ll W r | 7 WIN l V HI | > 113 824 HTHS TH! ANALYTECAL CHEMfiSTRY OF COPPER {Em Thesis §or the Dog!“ cf M. S. MICHiGAN STATE COLLEGE Donald Arthur Keywoflh 1954 ‘2 hi L 11‘ A}: .. E chh 15311 SP“? . Ur iversity It THESIS ms IJLLX‘I'ICAL cmumm a? COPPER (111) By Donald Arthur Kaymrth A THESIS 51.1111“th to the School of @mm Studies at Michigan State Colleg- of agriculture and Applied Science in partial Milwaut of tho retina-mont- tor th- demo of Pfiflifi W EILE’CE Department of Chemistry 195k ILCERMLLDQTQM‘ The author with“ ta apron hi: linear- thank- to Doctor Kenn-tn G. Stems, under when imitation, constant supervision, and unfailing patience this inflammation In. W, and to when the malt: m wraith dedicated. Th. author in I1» indebted to Doctor. an 1. Regan, Elm Loiuingor, 0nd Andrew rum» In their helpful suggestion and «autumn. fi'flflfififlfl‘fla“ MW *m it" WI! if i TABLE OF CUE-11' Ems Page mhijCTIONOOOOOOO'ODIIOOOQOODQOOO..IQGOQOOO.IJOUQOiOQOOi-QOOOOOO .‘ no.> r ‘ - EXthIHLNThLOICOIUQCI§.OOOOOOQOD.000.00....COOOOO’IIIQOOOOOOOOOOO Ao-Po..1b19 COPPGP (III) hcagent.onobooooonooascooocgtoooooo 3. Prepar‘tiafl'Of ‘h’lasagant'auo.0000ocutooootooDonut...out C. Datermination of the Concentration of Coppa‘ (III) “-44“ fisagant5oocucocuoooooo-ouonoocuoaooovvtoooocaooooooc 12 D. Titration. Suggeited hY'Becki-0......cocoaooooooOoaoodooo In E. Fatentiametric Titration: With the Fisher Titrmnar..." 23 1'. Dead-Stop A lied ’00 Copper III Titrauonl............... 25 G. Comm; (III Applied to the ustermination of Organic OOOOOOQOCUCOOOOOOIC0.00.0...00’OOOO‘OOOQOOO 29 a. coma.“ wakoooo0.0010000000000009000000060000000000 30 CORLLUSIONBaaotoogoc¢o¢o¢0¢noococ-oooaon¢cocooo¢ooooooo0.0000000. 33 LITEEéTUEEICITznni.O‘O‘OOItOOIOtOIOOOIOOOOOCOOIOCOOOOQIOOQOOOOOOO 3h IMROHICTION MOIECTIOH Tho «1-1: history or ouum has been Mama by um- (21). It was noted that in IBM; Kruger prepared a compound containing m trivalent copper by passing chlorine into tn alkaline toluuon cou- tuning divalent copper. Cm magnum shoved tho midi papa-ad by Ernest had roughly th- atouio ratio of 20mm. Iran, Viami, mar, Brenner, and Picimi mploying other oxidising Ignat- mh u pen-aim parables-ct. Ind brain. in alludin- ulutiom, 1nd petunia nuaummrwmtcwurmmuuppnnuuu propmd. Whflowkinguanparnioaothnnrimbyum arm-nit“. «Mum at taunt-1t. to “um-am Km (2) ma tn» 1: dup yum. «Int-ion realized it we. ot topper m prmnt. Erma-r (21) negated that the colon-ed Column contained copper (III). Inn «was: to mmuau Manual-'0 poutulation, and ”claw unfini- for which he reputed tmnlu man a 6:130, Cfltflflfflghfifi Ind {Eufia-CuO-JTQOyZKIOflaO. In one preparation all of the upper m "parka to ho trivalent, and th- fcrmln no reported to ho mug),- 31‘00. ~2x.oo133.o. Shit nay ho revs-nun u K‘Cugrofi" ‘mfi for marina nth a tomb reported by mutant: (7), am sum-nun“ by mm (25), than u KgCuFofiu'lefi. m» «gamma um. mu m ”It: a: a mylox copper tollurio acid (2). nun-r and Spitlor (2h) oxidized ilk-lino solutions or copper (II), and reported romlto 1n tom of €11, tri, and totrodvalont copper Mood. A (min: 611.0. m ”aimed to their ooppor oxide. arm (21) unaugaud tho role or t)» tollurato radical in tho tot-nation of mapper (III). Ho reported the formula XOR-Cn(m{)3° “Jam-T083). fibers :1 oxooods tin. He noted that periodato may ro- plaoo tolloroto when “n" exceeds one in tho formula. He suggested tho ooppor (III) m prmnt u the Ivaroxido and Itatod “this compound 1- peptiiod by‘tollurotoo (or periodotoo) yielding a oollodial solution «mung tdnlont cappu- in tho tom o: mm, {ou(m).)‘, which on Ion odoorption W! with tollurntol ." firth no math to 11nd Agents other that! tour.“ and poriodato to 'poptho oupritoo'. Potassium and Codi“: hydroxldo solutions mo utiofatoxy alkalin- nodia, but monim hydroxido , lithium hydroxide mo totruthylmnim wounds 357. mu solution! or copper (III). Imty oight pa cent or the copper (11) was oxidized to copper (III) lit}: potuoim poroulfate, but only 83.85 per oont oomion was niobium! by media oddation. It to now: known that-tollurato ion and periodoto ion tom Itablo amuse: with cog-pa:- (III). 3164er (19) has mom on. oryotalnm “1o, Ha,CnI.Ou°6K.O, and Kahuna (71 isolated tho corresponding pom-1m «It, :,cu(10.).°7a.o. Proof o: the tripomne nature or the copper found in thin complex 1- given by the magnetic concepti- bmty (1), at 18° In - ems-10" «3.3.... o value ohuootoriotio or dimmtio oonpamdl. Huttom noted that loud petunia! di-poriodato cuprete (III) in dark brown and easily soluble in water, but that it the wutor is acidified the ceppor (III) compound decomposes with the liboration or oxygen. Klomm and Hausa (23) have reported the preparation.o£ K,CuF. by the passage of fluorine ovor ouprouo chloride at 25090. The potassium percupri fluoride oorponnd is unstable in aqueous solution, decomposing to give capper (II) fluoride, and goons which hove not been identified. Lioter (25) has verified the formula reported by Halaprado for sodium di-poriodoto ouprato (III), and reports the formula HagCMToO‘ho Zlflafl for sodium di-tollurato ouprato (III). Lister oliminatod tho possibility of poroxido formation (27) which would give a pseudo oxidation Itato of copper (III) by using sodium hypoohlorito to prepare hi. solution, This supplemento tho ovifienco for Cu(III) based on the magnetic susceptibility talus (z) . Lccording to Lister, WhtnlCOppfir (II) chlorido is treated.with alkaline hypoohlorito a brown precipitate of 011(03):, appears, which tends to dissolve in strong alkaline solutions giving [Cu(3}z).]’. In tho prosonco or complexing agents nearly all the cappor io omlemd. Lister reports constants of dissociation for tho following reactions: {Gnu-30.)” o- hazo -~[Cu(ai)‘]- + 231.10.)" I In . 8.0 x 10"“ at to“ [ou(mao.).1" o 2W 0 23,0 _. “mama" O 2(33T00d“ on - 1.1 x 10"“ at m". Lister ototoo thot omlomo with o 1:1 ratio or ooppor to tauntin- Ind with o 1.1 ratio or cooper to iodino oxiot but that than complexes are unstablo (25). stonnoto ion, otibnoto ion, and oolonoto ion did not oomph: trivolont ooppor. Tho boat of reaction for tho di-tollunto unproto (III) oomph: woo twenty kilooolorioo par nolo and for tho di-pooiodato ouprato (III) complex on oovon and one-half kilooolorioo pa- .01.. _ ’ 'l‘ho tint noo or copper (III) oolutiono " titronto no reported by a. Book in 1950 (9), and o mioo o: pxporl hm followed (10, 11, 12, 13, 1h, 15). 3! Batch work boo boon on o lion ooolo, and no: boon oomornod largely no: 131on applications. Ioohnimo hon boon reported for tho detmimtdm or sugar in blood and m (9). 5mm. of tho pope:- (ll. 12, 13) doll with toot: which onoblo ono to drum oonoluoiono that tho no... ooioo md mum pruont in album Ind various oolto. Book aloo worked with o moor of inorganic noted-ill... An ottompt bu bosom to merino Book'o finding: in Tabla I and II. For tho uremia ”notion- Book has woolly ouggootod products, but for tho organ“ ”lotion. “produoibility of titan-o to tho only data reportod. 0n tho basis of tho titration performed by Book on o micro ooolo it was hopod thot mro volmotrio redo: dotorninotiono could to do- volopod, Ind that mo ondotivo selectivity mono; organic 4 mo night to Mad. thin otudy no tint-eta" begun to clarity tho analytical work dono, and to oxtond tho mtulnooo or copper (III) as on analytiool "agent. TIBLo. I lama-om ommmns VIII! Cu(III) m not: (10) #‘A , A m—h‘. , , V‘v— fi— ._7 “.4 4L...‘ v 77 Sobotnnoo Oxidisod "o93 813,0, KCr(SO.). '85. Pool. “‘15:”: 3'33: A“ “A if r“ :m WW J: Comment- »” oxidiood to on” on +o 5b oxiditod'to Sb End point is not oharp Noon 9 2mm 4- 50 .. “do, «- Ram, . 330 Slov’roto Hofiao. o ((0 «9 238-03 :- 2111.50‘ 4- 3.0 It..33 " 20 0 6m. . £039.. '0 $.50ai '0 38.0 “3,0,: 9 ho o 3.0 - “30,; o 8.30. A4 A TRBLE II comm mums Hm: mum) woo BR?! (11) _ . x , —._ 0311f iliquoto of Substanoo Oxidized Q 4313420131 o; .01 1!,”on Tye;- ; Titer II 38:11de 91 (fly-wow 162 Stitch 81 Mario Ac id 58 Glaoorin (.6 Emma 1:5 Laotooo 180 Forouldomrdo (0.02m) Potuoitn Sodium twtroto“ ‘ lhl w... —.’_V fiT W WW . 011 III titor in 0.52 ml of croonito (99 I13 ”.0. per 50 n). o: 0.01 a 1on oolution) . w413-11 oux" if?" a 0.1.8 0,148 0 .30 0 .28 0.1.3 0.1.0 1.0 0.36 0.50 0.1.9 0.75 0.75 0'50 2.13%. 0 .99 0.99 0.66 0766 i. 31: oquivolonto of Cu(III) ponnolo of tor-trots. _‘_.A EXPéRIfiEETfiL :7. . Pmiblo Cappor (III) Reagents 3m attempt I“ made to prepare salts of cappor (III) 15:51ng phoo- phato ion, periods“ ion, perchlorate ion, solonnto ion, taunt-ate ion, mama ion, eta-mu ion, 131th ion ,' mhbdato ion, mu.- mu ton, Mat. ion and hangout: ion. In W with previous mougators (21, 25) only periods“ 10m and Worth ion formed 0W0 oomphxoa lith supper (III) .‘ B. Preparation of the Eugen“ at tho vanity of method- nvailablo for preparing di-pctiodato supra: (III) lad «44mm ouprato (III), tho Implant and wont anti-tutor: technique as tho oxidation of the divalent copper in the pro-om: of tho emplonng ion in a potasaim hydroxide solution with potassium portrait“. Md to 175 :1 of boiling Wed at» 2.5 gm: of ooppor mutate pent: hydrate, and omnplouly dined". Then add 1.1.5 gnu of no. (0. F. 8mm: Chemical Co.) and (118801". A bright ”now-men pro- upimo Ippnro. Md 13.5 m o: potmiu hydroxide cautious]. Tho rum-m precipitate dissolves omxplotoly and the ole-:- solution remaining is deep you. Add to the boiling solution one gran portion-o of petunia: pmli'ato at intervals of one minute until twelve was but been added. Tho ”lotion is boilod fifteen minutes to dootroy the emu pots-aim pox-sulfate. The oolution is cooled, and tho final value is odjooted to 200 ml. The solution will in dark brown, tree of insoluble matter, and it may be stored in polyethylene bottles for some]. months without sign of decomposition. Prooocmro for the Preparation of 04135 H fatagsium Di-tolluratg Add to 175 ml a: boiling distilled water 2.5 gram of copper cults“ pout: hydrate, and oomplotoly dissolve. Add 8.8 arm of Ilium-330 (Fisher Chemical Co.) and boil tho «lotion fifteen minutes with mechanical agitation. Carefully add 10.1: grams or potassium hydroxide to the hot solution. The yellow-green ceppor tollurata precipitate partially dissolves in the potoooim Igor-oxide , and o dork goon slurry results. and one gran incromonta of K3333. to the boiling solution until 0. total or 10 grams of potaoaim pmulxato has been mind. Boil the Iolution for fifteen minutes to destroy the excess per-allots. Cool and atom in polyethylene bottles. Solid petunia di-poriodoto ouproto (III) may be prode by simpl- ovaporation of tho potassium copper (III) solution. This may be powdered and stand. 1% will redissoln in water to yield as oloar dark brown «lotion With the mrties of tho Iolution from which it no prepared. no. method of preparation gives a solid which is obviously oaixturo of all 01’ tho salts in the mother liquor, and d0" 00‘ fl" PW" W190)“ i lolntion 01’ divalent cappor pariodoto m wowed using the poooduro for tho preparation of tho trivalent cappor poriodato with tho omission of the porsulfoto oxidation. Divalent cappor periodato in a yellow-goon insoluble material whic'h dissolves in dilute potosoimn lyriroxido to give; a goon soluble oarrplox, and in strong potassium hydroxide to am a dark blue omzplex. It in known that periodic acid in aqueous solutions, has three roplocablo momma, the first being replaoad at o 133 or about 5, the ooooni at about 10 and tho third in Iolutiono in about tonth molar potassium hydroxide (28, 29, ', 36). ’ Because then In throo apparent species of divolont mppor, tho following equilibriu are ingested to account for these species: Hannah). """""""" Magnum). yellow goon :1 won solution E precipitate “operation to dryness oxidation CH" ,w m K.Hu(:.u(10.). Z" gamma). dork blue reduction dark brown solution solution K7611‘103); brown solid The yollwmon precipitate 53:311(I0‘). was shown to be potassium free by M11113 and opplgdng a flour-o test. A similar system of oquilihria apparently exists for the copper tolluratu, but the dinlont cappor tollurato requires very largo 1‘) comentrations of potoosdum hydroxiflo to hoop the greenish yellow divalent copper tolluroto in solution. Structures of the di-preriodato cuprato (II) and di-poriodato coprato (III) may be drawn and new: to bo consistent with the lawn ohmiotry of tho cmnpoun’is. Schmvticolly the orbital: in cappsr (II) and three my be represented as follows: 331 ha hp {11(II) 1-. .1- .— -- In. on. .- o- no. I I I a . Alternatively Cu( II) a n u a . (mun) o I u 0 Therefore 01:01) may have: spa two bowling or dsp' bowling. Tho tumor given I tetrahedral otmcturo, and the lattor a planar structure. Tho dop‘ bond is preferred since it in I stronger bond, and since not cooper covalent empoumin are planer. Both types of bonding goo tin usual coordination mnbor of four. Therefore it 13 3:135:98th that divalent copper periodato in boot represented by Itmtm‘o I for the amino Kfi‘fiuuca)” Eivalont copper commotion strootm'o I are paramagnetic with a magnetic susceptibility of about 0 1200 x 10.. 0.3.8. with one amt-1nd hp electron (32). Th: dI-poriodxato mun-am (III) resulting from the oxidation of the WCMIG.). (blue species) to the Kfi‘CMIOJ, may be written in two ways: 5‘ 0 33 OK HJ\II /:;K /I'~oa \ M |\ I uk 0 0 0‘ O 0 ‘x u / \ / \ f ‘ Co Co. / \ / \ ‘~ 0 0 0 O \ / \ KO- I\— OH K071— OX / 3 t, H0 SE K i! EEtruc turn I Structm'o II Structure I refinirea fom'toon aloctrom 1a the iodine sphere and thin 1.- knmm to ho poosiblo mince iodine tom o kept: flourida I?" Structm'o II 1. unsymmetrical uni regains I osp’ bond which in avail- ablo 1n the Calm) state of oxidation. Eitha- “motor. has no Wad elme, required by the magmatic susceptibility of «30.2 x 10'. mg... It must be mphaaizod that the structures suggested an based upon knowledge or the behavior of the omnplem and have not been absolutely proved by my ozqmriments. 12 c. .Detemination of tho Commutation of Copper (III) Reagents Although tho concentrotion or the reagents which were prepared as described on page: 'I and 6 is m from tho foot that potosoim pmltato oxidizn 98 pa:- oent of tho cooper (II) to oopyor (III) (21), an booms o tong: shock or the oomontratina of tho solution was node Iran an indirect thioonlrato prooedm, tho first wlmtrio work was concerned with an ottanpt to develop a method for atmdardizing tho reagentl. The indirect thiooulfnto procedure for the approximate determination or concentration m as follows 8 Two idontioal 1 m1 couples of the 0,05 K MIN} solution we taken. Tho am no phoad in an 10:11.!» nun: with m .1 of voter and six to “fit draw of I11: moi umurio acid m added. The wppor (III) lion-am ongon, being reduced to copper (II). The oxygen no most! by boiling for two minutes. The solution val cooled to about 60°C. and 2-) arms of U mm added. The stoppmd flask was vigorously shaken {or one minute. Dilute Ii: mall oodiml kvdroxide «a mood tin-ough the lip until all the brown 1. color had disappeared. Than 5-10 ml 91 31301.1 acetic acid was added and tho iodine libornted m titrated with 0.13 Hagan” Tho other 1 I1 “mph was placed in an iodine flask, diluted with 2 ml of Inter. Two to threo grams of potassim iodide wore added, tho Iolution m wan-med to 60°C. 1nd than acidified with :11 to eight drop. of six normal We said. Tho “append flask was nhnlcon for one nimto, and 2-3 l1 a: 811 normal sodium hydroxide were added by filling 13 the lip of the flask, and than mnoving the stopper so that no iodine escaped. Sodium hath-oxide m added until all the iodine is dissolved, and than 5-10 :31. of glacial aoétio acio more added. The iodine liberatod m titrated with 0.1!! sodium utioouli‘ate. Tho difforonoo in sodium thiosulfato consumed by ample: I am! II gm than iodino caninlont to the coppor (m) in Innpla n. The data ll amino. in Table 111. $131.13 III go's-"msxwm'mo‘e or cu III) em Ions BI THE manner mowwxu sax-moo l I 7 3%” so: I! _ mom 1 19.70 20.20 0.50 2 19 .13 20.18 0.1.6 3 19.68 20 .20 D .52 m. . 19.70 20.19 0.19 - L x A. A A W M ‘5‘ WV— Tho thiosulfato was 0.99923}: and therefore the copper (III) solu- tion was 0.9133. These data support tho ntatmont of Urtio that tho poruulrato oxidation achieves about 93,5 copper (II) to ooppor (III) conversion (21) . D. Titre-1.10m Suggested by Beck Arooaioua oxide on a Standard Sinoo Book had already reported experimental work boned on oraonious oxide titers of div-poriodato copra“ (III) , arsonious oxide was out of tho first materials aolocted for the atondardization of tho crapper (III) reagents. In the first. set of titrationo aliquots of potassium oraonito solution were titrated with di-porioéato ouprote (III). Ton m1 of standard 0.1!! arsenito solution veto pipettod into new 250 ml flask: each containing 50 ml of distilled Inter and two pans of potoaoizm hydroxide, with tho exception of the levonth, which contained only 0.2 grams of potaaaium lg'drosddo 1n the 50 m1 of dis- tilled «tor. Simple: one and two war. mad, but the remainder were titrated cold. The and point. token m the bran oolor produced by the first excess of the Cu(III) reagent. The results or this titration are moron in Table IV. ThBLE I? TITEw‘l’IDN no 1-3 241.. £.LI~;U«‘31‘S or 0.121 mason-24 grams (some Pomssmn DI ”ammo carom (III) . 1 4..“ t A A Lt... - _‘.~ A... l s M 4 ____‘. A“ .‘i Saggloflmobar A“ i m 1:3”; I: -T 6 7: not mun) 1.50 3.00 1.140 6.2h 6.66 7.h6 3.1m L— _._L _. ,A M __._ 15 I; variety of colored products appoarod in the titration. Foot of thm were white, blue or green. It was difficult to see the first excess of ooppor (III). Lack of reproducibility in the titers rowers this approach workable. Beck reported that the inverse titration (addition of monite solution to 011611) solution) gown a sharp end point and that. the re- oults were good (10) . Therefore the inverse titration was “impound. A fresh petunia: «bonito. solution was prepared tad round to on 0,153; This solution was once! to titroto amplco prepared by pipetting 25 m1 mm: or mun) solution into 20 ml or utor and scam; 3.5 ' pans. of potassium hydroxide. This approach gave a variety of colored products which “do the and point; difficult to no. ‘Konoo dead-atop and point detection was attempted. A 0.1 volt potential was appliod using a oomitivity of mm, am the sensitivity was increased to 50x may tho and 1mm. 8 drop from clown to zero guarantor unit: unit when tho last 0.03 m1 at await. were added. The results are mound in Tobin Y. $331.23 V micron-Ion or 25 m. armors oz: movamoooo ammo (111) mg 0.15:: POTASJUH 53336112 m iraonito 15.00 15.70 18.91: 16 The omo procoduro was followed substituting divfiollnreto ouproto (III) for diaperiodato cuprato (III). In trial on! to: precipitate appeared, and the visual and point noted in Table VI m anoint: by a color change from brown-groan to blue. In trial two a blue precipitate began to tom quite oat-3;,- and the solution so: no olouded by tho pro- cipitato that it to: nacossm to lot the precipitate nettle before the first omens diotollurato ouprato (III) could be soon. The results on smouorized in Table VI. ' TABLE VI TITMTIQH C? 23 E1 éLI’fi-Jrs OF moamun'mo senor-3:. (HI) 121m 0 .133 momma i ““7 A , fiL'ifoi: in“ 1‘: iii; “7‘ A; T; Sample 353.. of Lroonito to M1. of omnito to _ umber . 7 Visual End Point _ m Dead-{Rog 39:12.1 Point 1. 11.55 11.55 2 11.69 10.79 A L. Aw _._ L- 4. _. ._ , ‘1' —1 w’v -. —. The inverse noonito titration was abandoned duo to the look of roprodwibility. The look of reproducibility of the titers of the di-poriodato mate (III) can ho explained by a utopia qualitative experiment. cm can show that arsonito reaoto with di-pariadata mpg-at. (II) in on dkllino colution by mixing diupwiodoto ouprau (III) solution with alkalino croonito. A mcipiuto Iormn immdiatoly. The precipitate was separated by filtration and disoolroo in romantic: midi. It potuoim iodide in added free iodino is Liberated. If tho pmcipitato 17 1: dissolved in mm nitric acid and silver nitrate in added, white unm- 1mm tam (3h) . Transfer. di-periodato may. (II) is rammed by main. menus and the oxidation with di-periodate cuprato (III) 1! soldered in part by um cappu- (m) md in part by tha pal-loan“. Queens M I Standard Book has reported that the concentration of copper (In) aolutions may be “momma: datumimd amplq‘ing 5111:3030 u : cundard. A 0.312»! solution of glucose was propared and used according to the directions at Back (9) . When inoramenu at am all or 0.05% di—periodato euprata (III) were added to the 0.031% glucose solution, the initial rate or reaction was slow, that 1: Ibout thirty to forty seconds elapsed before eonmmPtion. Unfortunately tha rate decreased so that finally 1%. 1m impoaaiblo to $011 visually in th- higfly colored solution produced it the cappu- (III) was Bill meeting or 11 an sauces: had been added. fleeting improved tbs rate, but varied combimtim of imaturo, mainfly, and dilnuan £511le £56 produce a rate rapid enough for a “intact”: 11mm). and point. Even 1: the rate were an prohibitive, tbs reaction 1- non- mmmmo um some at the 5mm“ 1. reduced to lactate. m WNW or flu titration- glvu a finite precipitate of silver “data men treated with silver nitrite and nitric acid. 3m moment Malian of the “final: of pelylrwdroxy compatmds in dilute potassium hy'drozddo by periods“ has been publishad by tialapreda (35’) . He showed that Madam maize. we palyaleoholu with the Motion of various and: acids, that the Madam goes to 10:18“, and (but tho rate and “niobium rendw the reaction umuitnblo for mlmtrio use. immune.“ cups-eh (III) attach! glucose in an alkaline Imitation, but the and point. we difficult; ta see, this rate. are slow, and lack of reproducibility 1n the titer: rendered tin rescuer: unsuited to , volumetric mummy. It was shown um. 41.“an (mprato (III) 1.- reduced in a cold alkali» solution to a blue taunt-ate ouprau (11) complex. 12 mm glucose in "nibble, and um is allowed, the blue taunt-to mate (II) to reamed u m mm (11) tenant. precipitate. In a boiling salmon glucm raduocl di-tellurato auprm (m) to me tellwimn metal. One my test for tenants in tho presence at tantra. because sodium bauxite rapidly reduces mum-1m to tantalum metal in a all ma]. twdrochloru acid solution. ram-m u not reduced under than conditions. Tho m1; was am be be very sensitive to mall mm: of tellm‘ito by Initfile blanks. Sodim Tartrato 33g me Beck reported three identical check titan for the titration of tam-at. 21th u-poriodm “pm“ (111) , and that :1: equivalent! at W (III) we unnamed to:- am mole of tax-tram (11). On the basis or thin repm't it was Imped that primary Itmdm'd grade uodimn tantrum awn. could be employm as a reference standard for the capper (III) reagantl . 19 it 0.2% solution of the (1130:1133 tartrate dilgrdgrate 1m: pmpared. Ten ml. Eliciuou were added to £16323 oontairdng 50 1:21. of water and two gram or potassium igrfirozdfia, and them solutions ware titrated with di-periadato cuprtits (III) wlution. Occasionally a precipitate appeared. I! it did, the precipitate was allwad to aettlal and tha awernatant liquid m omimd to use 11‘ an amen at diaperiodato cuprate (III) had been. added. If no precipitate appear“ tho color tram-1121021 from blue to green was used. u an and point. tron Tabla VII 11'. can be seen that tho results were mafiafactory. mm m TIT-Imam a 1-3 m. mum‘s m 0.2:»: Nfigc‘fl‘fi.'2figg m“ ‘16);(‘10‘). ELMCuUII) h1.60 H.455 MAS 16.70 ELM 37.68 A A .— -._ _-_ _‘ v.1 —7 1 v. w...— '— _._v Ei-te-llurato cuprate (III) in reduced by ten‘trata to a soluble talus mum-aw mate (II) complex 11' the Wt? 13 high, but. to a yellow green tsunami «praise (II) precipitate in weakly album ”mum. Due to «I lack of mproéucibility or titan, and to mat difficulty in (1&th the and point finally becma of the highly calmed ”dim, manta was fauna mited to the standardization or dbulmrata «grate (III) by visual and point technique. L} a {)6 0.62‘ 4.58‘ OOSL L, 0 U1 C. 9 gr 0‘ ecntial 0 Relative Pot C o C ,. {’0 0,38. J l 1 l l I J Visual End Point I I l 0.31.- 12 20 28 36 ml of di- pericziate Cuprate (III) Fig.1. Potentiometric Titration of NaZChH h OéonOo bu L6 ha 20 It. was hoped that. a potanfiorzzctric determination of the and palm might 112;:va the regroducihility of titrations . I. Fis‘mr T‘itrizrwter was arsployod. a plum-camel electrode system was used. A ten ml. aliquot of 0.2%! tertrltte solution was added to 150 ml of. H3") con- taking 1.2 am at potuaim irydroxicia, The 0.05}! di-periociata cum-ate (III) m conszmad alouly, the first. 0.5 m1 reéuhing two mm, and seven mimtaa pasacd before the titrime’wr owe to equi- librim men aanr 2.20 In}. had been added. M. 15.60 :1 the ”lanai: contamd a bluish white precipitation and 15 aim“: are required for rwuum of the di-poriodato mate (III) . The titration ”(mired shunt three how. to cmleto and tha and point band on mm unea- ot tho cappu- (III) was abaut Mm. Figure I show m plot of tha titration, and it can be seen that among; than are several steep mes. than in m “up rice fur 3 mm mime increment charwwriatia or . potenumetric titration me an? point. élthough visually the and point In about L6 :1. 1% a men Iron Fig-gun I that the potentio. meta-10 plot baa mm improved the and point. The tax-train aysm was tainted a representative at tin redo: mm: encountered in copper (III) titration- ouggoatod by Beck, and m studied by new. of qualitatiw taste in an attempt to account for the variety of calm-l produced, am! to emlain the lack a: regrodtwic hint:- of titan. Fam- leeu were prepared to represent the initial reduction product: , tin mu encountered lntm' in the titration, the state at the copper la! the 1mm may the ”cm! point”, md the state of the cappar and the iodine man an amass of capper (III) rm. been add-3d. To each or four nests 10 m1. of 0.17:??? 30;:qu tartrate solution 50 m1. of distilled 1mm!" and 0.5 gram-:8 of yo‘oassfifim bydrorida Wire added, Five E1. of di-periodato Gupta-1m (m) was added to the first 25 ml. to the amend, 50 ml. to the third, and 75 ml. to the 11:31:. The four mixtures were filtered on Coach crucibles with aghast-as mats and washed wall. 3323913 I filtrate (Fl) colorless; precipitate (PI) palo blue. Test Conclusion 32:: (1) F1 1' BC}. «alas: solrx-—-2 no color Cu abaent (2) F1 . m1 . :1 —~ I. If," and/or IO: present (3) PI 9 solid E1 —-- no I, on cmstala IO" abamzt or in small ‘ Quantities (h) F; + flame teat m- x’ 3" present (5) II 4, mm, . RgEGa—pfiglca (mite: Io; prawns he! 3 _ (6) ’1 «t 301 -o no I. I‘ absent (since 1",“ peasant.) (7) F1 alkaline to 11m " on" present F1 contains 25:31:, KID, and possibly small amounts of Hi?“ mt m COPPWU (8) P1 0 881 a.» II —*I; 9 01.1.1... ‘ (inM present (9) P: 4» 112-3 _. blue cuppa periodata 10; present. . (sample): {10) PI + man, 9 12532-3, _. :10 ppt Io," absent (11) PI + mm, + time teat No K" PI contains only an” and 10: mi proba‘gly partly as HOCu(IO.). Dime the matezzrial is K free. h) R) Suploa II, 111 and IV wro examined Qualitative]; With tho teats aployod 1n amplu I. In was oolorloaa and contained x‘”, 10;, and of, but no oOppor, PH m pale blm and contained cappor (II) poriodato. I'm no groan Ind contained K103, Krizifiuufind 10; u the green complex of diperiodtto ouproto (II), H‘Cu(IG.).'. Pm was cooper (II) Perimiato. P“ m brown and contained 10;, on", on”, Io“, an", x‘ and probably largely a HCu(IO.).J (brown), 39410.). (green), no, and ma. PH no cappor (II) periodoto. Tho reduction or ctr-periods“ copra“ by tartrato does not proceed in a Iimpl. W. n in obvious that cappor (III) as fiCu(IO.)..fi cannot ho going to Rfiflmg). and IO; too, without the appearance of ooppor (II) in me on species. Rota the 009;)” (III) poriodato ratio 1- one to two, and in the reduced tom the copper (II) periodoto ratio 1- duo one to two. Tho iodato ion produced must come frog the periodoto ion and thin indicates that the bio: pfooipitato wont be a mixture of a copper (II) poriodam. Copper (II) periodstoo with tho formulae Cudlog). and $31410.) . hm boon iloiatod by 3am, Singh and Bali ()0, 26). In addition to than omliootianl than men 3.011010.) 3. amplox, or the blno B‘Cuum) .' may appear 11' tho alkalinity in high. It 18 soon that tho tut-rate is oxidized by both poriodete md capper (III). Ono night predict. on the basis of. the great. miety of colored Opooioo which are produced, and tho periodoto attack, that the and point would on uncertain, and tho reaction mn-Itoichimotrio in tho titration of Wtroto with di-poriodoto cuproto (III). The titration! in Table VI: and tho potentiomtrio our" in F 1m. 1 clearly dmomtroto the validity of cook 3 prediction. 23 E. Potentiomtria Titratiom with the Fiche]? Titrimeter Tho mood motion 0: tho volumetric undies m mooted toward finding o mph mm capablo of being oxidized in on alkaline mom by copper (III). Among tho notoriolo cmidmd veto hydrogen poroxldo, pans-1m: iodido, oodim thiooultoto, potassium iodine, oodiu bimlflto and potassium cyanide. Tho hydrogen poroaddo woo clininatod boom of o tendency 01‘ the pounds to decompose opontan- oouoly in tho prooonoo of tho oOppor commando, tho; pomoiun iodide, potassium iodatoi, and sodium biooIHto taro oxidized too olowly, and along tho remaining magenta, all of which hod fair ratoo the potassium Imooyanido m believed to be moot prowl-1n; boom" torrooyanido ohonld ho oxidiood directly to torrioyonido. Tho tint titrotionl mo con-loo out dually «uploying ten :11. aliquoto of 0.0m petunia: tomoyanido load. the titan ranged from 33.5 ml. to 35.0 :1. of 0.00% potassium pm}. poriodooo. A mum of "do: indicator: taro mloyod unsuccessfully to on ottempt to ism-mo tho our! point, so that the Fisher ntriootor woo Again why“ to improu tho one! point. Figures 2 mo 3 ohm titration mo for two 10 m1. monot- of 0.001% K‘Foum). with 0.009! copper (III) poo-Man. About 0.5 first: of potash: hydroxide no added, on! dio- ullod mm no added to uko tho 101m wont 130 m1. rho notation in Figaro 1 no dono of. room imperatm on! titration to 71m 3 on dono ot 70°C . Figaro 2 ohm no inflection point improving tho visual on! point or 32.50 31., but the m in Figaro 3 gum o good inflection pom and potentiamotrioolly tho end point no ohm to bo 22.70 :31. 2h Tho mm end point was 29.00 ml. :1 fresh 0.003362}! potassium tomoymido oolution was prepared to chuck the work , mo Figure 1; 51m o. titration «1?in out in an attempt to chmlioato the results of Flam" 3. Figaro! S and 6 Show titration; of 20 m1. aliquots of 0,003,353: potmim forrooyanido titrated at 79%. with 0.0034 di- poriodnto unproto (In). An inflection pom m obtained in only one out at five potentionotrio titrationo, and this inflootion point differed trill tho ond point obtaiuod by visual mm by 6.30 '1. Potontianotrio on! point dotomimtiom of potassium tomoyonido wing di-poriodato ups-m (In), «playing tho platinm mm). olo-otvodo couplo no: the Robot 11mm, oro not antistaotoo-y because of the absence of unit- ohlo innovation pointo in tho titration curvoo. Tho tomoylnidontorricyonido , and dioporiodoto cowato (In-ou- poriodato ouprato (III) ayatom, represent couples mm: ohonld bo ideally ouitod to dud-atop and point detection. A mu 0.13%! solution oat potuoiuo {mooyonido‘m prepared, and 20 ml. aliquots of thin oolution mo titrated with diuporiodato mprato (III). Tho Fisher EIootropodo m mod with platinum olootrodoo. Figuroo ‘l and 8 show pinto of tho (alternator deflection and ml. of 0.0524 ooppor (III) periodate oddod. Tho ond pointo obtained by graphical extrapolatim are soon to to 12.70 :1. Ind 12m :11. Condition buod on tho visual ond point titration ohm that about four «Mullah of copper (III) M solo of potoooim forrooyonido mo cameo. Booed on tho dead-atop titration- tho calculations indiooto about 1:5 oquivalonto of copper (III) par nolo or potaooiun C). .j @\ d.w4 \A r 0. pm ramvmn.x a: coapauufle oflpumyofluxmaua . .mam (\J Aunnkuapgzn mpwfipwgonlflfl Mo HE 0m v.2 mm mm gm 2, 2 S L 3. . ‘ ‘ ‘ _. ,. 3am?“ I. pcflom v a Hasmfl> I1 I- l J 3N0 K) 3 N 04a 'Ierqueuod aAta'rav J \l’ . u QQZN pm {Azwdvu u aw :uwpdgpfla owapaEOHpcauoL .m.na~ .i'. . 7.. A vavdhazo mujfiofiamglflfl .H0 ME mm mm am Nomm ON 0H NH . n 4 3 mom: anamfl> oakpmfioaucmpoa IWOCHQAW USN. 65v '5 ”’3 L.\ . illlleooo Y "13% I“. q. 'IBIQUGQDJ BAI (I) \ 5.9,..1 .Hu 7.3.31: paw SH: 4 34m.mm \J.4 4) \. v ‘as ,. opnmuflgagufla m3 omoaN oPCHO pm a C] H‘sm4> DJNL .Illl 33m 0mm A o; 3A11'13u A ¢ '131qua .n03\ an 0A=D,mmqm mo coapapgfla oapaagoflgaego; .m.mflm .—f\ .muavoflum «.Hvso .3 HF on S E E 2 B Q m mm 23 j . ‘ I r .pcdou new Hagmfi> flit Ilsa ll IIL ,1 lat. ill '1 Til! Ill 33 .11. I am 0mm 'Irtuua104 aAravrav Relative Potential. 830—— 79d 750 ~——— 730 Visual End Point. 55 07 69 71 73 m1 of ui-p~eriodate cuprate (111.) Fig.6. Potenticmetric Titration cr K Fe(CN)/ at 7ucc. . J u 77 Galvanometer deflection. Galvanometer deflecticn. O\ C) .—d h. '— C? h) C) End Point ? 0 G 4 8 1'2 16 20 m1 of Cu(n[) ailed. Fig. 7. Dead step titration of KLFe(3N)6 with di-perirdate cquate j i f Lnd Pcint J O x J I I 7 3 h 8 12 16 2d 111 Cf Cu(m) added. L;m4 c+nn +4+nq+4nn AP x wn/5N\/ farmcyenida were comxmd. Thie differs greatly from the one equin- “lent Gambian amt-ed and therefore the farrocyanide is not 31mph oxidized to terdcyanhie, but. oxidation of the terricyanida men: mat new. Potassium terrocymida was forum to be tmsuitablo for the atmdardixnuon or mtwaimn di-periodato cuprata (III) because no good we point detection: We could be round, and became the reaction does not. represent a smile oxidation with clear atoikzhiometzy. F. Dead-Step Implied to Cappu- III Titratiom It ha been mentioned in the second nation of volmtric axperb menu that potwsitm cyanide and aodim tumult“. reduced crapper (III) reagents ”puny. The fourth section in the volumetric experiments consider. the application or dead-etc}: anti point detection in the titration: of potassium cyanide and aodim Mamas with mapper (III) re :gento . Potassium Cxfle The results obtained when 10 :11. SUN“ at approximately 0.134 potassium cyanide are titrated finally in rotation. containing 1.5 am 0: Mazda: hydrofido and 10 ml. of water with an approfimatoly 0.0m «solution or mow-mm cnprate (III) , um: an: In Approximtely 0.09! solution of di-tellurato euprate (III) are summarized in Table VIII. Thu raproducibiliw of the tit-rattan has been greatly Moved by application at dead-atop and point detection. Figure 9 than that. the and point is marked by I large change in gflmometar reading. The I") C“ TJELE' VIII VISUIL THREE}? m“ 13012333me animal; um; COPPER (III) hum-ms *3 I" 3 W * *3 :- 33 - W’A 4—- -—* 3:“ H1. Ceppor (III) Periodata Kl. Cappu- (III) Tollurato _. ‘ ‘ . 1 ._ .- _._V_ w 1 hi0 . 5.16 2 h.15 $.00 3 km 5.10 Fisher unmade was used with pletimn slactrodes. It was found that 50 11. Aliquot. of 0.0m potassium cyanide diluted with distilled water to 125 $1., Ind containing 2 gram of potassim lwdroxid. we titrated to 21.503 0.02 ml" and calculntiona show that tile equivalent. or an. tallurnto cuprn’u (III) tom- use): male of potassium cyanide m (scammed. T1 31:5; 11 nuts-era? rmwrxou w museum cums WITH POTASSM BI-‘l‘fiLURMO meme (m) A A u. 1... .n... __ “ l h M 5a 10 Rmbar A "I H ‘ 5‘3 ‘3’ MIWMUM HI. Cum , Consumed 21.80 21.78 21.62 21.82 Sims two equivalents of the cappor (III) are consumed it is reasonable to write the following; reaction for the cyanide oxidation: deflection I l I I I 1 I I I *‘cr—fi i I l J ————- I ._4 F- ._ 2-3 —— -——- L Q) +3 Q) 5 — .H g: 5 ,._4 c3 Oo—O—o—(‘r + —’.% o——o-—c>—o—o—ol» ‘— l ' I Ear Point. 43 r n l 1 l l l l I + _ Q , o ’4 v 12 16 20 21.? m1 of di—pQrioaate Cuprate (BE) 13).”. 9o .Jea'i Stfp titration Cf K)“. T I ' l ' 1 1 I ' I l to —— ‘* “‘ 20‘“——— '—’_—‘ End PC‘into —“ WWW I l O h 8 12 1b.; 16 23 Galvanometer deflecticn 0 m1 of di-tellurate CUprate (351) £11. 10. Lbad step titraticn cf N3232®3 27 “cording to Treadwall and Hall (31) potassium cyanate rearranges in potassim hydroxide solution mm + 2:120 ~53 2:54:50, Lmnia is liberated from ammonim salts in alkalim solutions. mam, 4. 5:31: --- £383, + 23:3,? + 3,2: ._ If potasaium cyanide in oxidiaad to potassima cymate, mania amuld be evolved as a result of the rearrangement indicated. It was! shown that. M2911 the midation of potassim cyanide by di- tellurato cuprtma (III) in a dilute pow-531m mar-oxide solution is carried out in a Kirk micro diffusion cell, which has Heaslar'a reagent in the diffusion cup, arm-0111a in liberate-:1, as indicated by a very positive wander test. The postulated ofidatian or potasaizm maniac to potassium cymta has fixerafore elqserimantal “113W. It was obaemd in the introduction that Beck had suggestefi that. the reactian was EMS}! . ZKQH «p 50 u {'00, t Hafiz}. 4- H30 with the common or ten equivzhnts of copper (III) msgant for use): male of 00:11“!!! Cyanifia, Hy emmrhnental evidence incflcatea Beck‘s con- clusions about $213 cyanide oxidation are enormous. Sodium Thiosulta‘ho Sodium flWne may be titrated visually in a saturated bicarbonata solution with di-tallurato cupratea (LEI) . The oadxiation is slow in pomim Madam , and the reproducifiility is mt good if div-periodato 0W“. (111) in used in plans of copper (III) 9.9mm“ due to periodate attack of the tldosuli‘ato. Tho excess- white bicarbonatc and the green- yellow tellurato mm“ (11) precipitate produced in the titration temd to make it difficult to see the first excess of tho di—tollurato (suprato (III) . $119 reproducibility of titration values is greatly in‘qn‘omd by wing dead-stag) and point donation. Tobias X and It We the result: of the dead-atop titration of 5 n1. aliquot: of GAME oodim thioaulfata in 75 m1. of Rotor con- taining m grams of solid amiima bicarbonate with di-periocloto cxzprato (III), and di-tallorato ouprata (III) using tho Fisher? Electrcrpocm with at 0.2V potential and a sensitivity of Si. TéBLS I name? rum-moo 0? 50:31:33 rmowmc x-ma momma-go {2035:3145 (III) A...“ _n M A— _‘ #A fl #3 7—7 , '-r -r A‘ x » __.__. u A _.. - A A __ ———- x A Smplg limbo? ‘ ww_r ~§Ilw7ifltfii1ti _Jsi A? £1. of Cu( III) 25 .70 t 23 .65 23 .39 17 .70 16 .110 w m A A .4‘ A~__ ‘ A A...‘ ..! m ,, 1-19 Liflum n ELLE-31’??? TIER-CTIT‘TBI 33' 3777353"! TI’II'TTIT’JU'EiTE Ea'ITH Mariana; ‘1‘0 CUM-Tar; (III) 5mm Ema}: i A A-..Tlééf”f ‘th Ah Au: V— m. a: cum) nun now 11:30 113.363 124.30 ._._‘ W - 44...._ _‘._ _.;._ _.- -4.“ _‘ " f t’. ) 1a. heat-f grout: precipitate airy-cars roaring; tizo titration. Figures 13 and 11 show the galvazu‘ezotcr rccflinfi (luring be t trotion. If the and point is taken as tho first gsalvmwtor mailing of thirty or more which persists for tidrty commie moon the last five milliliters are tidied drop-lice procision of i 0.33 It]... may be obtained. The reduction of (ii-tcllm'ato cuprato (III) is slow mar the and point. According to the data in Table H one mol- of so‘iimz thioou‘ifam consumes one equivalent of dintollurato otrpratc (III) . Oxiciation of thiosuli'ata to totrathionate properly accounts for the data collected. 6. Copper (III) Applied to the Dctcminction of Organic Compounds The fourth section of tho volmnctric studies consisted of emeri- manta designed to investigate possible applications or copper (III) volumetric oxidiznctry in organic compound 8113132313. Tartrato and glucose haw alramiy been considered. It was shown tint benzene and cyclone-mm no not oxidized even when reflund with copper (III) for covert}. hours. 61min acid, colonic acid, acctona, and bonzoic acid are all attached, but the rate is very slow. ”men 0.05 gm of bcmoic acid was added to dilute: potassium hydroxide with only 0.5 m1. of 0.05 H (ii-periodato ouprata (III) the cappor (III) we not reduced after rive nitrates of boiling, but the cappor (III) was reduood utter boiling for ton mimtes. than 9.5 m1. of 0.05 24 div periodato cuprcto (III) is added to a refluxing; solution of ethyl alcohol the reduction of the copper (III) is instantaneous. The rate of 3'7 “WI! of diaper-inflate cuprata (III) in cold dilute ethyl alcohol 11 slow. Ton milliliters of 0.05:»! di-periodato cuprato (III) were awed to 10 m1. at 0.03}! cthvl alcohol containing 1.0 gram of potassium lvdroxido and tho solution was refluxed. Liter tlurty minutes the supper (III) had been reduced and ten (:31. more of o0pper (III) were added. latter six hours of incrememt additions the solution had booms very dark blue, and it was not possible to dotornim whether there was an comes: of cappor (III). Five more partial titration of stat-'1 alcohol with potassium di- poriodate cupreta (III) were perfomed and the results of these eager-1- monto are Mummed 1:: Totals III. Tho aliquots of ethyl alcohol should L278 matured 2-3 ml. of tho 0.03% copper (III) reagent to convert the alcohol to acctaldolzyde, is.) ml. for conversion of the alcohol to acetic acid, and 120 ml. to convert the alcohol to carbon dioxide and water. Both tho 51w rate of ozddotion, and tho lac}: of suitable end point Wanted this titration 19 m'matisfactory, fill of the ergo-nix: compound titration: «enamored had prolibitive ratea in tho ordimu'y sense or a volmetrio titration. H. Colorimtric For}: Absorption spectra were dotominod for 0530:1703 and 0.03053; di- periodato cuprato (III) swam-lug tho Bcclmzan DU Quartz Spectmphotometor. A solvent blank of dilute potassimn hydroxide was encloyed, and the cells tom matched to a precision of 0.2313). cm. Ilthough di-poriodzzto mm XII EmTES a? consmmm 0? 0.094 conga (III) P31101333 BI 10 KL. nuwora cm 0.0% mm mount L.‘ A.“ H! v "v— rvv———— w W w‘ “W . A. .. _ ..4 _. .4..... __ -—v #7 151111. Fraction For Time Renoir-d (rm liter- ot Comaion to to Reduce Tempora 0: ma mun) Immdemda cquI) atm Comnta ‘I h J ._4‘ __._ M 7' j..— W W V W W 0.2 0.5 0.025 nor: that: - room Bo apparent 1 hr “motion of Cu(III) 0.2 0.5 0.025 more tlun reflux Son. redun— 1 hr tion of Cu (III) reagent to a light precipitate o: cuux) pennant. 2.0 0.5 0.025 LS seconds reflux Initial at. "not" poa- uibly due to impuritiu. h.O 2.0 0.1 15 mm reflux dark goon divalent {Dapper perio- date I m precipitate uppcmd 2.0 11.0 0.2 2 hours reflux 601m- 01 solu- tion too In- tonso to be aura when the brown first disappeared A 4‘ ._ _ _ u... ¢_._._...‘ A A - 1— AA v ._._v W V W _. 32 mm (In) absorb. somewhat in the ultraviolct wagon no aboarption pom mo present. Suitable solution or (ll-periods.“ coprato (III) , stabilized by dilute potassium Maude vor- propmd, and the behavior from OS to 1005 trnmoittmcy for A a 1410 was investigated. '1‘ his range ‘UIS roohookod Iith fresh Galatians, and‘both note of Iolutionl showed marked deviation from Boar's Law. The second not of solutions did not reproduou tho talus: obtainod‘by-tho first set, and‘both not: of Iolnp mm mm upon naming. 3st I m nomad ama- standing 2.5 hours, and Set II in: noaaurod.1nnodiatolr otter prop-ration. ‘Tho concentration range. at 0.00053 to 0.09; hopper (III) pariodoto m Inn-tigatod using n.6onoo Photolomotor'Iuthra.yollav'glasa filtar. It was sound thnt Burk Lu 1: approximately mm to this range, and that emporium or solution.ltrongthl 1- pcusihlo to I precision.ot 10%. rm m1 mammnmx Rm'rzoumn To oomomrrxon momma we: , some mmmm TO IENES'I'IGME nI-muomxo comm (III) Wr r -A;}+ a“ w—o Conn K/‘L Dummy/b omentntion 0.0500 ' 0.31. ' 0.0200 0.39 0.0100 0.1.0 0.0059 0.1m 0.0020 0.31; 0 9&5 0 03h 6031311331353 A HHV mpmnasm maxnoflpoulwd mo hucmpqumCJLp Hmouuoon .HH .mflu ASEV npmnoao>ds 83 8m 8m 92 one :3 D 93 0- oomo _ _ I I , o l rd II a . Q m 3 U IVS? 1w J 8 U I a m IIII III|1 on.m Ill: lllll 00 F 214% . I. a OHN a... m Q 3 [All]? or lll®u\o lb! ll: 02 _ _ _ _ h _ _ _ (ptical density. 1.2 .\ 0K. \)o€)‘ u.3 GD Lbasured immejiately Qléeasurei after 21/2 hour‘s staminp. . . __ ——r— J l) 20 id bu 50 Concentration in moles per liter of di—periodate Cuprate (HI)XIU- Fig.12. Beckrnan Du Spectrophotometer calibration curve (A x 1410) S .m>h:; coflpxtntflao tcompopoc; oocmm .aa .;4; r, .uoawa \2 AHHHV mpapnzo opaooflquIHd mo coap1uo :vocoo Como 03m 304 30o DON 33H l/I'BOT 33 00313113 SI 0143 can m can. mm at trivalent copper, dioporiodato «put. (111) Ind 414mm. «pg-m (111) ms found. Tho m of trivalent cuppa: Mumm‘ 1n volumetric oxidimotry 1: limited by slow relation rates, uncertain and points and non-ltoichimtry or zany re- lation: resulting in non-reprociucibln titers. Son of the mu- mama-1: nation have been explained by thawing that divalent copper panda“, end to n leaner extent divalent mapper tollurato are partially reduced. In general, organic compound: are muted to metric 69th by cappu- (In) reagent.- ” a result of pro- hibitive rates. Putnam. cyanide, and with has maiden sodium fldomlfm , and potassium “moulds an: be Wally titrated with 00m (III) reagents, and the nature or the oxidation: or these mound- hu boon olwida’oad. Colorimetric damnation: of. di- puindata mxpnto (III) on limited by tho memo or an absorption peak, but empirical colorimetric emporium! may be aado 1n the eon- centration range of 0.0005 to 0.091 copper (III) periods“. LIT LEA}? Uh.» CITz‘D LIEPJ-Efififi CITED 1. Km, 1.. I. sang. Chem, g, 121—1“) (1907). 1. Brain, 3. and Inn, 3. Bar. 59,, 3362-71 (1901). 3. Hull” ., Inorganic CW, John “119' and Sons, Inc" 3.1., ’0 825 (1952) )o ho Mo, Pa 530. 5.5.11.» '1‘. her game Chemistry, humans, Green and 60., Laden, '01. 3: 9. .1249.51 (1923). 6.31%”, W. 1!. sad Hildebrand, J. IL, Form Book at Inorganic W, m 34., mam»: Co"! .1., p. 101 (1951). 'l. W, L. 6811. «his. 1m... 1;, hey-mu (191a). 8. Wu 9. 580. 1, ' 9. Book, a. munch-1o m. mm an". )5, 169-71 (1950). f 1*??? 1.5“" ‘ t 10. look, a. W var. w Act... 3;, 215-50 (1950). 1:' . 11. Deck, 0. rimma var. W Ache... 3g, 1‘10 (1951). V13," ‘ 12. 3933., p. 152459. If ' *9 13. Book, a. Hih'oohmio var. :W 50“., 22, 22-29 (1952). y“ ,6 it. Book, a. nun-om m. nun-mum Act... 59, 258-61; (1953). \» V I ,1 ' 0‘2” j; 0 txmfij 3-9,, ‘1 If"; 'r”~-"M~‘+ 15. Book, 6. Anal. cm. hath, 2, aka-h? (1953). . ’ “*' PM 16. noun-g, J. J. cm.E¢n ., a, 326 (1952). 17. new, A. s. more. cm... 2.3, 159-79 (1895). 18. Inst; D. 4. An. Chan. 500., 531, 152-51: (1926). 19. tin-puck, Caz-pt. and" 3323, 979-80 (1937) . f; 4' f {5 1",. I“ t. ‘4‘ 20. unmade, L. Capt. rend... 332,, 5013-5 (1910). 21. Eran, 3. Eco. trauma ., Mg, 1:25-31: (3.925). 22. 901:1. K. Am. Chung; .599 (1952). 23. noun.“ . md Run ii. I. anon. Gm. 353,, 221-) (19149). 2h. minor, E. and Spits», I. 3. meat-aches. 2.2, 25-37 (1907). 25. Lister, n. '4. Can. 4. cm. a, 638-652 (1953). 26. Sudan, 0. F. hriodia Acid and India Acid 5th Ed. 0. F. Smith . cum-an 60., Columbus, Ohio, 1:. :46, 50.32 (1950) . 27. Chit-mags, E. J. fia.C1nn. Soc. 1693-1703 (1926). 28. .Cérgflrml, ,Hook, Harm and Banks. J. in. Ch... 600. 1;, 3031-05 1 9 . 29. Crouthml, nuns and Hal-tin. a. An. cm. Soc. 1;, 82-87 (1951). 30. 3am, snub and am. J. Indian cm. soc. g, 588 (19151). 31. Bock, a. .Eww var. minnow. Act... 12, ELM-51 (1952). 32. Tamil, 1'. P. and Hall, 3. B. Qualitativ- W, John may . m Sm, m m.1o1. I, p. :60 {1931). 3). selmd{m Pierce 1%., Immune-y, Influx-science mums“ Inc. p. 100 3". a“, co ’0 as my; PP. 100. 35. Ida’s-ado, L. In)... I... can. Iran 5;, 690-696 (1928). min Rama I Donald Arthm' Keyworth Born! iapril 21, 1930 in Flint, Michigan kcaamlc Career: Flint ion-thorn High School, Flint, Eichigan BEL-191s? mm. Junior College, Flint, flichigan 19h7-19h9 University of Michigan , hm Arbor, Malagan 1939-1951 Michigan mate College , East. Lansing, Enchigan 19.52.1951: Degrees Held! 8. S, University of Michigan, 1951 MICHIGAN STATE U V Y filifiilhl ll WW 6 2 2 0 7 4 l ill ”HT” 3 3 1293 0 0