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Spectrophotometric Study
of Zinc, Cadmium and Lead
Complexes with Murexide in
Binary Ethanol-Water Mixtures
a a
Mohammad Reza Fat'hi & Mojtaba Shamsipur
a
Department of Chemistry , Shiraz University ,
Shiraz, Iran
Published online: 23 Sep 2006.

To cite this article: Mohammad Reza Fat'hi & Mojtaba Shamsipur (1993)
Spectrophotometric Study of Zinc, Cadmium and Lead Complexes with Murexide in
Binary Ethanol-Water Mixtures, Spectroscopy Letters: An International Journal for
Rapid Communication, 26:9, 1797-1804, DOI: 10.1080/00387019308010777

To link to this article: http://dx.doi.org/10.1080/00387019308010777

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 SPECTROSCOPY LElTERS, 26(9), 1797-1804(1993)

SPECTROPHOTOl~lCTRICSTJLIY OF ZINC, CADllILM kuD LEAD

COMPLEXES WITH IlUREXZDE IN BINARY ETIIANOL-WATER MIXTLTES

2+ , Cd2+ and Pb2+; fIurexide complexes; !fixed solvent;

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Key Words: Z n
Stability; Spectrophotometry.

*
M o h m a d Reza Fat'hi and Hojtaba Shamsipur
Department of Chemistry, Shiraz University, Shiraz, Iran

ABSTRACT
The complexation reactions between murexide and Zn2+, Cd"
2+
and Pb ions in C2B50€I-H20 mixtures have been investigated
spectrophotometrically. Formation constants of the resulting 1:l
complexes were determined and found to vary in the order Pb2+>
Cd2+>Zn2+, in all binary ethanol-water mixtures used. There is
an inverse relationship between the complex formation constants
and amount of water in the mixed solvent. A linear relationship
was observed between log Kf for complexes and the mole fraction
of ethanol.

INTRODUCTIOIl
Murexide, the ammonium salt of purpuric acid (I), is used as
a complexing agent for a large number of metal ions over a wide
range of experimental Since the metal ion-murexide

*Author to whom correspondence should he addressed.

1797

Copyright 0 1993 by Marcel Dekker, Inc.

 1798 FAT'HI AND SHAMSIPUR
5
e q u i l i b r i u m is very r a p i d l y e s t a b l i s h e d i n aqueous4 and methanol
s o l u t i o n s , t h e ligand has been used i n t h e t t ~ e r m o d y n a m i c ~ and
-~
k i n e t i c 5*10'11 s t u d i e s of a v a r i e t y o f metal ion-ligand molecule
complexes.
However, t h e s t a b i l i t y c o n s t a n t s of murexide complexes w i t h
most metal i o n s are n o t very large3D12 which could cause some li-
m i t a t i o n s i n t h e use of murexide a s a metallochromic i n d i c a t o r i n
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aqueous s o l u t i o n s . Since i n t h e complexation r e a c t i o n s t h e l i g a n d

must compete w i t h s o l v e n t molecules f o r t h e n e t a l i o n s , v a r i a t i o n
of t h e s o l v e n t i s expected t o change t h e apparent binding proper-
t i e s o f t1:e l i p n d . T h u s , t h e use of s o l v e n t s o f l o v e r solvatir:,
a b i l i t y and d i e l e c t r i c c o n s t a n t s than rrater13 i s expected t o l e a d
g r e a t e r s t a b i l i t y of t h e corresponding nurexide complexes.
It was of i n t e r e s t t o us t o study t h e i n f l u e n c e of s o l v e n t
p r o p e r t i e s on t h e stoichiometry and s t a b i l i t y of t h e murexide comp-
l e x e s w i t h d i f f e r e n t metal ions. We have a l r e a d y r e p o r t e d some re-
s u l t s obtained from t h e study of t h e complexes between a number of
metal i o n s and murexide i n nonaqueousl4-I6 and mixed s o l v e n t s . 17
I n t h i s paper v e r e p o r t a spectrophotometric s t u d y of t h e murexide
complexes w i t h zinc, cadmium and l e a d ions i n binary ethanol-water
mixtures a t 25 "C.

EXPERZXEUTAL
Reagent grade cadmium n i t r a t e (Fluka), zinc n i t r a t e , l e a d
n i t r a t e , anmonium n i t r a t e and murexide ( a l l f r o n P!erck) were of
t h e h i g h e s t p u r i t y a v a i l a b l e and used without any f u r t h e r puri-
f i c a t i o n except f o r vacuum drying over P205 f o r 72 11. Absolute
e t h a n o l (lierck) mixtures Giith doubly d i s t i l l e d deionized v:ater
 ZINC, CADMIUM AND LEAD COMPLEXES 1799

trere prepared by weight. T!ie v i s i b l e s p e c t r a were recorded on a

Beckmann DK-2A r a t i o recording spectrophotometer and t h e absor-
bance neasurements were made w i t h a Carzy 118 spectrophotometer
a t 25.0 f 0.2 'C.
The formation c o n s t a n t s of t h e 1:l complexes of murexide
w i t h t h e c a t i o n s used were deteruined a c c u r a t e l y by methods re-
A l l volumetric glassware used was c a l i b -
ported previously. l7*I8
r a t e d . Equality of t5e murexide concentrations i n d i f f e r e n t so-
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l u t i o n s and of t h e amounts of metal i o n s added w a s ensured by

weighing t h e naterials on a semimicro balance. The i o n i c s t r e n g t h
of a l l s o l u t i o n s w a s k e p t c o n s t a n t a t 0.1 11 w i t h ammonium n i t r a t e .
Equilibrium w a s assumed t o b e a t t a i n e d i f t h e r e w a s no f u r t h e r
change i n t h e s p e c t r a a f t e r s e v e r a l hours. The e r r o r s a s s o c i a t e d
with the log K
f
v a l u e s a r e r e p o r t e d as 2 standard deviations,

RESULTS AND DISCUSSION

The s p e c t r a of murexide and i t s complexes w i t h Zn2+, Cd2+ and
Pb2+ i o n s i n aqueous s o l u t i o n a r e given i n Figure 1. As i t i s seen,
i n a l l c a s e s , t h e resulting complexes are d i s t i n g u i s h e d by a r e l a -
t i v e l y s t r o n g s h i f t towards s h o r t e r wavelengths, by comparison t o
f r e e ligand. Generally, the e l e c t r o s t a t i c i n t e r a c t i o n of a bound
r?etnl i o n would not Le able t o produce such n pronounced e f f e c t on
t h e e l e c t r o n i c s t r u c t u r e of a &ye rlolecule, and hence on i t s spec-
trum. I t i s reasonable t o assune that t i = t w i s t i n g of t h e two r i n g s
of t k nurexide molecule r e l a t i v e t o each o t h e r (around t h e ii-bridge
a x i s ) , broug!it about by n e t a l i o n complexation, i s r e s p o n s i b l e f o r
5,15-17
such s p e c t r a l behavior.
The stoichiometry of l e a d , cadmium and z i n c complexes w i t h
murexide i n d i f f e r e n t ethanol-water mixtures BIBS determined by t h e
method of continuous v a r i a t i o n s (Figure d9
It was found t h a t ,
i n t h e c a s e of a l l complexes s t u d i e d , t h e metal i o n t o murxide mole
r a t i o is 1:l. The e x i s t e n c e of such a 1:l stoichiometry for d i f f e -
r e n t metal ion-murexide complexes i n aqueous, nonaqueous and mixed
1,3,14-17
s o l v e n t s has a l r e a d y been reported.
 1800 FAT'HI AND SHAMSIPUR

4 'I
PI

8
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P
0
P
4

430 455 480 500 520 540

Wavelength (nm)

FIG. 1. Absorption spectra of murexide (I) and i t s complexes w i t h

lead ( 2 ) . cadmium (3) and zinc ( 4 ) ions i n pure water.

0.4

0.3

0 .o
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction

FIG. 2. Continuous variation p l o t s for Pb2+ (l), Cd2+ (2) and Zn2+

(3) complexes w i t h murexide i n 24% ethanol.

 ZINC, CADMIUM AND LEAD COMPLEXES 1801

TABLE 1
Formation Constants of Lead, Cadmium and Zinc Complexes with
Ilurexide in Various Ethanol-Water Binary llixtures at 25 *C

Solvent Log I:
f
composition 'C~II~OH
(wt% C2H50H)
2+
Ph2+ Cd2+ Zn
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0 0.00 4,2120.02 3.9320.03 2.955.02

3 0.03 4.36+0.03 4.0320.03 3.09f0.03
15 0.06 4.6320.05 4.1120.04 3.225.03
24 0.11 4 . G9fO.03 4.Z F O . 03 3.39f0.93
32 0.15 - 4.37t0.04 3.53s.03
41 0.21 - - 3.77f0.05

All calculated formation constants for the resulting complexes

between Pb2+, Cd" and Zn2+ ions and murexide in different binary
ethanol-water mixtures ore listed in Table 1 and the relationship
between the logarithm of the formation constants of the complexes

and the mole fraction of ethanol in solvent mixture is shown in

Figure 3. It is seen that, in all solvent mixtures used, the sta-
2+ 2+
bility of the murexide complexes vary in the order Pb >Cd >
2+
Zn , The same order has already been reported in the litera-
ture. 1D3s14The highest stability observed for Pb2+ complex among
the cations used is probably due to the proper ionic size of this
cation, which could favor a suitable spatial fit with the flexible
donating atoms of murexide (i.e. the bridging nitrogen atom and
neighbouring oxygens). 15
However, it should be noticed that the thermodynamic stability
is not just a measure of the absolute netal ion-ligand interaction,
but is a measure of relative strength as cmpared to ionic solvation
 1802 FAT’HI AND SHAMSIPUR
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0.0 0.05 0.10 0.15 0.20

XE than01
FIG. 3. V a r i a t i o n of s t a b i l i t i e s of nurexide complexes w i t h
2+
i n t h e binary mixtures f o r Pb ( l ) , Cd2+ (2) and Zn

of a l l charged s p e c i e s involved i n t h e conplexation r e a c t i o n (i.e.

n c t a l ion, murexide and t h e i r conplex). Thus, t h e highest s t a b i l i t y
observed f o r lead-murexide complex r e s u l t s from a balance between
t h e binding and s o l v a t i o n energies.
The d a t a given i n Table 1 c l e a r l y i n d i c a t e t h e i n p o r t a n t in-
fluence of solvent p r o p e r t i e s on t h e s t a b i l i t i e s of t h e nurexide
complexes. As can be seen, i n t h e case of a l l c a t i o n s used, t h e r e
i s an inverse r e l a t i o n s h i p between t h e complex s t a b i l i t y and amount
of water i n the s o l v e n t mixture. It i s well known t h a t t h e s o l v a t i n g
a b i l i t y of s o l v e n t , as expressed by Gutmann donor nunber,13 plays a
fundamental r o l e i n t h e complexation r e a c t i o n s . I5’l6Water w i t h a
donor number of 3320 has a higher s o l v a t i n g a b i l i t y than ethanol
w i t h that of 1913. s o that i t can s t r o n g l y compete w i t h murexide
€or t h e cations. Therefore, i t i s not s u r p r i z i n g t o observe a sharp
i n c r e a s e i n Kf upon a d d i t i o n of ethanol t o water.
The lower d i e l e c t r i c c o n s t a n t of e t h a n o l ( 2 4 . 3 ) , conpared
w l t h water (78.5), could a l s o cause t h e e l e c t r o s t a t i c c o n t r i b u t i o n
 ZINC. CADMIUM AND LEAD COMPLEXES 1803

t o t h e bond f o r n a t i o n t o i n c r e a s e w i t h i n c r e a s i n g p e r c e n t a g e of
ethanol i n the solvent nixture.
From F i g u r e 3, i t i s s e e n t h a t t h e r e is a c t u a l l y a l i n e a r
r e l a t i o n s h i p between l o g Kf of t h e complexes and mole f r a c t i o n of
e t h a n o l i n t h e b i n a r y mixed s o l v e n t used. S i m i l a r r e s u l t s have
a l r e a d y been r e p o r t e d f o r a v a r i e t y o f metal i o n complexes w i t h
d i f f e r e n t 1i g a n d s i n m e t hanol-water2’, ace t o n i t rile-wa t er 22.23 and
ethanol-water m i x t u r e s . 17D24 It h a s been assuced t h a t t h e p r e f e r e n -
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t i a l h y d r a t i o n o f t h e metal i o n s is mainly r e s p o n s i b l e f o r s u c h
monotonic dependence of t h e s t a b i l i t y c o n s t a n t s upon t h e s o l v e n t
composition.

ACKXOWLEDGElENT
The a u t h o r s g r e a t e f u l l y acknowledge t h e s u p p o r t of t h i s work
by t h e S h i r a z U n i v e r s i t y Kesearch Council.

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Date Received: May 13, 1993

Date Accepted: June 2 1 , 1993