Talanta 51 (2000) 637 – 644

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Equilibrium studies on complexation in water and solvent

extraction of zinc(II) and cadmium(II) with
benzo-18-crown-6
Shoichi Katsuta *, Fumiaki Tsuchiya, Yasuyuki Takeda
Department of Chemistry, Faculty of Science, Chiba Uni6ersity, Yayoi-cho, Inage-ku, Chiba 263 -8522, Japan

Received 19 July 1999; received in revised form 15 October 1999; accepted 15 October 1999

Abstract

The formation constants (KML) in water of 1:1 complexes of benzo-18-crown-6 (B18C6) and 18-crown-6 (18C6)
with Zn2 + and Cd2 + , the sizes of which are much smaller than the ligand cavities, were determined at 25°C by
conductometry. Compared with Cd2 + , the crown ethers form more stable complexes with Zn2 + although the size of
Zn2 + is less suited for the cavities. B18C6 forms a more stable complex with each metal ion than 18C6. Moreover,
the extraction equilibria of these metal ions (M2 + ) with B18C6 (L) for the benzene/water system in the presence of
picric acid (HA) were investigated at 25°C. The association between L and HA in benzene was examined for
evaluating the intrinsic extraction equilibria of M2 + with B18C6. The extracted species were found to be MLA2 and
ML2A2, and the overall extraction constants (Kex,1 and Kex,2, respectively) were obtained. The values of Kex,1 for these
metal ions are almost the same, but the Kex,2 is larger for Zn2 + than for Cd2 + . The extraction selectivity was
interpreted quantitatively by the constituent equilibrium constants, i.e. KML, the ion-pair extraction constant of
ML2 + with A−, and the adduct formation constant of MLA2 with L in benzene. © 2000 Elsevier Science B.V. All
rights reserved.

Keywords: Complexation; Solvent extraction; Zinc(II); Cadmium(II); Crown ether

1. Introduction It is generally believed that a crown ether effec-

The selectivities of macrocyclic compounds to-
ward cations for complexation in a homogeneous
system and for solvent extraction have been the
subjects of intense research by many workers [1].
* Corresponding author. Fax: +81-43-290-2781.
E-mail address: katsuta@scichem.s.chiba-u.ac.jp (S. Kat-
suta)
tively complexes and extracts a cation of suitable
size to the ligand cavity. However, there has not
been enough experimental data explaining the
selectivity toward the cations that misfit into the
cavity. Both Zn2 + and Cd2 + are much smaller
than the cavity of 18-crown-6 (18C6); the ionic
radii of Zn2 + and Cd2 + for coordination number
6 are 0.74 and 0.95 A, , respectively [2]. The cavity
radius of 18C6 estimated from the CPK model is

0039-9140/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 9 9 ) 0 0 3 2 1 - 5
638 S. Katsuta et al. / Talanta 51 (2000) 637–644
1.38 A, [3]. A few papers have dealt with the
extraction of Zn2 + [4 – 6] and Cd2 + [6] with 18C6
derivatives such as dicyclohexano-18-crown-6 and
dibenzo-18-crown-6, and some analytical utilities
have been reported; however, the extraction equi-
libria have not been elucidated. In addition, no
reliable formation constants in water have been
reported for the crown ether complexes with
Zn2 + and Cd2 + . The purpose of this paper is to
evaluate quantitatively the selectivities of 18C6
and its derivative toward the size-misfitted small
cations through equilibrium studies of complexa-
tion in water and solvent extraction.
Conductometry is one of the most reliable
methods for obtaining the formation constants of
metal ion– macrocycle complexes [7]. However,
this method has not been applied to the determi-
nation of complexation constants in water of the
metal ions that are subject to hydrolysis. In this
study, the conductometric determination of the
1:1 complex formation constants in water of
Zn2 + and Cd2 + with benzo-18-crown-6 (B18C6)
and 18C6 was done in the presence of nitric acid.
Moreover, the overall extraction equilibrium con-
stants of these metal picrates with B18C6 in ben-
zene were determined. The association between
B18C6 and picric acid in the benzene phase was
examined for exact evaluation of the extraction
equilibria. The extraction selectivity was discussed
by analyzing the overall extraction equilibria into
the constituent equilibria.
2. Experimental
2.1. Materials
B18C6 (Tokyo Chemical Industry, 99%) and
18C6 (Acros Organics, 99%) were recrystallized
from hexane and acetonitrile, respectively, and
dried in vacuo. High purity Zn(NO3)2 · 6H2O and
Cd(NO3)2 · 4H2O (Wako Pure Chemical Indus-
tries, 99.9%) were used without further purifica-
tion. Benzene, nitric acid, and picric acid were
analytical grade reagents. The concentration of
picric acid in the stock solution was determined
by acid–base titration. Benzene was washed three
times with purified water. Water was distilled and
further purified with a Milli-Q Labo system (Mil-
lipore); the conductivity was less than 8× 10 − 7 S
cm − 1. Other reagents were of analytical grade
and used without further purification.
2.2. Conductometry
The conductivity was measured with a Fuso
conductivity apparatus, Model 362B, at 259
0.02°C. Cells with cell constants of 0.1963 and
0.2120 cm − 1 were used. In the cell, 200 cm3 of an
aqueous solution of (1.5–3.0)× 10 − 3 M (1 M=1
mol dm − 3) metal(II) nitrate, which was acidified
with nitric acid to pH 3.4–3.8, was introduced.
The atmosphere was replaced by nitrogen gas.
After the cell was thermally equilibrated in a
water bath, the resistance of the solution was
measured. A 5-cm3 portion of an aqueous solu-
tion of (1.0–2.0)×10 − 1 M crown ether was
added to the cell, and after stirring for 5 min, the
resistance was measured. This operation was re-
peated until 70 cm3 of the crown ether solution
was added.
2.3. Extraction of metal ions
Ten milliliters of a benzene solution of 7.0×
10 − 3 –1.0×10 − 1 M B18C6 and an equal volume
of an aqueous solution containing 6.2× 10 − 3 –
2.5× 10 − 2 M picric acid and 3.3×10 − 2 M
metal(II) nitrate (ionic strength, 0.11–0.12) were
placed in a stoppered glass tube. The tube was
shaken in a thermostated water bath at 259
0.2°C for 2 h and centrifuged. It was initially
confirmed that the shaking time was sufficient to
attain equilibrium. The pH of the aqueous phase
at equilibrium, 2.11–2.54, was measured with a
glass electrode. The metal in the benzene phase
was quantitatively back-extracted into 0.10 M
nitric acid aqueous solution, and the metal con-
centration was determined with an atomic absorp-
tion spectrophotometer (Hitachi SAS-725). The
metal concentration of the aqueous phase was
obtained by subtracting that of the benzene phase
from the total concentration, and the distribution
ratio of the metal was calculated. Scarcely any
metal was extracted into benzene when B18C6 or
picric acid was not present.
 S. Katsuta et al. / Talanta 51 (2000) 637–644 639

2.4. Distribution of picric acid in the presence of = (1− a)/a[L] (1)

B18C6
The apparent conductivity (kapp) of the metal
nitrate (MX2) solution in the presence of L and
Ten milliliters of a benzene solution of 2.5×
nitric acid (HX) is given by
10 − 2 –1.0×10 − 1 M B18C6 and an equal volume
of an aqueous solution containing 6.2×10 − 5 M kapp = kMX2 + kMLX2 + kHX (2)
picric acid and 4.5×10 − 3 M nitric acid were
shaken for 2 h at 2590.2°C and centrifuged. The where kMX2, kMLX2, and kHX denote the conduc-
pH of the aqueous phase at equilibrium was tivities of the metal salt, the metal crown ether
always 2.41, at which more than 99% of picric salt, and the acid, respectively. The molar conduc-
acid in the aqueous phase dissociates into the ions tivities, LMX2, LMLX2, and LHX, are written as
[8]. The picrate concentration of the aqueous
phase was determined by UV spectrophotometry LMX2 = kMX2/[M2 + ]
= kMX2/a[M]t (3)
(lmax =356 nm, o = 1.45 × 104 cm − 1 M − 1). The = kMX2/a[M]t
concentration of the picric acid extracted was
obtained by subtracting the picrate concentration LMLX2 = kMLX2/[ML2 + ]
of the aqueous phase from the total concentra- = kMLX2/(1− a)[M]t (4)
tion, and the distribution ratio of the picric acid
was calculated. LHX = kHX/[H ] +

= kHX/[H]t (5)

3. Results and discussion where [M]t and [H]t are the total concentrations of
the metal salt and the acid, respectively. The
apparent molar conductivity of the metal salt,
3.1. Complexation equilibria in water defined as Lapp = kapp/[M]t, is expressed as

When the crown ether (L) forms only a 1:1 Lapp = aLMX2 + (1− a)LMLX2 + ([H]t/[M]t)LHX
complex with the bivalent metal ion (M2 + ), the = aL%MX2 + (1− a)L%MLX2 (6)
complex formation constant (KML) can be ex-
pressed by the fraction of the free metal ion (a): where L%MX2 = LMX2 + ([H]t/[M]t)LHX and
L%MLX2 = LMLX2 + ([H]t/[M]t)LHX. The L%MX2 value
KML =[ML2 + ]/[M2 + ][L] equals Lapp at the start point of the conductomet-
ric titration. The concentration ratio, [H]t/[M]t, is
constant throughout the titration. Combining
Eqs. (1) and (6) leads to
L%MX2 − Lapp
KML = (7)
(Lapp − L%MLX2)[L]
where
[L]= [L]t − (L%MX2 − Lapp)[M]t/(L%MX2 − L%MLX2)
(8)
It is assumed that ion-pair formation, protonation
of the crown ether, and viscosity changes are
negligible.
Fig. 1. Plots of Lapp versus [L]t/[M]t for Zn(NO3)2 – and
Cd(NO3)2 – B18C6 systems in aqueous nitric acid solutions. , The plots of Lapp versus [L]t/[M]t for the
[Zn(NO3)2]init = 2.1× 10 − 3 M, pH 3.41; , [Cd(NO3)2]init = B18C6–Zn(NO3)2 and –Cd(NO3)2 systems are
3.0 × 10 − 3 M, pH 3.41. shown in Fig. 1. The Lapp decreases with an
640 S. Katsuta et al. / Talanta 51 (2000) 637–644
Fig. 2. Formation constants of metal(II) complexes with 18C6
and B18C6 in water as a function of ionic radius. The open
symbols denote 18C6, and filled symbols B18C6. The con-
stants for the alkaline earth metals and Hg2 + are cited from
the literatures [10–12].
increase in [L]t. The results show that the crown
ether forms a complex with the metal ion and that
the complex is less mobile than the corresponding
free metal ion. The KML was obtained by the
following procedure. The [L] of Eq. (8) was calcu-
lated using the L%MLX2 value estimated from the
Lapp at the highest [L]t. The values of KML and
L%MLX2 were evaluated from the slope and the
intercept of the (L%MX2 −Lapp)[L] − 1 versus Lapp
plot according to Eq. (7). The actual KML and
L%MLX2 values were obtained by an iterative proce-
dure. The final plot of (L%MX2 −Lapp)[L] − 1 versus
Lapp always gave a good linear relationship with a
correlation coefficient more than 0.97, indicating
that the above assumptions were valid. The con-
trol experiments without the metal salts showed
that the protonation of the crown ethers was
negligible. The formation constant of each com-
plex was determined from the average value of
3–5 measurements; the log KML of Zn(18C6)2 + ,
Zn(B18C6)2 + , and Cd(B18C6)2 + are 0.539 0.15,
0.6090.07, and 0.1190.02, respectively; that of
Cd(18C6)2 + was previously reported to be
−0.0590.03 [9].
In Fig. 2, the log KML values of bivalent zinc
group and alkaline earth metals with 18C6 and
B18C6 are shown as a function of the ionic radius
[2]. The values for the alkaline earth metals and
Hg2 + are cited from the literature [10–12].
Among the alkaline earth metals, the complex
formation constant is the largest for Ba2 + that is
best fitted into the ligand cavities. The ionic sizes
of the zinc group metals are all smaller than the
ligand cavities; they decrease in the order Hg2 + \
Cd2 + \ Zn2 + . 18C6 forms a more stable complex
with Hg2 + than with Zn2 + and Cd2 + , as is to be
expected from the size-fit concept. However, for
18C6 or B18C6, the complex of Zn2 + is unexpect-
edly more stable than the corresponding Cd2 +
complex. The complexation selectivity of these
crown ethers toward Zn2 + and Cd2 + does not
obey the size-fit concept, but is in accord with the
selectivity of oxygen-donating chelate ligands such
as oxalic acid and lactic acid that generally form
more stable complexes with the smaller cation
[13].
For Sr2 + and Ba2 + , the formation constant of
the 18C6 complex is larger than that of the corre-
sponding B18C6 complex. On the other hand, for
the smaller Zn2 + and Cd2, the constant of the
18C6 complex is almost equal to or slightly
smaller than that of the B18C6 complex. A similar
trend is observed for the alkali metal ion com-
plexes: 18C6 forms more stable complexes with
K+ and Rb+ than B18C6 does, whereas the
reverse holds for the smaller Na+ [12]. The differ-
ences in complexing ability in water between the
crown ethers can be discussed based on the fol-
lowing thermodynamic cycle:
DG oc,w = DG oc,g + DG oh(MLm + )− DG oh(Mm + )
− DG oh(L) (9)
where subscripts (g) and (w) denote the species in
the gas and water phases, respectively; DG oc,g and
DG oc,w are the Gibbs free energies of complexation
in the gas and water phases, respectively; DG oh is
 S. Katsuta et al. / Talanta 51 (2000) 637–644
the Gibbs free energy of hydration. From Eq. (9),
the difference in DG oc,w between the crown ethers,
DDG oc,w =DG oc,w(B18C6) −DG oc,w(18C6), can be
expressed as
DDG oc,w =DDG oc,g +DDG oh(MLm + ) − DDG oh(L)
(10)
where DDG oc,g =DG oc,g(B18C6) − DG oc,g(18C6),
DDG h(ML ) = DG oh(MB18C6m + ) − DG oh(M18-
o m+
C6m + ), and DDG oh(L) =DG oh(B18C6) − DG oh-
641
ion in the B18C6 complex is less effectively
shielded from the surrounding solvents by the
ether oxygen atoms than in the 18C6 complexes,
resulting in stronger interaction with water of the
metal ion in the B18C6 complex. Since the hydro-
gen bond interaction between water and the un-
complexed ligand is greater for 18C6 than for
B18C6, DDG oh(MLm + ) should be much smaller
than DDG oh(L) (i.e. DDG oh(MLm + )− DDG oh(L)
0). According to Eq. (10), the negative value of
(18C6). DDG oc,w indicates that DDG oc,g B DDG oh(MLm + )
For K+, Rb+, Sr2 + , and Ba2 + the size of − DDG oh(L). It can therefore be presumed that
which is close to the cavity, the crown ether the main reasons for the higher complexing ability
probably adopts the D3d conformation and its six of B18C6 than 18C6 for the size-misfitted small
oxygen atoms coordinate to the metal ion [14,15]. metal ions in water are the less effective shielding
It is well known that the benzo group exerts an of the metal ion in the B18C6 complex and the
electron withdrawing effect on the ether oxygens. weaker hydrogen bonding of the uncomplexed
As a result, for a given metal ion, the B18C6 B18C6 with water.
complex is less stable than the 18C6 complex in
the gas phase (i.e. DDG oc,g \0). The values of 3.2. Extraction equilibria between benzene and
DDG oh(MLm + ) and DDG oh(L) are also regarded as water
positive because of the hydrophobicity of the
benzo group. On account of the higher basicity of When the metal ion is extracted as a neutral
an aliphatic ether oxygen than an aromatic ether complex (MLi A2) into benzene with B18C6 and
oxygen, hydrogen bonding of the ether oxygens picric acid (HA), the overall extraction equi-
with water is stronger for 18C6 than for B18C6. librium constant (Kex,i ) can be defined as
In the complex, the interactions with water of the
[MLi A2]o[H+]2
ether oxygens and the metal ion are greatly de- Kex,i = (11)
creased by ionic bonding of the ether oxygens to [M2 + ][L]io[HA]2o
the metal ion. Therefore, DDG oh(L) is expected to where the subscript ‘o’ and the lack of subscript
be larger than DDG oh(MLm + ) (i.e. DDG oh(MLm + ) denote the species in the organic and aqueous
− DDG oh(L)B0). Such an expectation is supported phases, respectively.
by the data of transfer activity coefficients When M2 + and ML2 + are the dominant spe-
of the solutes between water and nonaqueous cies in the aqueous phase, the distribution ratio of
solvents [12]. According to Eq. (10), the positive the metal (DM) is expressed as
value of DDG oc,w means that DDG oc,g \ n
DDG oh(MLm + ) − DDG oh(L); thus the lower com- % [MLi A2]o
plexing ability of B18C6, compared with 18C6, DM =
i=1

for the size-fitted metal ions in water is ascribed to [M2 + ]+ [ML2 + ]

the lower stability of the B18C6 complex in the n

gas phase. % Kex,i [L]io

For Na+, Zn2 + , and Cd2 + that are much
smaller than the cavity, the crown ether needs to
be distorted from its stable planner conformation
to hold the metal ion; the conformational change
is less drastic for the benzo-substituted ethers
because of the rigidity imposed by the benzo
group [14]. Therefore, it is expected that the metal
i=1
= K 2HAK 2d,HA[A−]2 (12)
1+ KMLK − 1
d,L [L]o
where KHA, Kd,HA, and Kd,L are the protonation
constant of a picrate ion in the aqueous phase
(KHA = [HA]/[H+][A−]), the distribution constant
of picric acid (Kd,HA = [HA]o/[HA]), and the dis-
tribution constant of B18C6 (Kd,L = [L]o/[L]), re-
642 S. Katsuta et al. / Talanta 51 (2000) 637–644

spectively; the values at 25°C are available, i.e. [HA]o + [L·HA]o

DHA = =D oHA(1+Kass,o[L]o)
KHA =1.95 [8], KHAKd,HA =247 [16], and Kd,L = [HA]+ [A−]
8.76 [17]. (15)
Eq. (12) can be transformed into o
where D denotes the distribution ratio of picric
HA
n acid in the absence of B18C6, and Kass,o is the
% Kex,i [L]io association constant defined as [L·HA]o/
DM i=1
= K 2HAK 2d,HA (13) [L]o[HA]o. Eq. (15) is transformed into
[A−]2 1+ KMLK − 1
d,L [L] o
DHA/D oHA − 1= Kass,o[L]o (16)
The overall extraction constant can be determined
The plot of log(DHA/D oHA − 1) versus log [L]o at
from the dependence of DM/[A−]2 on [L]o. The
fixed pH is shown in Fig. 3. The initial concentra-
following equation is also derived from Eq. (12):
tion of B18C6 was made to be in large excess over
that of picric acid so that [L]o could be calculated
1+KMLK − 1
d,L [L]o
DM n
=K 2HAK 2d,HA[A−]2 (14) using only the distribution constant of the crown
% Kex,i [L]oi ether, i.e. [L]o = [L]t/(1+ K − 1
d,L ). The plot shows a
i=1 straight line with a slope of 1.0090.02, indicating
that B18C6 forms a 1:1 complex with picric acid
The log–log plot of the left side of Eq. (14) versus in the benzene phase. According to Eq. (16),
[A−] should give a straight line with a slope of Kass,o = 8.229 0.30 was obtained.
two. The mass balance equations in the extraction
In the calculation of [L]o and [A−], the associa- system can be written as follows:
tion between B18C6 and picric acid in the organic
n
phase was considered. When B18C6 forms a 1:1
[M]t − % [MLi A2]o = [M2 + ]+ [ML2 + ] (17)
association complex with picric acid in the or- i=1
ganic phase, the distribution ratio of picric acid n
(DHA) can be expressed as follows: [L]t − % i[MLi A2]o = [L]+[L]o + [L·HA]o
i=1

+ [ML2 + ] (18)
n
[A]t − 2 % [MLi A2]o
i=1
−
= [A ]+ [HA]+ [HA]o + [L·HA]o (19)
where [A]t is the total concentration of picric acid.
In the present experiments, S[MLi A2]o,
Si[MLi A2]o, and 2S[MLi A2]o were negligibly
small compared with [M]t, [L]t, and [A]t, respec-
tively. In this case, [M2 + ], [L], and [HA]o can be
expressed as
[L]o = [L]t/(a +b[M2 + ]+ Kass,o[HA]o) (20)
[M2 + ]= [M]t/(1+ b[L]o) (21)
[HA]o = [A]t/(1+ Kass,o[L]o + c) (22)
−1 −1
where a= 1+ K , b=KMLK , and c=
d,L d,L

Fig. 3. Plots of log(DHA/D oHA − 1) versus log [L]o for extrac- K− 1 + −1

d,HA + (KHAKd,HA[H ]) . The combination of
tion of picric acid in the presence of B18C6 at constant pH. Eqs. (20)–(22) leads to the following cubic equa-
The solid line is obtained by the calculation based on Eq. (16). tion for [L]o:
 S. Katsuta et al. / Talanta 51 (2000) 637–644
Fig. 4. Plots of log(DM/[A−]2) versus log [L]o for extraction of
Zn2 + and Cd2 + as picrates with B18C6. The solid lines are
obtained by the calculation based on Eq. (13).
Table 1
The overall extraction constants, the ion-pair extraction con-
stants, and the adduct formation constants at 25°C for the
extraction of Zn2+ and Cd2+ picrates with B18C6 into ben-
zene
M2+ log Kex,1 log Kex,2 log Kex,ipa
Zn2+ −3.2090.03 −1.3690.02 1.92
Cd2+ −3.179 0.04 −1.629 0.04 2.44
a
Calculated from Eq. (24).
b
Calculated from Eq. (25).
abKass,o[L]3o + [a{b(1 +c) +Kass,o}
+bKass,o([M]t +[A]t −[L]t)][L]2o
+ [(1+ c)(a +b[M]t) +Kass,o[HA]t
− {b(1+c)+ Kass,o}[L]t][L]o −(1 +c)[L]t =0
This equation was solved by Newton’s method to
obtain [L]o. The [A−] value was calculated from
the equation [A−]= [HA]o/KHAKd,HA[H+], where
[HA]o was obtained from Eq. (22). The log(DM/
[A−]2) versus log[L]o plots are shown in Fig. 4.
The slope of each plot increases from 1.4 to 2.0
(Zn2 + ) or 1.2 to 1.9 (Cd2 + ) with an increase of
643
[L]o. The values of the slope indicate that the
extracted species are MLA2 and ML2A2, because
the term KMLK − 1
d,L [L]o in Eq. (13) was much
smaller than 1 (0.04 at the most). The Kex,1 and
Kex,2 were determined by a nonlinear least-squares
method based on Eq. (13), and the logarithmic
values are listed in Table 1. The solid lines in Fig.
4 are obtained from Eq. (13) by use of the extrac-
tion constants and agree well with the experimen-
tal data.
The slopes of the log{DM(1+KMLK − 1
d,L [L]o)/
2 −
(Kex,1[L]o + Kex,2[L]o)} versus log [A ] plots were
2.019 0.04 and 2.06 9 0.06 for Zn2 + and Cd2 + ,
respectively; they are identical with the theoretical
value from Eq. (14). If the association between
B18C6 and picric acid in the organic phase is
neglected, the slope deviates from two (ca 1.7).
These results mean that the consideration of the
B18C6–picric acid association is essential for the
equilibrium analysis in the present extraction
systems.
The formation of ML2A2 in the organic phase
supports the preceding conclusion that the too
small metal ion in the ML2 + complex is not
effectively screened by the ether oxygen atoms of
B18C6. In water, the formation of the ML22 +
log Kad,ob complex could not be detected. The very low
stability of ML22 + in water can be accounted for
1.84
1.55
by the remarkable interactions with water of the
metal ion in ML2 + and the ether oxygens of
uncomplexed L.
In spite of the higher stability of ZnL2 + than
CdL2 + in water, the Kex,1 values for Zn2 + and
Cd2 + are almost the same. On the other hand, the
Kex,2 value is larger for Zn2 + . The extraction
selectivities can be explained by the constituent
equilibria: the overall extraction constants are ex-
pressed as
Kex,1 = KMLKex,ipK − 1 −2
d,L (KHAKd,HA) (24)
(23)
Kex,2 = Kex,1Kad,o (25)
where Kex,ip and Kad,o are the ion-pair extraction
constant of the complex cation with the picrate
anion (Kex,ip = [MLA2]o/[ML2 + ][A−]2) and the
adduct formation constant in the organic phase
(Kad,o = [ML2A2]o/[MLA2]o[L]o), respectively. The
values of Kex,ip and Kad,o were calculated accord-
644 S. Katsuta et al. / Talanta 51 (2000) 637–644
ing to Eqs. (24) and (25), respectively, and the
logarithmic values are listed in Table 1. The log
Kex,ip value is smaller for Zn2 + than for Cd2 + .
The decrease in log Kex,ip from Cd2 + to Zn2 +
just cancels the increase in log KML, which is
responsible for the comparable log Kex,1 values
of these metal ions. The log Kad,o value is larger
for Zn2 + than for Cd2 + , and the difference in
log Kad,o between the two metals is reflected by
the difference in log Kex,2.
The larger Kad,o value of ZnLA2 than CdLA2
suggests that, even in the MLA2 form, Zn2 +
has a higher ability as an acceptor than Cd2 + .
The Kex,ip is further expressed as a product of
two elementary equilibrium constants, i.e. the
ion-pair formation constant in water (KMLA2 =
[MLA2]/[ML2 + ][A−]2) and the distribution con-
stant of the ion-pair (Kd,MLA2 =[MLA2]o
/[MLA2]). At this stage, these underlying con-
stants are unknown. However, from the higher
ability of ZnLA2 to accept an additional ligand,
it is suggested that ZnLA2 be more strongly hy-
drated in water than CdLA2, and that the distri-
bution constant of ZnLA2 is smaller; thus the
stronger hydration of ZnLA2 is responsible for
the smaller Kex,ip value.
Acknowledgements
This research was partly supported by a
Grant-in-Aid for Scientific Research No.
11740407 from the Ministry of Education, Sci-
ence and Culture.
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