A C T A U N I V E R S I T A T I S L O D Z I E N S I S
__________ FOLIA CHIMICA 1 , 1982.
J o a n n a M asłow ska, Wacław Z a k rz e w sk i CHROMATOGRAPHY OF CHELATE METAL COMPLEXES,
V. COMPLEXES OF F e ( l I I ) , C r ( I I I ) AND A l ( l I I ) WITH VIOLET R*
A new m ethod o f c h r o m a to g ra p h ic p a p e r s e p a r a t i o n o f a m ix tu r e o f i o n s F e ( l l l ) , C r ( l l l ) and A l ( l I I J h a s b een e l a b o r a t e d w ith th e u s e o f d i f f e r e n c e s o f ^ o m p le x o g e n ic p r o p e r t i e s o f v i o l e t R i n r e s p e c t o f t h e p a r t i c u l a r i o n s . O rg a n ic d y e s t u f f s a r e o f t e n u s e d I n c h e m ic a l a n a l y s i s a s c o m p le x o m e tric i n d i c a t o r s [ 1 - 3 ] . T h ese s u b s t a n c e s a l s o h av e a s p e c i a l m eaning i n p h o to m e tr ic d e t e r m i n a t i o n o f m e ta ls w h ich do n o t h ave any ch ro m o p h o re p r o p e r t i e s . The r e a c t i o n s o f d y e s w ith i o n s o f m e ta ls w i t h ch ro m ophore p r o p e r t i e s a r e o f t e n l e s s s p e c i f i c , A c c o rd in g t o some a u t h o r s [ 4 ] , th e f o r m a tio n o f a dye co m p lex w ith m e ta l c a t i o n i s o f t e n a n a lo g o u s t o t h e f o r m a tio n o f an a d d i t i o n a l auxochrom e i n t h e c o m p lin g c h a i n . S a n o [ 5 ] i n v e s t i g a t e d th e p ro b le m o f t h e s p e c i f i c i n f l u e n c e o f p a r t i c u l a r ® e ta l i o n s on t h e s h i f t o f t h e dye a b s o r p t i o n b a n d . I n many c a s e s th e p ro b lem o f t h e a b s o r p t i o n ban d s h i f t t u r n e d o u t t o b e com plex s i n c e o f t e n I t i s n o t t h e f r e e m e ta l i o n s t h a t r e a c t b u t t h e i r h y d r o l i z e d fo rm s [ 6 ] . Azo d y e s e g . d e r i v a t i v e s o f s a l i c y l a c i d do n o t c h a n g e t h e i r c o l o u r d u r in g t h e f o r m a tio n o f c o m p le x e s w ith a lu m in iu m i o n s . S e a r c h in g f o r f u r t h e r *[11] c o n d i t i o n s o f c h r o m a to g ra p h ic s e p e r a t i o n o f a m ix tu r e o f i o n s F e ( I I I ) , C r ( I I I ) an d A l ( I I I ) we lu o k e d c l o s e r a c t a c i d azo -d y e s o f t h e o , o '- d i h y d r o x y a z o '
* The work h a s been c a r r i e d o u t w i t h i n t h e r e s e a r c h P ro b lem M R -I-1 4 .
s y s te m . E r io c h r o m ic b l a c k T a l s o b e lo n g s t o t h i s g ro u p o f d y e s a n d i s u s e d a s an i n d i c a t o r i n c o m p le x o m e tric m eth o d s [7] a n d i n s p e c tr o p h o tome t r i o d e t e r m i n a t i o n o f m a g n e s i u m d l ) [ 8 , 9 ] , Wa w r z y n ia k [ 1 0 ] e l a b o r a t e d a m ethod o f f o r m a ti o n o f s t a b l e com p l e x e s on f i b r e s o f su c h d y e s w i t h C o ( I I ) , C u ( I I ) , N i ( I I ) an d C r ( l I I ) . T h ese c o m p le x e s a r e fo rm e d o n ly a t i n c r e a s e d te m p e ra t u r e . The o .o '- d ih y d r o x y a z o s y s te m i s n o t c h a r a c t e r i s t i c f o r A l ( I I I ) , b u t f o r F e ( I I I ) b u t th e s e c o m p le x e s a r e n o t w e ll known. One c o u l d e x p e c t a b i g d i f f e r e n c e i n t h e c o m p le x a tio n o f t h r e e i n v e s t i g a t e d m a ta l i o n s w it h a o ,o - d i h y d r o x y a z o - d y e an d h e n c e t h e s u i t a b i l i t y o f su c h dye3 f o r c h r o m a to g r a p h ic s e p a r a t i o n o f i o n s : F e ( I I I ) , A l ( I I I ) an d C r ( I I I ) . A dye c a l l e d v i o l e t R, w i t h f o r m u la ( 1 ) , was c h o s e n f o r i n v e s t i g a t i o n s . OH HO HNS02 --N«N- / x ( 1 ) SOjH SOjH T h i s dye i s o b t a i n e d by d i a z o t i z a t i o n o f a 2 -a m in e p h e n o le - - 4 - c h l o r o - 5 - s u l p h o n n e t h y l a m i d e an d c o u p l i n g w i t h t h e 1 -N -p h e n y - l s u l p h o n y l o a m i n e - 8 - h y d r o x y n a p h ta l e n e - 3 ,6 - d i s u l p h o n i c a c i d . T h is d y e w as o b t a i n e d i n t h e I n s t i t u t e o f F i b r e P h y s ic s a t t h e P o - l y t e c h n i c a l U n i v e r s i t y o f Ł ó d ź . . I n t h i s p a p e r we e m p h a siz e d d i f f e r e n c e s i n t h e c o m p le x o g e n ic p r o p e r t i e s o f v i o l e t R' i n r e l a t i o n t o F e ( I I I ) , C r ( I I l ) an d A l ( I I I ) i o n 3, v a r i o u s c o n d i t i o n s o f t h e f o r m a ti o n o f c o m p le x e s a n d t h e i r d i f f e r e n t p r o p e r t i e s an d th e n w.e to o k a d v a n ta g e o f t h e s e d i f f e r e n c e s i n t h e p a p e r c h r o m a to g r a p h ic s e p a r a t i o n o f t h e m ix tu r e o f i o n s . E x p e r im e n ta l The b a s i c i n s t r u m e n t s , r e a g e n t s an d m etho d o f i n v e s t i g a t i o n s h a s b ee n d e s c r i b e d e a r l i e r [ 1 1 ] . F o r p H - m e tr ic an d s p e c
-tr o p h o t o m e t r l c i n v e s t i g a t i o n s we a l s o u s e d s o l u t i o n s o f s u l p h a t e s o f a lu m in iu m , i r o n an d chromium w ith t h e M e ( I I I ) c o n c e n t r a t i o n ■ 1 x 10“ 4 m ole.dm ” ^ an d t h e r a t i o MesL ■ 1 : 1 . F o r chrom a t o g r a p h i c i n v e s t i g a t i o n s we u s e d s o l u t i o n s o f th e. c o n c e n t r a t i o n 1 x 1 0 "2 m o le.d m "^ M e ( I I I ) and t h e r a t i o M e ( I l l ) : L « 1 : 1 . Du r i n g i n i t i a l i n v e s t i g a t i o n s we u s e d s o l v e n t s com posed o f w a te r an d m e th a n o l o r e t h a n o l and o f w a te r an d a c e t o n e a s w e ll a s p u r e w a t e r . A queous s o l u t i o n o f NaCl o r a q u e o u s s o l u t i o n o f NH.OH a r e o f t e n u s e d a s d e v e lo p in g s y s te m s i n p a p e r c h ro m a to g ra p h y f o r t h e s e p a r a t i o n o f d y e s u s e d f o r f o o d s t u f f s an d c o s m e t i c s [ 1 2 ] . Vhatman n r . 2 an d F l l t r a k 390 p a p e r s w ere u s e d a s c a r r i e r s . Sram ek [ 1 3 ] s u c c e s s f u l l y u s e d F i l t r a k p a p e r i n t h e s e p a r a t i o n o f d i r e c t d y e s . I n f o r m e r p a p e r [ 1 4 ] we a l s o o b t a i n e d s u c c e s s f u l l s e p a r a t i o n r e s u l t s u s i n g F i l t r a k 339 p a p e r . R e s u l t s an d d i s c u s s i o n C h a r a c t e r i s t i c f e a t u r e s o f c o m p le x e s f o rmed i n t h e s y s te m s : M e ( l I I ) - V i o l e t R-H20 U s in g t h e m ethod o f p H -m e tr lc t i t r a t i o n we s t a t e d t h a t c o l o u r e d c o m p le x e s a r e fo rm e d i n th e s y s te m s : F e ( I I I ) - V i o l e t R-HgO a n d A1 ( I l l ) - V i o l e t R-HpO. I n t h e f i r s t s y s te m w i t h i n t h e piH r a n g e o f 1 , 0 - 2 , 0 a r e d - v l o l e t co m p lex i s fo rm e d an d a t h i g h e r pH v a l u e s a v i o l e t - g r e y co m p lex i s fo r m e d . I n t n e se c o n d s y s te m w i t h i n t h e pH r a n g e o f 3 , 5 - 7 a b l u e - v i o l e t com plex i s fo rm e d an d a t h i g h e r pH v a l u e s a b l u e co m plex i s fo r m e d . T a b le T g i v e s c o l o u r s o f t h e s o l u t i o n o f t h e dye i t s e l f an d o f fo rm e d c o m p le x e s d e p e n d in g on th e s o l u t i o n p ti. Tne s o l u t i o n o f t h e dye i t s e l f a s w e ll a t t h e s o l u t i o n o f t h e d y e I n p r e s e n c e o f C r ( l I I ) a c t i n t h e same w ay . I t m eans t h a t o n ly C r ( I I I ) d o e s n o t form c o m p le x e s w i t h v i o l e t R a t room t e m p e r a t u r e . T h e se o b s e r v a t i o n s a r e c o n f ir m e d by r e c o r d e d a b s o r p t i o n s p e c t r a shown i n F i g . 1 an d c n a r a c t e r l s t i c b a n d s g iv e n i n T a b le 2 . From t h e s e b o n d s i t f o l l o w s t h a t F e ( I I I ) c o m p le x e s h av e tw o b a n d s i n t h e v i s i b l e r a n g e - A80 an d 625 n m ), and A l ( l l l ) co m p le x e s max . , . one b o n d a t 5^0 nm. The s p e c tr u m o f t h e C r ( I I I ) sy s te m h a s t h e cai-ie p o s i t i o n a s t h e s p e c tru m o f V i o l e t R . The s t a t e d s h i f t s o f
T a b l e 1 / T he i n f l u e n c e o f s o l u t i o n pH on t h e c o l o u r o f v i o l e t R an d o f i t s c o m p le x e s w it h m e t e l s . C o n c e n t r a t io n o f M e ( I I I ) ■ 1 x 1 0 '4 M/dm3; C o n c e n t r a t i o n o f d y e - 1 x 1 0 - i M/dm3; M e ( I I I ) : L • 1 s 1 S o l u t i o n pH C o lo u r o f s o l u t i o n v i o l e t R v i o l e t R ♦ F e ( I I I ) v i o l e t R ♦ C r ( I I I ) v i o l e t R ♦ A l( I I I ) 1 -2 r e d r e d - v i o l e t r e d r e d 2 - 3 , 5 p in k v i o l e t - g r e y p in k p in k 3 -4 p in k n « b l u e - v i o l e t 5 -6 b lu e H b l u e n 7 - 8 ft If b l u e ♦ g re e n b l u e d e p o s i t 8 -9 H tf H N 9 -1 0 W « W * T a b l e 2 S p e c i f i c a t i o n o f ¡\-max v a l u e s an d o f m o la r c o e f f i c i e n t o f a b s o r p t i o n E f o r s o l u t i o n s i n s y s te m s : M e ( I I I ) - v i o l e t R-H20 . Dye c o n c e n t r a t i o n • 1 x lO"11 M/dm3; M e ( I I I ) co n c e n t r a t i o n ■ 1 x 10~A M/dm3; pH - 3 , 5 ; 1 - 1 cm S y stem V i s i b l e r a n g e UV r a n g e ''•max. no S 2 4 (cm • m ole ) X max. nm E 2 A (cm • m o le“ ) V i o l e t R 520' 7 . 9 x 103 230 8 . 8 x 103 240 8 . 4 x 103 315 5 .0 x 103 V i o l e t R - C r ( I I I ) 520 7 . 7 x 103 230 9 . 6 x 103 240 9 . 2 x 103 315 5 . 2 x 103 | V i o l e t R - A l ( l I I ) 540 7 . 8 x 103 210 1 2 .8 x 103 240 9 . 2 x 103 ,315 4 . 8 x 103 V i o l e t R - F e ( l I I ) 480 5 . 2 x 103 225 1 2 .2 x 103 625 1 .4 x 103 240 1 2 .6 x 103 320 5 . 6 x 103
1 - v io le t- R 2 - Fe(lll) ♦ violet-R X [nrn] A. [nm J F i g . 1 . A b s o r p tio n s p e c t r a o f s o l u t i o n s i n t h e s y s te m M e ( I I I ) v i o l e t R - H jO . C o n c e n t r a t io n [M e3* ] » [ v i o l e t R ] - 1 x 1 0 m o le - • d a '3 C u rv e s : 1 - v i o l e t R; 2 - F e ( I I X ) ♦ v i o l e t R; 3 - A K I I I ) ♦ ♦ v i o l e t R; U - C r ( I I I ) + v i o l e t R a b s o r p t i o n b a n d s b o th i n t h e v i s i b l e r a n g e an d i n t h e UV r a n g e i n t h e c a s e o f F e ( I I I ) and A l ( I I I ) a s w e ll a s t h e l e e k o f t h e s e s h i f t s i n t h e c a s e o f Cr I I I a llo w to - p re su m e t h a t F e ( I I I ) an d A l ( I I I ) » form c o m p le x e s w ith V i o l e t R an d C r ( I I I ) d o e s n o t fo rm c o m p le x e s w i t h t h i s r e a g e n t i n t h e s e c o n d i t i o n s . C om plex r e a c t i o n s o f F e ( I I I ) an d A l ( I l t ) w ith v i o l e t R c a n be r e p r e s e n t e d by t h e f o ll o w in g e q u a ti o n : MeOH2* + H2R2’ « [(MeOH)CHR)]” ♦ rf* The s t r u c t u r e o f c o m p le x e s [(M e0H )(H R )] fo rm e d u n d e r su c h
c o n d i t i o n s w i t h t h e c o m p o s itio n Me s L - 111 c a n b e shown by s t r u c t u r e 2 .
C h ro m a to g ra p h ic s e p a r a t i o n o f a m ix tu r e o f i o n s F e ( I I I ) , C r ( I I I ) and A l ( I I I ) fro m an e n v iro n m e n t c o n t a i n i n g v i o l e t R I n i n i t i a l e x p e r im e n ts we u s e d m ixed s o l v e n t s com posed o f w a te r a n d m e th a n o l o r e t h a n o l and o f w a te r and a c e t o n e o b t a i n i n g c h r o m ato g ram s w ith s u p e r p o s e d z o n e s o f a l l t h e t h r e e io n s * Much b e t t e r e f f e c t s a r e o b t a i n e d u s in g a s a d e v e lo p in g s y s te m w a te r w ith
P i 2 . 2 . P l o t s o f v a l u e s o f c o e f f i c i e n t s ftp »for M e ( I Ï I ) . c o m p le x e s w it h v i o l e t ft a s f u n c t i o n o f s o l u t i o n pH. D e v e lo p in g s y s t e m : t HjO + HC106 o r NaOH; P a p e r : a - Whatman no 2 ; b - F i l t r a k n o ’
a p r e d e t e r m i n e d pH a d j u s t e d w ith an a d d i t i o n o f HCIO^ o r NaOH. C om p arin g r e s u l t s shewn i n F i g . 2 c a n n o t i c e t h a t when u s i n g F i l t r a k 390 p a p e r t h e c o e f f i c i e n t s Rp f o r c o m p le x e s o f F e ( l I I ) ^ w it h i n t h e pH r a n g e c f 4 - 1 0 ) h a v e c o n s i d e r a b l y lo w e r v a l u e s th a n when u s i n g Whatman p a p e r no 2 . B a s id e s t h e z o n e s o f i o n s o b t a i n e d on t h i s p a p e r h e v e more r e g u l a r s h a p e s an d s h a r p e r o u t l i n e s . Hence i t was a c k n o w le d g e d t h a t F i l t r a k p a p e r no 390 g i v e s b e t t e r e f f e c t s o f v a r i a t i o n s o f tn e s p o t s . D a ta from F i g . 3 show t h a t i n th e p r o c e s s o f o n e - s t a g e d e v e lo p i n g , u s i n g w a te r a s t h e s o l v e n t , one c a n s e p e r a t e Fe from C r ♦ A1 a t pH 2 - 3 , e n d C r fro m F e ♦ A1 a t p:i - 4 . Tne e x p e r im e n ts a llo w e d t o a ssu m e t h a t u s i n g a t w o - s t a g e p r o c e s s o f c h ro m a to g ra m d e v e lo p m en t i t w ould be p o s s i b l e t o s e p a r a t e a l l t h r e e i o n s . B a s in g on t h e f a c t s t h a t A l ( I I I ) fo rm s a co m p lex w ith v i o l e t R a t PH ■ 3 ,5 an d F e ( I I I ) a l r e a d y a t pH * 1 , and C r ( I I I ) a t room t e m p e r a t u r e p r a c t i c a l l y d o e s n o t fo rm a co m p lex w i t h t h i s dye an d t h a t c o m p le x e s o f v i o l e t R w i t h A l ( I I I ) a n d F e ( I I l ) h av e s i m i l a r c a r o m a to g r a p h ic p a r a m e t e r s ( F i g . 3) we th o u g h t t h a t t h e 0 6
a
6F
© M F eF i g . 3 . C h rom ato gram s o f a m ix tu r e o f i o n s F e ( I I l > , C r ( I I X ) and A l 'v l l l ) i n t h e p r e s e n c e o f v i o - l e t R o b t a i n e d i n one - s t a g e d e v e l o p i n g s y s te m . F i l t r a k p a o e r no 390, o t h e r c o n d i t i o n s a s p e r
u s e o f a s o l v e n t o f pH s m a l l e r t h a n 3 , 5 i n t h e s e c o n d s t a g e o f d e v e lo p in g s h o u ld c a u s e t h e f r e e i n g o f A l ( I I I ) fro m t h e 'c o m p le x a c c o r d i n g t o t h e e q u a ti o n : [(MeOH)HR]" + H* --- ► MeOH2* ♦ H2R2' an d e n h a n c e i t s m i g r a t i o n i n r e l a t i o n t o t h e co m p lex bound i r o n . E x p e r im e n ts f u l l y c o n f ir m e d t h i s a s s u m p tio n . S am p les o f s o l u t i o n c o n t a i n i n g s a l t s o f I n v e s t i g a t e d m e t a l s a n d v i o l e t R, w ith pH » 4 w ere p l a c e d on p a p e r an d u n d e rg o t o d e v e lo p m e n t u s i n g s o l v e n t o f pH ■ 4 . D u rin g i n i t i a l c h ro m a to g ra p h y w e ll v i s i b l e z o n e s o f t h e A l ( I I I ) com plex a n d o f t h e F e ( I I I ) com p lex w ere s l i g h t l y s h i f t e d a p a r t an d t h e i n v i s i b l e C r ( l I I ) zo n e was s e p a r a t e d fro m th e m . The p r o c e s s o f i n i t i a l d e v e lo p i n g was s to p p e d a f t e r 20 m in u te s a n d a f t e r d r y i n g t h e c h ro m a to g ram t h e d e v e lo p i n g was re n e w e d i n t h e s o l v e n t w i t h pH ■ 2 o r 3 . When t h e f r o n t o f t h e s e c o n d s o l v e n t c r o s s e d t h e s t a r t i n g l i n e we o b s e r v e d an a c c e l e r a t e d m i g r a t i o n o f t h e f u r t h e r p a r t o f a lu m in iu m z o n e . The c h a n g e o f t h e s o l v e n t h a d no d i s t i n c t e f f e c t on t h e m i g r a t i o n o f z o n e s o c c u p ie d by i r o n ( I I I ) and c h r o m i u m ( I I I ) . A f t e r e n d in g t h e s e c o n d 's t a g e o f d e v e lo p i n g t h e A1 zo n e i n t h e v o l v e n t w ith pH ■ 3 was c o l o u r e d an d i n t h e s o l v e n t w ith pH * 2 n o t c o l o u r e d an d n e e d e d make e v i d e n t ( b y a l u m i n o n ) . The z o n e o f C r i n b o th c a s e s r e q u i r e d make e v i d e n t ( b y EDTA). I n b o t h c a s e s t h e - z o n e o f F e w as c o l o u r e d . The s h a p e o f t h e Fe z o n e re m a in e d c o n i c a l d u r i n g th e s e c o n d d e v e lo p i n g w h i l e t h e s h a p e o f t h e A1 zone c h a n g e d fro m c o n i c a l t o r o u n d . A f t e r 15 m in u te s o f i n i t i a l d e v e lo p in g (pH ■ 4 ) an d a f t e r 60 m in u te s o f re n e w e d d e v e lo p i n g (pH ■ 2 ) t h e c o e f f i c i e n t s Rp w e re a s . f o l lo w s : C r ( l l l ) - 0 , 9 8 ; A l ( I I I ) - 0 ,6 5 and F e ( I I I ) - 0 , 2 2 . Chang i n g t h e tim e o f d e v e lo p in g i n t h e f i r s t a n d s e c o n d s t a g e one c a n c h a n g e t h e p o s i t i o n o f t h e A1 zone i n r e l a t i o n t o 2o n e s o f Fe a n d C r . F i g , 4 show s some ch ro m a to g ra m s o b t a i n e d i n t h i s w ay, w h ic h i n d i c a t e c o m p le te s e p a r a t i o n o f t h e i n v e s t i g a t e d m ix tu r e o f c a t i o n s .
The e l a b o r a t e d m ethod i s s i m p le , f a s t , , c o n v i n l e n t . and y i e l d v e r y good s e p a r a t i o n s .
P i g . 4 . C h rom atogram s o f a m ix tu r e o f t r i v a l e n t i o n s o b t a i n e d fro m a medium c o n t a i n i n g v i o l e t R . F i l t r a k no 3 3 0 ; D e v e lo p in g s y s te m : HoO ♦ HC104 ; Time o f i n i t i a l d e v e lo p i n g : 1 -2 0 ; 2-15? 3 - 2 5 ; 4 -1 8 m in . T o t a l tim e o f d e v e lo p in g 75 min REFERENCES [ i ] M a r c z e n k o Z . , S p e k t r o f o t o m e t r y c z n e o z n a c z a n ie p ie r w ia s tk ó w , W arszawa ( 1 9 7 9 ) . l2 ] B a n e r j e e G ., Z. A n a l. C hem ., 1 4 7 , 1 0 5 ( 1 9 5 5 ) ; ' 1 4 8 , 3 4 0 ( 1 9 5 5 ) . [ 3 ] W e h b e r P . , Z . A n a l. Chern., 142, 161, 24% 419 ( 1 9 5 6 ) ; 150, 186 ( 1 9 5 6 ) .' [ 4 ] C z e r k i e s o w A . I . , O p tik a i s p e k t r o s k o p ! j a , 2 , 827 ( 1 9 5 7 ) . [ 5 ] S a n o H ., B u l l . Chem. S o c . J a p a n , 3 3 , 286 ( 1 9 6 0 ) . [ 6 ] - D o r t a - S c h a e p p i , H ü r z e l e r H. , T r e a d w e l l W., H e lv . C him . A c ta , 34, 797 ( 1 5 5 1 ) . [ 7 ] B i e d e r m a n n W. , S e n w a r z e n b a c h G ., D ie K o m p le x o m e tris e h e T i t r a t i o n d e r E r d a l k a l i e n u n d a n d e r e r M e t a l l e m it E r i ochrom s c h w a rz , T . C h itn ia ( S w i t z ) 2 , ( 1 9 4 8 ) .
[f i] H a r v e y A. E. , K o r a a r m y J . M . , W y a t t G. M., C o l o r i m e t r i c D e te r m in a tio n o f M agnesium w i t h E rio c h ro m e B la c k T . i b i d . 2 5 , 49a ( 1 9 5 3 ) . [ 9 ] Y o u n g A. , S w e e t T. f t . , B a k e r B . B ., A nal C h e n ., 2 7 , 356 (1 9 5 5 ). [ 1 0 ] W a w r z y . n i a k A ., P a t e n t PRL n r 79279 ( P o l i t e c h n i k a Ł ó d z k a ). [ 1 1 ] M a s ł o w s k a J . , Z a k r z e w s k i W., Chera. A n a l . , 16, 419 (1971 )* 17, 317 ( 1 9 7 2 ) ; 1_o, 3B9 (1 9 7 3 ) ; 19, 823 (1 9 7 4 ) . [ 1 2 ] K a s p r z a k F. , K l i m e k B. , K w a p l ń s k a H ., C h r o m a to g r a f ia b arw n ik ćw , Warszawa ( 1 9 6 9 ) . [ 1 3 ] 3 r a m e k J . , T e x t i l , 1 3 , 346 (1 9 5 8 ) . [ 1 4 ] M a s ł o w s k a J . , Z a k r z e w s k i W ., A c ta U n i- v e r s i t a t i s L o d z i e n s i s , N auki M a t . - P r z y r . F o l i a C h lm ic a (w d ru k u ) . I n s t i t u t e o f F u n d a m e n ta l Food C h e m is tr y T e c h n i c a l U n i v e r s i t y o f Łódź
J o a n n a M asłow ska, Wacław Z a k rz e w sk i CHROMATOGRAFIA KOMPLEKSÓW CHELATOWYCH METALI. V. KOMPLEKSY F e ( I I I ) , C r ( I I I ) I A l ( I I I ) Z FIOLETEM R
■ F i o l e t R p r z e d s t a w i c i e l barw ników azow ych o c h a r a k t e r z e kwasowym, p o s i a d a j ą c y u k ł a d 0 , 0 ' -d w u h ydrok sy azow y w y k o rz y s ta n o z pom yślnym i w ynikam i ja k o c z y n n ik k o m p le k s u ją c y do c h r o m a to g r a f i c z n e g o r o z d z i e l e n i a n a b i b u l e t r u d n e j d o r o z d z i e l e n i a in n y m i m etodam i m ie s z a n in y k a tio n ó w t r ó j w a r to ś c i o w y c h : F e 3 *, C r 3* i A l 3* . S tw ie r d z o n o , ż e b a rw n ik t e n n i e k o m p le k s u je n a zim no z C r ( I I I ) , a k o m p le k s u je z F e ( I I I ) i A l ( I I I ) d a j ą c barw ne k om ple
k sy o w ła s n y c h pasm ach a b s o r p c y j n y c h .
Do m ie s z a n in y t r z e c h b a d a n y c h k a tio n ó w d o d a je s i ę wodny r o z tw ó r f i o l e t u ft w t a k i e j i l o ś c i , aby s t o s u n e k k aż d eg o jo n u M e ( I I I ) do b a rw n ik a n i e b y ł n i ż s z y n i ż 1 : 1 , C h r o m a to g r a f ię p r o w a d z i s i ę n a p a s k a c h b i b u ł y F i l t r a * 3 9 0 , s t o s u j ą c w c i ą g u 15 min. r o z w i j a n i e w s tę p n e z H20 ♦ HCIO^ (pH * 4 ) ' , a po w y s u s z e n iu p a s k a ponowne r o z w i j a n i e w c i ą g u 60 m in . z H20 + HCIO^ o p d * 2 . O trz y m u je s i ę b a r d z o w y ra źn e i p e ł n e r o z d z i e l e n i e . W sp ó łc z y n n i k i h F: C r ( I I I ) - 0 , 9 8 , A l ( I I I ) - 0 , 6 5 i F e ( I I I ) - 0 , 2 2 .
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