- Email: [email protected]
Synergic extraction and photometric determination of vanadium(V) with 8-quinolinol in the presence of phenols
, I n a l l t t t t l CIittntta , I t t a 75 ( 1 9 7 5 ) "167-~76 t El~c~,er ~t.nent,fic Pt, bl,,,hmg C o m p , m ) Am,,aerdanl
367 P r i n t e d m t h e Nealacrhmd,,
SYNERGIC EXTRACTION AND PHOTOMETRIC DETERMINATION OF VANADIUM(V) WITH 8-QUINOLINOL IN T H E P R E S E N C E OF" P H E N O L S
ISAO KOJIMA I.tthorctttn l o / ,-I,Itll~,tte tll (.ht,lttt~tt l N t n l o l t l hl~lttutt, ¢11 Ft,tllntlhlql MOTOI-IAR U rANAKA* L t t h o l l l t o r l ¢1/ I n t l l l t l t t t l ('ht,ttll~lrt (Rcq.et~ed 15th At,gt,,,t 197.4)
I Ilillll|
NttuOltl d66 ( dapalt )
O/ It'Clt'lliU N¢lllOla I. nttt'r~ltl, N a t l O l t t 4 6 4 f J l l p a n )
S y n e r g t c e x t r a c t i o n o f metul c h e l a t e s has b e e n m o s t l y e x p h t m e d m t e r m s o f the f o r m a t m n o f c o m p l e x adclatmn c o m p o t , nds. i e r e p l a c e m e n t r e a c t m n s o f w a t e r m o l e c u l e s bot, nd to the c e n t r a l m e t u l aon by basic n e u t r a l o r g , t m c m o l e c u l e s ( T B P . T O P O . p y r a d m e , etc ). o r the f o r m a t i o n o f s i m p l e a d d a t m n c o m p o u n d s . t e with no r e p l a c e m e n t r e a c t m n . Recently. s o m e novel e x a m p l e s o f s y n e r g t e e x t r a c t , o n h a v e been e x p l a i n e d e i t h e r as e s t e r l f i c a t , o n o f the c o m p l e x tn t h e p l e s e n c e o f . ' d c o h o l s ~-'*. o r as the f o r m u t m n o f b m u e l e a r c o m p l e x e s nn the p r e s e n c e o f a s e c o n d met.'d a o n ~ - ° The V-OH group m vanadmm 8-qumolmolate (oxo-bas(8-qumoltnolate)v , m a d a c a c a d ) macvdac a n d ts subJect to esteraficatton m the p r e s e n c e ol a l c o h o l s ' "* to g , v , n g rme to .'t h y p s o c h r o m v c effect O n the bas,s o f these p h e n o m e n a , m e t h o d s for the p h o t o m e t r i c d e t e r m m a t , o n o f a l c o h o l s h a v e been p r o p o s e d by m a n y w o r k e r s . T h e V = O g r o u p m the s a m e c o m p l e x as basac a n d reacts with vltraot, s a c i d s i n c l u d i n g p h e n o l s t 1-13 p r o d u c , n g it b a t h o c h r o m l c effect. Thuq the v a n a d m m c o m p l e x e s o f a o d o - d e r w . ' t t w e s o f 8 - q u m o l m o l h a v e been p r o p o s e d its r e a g e n t s for the p h o t o m e t r x c d e t e c t a o n o f p h e n o l s ~'~ T h e p r e s e n t p a p e r d e a l s w i t h the synerg~e e x t r a c t m n o f v a n a d m m 8q u m o l m o l a t e an the p r e s e n c e o f p - p h e n y l p h e n o l A sensntwe m e t h o d for t h e e x t r a c t m n - - p h o t o m e t r a e d e t e r m t n a t , o n o f w m a d , u m has been d e v e l o p e d T h e m e t h o d laas been a p p h e d successfully to the d e t e r m m . ' l t l o n o f v a n a d m m m sthcate r o c k s RESUL'I S AND
DISCUSSION
A h s o t p t u , t .~pectra oJ tile athhtct~ o[ l a n a t h m n 8 - q u t n o h n o h l t e
w i t h pllenol~ As s h o w n m Fag !. w h e n p h e n o l s are a d d e d to b e n z e n e solt, u o n s o f v a n a d m m 8-qumolmolate. VOOx2OH. the w a v e l e n g t h o f m a x n m u m absorption shifts to l o n g e r w a v e l e n g t h .tnd t h e a b s o r b a n c c i n c r e a s e s w t t h increasing c o n c e n t r a t m n o f p h e n o l s F o r eel 10-2 M c o n c e n t r a t i o n s o f p h e n o l s , the w a v e l e n g t h o f m a x n m u m a b s o r p t i o n as daffercnt for different s o r t s o f p h e n o l s ( T a b l e 1) At p h e n o l c o n c c n t r a t , o n s hngher th.'m 0. 1 M . a b s o r b a n c e ~.lt tile m a x a m u m w a v e l e n g t h r e m a i n s a l m o s t c o n s t a n t , a n d o n l y thr,, w a v e l e n g t h o f m a x a m u m . ' t b s o r p t m n shifts to a l o n g e r * q'o w h o m ~.orrc~pondcn~c ~hould he . i d d r e ~ e d
368
! KOJIMA. M T A N A K A
'°]A
B
O8 ~
g
6
OB
06
~
06
~o~ 02
O2 !
z,00
I
500 600 Wavelength nm
I
!
700
400
500
I
600 Wovelertglh
!
700 nm
Fig I Absorption specta of v a n a d m m 8-qumohnolate sn the presence or phenols (A) p-Chlorophenol (I) None, (2)250 IO - a M : (3) 100 10 - a M , ( 4 ) 100 10-: M: (5)100 M (B)p-Phenylphenol ( i ) N o n e . ( 2 ) 4 0 0 10 -'t M , ( 3 ) 1 0 0 I0 - 3 M . ( 4 ) 1 0 0 I 0 -2 M . ( 5 ) 3 0 0 1 0 - : M , ( 6 ) 5 0 0 10 - 2 M Cv=107 IO - 4 M . c , o , = l . 0 0 10 - z A,I TABLE l THE MAXIMUM WAVELENGTHS VARIOUS PHENOLS
Phenol Phenol p-Methoxyphcnol p-Chlorophcnol o-Phenyiphenol p-Phenylphenol
o-Methylphenol p-Methylphenol p-N,trophcnol
[Phenol] (M) 5 10 - 2 0.10 -2 0 10 - z 0 10 - z 0 10 - 2 5 10- z 0 10 - z 5 10 - z
OF THE COMPLEXES
FORMED
IN THE PRESENCE
OF
2. . . . (nm) 570 650 580 590 610 590 600 575
w a v e l e n g t h with increasing c o n c e n t r a t i o n o f phenols. Similar reactions were a l s o observed for the o t h e r p h e n o l s listed m T a b l e I. T o d e t e r m i n e the c o m p o s i t i o n o f the a d d u c t o f v a n a d i u m 8 - q u m o h n o l a t e with phenols, the a b s o r b a n c e at 6 5 0 n m w a s plotted against the c o n c e n t r a t i o n o f pheno!s. A s is evident from Fig. 2, t w o a d d u c t s are formed: o n e zs a 1:I c o m p l e x and the o t h e r a 1:2 c o m p l e x T h e cwcles in Fig. 2 are the experimental data a n d the hne is the theoretical curve calculated from the value o b t a i n e d by m e a n s o f the least-squares m e t h o d . C a l c u l a t e d values are in g o o d accord wlth e x p e r i m e n t a l values. T h e f o r m a t i o n c o n s t a n t o f the 1:1 c o m p l e x is a b o u t 103 z-a s ~rrespecttve o f the p h e n o l s p r e v i o u s l y m e n t i o n e d , while the molar a b s o r p t w l t y o f the 1:1 c o m p ! e x is larger for p h e n o l s h a v i n g a high resonance system. In the f o l l o w i n g experiments, p - p h e n y l p h e n o l is used as the p h e n o l because o f its large d m t r i b u t i o n coefficient and the high absorptw~ty o f the resulting adduct.
EXTRACTION-SPECTROPHOTOMETRY
369
OF VANADIUM(V)
07
i
°
05
03 =
-6
I
i
"3
-2 -1 -0 log CCI~0 H F i g 2 F o r m a t , o n f u n c t i o n of t h e a d d u c t o f v , m a d t u m 8 - q u m o h n o l , t t c with p - p h e n y l p h e n o l Cv = 107 i.-a M, tHo,=100 10 -2 M . l o g K t - - - - 3 7 5 , l o g K . , = 0 8 6 , r v o o , = o H = 2 3 6 10 a, t,,oo,.oH^,oH = 6 3 6 ' I0 a. r~,oo,~oHt^~oll)2=7 9 6 ' 101
Extraction equdtbrium oj vanadutm 8-qt¢molmolare m the absence am/ presence oJ phenols T h e p a r t i t i o n o f v a n a d i u m 8 - q u m o h n o l a t e b e t w e e n w a t e r a n d b e n z e n e ~s e x p r e s s e d as follows a' t 5
VOW- + 2 HOx,, m . h,,,, . VOOxzOH,,rt=+ H ÷
(1)
K . , = [ V O O x 2 O H ] , , , ~ [ H +] [VOW'] [HOx]~r=
(2)
V O O x 2 O H , , ~ = + HOx,,.. h_,,,,.t V O O x 2 O H " HOx,,.g
(3)
[ V O O x 2 O H " HOx],,,~
m,o , = [voox,Ola],,
[HOx]o,,
(4)
T h e n t h e d m t r i b u t l o n ratio is given by: D = K~,,[HOx],2,,=(I + KFto,,,[HOx],,,~)[H +] - '
(5)
At 8 - q u m o l i n o i c o n c e n t r a t i o n s l o w e r t h a n 10 - 2 M in t h e o r g a m c phase, r e a c t i o n (3) is n o t a p p r e c i a b l e In t h e p r e s e n c e o f p h e n o l , the d i s t r i b u t i o n r a t i o D t s a f u n c t i o n o f the c o n c e n t r a t i o n o f p h e n o l m the o r g a m c phase. H o w e v e r , it m difficult to d e t e r m i n e the c o m p o s m o n o f the a d d u c t by the l o g - l o g plot o f p a r t m o n , b e c a u s e o f the slow a t t a i n m e n t o f t h e e x t r a c t i o n e q m h b r i u m a n d possible d e c o m p o s i t i o n o f t h e c o m p l e x m acidic m e d i a (see Fig. 4) T h e 1:1 a d d u c t is r e s p o n s i b l e for the e x t r a c t i o n o f v a n a d i u m 8 - q u i n o l i n o l a t e m the p r e s e n c e o f p h e n o l (0.01-0.1 M ) ( s e e Fig. 2); at h i g h e r c o n c e n t r a t i o n s o f phenol, the f o r m a t i o n o f the 1:2 a d d u c t is evident. T h e I : I a d d u c t being a s s u m e d in the p r e s e n c e o f p h e n o l , tile d m t r l b u t i o n r a t i o o f v a n a d m m is given b y eqn. (6):
370
i KOJIMA
M
TANAKA
(6)*
D = K ~ , [ t - [ O x ) , ~ ( I -I- K,, rv,,[ArOH],,r~)[H +] - ' where V O O x : O H , , r ~ + A r O H , , ~ I, ....... V O O x : O H
(7)
•ArOH,,~
[VOOx~OH" ArOH],,~ Kr'""' = [VOOx:OHJ,,~[ArOH],,~
(8)
17,x'trat Itott o] vatyadntny ttl the, tll~sente told p~esence o / p - p l l e n l Ipllellol T h e p e r c e n t a g ~ e × t r a c t ~ o n o f van~ldtum 8 - q u m o h n o l a t e in t h e a b s e n c e an.d p r e s e n c e o f p - p h c n y l p h e n o l is g t v e n m Fig. 3 V a n a d m m ~s c o m p l e t e l y e x t r a c t e d i n t o b e n z e n e at pl-I 2 . 4 - 5 0 w r e s p e c t l v e o f the a b s e n c e o r p r e s e n c e o f p - p h c n y l p h e n o l . w h e r e a s , a b o v e p H 5 0 , t h e p e r c e n t a g e e x t r a c t i o n o f v a n a d i u m d e c r e ~ s c s w~th i n c r e a s i n g p H . It s h o u l d bc n o t e d t h a t e x t r a c t i o n m t h e p r e s e n c e o f p - p h e n . v l p h c n o l o c c u r s at a l o w e r p H t h a n th;tt in t he a b s e n c e o f p h e n o l , t . e synerg~c e x t r a c t i o n o f v a n a d i u m 8 - q t u n o h n o l a t e ~s o b s e r v e d m t he p r e s e n c e o f p - p h e n y l p h e n o l A s~m~l.'lr r e a c t i o n w a s al s o o b s e r v e d for t h e o t h e r p h e n o l s , a n d t h e synerg~c e x t r a c t i o n c a n be e x p l a i n e d by t he f o r m a t i o n o f t he I :1 a d d u c t
100 80 % E 60 40 20 i
3
I~H
FvL~ 3 E x t r , l ( . l t o n curve,,, or , , . m , l d t u m '.~,tLh ~-quvvlOhllol in II1~ ,ib,.,crl(.c ,rod prcsun~e o f I , - p l l e n y l p h e n o l qw,=
I O0 I 0 - " AI
t ,. = I 0 7
I(I - 4 AI
t ~,c3nn ( ~ )
0050
M
(0)
0010
M, (0)
none
E//'ect o/ Ihv shakmq tm~v on the e x / r a t ltml o/ l a n a d m m The extractzon ~me o r v a n a d m m 8 - q u m o h n o l a t e ,n the presence of/~-phen.vlp h e n o l ~s s l o w espee,all.v m acnd~c m e d i u m A~ ns e v i d e n t f r o m F,g 4. the perccnta~,_e e x t r a c t i o n o f v a n a d m m i n c r e a s e s with i n c r e a s e d ~ h a k , n g tlnle a n d m a × i m u m e x t r a c t i o n ~s o b t a i n e d w i t h i n 30 m m u n d e r t h e pre~ent e x p e r i m e n t a l c o n d i t i o n s T h e e x t r a c t i o n rate d e p e n d s on the c o n c e n t r a t i o n of p - p h e n y l p h e n o l . 8 - q m n o l m o l . a n d h y d r o g e n Ion At p H 2 4 - 5 0 . s h a k i n g for l0 rain is s u f f i c i e n t for c o m p l e t e e x t r a c t i o n m t he p r e ~ e n c e o f 0 0 5 M p - p h c n y l p h e n o l N o effect o f p r o l o n g e d e x t r a c t i o n w a s o b s e r v e d , a n d t h e e x t r a c t is s t a b l e for at least s e v e r a l h o u r s o n s t a n d i n g At l o w e r p H . t h e p a r t m o n e q u l h b r m m ts r e a c h e d s l o w l y a n d t he p e r c e n t a g e e x t r a c t i o n sometvme~ d e c r e a s e s m t h e c o u r s e o f p r o l o n g e d e x t r a c t i o n . * Taking D
Und0r
=
r e a c t i o n (3} t r i t e a~.L.ount, xse h a v e
/~¢,[I-IOx]~,,( I + t,r,o,,[HOx]..~u + Kr,,,,,,[ArOH]..,u)[H "]- '
the pre,,cnt expgrvnental
condmon,,
the ~econd term m the parenlhe,,e,, ma)
he neglec.led
EXTRA(." FION-~;PECTROPI
UM(V)
IOTOM ETRY OI- VANADI
371
1
100 80
3 %E:
60 40 20 I
30
I
I
I
60 90 EXITOCtTon time
t20 rn,n
I-'tg 4 [:ffet.t o f ~ h a k m g ttmt: o n e~tr,L~.tton o f v a n . i d t t t m ( I ) 4 1 7 ( 2 ) 2 4 0 ('~) I 2a
~,=1 07
10 "~ A t , ¢ , , ~ , = 1 (XI 10 ~-~ AI. p H
E / f e e t o/ D C ~ T A m the e x t r a c ' t m n o/ r c o u i d m m U n d e r the p r e s e n t e x p e r i m e n t a l cond~tzons, rn:my m e t a l ton.,, a r e e x t r a c t e d . O f these. , r o n ( l l l ) m t e r f e r e~ m t he e × t r a c t t o n - p h o t o m e t l x c d e t e r m i n a t i o n o f v a n a d t u m it has b e e n r e p o r t e d t h a t 1 . 2 - e y c l o h o × a n e d m m l n e . N . N . N ' . N ' - t e t r a a c e t l c ,tcld ( D C y T A ) laa~ o n l y a v e r y small effect o n t he c o l o r r e a c t i o n s o f v a n a d m m with x y l e n o l o r a n g e ~t' o r t h t ; l z o l y l t l z o r e s o r c m o l ~7 m a q u e o u s ,,olutlon. B a s e d on these results. D C y T A was us e d a~ a m a s k i n g a g e n t for w o n ( I l l ) m the p r e s e n t study. As I~ e v t d e n t From Fig 5. e x t r a c t i o n o f v a i n . A t o m 8 - q u m o l l n o l a t e m the p r e s e n c e o f p - p h e n y l p h e n o l ss c o n s z d e r a b l y a f f e c t e d by t he c o n c e n t r a t i o n o f D C y T A . Thin u n d e , , i r a b l e d e p r e s s i o n o f e x t r a c t i o n c a n be c o m p l e t e l y o v e r c o m e by t he use o f th e Z n - D C y T A l l gand buffer s o l u t i o n TM. t h o u g h the pFl r a n g e o f c o m p l e t e e x t r a c t i o n b e c o m e s n , u r o w e t t h a n m t h e a b s e n c e o f the l i g a n d buffer, in a d d i t i o n .
~
100
%E
20 2
I
%E
3
80
.,...o....~ ~
2 O-
"O-
10
!
60
2
I
I
I
3
4
5
DH
0 0
25
30
35
pH
F i g 5 Effect o f m a , , k m g a g e n t , , o n ct~ctr,tc,l l o n o f v a n a c l t u m m t h e p r e , , e n c ¢ o f 0 0 5 0 &! p - p h e n y l p h e n o l c ~ . = 1 ( ) 7 I0 - ¢ A! c . o ~ = 1 0 0 I0 - ~ At ( I ) c l r ) r ~ = l ( ) O 10 -'~ ,~I. ( 2 ) ¢ l ) c , r , , , = l O 0 10 - 2 :~f. ( 3 ) c r ~ . , i . ~ l 00 I 0 - ~ A / . ( 4 ) cl~c~r,,,~l O0 10 4 A l , ( 5 ) ¢ / . = 2 0 0 10- ~ AX-i-ctx~l,~ = I (X) I 0 - ~ A! F i g 6 Effect o f , , h a k m g t m l e o n e x t r a c t i o n o f t r o n ( l l l ) f r o m h g J n d b u f f e r ,,oluttc~n m t h e p r e , , c n c e of 0050 M p-pl'ienylphenol cry---g00 I0 -~ M ¢z,,-----200 I0 ~ M . tt~c,r,x=lOO I 0 - " M . r u e , = I O0 I 0 - ' M F x l r a c t J o r l t t m e ( l ) 20 m t n . ( 2 ) 4.5 m m
372
! KOJIMA,
M TANAKA
t h e u m e n e c e s s a r y for c o m p l e t e e x t r a c t i o n o f v a n a d , u m f r o m t h e h g a n d buffer s o l u t i o n b e c o m e s l o n g e r t h a n t h a t f r o m the s o l u u o n c o n t a i n i n g n o m a s k i n g a g e n t . A s h a k i n g t , m e o f 45 rain sufficcs for a l m o s t c o m p l e t e e x t r a c t m n o f v a n a d m m a n d the p H r a n g e for c o m p l e t e e x t r a c t i o n is 2 7-3.6. T h e b a c k - w a s h i n g o f t h e e x t r a c t with the Z n - D C y T A s o l u u o n o f p H 2.8-3.5 c a u s e s n o v.'trmt,on o f t h e absorbance of the extract B e l o w p H 3 2. o n l y a small a m o u n t o f w o n ( I l l ) ( < 0 5",,) is e x t r a c t e d into b e n z e n e flora t h e Z n - D C y T A s o l u t m n m the presence of p-phcnylphenol. The e x t r a c t i o n o f iron i n c r e a s e s w , t h , n c r e a s , n g s h a k i n g t i m e ( F i g . 6). T h e s a m e results for the e x t r a c t i o n a n d b a c k - w a s h i n g o f v a n a d m m a n d w o n c o m p l e x e s w e r e o b t a i n e d with d , c h l o r o e t h a n e i n s t e a d o f b e n z e n e as solvent. Cahbrat~o, curves/or
vanadium T h e c a l i b r a t i o n c u r v e for v a n a d , u m o b t a , n e d b y the p r e s e n t m e t h o d is g i v e n ,n Fig. 7. C a l i b r a t i o n c u r v e s o f o t h e r m e t h o d s with 8 - q t , , n o l , n o l a r e given for c o m p a r i s o n . As is e w d e n t f r o m Fig 7. the p r e s e n t m e t h o d ~s t h e m o s t s e n s , t w e o n e with 8 - q u , n o h n o l R e a c t s o n of v a n a r h , t m 8 - q , ~ m o l m o l a t e w t t h t,artous ne,~tral org(o.c stcbst¢mce.s As m e n t i o n e d b y B u s c a r o n s et al. II a n d b y B l a i r et al to 12. v a n a d i u m
8 - q u m o l i n o l a t e r e a c t s with m a n y n e u t r a l o r g a n m s u b s t a n c e s to form t h e c o r r e s p o n d i n g a d d u c t o r e s t e r in t h e o r g a n i c s o l v e n t s . T h e s e r e a c t , o n s are g w e n schematmally as follows: RNItz
VOOxzOH" HzNR (acid-base reaction) VOOxzOR (esterlficatlon) VOOx2OH HOOCR (at,d-base react,on) VOOxzOH HOt/, ( a c i d - b a s e r e a c t i o n ) VOOxzOH. HOx (acid-base reaction) VOOxzOH. HzN4, (ac,d-base reaction)
ROll RCOOH
VOOxaOH
-
-
,~oH ltOx 4,NH:
1 D
5 08
i °°
2
0 4
1
0 2
2
t,
6 B 10 _ 12 Vanadium 10-5M F , g "7 C d h b r a t l o n c u r v e s ( I ) ! 0 0 10 - 2 M H O x at 550 a m , ( 2 ) 1130 10 - 2 M H O x + 2 0 M cdprlc a c i d a t 550 n m , ( 3 ) 1 0 0 10 - 2 M H O x + O I 0 M o c t d n o l ,at 4 7 0 n m , ( 4 ) 0 5 1 M H O x at 550 n m , (5) I 00 10-' M HOx+0050 M p.phenylphcnol .,t 620 n m
EXTRACTION-SPECTROPHOTOMETRY
373
OF VANADIUM(V)
A c i d i c o r g a m c s u b s t a n c e s react with the V = O g r o u p m the v a n a d m m 8 - q u m o iinolate to form the c o r r e s p o n d i n g a d d u e t , g w i n g r~se to a b a t h o c h r o m i c effect. w h e r e a s a m i n e s react with the V - O H g r o u p m the s a m e c o m p l e x to f o r m an adduct, p r o d u c i n g a h y p s o c h r o m l c effect. F o r the v a n a d m m c o m p l e x e s o f the other reagents, e . g . f l - l s o p r o p y i t r o p o l o n e , b e n z o y l p h e n y l h y d r o x y l a m i n e ( B P H A ) , maltoi, etc., s l m d a r p h e n o m e n a w e r e o b s e r v e d . T h e s e p h e n o m e n a will be reported e l s e w h e r e ~9. R e c o v e r y o f vanadnun tn the pre.sencv oJ t r o n M a n y metal i o n s are extracted under the present e x p e r i m e n t a l c o n d i t i o n s , but o n l y the interference o f l r o n ( l I I ) w a s e x a m i n e d . T h e analytical results of v a n a d m m m s y n t h e t i c c o m p o s i t e samples, m which the c o n c e n t r a t m n o f ~ron w a s v a n e d to a b o u t 100 times as high as that o f v a n a d i u m , are s h o w n m T a b l e If. As can be seen, satisfactory, rehable, and r e p r o d u c i b l e results for the r e c o v e r y o f vanadmm were obtained. Applicatzon to analysts o / s d t c a t e s T h e analytlcal results for v a n a d t u m m standard silicate rock s a m p l e s , t e
U S G S - B C R - I (Spht 56), U S G S - W - I , U S G S - P C C - I (Spht 1), U S G S - G - 2 (Spht 75), G S J - J B - I (Split 2), G S J - J B - I (Split 1) are s h o w n m T a b l e III. T h e s e v a l u e s are m r e a s o n a b l y g o o d a g r e e m e n t with t h o s e o b t a i n e d by D o n a l d s o n z°. F l a n a g a n 2~, A k a t w a et al zz, and A n d o et al. za EXPERIMENTAL
Retl~ellt.~
All the reagents
used
wele
of G.R
grade
Benzene, d i c h l o r o e t h a n e ,
T A B L E !i RECOVERY Vamtdmm
OF VANADIUM
IN T H E
PRESENCE
I r o n pre~enr
tal, e n
( l~
(mg )
OF IRON(Ill)
Vamtdmm /ound (l~fl)
Betl~.Ottt, (l~ ~oh l i l t
54 5
0 2 24 4 49 6 73
1363
Dtchlorovtluuw 545
1363
a..
54 54 54 55
5 7 54 3 3, 54 8 5
0 224 449
1363 1361. 1 3 6 0 135 7. 1 3 6 0
0 4 6 0 4 6
54 54 54 136 136 135
~oh v n t 49 73 49 73
5 8 2 3 1 8
p-
374 TABLF
I Kf)IIM;~
M TANAKA
II1
ANALYTICAl ~'amph,
RE~;UI.TS OF a anathum
U S C I S - B C R- I USGS-W- I USG~;- PCC - I U~JGS-G.2
VANADIUM
IN SI'ANDARD
SILIC'ATL
(p p m )
[JOlltlld~t ll" ~
I'hllltltltll121
420. 424 _7_ " "~ 274 22 2a ;~ 5 35 ~;
399 264 3() ~5 4
|AIIII~I! L'I Ill 22
GSJ-IIJ-I
178 _+74
GSI-IG-I
2~';-4- I I
" Obt,nned
ROCKS
| l l d l l t'l Ill 2~
2111) 3O0 25
21
PII'S('III I l l l , t h o d
41 t) 274 ~1 a4 ~'~ 227" ._4 29
b ) t h e ~t,tntl,~rd , t d d H r o n n l e a h o d
p h c n y l p h c n o l , un"lmonRam met.'lvanada1,e, p e r c h l o r t c dcad. s o c h u m a c e t a t e . D C y T A . a n d a n h y d r o u s ~ o d m m c q r b o n a t c w e r e o b t a i n e d flora W a k o P u r e C h e m i c a l Co.. O s a k a . J a p a n . B e n z e n e w a s first s h a k e n w n h c o n c e n t r a t e d ,,ulfurac acid a n d t h e n successively w n h w a t e r , d i l u t e s o d m m h y d r o x i d e solutaon, w a t e r , d d u t e h ~ d r o c h l o r l c acad solu1,]on, a n d fin,'dly wa1,h w a t e r 5 tm~cs a n d s1,oTcd w i t h o u t d e h y d r a t i o n D t c h l o r o e t h a n e w a s samalarly trca1,ed a n d s t o r e d w a t h o u t d e h y d r a t t o n p - P h e n y l p h e n o l a n d 8 - q u l n o l m o l w e r e l e c r y , , t a l h z e d from a q u c o u s e t h a n o l S o d m m a c c t a l e w a s r e c r y s t a l h z c d f r o m wnter a n d s t o r e d o v e r sdaca gel Z m c - D C y T A Iig.'md buffer s o l u t a o n wus p r e p a r e d by m i x i n g equ,'d v o l u m e s o f zinc ( 4 0 0 10--" M) a n d DCyTA (200.10-: M)solt,1,aons. S t a n d a r d v a n a d i u m s o l u t i o n ( 5 3 3 5 10 -'~ M ) w a s p r e p a r e d by d i l u t i n g a s t o c k s o l u t a o n ~ t a n d a r d J z e d g.ravunetracally a n d 1,1trlmctncally. l r o n s o l u t J o n ( I 013 10--" M ) w a s p r e p a r e d by d a s s o l v m g 4 ( ) l . 2 m g o f F e z O ~ ( S p e c P u r c ) an 500 ml o f d d u t e h y d r o c h l o a a c aczd s o l u t i o n a n d w~ls s t a n d a r d i z e d ~agam,,1, s t a n d a r d E D T A ~olutaon x~ath the C u Y - T A R ]ndJca1,or ,,ystem 2.' B c n z c n c ~ o l u t l o n s of p - p h e n y l p h e n o l (0 05 M ) a n d 8 - q u m o l m o l ( 0 0 1 M ) wcrc used ~ . ~ l i ( . J l ' ( l l p l 0 £ edlll'(?~
All e x p e r i m e n t s w e r e c a r r i e d otl1. in a r o o m t h e r m o , , m t e d ,11, 254- I C T h e im1,ml v o l u m e o f t h e d q u e o u ~ a n d o r g a n i c p h a s c s was a l w a y s 25 mi except for thc e x t r a c 1 , J o n - p h o t o m e t r m d e t e r m i n a t i o n o f v a n a d m m m the prc~cnce o f iron a n d m s d l c a t c rock~ (aq ' o r g = 5 0 25) T h e anatlal c o n c e n t r a u o n o f v a n d d m m m the s y s t e m w a s below i 5 10 -'~ M n n d t h e Ionic s t r e n g t h o f thc a q u e o u s p h a s c w~m kept c o n s t a n t at O ! M ( N a . H ) C I O . ~ e x c e p t for t h e extrac1,aon--photometr]c d e t e r m i n a t i o n o f vanadatan'! T h e a q u e o u s , m d organac p h a s e s w e r e c o n t a c t e d an a s e p a r a t o r y funncl, a recaprocaUng s h a k e r ( 2 0 0 - 2 5 0 ~1,rokes per anm) being used After t h e cquflabrat~on, thc p H o f the a q u e o u ~ s o l u u o n w a s m e a s u r e d wlth a R a d i o m e t e r t y p e P l q M 22 pH m e t e r V a n a d m m m thc o r g a m c p h a s e w,~m m e a s u r e d p h o t o m e t r i c a l l y with ;~ B e c k m a n D U o r S h n ~ a d z u Q V 50 s p e c t r o p h o t o m e t e r Jn 10-ram sahca cell,, T h e a b s o r b a n c e was read at 620 n m a g a i n s t b e n z e n e T h e a m o u n t s o f v a n a d m m were e v a l u a t e d by c o n s u l t i n g t h e cal~bratlon c u r v e previously constructed
375
EX F R A C T I O N - S P E C T R O P I I O ' I OME'I !~,5 O F V A N A D I U M ( V )
DL~IC~I'IlllIICIllOll o / tLlll(ldllllll III '~l(llldtltd I't]ul~ ~¢llllple~ F u s e I g of ,,t,mdard ~ock ~dmple ~ t h 5 8 g of a n h y d r o u ~ ~ocl~ttm c a r b o n a t e tn a p l d t m u m crt.c~ble m the U,,udl w a ) After c o m p l e t e decornpc~,.,~lton. alloy,
to c o o l .
add
hot
water, and
cru,.,h ~ n d
gnnd
the c a k e
wtth
d fldttened
glass rod R e d u c e m a n g a n ~ , t e b~ ;|(.Idmg 2 drop.,, of e t h a n o l , filler t h r o u g h a m e d t u m - t e x l u r e pdper, d n d finally ~d,,h the ~e,,~dt.e well x~tth hot I".. (w ~) s o d i u m c a r b o n a t e ,,olut~on Dflulc the fiitrdte wHh x~dter to 100 ml m ,i v o l u m e t r t c fldsk Ptpe! !0 ml o f the s o l u t i o n thu,, p r e p a r e d i n t o d iO0-ml , , e p a r d t o r y funnel. a d d I0 rnl o f Z n D C y T A s o l u t t o n a n d I0 ml o f 0 0 5 M ~ o d m m d c e t d t e ~olt|tlon A f t e r a d j t ' ~ l t n g the p H to 2 8 3 I xgRh I AI p e t c h l o n c dcld ~olut~on. follow the r e c o n , , n e n d e d p r o c e d u r e below R~"( O l l l l ? l e l l d £ ' d p l ' o £ £ ' d l l l c"
Place 50 ml o f tc,,t s o l u t i o n c o n t d t r t l n g le',', t l l a n 150 Hg o f v d n a d J u m :]nd n o m o r e t h a n 8 m g o f it on m a .,,cparatory f u n n e l A d d 15 ml o f ,R d d u t c d Zn-DCyTA ,,olutlon contu]nmg 200 I0-' AI / m e a n d I 0 0 I 0 -~ M D C y T A .
a n d a d j u s t the p H o f the ,,olut]on to 2 8 3 2 wHh s o d i u m a c e t u t e Extrdct for 45 m m with 25 ml o f a 0 0 1 A! b c n z c n e s o l u t m n o f 8 - q u m o l m o l c o n t a t m n g 0 0 5 AI p - p h c n y l p h e n o l . After d e h y d r a t i o n o f the o r g a m c p h a s c w~th pur:ficd a n h ) d r o u q s o d m m sulfate, read the d b , , o r b a n c e at 62(.) n m agu]n,,t b c n z e n e F s t d b l m h the vanadR~m c o n c e n t r a t i o n from a c a l l b r , l t m n c u r v e p r e v m u s l y c o n s t r u c t e d in t h e a b s e n c e o f Hon the ,Idd~tlon o f the l t g a n d bt, ffcr m a y be o r n l t t c d a n d the e x t r d c t l o n ~ -Itianttlttt~,c oxer a v~dct p H range. ~e 3 0 4 5 F m a n c m l s u p p o r t from the M,m.~try o f E d u c d t m n ( J a p a n ) r, gr~lteft, lly a c k n o w l e d g e d O n e o f us (l K ) w o u l d like to t h d n k P r o f C ildd o f N a g o y a I n s t i t u t e o f T e c h n o l o g y for hi,, tntere,,t in thP, ~ o r k SUMMARY
V q n a d m m ( V ) 8 - q u m o l l n o l a t e reacts wwth phenol.,, to form d i I d(IdlttOl~ c o m p o u n d in o r g a m u s o l v e n t s E n h a n c e d ¢xtt dCtlon Of v d n a d l t l l T i 8-qumc, l m o l a t e m t h e p r e s e n c e of p h c n o N can be a c c o u n t e d for tn t e r m s o f the f o l l o w i n g re,tctton: V O O x 2 O H , , r . + A r O H , , ~ , ~ - ' V O O x : O H ArOi-I,,,. O n the bast~ o f the b a t h o c h w o m l c effect o f p h e n o l s a n d the hzgh m o l d r :~b.,,otpt~vtty o f the c o m p l e x f o r m e d , a sem, tttve m e t h o d for the e x t r a c t | o n - p h o t o m c t r | c d e t e ~ m m a t m n o f v a n a d i u m has been d e v e l o p e d T h e a n a l y t , c a l results for vd,md~um ~n the s t a n d a r d stl,cate rock,,. U S G S - B C R - I , U S G S - W - I , U S G S - P C C ' - i . U S G S - G - 2 , GSJ-JB-1. and G S J - J G - I . a g r e e d well w , t h the d a t a r e p o r t e d prev,ou~ly REFERENCI.S
I H E Jungn,~kcl dnd W K l m g c r , Z Dud Clwm 203(1964) 257 206(1964) 275 2 N K t l r m , l t d h D S,Ityandtdy,m,t dnd V P,mdt, Rdngd Rdo l ' a h m t t l 14 ( 1 0 6 7 ) 4 9 5 ,rod pdper~ cRed thereto 3 M T , m d k d dnd I K o j , m a . d I n o m l Nl#t I ( hvm 29 (1967) 1769 4 H K , i w , l m o t o ,in(:l H A k d t w d , Nil~pon Kaool, u Ztl~sht 9 4 ( 1 9 7 3 ) 90 5 N V Shdkhov,t. I P A h m a r m dnd ~t, A Zoloto~,. I)oI, I ,ll, a d N a u l , SSSR 152(1963) 1,184
376 6 7 8 9 10 II 12 13 14 15 16 17 18 19 20 21 22 23 24
I KOJIMA.
M TANAKA
T V Healy. Solvent Eztractlon Claemi~try. N o r t h - H o l l a n d . A m s t 0 r d a m . 1967. p 119 R A A l e k p e r o v and N N M a k o v , Z h Ailal K h l m . 23 (1968) 460 Yu A Z o l o t o v . Dokl Akad Nauk S S S R . 180(1968) 1367 N. Nakasuk,i, Y M i t s u o k a and M T a n a k a , J Inorft Nucl Ch em . 36 (1974) 431. N N a k a q u k a . T [to and M T , m J k a . Chem Lett..(1973) 553 A J Blair. D A P a n t o n y a n d G [ Mmkoffo J Itlorff Nucl C h e m . 5 (1958) 316 F Buscarons. J L M a r m a n d J C l a v e r . Anal Chlm Acta. 3(1958) 310 A J Bl:ur a n d D A P a n t o n y , Anal Chim Acta. 13 (1955) I A J Blaw atnd E B~.,.~r. Ju~tz~ Liebtg~ Ann. Chem. 6 8 4 ( 1 9 5 3 ) 96 ] M K o r c n m a n . V G G a m n a , G R B a r a n c h ] k o v a and V I Z y u z m d . Tr Kh#m Teldmol. (1969) 124, C h e m A b ~ t , 7 4 ( 1 9 7 1 ) 9 4 1 8 c M T a n a k a a n d I K o j i m a , Ancll Clffm A c t a . 36 (1966) 522 O Budovsky a n d R Prtbtl. Tala,ta, II (1964) 1313 O Budovsky a n d L J o h n o v a . Ttdaslta. 12 (1965) 291 M T a n a k a a n d N. Awata, Anal Cinm Acta, 3 9 ( 1 9 6 7 ) d85 I Kojima. to be pubi.shod E M D o n a l d s o n . TcJlanta. 17 (1970) 583 F. J F l a n a g a n . Geocisim Cosnaochma Acta. 37 (1973) 1189 H Akalwa. H K a w a m o t o a n d H K o n d o . BLm~eki Kagak,. 23 (1973) 402 A Ando. H K u r a s a w a . T O h m o r t and E Taked:l. Geothem J . 5 ( 1 9 7 1 ) 151 H Yamdda. T M a c d a and ! Kojzma. Anal C'llim Acta. 7 2 ( 1 9 7 4 ) 426
367 P r i n t e d m t h e Nealacrhmd,,
SYNERGIC EXTRACTION AND PHOTOMETRIC DETERMINATION OF VANADIUM(V) WITH 8-QUINOLINOL IN T H E P R E S E N C E OF" P H E N O L S
ISAO KOJIMA I.tthorctttn l o / ,-I,Itll~,tte tll (.ht,lttt~tt l N t n l o l t l hl~lttutt, ¢11 Ft,tllntlhlql MOTOI-IAR U rANAKA* L t t h o l l l t o r l ¢1/ I n t l l l t l t t t l ('ht,ttll~lrt (Rcq.et~ed 15th At,gt,,,t 197.4)
I Ilillll|
NttuOltl d66 ( dapalt )
O/ It'Clt'lliU N¢lllOla I. nttt'r~ltl, N a t l O l t t 4 6 4 f J l l p a n )
S y n e r g t c e x t r a c t i o n o f metul c h e l a t e s has b e e n m o s t l y e x p h t m e d m t e r m s o f the f o r m a t m n o f c o m p l e x adclatmn c o m p o t , nds. i e r e p l a c e m e n t r e a c t m n s o f w a t e r m o l e c u l e s bot, nd to the c e n t r a l m e t u l aon by basic n e u t r a l o r g , t m c m o l e c u l e s ( T B P . T O P O . p y r a d m e , etc ). o r the f o r m a t i o n o f s i m p l e a d d a t m n c o m p o u n d s . t e with no r e p l a c e m e n t r e a c t m n . Recently. s o m e novel e x a m p l e s o f s y n e r g t e e x t r a c t , o n h a v e been e x p l a i n e d e i t h e r as e s t e r l f i c a t , o n o f the c o m p l e x tn t h e p l e s e n c e o f . ' d c o h o l s ~-'*. o r as the f o r m u t m n o f b m u e l e a r c o m p l e x e s nn the p r e s e n c e o f a s e c o n d met.'d a o n ~ - ° The V-OH group m vanadmm 8-qumolmolate (oxo-bas(8-qumoltnolate)v , m a d a c a c a d ) macvdac a n d ts subJect to esteraficatton m the p r e s e n c e ol a l c o h o l s ' "* to g , v , n g rme to .'t h y p s o c h r o m v c effect O n the bas,s o f these p h e n o m e n a , m e t h o d s for the p h o t o m e t r i c d e t e r m m a t , o n o f a l c o h o l s h a v e been p r o p o s e d by m a n y w o r k e r s . T h e V = O g r o u p m the s a m e c o m p l e x as basac a n d reacts with vltraot, s a c i d s i n c l u d i n g p h e n o l s t 1-13 p r o d u c , n g it b a t h o c h r o m l c effect. Thuq the v a n a d m m c o m p l e x e s o f a o d o - d e r w . ' t t w e s o f 8 - q u m o l m o l h a v e been p r o p o s e d its r e a g e n t s for the p h o t o m e t r x c d e t e c t a o n o f p h e n o l s ~'~ T h e p r e s e n t p a p e r d e a l s w i t h the synerg~e e x t r a c t m n o f v a n a d m m 8q u m o l m o l a t e an the p r e s e n c e o f p - p h e n y l p h e n o l A sensntwe m e t h o d for t h e e x t r a c t m n - - p h o t o m e t r a e d e t e r m t n a t , o n o f w m a d , u m has been d e v e l o p e d T h e m e t h o d laas been a p p h e d successfully to the d e t e r m m . ' l t l o n o f v a n a d m m m sthcate r o c k s RESUL'I S AND
DISCUSSION
A h s o t p t u , t .~pectra oJ tile athhtct~ o[ l a n a t h m n 8 - q u t n o h n o h l t e
w i t h pllenol~ As s h o w n m Fag !. w h e n p h e n o l s are a d d e d to b e n z e n e solt, u o n s o f v a n a d m m 8-qumolmolate. VOOx2OH. the w a v e l e n g t h o f m a x n m u m absorption shifts to l o n g e r w a v e l e n g t h .tnd t h e a b s o r b a n c c i n c r e a s e s w t t h increasing c o n c e n t r a t m n o f p h e n o l s F o r eel 10-2 M c o n c e n t r a t i o n s o f p h e n o l s , the w a v e l e n g t h o f m a x n m u m a b s o r p t i o n as daffercnt for different s o r t s o f p h e n o l s ( T a b l e 1) At p h e n o l c o n c c n t r a t , o n s hngher th.'m 0. 1 M . a b s o r b a n c e ~.lt tile m a x a m u m w a v e l e n g t h r e m a i n s a l m o s t c o n s t a n t , a n d o n l y thr,, w a v e l e n g t h o f m a x a m u m . ' t b s o r p t m n shifts to a l o n g e r * q'o w h o m ~.orrc~pondcn~c ~hould he . i d d r e ~ e d
368
! KOJIMA. M T A N A K A
'°]A
B
O8 ~
g
6
OB
06
~
06
~o~ 02
O2 !
z,00
I
500 600 Wavelength nm
I
!
700
400
500
I
600 Wovelertglh
!
700 nm
Fig I Absorption specta of v a n a d m m 8-qumohnolate sn the presence or phenols (A) p-Chlorophenol (I) None, (2)250 IO - a M : (3) 100 10 - a M , ( 4 ) 100 10-: M: (5)100 M (B)p-Phenylphenol ( i ) N o n e . ( 2 ) 4 0 0 10 -'t M , ( 3 ) 1 0 0 I0 - 3 M . ( 4 ) 1 0 0 I 0 -2 M . ( 5 ) 3 0 0 1 0 - : M , ( 6 ) 5 0 0 10 - 2 M Cv=107 IO - 4 M . c , o , = l . 0 0 10 - z A,I TABLE l THE MAXIMUM WAVELENGTHS VARIOUS PHENOLS
Phenol Phenol p-Methoxyphcnol p-Chlorophcnol o-Phenyiphenol p-Phenylphenol
o-Methylphenol p-Methylphenol p-N,trophcnol
[Phenol] (M) 5 10 - 2 0.10 -2 0 10 - z 0 10 - z 0 10 - 2 5 10- z 0 10 - z 5 10 - z
OF THE COMPLEXES
FORMED
IN THE PRESENCE
OF
2. . . . (nm) 570 650 580 590 610 590 600 575
w a v e l e n g t h with increasing c o n c e n t r a t i o n o f phenols. Similar reactions were a l s o observed for the o t h e r p h e n o l s listed m T a b l e I. T o d e t e r m i n e the c o m p o s i t i o n o f the a d d u c t o f v a n a d i u m 8 - q u m o h n o l a t e with phenols, the a b s o r b a n c e at 6 5 0 n m w a s plotted against the c o n c e n t r a t i o n o f pheno!s. A s is evident from Fig. 2, t w o a d d u c t s are formed: o n e zs a 1:I c o m p l e x and the o t h e r a 1:2 c o m p l e x T h e cwcles in Fig. 2 are the experimental data a n d the hne is the theoretical curve calculated from the value o b t a i n e d by m e a n s o f the least-squares m e t h o d . C a l c u l a t e d values are in g o o d accord wlth e x p e r i m e n t a l values. T h e f o r m a t i o n c o n s t a n t o f the 1:1 c o m p l e x is a b o u t 103 z-a s ~rrespecttve o f the p h e n o l s p r e v i o u s l y m e n t i o n e d , while the molar a b s o r p t w l t y o f the 1:1 c o m p ! e x is larger for p h e n o l s h a v i n g a high resonance system. In the f o l l o w i n g experiments, p - p h e n y l p h e n o l is used as the p h e n o l because o f its large d m t r i b u t i o n coefficient and the high absorptw~ty o f the resulting adduct.
EXTRACTION-SPECTROPHOTOMETRY
369
OF VANADIUM(V)
07
i
°
05
03 =
-6
I
i
"3
-2 -1 -0 log CCI~0 H F i g 2 F o r m a t , o n f u n c t i o n of t h e a d d u c t o f v , m a d t u m 8 - q u m o h n o l , t t c with p - p h e n y l p h e n o l Cv = 107 i.-a M, tHo,=100 10 -2 M . l o g K t - - - - 3 7 5 , l o g K . , = 0 8 6 , r v o o , = o H = 2 3 6 10 a, t,,oo,.oH^,oH = 6 3 6 ' I0 a. r~,oo,~oHt^~oll)2=7 9 6 ' 101
Extraction equdtbrium oj vanadutm 8-qt¢molmolare m the absence am/ presence oJ phenols T h e p a r t i t i o n o f v a n a d i u m 8 - q u m o h n o l a t e b e t w e e n w a t e r a n d b e n z e n e ~s e x p r e s s e d as follows a' t 5
VOW- + 2 HOx,, m . h,,,, . VOOxzOH,,rt=+ H ÷
(1)
K . , = [ V O O x 2 O H ] , , , ~ [ H +] [VOW'] [HOx]~r=
(2)
V O O x 2 O H , , ~ = + HOx,,.. h_,,,,.t V O O x 2 O H " HOx,,.g
(3)
[ V O O x 2 O H " HOx],,,~
m,o , = [voox,Ola],,
[HOx]o,,
(4)
T h e n t h e d m t r i b u t l o n ratio is given by: D = K~,,[HOx],2,,=(I + KFto,,,[HOx],,,~)[H +] - '
(5)
At 8 - q u m o l i n o i c o n c e n t r a t i o n s l o w e r t h a n 10 - 2 M in t h e o r g a m c phase, r e a c t i o n (3) is n o t a p p r e c i a b l e In t h e p r e s e n c e o f p h e n o l , the d i s t r i b u t i o n r a t i o D t s a f u n c t i o n o f the c o n c e n t r a t i o n o f p h e n o l m the o r g a m c phase. H o w e v e r , it m difficult to d e t e r m i n e the c o m p o s m o n o f the a d d u c t by the l o g - l o g plot o f p a r t m o n , b e c a u s e o f the slow a t t a i n m e n t o f t h e e x t r a c t i o n e q m h b r i u m a n d possible d e c o m p o s i t i o n o f t h e c o m p l e x m acidic m e d i a (see Fig. 4) T h e 1:1 a d d u c t is r e s p o n s i b l e for the e x t r a c t i o n o f v a n a d i u m 8 - q u i n o l i n o l a t e m the p r e s e n c e o f p h e n o l (0.01-0.1 M ) ( s e e Fig. 2); at h i g h e r c o n c e n t r a t i o n s o f phenol, the f o r m a t i o n o f the 1:2 a d d u c t is evident. T h e I : I a d d u c t being a s s u m e d in the p r e s e n c e o f p h e n o l , tile d m t r l b u t i o n r a t i o o f v a n a d m m is given b y eqn. (6):
370
i KOJIMA
M
TANAKA
(6)*
D = K ~ , [ t - [ O x ) , ~ ( I -I- K,, rv,,[ArOH],,r~)[H +] - ' where V O O x : O H , , r ~ + A r O H , , ~ I, ....... V O O x : O H
(7)
•ArOH,,~
[VOOx~OH" ArOH],,~ Kr'""' = [VOOx:OHJ,,~[ArOH],,~
(8)
17,x'trat Itott o] vatyadntny ttl the, tll~sente told p~esence o / p - p l l e n l Ipllellol T h e p e r c e n t a g ~ e × t r a c t ~ o n o f van~ldtum 8 - q u m o h n o l a t e in t h e a b s e n c e an.d p r e s e n c e o f p - p h c n y l p h e n o l is g t v e n m Fig. 3 V a n a d m m ~s c o m p l e t e l y e x t r a c t e d i n t o b e n z e n e at pl-I 2 . 4 - 5 0 w r e s p e c t l v e o f the a b s e n c e o r p r e s e n c e o f p - p h c n y l p h e n o l . w h e r e a s , a b o v e p H 5 0 , t h e p e r c e n t a g e e x t r a c t i o n o f v a n a d i u m d e c r e ~ s c s w~th i n c r e a s i n g p H . It s h o u l d bc n o t e d t h a t e x t r a c t i o n m t h e p r e s e n c e o f p - p h e n . v l p h c n o l o c c u r s at a l o w e r p H t h a n th;tt in t he a b s e n c e o f p h e n o l , t . e synerg~c e x t r a c t i o n o f v a n a d i u m 8 - q t u n o h n o l a t e ~s o b s e r v e d m t he p r e s e n c e o f p - p h e n y l p h e n o l A s~m~l.'lr r e a c t i o n w a s al s o o b s e r v e d for t h e o t h e r p h e n o l s , a n d t h e synerg~c e x t r a c t i o n c a n be e x p l a i n e d by t he f o r m a t i o n o f t he I :1 a d d u c t
100 80 % E 60 40 20 i
3
I~H
FvL~ 3 E x t r , l ( . l t o n curve,,, or , , . m , l d t u m '.~,tLh ~-quvvlOhllol in II1~ ,ib,.,crl(.c ,rod prcsun~e o f I , - p l l e n y l p h e n o l qw,=
I O0 I 0 - " AI
t ,. = I 0 7
I(I - 4 AI
t ~,c3nn ( ~ )
0050
M
(0)
0010
M, (0)
none
E//'ect o/ Ihv shakmq tm~v on the e x / r a t ltml o/ l a n a d m m The extractzon ~me o r v a n a d m m 8 - q u m o h n o l a t e ,n the presence of/~-phen.vlp h e n o l ~s s l o w espee,all.v m acnd~c m e d i u m A~ ns e v i d e n t f r o m F,g 4. the perccnta~,_e e x t r a c t i o n o f v a n a d m m i n c r e a s e s with i n c r e a s e d ~ h a k , n g tlnle a n d m a × i m u m e x t r a c t i o n ~s o b t a i n e d w i t h i n 30 m m u n d e r t h e pre~ent e x p e r i m e n t a l c o n d i t i o n s T h e e x t r a c t i o n rate d e p e n d s on the c o n c e n t r a t i o n of p - p h e n y l p h e n o l . 8 - q m n o l m o l . a n d h y d r o g e n Ion At p H 2 4 - 5 0 . s h a k i n g for l0 rain is s u f f i c i e n t for c o m p l e t e e x t r a c t i o n m t he p r e ~ e n c e o f 0 0 5 M p - p h c n y l p h e n o l N o effect o f p r o l o n g e d e x t r a c t i o n w a s o b s e r v e d , a n d t h e e x t r a c t is s t a b l e for at least s e v e r a l h o u r s o n s t a n d i n g At l o w e r p H . t h e p a r t m o n e q u l h b r m m ts r e a c h e d s l o w l y a n d t he p e r c e n t a g e e x t r a c t i o n sometvme~ d e c r e a s e s m t h e c o u r s e o f p r o l o n g e d e x t r a c t i o n . * Taking D
Und0r
=
r e a c t i o n (3} t r i t e a~.L.ount, xse h a v e
/~¢,[I-IOx]~,,( I + t,r,o,,[HOx]..~u + Kr,,,,,,[ArOH]..,u)[H "]- '
the pre,,cnt expgrvnental
condmon,,
the ~econd term m the parenlhe,,e,, ma)
he neglec.led
EXTRA(." FION-~;PECTROPI
UM(V)
IOTOM ETRY OI- VANADI
371
1
100 80
3 %E:
60 40 20 I
30
I
I
I
60 90 EXITOCtTon time
t20 rn,n
I-'tg 4 [:ffet.t o f ~ h a k m g ttmt: o n e~tr,L~.tton o f v a n . i d t t t m ( I ) 4 1 7 ( 2 ) 2 4 0 ('~) I 2a
~,=1 07
10 "~ A t , ¢ , , ~ , = 1 (XI 10 ~-~ AI. p H
E / f e e t o/ D C ~ T A m the e x t r a c ' t m n o/ r c o u i d m m U n d e r the p r e s e n t e x p e r i m e n t a l cond~tzons, rn:my m e t a l ton.,, a r e e x t r a c t e d . O f these. , r o n ( l l l ) m t e r f e r e~ m t he e × t r a c t t o n - p h o t o m e t l x c d e t e r m i n a t i o n o f v a n a d t u m it has b e e n r e p o r t e d t h a t 1 . 2 - e y c l o h o × a n e d m m l n e . N . N . N ' . N ' - t e t r a a c e t l c ,tcld ( D C y T A ) laa~ o n l y a v e r y small effect o n t he c o l o r r e a c t i o n s o f v a n a d m m with x y l e n o l o r a n g e ~t' o r t h t ; l z o l y l t l z o r e s o r c m o l ~7 m a q u e o u s ,,olutlon. B a s e d on these results. D C y T A was us e d a~ a m a s k i n g a g e n t for w o n ( I l l ) m the p r e s e n t study. As I~ e v t d e n t From Fig 5. e x t r a c t i o n o f v a i n . A t o m 8 - q u m o l l n o l a t e m the p r e s e n c e o f p - p h e n y l p h e n o l ss c o n s z d e r a b l y a f f e c t e d by t he c o n c e n t r a t i o n o f D C y T A . Thin u n d e , , i r a b l e d e p r e s s i o n o f e x t r a c t i o n c a n be c o m p l e t e l y o v e r c o m e by t he use o f th e Z n - D C y T A l l gand buffer s o l u t i o n TM. t h o u g h the pFl r a n g e o f c o m p l e t e e x t r a c t i o n b e c o m e s n , u r o w e t t h a n m t h e a b s e n c e o f the l i g a n d buffer, in a d d i t i o n .
~
100
%E
20 2
I
%E
3
80
.,...o....~ ~
2 O-
"O-
10
!
60
2
I
I
I
3
4
5
DH
0 0
25
30
35
pH
F i g 5 Effect o f m a , , k m g a g e n t , , o n ct~ctr,tc,l l o n o f v a n a c l t u m m t h e p r e , , e n c ¢ o f 0 0 5 0 &! p - p h e n y l p h e n o l c ~ . = 1 ( ) 7 I0 - ¢ A! c . o ~ = 1 0 0 I0 - ~ At ( I ) c l r ) r ~ = l ( ) O 10 -'~ ,~I. ( 2 ) ¢ l ) c , r , , , = l O 0 10 - 2 :~f. ( 3 ) c r ~ . , i . ~ l 00 I 0 - ~ A / . ( 4 ) cl~c~r,,,~l O0 10 4 A l , ( 5 ) ¢ / . = 2 0 0 10- ~ AX-i-ctx~l,~ = I (X) I 0 - ~ A! F i g 6 Effect o f , , h a k m g t m l e o n e x t r a c t i o n o f t r o n ( l l l ) f r o m h g J n d b u f f e r ,,oluttc~n m t h e p r e , , c n c e of 0050 M p-pl'ienylphenol cry---g00 I0 -~ M ¢z,,-----200 I0 ~ M . tt~c,r,x=lOO I 0 - " M . r u e , = I O0 I 0 - ' M F x l r a c t J o r l t t m e ( l ) 20 m t n . ( 2 ) 4.5 m m
372
! KOJIMA,
M TANAKA
t h e u m e n e c e s s a r y for c o m p l e t e e x t r a c t i o n o f v a n a d , u m f r o m t h e h g a n d buffer s o l u t i o n b e c o m e s l o n g e r t h a n t h a t f r o m the s o l u u o n c o n t a i n i n g n o m a s k i n g a g e n t . A s h a k i n g t , m e o f 45 rain sufficcs for a l m o s t c o m p l e t e e x t r a c t m n o f v a n a d m m a n d the p H r a n g e for c o m p l e t e e x t r a c t i o n is 2 7-3.6. T h e b a c k - w a s h i n g o f t h e e x t r a c t with the Z n - D C y T A s o l u u o n o f p H 2.8-3.5 c a u s e s n o v.'trmt,on o f t h e absorbance of the extract B e l o w p H 3 2. o n l y a small a m o u n t o f w o n ( I l l ) ( < 0 5",,) is e x t r a c t e d into b e n z e n e flora t h e Z n - D C y T A s o l u t m n m the presence of p-phcnylphenol. The e x t r a c t i o n o f iron i n c r e a s e s w , t h , n c r e a s , n g s h a k i n g t i m e ( F i g . 6). T h e s a m e results for the e x t r a c t i o n a n d b a c k - w a s h i n g o f v a n a d m m a n d w o n c o m p l e x e s w e r e o b t a i n e d with d , c h l o r o e t h a n e i n s t e a d o f b e n z e n e as solvent. Cahbrat~o, curves/or
vanadium T h e c a l i b r a t i o n c u r v e for v a n a d , u m o b t a , n e d b y the p r e s e n t m e t h o d is g i v e n ,n Fig. 7. C a l i b r a t i o n c u r v e s o f o t h e r m e t h o d s with 8 - q t , , n o l , n o l a r e given for c o m p a r i s o n . As is e w d e n t f r o m Fig 7. the p r e s e n t m e t h o d ~s t h e m o s t s e n s , t w e o n e with 8 - q u , n o h n o l R e a c t s o n of v a n a r h , t m 8 - q , ~ m o l m o l a t e w t t h t,artous ne,~tral org(o.c stcbst¢mce.s As m e n t i o n e d b y B u s c a r o n s et al. II a n d b y B l a i r et al to 12. v a n a d i u m
8 - q u m o l i n o l a t e r e a c t s with m a n y n e u t r a l o r g a n m s u b s t a n c e s to form t h e c o r r e s p o n d i n g a d d u c t o r e s t e r in t h e o r g a n i c s o l v e n t s . T h e s e r e a c t , o n s are g w e n schematmally as follows: RNItz
VOOxzOH" HzNR (acid-base reaction) VOOxzOR (esterlficatlon) VOOx2OH HOOCR (at,d-base react,on) VOOxzOH HOt/, ( a c i d - b a s e r e a c t i o n ) VOOxzOH. HOx (acid-base reaction) VOOxzOH. HzN4, (ac,d-base reaction)
ROll RCOOH
VOOxaOH
-
-
,~oH ltOx 4,NH:
1 D
5 08
i °°
2
0 4
1
0 2
2
t,
6 B 10 _ 12 Vanadium 10-5M F , g "7 C d h b r a t l o n c u r v e s ( I ) ! 0 0 10 - 2 M H O x at 550 a m , ( 2 ) 1130 10 - 2 M H O x + 2 0 M cdprlc a c i d a t 550 n m , ( 3 ) 1 0 0 10 - 2 M H O x + O I 0 M o c t d n o l ,at 4 7 0 n m , ( 4 ) 0 5 1 M H O x at 550 n m , (5) I 00 10-' M HOx+0050 M p.phenylphcnol .,t 620 n m
EXTRACTION-SPECTROPHOTOMETRY
373
OF VANADIUM(V)
A c i d i c o r g a m c s u b s t a n c e s react with the V = O g r o u p m the v a n a d m m 8 - q u m o iinolate to form the c o r r e s p o n d i n g a d d u e t , g w i n g r~se to a b a t h o c h r o m i c effect. w h e r e a s a m i n e s react with the V - O H g r o u p m the s a m e c o m p l e x to f o r m an adduct, p r o d u c i n g a h y p s o c h r o m l c effect. F o r the v a n a d m m c o m p l e x e s o f the other reagents, e . g . f l - l s o p r o p y i t r o p o l o n e , b e n z o y l p h e n y l h y d r o x y l a m i n e ( B P H A ) , maltoi, etc., s l m d a r p h e n o m e n a w e r e o b s e r v e d . T h e s e p h e n o m e n a will be reported e l s e w h e r e ~9. R e c o v e r y o f vanadnun tn the pre.sencv oJ t r o n M a n y metal i o n s are extracted under the present e x p e r i m e n t a l c o n d i t i o n s , but o n l y the interference o f l r o n ( l I I ) w a s e x a m i n e d . T h e analytical results of v a n a d m m m s y n t h e t i c c o m p o s i t e samples, m which the c o n c e n t r a t m n o f ~ron w a s v a n e d to a b o u t 100 times as high as that o f v a n a d i u m , are s h o w n m T a b l e If. As can be seen, satisfactory, rehable, and r e p r o d u c i b l e results for the r e c o v e r y o f vanadmm were obtained. Applicatzon to analysts o / s d t c a t e s T h e analytlcal results for v a n a d t u m m standard silicate rock s a m p l e s , t e
U S G S - B C R - I (Spht 56), U S G S - W - I , U S G S - P C C - I (Spht 1), U S G S - G - 2 (Spht 75), G S J - J B - I (Split 2), G S J - J B - I (Split 1) are s h o w n m T a b l e III. T h e s e v a l u e s are m r e a s o n a b l y g o o d a g r e e m e n t with t h o s e o b t a i n e d by D o n a l d s o n z°. F l a n a g a n 2~, A k a t w a et al zz, and A n d o et al. za EXPERIMENTAL
Retl~ellt.~
All the reagents
used
wele
of G.R
grade
Benzene, d i c h l o r o e t h a n e ,
T A B L E !i RECOVERY Vamtdmm
OF VANADIUM
IN T H E
PRESENCE
I r o n pre~enr
tal, e n
( l~
(mg )
OF IRON(Ill)
Vamtdmm /ound (l~fl)
Betl~.Ottt, (l~ ~oh l i l t
54 5
0 2 24 4 49 6 73
1363
Dtchlorovtluuw 545
1363
a..
54 54 54 55
5 7 54 3 3, 54 8 5
0 224 449
1363 1361. 1 3 6 0 135 7. 1 3 6 0
0 4 6 0 4 6
54 54 54 136 136 135
~oh v n t 49 73 49 73
5 8 2 3 1 8
p-
374 TABLF
I Kf)IIM;~
M TANAKA
II1
ANALYTICAl ~'amph,
RE~;UI.TS OF a anathum
U S C I S - B C R- I USGS-W- I USG~;- PCC - I U~JGS-G.2
VANADIUM
IN SI'ANDARD
SILIC'ATL
(p p m )
[JOlltlld~t ll" ~
I'hllltltltll121
420. 424 _7_ " "~ 274 22 2a ;~ 5 35 ~;
399 264 3() ~5 4
|AIIII~I! L'I Ill 22
GSJ-IIJ-I
178 _+74
GSI-IG-I
2~';-4- I I
" Obt,nned
ROCKS
| l l d l l t'l Ill 2~
2111) 3O0 25
21
PII'S('III I l l l , t h o d
41 t) 274 ~1 a4 ~'~ 227" ._4 29
b ) t h e ~t,tntl,~rd , t d d H r o n n l e a h o d
p h c n y l p h c n o l , un"lmonRam met.'lvanada1,e, p e r c h l o r t c dcad. s o c h u m a c e t a t e . D C y T A . a n d a n h y d r o u s ~ o d m m c q r b o n a t c w e r e o b t a i n e d flora W a k o P u r e C h e m i c a l Co.. O s a k a . J a p a n . B e n z e n e w a s first s h a k e n w n h c o n c e n t r a t e d ,,ulfurac acid a n d t h e n successively w n h w a t e r , d i l u t e s o d m m h y d r o x i d e solutaon, w a t e r , d d u t e h ~ d r o c h l o r l c acad solu1,]on, a n d fin,'dly wa1,h w a t e r 5 tm~cs a n d s1,oTcd w i t h o u t d e h y d r a t i o n D t c h l o r o e t h a n e w a s samalarly trca1,ed a n d s t o r e d w a t h o u t d e h y d r a t t o n p - P h e n y l p h e n o l a n d 8 - q u l n o l m o l w e r e l e c r y , , t a l h z e d from a q u c o u s e t h a n o l S o d m m a c c t a l e w a s r e c r y s t a l h z c d f r o m wnter a n d s t o r e d o v e r sdaca gel Z m c - D C y T A Iig.'md buffer s o l u t a o n wus p r e p a r e d by m i x i n g equ,'d v o l u m e s o f zinc ( 4 0 0 10--" M) a n d DCyTA (200.10-: M)solt,1,aons. S t a n d a r d v a n a d i u m s o l u t i o n ( 5 3 3 5 10 -'~ M ) w a s p r e p a r e d by d i l u t i n g a s t o c k s o l u t a o n ~ t a n d a r d J z e d g.ravunetracally a n d 1,1trlmctncally. l r o n s o l u t J o n ( I 013 10--" M ) w a s p r e p a r e d by d a s s o l v m g 4 ( ) l . 2 m g o f F e z O ~ ( S p e c P u r c ) an 500 ml o f d d u t e h y d r o c h l o a a c aczd s o l u t i o n a n d w~ls s t a n d a r d i z e d ~agam,,1, s t a n d a r d E D T A ~olutaon x~ath the C u Y - T A R ]ndJca1,or ,,ystem 2.' B c n z c n c ~ o l u t l o n s of p - p h e n y l p h e n o l (0 05 M ) a n d 8 - q u m o l m o l ( 0 0 1 M ) wcrc used ~ . ~ l i ( . J l ' ( l l p l 0 £ edlll'(?~
All e x p e r i m e n t s w e r e c a r r i e d otl1. in a r o o m t h e r m o , , m t e d ,11, 254- I C T h e im1,ml v o l u m e o f t h e d q u e o u ~ a n d o r g a n i c p h a s c s was a l w a y s 25 mi except for thc e x t r a c 1 , J o n - p h o t o m e t r m d e t e r m i n a t i o n o f v a n a d m m m the prc~cnce o f iron a n d m s d l c a t c rock~ (aq ' o r g = 5 0 25) T h e anatlal c o n c e n t r a u o n o f v a n d d m m m the s y s t e m w a s below i 5 10 -'~ M n n d t h e Ionic s t r e n g t h o f thc a q u e o u s p h a s c w~m kept c o n s t a n t at O ! M ( N a . H ) C I O . ~ e x c e p t for t h e extrac1,aon--photometr]c d e t e r m i n a t i o n o f vanadatan'! T h e a q u e o u s , m d organac p h a s e s w e r e c o n t a c t e d an a s e p a r a t o r y funncl, a recaprocaUng s h a k e r ( 2 0 0 - 2 5 0 ~1,rokes per anm) being used After t h e cquflabrat~on, thc p H o f the a q u e o u ~ s o l u u o n w a s m e a s u r e d wlth a R a d i o m e t e r t y p e P l q M 22 pH m e t e r V a n a d m m m thc o r g a m c p h a s e w,~m m e a s u r e d p h o t o m e t r i c a l l y with ;~ B e c k m a n D U o r S h n ~ a d z u Q V 50 s p e c t r o p h o t o m e t e r Jn 10-ram sahca cell,, T h e a b s o r b a n c e was read at 620 n m a g a i n s t b e n z e n e T h e a m o u n t s o f v a n a d m m were e v a l u a t e d by c o n s u l t i n g t h e cal~bratlon c u r v e previously constructed
375
EX F R A C T I O N - S P E C T R O P I I O ' I OME'I !~,5 O F V A N A D I U M ( V )
DL~IC~I'IlllIICIllOll o / tLlll(ldllllll III '~l(llldtltd I't]ul~ ~¢llllple~ F u s e I g of ,,t,mdard ~ock ~dmple ~ t h 5 8 g of a n h y d r o u ~ ~ocl~ttm c a r b o n a t e tn a p l d t m u m crt.c~ble m the U,,udl w a ) After c o m p l e t e decornpc~,.,~lton. alloy,
to c o o l .
add
hot
water, and
cru,.,h ~ n d
gnnd
the c a k e
wtth
d fldttened
glass rod R e d u c e m a n g a n ~ , t e b~ ;|(.Idmg 2 drop.,, of e t h a n o l , filler t h r o u g h a m e d t u m - t e x l u r e pdper, d n d finally ~d,,h the ~e,,~dt.e well x~tth hot I".. (w ~) s o d i u m c a r b o n a t e ,,olut~on Dflulc the fiitrdte wHh x~dter to 100 ml m ,i v o l u m e t r t c fldsk Ptpe! !0 ml o f the s o l u t i o n thu,, p r e p a r e d i n t o d iO0-ml , , e p a r d t o r y funnel. a d d I0 rnl o f Z n D C y T A s o l u t t o n a n d I0 ml o f 0 0 5 M ~ o d m m d c e t d t e ~olt|tlon A f t e r a d j t ' ~ l t n g the p H to 2 8 3 I xgRh I AI p e t c h l o n c dcld ~olut~on. follow the r e c o n , , n e n d e d p r o c e d u r e below R~"( O l l l l ? l e l l d £ ' d p l ' o £ £ ' d l l l c"
Place 50 ml o f tc,,t s o l u t i o n c o n t d t r t l n g le',', t l l a n 150 Hg o f v d n a d J u m :]nd n o m o r e t h a n 8 m g o f it on m a .,,cparatory f u n n e l A d d 15 ml o f ,R d d u t c d Zn-DCyTA ,,olutlon contu]nmg 200 I0-' AI / m e a n d I 0 0 I 0 -~ M D C y T A .
a n d a d j u s t the p H o f the ,,olut]on to 2 8 3 2 wHh s o d i u m a c e t u t e Extrdct for 45 m m with 25 ml o f a 0 0 1 A! b c n z c n e s o l u t m n o f 8 - q u m o l m o l c o n t a t m n g 0 0 5 AI p - p h c n y l p h e n o l . After d e h y d r a t i o n o f the o r g a m c p h a s c w~th pur:ficd a n h ) d r o u q s o d m m sulfate, read the d b , , o r b a n c e at 62(.) n m agu]n,,t b c n z e n e F s t d b l m h the vanadR~m c o n c e n t r a t i o n from a c a l l b r , l t m n c u r v e p r e v m u s l y c o n s t r u c t e d in t h e a b s e n c e o f Hon the ,Idd~tlon o f the l t g a n d bt, ffcr m a y be o r n l t t c d a n d the e x t r d c t l o n ~ -Itianttlttt~,c oxer a v~dct p H range. ~e 3 0 4 5 F m a n c m l s u p p o r t from the M,m.~try o f E d u c d t m n ( J a p a n ) r, gr~lteft, lly a c k n o w l e d g e d O n e o f us (l K ) w o u l d like to t h d n k P r o f C ildd o f N a g o y a I n s t i t u t e o f T e c h n o l o g y for hi,, tntere,,t in thP, ~ o r k SUMMARY
V q n a d m m ( V ) 8 - q u m o l l n o l a t e reacts wwth phenol.,, to form d i I d(IdlttOl~ c o m p o u n d in o r g a m u s o l v e n t s E n h a n c e d ¢xtt dCtlon Of v d n a d l t l l T i 8-qumc, l m o l a t e m t h e p r e s e n c e of p h c n o N can be a c c o u n t e d for tn t e r m s o f the f o l l o w i n g re,tctton: V O O x 2 O H , , r . + A r O H , , ~ , ~ - ' V O O x : O H ArOi-I,,,. O n the bast~ o f the b a t h o c h w o m l c effect o f p h e n o l s a n d the hzgh m o l d r :~b.,,otpt~vtty o f the c o m p l e x f o r m e d , a sem, tttve m e t h o d for the e x t r a c t | o n - p h o t o m c t r | c d e t e ~ m m a t m n o f v a n a d i u m has been d e v e l o p e d T h e a n a l y t , c a l results for vd,md~um ~n the s t a n d a r d stl,cate rock,,. U S G S - B C R - I , U S G S - W - I , U S G S - P C C ' - i . U S G S - G - 2 , GSJ-JB-1. and G S J - J G - I . a g r e e d well w , t h the d a t a r e p o r t e d prev,ou~ly REFERENCI.S
I H E Jungn,~kcl dnd W K l m g c r , Z Dud Clwm 203(1964) 257 206(1964) 275 2 N K t l r m , l t d h D S,Ityandtdy,m,t dnd V P,mdt, Rdngd Rdo l ' a h m t t l 14 ( 1 0 6 7 ) 4 9 5 ,rod pdper~ cRed thereto 3 M T , m d k d dnd I K o j , m a . d I n o m l Nl#t I ( hvm 29 (1967) 1769 4 H K , i w , l m o t o ,in(:l H A k d t w d , Nil~pon Kaool, u Ztl~sht 9 4 ( 1 9 7 3 ) 90 5 N V Shdkhov,t. I P A h m a r m dnd ~t, A Zoloto~,. I)oI, I ,ll, a d N a u l , SSSR 152(1963) 1,184
376 6 7 8 9 10 II 12 13 14 15 16 17 18 19 20 21 22 23 24
I KOJIMA.
M TANAKA
T V Healy. Solvent Eztractlon Claemi~try. N o r t h - H o l l a n d . A m s t 0 r d a m . 1967. p 119 R A A l e k p e r o v and N N M a k o v , Z h Ailal K h l m . 23 (1968) 460 Yu A Z o l o t o v . Dokl Akad Nauk S S S R . 180(1968) 1367 N. Nakasuk,i, Y M i t s u o k a and M T a n a k a , J Inorft Nucl Ch em . 36 (1974) 431. N N a k a q u k a . T [to and M T , m J k a . Chem Lett..(1973) 553 A J Blair. D A P a n t o n y a n d G [ Mmkoffo J Itlorff Nucl C h e m . 5 (1958) 316 F Buscarons. J L M a r m a n d J C l a v e r . Anal Chlm Acta. 3(1958) 310 A J Bl:ur a n d D A P a n t o n y , Anal Chim Acta. 13 (1955) I A J Blaw atnd E B~.,.~r. Ju~tz~ Liebtg~ Ann. Chem. 6 8 4 ( 1 9 5 3 ) 96 ] M K o r c n m a n . V G G a m n a , G R B a r a n c h ] k o v a and V I Z y u z m d . Tr Kh#m Teldmol. (1969) 124, C h e m A b ~ t , 7 4 ( 1 9 7 1 ) 9 4 1 8 c M T a n a k a a n d I K o j i m a , Ancll Clffm A c t a . 36 (1966) 522 O Budovsky a n d R Prtbtl. Tala,ta, II (1964) 1313 O Budovsky a n d L J o h n o v a . Ttdaslta. 12 (1965) 291 M T a n a k a a n d N. Awata, Anal Cinm Acta, 3 9 ( 1 9 6 7 ) d85 I Kojima. to be pubi.shod E M D o n a l d s o n . TcJlanta. 17 (1970) 583 F. J F l a n a g a n . Geocisim Cosnaochma Acta. 37 (1973) 1189 H Akalwa. H K a w a m o t o a n d H K o n d o . BLm~eki Kagak,. 23 (1973) 402 A Ando. H K u r a s a w a . T O h m o r t and E Taked:l. Geothem J . 5 ( 1 9 7 1 ) 151 H Yamdda. T M a c d a and ! Kojzma. Anal C'llim Acta. 7 2 ( 1 9 7 4 ) 426