Colloids and Surfaces A: Physicochem. Eng.

Aspects 287 (2006) 203211

Characteristics of simplified ferron colorimetric solution and

its application in hydroxy-aluminum speciation
Chenghong Feng a, , Baoyou Shi a , Dongsheng Wang a , Guohong Li b , Hongxiao Tang a
a

State Key Lab of Environmental Aquatic Chemistry, RCEES, Chinese Academy of Sciences, Box 2871, Beijing 100085, China
b School of Water Resources & Environment, China University of Geosciences, Beijing 100083, China
Received 22 January 2006; received in revised form 27 March 2006; accepted 31 March 2006
Available online 7 April 2006

Abstract
Despite the wide application of ferron assay in hydroxy-Al speciation, the complexation mechanism in function remains unclear and there is
no generally accepted quantification stipulation. In this study, a simplified ferron colorimetric solution was suggested and characterized in its
application to the speciation of different hydroxy-Al samples with the aid of 27 Al NMR spectroscopy. Results show that with no addition of
hydroxylamine and orthophenanthroline, the simplified ferron colorimetric solution can become more stable and is applicable in speciation for Al
solutions with no or low content of iron ions (i.e., [Fe]/[Al] 0.05). Polymeric aluminum species, especially Al13 ([AlO4 Al12 (OH) 24 (H2 O)12 ]7+ )
may not react with ferron directly but via the process of Al decomposition. Al species of the similar form may have the same level of reaction
rate with ferron. The Ala -ferron interaction time adopted to quantify Ala can greatly affect the speciation of hydroxy-Al solutions. The longer the
time adopted, the higher the content of oligomer Al species included in Ala (mononuclear and oligomer Al species). However, the adoption of the
duration of ferron interaction with Ala + Alb has little effect on the speciation of Alb (soluble polymeric Al species) only if the time is long enough
to ensure no further detectable absorbance increase. At least five kinds of Al species, such as mononuclear Al (Almon ), Al2 , Al6 polymers, Al13 and
colloidal Al (Alc ) exist in hydroxy-Al solutions. Generally, Ala includes Almon , Al2 and possibly part of Al6 polymers. In most cases, Alb is mainly
composed of Al13 and other species like Al6 polymers can also contribute. Only under certain conditions (B value ranges), Alb can be equivalent
to Al13 .
2006 Elsevier B.V. All rights reserved.
Keywords: Ferron colorimetric solution; Speciation; Hydroxy-Al solution; Al13 ; 27 Al NMR spectroscopy

1. Introduction
Ferron assay has been widely used for the speciation of
hydroxy-Al solutions because of its relatively high operability and reliability. The principle of this method is based on the
reaction kinetics of ferron with different hydroxy-Al species. By
differentiating the reaction kinetic behaviors of ferronhydroxy
Al system, the Al monomers, oligomers, polymers and even
colloidal constituents could be determined qualitatively and
quantitatively [1,2]. The commonly used ferron colorimetric
reagent is a complicated solution system. Besides ferron, sodium
acetate and hydrochloric acid are added to provide buffer capacity. Hydroxylamine and orthophenanthroline are always added
to eliminate the disturbance of coexisting ions, especially fer-

Corresponding author. Tel.: +86 10 62849144.

E-mail address: fengchenghong@hotmail.com (C. Feng).

0927-7757/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.03.053

ric/ferrous ions [3,4]. However, it has been reported that the

existence of hydroxylamine and orthophenanthroline has a
great influence on the stability of the colorimetric solution and
consequently reduces the credibility of this method to some
extent [5,6]. In fact, with no addition of hydroxylamine and
orthophenanthroline, ferron assay has been used for the speciation of hydroxy-Al polymers in iron-free solutions [2,5,7,8].
However, the application of this simplified colorimetric solution
in speciation of Al species has not been systematically evaluated.
The reactions of mononuclear Al species with ferron are
much simpler and have been studied in depth by some
researchers [9]. However, the reactions of ferron with polynuclear hydroxy-Al species are extremely complicated. On one
hand, these kinds of Al species are metastable, and once mixed
with ferron colorimetric solution of high pH, they may undergo
ageing and evolutionary formation hydrolysis. On the other
hand, the complexation mechanisms have not been fully understood. It has been proposed that the reactions of ferron with

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C. Feng et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 287 (2006) 203211

different hydroxy-Al species may exhibit different kinetic rates

and constants [10]. Based on this assumption, pseudo first-order
reactions and nonlinear regression methods are put forward as a
tool to distinguish Al species [1113]. However, several kinetic
parameters deduced from fitting calculations may not represent each Al species in solution. They only reflect the common
characteristics for a group of components [10]. Additionally,
such kind of mathematic approach to Al speciation requires a
large number of experimental data and complex data processing
techniques, which is not suitable for wide-range application.
Thus, empirical approaches based on operational protocol of
choice are still well acceptable by most researchers [1]. With
this method, the duration of the overall reactions between ferron
and Al species is divided into different phases, and each phase
is attributed to a certain category of species. The species reacted
immediately in the initial short period is defined as Ala (usually
regarded as mononuclear species); the low to medium polymeric species reacted in the following relatively longer period is
defined as Alb ; the species that cannot react with ferron in limited
time is defined as Alc (including high polymeric or colloidal Al
species). An obvious problem with this method is the protocol of
choice to divide each phase. Different operation protocols have
been suggested by different researchers [2,3,7,13]. As a result,
discrepancies often exist between the analytical results obtained
by different researchers even for the test of the same hydroxy-Al
solution. To date, there is little documentation about the effect
of operation protocol choosing on the Al speciation. Therefore,
it is necessary to investigate the inherent relationships between
the operation protocol using and the sample speciation.
In this paper, the characteristics and applicability of simplified ferron colorimetric solution were evaluated in detail.
And then using the simplified colorimetric solution combined
with 27 Al nuclear magnetic resonance spectroscopy, the reaction
behaviors of ferron with different Al species were elucidated.
The objective of this study is to further improve the reliability and operability of the ferron assay in the application of
hydoxy-Al solution speciation. Emphasis will be laid on the
complexation mechanisms of hydroxy-Al species with ferron
and the effect of different operation protocols adopted on the Al
speciation.
2. Materials and methods
In this study, deionized water was used to make all solutions.
And all the reagents were analytical grade chemicals.
2.1. Preparation of the simplified ferron colorimetric
solution
Reagent A (0.2%, w/v, ferron): under rapid stirring, 2 g ferron
(8-hydroxy-7-iodoquinoline-5-sulfonic acid, Sigma Chemical
Co., U.S.A) was dissolved in deionized water (pre-boiled to
remove dissolved CO2 ), and then diluted to 1000 ml.
Reagent B (20%, w/v, NaAc): 200 g sodium acetate was dissolved in 1000 ml of deionized water.
Reagent C (1:9, v/v, HCl): 100 ml hydrochloric acid (37%)
was mixed with 900 ml of deionized water.

Each individual reagent mentioned above was filtered

through pre-washed 0.45 m membranes. The ferron colorimetric solution was obtained by mixing the above reagents A, B,
and C at a ratio of 2.5:2:1. The latter two were mixed prior to the
addition of ferron. After preparation, the colorimetric solution
was stored in refrigerator for later use.
2.2. Preparation of hydroxy-Al solutions
Under rapid stirring, a calculated volume of 0.5 M AlCl3 solution was neutralized slowly with 0.5 M NaOH with a titrometer
(665 Dosimat, Metrohm, Switzerland) at 25 0.1 C. The volumes of NaOH added varied with the target B values (OH/Al
molar ratios). B values of 0, 0.5, 1.0, 1.5, 2.0, 2.2 and 2.5
were chosen in this study. The resulting solutions (usually called
polyaluminum chloride, PAC) obtained were denoted as PAC0 ,
PAC05 , PACl0 , PAC15 , PAC20 , PAC22 and PAC25 , respectively. In
addition to the above solutions, purified Al13 solution (denoted
as PACp ) was also used, which was separated and purified from
PAC22 with sulfate precipitation method. The detailed procedures can be found in [14]. The final concentration of total Al
(AlT ) in every sample was measured by ICP-OES (Perkin-Elmer
Co. U.S.A.).
2.3. Characterization of the simplified ferron colorimetric
solution
2.3.1. Absorbance spectra at different pH values
Various volumes of 0.5 M HCl or NaOH were mixed with
5.5 ml colorimetric solutions and then diluted to 25 ml. The
final pH of every mixture was measured with MP220 pH meter
(Mettler Toledo, Switzerland). To analyze the effect of pH
variation on the absorbance spectra of the colorimetric solution, wavelength scan of each mixture was performed on a
UVvis 8500 spectrophotometer (Tianmei Co., China) using
a 1-cm quartz cell. Meanwhile, with the addition of 20 l
0.1 M AlCl3 solution to the above colorimetric solutions, the
effect of pH on the absorbance of Al-ferron systems was also
observed at 364 nm (after the addition of AlCl3 , the systems
were allowed for five minutes of reaction prior to absorbance
measurement).
2.3.2. Stability comparison with traditional ferron
colorimetric solution
The traditional ferron colorimetric solution was prepared by
adding hydroxylamine and orthophenanthroline to the simplified
one at ratios of 0.24% (m/m) and 0.0056% (m/m), respectively.
Then after different ageing times, wavelength scans of the two
solutions were performed to assess the effect of ageing time on
absorbance spectra changes.
2.3.3. Effect of ferric ions on Al speciation
Various volumes of 0.1 M FeCl3 solutions and 20 l 0.1 M
AlCl3 solutions were pipetted into 25 ml graduated glass tubes
with Fe/Al molar ratios fixed at 0, 0.01, 0.025, 0.05, 0.1, 0.5
and 1.0, respectively. Then 5.5 ml simplified ferron colorimetric

C. Feng et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 287 (2006) 203211

205

solutions were added, and finally diluted to 25 ml. The wavelength scan of each mixture was performed using the procedure
mentioned above.
2.4. Aluminum speciation using simplified ferron
colorimetric solution
The operation procedures are as follows: 20 l test Al solutions and 5.5 ml ferron colorimetric solutions were transferred
into a graduated glass tube; then diluted to 25 ml and homogenized by quick shaking; the absorbance of the mixture was
measured at 364 nm immediately. The operations were carried
out as quickly as possible to avoid any unnecessary delay. The
timed complexation reaction kinetic curves of Al species with
ferron were automatically recorded.
2.5.

27 Al

NMR spectroscopy

Hydroxy-Al solutions with different B values were

also studied with 500 MHz 27 Al NMR (Brookhaven Co.,
U.S.A). The instrumental settings and experimental conditions
were: NS = 128, P1 = 20 s, PL1 = 3dB.Solvent: D2 O, and
T = 298 K. The inner standard was 0.05 M Al(OD)
4 solution.
The chemical shift of Al(OD)
4 is 80 ppm. The signals near 0,
34 and 62.5 ppm represent mononuclear Al (Almon ), dimeric Al
(Al2 ) and Al13 , respectively. The concentration of each species
was determined by the ratio of the integrated intensity of the corresponding peak to that of Al(OD)
4 at 80 ppm [15]. The amount
of the undetectable species (denoted as Alun ) was obtained by
subtracting the sum of the detected Al species from the AlT
concentration in the solutions.
3. Results and discussion
3.1. Characteristics of simplified ferron colorimetric
solution
Ferron, a dibasic acid (H2 A), dissociates to HA and A
2 with
increased pH. The pH value of ferron colorimetric solution can
greatly affect the distribution of ferron species and thus affect
the characteristics of the colorimetric solution.
Fig. 1a shows the wavelength scan curves of ferron colorimetric solutions with different pH values. When the pH is at
the high value end (8.0 and 8.9, corresponding to curves 1 and
2, respectively), the absorbance intensities around 364 nm are
extremely strong; while the pH is at the low end (1.98 and 3.0,
corresponding to curves 3 and 4, respectively), the absorbance
within the same wavelength band are much decreased, but still
higher than those associated with medium pH values (4.52, 5.25,
5.49, corresponding to curves 5, 6, 7, respectively). Curves of
the colorimetric solutions associated with the medium pH values (curves 5, 6, 7) exhibit much similar absorbance spectrum
patterns. The differences of absorbance spectra within different
pH ranges could be attributed to the changes of ferron species
distribution (data not shown), which can be obtained by calculations using pH values of the colorimetric solutions and the
two acid dissociation constants of ferron [16]. HA is the dom-

Fig. 1. Effect of acidity on the absorbance spectra of (a) simplified ferron colorimetric solutions at different wavelength; (b) Al-ferron complexes at 364nm.
(1) pH 8.0 (2) pH 8.92 (3) pH 1.98 (4) pH 3.0 (5) pH 4.52 (6) pH 5.25 (7) pH
5.49.

inant species in colorimetric solutions when pH is around 5.2.

With increased or decreased pH, HA will be converted to A
2
or H2 A. Moreover, the HA dominated colorimetric solutions
have the weakest absorption around 364 nm, while the other
two species dominated solutions yield a strong absorption background near 364 nm. According to Beers law, as blank solution,
the choice of pH around 5.2 is favorable for the ferron assay.
However, once hydroxy-Al solution is added, the pH of colorimetric solution would be subject to variation due to their pH
difference. Moreover, the Al species distribution to be determined would also be affected. Therefore, an optimum pH range
should be determined to ensure the sensitivity of measurement.
Fig. 1b illustrates the absorbance changes of Al-ferron mixture
with different pH values at 364 nm. The absorbance of Al-ferron
complexes was greatly influenced by pH, whereas within the
small pH range of 5.05.4 the absorbance reached maximum
and was relatively stable. Therefore, this pH range should be
adopted for the assay operation, which matches well with the
estimation of Hsu and Cao [5]. In this study, it was verified that
the pH changes caused by the hydroxy-Al solution (with pH of
3.05.5) addition could not lead the final pH to fall out of the
optimum range. Moreover, the content of HA in the colorimetric solution with this pH range could exceed 95%, which is also
in favor of Al speciation. This pH range is also suitable for Al
speciation with the traditional ferron colorimetric solution [3].
Thus, whether hydroxylamine and orthophenanthroline exist in
colortimetric solution or not will have little effect on the solution
pH and ferron species distribution in these two kinds of ferron
colorimetric solutions.
Ferric/ferrous ions are the commonly encountered disturbing factors for Al speciation using ferron assay. They could
be introduced by the reagents adopted during the preparation of hydroxy-Al solutions. Therefore, hydroxylamine and
orthophenanthroline were often added to the traditional ferron
colorimetric solutions. Hydroxylamine could reduce ferric ions
to ferrous ions and then the ferrous ions were complexed by

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Fig. 2. Absorbance spectra of Al-ferron complexes using simplified ferron colorimetric solution under the existence of ferric ions (Fe/Al molar ratios fixed at
(1) 0 (2) 0.01 (3) 0.025 (4) 0.05 (5) 0.1 (6) 0.5 (7) 1.0, respectively).

orthophenanthroline. Consequently, the formation of Fe-ferron

complex could be minimized and the disturbance from ferric/ferrous ions for Al speciation could also be avoided. Thus, it
may become an unnecessary operation to add these two reagents
to the colorimetric solution for the Al speciation in Fe-free
solution.
When the simplified colorimetric solution was adopted, the
significance of disturbance from ferric ions was assessed (Fig. 2).
Absorbance spectra of the Al-ferron mixtures with high iron
concentration (curves 6, 7) are significantly different from those
with low iron concentration (curves 2, 3, 4). Moreover, absorption maxima for both iron and Al complexes occurred at around

364 nm, while at about 600 nm only the colored complex of

iron had relatively high absorption. Thus, these experimental
results further proved that the existence of Fe ions in solution
could affect the Al speciation. However, it can also be seen from
Fig. 2 that no significant difference between curves 2, 3 and 4
existed near 364nm. Consequently, if the ferric ion concentration in solution is sufficiently low (i.e., [Fe]/[Al] 0.05), the
addition of hydroxylamine and orthophenanthroline to ferron
colorimetric solution is unnecessary and the simplified ferron
colorimetric solution can also be used for the speciation of this
kind of hydroxy-Al solution.
Additionally, without these two reagents, the preparation procedure of ferron colorimetric solution could become simpler and
the reliability of measurement could also be improved. Fig. 3
demonstrates the comparison of absorbance spectra between
the simplified ferron colorimetric solution and the traditional
one. With the addition of these two reagents, the absorbance
of the traditional ferron colorimetric solution changes significantly with ageing time, especially in the initial several days
after preparation. This might be due to the slow reaction of ferron with hydroxylamine. Such kind of continuous absorbance
change could unavoidably cause experimental errors. Furthermore, higher concentration of hydroxylamine and orthophenanthroline could result in higher instability of the colorimetric solution and a shift of its maximum adsorption wavelength (max )
after long ageing time [12]. Thus, the traditional colorimetric
solution is often used for Al speciation in a comparatively stable
period (i.e., 525 days after the preparation), which inevitably
adds to the complexity of ferron assay operation. In the case of
simplified ferron colorimetric solution, the absorbance spectra
did not show any appreciable change at the wavelength of near
364 nm within the 30 days of observation duration, which indi-

Fig. 3. Effects of ageing time on the absorbance spectra of ferron colorimetric solutions in the presence (a) and absence (b) of hydroxylamine and orthophenanthroline.(1) 0 day (2) 3 days (3) 7 days (4) 11 days (5) 30 days.

C. Feng et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 287 (2006) 203211

207

Fig. 4. Absorbance spectra of simplified ferron colorimetric reagent with

hydroxy-Al solutions (1) PAC0 (2) PAC05 (3) PACp (4) PAC25 .

cates the simplified colorimetric solution possessed much higher

stability than the traditional one (Fig. 3b). Besides, hydrochloric acid and sodium acetate added as buffer had no effect on the
distribution of the ferron species with time elapsing. Thus, the
simplified ferron colorimetric solution can be used immediately
after preparation. Moreover, the simplified colorimetric solution
may have a wider application for Al speciation in solutions with
no or low content of iron ions than the traditional one because
of its simpler preparation procedure and higher stability.
The effect of the temperature variation on the characteristics of the simplified colorimetric solution was also tracked
(data not shown). Within the range of room temperatures, no
absorbance variation was detected for the simplified ferron colorimetric solution.
3.2. Complexation mechanisms of ferron with
hydroxy-aluminum solutions
The reaction kinetics of ferron with hydroxy-Al solutions
are shown in Fig. 4. The common characteristics of the kinetic
curves can be seen: an initial rapid absorbance increase followed
by a gradual increase, and then ending in a plateau. However, the
reaction behaviors of different types of hydoxy-Al solutions varied significantly. For PAC0 and PAC05 , the absorbance started
from a much high level, and then experienced a short period
of gradual increase before reaching the plateau. However, in
the cases of PACp and PAC25 , the absorbance at the beginning
was very low, and the gradual increase of absorbance lasted
much longer before reaching the plateau. The initial absorbance
increase is believed to be associated with the reaction of ferron with mononuclear Al species, and the following gradual
increasing phases are related to reactions of ferron with various
hydroxy-Al polymers. When all of the Al species mentioned
above react completely with ferron, the kinetic curve of Alferron interaction would reach the plateau.
Essentially, the colorimetric assay can only give indirect
information about the speciation of hydroxy-Al solutions. The
quantification of specific species depends on the interpretation

Fig. 5. 27 Al NMR spectroscopy of (a) 1. PAC05 , 2. PACl0 , 3. PAC15 , 4. PAC20

5. PAC25 ; (b) PACp and (c) PAC0 .

of the reaction kinetics data. Unlike the ferron assay, the instrumental technique of 27 Al NMR has the advantage of revealing
part of the structural information about some Al species, such as
Al monomers and Al13 polymers. Fig. 5 shows the 27 Al NMR
patterns of different hydroxy-Al solutions used in this study.
Each peak on the 27 Al NMR spectroscopy corresponds to a specific species as mentioned before. The integrated area of each
peak is related to the relative abundance of that species.
The speciation of hydroxy-Al solutions determined by 27 Al
NMR is presented in Table 1. Only mononuclear Al species was
detected in PAC0 (Fig. 5c). According to some researchers, the
complexation reactions of mononuclear Al species with ferron
in the assay could be completed immediately after the mixing
[4,13]. However, it actually took 35 min for all mononuclear
Al to react completely with ferron (curve 1 in Fig. 4). A possible
explanation is that after the PAC0 sample was transferred into the
colorimetric solution, some of mononuclear Al might undergo
further hydrolyzation and transform into dimeric or oligomeric
Al species due to the effect of pH environment change (the sam-

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C. Feng et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 287 (2006) 203211

Table 1
Speciation distribution of hydroxy-Al solutions determined by 27 Al NMR spectroscopy and ferron assay
Solution

PAC0
PAC05
PAC25
PACp
a
b

pH

3.04
3.67
5.21
4.35

27 Al

NMR spectroscopy

Ferron assay

ICP-OES

Almon (%)

Al13 (%)

Alun (%)

Ala (%)

Alb (%)

Alc (%)

AlT a (M)

100
55.20

3.15

b
25.21
45.59
96.15

19.59
54.41
0.70

88.1
60.97
2.87
1.08

11.9
37.56
62.86
95.35

1.47
34.27
3.57

0.102
0.103
0.103
0.095

AlT = Ala + Alb + Alc ; the fractions of Ala and Ala + Alb were calculated using the absorbance measured in the initial 30 s and 7200 s of Al-ferron interactions.
Undetectable.

ple pH was 3.04 and the colorimetric solution pH was around

5.2). And consequently the in situ formed oligomer species
resulted in a lower reaction rate with ferron. This assumption
can be supported by the comparison of the PAC0 speciation
obtained with ferron assay and 27 Al NMR (Table 1). In the case
of PAC05 , because its B value is higher than PAC0 , there existed
certain amount of oligomeric and polymeric Al species in the
original sample, and once PAC05 was introduced into colorimetric solution, more of such species were supposed to exist.
Consequently, it took much more time for curve 2 in Fig. 4 to
reach the plateau and such species to react completely with ferron. The rapid absorbance increase of curve 2 during the initial
100 s is also lower than that of curve 1, which indicates the content of mononuclear Al species in PAC05 is less than that in
PAC0 .
As for PACp and PAC25 , it has been proved that their speciation stability is relatively high because of their higher polymerization degree and the stable Keggin structure of Al13 [2].
Additionally, the pH values of PACp and PAC25 are close to
that of ferron colorimetric solution so that the mixing operation might not lead to significant further hydrolysis of these two
hydroxy-Al solutions. Thus, curves 3 and 4 in Fig. 4 should be
able to better represent the actual reaction kinetics of ferron with
PACp and PAC25 , respectively.
Due to the high B value of PAC25 , its mononuclear or
oligomeric Al species should be at a very low level and most
of its Al species exist as Alb and Alc (Table 1). As evidence, the
beginning absorbance of curve 4 in Fig. 4 is approximately zero.
Consequently, the absorbance increase of curve 4 was mainly
ascribed to the reaction of ferron with Alb . Generally, in PAC25 ,
Al13 is the primary species of Alb . Fig. 4 shows no significant
differences of the slopes in the initial 500 s between curves 3 and
4, which confirms that the Alb component in PAC25 was primarily composed of Al13 . After 500 s, the much slower reaction rate
indicated by curve 4 is attributed to the other Al species in Alb .
These Al species may have higher polymerization degree than
Al13 , so the rates of their reaction with ferron are much lower.
PACp , namely the purified Al13 solution, contained very small
amount of mononuclear and colloidal Al species, and the content of Al13 accounted for 96% of the total Al concentration
(Table 1). The 27 Al NMR pattern of PACp is shown in Fig. 5b.
The resonance peak of mononuclear Al species is almost unobservable. Obviously, the content of Al13 in PACp is higher than
that in PAC25 . Accordingly, the reaction curve of PACp with
ferron goes higher than that of PAC25 . The relatively rapid reac-

tion rate of PACp with ferron kept constant for more than 500 s.
According to the conclusions of Jardine and Zealzy [12], this
rate should be the eigenvalue of the reaction between Al13 and
ferron under the experimental conditions. However, the reaction
pathways of Al13 with ferron have not been fully studied as yet.
It has been suggested that Al13 does not react with ferron directly
in the form of a whole polymer unit, and complexation products
be formed only by mononuclear Al species with ferron. Possibly, ferron firstly attacks octahedrally coordinated Al in the
cage-like structure of Al13 , and thus distorts the symmetry of
the centrally located tetrahedral Al [17]. The reaction behavior
of PACp with ferron observed here seems to be in support of
this mechanism. During the initial phase, the reaction of Al13
with ferron is going on at a very high rate, thereafter, the rate
decreases gradually (curve 3 in Fig. 4). This phenomenon could
be explained as follows: at the initial stage of the Al13 -ferron
interaction, the decomposition of Al13 and the formation of Alferron complexes were running at a relatively high rate. There
existed a balance between Al13 and its decomposed products.
This balance guarantees the same level of reaction rate of ferron
with PACp and the same level of slope in the initial section of
curve 3 in Fig. 4. However, with the reaction time elapsing, the
concentration of Al13 decreased and its decomposition and the
Al-ferron product formation rates also became slower. The balance was also gradually broken. After all Al13 were decomposed
and transformed into Al-ferron complexes, curve 3 eventually
reached a plateau. The decomposition rate of Al13 might be the
limiting factor for the ferron interaction with Al13 .
Therefore, mononuclear and oligomeric Al species are more
liable to react with ferron and their reaction rates with ferron are
much faster. However, as far as the higher polymeric Al species
are concerned, since most Al atoms are located in the inner
position of their corresponding structures, ferron would attack
the Al atoms in the outer spheres first. Only after these outer Al
atoms are separated, ferron can react with the inner atoms. Thus,
different forms of Al often react at varying rates with ferron.
3.3. Effect of reaction duration adoption protocols on the
speciation of hydroxy-Al solutions
A general description of determining the speciation of
hydroxy-Al solutions is illustrated in Fig. 6. Ala , commonly
recognized as the mononuclear Al species, reacts with ferron
at a very fast rate immediately after the addition of sample
to ferron colorimetric solution. If the time of k is adopted as

C. Feng et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 287 (2006) 203211

Fig. 6. Schematic diagram of the speciation of hydrox-Al solutions with ferron

assay.

the reaction end point of mononuclear species, the content of

Ala is denoted as Ala (k) for simplicity. Then the subsequent
absorbance increase with time till the kinetic curve reaches a
plateau is ascribed to the reaction of Alb species with ferron
and the content of Alb is marked as Alb (k) here. Since the Alc
species is rather inert in terms of its reaction with ferron [6], its
content can be obtained by the difference between Ala (k) + Alb
(k) and the AlT value.
The reaction of Alb with ferron can be affected by many factors, such as the polymerization degree, ferron/Al molar ratios
and compositions of ferron colorimetric solution [13]. Conse-

209

quently, the adoption of end time for Alb reaction may bring
some influences on the quantification of Alb content. No consensus on the end time has been reached as yet. Most researchers
suggested 2 h as the end time of the Alb -ferron interaction [2,18],
while others believed that 30 min or 1 h should be the best
choice [13,10]. As a principle, the end time adopted to quantify the content of Ala + Alb should ensure the completion of
reaction between Alb and ferron, which can be indicated by the
negligible absorbance increase of the kinetic curve. Therefore,
if this principle is followed, the end time adoption could not
become an important factor of interfering with the quantification of Ala + Alb . According to the reaction pathways discussed
above, once the kinetic curve reaches a plateau, polymeric Al
species consisting of Ala and Alb have been decomposed completely into mononuclear Al species and reacted with ferron.
Solution pH and further ageing might not affect their existing
status any more. Longer time adopted to quantify Ala + Alb has
no effect on the speciation of Alb . Thus, the adoption of two
hours for determination of Ala + Alb is safe and rational.
Unlike the adoption of end time for the quantification of
Ala + Alb , there is currently no general principle to determine
the reaction duration of k for Ala quantification. The adoption
of different k value may greatly affect the speciation of Ala
and Alb in a hydroxy-Al solution. Various k values have also
been proposed in literature, such as 30 s, 40 s, 60 s and 90 s, etc.
[2,3,7,13]. However, it is still unclear which one is the most reasonable choice for the Ala -ferron interaction. Fig. 7a gives the
comparison of Ala contents determined by choosing k value of
30 s [Ala (30)] and 90 s [Ala (90)] in hydroxy-Al solutions with
different B values. The corresponding contents of Al monomers
determined with 27 Al NMR are also shown. Both Ala (30) and
Ala (90) are higher than the contents of Almon , which indicates

Fig. 7. Distribution of various Al species in hydroxy-Al solutions with different B values (a) Almon , Ala (30) and Ala (90); (b) Ald (k), k is 30 s, 40 s, 60 s and 90 s,
respectively; (c) Alb (30) and Al13 .

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C. Feng et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 287 (2006) 203211

that not only mononuclear Al species such as Al3+ , Al(OH)2+

and Al(OH)2 + , but possibly some oligomeric Al species (Ald )
might be included in the Ala component. Therefore, Ala could
not be simply regarded as mononuclear Al species.
The distribution of oligomeric Al species (Ald ) in samples is
shown in Fig. 7b. Here, the contents of Ald were denoted as Ald
(k) (k is 30 s, 40 s, 60 s and 90 s, respectively), and they were
calculated by subtracting the mononuclear species content measured with 27 Al NMR (Almon ) from Ala (k) obtained by ferron
assay [Ald (k) = Ala (k) Almon ]. Baes and Mesmer [19] have
suggested that two oligomeric Al species exist in hydroxy-Al
solutions, i.e., dimeric Al (Al2 ) and trimeric Al (Al3 ). However,
only the former can be detected by 27 Al NMR spectroscopy and
the existence of the latter has not been identified [20]. In this
study, dimeric Al (Al2 ) was also the only oligomeric Al species
which was detected at 34 ppm on the 27 Al NMR spectroscopy
in Fig. 5a. However, only in some hydroxy-Al solutions with B
values ranging from 0.5 to 1.5, dimeric Al have been detected.
Fig. 7b shows the comparison of the contents of dimeric Al with
those of oligomeric Al in hydroxyl-Al solutions with different
B values. Ald (k) values were significantly higher than the contents of Al2 , particularly in the hydroxy-Al solutions with lower
B values. It can be inferred that the difference between them
might be ascribed to the existence of other oligomeric species,
such as Al6 polymers. Al6 , with a six-member ring structure,
has been believed to play a crucial role in the hydrolyzation of
Al and the formation of solid Al hydroxide for a long period of
time. Unfortunately, Al6 species is undetectable by 27 Al NMR
[7].
With the increase of B value, Ald (k) exhibits a decrease trend
and this trend is more obvious with higher k values. In addition,
the differences between Ald (k) values (k is 30 s, 40 s, 60 s and
90 s, respectively) become smaller in hydroxy-Al solutions with
higher B values (Fig. 7b). The results indicate that the contents
of oligomeric Al species in hydroxy-Al solutions with lower
B values were higher than those with higher B values, and the
oligomeric species contained at least two kinds of species: Al2
and Al6 polymers. For a hydoxy-Al solution, a bigger k value
adopted could result in a higher value of Ald (k) and a lower
value of Alb (k). Therefore, the choice of the k value is vital
to the speciation of Al-polymer using ferron assay. Ald (30) in
every hydroxy-Al solution is less than 10% and relatively closer
to Almon . Thus thirty seconds of k value might be the rational
reaction duration of Ala with ferron, particularly for hydroxy-Al
solutions with high B values.
Generally, soluble polymeric Al species is composed of Ald
and other higher polymerized Al species. Al13 is just one of the
soluble polymeric Al species. Fig. 7c demonstrates the comparison of Al13 content and the ferron colorimetric determined
Alb (30) in samples. Clearly, the contents of Al13 are equal to
Alb (30) values when the B values are 1.5 and 2.0, which agrees
roughly with the conclusions of Bertsch and Park [13]. However,
in the hydroxy-Al solutions with lower and higher B values, Alb
(30) values are higher than the contents of Al13 determined using
27 Al NMR spectroscopy. The differences between them might be
due to the existence of some Al6 polymers as discussed above.
Therefore, only within certain B value ranges (i.e., 1.52.0),

Alb could be reasonably regarded as a surrogate of Al13 . From

the comparison of Al speciation obtained by ferron assay and
27 Al NMR, it can be concluded that at least five kinds of Al
species, such as Almon , Al2 , Al6 polymers, Al13 and Alc , exist
in most hydroxy-Al solutions. However, more detailed information about their speciation needs further studies using more
sophisticated analytical methods in the future.
4. Conclusions
In this paper, the comparison of the traditionally used ferron colorimetric solution and the simplified one was conducted.
The empirical approaches to the speciation of hydroxy-Al solutions using the simplified ferron colorimetric solution were
investigated with the aid of 27 Al NMR. Compared with the
traditional one, the simplified ferron colorimetric solution had
much higher stability. Within a suitable pH range of 5.05.4,
the simplified ferron colorimetric solution can be used for Al
speciation if the samples have no or low content of iron ions
(i.e., [Fe]/[Al] 0.05). Theoretically, the kinetic curve of ferron
with hydroxyl-Al solutions can be divided into different phases
according to the evolution of reaction rates, and each phase can
be assigned to certain specific Al species. However, due to the
limitations of actual operation, it is hard to distinguish the reaction end times of mononuclear and oligomeric Al species. The
adoption of Ala -ferron reaction durations had significant effect
on the speciation of hydroxy-Al solutions. Even within the initial 30 s, Al species other than mononuclear one had involved in
the reactions with ferron. Combined with the 27 Al NMR technique, the speciation results obtained from ferron assay can be
better interpreted and more reasonable operation protocols can
be selected.
Acknowledgements
The authors thank gratefully professor Deng and Wang of
the Analytical and Testing Center, Beijing Normal University
for the valuable help in 27 Al NMR Spectrum. The support from
National 863 program under 2002AA601290 is acknowledged.
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