Analytica Chimica Acta 470 (2002) 263276

Specific adsorption of halogen anions on hydrous -Al2 O3

W. Szczepaniak , H. Koscielna
Department of Analytical Chemistry, Faculty of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznan, Poland
Received 7 January 2002; received in revised form 26 June 2002; accepted 12 July 2002

Abstract
The paper reports results of a study on the specific adsorption of F , Cl , Br , I , ClO3 , BrO3 , IO3 and IO4 on
hydrous -Al2 O3 . The isotherms of the anion adsorption and the adsorption dependencies on pH and the ionic strength of the
solution have been determined under the equilibrium conditions. According to the degree of affinity to -Al2 O3 , the anions
can be ordered as: I < ClO3 < Br < Cl < BrO3 < IO3 < IO4 < F . It has been established that the sorption
of IO4 and F involves the formation of surface complexes in the inner co-ordination sphere, whereas that of Cl , Br ,
I , ClO3 , BrO3 and IO3 takes place through formation of ion pair complexes in the outer co-ordination sphere. In the
dynamic system, the exchange isoplanes and elution curves have been determined for selected anions on columns filled with
Al2 O3 . It has been shown that -Al2 O3 can be used for isolation and concentration of IO3 from natural waters in order
to decrease the limit of the ions determination to 2 g l1 . Using differential pulse voltammetry (DPV), after isolation and
concentration on -Al2 O3 , the content of iodates has been determined in mineral, marine and tap water doped with these ions.
2002 Published by Elsevier Science B.V.
Keywords: Hydrous -Al2 O3 ; Anion adsorption; Differential pulse voltammetry

1. Introduction mechanism of the charge appearance is related to the

Oxides of amphoteric metals dispersed in water en-
vironment undergo hydration and the surface oxide
and hydroxyl groups associate with the protons form-
ing positively charged complexes. The charge on the
solid interface depends on the pH of the water phase,
and for a certain pH, defined as the point of zero charge
(PZC), the surface charge is zero [1]. Below PZC, the
surfaces of the amphoteric metal oxides are positively
charged, while above PZC negatively. For -Al2 O3 ,
PZC varies from 7.4 to 8.6 [2,3]. Many authors have
been concerned with the phenomenon of the appear-
ance of primary charge on the surface of amphoteric
metal oxides. It has been commonly accepted that the
Corresponding author.
E-mail address: hkoscielna@poczta.onet.pl (W. Szczepaniak).
adsorption and desorption of protons by active surface
oxygen centres. This explanation is based on the 2-pK
model [46] and the model of multisite complexation
(MUSIC) [711]. According to the first model, the
surface oxygen centres are homogeneous and the reac-
tions describing the appearance of the primary charge
on -Al2 O3 are as follows:
AlO + Hs+
AlOH (1)
AlOH + Hs+
AlOH2 + (2)
where Hs+ is a proton in the hydration layer of the
surface.
According to the MUSIC theory, the surface of
metal (hydro)oxides is heterogeneous, as indicated by
spectroscopic studies. The active oxygen centres can
be bonded with the central atom through a single,

0003-2670/02/$ see front matter 2002 Published by Elsevier Science B.V.

PII: S 0 0 0 3 - 2 6 7 0 ( 0 2 ) 0 0 6 6 1 - X
264 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276
double or triple bond. On the surface of -Al2 O3
there are groups AlO, Al2 O and Al3 O, and
their formal charges are AlO3/2 , Al2 O and
Al3 O1/2 . The groups undergo protonation similarly
as it is assumed in the 2-pK model.
This model and the MUSIC theory imply that de-
pending on the pH of the environment, the surface of
hydrous aluminium oxide can host positively or nega-
tively charged groups. To satisfy the principle of neu-
trality, the surface of hydrous aluminium oxide adsorbs
cations or anions from the electrolyte solution at pH
higher or lower than PZC, respectively. The process
of sorption of the cations and anions on the charged
amphoteric metal oxides is described by the surface
complexation models (SCMs) [1216] of which we
are interested in the triple-layer model (TLM) [1719]
because this model gives a good explanation of the dif-
ferences between anions weakly and strongly bonding
with surface oxide.
According to this model, the sorption of anions
leads to formation of the following.
1. Surface complexes in the inner co-ordination
sphere.
2. Complexes of ion pair in the outer co-ordination
sphere.
3. Diffuse layer.
The surface complexes in the inner co-ordination
sphere are formed with the anions relatively strongly
bonded with -Al2 O3 , e.g. selenates(IV), while the
ion pair complexes in the outer co-ordination sphere
are formed with those making weaker bonds -Al2 O3 ,
e.g. nitrates(V) and selenates(VI) [18].
The specific adsorption of anions on hydrous
-Al2 O3 was used for separation of anions by the
ion chromatography [20], thin-layer chromatogra-
phy [21,22] for separation and concentration of
Se(IV) and Se(VI) [23], and Cr(VI) [2426]. More-
over, the specific adsorption of organic anions
[27,28], [Fe(CN)6 ]4 and [Fe(CN)6 ]3 was studied
[29].
This paper presents results of a study on specific
sorption of halide anions (F , Cl , Br , I , ClO3 ,
BrO3 , IO3 and IO4 ) on hydrous -Al2 O3 . The
study was undertaken to find out whether -Al2 O3
can be used in analytical methods of isolation and
concentration of bromates and iodates from water
solutions.
2. Experimental
2.1. Reagents and solutions
All reagents used for preparation of solutions were
of analytical grade. The following reagents were em-
ployed: NaF, NH4 F, NaCl, KCl, KBr, KI, KClO3 ,
KBrO3 , KIO3 , NH4 OH, NaClO4 and H2 SO4 (all from
POCh, Gliwice), KIO4 (Aldrich), HClO4 (Hopkin &
Williams Company), brucine (U.C.B., Belgium). The
water used in solutions was purified using a Milli-Q
Plus instrument (Millipore, S.A. 67120 Molsheim,
France). The aluminium oxide was commercial 90
active acidic (Merck, Darmstad, Germany) with grain
size 0.060.2 mm. The surface area of alumina de-
termined from measurements of low-temperature
adsorption of nitrogen on ASAP-2010 spectropho-
tometer (Micromeritics, USA) was 97 m2 g1 . Prior
to use, an Al2 O3 sample of a given weight was first
washed with 102 M NaOH and then eluted with wa-
ter to a constant conductivity of the supernatant. Solid
and solution were separated by centrifuging and the
treated Al2 O3 was redispersed in a given volume of
the solution investigated.
2.2. Apparatus
Bromates, iodates and periodates were determined
by differential pulse voltammetry (DPV) [30] with
the use of micro-Autolab (Eco Chemie B.V.) coupled
with a Metrohm 663 VA Stand. The three-electrode
system was made of a hanging mercury drop elec-
trode (HMDE), an Ag/AgCl (3 M KCl) reference
electrode and an auxiliary electrode of glassy carbon.
For voltammetric measurements, a 10 ml portion of
the solution studied was placed in a polarographic
vessel from which oxygen was removed by bubbling
with argon for 10 min. The accumulation of bromates
and iodates on the HMDE was carried out with stir-
ring at the accumulation potential (Eacc ) for 10 s,
Eacc = 1.3 V for BrO3 and 0.6 V for IO3 and
IO4 . The pulse amplitude was 50 mV and the pulse
interval time was 0.2 s.
Chlorates were determined spectrophotometrically
making use of the reaction between the ClO3 ions
and brucine in sulphuric acid [31]. Measurements of
absorbance were carried out in a quartz cell (optical
path length 10 mm), in a single-beam Hewlett-Packard
 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276
8453 spectrophotometer, with a diode array detector.
Fluorides, chlorides, bromides and iodides were de-
termined by direct potentiometry using ion-selective
electrodes using the multi-titration system DTS-800
(Radiometer, Copenhagen).
Chromatographic analysis was performed on
an ion chromatograph (LaChrom, Merck, Hitachi)
equipped with a L-7100 pump, a conductivity detector
(type L-7470), an electrochemical suppressor (ERIS
1000HP autosuppressor, Alltech), a column oven
(L-7350) with a 20 l loop injector and a diode array
detector (L-7455). Chromatographic separations were
made on an analytical column filled with Al2 O3
Alusphere Al 100 (250 mm 4 mm, 5 m particle
size, Merck) at 25 C. The mobile phases applied
were: 102 M benzoic acid, pH 6.8 (POCh, Gliwice),
5103 M propionic acid, pH 6.74 (Roalar, Hungary),
2 104 M 2,5-dihydroxy-1,4-benzenedisulfonic
acid, pH 6.5 (Acros Organics, USA) and 5 103 M
p-hydroxybenzoic acid (KOCh-light Laborato-
ries Ltd., UK). The flow rate of the eluent was
1 ml min1 . The range of the conductivity detector
was 100 S cm1 . The wavelength of 312 nm was
used in spectrophotometric detection. The pH values
of the eluents were adjusted to desired values with
the help of 1 M NaOH. The concentration of the stan-
dard solutions was 1 g ml1 . The pH values were
controlled by measurements on a pH meter made
by Mera-Elwro type N517 with a combination glass
electrode OSH 1000 (Metron).
2.3. Adsorption in a system at equilibrium
The isotherms of anions A (F , Cl , Br , I ,
ClO3 , BrO3 , IO3 and IO4 ) adsorption were de-
termined in solutions of a constant ionic strength of
0.06 M, in the HClO4 NaClO4 A system. Portions
of 1 g of earlier prepared -Al2 O3 were placed in six
polyethylene bottles to which portions of 25 ml of
2102 M of HClO4 were added. After 24 h, NaClO4
and A were added to obtain 50 ml portions of the
solutions with the initial values of ions A concen-
trations: 5 102 , 2.5 102 , 1 102 , 5 103 ,
1 103 and 5 104 M.
The bottles were placed in a shaker bath at 25 C for
2 days. The supernatant solutions were then analysed
for the content of A anions. In the same conditions
the following adsorptions were determined.
265
Adsorption of hydrogen ions from the solutions
HClO4 NaClO4 .
Adsorption of BrO3 , IO3 , IO4 and F anions
as a function of pH of the water solution in the
HClO4 NaClO4 A system.
Adsorption of BrO3 , IO3 and IO4 ions from
the solutions of a constant pH 4 and different ionic
strength in HClNaCl5 103 M A system.
2.4. Adsorption in a dynamic system
In the dynamic conditions, the exchange isoplanes
(the exchange isoplanein the method frontal anal-
ysis is a curve relationship between the c/c0 ratio
(where c is the initial concentration of solution and
c0 the concentration in fraction after pass through
the column) and the volume fraction) and elution
curves were obtained for some selected anions on
columns filled with -Al2 O3 . The exchange isoplanes
were determined on glass columns of 0.8 cm in di-
ameter filled with 10 g of -Al2 O3 . The column was
washed with 102 M of HClO4 (or NH4 OH for F
and IO4 analysis) until the concentration of the acid
(NH4 OH) in the eluate was 102 M. Then an amount
of 102 M A in 102 M HClO4 (or NH4 OH) was
passed through the column. The eluate was collected
in 100 ml fractions and the concentration of anion A
was determined. The flow rate of the solution was
1 ml min1 .
The elution curves of a given anion A were de-
termined on SPE columns packed with 1 g -Al2 O3 .
The amount of 0.1 mmol of the anion A was sorbed
on the columns and then eluted. The eluate was col-
lected in 2 ml fractions in which the concentration of
the anion was determined.
3. Results and discussion
3.1. Exchange in the system at equilibrium
3.1.1. The isotherm of proton adsorption
The isotherm of proton adsorption is shown in
Fig. 1. The sorption of protons is related to the ap-
pearance of primary charge on the surface of hydrous
-Al2 O3 , according to reaction (2). The shape of the
isotherm resembles the letter S and the proton ad-
sorption can be read out to begin at pH 7.5, taking a
266 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276

Fig. 1. The isotherm of the protons adsorption from a solution of HClO4 NaClO4 on hydrous -Al2 O3 (the equilibrium reached after 48 h
at 25 C).

maximum value of 0.919 mmol g1 or 9.77 mol m2 classical ion exchange reaction according to the
for pH of 12. scheme:
Kip
3.1.2. The sorption of the anions BrO3 , IO3 , AlOH + H+ ClO4
AlOH2 + ClO4 (4)
IO4 and F versus pH of the external solution
The data describing the adsorption of the anions AlOH2 + ClO4 + BrO3
BrO3 , IO3 , IO4 and F on hydrous -Al2 O3 as Kex
a function of pH of the external solution are given in
AlOH2 + BrO3 + ClO4 (5)
Fig. 2 and Table 1.
As follows from the data presented in Fig. 2 and
AlOH2 + ClO4 + IO3
Table 1, the adsorption of BrO3 and IO3 signifi-
Kex
cantly depends on pH and increases with increasing
AlOH2 + IO3 + ClO4 (6)
concentration of protons in the solution, so with in-
creasing protonation of -Al2 O3 , in agreement with The apparent constant of the ion exchange reaction
Eq. (2). In neutral solutions, the sorption of BrO3 can be expressed by:
and IO3 is close to zero, and with increasing concen- {AlOH2 + A}[B ]
tration of hydrogen ions it increases, which means that Kex = (7)
{AlOH2 + B}[A ]
these two anions are adsorbed according to the mech-
anism of ion pair formation in the outer co-ordination where Kex is the apparent equilibrium constant of the
sphere: ion exchange reaction, {} the concentration of the
AlOH + H+ A
AlOH2 + A anion bonded to -Al2 O3 (mol kg1 ), [] the concen-
(3)
tration of the anion in the outer solution (M), B the
It should be noted that the adsorption of BrO3 and anion originally bonded to -Al2 O3 (in this reaction
IO3 takes place in the excess of ClO4 so it is a ClO4 ) and A the anion in the outer solution under-
 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276 267

Fig. 2. The adsorption of the ions BrO3 (), IO3 (), IO4 () and F () on -Al2 O3 vs. pH of the solutions, in the presence of
the ions ClO4 (C0,A = 5 103 M).

going the ion exchange (in this reaction BrO3 and groups on the surface of -Al2 O3 . Therefore, this
IO3 ). sorption is concluded to take place through the forma-
The selectivity coefficient is equal to the ratio of the tion of complexes in the inner co-ordination sphere,
coefficients of partition (Ds): according to the schemes:
Kis
{AlOH2 + A } {AlOH2 + B } AlOH + IO4
AlIO4 + OH (9)
DA = , DB =
[A ] [B ] Kis
(8) AlOH + F
AlF + OH (10)

The partition coefficient DA can be calculated from where Kis for F > Kis for IO4 .
the analytical data, that is, from the known initial In acidic solutions, along with the complexation in
concentration of the anion A (C0,A ) and the equi- the inner co-ordination sphere, also the formation of
librium concentration of the anion A (Ceq,A ) (the ion pairs takes place in the outer co-ordination sphere,
values given in Tables 1 and 2 are mean of three according to the schemes:
measurements; n = 3). On the basis of the analytical AlOH2 + ClO4 + IO4
data, the sorption of A on -Al2 O3 (A ) can be Kex
calculated in mmol g1 or in mol m2 . The changes
AlOH2 + IO4 + ClO4 (11)
of the pH of the solution have a small effect on the
sorption of the anions IO4 and F . In the neutral or AlOH2 + ClO4 + F
basic solutions, the sorption of IO4 is 0.19 mmol g1 Kex

AlOH2 + F + ClO4 (12)
and F is 0.203 mmol g1 , while in acidic solutions
it increases to 0.208 and 0.24 mmol g1 , respectively. In this case, Kex for F
> Kex for IO4 .

This observation means that -Al2 O3 adsorbs these The total sorption in an acidic environment T is a
anions at PZC, although then there are no AlOH2 + sum of the sorption in the inner co-ordination sphere
268 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276

Table 1
The sorption of BrO3 , IO3 , IO4 and F on hydrous -Al2 O3 as a function of pH of the solution (n = 3)
Anion A pHeq Ceq,A (103 M) Adsorption A DA Percentage sorption

mol kg1 mol m2

BrO3 1.50 2.580 0.124 1.28 48.06 49.5

3.97 3.340 0.083 0.85 24.85 33.2
4.30 3.710 0.064 0.66 17.25 25.6
6.30 4.240 0.0039 0.04 0.92 1.56
7.28 4.900 0.0005 0.05 0.10 0.2
IO3 1.45 0.610 0.220 2.27 360.65 88.0
4.00 1.650 0.167 1.72 101.21 66.8
4.73 1.900 0.142 1.46 74.74 56.8
6.04 3.820 0.062 0.64 16.75 24.8
7.04 4.970 0.0017 0.018 0.34 0.68
IO4 1.46 0.960 0.202 2.08 210.42 80.8
3.34 0.848 0.208 ( T ) 2.14 245.28 (DT ) 83.2
3.80 0.881 0.206 2.12 233.82 82.4
7.04 1.250 0.188 1.94 150.40 75.2
7.54 1.210 0.189 1.95 156.20 75.8
9.30 0.190 ( is ) 1.96 224.05 (Dis ) 76.0
0.018 ( ip ) 0.186 21.23 (Dip ) 7.2
F 4.00 0.192 0.240 ( T ) 2.47 1250.00 (DT ) 96.0
9.30 0.203 ( is ) 2.09 1057.30 (Dis ) 81.2
0.037 ( ip ) 0.38 192.70 (Dip ) 14.8

C0,A = 5 103 M; C0,ClO4 = 5 102 M.

( is ) and that in the outer co-ordination sphere involv-
ing ion pair formation ( ip ), so:
T = is + ip
The values of T , is and ip obtained from the
anions IO4 and F , together with the corresponding
partition coefficients (DT , Dis and Dip ), are shown in
Table 1.
Thus, the above evidence suggests that the opin-
ion of some authors that the oxides of amphoteric
metals adsorb anions at pH below PZC needs some
specification. This view is correct only for the anions

Table 2
Partition coefficient (DA ), the equilibrium concentration of the anion A (Ceq,A ), the sorption capacity of the anions A (A ) (in the
equilibrium conditions) and the percent of the anions sorption on hydrous -Al2 O3 (n = 3)
Anion A Ceq,A (M) A DA Percentage sorption

mol kg1 mol m2

I 4.78 103 0.011 0.113 2.30 4.4

ClO3 4.56 103 0.022 0.227 4.82 8.8
Br 4.54 103 0.023 0.237 5.06 9.2
Cl 4.22 103 0.039 0.402 9.24 15.6
BrO3 3.26 103 0.087 0.897 26.69 34.8
IO3 1.62 103 0.169 1.740 104.32 67.6
IO4 8.40 104 0.208 ( T ) 2.140 247.62 (DT ) 83.2
F 1.92 104 0.240 ( T ) 2.470 1250.00 (DT ) 96.0

C0,A = 5 103 M; C0,ClO4 = 5.5 102 M.

 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276 269

forming complexes in the outer co-ordination sphere.
The anions strongly adsorbing on these oxides and
able to form complexes in the inner co-ordination
sphere can be adsorbed not only at the acidic but
also at neutral and basic pH so above and below
PZC.
3.1.3. The isotherms of halide anions adsorption
at a constant ionic strength and a constant pH.
The isotherms of adsorption of halogen anions on
hydrous -Al2 O3 , showing the anion A adsorption
in mol m2 as a function of the equilibrium con-
centration of a given anion in the outer solution, are
given in Fig. 3. The course of the isotherms implies the
following.
Significant differences in the affinity of the anions
studied to hydrous -Al2 O3 at pH 4.
The presence of the two types of isotherms: type H
(high affinity) for the anions F , IO4 and IO3 ,
and type L (Langmuir plot) for the anions Cl , Br ,
I , ClO3 and BrO3 .

Fig. 3. The isotherms of the anions F , Cl , Br , I , ClO3 , BrO3 , IO3 and IO4 adsorption on hydrous -Al2 O3 in an environment
of ClO4 (pH 4; ionic strength 0.06 M).
270 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276
Considerable differences in the partition coefficient
D (significant differences in the slopes of the curves
in the range of low concentrations).
Table 2 presents the sorption capacity, partition co-
efficient DA and the percent of sorption for the initial
concentration of the anion A of 5 103 M and the
anion ClO4 of 5.5 102 M.
According to the affinity of the anions to hydrous
-Al2 O3 in an acidic environment, obtained on the
basis of the partition coefficient DA , the anions can be
ordered as:
ClO4 < I < ClO3 < Br < Cl < BrO3
< IO3 < IO4 < F
The anions Cl , Br , I , ClO3 , BrO3 and IO3
react with -Al2 O3 according to the mechanism of
ion pair formation (Eq. (4)) and in the system studied
the ion exchange reaction takes place (Eq. (5)). As
evident from Table 1, the strongly adsorbed anions F
and IO4 form complexes in the inner co-ordination
sphere and ion pair complexes.
Fig. 4. The adsorption of the ions BrO3 (), IO3 () and IO4 () on hydrous -Al2 O3 vs. the ionic strength of the solutions, in
the presence of Cl (C0,A = 5 103 M).
3.1.4. Adsorption of the anions BrO3 , IO3 and
IO4 versus ionic strength
A suitable model for investigation of the effect of
ionic strength on the anion sorption is the TLM [17],
because other SCMs treat only one type of complex
and this model gives a good explanation of the dif-
ferences between anions weakly and strongly bonded
with the surface oxide. It is expected that a change
in ionic strength would have a different effect on the
sorption of the anions forming the ion pair complexes
in the outer sphere of co-ordination, according to re-
action (5), and those forming complexes in the inner
sphere of co-ordination, according to reaction (9). The
adsorption of the anions BrO3 , IO3 and IO4 ver-
sus the ionic strength varied in the range 0.030.18 M
at a constant pH 4 and a constant concentration of
the anion A 5 103 M is presented in Fig. 4.
The ionic strength and pH were controlled by HCl
and NaCl.
The changes of the ionic strength in the range
0.030.18 M had little effect on the adsorption
of IO4 , but significantly affected the adsorp-
tion of BrO3 and IO3 . This provides additional
 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276
confirmation of the different mechanisms of adsorp-
tion of these anions.
3.2. Selectivity of the ion exchange of the
anions on -Al2 O3
An interesting question is a different sequence of
the anions in the series according to the affinity to
-Al2 O3 and to the classic anion exchangers contain-
ing quaternary ammonium salts as active groups. For
instance, the series arranged according to the affinity
to Dowex 50 X8 anion exchanger is:
F < IO3 < Cl BrO3 < ClO3 < Br < I
The sequence of the anions in this series is the op-
posite to that in the series according to the affinity to
-Al2 O3 . First of all, it must be noted that the series
of the anions affinity on the classical ion exchanges
have been explained on the basis of the two following
effects [32].
1. Electrostatic interactions between the ion ex-
changer functional groups and counter-ions.
2. Energy of the counter-ion hydration.
Fig. 5. The log DA for the ions F (log Dip ), Cl , Br and I vs. the hydration energy on hydrous -Al2 O3 .
271
Thus, the series of the anions according to the
affinity to the anion exchangers containing quaternary
ammonium salts as active groups is the same as that
according to the Hofmeister lyophility, so the lower
the hydration energy the stronger bonded the anion
of the same valency. For hydrous -Al2 O3 , the situa-
tion is the reverse. The hydration energy increases as
I < Br < Cl < F and the same is the sequence
according to the affinity to -Al2 O3 . The log DA
for the halide anions versus the hydration energy is
shown in Fig. 5.
To explain this anomaly we used the Pearsons the-
ory of hard and soft acids and bases (HSAB) [33]. The
cation Al3+ is a hard Lewis acid and, according to the
HSAB theory, it forms stronger bonds with hard bases.
The series of halogenides and OH group, according
to decreasing hardness (the hardness parameter of the
bases En + is given in parentheses) is as follows:
I (8.31) < Br (9.22) < Cl (9.94)
< OH (10.45) < F (12.18)
so the lower the value of En + , the harder the base.
Therefore, the fluorine anion forms the strongest,
while the iodide anion the weakest, bonds with a hard
272 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276
Fig. 6. The log DA for the ions I , Br , Cl and F adsorption on hydrous -Al2 O3 vs. the bases hardness parameter En + .
acid. Fig. 6 presents the dependence of log DA on the
value of En + . For Cl , Br and I , these dependen-
cies are linear. For fluorine anions (F ), the value
of log DA significantly deviates from linearity, which
can be related to the two-fold mechanism of fluoride
bonding, as mentioned above.
Fig. 7 presents the partition coefficient DA , for halo-
gen anions as a function of the ionic radius of the
anions. For halogen anions, the smaller their ionic ra-
dius the harder the base and the stronger the anion
bond with -Al2 O3 , whereas for halate anions (ClO3 ,
BrO3 and IO3 ), the smaller the ionic radius the
weaker the anion bond with -Al2 O3 .
3.3. The exchange in the dynamic system
The exchange isoplanes for the anions Cl , BrO3 ,
IO3 , IO4 and F , were determined on columns
filled with 10 g -Al2 O3 , from the A solutions of a
concentration 102 M and against 102 M HClO4 (or
NH4 OH). The total sorption capacities in the envi-
ronment 102 M HClO4 were 0.152 mmol g1 (Cl ),
0.245 mmol g1 (BrO3 ), 0.34 mmol g1 (IO3 ) and
0.3 mmol g1 (IO4 ), and the working sorption ca-
pacities were 0.145 mmol g1 (Cl ), 0.195 mmol g1
(BrO3 ), 0.2 mmol g1 (IO3 ) and 0.2 mmol g1
(IO4 ). The total sorption capacities in the environ-
ment 102 M NH4 OH for IO4 and F were 0.19 and
0.203 mmol g1 , respectively, and the working sorp-
tion capacity was 0.095 mmol g1 for both anions.
The curves of the anion elution were determined
on SPE columns filled with 1 g -Al2 O3 . Portions of
10 ml of 102 M of KA salt in 102 M HClO4 were
passed through the column. The anions adsorbed were
eluted with 0.1 M NH4 OH, the elution was successful
for Cl , BrO3 , IO3 , Br , I and ClO3 .
The anions BrO3 and IO3 can be also effectively
eluted from a column with -Al2 O3 using an ammo-
nia buffer of 0.1 M NH4 OH/0.1 M NH4 Cl and of pH
9.7, being simultaneously the basic electrolyte in the
voltammetric determination of these anions. The bro-
mates are totally washed out in 5 ml of the buffer,
while iodates in 10 ml.
The alkaline eluent neutralises the positive charge
on the -Al2 O3 surface, which consequently loses
its sorptive properties towards anions forming ion
pair complexes. Unfortunately, no suitable eluent was
found for fluorides and periodates.
 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276 273

Fig. 7. The partition coefficient DA determined for the ions Cl , Br , I , ClO3 , BrO3 and IO3 as a function of the ion radius, on
hydrous -Al2 O3 .

3.4. The exchange in a dynamic system by the
method of ion chromatography
The adsorption of the ions ClO4 , I , Br , Cl ,
ClO3 , BrO3 , IO3 and IO4 on Al2 O3 was studied
by the method of ion chromatography. The mobile
phases, retention times and the method of detection
are given in Table 3.
Periodates and iodates are not eluted with any of
the eluents studied. The series according to selectivity
determined on the basis of the retention data is as
follows:
ClO4 < I < ClO3 < Br < Cl < BrO3
which is in agreement with the series established
on the basis of the sorption studies in a equilibrium
system.
3.5. Determination of iodates in the sea, mineral
and tap water
The study of the sorptive properties of -Al2 O3
towards halide anions was undertaken in order to find
a selective sorbent suitable for isolation and concen-
tration of trace amounts of bromates and iodates from
water solutions. The results of the anion sorption in
a system at equilibrium and dynamic system allow a
conclusion that in certain conditions (ionic strength

Table 3
The retention times of the anions ClO4 , I , Br , Cl , ClO3 and BrO3 for a few acidic eluents on hydrous -Al2 O3
ClO4 I ClO3 Br Cl BrO3 Detector

Propionic acid 7.23 7.86 8.50 9.00 9.19 13.85 Kond

Benzoic acid 4.85 5.18 5.46 5.63 6.01 7.49 Kond
p-Hydroxybenzoic acid 5.14 5.53 5.87 6.04 6.53 8.69 Kond
2,5-Dihydroxy-1,4-benzenedisulfonic acid 4.85 5.08 5.58 5.73 6.67 9.24 DAD
Kond, conductivity detector; DAD, diode array detector.
274 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276

and pH), alumina is a suitable and selective sorbent
for the process of concentration. The concentration
of IO3 and BrO3 ions before a voltammetric mea-
surement permits a decrease in the determination limit
of these ions. The drinking water subjected to the
process of ozonisation contains harmful bromates and
iodates and for some time a simple method of their
determination has been looked for. In this study, we
used -Al2 O3 for isolation and concentration of IO3
from mineral waters and marine water from the Baltic
Sea.
We have proposed a method of determination of
iodates in an environment of ammonia buffer 0.1 M
NH4 OH/0.1 M NH4 Cl of pH 9.7, based on DPV.
The iodates are reduced at a potential of about
1.05 V. The peak of the reduction is well resolved
and its height depends linearly on the concentra-
tion of IO3 anions. The standard curve equation is:
y = (1.94 103 )x + (2.3 1010 ), where y = peak
height (A) and x = IO3 concentration (M) with
the correlation coefficient r 2 = 0.9993 (n = 5).
The limit of quantification is 9 108 M (16 g l1 )
(LQ = 6 b /a). The concentration of iodates on alu-
mina permits a reduction of LQ and thus enables their
determination at 10-fold concentration at the level of
2 g l1 . As follows from the study of the sorption of
iodates in the dynamic system, they are well sorbed
on -Al2 O3 from acidic solutions (102 M HClO4 )
and can be easily eluted from the column by the am-
monia buffer of pH 9.7. Such a system was applied
to isolate and concentrate of IO3 from tap water.
The portions of 1 g IO3 and 1 ml of 1 M HClO4
were added to 100 ml of tap water and the solution
was passed through an SPE column filled with 1 g
-Al2 O3 , at the rate of 2 ml min1 . The column was
washed with 2 ml of 102 M HClO4 and the iodates
were eluted with the ammonia buffer composed of
0.1 M NH4 OH/0.1 M NH4 Cl used in the amount of
10 ml. The iodates were determined in the whole vol-
ume of the buffer by the DPV method with threefold
standard addition technique.
Table 4 presents results of determinations of 1 g
IO3 in nine samples of 100 ml of tap water each, to-
gether with the statistical analysis. The accuracy of the
determinations is acceptable and the recovery of io-
dates is 80106%. The precision of determinations of
such a small amount of the iodates should be accepted
as good (R.S.D. = 9.5%).

Fig. 8. The differential pulse voltammograms for IO3 ions in mineral water (a) and for successive standard addition (b) 0.1, (c) 0.2 and
(d) 0.3 g ml1 IO3 . The pulse amplitude was 50 mV, the interval time was 0.2 s and the modulation time 0.05 s, tacc = 10 s.
 W. Szczepaniak, H. Koscielna / Analytica Chimica Acta 470 (2002) 263276 275

Table 4 co-ordination sphere, while that of the anions Cl ,

Results of the determination of IO3 (g) in 100 ml of tap water Br , I , ClO3 , BrO3 and IO3 to occur through
after concentration on -Al2 O3 (n = 9, = 95%)
formation of ion pairs in the outer co-ordination
Determined value of IO3 in Recovery (%) sphere. The exchange isoplanes and elution curves
100 ml of tap water (g/100 ml) have been determined for some anions on the columns
0.98 98 with -Al2 O3 in the dynamic system. It has been
1.04 104
shown that -Al2 O3 can be successfully used for iso-
0.80 80
0.87 87 lation and concentration of IO3 ions from samples
1.06 106 of natural waters, by using DPV.
0.93 93
1.01 101
1.01 101 Acknowledgements
0.86 86
x tsx = 0.95 0.07, R.S.D. = 9.5%. This work was supported by KBN Grant No. 3
T09A 06317.
The above-described method was used for determi-
nation of iodates in the marine water from the Baltic
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