USB t M t w a w . yapyrwwnr OF (HMOB9DXH ftynra flmmunraB OF m a n s m m , ir a d s ir a , c m a a m , w > v m m m 9r A ^ ! fTN?IS3iS Subiaiiiod to the Softool for Mvaaeed Graduate Studies of Michigan State ^nivsrslt^r of Agriculture and Altetoif AdS SlSdLQOfi^ H.rtirfrjntfHt-Mfi S3EI- M iaOE vbwAImAm I A%1#411»mmA a# j&J^pwwdMwl ^M m L X^ X x XXXflBQIOw OX tb* requirements for the degree of SOOfOK OF imoaOFHt D ^ U tM S t O f 19S8 ProQuest Number: 10008556 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy subm itted. In the unlikely event that the author did not send a com plete m anuscript and there are m issing pages, these w ill be noted. Also, if m aterial had to be removed, a note w ill indicate the deletion. uest ProQ uest 10008556 Published by ProQ uest LLC (2016). C opyright of the Dissertation is held by the Author. All rights reserved. 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So© «ot> ^ t y ®$tit but ulrf*** & «^|a> m%io of fS»oyiste to tttngatea im Iran ?«1 to IDiL fo r vsanMm$ th@ yat&our «jwei«s £$»o$ a»»® oo^toMLy &i the iscsXootrie point of pH 2.2. £v iS s S ts y y jy rife # Jrfk P WW Mp bA AfciP ImKMf© j4MI |M|&*H,Aw ©X j|^6^9W8t iRR@i33R^R^^RHRtfc WNffi ll® ©5P5MlSi» M©l§ fflliBflSL#BE* X& WSM l^ p w i iw iS ttlilifliiw i i& 1&m i Al kuI^AM mm^WjMI jlh-tf* JlMlkAjMMi JBtfUiMMdtoMNhAilfctf# 4kA PlmWf wttBji itAIBw WwW r IMs JPWWnWPw #WM#wWS*llS *“® ^(^RW(R |RRR^RPiRK9^£RS^6RR^Rfe(i^8RR^^KaRR^felRR^R^ ^SfeWSRRRRRBSRP^JMRRRE ®©&llti3»tMb©ll Mil il&pj£ljS 0^? th© JMiS tfeMI 4««»KMw||ila ■ faai f M » 4?i i>iata.wfe.44u>’fe4tgflt vm tm 4 «j4aii MiMH sSj^BlSlSii# 4 of uritiSBdiSsiia umi isiffiffi jPoiukS to rJ®p^P#Si M tBM IBUUtL^ida^di^ H.^1M L fflKf^Mjm Jh.tfM% *.an!!■■»H >-^ Jfe.*M .r.-^. m m M ?%*WJlM -M t AjMMMuiA fedM h-A'M «BkM fc^k Jk. lM«ik' la# 3iS 0 ^r«r HHL© %M 35®6MI®MI Hi© JTOIJwGM VJM&1MI X© H©» mmMwa ml% att.-—-MjMjM kift.dU iti iiliMlMM-ttHft< 4tBBuflfe4i jM UBL rtj© fr* ■jfcitbwRKSMp rifc■JfcfcM iAAitI'HRm1'tf^lT PM Pli Atiiftl 4tvk «M m kAUM .&M M ©AmmAi©JUtfk 3PWSPMt®w 3KBt S w wOlSyp^Wv® y|PwF*j^LMWw3w^ ®3|*wfiO m Wm !&$£* «*£ tfeMi srftidi®* m | I i M » th® iim&& pp®pom& ascfcwwsticaa p?w©dh©w Jtos* XHSMM&tMl $3& 88BteS$l© (X) *#* &©$& iwissdi.* swisic^t Isa© li#$i$llS© S^©6iS»^S# 4?#lf ®fi3|©l©AMB!Mik Xt m& mm b# jf«S$$ tHfcit.M ®@£w -n.*■-..A._ .-i— i. ■■» J A*J3L^i0r © ■A niB MW liJttMnktM 06 ^^j4C b8un kJI AthM i -Afc—— -X 3Td®® aJ&5*0 J38P3tia* SW T? A ^tTP WtfP i^HS^BvfWB @ ^A S*£ nlfM lJ BM KM ®W 1fSw ws*i® a®®w it twfcaft Waftd® not €SJt3W2t m© a dfiRNS^UlBSWaat o£ a c©lloi^ul w*«t V ^swipltat® m $$ J|gj ®SlHSN8llB#S y>#y ■**$■t £% tfBlf^ti yil i #1SKt8S#t4#ll Of %fofr Hfl®6dtitiH£l ##ffl|8UlBI ja^. A^pjii>ii»t^. - U m rn $j$f fffflroll Offef tftifr f@#E#f tW ||J y # motfeodt H # tf# #HtfH000P # ® f %# A fl&|.($J& #K taO & * 1&# UXWDjfX t a n * m (1) Sw^ptibiii9Ut®663L mrn^m of wm&am of &H gfc |g SJ*1I* HNHHWMHt M . 0iE$S® $taBtag* H* &** «09f aMLat« 0«t.Hal* tifem* Jg* v l flfflf 3&ELB OF OCOTHUS am p * ****•*•*•..»**»*.••*•*♦* *.*•*•»«#•**..•••**. A. X X X* flMWWAiy Of flMNflllSOJill HflSllWI |WB6Sdhi8NHI**•***■*••**# X 2* Ifoffiff1 fff vwcyulXanif aoXybdGfflttsi, tllAXBttIB BfMSoXfMI fB SKMXSa .*••##*.•..*♦•* 6 A* *.8N0pQ3^T •fiKMU?**■*:..■■*.*■**.■*•*«.-.**•*•••••■**** © i»* *01*10...••.*..*•.•**#••..••*.... XX XI* S B W f B s &WAMWB, ABB HBTHQDS................ 16 * JM AfP&wlt ASICS A ffiffA tw R#§ IpAACI.» . * * * * * . • • • • • . • * » ■ • • # . * * * . • * * WQBmBMm# fflllqpi^lwWBPWMu IWlaW aM* »■*****.».*-».*»»*»» ..♦»*».« *© JLf X. 3?yAcl%^tfttX©ii jppoAWdmwEi'*.***•• .... .......... X? X* S&tcAo&tosi j a t K s w ^ u r ^ a . . 18 H i . ...................................... . . . . . . . ............. xx X • BaaiiXXa of "BaiSe*.•■•**»**»•-••••*.••....••.*• XX B. Sxtr$w$t#i.cai lBthod0 t© 1I©i#*88II8©1b ( M w * Saiio.. . . . . . . . . . . . . . . . ........... . . . . . . . ........... 2b 0. 1 . & r t r * c t iG * i tr m $ f « 8 l4 » ........... ............... 2 * Extraction At ftt 2 . 0 . fldtrX tttlR L © I ll(S^tNiASE93ll B S C t)W 0tt6il F3PO©©€&U*0. • . • • .............. ft mtiMuammat 2b 27 28 81. _ A• SdMlsn M 3 m B. I&itfAQtloR E a c p a O * B p » © ip itA tX c a i ^ p o i t o n t e . . ... ........ n t o a n t s . . ................. . . . . . . 3b 36 b2 X. Establishing tungstenj a*-benscin m im mtio of COP5J0.SOC.. . . . . . • 1$, 2. Attaaptad graarijaotrle p M n . . ................ U6 v. Q m m m t** ..... 52 A. Extraction Attomjto...•••»••.»••*•••••*................ $2 B. Fireetplt&tim Attempts................... S3 H i m m m CONTENTS - Continued Bago U . VAMDiim...,. A. 55 *.... f1 rTTr.JrirTTTfftf.Jf. fTr^f.T>T.-J. , 55 1 . pB offoctt* In . . . . . . . . . . . . . . . . . . . . 55 twwoiHtfeto*. . « » • • . . « • • * 56 t . A i& antt to 3* Oom iXftticai o f r©ettlfcs w ith lit#i*at*ifffc d a t a . . . . . 52 41# #* * #* #* M««#»MMI**Mf #•«*#** «##»**«#*♦#» 04* .... 61 f . M rH o p M t fc£eoloHrafetrlc mothod.. . . . . . . . . . . . . 63 H I* SBiyRSt* ............ » . * • « • • • . . • • « * • • • . • . » .......... 62 m $0BA!ilBS® OXf JSI i ** * # * * * * * . * * # . * • « * # # . . . . • * * • * » 7 1 73 .............................. H i d ItX 9T 0 ? s s ® 3E-# liltlfllflSOtibMft Of JoiWMCf<9J!MMI0O Of iWili !>0XI|jp9t0ft jjst SEtiiWSHbijOB iWOtN^bSQPW**»#•*■#•♦* ............................... n U». Pxwlpltotljan of ftgngot&n with fiwflrlag Amount* of OwJJmusoIb @ate*t|«**M*MM*##tM««t»#tt»*M»««*«*ttM«»*«*t«*««t»M J|3 JUL&+ CCt JrWr ll«W v IpXragPlHMR 321 IXNMphVPSh UKXXBm ^£3^08S(^Sfj^)((2Ei ' |fl AI^I0l?b*lll06 Of of CltSPOffldSUB Sbctf&ctod with #*M3ftoiii owt-w &1 V&rping Aoidltioo**««*# •• S3 ? • M t o o t o f V w flo a o Io n s m th o B o t o t t d ^ t lo ) ! * o f T a n o a io B ). . . . Iff 6? U B ff W TZ&SS&8 X* tmtmmftmMm of Ma^^tsdoaaimfcH&BMsoJUi Os±m ft&ilo by j®B^groro^M0Ei * -pcwswri*^®*#■♦ • • # * * • < * *•# ♦ • * *®• * * * « « * * # • * * # # * * * * * ®# * icq 2 # AbOOX|*iioil SpfKyt*JO$I& ©f Tti3lgE?t^*C^©^0 tSB CG6ipil®3£ V&F88SB »***********•**•***.*«**«•*#»•#••#*•****##*•<»*•#»»* 37 3* I^p®KSlpit®‘ll,«3ji of Ito^g&oii CosMgiLoae tdth 7itf7iag Asaotsot® of ^P ^P ^P^P ^P^P^P^P ^P^P^W ^P^P ^P^P ^P^P M fi, jJL k « IflraCTO m ifflfctl_im m _if._fflJIl YikMk EmMflSWM rfUPh Jtuih flM U*M Ub^M dPpJb-MM T"W i*lil ilW TM iPT JO© U 0$U ?&»3^& £Kl090 l« lip « ® i r lM X p ^ » %Kt&Olk* **« •M*«*t««t»«**it*f(**M««*f«**«>fM«**t*«t«i«*»*** tSf• > Vtuttulb *kM*. OX Extraction.. t$ ftirti niHtifcf>% /TbM «w dlwm m . flftiilO TfrO h4Jrt lu ut VlTWCiAHm*w»xwwiWAB 33SS9 wgr 6$ ..... X V m oX N G 'S m t 1 A« Historical X# 8wmm& of a^bwMQbn wdm procedures. The rea ge nt, a-bemsoin oasim, has b®m used fo r q p a & tlta iiv e de te rm in a tio n s sine© 1£23 whan F e tg i (6 ) f ir s t re p o rte d a < ^ n tita iis re procedure fo r th e p re c ip ita tio n o f copper from m ammoniacal s o lu tio n . L a te r when B o w le s (17 ) was checking th e in te rfe re n c e s in th e copper d e te rm in a tio n he discovered th a t molybdenum could be ^ a a n tita tiv e ly p re c ip ita te d from a m in e ra l a c id s o lu tio n w ith a*bansoin cadiss* L a te r work (3 0 ) p®wed su cce ssfu l fo r th e s im lta n e o u s p re c lrd ta tio n o f tungsten and molybdenum u sin g th e $rocedure devised by Knowles. The s tru c tu re o f c^benaoia-osdjaa is as fo llo w s * I t s m olecu lar w eight is 227.3 and i t m alts a t C. I t Is s o lu b le in acetone* a lc o h o l and e th e r, b u t in s o lu b le in w a te r. Knowles (1 7 ) method fo r iM&ybdeunm in v o lv e s p re c ip ita tio n o f th e Gmsgkm. from m a cid s o lu tio n fo llo w e d by i^ a ltio n to molybdenum trio s tid e in a m u ffle furnace a t 500-525° C. ^ d ro e h lo ric , n itr ic * o r s u lfu ric a c id may be used and th e recommended a c id ity is $% by volume* a lth e u # up to 20$ a c id is p e rm is s ib le . A two to fiv e tim es excess o f reagent* on th e b a sis o f a p o stula ted complex o f th re e © -bsasoia cotfme a molecule* par molybdenum# 1* repaired in this method. Also the presence of a slight excess of bromine sad preoipitstion £rm a sold solution sara necessary to prevent reduction of molybdenum by the resg^it. <{thseV *M & w id e ttfattKt et y o f e le m e n ts f o r in te r f e r e n c e } tnQb»Ai«0 silver# lead# mercury* bisonth# copper# antimony, tin# ewl. vni’ Sffl# s!Aiee®i# ursnSjUca# rh e n iu m # tantalus# niobisnai# cartas# c o b a lt# s s n g s o s s e # metals* Me found that of these only tottgat m i (Yl)# vanadium (V) arsenic# a *id th e wtw p la tin u m (IX), chromium foam precipitaites with etssoia in mineral sold eolutioos* Of those# only tungsten end palladium gave prsoipitstes were ^seesaSjig^ly tstiw -11 Precipitation of ftby^wwlt^ And vanadium could be edisiuated completely by reduction of the dements before addition of the reagent* He reported the precipitate of to be that of the hydrated nftid rather then a compound with the reagent. Miobiura and silicon ware also found to coataminato the wirt^y^dfaiann |y*eciidtst# fojsaaliosa of 1,nfK>1MiM c hydrated adds* Ifcgode and Pfcle® (JO) adopted the original method for the quanti­ tative precipitation of coabined mblybdensw ftyyd tungsten. Ihoy redissolved the jsrecipitate and separated the molybdenum and tungsten by means of hydrogen sulfide. Dtu to the fact that Ip&tion to the trioxide resulted in precipitates of mm£L weight# especially for low concentrations# they rediasolved th© tungsten triodde and rrolybdanum trleocide sad converted to tballous tungstete and thallous laolybdate for welding* It is interesting to note in their results that 3 «ttwnla»UoHi m paw sedlsm tungstata la all h i m & tn • nagrt&re mm** W m m rm , this m m not tent* t a r stwfl. santfUs tra m which b a th ANAA SM kM itfV s-M fesfl • T¥* that seeiese mgr bo SttOfyfMHiilfafr 1 y s u b s t it u t e d f o r e th s iifV I a s ^ 9 o M b s iis o iii s K in e gt f t r s itS $SeipNMNi tfEIQSOSISMNI* SSStllOda ®mvwm jHj^« (t>) used the method for tbs determimtim of laol^bdflcniitt in tungsten bearing stools* Following tJis eo^lned pstelpl* teiien, tlio molybdenum is determined 'by tbs fsriaebleil of bhloeol^ptadate III SOllUtlOft*' P*Sy is %f> tlS Jittrtrftdto Sitb dtl*## «mi tfptiSsd in sim eaide* In the method of Sterling said JSpifcr (2?) tbs tiwl^bdsMain-e^bensoin is dissolved in hydroacldo gput hydrogen peroxide* f3S!% Kb&hiXS*^w U i^ & Si M W fei.M emSlS3kiM S'VHWSJ® ^wSBI'- suMKK fBeM iltJ a^rktOaM fc0j4fe JCIvPi Arip JvBBm JK lh tj& ilim ff ifc erwifjS fM iH w ii4 fM Wk iS jkLS wSA vlt BM fH lA BL I■ pF®B ^9rA kvHrWBW lH Sk flfe c^ l O& n-^ lL i.d e acetate buffer mixture* fticholls end Badgers (2J) used SCoc*ae©« palpitation method for tbs dwlni9fllnefeldB of molybdeniisi in potent Bniertsls* They essl^ssd ns little ss 0*0005$ iwljplxienos* by precipitating tits e^bensoin oaeSans ossfftss> ddSENSirlsig tbs iswipitsts end determining A good itw&m of these modifioations es well as Wm&mb* original method war be found In Bagg*» Organic Reagents (9 ). Also, serer&X methods for molybdenum end tungsten ell involving a ssgnsntion of b H O ffM a n n « a d ts n g s ts a m O m i t t S am O m m ar tr m b ® iw Om m la b u lk o f th a a o lu t l e n a s c o r d ln g A n s ly t ic s l C fa s a its tg r o f to tb s Ito h s tts n Pwdsct (IS). Want r s o s o t ljr , IfiSIOIlSL##* tit© t h is s a tb s r (12) las H m r ODfttftilatod SiX .aaaatitoi^iwJi th a t, o o n tv s iy t o flgiim fett inols'l^iisiin TfflTlJf^ f QfiPIn ©A t3liS - $$1® IfrOffrftlflflf h*M I iH poafettlatod .&© HoO8(0^^f%^O#)8^ whleh oontato X6s$lg molybdanma* m to ttsla* X£ tin jjg e«yrri©d to arold IWttifliMlM.iffiil ©f M O I M rfafflfflt with ^no corapLeot, ©81# it 1ft Wftfthftd fro© CKf CPiUblt Cfteft8lWe88 SrePSbgjpaaft^- iiiwr fiflL t.^ ’I ^Ll^yiLjg th ® CNMPfStSPISpfST^tePPf 8fc?t 3y(3EjiE^^ X6w53j6 O f ftSjEPcE ©0®J5l©3£ fpftT© fOO# JN M & tltft fo r A nnafcar of H»5*$« ©tael «am|X«B. $a th is nathod o o ite ^ is erapiloyod aft itto no&MKt to givo a grantor 8©lubiJLi,ty o f T.* 1EES® ■>.M«tm ii9 J0UP(5 A t«iii S©23© 63w .m u^m A L *® B © S SLO §K tui© whose ehew&stry In aeid solution is so poorly characterised due to the formation of isopoly and huteropoly acids .and salts. On tha basis of the postulated formula of HoO^C^H^OjgKjg for tha molybdenum ccmpLeas: It would appear that the complexes of the other 6 group TO and QidM. TCB metal* will also tea compounds of caygenated cationic ftlladlnm again la an aseepfeiea and dees not belong In this & w p , the wupoiAlsSm of its eeng&SK already haring been established as PdCO^H^aSJa (25). 3B» probability that thaaa compounds are foirrosd 6S^yjg@BWll(Sdi cations of these aatala is further indicated by the eemptLemee which these metala fora slth S-^piM&lnal.. Siwloker and Treadwell (3k) bare defesmriaad the best method for preclpltatien of theae elements as 8-euimoliaclatas wring controlled p preoipitetianB. they report the composition ef these eoriSasoHi to be WOstObHSBOs* KoOgCCoHaOH)*, sad While the acidity tea- these preeipitaiiloas is much less than for the formation of the a-bensoia «*me coapHnces, they are Still all precipitated from acid madia. 2. grief a u w of poatelated vanadium, molybdgpam, and tungsten According to Jonaasen and Kirschner in Sailer's (1) poOy-aclds are those which contain mere than one sold anhydride molecule par acid anion. If thay contain m e M«d of add anhydride they are laopoly acids, if more than cine, heteropoly adds. The elements capable of this type of conden- cation are vanadium, niobium, tantalum, chromiuja, molybdenum, tungsten and uranium. a. laopoly adds.. 33m above elements have been shown to fom a aeries of f>dyasids in the crystalline state, the 6- and 12>poly acids. A great deal of woric has been don® m them, and their structure and 7 composition haveb*m t*m & However* the m lM state af these poly acids 4a of m iraportame 4a the present work and can therefore be ignored at this tine. Of Inporteee to tills im k is tits aggregation or degradation phanoaana mmm ^m in relation* m i three are unfortunately vary poorly understood* Ore of the host co&Xe^iojae of data and theories concerning this irebleni 4s Ifrss# in !&tekflsX*9s Stxnctural ^Ohssdstrgr of tt^MmSmSmSS Tw/»T»ggn>4^ X coraootinds *** mm j^SSSSiSSSff* +£& imtmSmSSmSSS (23)* Wofortem&taly, there has bare a g re a t d e a l o f work done sin se th e p u b lica tle m o f th is bock w hich hoe n o t been ©©Heoied and evaluated m th e b a s is o f work 4em by o th e rs* Because 1&e s e v e rity o f re se n t deals only with the pheafflWiB observed with ^ eiaaasnt, It M mA*I <1 w k.ikk -■--^»* MttjlLateak ajh dilik^*. ,jBla.MAk n -a<>^ M ^g»iTM l— a,d* w Imm*os of more vain# «o erefiowssr the cate sor vanaossn# noiyooeKion and eepii&ntely* f ly# r e s u lt s o f e ta d ie # o f v a n a d iu m 4 a a d d w e re jW fffl^iM iSs d earlier by Hooked (41) as follows* $« m l aggregations observed in the aUsaUne pi! region load to the installation of mono**, di-, and tetra* mmid40 sold above pH 7* fs» pH ? to 2*2* a m id is postulated which fores Slowly fro© tetre« the speofse t» really a dee&vanadie aeid, rather than psatavanadlc acid as previously postulated, fluey alio believed that fa the region of the isoelectric point, pit 2.31, there is a formation of a linear polymer which fa in oqailibrinja with lowr molecular weight deeavaaadlc aeid# this polymer fa in torn ecmh verted to tOa* by etaiage caused by farther acidification. fhia could be re p rs ie s ftte d a e * * * * * s£s (TO ,*)«(oif)p g j * . to ,* ( m »r* « » io ) . Die species postulated by Buerei (5) for this lour sold region do not corresixaid to those poetixlited by meet other voitero• However. it _ _ W&M ’ yiHlfflti ^S^TTn Sttt&L*fl of o o lt T O aT O « * i^lyyy^ad-7iimarrids ajpe ^fKIMylsMiCWI JfodUCtS S6IS iKICtl#®UX01i* ffiNft.ff ffitfl^llFifffr' p o in t tb o XX0 & 1i& 1wmi3j® ixdct ttHQf y^fff.fpfiifl life# Jtol3*owiivg tla i isopolyw ^fctt* dgr*t*& iia th# fttag* £mat $81 *0*5 to 6*5* ICTOa4, «*. * ®yt -ja W u fim ~*> «»• * ^ ^•Tio^a#*i*» *§• 3j3t ®*W^»o » *%• 3 * ^is^ao”* # *?• ♦ ^ io®»b * Wl* * ^ Bay found TO**, *q. to Iso tfaa ool* species &a MOatlea trm jB -0.5 to 1 .3 , sjft/fim 2.5 to 3.5# Hf^oo *& the gmdaidaast epooioe in the pH zange from fans* it to 3.S* and Vj«Oao" **°® 6 to T* ® » a H a ^a ^a o ” ecareetij»ada to the * d been suggested oy Basel, jfeNitb* * 3Sm «A JVk^a± «W ® tt'» \Jk>/l V skk TJ^ O 4^n 8R & slkaUno so&ttiocu W & tom m $$ f sad S$ s^grsgoiion occurs which fn©» iQfJfljOntsyfr WlOaSSSi Sp$*#SSil to SdbiSil H SOU* Ho jtUffthOX* Pfe ^^01 PSJT 3* lBOvi A«#| mbwo nof^ solutions th itt t$$6 pH o *f s t tho isoslootYio point OCNBOSPO* %■ S^P®^3?tsn nS0ll3LtO 0^ SJjHWltm OSf OSS$W3Wffllt O- OOOtslnlltg HwCQL POttoo nf XiBf XiJ ooO t ill in othoa?1* Hoomso of** CoOk (21) A tts ip ts l to ffbft* tbs s^osdtos yyosiiiit f ** 3POSOuLtn gioi o upos r ShsSy th st tfeo moot 3n$ioaflsnt spsoloft In thot oontslolng tOO Oh3j05Plii» 3 f08? SOiOlWB MOB? thi# spocios GCCU2*© &t 5 -$|*BSlh* A t gCOSfbW OO^i^t t lO# S jfO^OQ OOtttsSnlUg tto tttt o ^ o ito s i bsooatss soro l^ o rtm t* lyssonso pjf n o Q im m m 0 ) s & m im & & m M s m - o to lodiosts In solntloxMi* m n^ jtltl oii ♦3 4u» »Ma. 4Vm> wp«un|»uvfi o f tbS MOD* aftfcjiMi ha^ btMBft 4nij4ftatftri i ll a/»id B8di« auoh M r ll« r irtwa NlchciUSji Saengar «ad ««r«Uw (22) ahomd the prrotimre « f ifeO^S04 ia e u lftirlc add edati © .$g$p© recant stac^y of th© 0 p6Oi©s in acidified s o lu tio n © ' he© b e a u © a rr& s d © n t t^ r J ^ s ttd n ip ir a n d C f^ # B it s m rfe siiaply rorifies th© p>3^©n?is©tion ©©earring# bat ©it©© tbs fast that ttior© in ©vidian© of a© bfyfeffoon tho with prodca5dn©nt #|j©oi,©© ©ocnrrlng bnopior* Bair resaXt© ©r© tf©t3t ooBpatibXo ^yiio^f,©© ©f tbs b. tungsten spool©©* Hateronoly acids. A© stated before, byroad th© isoelectric point for tungsten, bpdrated tang©tin acM pr©ei|dtat©s from solution. Sownrer, if phosphate inn i© yr^©nt# ibis | t e M i© not cbantvod* B n reason for tbia i© tbat tartan ©a waXX ©a th© otbor gr^P ^ «»d VZ m teOa for© hataropoljr ©a w»3X ©a iaopolsr acids, m proviaaa^y toontionod* 2* A **!# # sbk$3i as p&ospkoruj#* sHlocm, beaEWt* c£ tjjSfpSit skbB wrmml^ s-yiy tks 3Pols of OOKtoL * t o t o totoplsr tod §m m M m * I&e -phospkGtotoropoJy t o 1mm t o n m m t o s t o to ^ r s to to u ^tgat^.iBtti'.ai> pllffii $gg| ffearafore, t o folX to ng b ria f SOldS^ ■3AlM«fcgJhi tho ■ ahAitiJr-ypit w SB ltt''mm&-m*9>' iM M fibkm ftM fa iM iKHk^i^l^Sfcr ^ ^ifetw fM fw e*-JU K'itQ f&im uat €** 1m fljffiftikm ’ifch^ rfftfcm i&iA tSirW ferii*. ^pQW m JtorfcM g ftM b^^rS# M l* ISiaM 3R mmM, jm W m tm JW As ifitli S#tip@^r ssSdH#- th s a sss f tlito y J&ots&op©2jjr ^ 13Elyigr fty^ W mmkfSm %m «B*1W jOPOB wBlffli mmmm^ am sfttoli sa a i2q3r po^psyaci ^jr WBmmRMSlm $mt9 3101# WmmSmm- SSI «&lMU»Sraft SgjpO tb&fl Nffllt- l&tSlllSsdj l< 'tubs 1 iii^ ^.^^a^^iii yrw^ t o t As* t o $sa NftfflffN 1 M fa jita f^y f|$g tySgEI ftflBS %ft $)$ 3*2 ’p j# 0XH| Oi$£0&a&» StsStt* ^ t o N t o t o « M f t t o d $$ n HUX* &U&# XOtX* fix * X fs i* t o • t i » 3*63Saj© (1 ))* to pfecffipfaorita iJSti.© o f X 2 il| B tX a m ingi t&a& f ^ y jy kacam (IS )# eatabXlalvitig tfas g M » in #©*►fch© t&*fft.M.»isf SOMa .for llStAKOmfcr OOmTKHKldS• k t thoro is t o l l m g m t to X t s IN t o s ^ t o s s ito to im g to o o r Me03 m W% giwpSf 4nw> Xsss is tessan #K«^r t N NNsspeStir in solsMioai. A iFSSgT SVRPoflaw pSipST Ggr ffiBKSSarf l#SO|i wia vliG%* \XO/ QOPSI^lSffii v«0 sf t o t o t o t o # N of t o tostotogto^ ssto in a Stoss o f t o f t o s N H t o scatto iag tQcfeai^aas. th s ir stowossssita in a zm to r o f orspaxic to ir to s shosr Vm m Xoenlsr ^eig lit o f 12^pliosto« togstio #eM o o x rssp to s to t o wmmxm* %IW^o40f t o lo t o t of 33 oowsspwsSa to th« dimer* UsT ^ u Oaa, S-jboephotimgatio U X lifc s H b U Z m tftX y * # © ©*© 1 *11 .ii^ t ia 4 A ^ |ji. S o X u iie m%d a c i^ s &© W !W “ a yt&m b id & g & l$ © i^ y p s w s o ^ iB g s o X & lj& c iju 4$$^ te © Q t© y v © © & y & 1 n $ tm & Id a iP L aW © e fc ;ra CW tyP t« W eW * fl* in_a vp^W M Q p^H M £ligy a taW irfx^tr*m^’W W flB [ tl©P!W P*W W *^ W W W W m nm w^IflrwBff'W 'W 'W IW { X ) iB ^d U iS i. JL© f jn ^ t% ®£ %%%$$¥*& p s ^a s -a a a a © f it o a f f ijt i© $3gg& © © ' © ^ © @ S iitt© . j|W © is & s t3 $ & A c t w a ll^ S W lW iM * © I? h® ^*© is*© |3© l§r w fy flffi <$ # im fy r tfc ttA In n 0 s o ^ r n s ris h o d tv& & © n j m ff H f f© * © im s a s O if n © m $3U nk ^ S d ^ w © © ^ d ^posi. % lffi|fff4 H ffl1i ;|j$ © s»i)gj j^ ^ ^ ij^ ^ g p y w j ©J$s?©GRdi>us^ ii^ d c & d ti& i ism d ^ s ts rfc iO n s s © X u© ^o x s ® © ^ ^ © s s in B c id JJ3n©3?,id © c © jn $ & m © 9 c fif t e is % ^p © # % $ ^ 2% F © d $ $ l ( B ) |i* M - 4 ijih iff8M©» •«■jrrtin^vfWWefc* -kr ©»— £-& t ©i>M A d X fs © u © « X m © .. -*^ ijatSSSSAflP© © £ tb » p a le r & o M © © f e to o m ta s aLu — ' — .-IK — .1M -.Ji±.-JlJi «f^Lu|i jLl h m hmex 1.^^at^jaL■^g.4fc kA^.MlU,>S-dUHk ■KM Sldlilh 3?©S(Siyu%© ©18?©8!0b!01©Q> 3hSI' ^ pbPiO © 9 in © ^© n w n ili©JS > ^0@ PvwC$l © m p© iM tin p o y ^ s w E d T0&p&aiSt a s d tta d *1© t i i s 4 ^ 1 ^ b o in g ft© r e — ® 3 © fl © ^ ra © m d a d « 14 ® 4SSf 3?3Pfife3ii0l8 tMBmmoSa to u ts ha* ham i& mm m m a m ly tlo a l reagent t o a o f y e a rs , to t o t , aim® F e ig t (6 ) t o s t published M s awsihod w iw to to o f copper. I t has beea employed vw& to e lg r to s s l y j f m m K a to e s (1 ? ) d e e to b sd I t s use Is t o mx&#to&mmk» m i s lim 1£3$ m m m goda t o Of d e te rm in a tio n of U to s (3 0 ) re p to to tb s qenA tSSgStSEl fey t£ll@ $t8Sg6H$te Wsmwm* i t mm o n ly s iM K tily t o t t o e a w rto r (1 2 ) discovered tb s o rig & a a l suggestion fey Knowles o f a th re e to cm compleac was In SSMP and tb & t tb s Is aetasutly two cs-foensjoin jwhf—i pm mlgfedostsM* I t mm a ls o shown a t tb s saws tim e th a t tb s re p o rte d iu s ta b H ltg r si* th e compi®K mm imaorrmh# md th a t by xsRMsratX of assess reagent t o oompOLsss; could ha d rie d a t 105° 0 . t o IN fftfijg M l sm ss fHSP&ed o f tS a S | s o o£ tbs to tbs weighed. aRiggsstlosi n bees, made a s complex. f& fast I t bad' S ot even bam established. m ie ttia r a o c s ji& is e Is fonsied or i f assess mmpmfc Is to|dy carrying dom t o l^&misd tungatie sold* Siaoe ptopitatto t o l t o s are saltole t o formation of hydrated tungsiic acid this sosM oessr* la a d d itio n to Ib is to i& e s sta te d t o t om&msm o f c to to m (VX) to t o t e (T ) worn observed to t o a ia* t o n m oo t o t o r work t o to to ass o f t o o t o e on to s s emt&maa* to m m id so3ntlcaaf y e t to t o t , asoept to m&ewt m ly to s s a a t o ta n g s to t o IS fastommfimHrn bgr cith e r eolorim ^rio method© (11*,10), n o th in g had been te n s w ith th is reagent except m inor jm a d iflo a tio n e o f Knowles o rig in a l JftStllOd* fm m th e long lis t o f which f a il $& to m complexes w ith e-benssoin mtom $m w tam tik m M s e ln tia n i t Is apparent th a t w ith the exception o f palladia*® , th is reagent fe rn s eomplaxee e xclu sive ly w ith peeps ¥B and VH issetaXe# I t appeared fro® a survey o f the :U te ra tu re th a t m stad&r o f these m etal complQxe* is n o n -e xiste n t, and th u s, due to the s p e c ific ity o f these re a ctio n s, th a t a valuable reagent was heing i|p o re d * W ith th is in satai, I t m m sd destoshle to conduct a a tu d f o f the complexes o f »bens50ln etsrQsiimjsi, soi^weNsisps, ana vertginmit** aaplciyed fo r th is purpose ‘sere with vanadium, *8i© ssassi sepsrajasBwBUL w®cinijujii.e8 end extrvwstion methods# ix . mixmns, x m s in s , SSPSRIffiJimL MKEHDBS and 16 A. and S m m & * Psed fin following in « llafc of the raagsate used in this nogfe. Alasilw* eBlfirhe, m ilinekncdt A n alytical Reagent. «-§eniata eaclaw, 0»S%»Gb*** Bawgai Starting Inbonrtoriee. Whan high Iw leo fe w ©SsmoXe Bismuth efclorM©, Jie*g®st. Chl0 ro£c*%# HGCX3# Keraik ftaagont grade* M re te .fld ftq e id ** g fc ^ * & y s t, reagent grade tmm G#mmX Qhm&c&l m A liiM m m * isssd %& Corp. 8 «MXM&taA» CgEyOK, Herak Braga&t grade* €«Mw»l)tli!s*©ji A i r $WwlM#SEp^8 J*JinCw*w©j| iUT : &iljjj^/j( 6 jft0 nte fr-3 fo^fff^u1 vi w>iV>»nAreflwi4t<-> MW 3 0tf* Bodta ta n g e t*!© * Araraj^ ^iCL0jBiX ll©a^©c!Iu» i*©eg©Kiw* ftf|^yfc4gM»|t l ‘B0iS^tSSXt» SWfeBjSHS^toll Jjfa©0 J$l8»t©i | Qaeraetia* Gi6$ra^*2% P# i * M prajnration, Mep« 195° 0* A ^JSWIMB®® t,VJW fclj~#* AiMUyS fttlLifL*!|imj6maH i#W T3j*A/•»sm4! lallinteodi JvaO^ieeX l& iageat. Sodium wradfcte* $a?£Vta#* JMsei* Selo»titie Co.* Ei&ar mad Aaesad* 0 * F# Grade* M a acetate, tfO^0 ^ O ^ 9 *^y^# '•Baker*© Ai^O^sed* fteagent. Bn addition to the ab©*©* distilled rate? and 0 * P. grad© ethanol and acetone veie ©ajloyed In sssking all ©ttier solutions. A$>jmratu© need In tkeae ^periinettts included tb© following* 17 Beekmn nsy fy t*M A^ ra oa m t0 Wn In 0T^n^niO tt# '' SiS^h^^ SB ^t^^ ep^R¥iwy ^tW ggg m bsr* ePVKntl Beckman w model W M reoca^in® iroviliof^^ WF^!wlWw nR ^D V antow atio w WW’W lf*W HW W W ji ^eiem Wag^***r^W B*^rB tSR ^|iW r • ^ BlSMPfi^OL Tet&miOal l^ wmfrfaiy w**^***!- flft a**i4MMaa,-fc4<» Wkifaai* W&S - m odified to 0m a m m wX$mm® a g ita tio n fo r e x tra ctio n tms&. T lite m e by a tta ch in g the olassps to e ith e r #11$ o f om fo o t lengths o fwhich m m la ta rn foete&ed perpaadicu** $ *& i^ to til# roolsOir or® o f the shaker* Several procedures vert aged ^xtenelTely during the course of thie $mmfo&0M®&* aod therefore, fa order to atroid repetition later, thagr are deeeribed here fa detail* 1* ffreeii&tation nrmodfrpsy* The preclpitatioa reactions vert studied for these elements using the following procedure* Solution castfs&hning tins desired of the eSUsamt being studied vat pipeiedf by mma of a calibrated |ip«t» Into a 1#G~2£0 al* beaker. tbs acidity of the *feteli*fe4fflS fffla Adjuntsd to the (|ai|V3 Value &**<& atw a/4fHfc-Cmal taawi&ls m m added* The desired amount of c-bensoia o&trae dissolved in $0$ acetone, or &* a fm instances, $G$ ethanol, m e then added drop-vie© from a buret# The solutions m m stirred daring the addition of reagent# After the p ’acipiiaies had bom allowed to stand for the desired length of time, they ware filtered with tactic® cm pamioasly voiced JO ml** medium porosity seintered pats crucibles* The pre­ cipitates were mashed with varying wash solutions, bat in each ease extreme care m « used in washing down the sides of the crucible. The precipitates were then dried to constant weight at 105° C* xa For the dstemlimtiea of the per emt by might of the metal* Itt the complexes the following procedure m s A portion of the complex m * placed la * silica crucible and dried to constant wight in * 105° 0* oven* It m s than ignited to the ecrresponding codde in ft muffle furnace at 500^550° C. l a i the insight of the ascide it mm poasi&U to cfticulaie the ml$it of metal and tints the per cent motel la the e-tamelm tatae oeglm* 2# Extraction arooeiy^ii* A H of the estimation wrk done involved type of esstmctlon# fhe eoMtlond to be extracted m m pipcted into 6© ®&# eepemtory funmsla* In moot eases any eddltioiml mieriaXs mere added in eolation directly to the content* of the Darnel* In cases where strict acidity control m e mot the acidification mm carried out by direct addition of the 1C separatory funnel. Where controlled pH m e important* the pi of the eolation m e adjusted using a pH meter before samples mere p&pefced into theseparatoiy funnels. E&fcmcrtlons mere carried cot using solutions of ©•benzoin oxirae in chloroform taring the desired reagent concentrations- £a all cases, the 'amount of ehloroforBi solution used for extraction m s carefully controlled by adding the reagent from a buret- Extraction m s carried art by shaking the separately $mm&& on the modlfled Burrell shaker previously described* Ibis aHewd a more careful control of extraction conditions than shaking by hand, when each control m s desired* It also mads it possible to run a larger murker of samples in a shorter period of time* WHwi the chlorofeimoia coclta© seiaiiarij its emoostmtim wmM be a x 10 M* % determining th© aasount of saatal extracted sp©otro|^to®rlirioally', a plot of the absorbance versus raetalso^ben&oin oxim® ratio resulted la a cmrtm with a sharp break at the m©t&X-a*ben&oin <&dm ratio of' the Other specific procedures which were ttead* but not esrte&sirelgr* will be described wtai applicable during the dtscossicn of the expertmental work* XII. HOLJBCSNUM 21 S im * earlier voile on molybdenum actually gave rise to this study, molybdenum has been selected as the starting point for the discussion of these complexes# A. Results of Qmrlmetrie Work A brief report of earlier work by this author (12) Is included hare as a starting point for a discussion of the experimental work conducted more recently# Although the o-bensoia codas complex was originally reported as unstable when heated. It was found that when all excess reagent m s removed, the complex could be dried to constant might at 105° C. and weighed* Using the method earlier described in the experimental procedure section, the complex m s found to contain 16*51$ molybdenum# This gives a much snore favorable gravimetric factor than ignition to the trloxide which contains 66.65$ molybdenum. On the basis of these remits the complex of molybdenum with a-bsnaoin oxlrae was postulated as bis(a^enaoinoximto)dioxoraolybdenum (?I). This postulated complex contains 1 6 *51 $ molybdenum, the value determined experimentally* It was also shown that the large excess of reagent used in the original method m s not necessary# In fact a 10$ access of a-beneoin oxirae was all that was required for quantitative precipitation of molybdenum from a solution 5 to 20$ acid by volume, ibis mads possible the complete removal of excess reagent, which was necessary to obtain the complex in a stable weighing form. 22 Th© quantitative precipitation was shown to b© successful in the PMMmum of iron (III)* ehvotafom (VI)* and vanadium (?) when the chromium (VI) and vanadtoa (V) war© first reduced with sulfurous add or f a r m s ammonium sulfate* On this basis © method far the determination of molybdenum in non* tungsten ©tool© wo© developed. Ib© samples m m dissolved in 1 *5 sulfuric acid* followed by th© addition of sufficient nitric acid to ©xMiae the carbon m& molybdenum present. Sufficient sulfurous acid or ferrous ammonium sulfate m s added to reduce our chromium (VI) or (V). Hi© mol^enum mm then preGipit&ted by th© drop-wise addition of a 30 to h0% mmm of the a-bensoin ^ dH) 8 on th© baeie of the per cent molybdenum determined# However, additional evidence to support this postuXation ©me desired* literature data indicate that th© MoQa*+cation ie the major species In solution only when the acidify ie increased beyond the isoelectric point at pi 0.5. On this basis it appears ctraction Methods to Substantiate ,:1 T O a * 8S ^ 111,1 At this point, another method to establish the complex ratio ana carried out* fhis matted ana baaed upon the procedure involving spectrostetomeirie measurement of the q^ercetin*mol^b used for abeorbanoe gsftaoxessits on the- sisedbmatihnteanHba#* It Is also of Interest that for sanbLss eontjain«» log m m than 0 *5 ng« of jooljfhdeims, the confined chloroform eaetracta have a eloudy appeurenee* This is due to the Jbeb that the aolytedem® ecsnpXeefc has a esgr liaiied solubility* hut is still extracted into the ©feXoroform layer* .If these solutions are aliened .to stand, the preoipitates atm be earn to eeagalate into a shite floooulent precipitate, fbr this reason it is very lajportant that they be thoroughly shaken before the c m mi* ali<|tt©t is restored for eolor development. the first attest to eliwdnate the interference of tungsten involved a decrease In the voluoe of ©hXoroforra used for the extraction 30 o f soc & frd m m n. Howmrar, attempts Dm develop a calib ratio n m m under theae conditions p n very poor re su lts. Sfcerefore, the exact wctxttction p e iiw i m i M M 6*5 Dm to tom necessary. this point a cal3bmiien c a m was prepared for the range from l«j»0 mg* Of molybdenum. Os&y bee modifications of the mmm t Utsratur® procedure wire incorporated* She first involved dilation of the combined chloroform extracts to 100 mi. with ethanol rather than m m m im w* this asm a much greater solubility of m i compla* and thee moan aamusanc© of a homogeneous system for removal of the aliquot, la addibicaa, since a loner mlybdeimm range was being studied, tee ml. alit ham. definitoly established, am it ma& be this cattaatc apoetos whteh unitas with a hpdxwtod tungsten blonde spools* to form the hgpiratoci tamgablo acid which precipitates. At assy mte, jwcipttattoa M i begrand the isoelectric point, and bee boon otowosrod in aoluti^is loss acid than pH 1 after long periods of time* ftegetm map be smintained in sold eolation br tbs addition of phosphate or other Ion* which form hotoropoly acids with tungsten, aim® the hetoropoly mold* are we*gr soluble in atpeous media. Tungsten m r *&*© bo eompOLejced with tartrate, citrate or fluoride. 35 fb» temmMm of the fluoride m m $m has been qpite extensively used for preventing precipitation of taxgatie acid. m addition, the ilueride eoraplere is reported to be WO3F4*, whieh gives m m evidence for the eatisbence of the WOa*+ie&* Hhi acid used for acidif^dug tungsten solutions is aim important. w* If# for easasiple, a 1 n ID H. eodiuja tungstate solution is acidified with tK *W l, there is an i»»diate formiion of hydrated tungstic i s s ^ * if ^S^SO* is used, there is no evidence of precipitation for ffiftfffft to twenty sdbseitss* With respect to the addition of phosphate or fluorid© to keep tungsten in acid eolation, the following facts wmm observed. With tbs addition of a slight sleeve of phosphate ovw the a&ount repaired for the ferantlen of the 12 «p2K)Cphotungstic acid, no difficult was eiMNsanxter^i with precipitation of tungsiio acid for any of the solutions *.* in this CKperisaental week* When a solution 2 % 10 H. in tungstate and 1 * IfT^U in fluoride wm m M $$ in milfuric acid, no tanediate pracif&taiion occurred. However, after staging for fifteen to twenty idnuteB, the yellow p^tuagstio acid, began to precipitate from the solution* fhis solution contained a 20g aoceass dt fluoride on the basis of a 08 >a%)* eomplsae. When the fluoride ion concentration was doubled, this was not observed in the sane tim© period, hat standing 0 vexwni#t gave the mm restate* Shis Is Just a brief description of solubility problems and the affect of ecroi&axlag reagents* Further discussion is included as the factors apply to specific eases la the c-benssoin cadas procedures. #a til* basis of the smaseesa achieved in establishing the ratio of the molybdenum comj&aat by means of extraction Into chloroform, similar remote m m predicted for toaptea. dteffrey (Hi) had reported no in %!$■procedure fo r tb s ew&raclion of mXoxogmftm ^jAsntibios o f end tmngsfasm e*bsosseta amlns oompXeoBes Isto ohXeoroferst# ^ince th© tslnane**]^^^t**difchioX method is mihsr iittvolvodp and also meed for inssy wall qtiantiti^s of tunpt^ci, it mao hoped that a dif* for toogstei th e ^ofN ootin ppoetN^sira fo r ho dsrissd# After the of and the roportod in te rfsrsa ce odt tungsten, the possibility of naHyig the same procedure for tungsten isas comsldss^ad'# With this purpose in mini the spectra of the t*mgstm~c^bemoln odma complex mas detemined using the Bsckram m~ft* and is shown in ftmm $• for this purpose chloroform mas employed as the solvent and qpereebln in chloroform mas ussd aa the reference* Comparing %hese results mith the reported speetesm for weatfb&mem it f*s»arhe seen that both exhibit the same afoeorptixm maxim, the ©hlgr difference being a elicit diapLaeeiaenb. for imaSyhdmim the peek occurs at U20 m t for tungsten a t b&5 m . In addition, the absorbance shorn by tungsten tilth a bread peek occurring from 370-380 m is not reported for jmOybdMmt* o 2 2 30NV880S8V OSO gZZ' o Thie suggested two opardaastel p o s s ib ilitie s . 3b* fir s t being the deteraiBatiQU o f the eeHj&ax ra tio using the m m method as th a t ffca* molybdenum. the second* a almultaneaaa, d iffe re n tia l method fo r molybdenum wad tungsten by m u u m m I o f the color developed by the «M »e«tla eomgiUK a t Wm m m iO O and 375 m . extraction procedure aa reported la the procedural section, IM l $s$£11■lejm m *A in an MMawwli fc ^p*^ri juilaaiwiejp- v < vem pnem ^telybigyep^jtoifli’ fei.CBR* tte ti^ggstoo ooiaj&eeE Is* wit «fcta?acfca!b30 Into ^tiSi668is69@6Kiffli %& m y m fo m k f $ & ^ tdtti' ’ of $9P8fP#wfcs tste® comp-lox# 1^ ^dwyig tm 'Hig ia% t«r, t&e 03310% pSWSdhBW W&9 bo liiospfmlj# iM i Hg&M* ffe n i thfttS I f 010$$* fflffifflflfo f*%ff fm W * If it ll tfe© i t ttaM i lo ir eoih gp»i lifjth. m& tamMMilSttoSt f O ftfiM OCCUri*0d. «erfyj(pm eir.•asP' wneswe0f t*MO11f1tllf ^yl.*S '~f1 1k■i Jw ■ —~ m tPQ VfiM M W VlPsm TW w m ssn iho tm & m im o f tiio M *hl® m m i# the s ^ i t e i j^soswas&i* w io d l J&eH *0$3 to .0 0 # te e , agftiB* nit&&a aotpeorimorital. mmm* tm m m m & t® pw iw t tte t ^1 1 0 q aite 18m m s & m ttM m o i p m ^ M t o f £ te |& s t« , tbs to te v m s y u l& $ & tu»gtft«n is m &m of ths tungo tr n i- a ^ m factor z o in o©is|£Mi3te. Xs fe e t* Ig n itio n o f a portiaa o f ths white s a te ria l m M nK eoUootod a t the interfuse o f the too H qoiiia ehomd the fweeoaee o f tu n ifs ilth o a # sons white m ter3a l Is obaerred to fo ra a t the ko moXyb^msm mXm/eMm# tfiwisig * m& $om m% t h is is mem o ia p ly s m g s u i* w t t ls i &g&$Mmssu ^A Ew lttt^i Uw ttE K' A^isw^SiJsrCw 53^ #6* iilSl jflF *iM ilrlK^f-Awi A iAW taE nP itiw a wSJSw i'TAffir'JR w®0 MAKfr^|nwrilfc4i &ntoIBwuMjgtfi 93W9 iMHwWBNBJNKp^ W jPW BftU ^fhlPfhi^fcWW M&kA fe feA D® Wp lW t^ tWJPlirWt*KWIW^ §F k fecfifR®RptwWtWASi8si T &^4*& mWnpii jiA iinKi^ F^ U^ I^t& r^Bb & mM mw uH Ar j ifp‘ dm tdp W& pm r&^P Wn# PPm WSil 8vIff ^ fw*& ilrA ^a Wt Wa du jp ^ipipnPkwaRMii^k®m dB itim H^ t t •PfPPfPprpppi' IPP Pr^PBWP1 ' flSlfefttM 4wPWpiMVV>iM^^piyFlffrt# iBpp^!P1ah# fMa^ sWSWWiM Jp^SP ff aaWps®olSIIISWa pHrSflpapOfliaRlP^WtoBr^ fe fljr d t ju fttflffiX * IS W K fcdfiS l O f th O la ite 'fa ir it 'ir t li A « |S M w in t f a l M tt&AtoM t padK &$ S6ttfi9SB*A to r t* * cw r m SM M m m &£ X *® t i t t i 3® a£U tawt t$ia& tuo tfta.ajl* jg ^ f t jii -r o a w to ia to g O A m o b ta in is a j^is s N S O d ia a 'a a a i io ]|!^Di> iito d i o (la @ i^b a S 0 ^ Id a J f l* * igj&f%& H « p e a ^ lo B B ^ p fpysffiyj^ ^ y i In , p th W S Q l IS b a * to to n dt r jw A m . B » m s lto a a . v e d a M to to ® i« s « * * in to t o to M o e « M H O to t o t o t t x i w a rn o f n o v a O n e . £ U tto s w it h a o O n titn m m um A a ttr ts a a ta m » to te d , *% la $ m . U1 B » a lta ra a tira extraction proeadxra smfc w ith tol uao«-3tU««*lthlol ate p ro p o s e d mmmd to bo color darelop- by Jeffrey ( lit ) . Hcewer, -b ato n m » m e rodartakan, i t appearad d w lw b l* to datandns, a t la w * aj»j»w lw ta9y» the maxtnua «© lnbilH y o f m ym M i< m e tungsten eomplax in IW th is purpose, a portion o f chloroform wa* aatam tad w ith aadg&m by Shaking it o w *n i# it on m aotom tlc shaker in the pwtsewse « f axoesa tungsten nangUR. the ablation m filte re d , Uto adu « m y&psfeed In to * in riiw a jr veigM d plAtinum diah, and evaporated to daymens on a etaea bath, the residua m found to wadgi 0 .0 1 0 0 gm, and taro Mm M laM U tgr o f the tuagstenMMMaaain eadro complex to bo 0.12 m g ./iil. o f ehLwafom . On the basis o f a proposed eang&an haring the fem ale W D eC ej^S^^a* whish woald ha- expected follow ing the molybdenum went, th is woald make 4 the e# & anfctw^ted etolcarofatfm 1*8 x io M* wBwMHP w 9 CSfl®i®wLwILCSl® <8Kk$C™B$^99fWw S8SSL IKS $!®19®06$IEP6j| 3Uv VvaUQ he litposelhle he aattfuwkhe the efeXosrodfoisfi la^gw^ iiyy* hhtt® tha ro® r o ta n H M I m a id b a la w th a n . 1 0 nail* I n $ 0 X t . X n o r d e r t o fo lly a p p ly t b s p r o p o s e d e x t r a c t io n oadwt t n g r t n io t a a a ia ba M U W 1 ta a g s ts m x w it h ia q p e fe a h & s . 5 0 **S . an r a t io x r im ■ tm w n ln i a o d a e « M a S e a t o t h a r e o ro o n ftw o fa w e x im S h a p o s s ib ilit y c h lo r id e , e t h y l e t h e r , r o d n th e p re e s d a re c o n c e n tr a tio n o f s m e s a s f ta iy o f s a o h lo w w o o ld th e w m e x t r a c t in g c o n c e n tr a tio n iw a r ily th e m onad n e a r e s t * , a m e h a s b a n a a n a , e a x fc o n t e t s a - e t h y l a s s is t s , sho w e d a w n t a e t o l* p n o e s d a r * w a s d e r ls a d tg ^ M r a t io . a f o r d a ta n s ln in g m a e e s ** lo w p ra d x e . f t s r e s t a b lis h in g th e 'Jj^SkkMPflk^Owp^^^wWr' ®w^^F^«jfcf^|pRP0L kMRngi , m sp' #^& m(W *4k .^m**u*r nttii*m* *-*^WttHm Pk^BP|rmm i kPPk P(*(i , iP .BSSSp^KkmSpW^* Tji^P ^p^B^P’^^^p^^P^BjgFfOTMw ft 4H * mi mk . tw ,k tka >awi &*«* iB tP l w>J fpP lW -Ffeii l^^ a l^'n£ M. 4 Bl!l4 lkHk% 4fckt* a fitwlm W fc 'W W*W wM j|PBii^W ^w kp m -k*iW Kw^ ™ I t DM postulated th a t tip m itfifc a t A m a m fim . foamed m old iscaraase w ith iaasmsiBg « d m ad d itio n . fb ia shcald ought u n til MfiCUtiUmt oatae is added f « preelpltatloR o f the swan* o f tungsten. chosen. Further addition a t reagm t iMQraad th is point ahead*! ew eti* la as fu rth er inoraiwe la th * w tig rt o f faw etfdtake. Therefore, a p lo t o f m ig h t o f p recip itate w m m O * m tta a t tungsten to reagamt s in y ie ld a brook man e ^ tirs le n t amounts are present. Iter th is purpose a s o la tia * o f 1 a 10 K. sodium taagstate idaleh m a im 1 a 1Q~*K. la phoephato sad Id* la a u lfte te aeid m s aad* up. m s yawidsd Just a S light m oan o f phosphate to prsraat pw eeipitation a t tuagstle sold. tm s&. portions K ith m s y in * Measured portions o f a t th is solution wars precipitated a ^ o m m ta a s S m , procedure it . **.c ,« *t ^aC0x4%##/** i** m, iar\ I M I l or alju H i «..o... sap.*Lti«,v|KWw by W qgf tfe® tm # owo« no in a »O » wW »M iPW if>O t f ^yV *» .*P y® aO Om 0"l^OlOPiOW< O O w K W lHM w O W ^O W ^PPP*^ iwoodow* M tho fta& t ab tw yl a t a g m yi^ tri© p ro ei|d tatim , a slig h t mmm o f fg w n liio m o %Mm I sad t&© s c ia tic a s mm wMWM v itit Bus to form tion o f tatgsfcio mte* m£M prfmmttm wo.oddM m$£k te * p w ip ita t© diooeOwd I m&mt addition o f tbo s^w aw to mim w3%Mm* W mowtt&t* obtaiaod O iw «i that lo w t t e ta& f o f tbo tegs#toa w o foooiwode fhmrofsseo* in wajeasei&ag WKWObWOfto*■tntlfiH&le sold w o nood so that **»* M m um a^ « f fimuMFtA# ^8NSS^l3^^ 3feW3lO^^^ .#te ih io ot*w|r* a o.0$?2 K. tm gatato «©3Aj&tes* w o pmp*m& so W at WO lit# im^ifjt JUO0 W * Of tWgOtflffle ond 000- sootooo* On® oil* of INPWMOl M WHO 3 W W » *OT W jf m p C llW Ok «*o© Big* 00 tttttgOWft. BofW s o f oX l^iots o f tiis W ow twgidMvto f^y*^ toiBBRM ffif 043 6 M. pefcoaaixta Oso»M* warn «dd*d. Uda jaw ided * 205 «HMt» o f fUw rM e ion fo r « M “«T &«wrtA# 3,. .^ny lo o * Wm £X®w$d& WO' «isoWod fcr w pew&pMmWm. M B&mtm&f oSosn Wo tttW f fliio rid o ooq oaxysrlng i o t ^ s r o p n a o id iia w tto a , Wo naoewwy o f tow oW o w o lo w Won M L f« ^ rw s a to t o n fo w d to bo lo o aloo «^utt«i .^ #sa#t^4jiaEi£sy fo tw o ■Bw^HnuE| jm flpK M IO O oaW lW lKO P^aO iO W ilM p o f f lu<>i*i^ xknMuttiiHe^v to fa**** qpita « lM d jr tea te&cfttcnt aw tes* « f te a atnjaa bsftaw p w s ijd ts ttfln . S n r He* earns teas* ttala maw tens, m A m I e£ tee ftaasM e Is a would ho ofwoot topaoofhl© doe to the peooomoo of the forgo ombb0wo? o f other m#k oo i fwpQj; vhleh ©i O e fo rw oooiiLiQcoe* o f to o## rosoSLts I t to d iffic u lt to u e O ritie i 000 tho VOwMF «Qw OOOOnOO WBImim'-mlOIKWIOAO» *110 OTwlSwJ pProipilWweHi XB OwPPlABQ. oat front mtk *#■*■& imtnaflott to wtafa*ii &© e&ffl&eocl&g aaente have bean aided* flu ifg&sli t ^ h A l e hQrctratod tongotSo aeld to ea** 4f.> 11^ s m O S J tr IWMgWet fccttrtd. Xu addition to HAS, tea safawMMOy 3avga amass o f »e|K&ite W?% PMftly flft. OtMii. OOfflipilste ptfldfttfl o f the mo3$tidmim oomi&«®£, hat oleo M $erti*l precipitation of the tamgstea complex, oaf wmmi reegewt. m»- to the nooculsnt Before of these oomplSKOO* the formation of O H toie preoipitef# could quite eoeHy « « i^ deem the hydrated tungatic eeld, todUsh le quite oftm colloldaaSince the precipitate fa this method 1« a©t welded, the nature of toe 51 ppoolpit&ie I* not lKj»rta»i* ffcie ecnM quit® oooily i&er thou* outhoro reported * xtogaitive mm& m *2 1 detemfaottenft StSO QB p m eodiam tongofcate eolation® and not on oteel ewaptUa. So the ahsonee of tip large amount of iiiolafodomija eosglasc, I t m M bo quit* lo g lo a l fo r e priiam of tungsten to im*£$* tmp^ipitoied* AlOiail^l 4M tUMf iw^piviwipwpp is# wvoi ’O O O M NO ieiO im O W e«O O O RrPipOr 40*r^aB KHrr® rO frora tMS OtOdr it 0*0.btt PWiSllaF abb^ a *!*** pjr the *X±0ti*Uf QtfthO^IP |ydftM ** %J$ *“0>* SWBBttdbFO OOl03!i3^®t3|PiiO OOthOd VOX^S H*f!f|ieooo that ooO^r <11010 y ij^ i fltioQ'of tb o #f ssSfw isly ooo inspired* no AJtariMKkkfl.jkUhM i 34*tmetme OnJLCtirO*©3r®li 3A*M ©GH^wBEK St OeaOOHreBONrBO* j^y the problem o f the O uk » jlAtfplui^. O fc^fc 4vlu *^VPM i0M| (w«# M tVPiPfe IPjlilUliM L JL u OCnXXwbOn wO B onioo ee#i|3SL09K boo boon ootobXii^oM)^ oof ogbbo Amim #tfa tfof* OpOOiOB if* OCld OOjOitft*!! Containing JSaceriM* tas b m n wwwdad. finally cm the of the inttainMitiy of the ttmgotoa ccmgj&ooej. »wi < feiMi *— ■* dooreaso of &#*&*&<*# fmmtioii in the iopoooooo of otaeoreii&ie* the aoeer coctamotiraa eethed boo boom rooiawS to be opocific to * MC&y* bdoom* fblo m s deoerSbed 1m the aolybdmiai section* & A A m H iN d t n a w to n ^ - tM a llg r * no A lth o u g h fiw * flo c te m o tio n to c h e e k th * d e e p ro d *»§e*ib«d te m n m & te o f th a b b d m o le « w o o p o o O o fl iB b o o fo o o B o o a a r tn u r tlc s * o * o r » wade o f c o lo r th e d n tix p d AaOTblio^. O d b g n ttfjM tsyr o b v o n ts tt o -b m s e & i o d M xoago c o lo r im of M e t r ic ld it p w e ih o d f r e w litiy of tb o boo b *fli , I t d m m O soo. fo r b p d lp h m g r lm x b e a ld e . H a n h o tta a A eerlae of relwfrdiifrffs @f warping eeddltgf were »g* of chrcwttte per m l* o tp w & M B te aaa bo w fe in O y u n tu e e w M & a . p o o o o d a r o i M ffta p ita g p a rp o o o , b o o o o o tb o o f th e o o p o o to d 0000000 x 7 P o e t h lo c h x o m tu w o a i& g 3 b io M e th o d P r o je c t la (35)* tyiMtaliffliding 0oQ5 foci si* portions of these solutions ware laeliietid with tan wOU of O.lf c-benaoin rate in chloroform, S!ha ratrasts mere dream off into 100 ml* woteetrie flask* containing tan isi* of 0.1J6 dlphai^oastiwsida to ethanol and ten ad* of natter* One drop of fit* W% was added to each* end thagr ware dilated to votes with siMmA* For an estimate of the amount of chromium extracted, the following standard was prepared. fsa m l. of the chromium eolation, O,0 g mg./ml*, was jdpetsd into a 100 ml* volumetric flask* To this were added 10 ml. of the 0 *1$ o-bensoia rate in chloroform solution, ten B&. of the dlpte^leateste eolation, and one drop of 6 H* 8 EL, and It was diluted to totes with ethanol, this gave exactly the same oompoetticm of solution as for the mai&m, and would correspond to 100$ attraction of the chromium* The absorbance was then measured at 5hD 53 m $ 10m rnmosAmum peek x m m * *# * th e n M i a e id c q » j* U k fo m e d . 2h* recorded In Tfcbie r r . M « £ £7 a b s o rb a n c e o f m m m m m kzm w m M o f c h h o h b jh scm o xso w o t o-bewsoin ox3» A t is y m m m m 1 .. «g pH, or acidity 5.6 34* forQmt y x 6.1 0.? 0.008 0.00? 0*009 0.0IF AbtfOfbaaee 1.0 2.5 5-0 0.022 0.021 0.021* Ab0oi^b>iwt ol standard ooi^np^iQg to 3005 oatreeiion «* 1.80 Iiiiijiiii»il iniii ui.n^waoi^wm.#MjimHiiWf^ liiiiin.»i 9 wm 10mm m m fiM it mm ke mam that wan In higher aoM conc«ai- tration the asBOixnt of ehroiaittsi extracted la only apprcadmbely 15 of that p m A . of Whether this lack of extraction la dee to aen^formation insolubility of 1te complex formed, or redaction of chroraittia by reagent ooixl6 not be dete»»s3nedi since it was laapoaolble to obtain aay pore complex for aoXubility imeareaeiits. this will be shown in the neat aectlon. B . P r e o ln t t a t lc n A tte m s ta fo check on the complasc famed by precipitation of chron&xtm (71) with a~b«n»oi» mimsi, a eolation of potassium ohrcaaate In 55 hydro­ chloric m M was prepared, the efcrcadnss In a sample of this eolation Bh m s fsmlpltatsd bgr the drop-wise addition of a eolation of «*bensolii eodaas In SO# acetone. At first, an o m g s preeipitats started to fern, tot ea I W I n r reagent m o added, it tamed to a gramish^brcwn ganssy residue efeioh could not he filtered, as It m s absorbed Into the filter paper* It m s also found that when the addition of reagent m e halted utth the first appeamtee of orange pmlpltate, the same fSmmmsa m e Observed' th e reason fo r these results la bemuse o f the stranger caddising power of chromium ( f t ) In sold solution* fhie results In reduction of the chrcsslujR by the e*he®sodhi eadbae* therefore, o-beoooln wdm is of no nee sisd gives no clean-out reactions to yield a stable M g & S K with chromium. It Is therefore fortunate that the Intsafer*®©* o f elsm d&N In other reactions sen be eiiiatxiated hy the previous rednst& m of the ehrsnta (V I) to a 1e a r m im e * state. WULDHIH SV to a to to ^ wmh m m d if f ic u a s e h ib lta d In c r e a s e d lit e r a t u r e d if f ic o i m m M a m -w ith tto u lt lt to m f o r iw ltfto w s a m to a c id s o lu t io n s to to to to to g o f m r e s u lt s o -b a ta a o in and to v h ic h » tu n g s te n . (? ) c o u ld m tm paw ed to o a c c o u n ts g r e a te r fa r tto to w rm latod a lt o d a ta * I* toe Utorature data have « **m ito f tprtagngfcnrtnn w o lB tte ta . fin tte ten ia o f t t m m a ttm p t to o o tto llto too f i r oonfc m m itom to too yellow pwotp&tato m o m dorttoaiu 4 Mototton o f oodisua vanadate; mo adjusted to pH 2 , and tom tom tto t o t o t o l o n to o f o-benaoin eotoo mo M flo i* too to to yollow p recipitate m o filte re d and mtood o ito aceteno* too pm> omfc m rtmtity dimuaood to $0% m o totom tood according to too |» o - procedure* too m ly m otoblo to too o rig in a l fneeedure m i too metoed o f drying too eam jl«# a m toor o f vhioh moo need. o f 130®, 105®, ate 75° 0 ., • * m il to o t mom tm q m to m to o m m doadLcoater fo r m rtotto maefiM* Ha® pwej.j&aatoe raieo m m oreaa or&oes attained o m ia & i m ig h t only a fte r i m m periods o f drying^ # o to moot ooooo atomd stidm oo of mooompomti^OKi py vasiMiig ipmgr ^ wuxori ms ^ axi,w w im pm w kv om atio, and m old not I ni mjroduced. too m ines to r por coat m m dim -varied torn it« 8 to lt»«l* too 1m m m ines m m obtained to r drying to a m u i dooiooator ami drying a t ?5°8. to la eottld indicate in te r feeing drieaa o ff a t too higher tm tom tarosa' to addition to toto m m too w aiting point o f too r n p m «m determined, too compt®t turned tom yellow to gmy batmen 11^° and 130° C* H ilo em M also indicate too looo o f m te r torn to# structure o f too oomplojc* Stnoe i t mo aloo possible toot tto pmaance o f mess* reagent m M mom to io color towage ty reduction o f too m o lto , too foilcun lug axperiwmt m o carrlod oat. The yellow cm$um precipitated oo before m o thoroughly sashed w ito several portions o f acetone, tom 51 * lt d to w t« r ( a e a a to B ft sat fin a lly w it h v tA & k m a m s > * «w * IK M to . to * aora atafema. B » dwiomtor * m emg&tK w t o t o w d a * t i« n tfe m t r ia d of t o o toaalto to a m to d to toto nannm* a m oanaftlan pareaotagM batwosa lb mi UJf. Keetiag tteta tamg&at atom WcPc. aloe vomiltoS to to t eo ltv ebaap, to m todttoatong to m o f m fe tr . Alttwap tot pmoattog Mtptrtaairt tto not msotto to toamatoiljr ettatotohtog tot atom* of w a d t o to tot jtUM eeoqpitat it toad to another ttoeartiy. Watotog wito put' atatona of emtrtt rmoltad to dttttdtotog t Imp* postioB of taagSm* Warn totm ftltcwlaa tarn aHowefi b© ^ ebsgii for pr p yaPrm several totrt n*mPPW Hhours m tottore tlpolniftom B rtwmrmeat^md *ttp t&omtome ttoflRW*m to^ toMtommMW©# toW pi fleotoXeaat wliib# t*r«ei|sltttte* tfM-# coaid eeeiiy Ini diffezfoitiftted ts&m tto &e$dl&»8toped ©styebftto of it-toasoin c&isMfr* It ttoreftoe tooetus eyMtofe ttob ftnsffito toe disttoeb oeB|0Ls®®B with »*beasoS$i ooci&te* o^SftjK tofM f!Sto StofxR whw i|UuK t toto o ytoit'o *% '*pito totW l * *toW#t Btem littto m a & m & m m m m m & m m S fit determining tto exact of tto yellow £«**** attoatioa w e foensto m m m M m ps^il&tabe* It wswi t a d btot thie eoato to tto white easily prayarod by porecipdtoting tto y d & m complex m & allowing tto pofeoipltate to etonxI ewe*isf#i* fhia 3*es&tli«! fit * m m w m i m to tto white pri©i|&b&te* this ©oeM bo exgtodMft wton it m m t yap&cw to o tito yp tfiipftfrto t Ha tow fli* fihflt iloBdy>'*wp'^p *rf*kat #m *1iiw 0(k1 tpwaamwi aO varaM aom ajiw ^WMaofjplliM ^p^^aw ^ap^w*w4 i^p wwWail wwi'' 0029 vwwww a OBt. a ■iw^t^valSMtil wwin^w KatTmf 0 %»$ m yeiUow pxwoij&tato mm fomed* Bmmrme, t it e r steading te r w w w l tooae preoipltotioa a* tto todto epesiea took jd *ee. Whan the peeeifdtotien mm carried eat a t pH 3 , tto yviiim p re o ip ita t* Im id im ediataO y. Allowing tto ewlatdflB to stead fo r setae*]. deya resulted to 00 ooBMiwUm to tto M tiite apseto*. m * fto tto r w r f f lo the ■aggMtod m & *M tom te f tto fto a a m etoereed. 3* OogtototioB o f wwwlto Mith U teretore dot*. Foramtim of tto id tito ppooipttoto tovtog • toaedtao eontoot corraepondin* to $9 mm expected m the beaele o f apeelee etadiee te m U ead the m a ilta o f eelpWaaae and tangetan aapevteaBhe. Banner, i t wee hoped th a t a q u m tlta tire procedure coaid be waked cot fwe» th is In ehich the preoipltate te dated nod w&ghed. flite te lapeaalbte, hoaawee te e to tea long parted o f standing reqpirsd, aateeea octee also jffjHy ^BwKnRBEw03* Wm mmm mm&mfo« Id * ««^r m WttB^WP mm Mamam mq m t l t s r o f *h» pm m M &M p w m M p ro c ip ito te . bo $b* long tarolvod proeo&ir* firv b lo t M ®&t fo r m l ybdtessai* 2h*fc is f oo&ag H*wO. ig n itio n o f ih» pr*cipit*fco to to * MOffte -iMikOO* HI** f|yK^|| ntt0l3SS ij^lt0if|lll t f4 in MtfcMgtt to tfrtWftfl111?*1 * t$MI OWBBStBS se#0^Nmt' o f tbo y#B3Uoi i^ool#o oro nor o^pBsSiioti« Hfeo $#pooif&ibftto iiy to tiy to cofitsSja otruotux'oX inttor wblcb lo drtvon o ff ofc IniofOBO^OHPos* | b 1(1^ 4 tfffli to tb it# tho igofo no o o ffo o t tb# djrying o f tin * boforo flitw ttio fi ooixvorfeiMi to oteito 8^($M % alM Q * fhe greater w M iflitr o f tbs yaOlo* eaegiUK, in addition to tin ea other teeters also ante i t tepoaaiblo te develop a g n a te e tite proeateve based an paeeipttatien o f tea yallcw fe rn . fee w*at important ocotrtim tiee o f th is portion o f the state io tea ecwrallettaa i t prw idas eeeeenitog tee apeelee stadias a t ik e teeatteetste point o f pB 84!. Jteaaetti end Boaeottl (86) tern oemOated th e ir sscperteental rotates w ith e a rlie r vote done te shoe th at a t the is o e ls e tri* p oint, the e^HUbrtwa io 10 TO ,*, eg. + 8 H^O -r~ » H,Vvflm » ag. ♦ Ut tf*. 60 S ta y a a g p w ta d t h a ir d a te c o r r a a ijo n d a d to th a a q p ilt o a t o a p g o p o a o d 1g r awta* m m * , and m m m . <11 ), 3 tS& (TOa*}%(^sr)p 3 SS *»eAw“ « »10 « d p < t ) . M om m as tt u g r n q p e r ta d n o • p a e to ii p r o p p a a d to t h ia o v to a a e e t o r to o h ig h ly jw a y n o r to a d o a tt o a to a ^ U to o to M . W to praam* w w* -way otoangjy todtoatoa that aaaii * aattonto apaetoB mat bn imatoadi in tha aftlXgbftoau Atooa (I'towto otto* $Xfw&$ WBKpgj $ X09H98 flraflypMRKTOlWKlwl smil% Ini %i®b> - # Cill $ Wl + upd^^Et# lisvc&v^tl lut $1mi #(gt&l3J&v$3i8Ka $!Imi Jfelfttbb fKlfey^folXffr OCBtBlBlXlg 0g&3*i>1&!^ I foOTfrfiTlf ‘ y ffllfit|m & llSt^hO^y J5CO«^3WflK*!S<3S^0R3 fl^*lM3IW5'OiJOL fSSClxtflt 6toM^p0bl8BKj|. 'WfttfNP* wlWw Bili Is %qm UtiSft 4NN|pMi TW&£L% l» x’&vt&fc In *w vf the pol^wer ewaaiitg the oolor change observed la heating. At aagr mt*, thn vaaaxta abmr that too rini* tOs* ton iB todnnd tavoload to to* *$tiOila*to» at too tooalootrie point, and antoka at gtmtonr acidity aatoaa. ltosr alao gtoa good artoanw of to* proa*aoa a* another aattonto apoden actottoR to tola acidity rogtoa. Sma atrangthOBtog to* raaolta i n t t o M by Huai, Ketobb and eanttol, to* only m m to bm** poatatotad into a oattoato apaotoa. 63. B. teteaotion* ^Pp- ^PlW *W tejpw M W W tte f j e* g iwmrtnrl y8iaft*M4Wtto. fke wftllmr flAlnflterij #«wta*te faw tt e'^eten el-tvteeljteyiP ge te# W efilti ett em !W ^te*^*R J^W totetef *»i44m* •sW ^eP ? ^^rtePm m '1 £*telpitetoM ^* «»k4k4trf*i m ^ rn ^ M m M the v & iiM * tw&csr Soo m * ..teA lA^-.jite^-w ._A. HSIp ^-.— * wk. ..M fte * *b*G &m w e *%1&Q m Jfrm iU&ki-tW eM dBm lfclite wV&summ» IWwww| » 41ft {Nil 4a«M4fc4ftil' tHWKHKP f itelJ*ft XwF rate****** pwwdate* gat* m a y 1S.U1* e m w . tea jnmumb* ter tela teoaa* tertea* ft* te* w «Se ia*gi**sad. Sb* waawaa te r te * tes te r* o f te l* work are aa tellaw *. (1 ) te * asteaatton of te* mnetee* 1 * M p t e o t ayea te* pH, «Ste te* * * f » antemtteen oesmawtag a t te * taeeflaeteto petefcf git 2 .8 . (2 ) teteaottan i« *e™« dependent, with te * mxteoa ooouwing v ite ten ntm te shaking 62 on the antaw tte M ir < ta t ( I) She yeOJm egtarta to q ta u a rt etahla ta to * progrew is'ely tartf $$MI far ilittlflHITirinliri tata4«nte 4rt4rt isfcirif.v**tfVnr*n.. #irt IfliJfiflf atmMftUflad 1l© be the taetaepaW o f a stable sole*. A eetastaettae Method (28) Snrtatasg the and eotaar ®* the vawdiaa 8-qoiaoliaetate eoagiUoc la the freem ee « f ethanol h»# tana «a&te eaeewafal. taestatag te th ie mB tR aF f|t s w tm ai mi * 4k■P lw dP9 s»i 2 *** tI^ a|IM ftim gwN rt ^ Pli tlf wi Hr wH«e te te* Mteeettan netted preciously dsserited for nelyhdaasm. Tho twndhan swteeeted w** deterainod eotorteeteioatty using te* 8-epinoUnol method just described. 6b fm this purpose a *** *** of t w i t e sciaticas at pH 2.2 sad of concentrations from 1*0 a 10** to 2*7$ m 10**M. were prepared. Tan al* portions of those sciatica* m m extracted with two 10 slL* portions of 1*0 x 10**St* o-ben»oi» cxSsm la chloroform wad m * 30 ail* portIan of chloroform. The color was developed on tho combined e x tr a c ts ty tho method just described* k plot of the absorbance versus tho mol* ratio of vanadium to <*-b«nwoin m *m is ttatm la Figure $$ the data for which are given la tho Appendix. Tho absorbance values Show looo than eeaf&ste extraction due to aactreciioa with nxxro dilate a»bansaiii codao solution. However, *»8 tho definite break occurring at 2 as 10* ailllaelo of vanadium hr «f0 •attraction with f a 10 w U l h a to of e»bsn*oln oadae definitely ootaoliohoc the owswotasoia aMfttVftywn»}tw ratio ao ltx* This corro#** ywjyy^ f f t o th o r e s u lt s a n t ic ip a t e d « the eolorimtrie stabbed for vanadium M been wowosed oileiMlhr as an ebbanct- to determine tho wmd^ratse^aaiisola calm ratio* However, duo to tho adherence to ascr’s law plot la tb* ooncmtration range stated, it woo deased possible that It could bo wood for a ijaantitaiive method. tho major advantage of thia method over the direct extraction of ttis d^iaolinol coaias* as proposed by Talwitil (26) would bo that ao extraction of iron would occur* Ihis would eliminate the necessity of removing iron before the extraction of vanadium. Ptor this purpose, a m d t a a M t o n was and* up at p& 2.2 which, as the moult of several detersdnatloas hr this method, m the jars 65 ABSORBANCE 0.5 0.4 0.3 0.8 0.6 MOLE Figure 5>. R A TIO 1.0 1.2 1.4 V^GC-BENZOIN OXIME Determination of Vanadiums a-Benzoin Oxime Ratio by Extraction. 66 solution* sea Zmg& to ecntain 0.C&9 ng./kl. of vaaadl&a. fo tea s£L. portion® of this eolation sere added % side mrlety of elansnt® coiaacnly oooaarapfKf with saaadiaw, and the TOaadima *a« determined according to tho p e m t a * outlined* tho offsets of these fwftemo lane mem shown in Mlif# flit results shew tint tho only mtaia interference cwsewrred in tho ease of antimony. The »»j©r difficulty In this m m was tho precipi* haMon of hydrated aatijsony oxide from m M xssdl*. This precipitate which was at first white toon appeared to hart a yellow color. This yells* color booant sale Intense m the eolation aged. This indicated that the tntlnooQT m o ThlS SUff** tho pwssnee of tho vanadiuutt ftwst Why the nSgttSnt mevmt In tho la tlnoot In iwMsxtar. yygpwyjfliafryt fr yt at greet* The timt eolation tat mw& In both eases* hut tho second een$le tat run after the eolation tae aHoned to stand for twenty-four hours. Btermth and uraagrl Ion also Shew a certain amount of iafcsetfpwnee* It la ftleo Interesting to m to that «eOy negative errors s e n encountered when interferences sere present* m l this only shea lone eaphlft of hateropoly sold fcassation with saaadlan sere present. This indicate* that hatsropoly said temmMm m less entraetica eugctiy more dimoaltfhe naln adaantftga of this nsthod la shown by the results obtained In the pessaee of farrio ion* % this aieihod a simple extraction gWweednre is Oil that la H f M i with no previous reamal of Iron. m a n m m asm sens o s m s B n s a c a tm a H o r v u ju o tm VmteSSaetoe Mc« Quastltgr, Mg. lea 2 .50 dfferanee VlWMBt He (71) 04t9 V (V I) Cr Ha Ctt HI (V I) (V I) (XX) (IV ) in (n x ) AX 00a 8b ( H I) F0*s i .as re ( m ) a i (n x ) I t is thsraffflFe a can be e iB jO e , * » j4 0 e a r r le d eat la tb s ra e t& o d f o r pw w w ee o f 0.48 0.47 0.47 0.46 0 .(0 0.49 0.49 0.47 0.47 0.46 0.45 0.46 0.46 0.43 0.35 >0.01 •0.02 •0.02 •0.03 •0.00 0.00 0.00 -0.02 •0.02 •0.03 •04)4 -04)3 -04)3 -0.06 •0.14 0.49 0.49 0.49 0.49 0.00 0.00 0.00 0.00 s n a il a a m m ts nest o f v a n a d iu m e a rn e s t a le ra e n fe s . ra. soitsuff 68 ■ te i 4 M i mtom mq&mm u f w m d iia i w&ybdunua, and tailgate te* te«t thoroughly ata&ad- An attef* to do t e m e vtth teewtam i n tend to lie Impoaaiblo t e to t e tetetetal retetion i f te te M bgr t e te fte * t e aateda «rap£Loy*d t e tim e otadlaa tM#te*6 both precipitation and attraction techniques. t e molybdecrani eaa$£L«£ has been teawsixMiel to be M a (a te m ta i» d te ta )te s te S g te m (U )i « i t e te g o te , bte{ii-feen«ola(7 1 ) f ^ 2(C 14Hia O ^ ) 2 . Vanadium has been fosmd to te n tee d iffe re n t mmtflmm, a sh ite pre cip itate and a dark yellow p re cip ita te * t e efedte fea» haa te a established aa arbm olxieadteo* d te e e m d lm (V ), t e fe llo e te a , also containing one #*ta#iaelsi oQcisse lesiaaaX# par vnedhuii $m the re s u lt o f complex form ation betas** dMsJhdM*i»trvty imiptm ^*ni tsptgffiy pelytaspisad laouuitaift spedes. "jHWP JPenNmwHMSw SSS CH» w JmIi w^nMVV wpR^^MBmB9Q BWI W w©Cnl tSwPaiftiMlmWCI wjUvS JLiwnKsmwBuP® 4%%i ewiesieftaig the specie# i f mess metal# la sohttiots* f t * aoQtybdamot* tbs asst scsq&sts conjas* Tarnation ocean In scia tica s M liia tR g fwm 5 te 20* sdnswal « o iri. te r tungsten tbs most OMtf&sto ftaw atian bo* been found nob only to rw p irs sn sold eolation* hat also a mole n ttio o f flu o rid e to tungsten ion between 711 and 10«1. This has been axpiUinad on the basis o f the a v a ila b ility of V?o3* +frcre the fisesids oasplsK. f t r vanadium, tbs jrsilsw , o r jxdjm srlaed to m , has bean found to fa n sore re a d ily and eoHgUfcsSy « t the iso e le ctric point o f jB 2.2. Although ths s h ite ferns also pne iB lte tes in th is region, i t w impossible to deteynla* the best a c id ity fa r its form ation. This was & Am %o th® fact that «m **t» of fexMftien o f fO,(CMRuA £ ) la ao it a r th a t tta proeipttaticn also reeults In tho proclpLtatlen o f a tm **•« *& 'ite m aeSatloa. Ihansfow*, It w iwposaihl* te ehoek fo r eoogftetetieaa o f fMeijdLtatleki off tho whit® p raeip ltat* by grwriMBtric Sifcei&Mikdife IWWwygf k» i resu lt o f tbo afcady, « nmbear of fStotom oaneomlng tha oao o f aMnutola ootteo 08 aa analytical voogsat fe e those elanonts hnro been deters*istsd* Molybdenum m?§ as debsmined earlier, be quantitatively ispocdpi%MMS by iMbensoln oxime fsem aeid solution* V ) n the precipitation is tas ps*pu?ty* tho complex map ho dried ami weighed and tho imjlybdenum determined ao 3 i « ^ of the complex* S8B6^8tOII (mu not bo dtberwlassd Io this same maimer elm * tho piwlpitotiicaa lo nob gait# complete eve®, fte tho fluoride turn ooneen* tMtico *t*i* been aconiutslv adiusbsd to eIvo ottlisiii wseisltitioo conditions. tho 01x00000 of tho earlier method for tho coafcined precipi­ tation of mlyMs*gi*» o M tungsten probably results frea* carrying down of hydrated timgfitle 00 M by tho eosfclaad eoMpdosceo and tho excess reagent* ft has Olio boon found impossible to determine vanadium by the ps«m» type of gxwhnetrlo procedure employed for molybdenum. She reason for this being the foot that the yellow precipitate is not a stable fo m * cad the length o f tine re q u ire d fo r complete precipitatim of the white form results in prec&s&tetian o f excess reagent. fhis excess reagent can not be removed fey washing without the loss of complex. 10 On the basts of the studies completed, the newly proposed extractiok procedure for molybdenum (Io) involving final color dsvelojsaani with <$tero©iin haw been revised* This revision has resulted la making the method spectfln for molybdemam. It may now be employed even in the presence of moderate eraoonta of tungsten. He m»Mr extraction procedures for the detersainaticai of tungsten here been possible on the basis of the work completed* the major difficulty is the extreme insolubility of the tungsten comple^^ and the ffcet that It done not extract m a colloidal precipitate into onjy@PD*ori» e® v«® nwj-ywwsi® c€m*p*r*ic ooos* A# & final result of the study consisted* m extraction procedure fo r the detemimtica of vanadium has bmm developed. Shia method involves extraction of the vanadium complex Into chloroform from a solution at pH 3.2. the vanadium complex of 8«^xinollnol is developed directly in mo presence of the o»hen&el& catlm© and the absorbance measured. She concentration range for successful extraction is from 5 to 80 Programs per a&. She only serious interference is caused by antimay where the formation of a precipitate of hydrated antim^ oxide Ur found to esrsy down vanadium* Bismuth and uraayl ion also cause a slight negative rnm r * LITSH&TORE CITED 71 1* ®*» "Chaniotry of tho Coordination O aqw odt.' tetetea* r a a . Corp., « •» » » * , 3956. ib . t. W H i B g w « B. 7. and S p m , s. (1957). 3. aM M , C. 7. , c e n t. xw d. a a , n s u -7 ( 1956 ) . A. Jg|, 11875a (1956). b . Cwm m , S. W. f t fiL , 5 . j. An. 81m*. Soe. 79, 3355 Boors*, 1>. 9 .* A n . J. ehi*. Xrtn Steal lo s t., JJJ, 75«80 (1952). 6 , 705*73 (1951}. . Poigl, 7., Bor. £ 6, 2083 (1923). 6 7. 7., "Quolitetlvo Analysis ty Spot Xoate.* Bordanaim WKL. C o ., Xus., S a w I n k , 1939. p . 70. 8. M A , 7 ., Ana. O k la . Aote. 2, 397 (19bS). 9. 21*88, J* y*» *Org»nlo B w g m t e good la Gravimsiric and Tolunotrlo As*ly*io.n Interoelone# Fnhllehors, tea., Bow Toxic, 19U8, pp. 121-32 10* Ooldotaitt, s ., Manning, B. l . , and Mania, 0 ., Anal. Ohm. 30. 5 3 9 * 2 i2 (1 9 5 8 ). U . B n A , A 7 ., SeBabb, V. M ., and S antlai, a ., 2. Bjyn. O n . $Lt m (1953). 12* Anom , 1 . A , H. 8. S teal*, Michigan State U nivw rslty, 395k1 3 . M a n te l, W ., ■Stenateanl c tm te tx y o f S a o p g a a te G o o p o u a d o .* Tlnwtanr. ten Tot*, 1950, p. 179b. lb . JafXVagr, 7. 0 ., Analyst fo. 1£M> (1956). 15. J te a n , I . J- and Vonvar, B ., H a t'l. Maeloar a»*®r Soar., Div. TUX, 1, "Analytical Chawiatry of tte Manhattan Project,* UU5-58 (1950)7 15. Satear, M., too, D., and Chou, A., J. An. Chare. Soe. 80, I539*b2 (1 9 5 8 ). 17. SmnrlM, B. B ., J. Bos. K a t'l. Bap. 3tda. £, 1-7 (1932). 72 18. K. 0 . and Wang, C. I . , "Tungataa." Ban Xoik, 19U7. tik p 19. U n ftg iis t, X ., la ta Chem. Seand. ftalnholri Fabl. Corp., 850 (1950). 80. KoraehwraJd.. X. X . and Balyaem, 1 . I . , Zfaar. A n a. Khin. U , 672-7 (1956). C. A. £1, 79W* (1957)* 21. Bowman, B. B. and Cook* B. 2. An. Chen. Soe. 22, 3155 (1957). 22. I M d U i F. 8 .| Saengar, H ., and Wardian, W.„ J. Chaa. Soe., U&3 (1931). 23. HichoU#, B. I . and Rodgara, X.. H ., Had. Bag. Ohan. Anal. Btt. a , 137 (1914*). 21*. K iarioker, B. and Proadwall, V . 35. Hole. Chin. Aeta 29, 11*72-83 (191*6). * 3$. Pah«»ifcayn, B« K. and M m w n , Q. A ., Xavmt. SeMem F la tin r l Bang. SUgavod. M etal., X m t. Obsehel i Soorg. KtaUn.* Akad. Bank S.8.S.R . 2 8 , 59-70 (1955). 0 . A. |g> 9926o (1956). 26. Koaootti, P. 2. 0 . and Jteeaottl, K ., Acta Chan. Soand. 10, 957-8U (1956). 27* StMFling^C. and Sp&hr, W. P ., Bid. Sng. Chaa. Anal. Ed., 12, 28. X a le iiU ., H. A .,A nal. Chan. jg * 601* (1953). 29. HejaoiHtastin, S ., Analyst 62, 107 (1937). 30. ISbgoda, 8 . and Malm* H. A ., <7. An. Ohan. Soe. 60* 61*0 (1938). apeehdix 73 fOR 1J*» M S!*/-*/• yTflgJM ^m iUW AfwSP « attra ctio n o f Holybdanui* iftth 2 x lo “* H illla o le of la OMajPtdPeasto M©®**# 3XX&&* jOMHStietMHaEHB of { t e t i i i a nfli»wi«ir fro m 55 831 D m p 2.2 1*8 x IO*® 0.670 0.530 1 .5 * J®*’9 , 0.668 0.516 1 .2 x io ”* 0.668 0.502 1.0 X 10”* 0.639 O.bSU 0 .8 x 10”* 0.581 0.107 o.g x 10”* 0.380 0.260 0.8 X 10"* 0.195 0.133 7k m u res n r n m i* B£f*ot of nuorld« Xen on Daaggfaa FwcipltnUon HM) w takm , a.________ f f v t n * j .025© 0 0.5 5 6.6 8 K) 20 Uo .oSoo 0 0.5 i 5 6.6 6 10 20 liO W Pptad., 9. .0063 .0170 .0239 .021*5 .021*3 .021*3 .0215 .011*6 .0221 .0310 .0355 .01*78 .01*90 .01*88 .01*89 •01*15 .0275 75 mm m m m e fc S m n rn m $ of Vamdium with 2 x K f * m iim o l* of ft-Beaaoia OskI smi S» Chloroform V* m & *« Absoitem of 8*«QuimXin©X 2.75 * J®*8 0.51(0 2.lt5 * 2®** 0.53k 2.16 x 10** 0.525 1.86 x I® "* 0.k£6 1.57 x 10*“ 0.U27 1.28 x 1®“* *js 0.58 x 10 0.356 0.273