Analytica Chimica Acta 419 (2000) 107114

Kinetic study of Ni(II) and Zn(II) complexation with a pyridylazo

extractant by a centrifugal liquid membrane method
Yoki Yulizar, Akira Ohashi, Hirohisa Nagatani, Hitoshi Watarai

Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
Received 6 March 2000; accepted 10 May 2000
Abstract
The centrifugal liquid membrane method, which provides an ultra-thin two phase liquid membrane system in a rotat-
ing glass cell, was successfully applied for the kinetic study of the liquidliquid extraction of nickel(II) and zinc(II) with
2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) in toluene. The initial extraction rate of the metal(II) com-
plexes depended upon the concentrations of the metal(II) ion and ligand. The rate determining step was revealed as 1:1 chelate
formation of Ni(II) or Zn(II) with 5-Br-PADAP adsorbed at the liquidliquid interface. The interfacial complexation rate
constants of Ni(II)5-Br-PADAP and Zn(II)5-Br-PADAP were determined as (4.10.1)10 and (2.40.6)10
3
M
1
s
1
at pH 6.500.02, respectively. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Liquidliquid extraction; Interfacial complexation; Extraction kinetics; 5-Br-PADAP; Centrifugal liquid membrane method
1. Introduction
Complexation at the liquidliquid interface is an es-
sential subject for understanding the mechanisms in
liquidliquid extraction of metal ions [1]. The study
of interfacial complexation in such extraction systems
provides signicant insight into the mechanism of the
related separation and detection methods, including
liquid membrane separation, ion selective electrodes,
optical sensors, and countercurrent chromatography.
To elucidate the fundamental features of the role of
the liquidliquid interface in the kinetics of chelate
extraction, Watarai et al. [2] have studied the inter-
facial mechanism in the extraction kinetics of Ni(II)
with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol
(5-Br-PADAP) by high-speed stirring spectrophotom-

Corresponding author. Tel.: +81-6850-5411;

fax: +81-6850-5411.
E-mail address: watarai@chem.sci.osaka-u.ac.jp (H. Watarai)
etry. Interfacial adsorption and dissociation of the lig-
and were the important factors governing the extrac-
tion rate.
Dynamic interfacial tensiometry, which is widely
used for the analysis of interfacial adsorption of vari-
ous surfactant [36] was employed to assess the com-
plexation kinetics at the liquidliquid interface in a
liquidliquid extraction system. This technique can
evaluate the interfacial concentration, which is dened
as the excess amount of molecules at the interface [7].
Recently, Nagatani and Watarai have developed a
new in situ spectrophotometric method, the centrifu-
gal liquid membrane method, to study the reaction ki-
netics of the demetallation of metal porphyrins at the
liquidliquid interface [8]. The ultra-thin two phase
liquid membranes were produced in a rotating opti-
cal cell, and the change of UVVIS spectra of the
ligand in the membranes including an interface was
observed directly by a photodiode array spectropho-
tometer. In the present study, we have applied the
0003-2670/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S0003- 2670( 00) 00970- 3
108 Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114
centrifugal liquid membrane method for the measure-
ment of metal(II)5-Br-PADAP complexation at the
toluene/water interface. In this case, a part of the lig-
and can adsorb at the interface and the complexation
with metal(II) in aqueous phase can take place at the
interface.
5-Br-PADAP was developed by Gusev and
Shchurova [9] and became a commonly used sensi-
tive reagent for traces of several transition elements
[1014], viz. V [15], Cu(II), Ni(II), Co(II), and Zn(II)
[16]. The present paper demonstrates the advantages
of the centrifugal liquid membrane method in the
study of the extraction kinetics.
2. Experimental
2.1. Reagents
Toluene (Nacalai Tesque Inc., G.R.) was puried
by fractional distillation after being stirred with con-
centrated sulfuric acid for 1 day (twice), washed suc-
cessively with distilled water and 5% sodium hydrox-
ide aqueous solution, and dehydrated by anhydrous
calcium chloride overnight. 5-Br-PADAP was used
as purchased from Dojindo Laboratories (Kumamoto,
Japan) without further purication and dissolved in
toluene. Astock solution of Ni(II) was prepared by dis-
solving nickel powder (>99.99% purity); the powder
was washed with 6 M HCl, which was evaporated, and
the residue dissolved in HNO
3
:H
2
O (1:1). The nitric
acid was evaporated by heating with a small amount
of perchloric acid. A stock solution of Zn(II) was pre-
pared by dissolving pure zinc metal (>99.998%) in a
small amount of perchloric acid. The ionic strength of
the aqueous phase was maintained at 0.1 M by sodium
perchlorate and perchloric acid. The pHwas controlled
by MES (510
3
M) and sodium hydroxide. All other
chemicals were reagent grade. The aqueous phase was
prepared by using distilled, deionized water puried
by a Milli-Q system (Millipore Corp.).
2.2. Extraction equilibria of metal(II) complexes
In advance of the kinetic investigation of the extrac-
tion behavior of metal(II) species with 5-Br-PADAP,
the extraction equilibria were determined by the batch
method [17], in a thermostated room at 2981 K.
The concentration of Ni(II) or Zn(II) in the aqueous
phase was 1.010
3
M. The ionic strength was xed
at 0.1 M with (H, Na)ClO
4
and the pH was changed
in the range of 1.996.84 for the Ni(II) system and
3.306.90 for the Zn(II) system, respectively, using
MES (5.010
3
M) and sodium hydroxide. The pH
was measured by a Horiba F-14 pH meter. The ini-
tial concentration of liqand in the organic phase was
2.010
5
M. Equal volumes (5 ml) of the two phases
were shaken in a glass tube for 24 h. After phase
separation, the absorption spectra of the aqueous
and organic phases were measured with a UVVIS
spectrophotometer (V-550, Jusco).
2.3. High-speed stirring measurement
A procedure of the extraction rate measurement of
Zn(II) with HL in toluene/water systems examined
by the high-speed stirring method was analogous to
that reported previously [1823]. An aqueous phase
(49.5 ml) without metal(II) solution and 50 ml of HL
in toluene were put into the glass stir cell, thermostated
by a water-jacket at 250.1

C and stirred at 5000 rpm.

The stirring rate was monitored by a speed controller
(Nikko Keisoku SC-5). The organic phase was contin-
uously separated from the agitated mixture by means
of a PTFE phase separator and circulated through a
ow cell with 10 mm optical path length installed in a
Shimadzu photodiode-array detector SPD-M 6A at a
ow rate of 15 ml min
1
by the Flumax Junior pump
(Fluid Metering Inc.). Before the addition of Zn(II) so-
lution, the interfacial adsorptivity of 5-Br-PADAP was
observed at the stirring speed of 5000 rpm. When the
stirring speed was decreased to 200 rpm, an increase of
organic phase absorbance was observed (Fig. 1). Zn(II)
stock solution (0.5 ml) was injected into the mixture
stirred at 5000 rpm and the extraction was initiated.
The initial concentration of HL in the organic
phase was 2.010
5
M and the Zn(II) concentration
in the aqueous phase was between 5.010
5
and
5.010
4
M. The pH was 6.50.05 and the ionic
strength was xed at 0.1 M with (H, Na)ClO
4
. Both
the consumption rate of 5-Br-PADAP and the forma-
tion rate of the complex in the organic phase were
recorded simultaneously at the absorption maxima,
462 and 527 nm, respectively. The absorbance change
was tted to a second order equation by the least
squares regression and the observed initial extraction
Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114 109
Fig. 1. Typical absorbance changes in toluene as a function
of extraction time measured by the high-speed stirring method;
[HL]=2.010
5
M, [Zn(II)]=5.010
4
M, pH 6.47.
rate (r
0
obs
) for the absorbance increase of the Zn(II)
complex in the organic phase was determined at the
start of the extraction.
2.4. Centrifugal liquid membrane measurement
An aqueous solution, 0.250 ml, containing metal(II)
ion, and 0.150 ml of toluene as the organic phase, were
put into the cylindrical glass cell. The inner diameter
and inner height of the cylindrical glass cell were 19
and 32 mm, respectively. The cell was stopped by a
PTFE plug attached to the rotation shaft of the high
speed motor Nakanishi Inc., NK-260. The high rota-
tion speed (10,000 rpm) was controlled by a Nakanishi
Inc., NE-22E 105 and monitored by a digital tachome-
ter (Ono Sokki HT-431). Because the density of the
toluene phase (0.862 g cm
3
) was lower than that of the
aqueous phase at 298 K [24], the two phase system
was spread out at the inner wall of the cylindrical glass
cell and produced a stable ultra-thin two phase liquid
membrane system that can be seen like a coated liquid
lm. The toluene phase was spread as an inner liq-
uid membrane with 80 m thickness and the aqueous
phase as an outer liquid membrane with 132 m thick-
ness which was sandwiched by the toluene layer and
the glass wall. The interfacial area between the two
phases, S
i
, was 18.8 cm
2
and the specic interfacial
area, S
i
/V
0
, was 125.6 cm
1
. The light beam passed
twice through the liquidliquid interface, as shown in
Fig. 2, and the summation of the absorbance of the
Fig. 2. Schematic drawing of the centrifugal liquid membrane
apparatus.
interfacial and bulk phase species in the rotating op-
tical cell was measured with a Hewlett-Packard HP
8452 A diode array spectrophotometer. The absorp-
tion spectrum of the liquid membrane systems was
recorded at 3.0 s intervals with an integration time of
3.0 s. From the absorbance change at the start of the
extraction, the observed initial rates (r
0
obs
) for the in-
crease of absorbance were calculated at 524 nm for the
Ni(II) complex and 527 nm for the Zn(II) complex.
To investigate the dependence on metal(II) con-
centration, the initial concentration of HL in the
organic phase being xed at 2.6410
4
M, the con-
centration of Ni(II) or Zn(II) in the aqueous phase
was changed in the range 3.010
3
1.010
2
M
and 2.010
5
1.010
3
M, respectively. To investi-
gate the dependence on HL concentration, the initial
concentration of HL was changed from 3.9610
5
to 1.9810
4
M at a constant concentration of
1.010
2
M Ni(II). As for the Zn(II) system, the ini-
tial concentrations of Zn(II) and HL were 1.010
3
M
and 2.010
5
1.010
4
M, respectively. The pH
and ionic strength were xed at 6.500.02 and 0.1 M
(H, Na)ClO
4
, respectively.
3. Results
3.1. Absorption spectra of extracted
metal(II)5-Br-PADAP complexes
Complexation was observed when 5-Br-PADAP
in toluene was shaken with metal(II) solution. The
red-violet Ni(II)5-Br-PADAP complex and the dark
red Zn(II)5-Br-PADAP complexes were extracted
110 Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114
Fig. 3. The absorption spectra of 5-Br-PADAP, Ni(II)5-Br-PADAP
and Zn(II)5-Br-PADAP in toluene.
into the organic phase, and the concentrations of the
complexes were determined spectrophotometrically.
Fig. 3 shows the spectra of the complexes in toluene
after factor analysis [25,26]. The molar absorptivi-
ties of 5-Br-PADAP at 462 nm, Ni(II)5-Br-PADAP
at 524 nm and Zn(II)5-Br-PADAP at 527 nm in
toluene were determined as 4.1910
4
, 9.9710
4
, and
1.0110
5
M
1
cm
1
, respectively.
3.2. Extraction rate measured by the high-speed
stirring method
When the high-speed stirring measurement was
conducted using a toluene solution of 2.010
5
M
HL, a very small amount of extractant was adsorbed
at the interface, as shown in Fig. 1. When the stir-
ring speed was changed from 200 to 5000 rpm, the
concentration of adsorbable species in the organic
phase decreased due to the increase in the interfacial
area. The amount of interfacial species, n
i
(mol) was
calculated by
n
i
=
i
S
i
= (A
200
A
5000
)
V
0
b
(1)
where
i
is the interfacial concentration of the species
(mol cm
2
), S
i
the interfacial area (cm
2
), A
200
and
A
5000
are the absorbances in the organic phase under
the low speed stirring (200 rpm) and the high-speed
stirring (5000 rpm) conditions, respectively, V
o
, and
b are the volume of the organic phase (l), molar ab-
sorptivity (M
1
cm
1
) and the optical path length of
the ow cell (cm).
The adsorption constant, K

, is dened in a dilute
solution of HL as
K

=
[HL]
i
[HL]
o
(2)
where [HL]
o
and [HL]
i
are the concentrations of HL
in the organic phase and at the interface, respectively.
From Eq. (1) the value of HL concentration at the in-
terface using S
i
=1.710
4
cm
2
[27] was obtained as
6.6810
13
mol cm
2
at the initial bulk phase con-
centration of 2.010
5
M HL. Therefore, the K

value
for 5-Br-PADAP was calculated as 3.3410
5
cm.
The addition of Zn(II) solution under high-speed
stirring caused a gradual increase of the complex
concentration and decrease of the ligand concen-
tration in the organic phase. A sudden lowering or
increasing of the stirring speed resulted in reversible
desorptionadsorption of the complex from the inter-
face, as shown in Fig. 1. These results indicated that
the zinc complex was adsorbed at the interface.
The initial extraction rate of the complex was
dened as
r
0
=
d
dt
[ZnL
2
]
o
(3)
and was obtained from r
0
obs
. The value of r
0
T
increased
linearly with the initial Zn concentration, as shown in
Fig. 4.
Fig. 4. The Zn(II) concentration dependence of the total initial
extraction rate of Zn(II)5-Br-PADAP measured by the high-speed
stirring method; [HL]=2.010
5
M, pH 6.50.05.
Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114 111
3.3. Extraction prole in centrifugal liquid
membrane measurement
The kinetic extraction proles observed for the
centrifugal liquid membrane measurement are shown
in Figs. 5a and 6a for the Ni(II) and Zn(II) systems,
respectively. The extraction of these complexes was
indicated by a gradual increase of absorbances at the
absorption maximum wavelength,
max
=524 nm for
Ni(II) and 527 nm for Zn(II), accompanied by the de-
crease of 5-Br-PADAP adsorbance at
max
=462 nm.
The initial absorbance increase of the Zn(II) complex
(Fig. 6a) was faster than that of the Ni(II) com-
plex (Fig. 5a). Figs. 5b and 6b show typical spectral
changes during Ni(II) and Zn(II) extraction in the
toluene/water system. Ni(II) complexation reached
equilibrium after ca. 3300 s from the start of the ex-
Fig. 5. Extraction prole of Ni(II)5-Br-PADAP measured by
the centrifugal liquid membrane method. (a) Absorbance changes
at xed wavelengths; (b) spectral change; [HL]=2.6410
4
M,
[Ni(II)]=1.010
2
M, pH 6.49.
Fig. 6. Extraction prole of Zn(II)5-Br-PADAP measured by
the centrifugal liquid membrane method. (a) Absorbance changes
at xed wavelengths; (b) spectral change; [HL]=1.3210
4
M,
[Zn(II)]=1.010
3
M, pH 6.49.
traction, while extraction equilibrium of the Zn(II)
complex was reached at ca. 240 s.
4. Discussion
4.1. Extraction scheme proposed for the
metal(II)5-Br-PADAP system
Metal(II) complexation at the liquidliquid interface
and the extraction mechanism of a metal(II) ion with
the extractant, HL, is schematically shown in Fig. 7.
The HL distributes between the bulk toluene phase and
the interface with the adsorption constant dened by
Eq. (2). In the high-speed stirring condition, the metal
ion in the aqueous phase at rst produced the inter-
mediate complex ML
+
i
at the interface. ML
+
i
further
112 Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114
Fig. 7. Scheme for metal(II) complexation at the liquidliquid interface and the extraction mechanism of a metal(II) ion with the extractant,
HL [2].
reacted with the HL
i
to form the uncharged complex
ML
2
adsorbed at the interface and extracted in toluene.
The total initial complexation rate, r
0
T
, was repre-
sented as
r
0
T
=
d
dt
[ZnL
2
]
o
+[ZnL
2
]
i
S
i
/V
o
] (4)
r
0
T
= r
0

1 +
[ZnL
2
]
i
S
i
[ZnL
2
]
o
V
o

(5)
The initial extraction rate has to be analyzed by
taking into account the distribution of the ligand, the
interfacial adsorption of the ligand and complexation
both in the aqueous phase and at the interface. We as-
sumed that the initial reaction proceeded by the fol-
lowing equations:
HL
o
HL
i
HL (6)
Zn
2+
+HL
i
k
i
ZnL
+
i
+H
+
(7)
Zn
2+
+HL
k
ZnL
+
+H
+
(8)
The rate lawfor the production of Zn(II)5-Br-PADAP
was predicted as
r
0
T
=

k[HL] +k
i
[HL]
i
S
i
V
o

[Zn
2+
] (9)
where k and k
i
are the formation rate constants in the
aqueous phase and at the interface. Considering the
distribution constant of HL in toluene, K
D
=10
4.78
[2] and the low concentration of HL in toluene,
k[HL]k
i
[HL]
i
S
i
/V
o
under the high-speed stirring
condition. Therefore, Eq. (9) can be written as
r
0
T
=
k
i
[Zn
2+
][HL]
i
S
i
V
o
(10)
From the slope in Fig. 4 and S
i
=1.710
4
cm
2
, the
value of the formation rate constant of the Zn(II) com-
plex at the interface (k
i
) for the high-speed stirring
method was calculated as (9.50.5)10
2
M
1
s
1
in
the toluene/water system.
4.2. Metal(II) concentration dependence of the
extraction rate
The absorbance increase of the metal(II) complex at
524 nm for NiL
2
or 527 nm for ZnL
2
observed by the
centrifugal liquid membrane method gave the initial
extraction rate, r
0
obs
, dened as
r
0
obs
=
d
dt
[[ML
2
]
o
+[ML
2
]
i
S
i
/V
o
] 2l (11)
where l is the thickness of the organic phase.
Fig. 8 conrms the rate law for metal(II) complexa-
tion since the concentration of HL in the toluene phase
is constant
r
0
obs
= k
obs
[M
2+
] (12)
where k
obs
(s
1
) is the observed rate constant. In the
Zn(II) system, when the initial concentration of Zn(II)
is >8.010
4
M at pH 6.5, Zn(II)5-Br-PADAP com-
plexation was very fast so as to occur before the mea-
surement, so that the observed initial rate was obtained
from the extrapolated absorbance change before the
start of measurement.
Because this method has a small specic inter-
facial area, we assumed that the initial complexa-
tion occurred both in the aqueous phase and at the
interface, as predicted by Eq. (9).
Eq. (12) was correlated to Eq. (13)
r
0
obs
=

k
K
D
+
k
i
K

S
i
V
o

[M
2+
][HL]
o
2l (13)
Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114 113
Fig. 8. Metal(II) concentration dependence of the initial extrac-
tion rate measured by the centrifugal liquid membrane method;
[HL]=2.6410
4
M, pH 6.50.02.
By using the values of the interfacial adsorption
constant, K

=3.3410
5
cm, for 5-Br-PADAP in
the toluene/water system obtained by the high-speed
stirring method, the complexation rate constants,
k=5.310
2
M
1
s
1
for Ni(II) [2] and k=4.510
4
M
1
s
1
for Zn(II) [28] in the aqueous phase de-
termined by stopped-ow spectrophotometry, the
distribution constant, log K
D
=4.78, V
0
=0.150 cm
3
and the interfacial area, S
i
=18.8 cm
2
, the values
of the complexation rate constants at the interface,
k
i
, in the toluene/water system were calculated as
(4.20.1)10 M
1
s
1
for Ni(II)5-Br-PADAP and
(2.80.1)10
3
M
1
s
1
for Zn(II)5-Br-PADAP.
4.3. 5-Br-PADAP concentration dependence of
extraction rate
When the concentration of metal(II) ion in the aque-
ous phase is in large excess over the ligand, the initial
rate law for metal(II) complexation was described as
r
0
obs
= k
obs
[HL]
T
(14)
as shown in Fig. 9.
By using Eq. (13) and the slope of the linear plot
in Fig. 9, the values of the complexation rate con-
stant at the interface of the Ni(II) and Zn(II) com-
plexes in the toluene/water system were calculated as
(4.00.1)10 and (2.00.0)10
3
M
1
s
1
, respec-
tively. From both of these concentration dependencies
Fig. 9. 5-Br-PADAP concentration dependence of the observed ini-
tial extraction rate of the metal(II) complex; [Ni(II)]=1.010
2
M,
[Zn(II)]=1.010
3
M, pH 6.50.02.
it was calculated that the percentage of the interfacial
complexation rate compared to the total reaction rate
was 95.2% for the Ni(II) complex and 93.0% for
Zn(II) complex in the toluene/water system.
5. Conclusions
The centrifugal liquid membrane method was
applied to kinetic studies of the extraction of
Ni(II)5-Br-PADAP and Zn(II)5-Br-PADAP in
toluene/water. The metal(II) extraction rates, which
depended on the concentration of 5-Br-PADAP in the
organic phase and the concentration of Ni(II) or Zn(II)
ion in the aqueous phase were measured directly by
spectrophotometry. The values of the interfacial com-
plexation rate constants obtained from the metal ion
and 5-Br-PADAP concentration dependence showed
good agreement, as shown in Table 1. Meanwhile,
the average values of the interfacial complexation
rate constant obtained by the centrifugal liquid mem-
brane method were a little larger than those obtained
by the high-speed stirring method. This may be due
to the difference in the experimental concentrations
between the two extraction systems; the centrifugal
liquid membrane extraction was conducted under
higher concentrations of HL and metal ion.
From all of the results, we proved the advantages
of the centrifugal liquid membrane method over
the high-speed stirring method as: (i) the reactions
114 Y. Yulizar et al. / Analytica Chimica Acta 419 (2000) 107114
Table 1
The values of the complexation rate constant of Ni(II) and Zn(II) with 5-Br-PADAP at the toluene/water interface (pH=6.50)
Metal(II) High-speed stirring method Centrifugal liquid membrane method
Metal(II) conc.
dependence
5-Br-PADAP conc.
dependence
Averaged value
of k
i
(M
1
s
1
)
Ni(II) k
i
=1.810 M
1
s
1
[2] k
i
=(4.20.1)10 M
1
s
1
;
[Ni
2+
]=3.010
3
1.010
2
M;
[HL]=2.6410
4
M
k
i
=(4.00.1)10 M
1
s
1
;
[Ni
2+
]=1.010
2
M;
[HL]=3.9610
5
1.9810
4
M
(4.10.1)10
Zn(II) k
i
=(9.50.5)10
2
M
1
s
1
;
[Zn
2+
]=5.010
5
5.010
4
M;
[HL]=2.010
5
M
k
i
=(2.80.1)10
3
M
1
s
1
;
[Zn
2+
]=2.010
5
1.010
3
M;
[HL]=2.6410
4
M
k
i
=(2.00.0)10
3
M
1
s
1
;
[Zn
2+
]=1.010
3
M
[HL]=2.010
5
1.010
4
M
(2.40.6)10
3
in the bulk phase and at the interface can be ob-
served simultaneously; (ii) a fast extraction rate, up to
210
6
Ms
1
, is readily measurable and (iii) small
amount of sample solution is required.
Acknowledgements
This study was nancially supported by a
grant-in-aid for Scientic Research (B) from the Min-
istry of Education, Science, Sports and Culture, Japan
(No. 10440222) and for JSPS Fellows (2308).
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