Naphthoquinonedioxime derivatives as analytical reagents for the spectrophotometric determination of nickel

Naphthoquinonedioxime derivatives as analytical reagents for the spectrophotometric determination of nickel

•Imd~. t k a C h o m ( a ,1{ ta 75 ( I t ) 7 5 ) 3 2 a "~34 El,,ev~er StJent~fi~. P u l ~ h q ~ m g C o m p , t n ~ A m , , t c r d d m 323 Printed m...

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•Imd~. t k a C h o m ( a ,1{ ta 75 ( I t ) 7 5 ) 3 2 a "~34 El,,ev~er StJent~fi~. P u l ~ h q ~ m g C o m p , t n ~ A m , , t c r d d m

323 Printed m The Nethcrl,tnd,,

NAPHTHOQUINONEDIOXIME DERIVATIVES GENTS FOR THE SPECTROPI-IOTOMETRIC NICKEL

KYOII

T(')EI

~;I-IOJI M O T O M I Z U , m d

~;ATORU

30th Md~

REAOF

KUSE

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AS A N A L Y T I C A L DETERMINATION

T~u~homt Ol,{ataolct-~hl 701)(,htl~a~)

1974)

Man.~ dlo•lme c o m p o u n d s hdve been s y n t h e s i z e d since d l m e t h y l g l y o x l m e w a s first p r e p a r e d a n d a p p l i e d to a n a l y t i c a l s t u d t e s m 1905 t F e w n a p h t h o q u m o n e d l o x l m e d e r i v a t i v e s , h o w e v e r , have been e x a m , n e d R e c e n t l y : 3 the a u t h o r s syntheslTed several d t o × t m e c o m p o t , nd~. a n d f o u n d t h a t o f st×teen d l o n , m e c o m p o u n d s e × a m m e d , n a p h t h o q u m o n e d t o x J m e - 4 - s u l f o n l c acid h a d high sensitivity for m c k e l in the w o r k described here. ~everal o t h e r new n a p h t h o q u t n o n e d l o x i m e dcr~.at~ves were prep;wed a n d their sensmv~ttes for ~ome m e t a l tons were exam=ned. T h e c o m p o s ~ t l o n r a t i o o f t h e n l c k e l - d l o x l m e c o m p l e x e s a n d the effects o f d l o x u n e a n d z e p h l r a m ~ n e o n e n h a n c e m e n t o f the senstttvtty were s t u d i e d , a n d the n a p h t h o q u m o n e d l o x x m e ~ were c o m p a r e d with the c o r r e s p o n d i n g n~troson.'tphthols T h e seven n a p l a t h o q u m o n e d l o x l m e s used m thin w o r k are s h o w n b e l o w . five o r these r e a g e n t s ( a s t e r i s k e d ) are new c o m p o u n d s NON

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e x t t , t c t a b f l ~ t y T h e e x t r , t c t t o n s ~ e r c tll~tCfo~e ,tlmo~t all ~.,lllzed o u t ~ ) t i ] c h l o r o f o r m T h e o p t ) r e a l p H . t h e %~a~elength,, oF t h e 4 b , , o ~ p t l o n m.'l\m~,t a n d t h e

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zt Is ~gut't th,lt t h e d b ~ o I p t l o n , , p ¢ ~ t l u n ] o r t h u m e k u l c o m p l e x o f r¢,~gent I! ~,, dlffgrgntfiomthatolth¢othel,,(lll V), r e a g e n t s I i I ~ V , , h o w l a l g e a b , , o l p t k m ol th~ c o m p l e x a n d s m a l l 4 b ' ~ o t p t l o n ol thu t u , l g c n t tt~ell ,~t the tll,Ixlnldl a b , , o r p t k ~ n w a v e l e n g t h of t h e c o m p l e x m th~ va,,fl~l¢ t u g l o n , w h l l u thu a b s o r p t t o n s p e c t l u m o f r 0 a g e n t !1 is s m l l l a r t o th,ll o r n J t r o , , o n a l n h t h o l ~ T h i s t~ d u u t o t h e I o l l o w l n g r(~d,,on. R e a g e n t I! as m o r e d~Om4tlC t h a n r~aLzunt,, i l i V be~,,Lu,,c o f the e l e c t r o n s b01ng fixed in t h e r i n g i.-'~nl~.lllllllg [hi2 l.wt) o x i n ' l c g r o u p , , b y t h e e l c c t r o p h l l J ¢ ¢llcct o r t h e ~ u l f o m c g r o u p ,it t h e 4opO,,]lttm. l e d g e n t , Iil V t l p p e a ! m o t e a l i p h a t l c t h d n at o m a t z c b e c a u s e o f e l e c t ! on.,, b e u l g ,tt t r a c t c d It) t h e o t h e r r i n g b y t h e .,,ulloni(. LZlot, p ;it t h e 5=. 6= o r 7=po,,~tk)n T h e r e f o r e . t h e a b s o ) p t z o n m a x , m a ol r e a g e n t , , III V .,,h~It t o , , h o r t w a v e l e n g t h , a n d r e a g e n t , , III V , u e m o ) e 4 k , n t o the a l ) p h a t ~ c d~oxm~es. s u c h .'~s b u n z ~ l d t o x m ~ e ~ , t h e y ~1]()%~ h~ghel ,~el¢ctivlty f o r nnckel th~.m u e a g c n t II

330

K TOEI. S MOTOMIZU. S KUSE

The absorptlon spectra of the mckei chelates of the naphtlaoqu]nonedloxlme s u l f o n l c a c t d s I I - V a r c s h o w n m Fig. I. F r o m T a b l e s II a n d II1 a n d Fig. I. t h e molar absorptivity of the mckei chelate increases about twice on extracuon as a ternary complex E//eet

~ff eho~:at;e m aqtteot~s s o l u t t o n The effects of addzng dlox.'me to aqueous soltmons of the ntckcl chelate~ of reagents II-V and the corresponding mtrosonaphthols on the absorption maxima m the visible region and the molar absorpt~vmes a r e s h o w n m T a b l e I V It c a n b e seen that the molar absorpuviues of the complexes w~th II-V increase i 4-1.7 ttmes on adding d]oxane, while those of the corresponding nltrosonaphthols increase about I 2 times The stability of nickel chelates on adding dlox,'me was examined, Fig. 2 shows that the mckel chelates were ngt very stable except for the chelate of r e a g e n t II

E//ec't o/ : e p h o ' a m m e m aqueou~ solutton T h e effect o f a d d e d z e p h l r a m m e ( I 0 - 2 m o l e I - ~ ) o n r e a g e n t III is s h o w n m 08 1

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Fig 3. a b o u t 1.4 ml o f z e p h l r a m m e s o l u t | o n sufficed to gi ve m a x m a a l effect T h e m o l t o a b s o r p t t v l t l e s o f t h e nsck¢l c h e l a t e s o f f o u r n a p h t h o q u | n o n e d l o g m l e s I I - V a t t h e a b s o r p t i o n m a x m m , on a d d i n g 1 4 ml o f z e p h ] r a m l n e s o l u t i o n , a r e shown m Table V T h e s t a b d ] t y o f nickel c h e l a t e s o n a d d i n g z e p h l r a m m e w a s also e x a m i n e d Ior l e a g e n t 11I T h e z e p h m m a m e p r o d u c e d a r e m a r k a b l e | m p r o v e m e n t m s t a b d l t y . as m F i g 2. the a b s o ( b a m . c i n c r e a s e d up to I h. but t h e n ~ c m a m e d s t a b l e for at least I 0 h T h e results s h o w e d that. on a d d i n g a 140-fold a m o u n t o f z e p h w a m m e c o m p a r e d to mck¢l I o n . . ' t s t a b l e c o m p l e x w a s f o r m e d a n d t h e m o l a r a b s o r p t w ( t y i n c r e a s e d 1.4--I 7 u m e s In the c a s e o f the c o r r e s p o n d i n g m t r o s o n a p h t h o l , , , the mckel chelate precipitated

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h) +itldln~ #+1+1111,1111111~.+llld Ih+ i+lllO~ Oil d d d l l l ~ i.hoX,llll. %~1:i~.d+t~.lHlllll~d %%llhln +I(] I l l l n ol , l d d i l l O n ol d ItiX+llll~ l, ii~l+iol, hii.ll+h, s , , i h l ~ i.otlld i l t i t hi., llhi+linl.~.I

+ x t r + t c t l n ~ ,,ol+~:nt l'hu ~u,,tilt,, ,i~t: ~ , h o w i l ll'i T + l h l c Y l T h u ~ . o m p o , , i t l o n r,ttio c h a n g e d fl o m 1 3 t o 1 4. o n ddi.llng t.llt+x,lriu "I h~.,, l'ihui+oni¢litm ,tl~,o C~C+:tll r e d in t h e

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NAI)HTHOQUINONEDIOXIME

D E R I V A T I V E S AS N I C K E L

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[ l i l l t l . [111]= I0 ¢ M (408 n m ) C u P , ~ 2 [ l l l ] . . ~ , . [ l I l l = I(.) -4 M '~ M ( 4 7 0 n m ) C ' u r ~ e 4 [ l | l ] l ) , , [111]---5 I0 '~ ,%1(4"/0 n m )

I Ig 5 ConttnLIOLl% ~,.trldtlOn% m e t h o d CLir~,e I [ l l l J c i . [ N i : ' ] + [ l l l ] = 2 [111] ..... [ N t " ' ] + [ l l l ] = 2 iO ' ~ M ( 4 6 6 n m ) Lm~e3 Jill],,, [Nl:']+[lll]=2 [ill]n,,, [Nl:']+[lll]=2 I() -4 M ( 4 . 7 4 n m )

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increases 1 4-1 7 t t r n e s on a d d i n g d t o x a n e o r z e p h ~ r a m m e , t h e c a u s e o f e a c h ~ncrease :s dlffcrcnt T h e i n c r e a s e o f the moltlr a b s o r p t l v z t y o n a d d i n g d l o x a n " , d e p e n d s o n tile m c r c a s c m n t , m b c r o r the c o o r d i n a t i n g llg,|nd, a n d m the case o r z c p h l r a m l t | c , the increase d e p e n d s o n f o r m | n g thc ion pa,r T h o u g h t h e series o f n a p h t l a o q u m o n c d l o x m l c s has the d i s a d v a n t a g e or lack o f selcctlvlty for mckcl, the m o l a r a b s o r p t i v i t y in the c x t r a c t , n g s o l v e n t o f the t e r n a r y c o m p l e x ( N~-" ~- r e a g e n t - z c p l a ~ r a m m c ) is a b o u t 2 I 0"* in t h e vm|ble region, a n d thc scnsltJv~ty ~s the h t g h e s t o f all w e l l - k n o w n d l o x | m e , , F u r t h e r m o r e . as p r c v , o u s l y r c p o r t c d ~. the cxccss o f r e a g e n t m c x t r a c t m g sol,,cnt can be r e m o v e d by w a s h i n g with c h l o r i d e 1on s o l u t i o n , so t h a t thc a b s o r b : m c c o f the r e a g e n t b l a n k m the vIMblc r e g i o n b c c o m c s very s m a l l in the scrzcs o r n a p h t h o q u | n o n c d t o x l m c s u l f o n l c acids ( I! -V). t h e new r c a g c n t IV. L e . n , | p h t h o q t | m o n c d l o x | n a c - 6 - s u l f o n t c acid. a p p e a r s to be very useful for the s o l v e n t e x t r a c t | o n - s p c c t , o p h o t o m c t r , c d c t c r m | n a t t o n o f n~ckcl. h a v i n g t h e f o l l o w i n g a d v a n t a g e s I,trgc s c n s | t | v l t y fol mckcl, h t t l c a b s o r b a n c e o f the r e a g e n t ttsclr at t h e a b s o l p t t o n m.'lMmum o r the m c k e i c o m p l e x , solt, b d t t y o r the r e a g e n t .'rod t h e c o m p l c x m a q t | c o u s s o l u t | o n , a n d s t a b d z t y o f t h e r e a g e n t a n d the complex. T h e a u t h o r s ure very grateful to M r T a k a s h l K o r e n a g a o f O k a y a m a verslty for v a l u a b l e d i s c u s s | o n s a n d asMstance in the e x p e r i m e n t a l w o r k

Um-

SUMMARY

Seven n a p h t l a o q u | n o n e d l o x | m e c o m p o u n d s , m c l u d | n g fi~e new c o m p o u n d s . were s y n t h e s i z e d a n d their r e a c t i o n s w~th m c k e l , c o b a l t .'rod t l o n ( l l ) i o n s were e x a m i n e d T h e m e t a l chel.'ttes or these dlox~mes a b s o r b m t h e visible r e g i o n , a n d the m o l a r absorpt~v~t~es o f the c o m p l e x e s a r e a b o u t 1-10"* I m o l e - ~ c m - ~ in

334

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a q u e o u s s o l u t i o n T h e c h e l a t e s c a n be e x t r a c t e d rote c h l o r o f o r m w~th z e p h | r a m m e . and themolarabso|ptlvltles of the mckelchclatcsa|eabout 2 10 '~ l m o l e - t c m Of the dloxlmes examined, 1,2-naphthoqu|noncdlox]me-6-sulfonxc aczd s h o w s t h e h~ghcst s c n s | t l v ~ t y for m c k e l , the m o l a r a b s o r p t i v i t y or t h e m c k e l c o m p l e x e x t r a c t e d r o t e c h l o r o f o r m w i t h z e p h l r a m m e is 2 . 1 9 . 1 0 4 I m o l e - ~ c m - ~ at 4 6 8 n m REFERFNCES

I 2 3 4 5 6

L S S H K T

A Tsehug,tcff, Z A m n q AI#I Chem 4 6 ( 1 9 0 ~;) 144 Ku~,e. S M o t o m l / u a n d K, T 6 c l N i p p . n l%'tqltll,tl Kat~hl. ( 1 9 7 3 ) 1611 Ku~e, S M o t o m t T u a n d K T b c l Anal Chtm ,'ltttl, 7 0 ( 1 9 7 4 ) 65 G o l d s c h m l d t a n d H S c h m l d l . Bvt Bl.lSvngv~ PIl~S Chvnt. 17 ( 1 8 8 4 ) 2 0 6 6 T6ez. S M o l o m l v u , NtlIp¢.t gtqltal~. Ztls~111, 92 ( 1971 ) 92 K o r c n a g a , S M o t o m ~ z u a n d K The1. Nil,Iron Ktl¢ltll~ll I%~lp,hl (1972) 2445