppe. p. 35-5.Sp3'1nger-Vor1eg, 3019.111. 1. Jomd, a. comma et Mums 21, 551-7 (19h?) . 8. m%§3§e.mdschmmn' ’e GNOME. 7‘10 ‘19m0 00 ‘CE.’ 9. WW,V. 8.0411833"; E. V. Zemdekeyeleb 1015-19 (191:9). c. .AA. 1357 f '5' 100 Mun, J. H. ‘31. Chill. g, 1632.13 (1952). 11. Timutml,w. 1!. Them»). p. 127A. 0. S.Hono¢reph8er1eo. Channel Geteing 6m, 130. Ice Iark. 13.Hertaln,!'.8.,i¥e1ker r..,rollor,n c.0001: 24.1..cod Antler-eon, 3.1.. 53mm at m fir-ulna n Boulder City, Honda. Bureau: at Kim Bulletin 2.1.1519. pp. 2-3 a. 8. Dept. of the Interior. 13.W111erdn.l.end01eh1,n. Advanced Qumtitetive may-u. p.15. D. unfioetrendcmyerv,1ne. lawful-k. w lh.w11hrd,3. mendhn-un 1.3.Elnanurymiut1ve1m1fiie. meat-5. D. 11an Gm,1nc. Hortork. Evfim 33 15. W, a. 3. end M, I. n. momenta-y Quentitetive Amy-n. p. Ely-5. D. an loetrend Compeny, Inc. New tort. 16. Willard, H. 8. end fur-en, !. H. momenta-y thite‘hive truly-1e. p. 2h8. D. an 30er Oompeny, Inc. In lurk. w_ ‘ '1"! ,e e. I . ‘ ._O' . .-.. . . .c'iin‘. ‘31-)“. "’5‘ 51» x“! - " ~' 1‘, 1. 55,44 - -. - " e'wd.\2. 1 ‘ gag-M} . 4 ( -.> ,3“ eA _‘._-~ muons SOLUTIONS ram KHAN-IO mm 3: WMHJM J! J‘ an Les-rm wruaummnormmumamm mete College of Agriculture end Appned Seine upmmmmnmoruew toothedegreeof mum a 30mm: Wt o: con-um III! 1953 Approved 3;; . fiz‘fiémqj *L/ (J j: «.1 ;,':‘j‘;:rz"le: . ' . x ‘ w.-. frfiv /:‘~". 1 l T H v a f A i .- I {f ‘ - l *'- 4' 4" 4 .- A'} ' ‘ . I r - l ‘ I‘vf‘ ’ \ 'A ‘ ' a J ' C a" ! ' l r ' - ' ' I J v o | ‘ ’ \ _ .2. -\ ‘ '. ‘ ’f - _. . d r '9 t C 0", - L. I“. ‘.' -. t , H I ‘l‘ 5‘ — ' e. O 4" ' f4" -I]'- . "’3' ~ g. ' ' a ' .‘ .J \ I ." - r 9 ‘ L ’ e' l p"‘§ u I .7,‘ X . :1 V '(, t" . I —- N _—l ' “I ‘. ' . .L— - | 9 - .fl ‘ I‘ 4 I k \ - ‘-.:' ,A LI. 1 ' f I ‘ k r. . .', "K , ' '3. I I. U . -"|' 'x .‘ ' (I , .1"¢"e ' ‘3“; _' l \ 1i . I .."‘\ . - S ’ . " “xix - r ‘ ._ . . ' ~ 4' D ' ‘\Jel .“k ‘ I o ‘ > 'f" ‘ ”Ii ~‘1‘ 1" I atr‘L . ‘ I “t .- . - r ,, [’31 ' .\~ ‘ ' e, ‘ ’ ‘ x . 391 - . ~ ' . . ‘ I f ’1‘".' '0: '. ‘ ‘ I . . I, r .e I \ .L . l n _ 3,. fl . -f.‘i‘ . . .‘V. ' I ‘\:~‘ d 1"t'?’-.‘: ‘-, ' I ‘ ‘ , - . i _'.z . V — t ‘I i o _ . - 1' ”oh , .. N0_ ’ e ' e‘ _ e ‘_- c r ‘ .8 v L \ 1' ' k” 7" " . q“:- ' _ - ‘ 0’3. ‘ ) l-' ‘ . . "1" . L" O .1 .__ T. ff" ‘3' . \.\. -‘ ‘o-Zr\ _. r , , - . ‘ O . . ‘ . - '0 I O . . e\' ’ A ' ‘I ' a ' . ' c ‘,.‘ ' e I- J ‘ ‘. ‘l‘ .' \‘R‘ I Q \ v ' .— —. ——_-—. -__ —. ——_—-——_. wwmn 733818 1353353? Itwumeldimlflduhymmnmewmtm «umuummuumu (m).wm.ommulo- Mupwmmmmuuuueomumm dieddewmmcll. mwmuemhmmmmommmum Mtyefutldmlem,lethebmenyd—m¢epmmuoaet nun-(mama. mmmuuuduumumooymmmno: Wanna-aunt”. . mum(m)mummm~ummam wmuudutmuma.mumuooummmt etuen(n)euhuehreutooeeenie. mnemmd ummuuulnumcmmupmmw.mmem not Interfere 1th the “Wet-ion. um 0M0 “letter! M crater teem fie e1: enthuse manna-amount“... rams-,mumeolumuo: umwmwmmmnmmuuuuuot mmvnenmmmaukmmmunoowo: greet-ethane”. mmwmdummwmm Mmmuweuhfiumheemdmmmmm “mun-Lees». Aumamuumwumnn .1. lemudlhbefl Jam ouumdwsmugonmmumnm Wee. mmmmuuuummnmam W. Admhum(m)mumheflmuuueoluthe overowmummmmemmmmmuwe- my. Infantileremeenm. louver-,ehydreemmeeeu ”1mm damning in uterine: (III) mmmum doee mm: en magma-nay. momuuumuhuonuwmuommoo. «mum at mania. dune um alters Mu edhre to peer“ . hvmfinmgeotmtmm. m.mmie\m mmummaumguqmmurlm. wmummmyummmummfi eel-pie. ‘ .2. "IT'EW'L'WL'@"l’vul'flfli'flfifliflfl‘s