Ta/anro,

Vol.39,No. 9,pp.1209-1212,
1992 0039-9140/92
$5.00+0.00
Printed in Great Britain Pergamon Press Ltd

SPECTROPHOTOMETRIC STUDY OF COBALT, NICKEL,

COPPER, ZINC, CADMIUM AND LEAD COMPLEXES
WITH MUREXIDE IN DIMETHYLSULPHOXIDE SOLUTION
MOJTABA SHAMSIPUR*
Department of Chemistry, Shiraz University, Shiraz, Iran

NAADER ALIZADEH
Department of Chemistry, Tarbiat Modarres University, Tehran, Iran

(Received 4 November 1991. Revlsed 9 January 1992. Accepted 9 January 1992)

Summary-The complexation reactions between murexide and Co*+, Nil+, Cu*+, Zn2+, Cd*+ and Pb*+
ions have been studied spectrophotometrically in dimethylsulphoxide solution at 25”. The stoichiometry
of the complexes was found to be 1: 1. The stability constants of the complexes were determined, and
found to follow the Irving-Williams rule for the cations of the first transition series. In dimethylsulphoxide
solution, the complexes are much more stable than those in aqueous solution.

Murexide, the ammonium salt of purpuric acid
(I), is frequently used as a complexing agent
for a large number of metal ions, including
the divalent ions of the first transition series,
in aqueous solution over a wide range of
experimental conditions.‘-’ It is known as a
convenient ligand for the quantitative determi-
nation of metal ion concentrations in aqueous
solution with visible spectrophotometry.6*7 The
equilibrium between various metal ions and
metallochromic indicator murexide has been
used to determine the stability constants of
metal-ligand equilibria by monitoring spec-
trophotometrically the displacement of metal-
murexide equilibrium due to metal-ligand
binding.‘-” Some of the metal-ligand equilibria
involve biologically important macromolecules
as ligands.”
However, the stability constants of murexide
complexes with most metal ions are not very
large in aqueous solutions2-5 which possibly
cause some limitations in the use of murexide
as a chromogenic indicator. Since, in the
complexation reactions, the ligand must com-
pete with solvent molecules for cations, use
of solvents of lower dielectric constant and
solvating ability than waterI is expected to
lead to greater stability of the corresponding
murexide complexes.
It was of interest to us to study the effect
of solvent properties on the thermodynamics
of the metal ion-murexide complexes. We have
already reported some results obtained from
the study of murexide complexes with a number
of metal ions in non-aqueous’3.‘4 and mixed
solvent.15 In this paper we report a spectropho-
tometric study of the murexide complexes with
Co’+, N?+, Cu2+, Zn*+, Cd*+ and Pb2+ ions in
dimethylsulphoxide solution at 25”.
EXPERIMENTAL
Reagent grade CoCl, .6H20, NiC12. 6H,O,
CuCl, . 2H20 and Cd(NO,), .4H,O (all from
Merck) were completely dehydrated by heating
in an oven of proper temperatureI until a
predetermined weight was reached. The result-
ing water free solid salts were stored over phos-
phorus pentoxide under vacuum before use.
Reagent grade zinc chloride, lead nitrate (both
-

*Author for correspondence.

1209
1210 ~~OJTABA SHAMSIPUR and NAADER ALIZADEH

from Merck), tetraethylammonium perchlorate

(TEAP, Fluka) and murexide (Merck) were of
the highest purity available and used without
further purification except for vacuum drying
over phosphorus pentoxide for 72 hr. Spectro-
scopic grade dimethylsulphoxide (DMSO,
Merck) was used as received. All spectra were
obtained with a Model 2100 Shimadzu UV-Vis
spectrophotometer at 25 f 1”.
The formation constants of 1: 1 complexes
420 480 540
between murexide and the metal ions used Wavelength tom)
were determined by the absorbance measure- Fig. 1. Visible region spectra of murexide and its metal
ments, at A,,, of each complex, of solutions complexes in DMSO: 1, murexide; 2, Pb*+; 3, Cd’+; 4, Cu*+;
in which varying concentration of metal ions 5, Zr?+; 6, Ni*+; 7, Co2+.
(2.0 x 10-4-1.0 x 10F3M) were added to a fixed
concentration of murexide (2.0 x lo-‘M) in Dividing equation (7) by A, and its rearrange-
DMSO. The ionic strength of all solutions was ment gives
kept constant at O.lM with TEAP. All solutions
were neutral and, hence, the ligand existed in (A/A, - 1)/C, = LMM&M& - &A IA, (8)
its monovalent form, Mu-, throughout.2*‘3,‘4*‘7 According to equation (8), there is a linear
Attainment of equilibrium was checked by the relation between (A/A, - 1)/C,,, and A,/A
observation of no further change in the spectra (Fig. 3). From the intercept of the line, the
after several hours. formation constant of the murexide complex
When a metal ion, M’+, reacts with murexide, could be obtained.
Mu-, to form a 1: 1 complex, the formation
constant is given as RESULTS AND DISCUSSION

(1) The visible spectra of murexide and its

complexes with the metal ions used in DMSO
solution are shown in Fig. 1. All the complexes
(the charges are omitted for simplicity). The
are distinguished by a strong and ion specific
total concentration of Mu, C,,, and the ab-
blue-shift, the reasons for which are discussed
sorbance at Lmax of the complex, A, are
elsewhere.‘3,t4 The stoichiometry of the com-
expressed as
plexes was examined by the mole ratio method,
c Mu= [MMu] + [Mu] c-4 i8~19and found to be 1: 1 in all cases. Some of
the resulting absorbance-mole ratio plots are
A = s,,,[MMu] + cMu[Mu] (3) shown in Fig. 2. As can be seen, each plot
consists of two straight lines, the intersections
where fM&&and cMUare the molar absorptivities
of which determines the stoichiometry of the
of complexed and free murexide, respectively.
complex (Table 1).
By substitution of equation (1) into equations
The complexation equilibria between
(2) and (3) we obtain
murexide and the metal ions were studied
C,, = (&WI + 1)[MuI (4)

A = (cm+,u&tW + cm,1EMuI (5) __

Dividing equation (5) by (4) gives 0.6

A
--_
c MU
GW,,~Kr[Ml + eMu
(6) !04
z:
KrPfl + 1 9
02
By considering [M] = C, - [MMu] = C, (since
C, % C,,) and A, = cMuC,, and rearrangement 0 05 IO 15 20 5
of equation (6) we have Mu, M
Fig. 2. The absorbance-mole ratio plots for some of the
AK& + A = ~m,uK& + A, (7) metal ions used: 1, Cd2+; 2, Cu*+; 3, Co*+; 4, Nil+.
 Spectrophotometric study of cobalt, nickel, copper, zinc, cadmium and lead 1211

Table 1. Log K, of different metal ion-murexide complexes in DMSO and water

Stoichiometry,
Solvent Cation &,,nm (Mu-/M2+) log Kr
DMSO Murexide 533 - -
car+ 475 1.02 4.56 f 0.03
Ni2+ 461 1.01 5.45 * 0.05
cur+ 477 0.96 5.65 + 0.03
Zn2+ 460 0.97 4.27 f 0.04
Cd2+ 483 1.02 4.63 & 0.03
Pb2+ 515 1.11 4.52 + 0.03
f-W Murexide 522 -
car+ 470 1 2.48
Ni2+ 460 1 3.38
cur+ 478 1 4.36
Zn2+ 452 1 3.00
Cd2+ 483 1 4.15
Pb2+ 502 1 4.40

spectrophotometrically, by using solutions expressed by the Gutmann donicity number,12

containing the ligand and the metals of the
concentrations, C, % C,, . The absorbance at
the peak of each murexide complex (Table 1)
was observed to increase with increasing con-
centration of each cation. The experimental
results obtained showed the linear relations
between (A/A, - 1)/C,,, and A /AO, according to
equation (8), for all the metal ions used which
were independent of C,,. The corresponding
plot for Zn*+ ion is shown in Fig. 3. From
the slopes of the lines, the formation constants
of the murexide complexes were obtained. All
calculated formation constants of the resulting
1: 1 complexes along with the corresponding
1max values and their stoichiometries are pre-
sented in Table 1. The corresponding reported
values in aqueous solution2 are also included for
comparison.
From Table 1, it is immediately obvious that
the solvent plays an important role in the com-
plexation reactions. The resulting complexes in
DMSO are much more stable (up to about
2 orders of magnitude for cobalt, nickel and
copper complexes) than those in aqueous sol-
ution. There is actually an inverse relationship
between the solvating ability of the solvent, as
and the stability of the complexes. Water is a
solvent of higher solvating ability (DN = 33)20
than DMSO (DN = 29.8)12 and, hence, can
compete more effectively with murexide for
the cations. Thus, it is reasonable to expect
an increase in the formation constants when
changing the reaction medium from water to
DMSO. A similar solvent effect has already
been reported.g.‘0.‘3*‘4.2’
Moreover, the lower dielectric constant of
DMSO (46.7) in comparison with that of
water (78.5) would also cause the electrostatic
contributions to the bond formation between
the two charged partners (i.e., M2+ and Mu-) to
increase in DMSO solution.
The data in Table 1 show that the
sequence of stability of the murexide com-
plexes with the cations of the first transition
series (i.e., Co2+ c Ni2+ < Cu*+ < Zn’+) follows
the Irving-Williams order,22 which generally
holds for the equilibrium constants of transition
metals. However, among cations Zn2+, Cd2+
and Pb’+, cadmium-murexide complex in
DMSO solution shows the highest stability,
this is probably due to the proper size of Cd*+
ion which could favour a suitable spatial fit
with flexible donating atoms of the ligand
(bridging nitrogen atom and neighbouring
oxygen atoms). I4 Cadmium ion has about the
same ionic size as Na+ and Ca2+ ionsI which
has been shown to form the most stable
murexide complexes among alkali and alkaline
earth ions, respectively.2*‘3v’4

A /A,,
Acknowledgement-We gratefully acknowledge the support
Fig. 3. Plot of (A/A, - 1)/C, vs. A/A,, for murexide-Zn2+ of this work by the Shiraz University Research
system in DMSO. Council.
1212 MOJTABA SHAMSIPUR
and NAADERALIZADEH

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