Title Acetylacetone-Butyl Acetate. Author(s) Shigematsu, Tsunenobu; Tabushi, Mas. Citation University (1963), 40(5-6):

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for Chmi Univrsity (1963), 4(5-6): 374-38 Issu Dat 1963-1-3 URL http://hdl.

1 Titl Countrcurrnt Distribution Actylacton-Butyl Actat of Iron Systm Author(s) Shigmatsu, Tsunnobu; Tabushi, Mas Citation Bulltin of th Institut for Chmi Univrsity (1963), 4(5-6): Issu Dat URL Right Typ Dpartmntal Bulltin Papr Txtvrsion publishr Kyoto Univrsity

2 Countrcurrnt Distribution of Iron and Coppr in Actylacton-Butyl Actat Systm Tsunnobu SHIGEMATSU and Masayuki TABUSHI* (Shigmatsu Laboratory) Rcivd Novmbr 9, 1962 Fundamntal study on th countrcurrnt distribution was mad on th frric- and coppr actylactonat systm, using 1% actylacton-butylactat as an xtracting solvnt. Distribution curvs of th mtals wr obtaind by twnty stags fundamntal procdur at ph 2., 2.5, 3., 3.5 and 4.. Exprimntal rsults showd a good agrmnt with thortical valus calculatd by th binomial thorm from maximum position of th curvs, and distribution ratios of frric actylactonat drivd from maximum position agrd with th valus obtaind from th batch xtraction. At ph 3, 3.5 and 4, th sparation of frric iron and coppr was xamind and th rsults wr compard with th thortical stag numbr ncssary for th sparation, which was givn by an approximat quation with sparation cofficint. INTRODUCTION Rcntly, solvnt xtraction is widly usd as a powrful mthod for th sparation of mtals. Espcially many chlating ragnts such as 8-quinolinol, dithizon, cupfrron, TTA tc. play important rols in th dvlopmnt of this tchniqu. Howvr, th usual singl xtraction procdur is not ffctiv for th sparation of matrials which possss similar chmical proprty. Th multistag xtraction countrcurrnt procdur has bn mployd as a usful mthod in th sparation of such substancs as zirconium and hafnium", rar arths", fission products or actinid lmnts", platinum group". tc. Ths wr carrid out mainly with an ion association systm, such as TBP- or TBPO-minral acid systm. Th authors hav studid on th solvnt xtraction and th sparation of mtal actylactonat, as prviously rportd", and now attmptd to apply this chlating systm to th countrcurrnt tchniqu, for th purpos to dvlop actylacton xtraction mthod. In this papr, th fundamntal problms whthr th xprimntal rsults agr with thortical distribution curv or not, whthr distribution ratios obtaind from th curv agr with th valu obtaind from th batch xtraction or not, whthr actual xprimntal rsults agr with calculatd stag numbr for complt sparation or not, tc. wr xamind, using frric and coppr actylactonat, of which th xtraction bhaviours wr wll known. APPARATUS AND MATERIALS A Mitamura's Smiautomatic Countrcurrnt Distribution Apparatus, Modl ta (374 )

3 Countrcurrnt Distribution of Iron and Coppr 55-B, was usd for th discontinuous multistag xtraction. This apparatus basd on th dsign of Craig" consists of on hundrd distribution clls. A diagram of a unit cll is shown in Fig. 1. Spctrophotomtric, polarograghic and ph masurmnts wr mad with a Hitachi's Photolctric Spctrophotomtr, Modl EPU-2A, using 1cm silica clls, a Yanagimoto's Polarograph, Modl PA-15, and a Hitachi-Horiba's ph Mtr, M-3,. rspctivly. to th nxt cll b '--_-- 11 cm -, Fig. 1. Unit cll of countrcurrnt apparatus. Frric prchlorat solution, 1 jig F/ml and 1. mg F/ml. Coppr sulphat solution, 1. mg Cu/ml and 5. mg Cu/ml. 1% Actylacton butyl actat solution. 5% Actylacton aquous solution. 4M Ammonium chlorid-4m ammonia solution. EXPERIMENTAL RESULTS AND DISCUSSION Twnty stags fundamntal procdur was carrid in this rsarch, using 21 clls numbrd, 1, 2,...2 starting from th first tub, in which solvnt was flowd. Distribution procdur was dsignd as follows : Two hundrd and fifty millilitrs of watr, whos ph is controlld to a ( 375 )

4 Tsunnobu SHIGEMATSU and Masayuki TABUSHI dsird valu, ar shakn with 25 ml of 1% actylacton-butyl actat. Aquous solution is sparatd, aftr ph is adjustd again, transfrrd to th xtraction apparutus, and vry twnty tubs xcpt th first on ar filld up to th mark of 1 ml. On tnth to fiv tnth millilitrs of iron or coppr solution ar dilutd to 1 ml with th aquous solution obtaind abov, and aftr ph adjustmnt injctd to th first tub (cll No. ). Thn tn millilitrs of xtracting solvnt tratd as dscribd abov, ar addd to th first tub and shakn for 6-7 minuts (oscillation procss). Aftr th sparation of two layrs, uppr organic layr of th first tub is transfrrd to th scond on, and in th sam tim nw 1 ml of xtracting solvnt to th first tub (transfr procss). Th similar procsss of oscillation, sparation and transfr ar continud until first organic layr rachs to th last tub (cll No. 2). Aftr th twnty first transfr procss (thrfor 2 tims oscillation and sparation procss), iron and coppr containd in vry clls ar dtrmind by th following analytical procdurs. Frric iron : In th cas of iron, organic and aquous layrs wr sparatly analysd in ordr to obtain distribution ratio in batch procdur. Actylacton mthod was applid in both cass. Namly, organic solution sparatd is dirctly usd for th spctrophotomtric dtrmination by masuring absorbanc at 44 mµ against th xtracting solvnt". Aquous layr is transfrrd to 5 ml bakr, and aftr 2 ml of 5% actylacton aquous solution is addd and ph is adjustd to 7, dilutd to th mark in 2 ml volumtric flask. Absorbanc is obtaind at 44 mp, against th ragnt blank". Coppr : Coppr was dtrmind polarographically. Namly aquous layr in ach tub is transfrrd to 5 ml bakr and organic layr is washd with thr portions of 5 ml of 2N hydrochloric acid. Th stripping solutions ar combind to aquous layr of th sam tub, and th rsulting solution is vaporatd to almost drynss. Th rsidu is dissolvd with small amount of watr, and 5 ml of 4M ammonium chlorid-4m ammonia solution and.5 ml of 2% glatin solution ar addd. Aftr dilutd to 2 ml and doxygnatd with nitrogn gas, polarogram is rcordd. Distribution curvs of frric iron and coppr at C wr shown in Fig. 2 and Fig. 3, using 25 jtg iron and 1 mg coppr, rspctivly. Opn circls in figurs rprsnt xprimntal data, whil points and curvs, thortical valus which ar calculatd from maximum position by quation (1) and th binomial thorm, quation (2). r,a x-.5 K (1) 2.5 r,nfx Tr_ 2!Kr (2) r! (2--r)!_(K.1)ZO whr Tr is th fraction of substanc prsnt in th r-th tub, K, distribution ratio, and r,nnx, maximum position of th distribution curv. As sn in figurs xprimntal rsults ar in good agrmnt with th calculatd valus. On th distribution of iron, maximum position of th curvs and distribution ratio calculatd by quation (2) wr compard with th valus in batch ( 376 )

5 Countrcurrnt Distribution of Iron and Coppr p11 rl pg 1,1 CO pll y 4 c/ pll 3 2 o ^.-3?/ !! 1, Cll numbr Fig. 2. Distribution curvs of iron. Cu pl I 5 1,11,1 16\ \.1 1\ \,) 511)152 Cll numbr Fig. 3. Distribution curvs of coppr. xtraction. Th lattr distribution ratio, K', is givn by quation (3), and maximum position, rra., is calculatd by quation (4). (3) concntration of iron in (r )th organic layr K' concntration of iron in r-th aquous layr 2.5 K'-.5 max =1 K'(4) Rsults wr shown in Tabl 1, of which th first column rprsntd th valus from distribution curvs and th scond, man valus of batch xtraction. Both ( 377 )

6 ph Tsunnobu SHIGEMATSU and Masayuki TABUSHI KmaxK'r'max Tabl b a Avrag of 6 masurmnts o±.5 5 // of 7 masurmnts o n of 6 masurmnts c -A-. 6o distribution ratios and maximum position show good agrmnts. Distribution curvs with diffrnt amounts of iron or coppr (1 jig mg) undr th sam condition gav th sam shap, although th figurs wr omittd. This fact indicats that actylacton xtraction may b an idal systm. On th basis of ths rsults, th sparation of iron and coppr was xamind. Tabl 2 showd th width of distribution curvs and numbr of clls in which 99.7% of substanc was containd. Th width of th curvs wr calculatd on an assumption that thy wr Gauss' normal distribution curv*. Tabl 2 rvals distribution at ph 3., 3.5 and 4. ar suitabl for th sparation. Thrfor volum factor**, a, sparation cofficint***, and th stag numbr ncssary for th sparation**** undr ths conditions wr obtaind. Tabl 3 shows that 99.7% Tabl 2. phk Lir 99.7%Cll No. F ii ii Cu Tabl 3. phan99.,%n 99%II 95% , * Ar 99.7% = 6A 4/2 (1- K)2 ** a ---- KF KOu *5* /Kc. **** It was givn by an approximat quation, which was obtaind by assuming volum factor unit : + 1 i s, 2 whr CR was purity constant, and 36 for 99.7%, 31 for 99.% and 21.6 for 95% purity. ( 378 )

7 Countrcurrnt Distribution of Iron and Coppr of iron and coppr can b sparatd at ph 3. ; 99%, at ph 3.5 ; and 95%, at ph 4.. Distribution curvs of th sampls, containing 25 pg iron and 5 pg coppr; wr shown in Fig. 4, Fig. 5 and Fig. 6. Rcovris and contaminations of iron and coppr ar as follows : Cll No. FCu ph % <.2 ph < <.2 ph <.2 rg l- co 1, F 5! o Cll numbr Fig. 4. Distribution of iron and coppr at ph Cu of 5 o c7cl Cll numbr Fig. 5. Distribution of iron and coppr at ph 3.5. ( 379 )

8 Tsunnobu SHIGEMATSU and Masayuki TABUSH _ 1 - Cu F b. o1 152 Cll numbr Fig. 6. Distribution of iron and coppr at ph 4.. Ths rsults ar somwhat wors than th valus abov calculatd. It may b du to th fact that th thortical valus ar drivd from th approximat calculation. Th purpos of this invstigation is a fundamntal survy on th countrcurrnt xtraction using actylacton as a ragnt. In th furthr rsarch, th authors will study on th sparation of th matrials of which th sparation can not b don by th singl xtraction procss. REFERENCE (1) W. Fishr, W. Chalybaus and M. Z, Zumbusch, Z. anorg. allg. Chm., 255, 79 (1948). R. P. Cox, H. C. Ptson and G. H. Byr, Ind. Eng. Chm., 5, 141 (1958). (2) D. F. Pppard, J. P. Faris, P. R. Cray and G. W. Mason, J. Phys. Chm., 57, 294 (1953). B. Wavr, F. A. Kapplmann and A. C. Topp, J. Am. Chm. Soc., (1953). (3) T. Ishimori and H. M. Sammour, J. Atom. Enrgy Soc. Japan, 3, 344, 41 (1961). (4) E. W. Brg and W. L. Sn, Jr., Anal. Chim. Acta, 19, 12, 19 (1958). (5) T. Shigmatsu and M. Tabushi, This Bulltin, 39, 35 (1961). (6) L. C. Craig, W. Hausmann, E. H. Ahrns, Jr. and E. J. Harfnist, Anal. Chm., 23, 1236 (1951). (7) T. Shigmatsu and M. Tabushi, J. Chm. Soc. Japan, Pur Chm. Sc., 8, 118 (1959). (8) T. Shigmatsu and M. Tabushi, Japan Analyst, 8, 71 (1959). ( 38)

Determination of Vibrational and Electronic Parameters From an Electronic Spectrum of I 2 and a Birge-Sponer Plot

Determination of Vibrational and Electronic Parameters From an Electronic Spectrum of I 2 and a Birge-Sponer Plot 5 J. Phys. Chm G Dtrmination of Vibrational and Elctronic Paramtrs From an Elctronic Spctrum of I 2 and a Birg-Sponr Plot 1 15 2 25 3 35 4 45 Dpartmnt of Chmistry, Gustavus Adolphus Collg. 8 Wst Collg