Advances in Colloid and Interface Science

103 (2003) 5776

Synthesis and characterization of goethite and

goethitehematite composite: experimental study
and literature survey

Marek Kosmulskia,b,*, Edward Maczkaa, Elzbieta

Jartychc,
b
Jarl. B. Rosenholm
a

Department of Electrochemistry, Technical University of Lublin, Nadbystrzycka 38 A, 20618 Lublin,

Poland
b

Department of Physical Chemistry, Abo Akademi University, Porthansgatan 3-5, 20500 Abo,
Finland
c
Department of Experimental Physics, Technical University of Lublin, Nadbystrzycka 38,
20618 Lublin, Poland

Abstract
Aging of synthetic goethite at 140 8C overnight leads to a composite material in which

hematite is detectable by Mossbauer

spectroscopy, but X-ray diffraction does not reveal any
hematite peaks. The pristine point of zero charge (PZC) of synthetic goethite was found at
pH 9.4 as the common intersection point of potentiometric titration curves at different ionic
strengths and the isoelectric point (IEP). For the goethitehematite composite, the common
intersection point (pH 9.4), and the IEP (pH 8.8) do not match. The electrokinetic potential
of goethite at ionic strengths up to 1 mol dmy3 was determined. Unlike metal oxides, for
which the electrokinetic potential is reversed to positive over the entire pH range at
sufficiently high ionic strength, the IEP of goethite is rather insensitive to the ionic strength.
A literature survey of published PZCyIEP values of iron oxides and hydroxides indicated
that the average PZCyIEP does not depend on the degree of hydration (oxide or hydroxide).
Our material showed a higher PZC and IEP than most published results. The present results
confirm the allegation that electroacoustic measurements produce a higher IEP than the
average IEP obtained by means of classical electrokinetic methods.
2003 Elsevier Science B.V. All rights reserved.

Keywords: Point of zero charge; Adsorption; Isoelectric point; Goethite; Hematite; Mossbauer
spectroscopy; X-Ray diffraction
*Corresponding author. Tel.: q48-81-5381355; fax: q48-81-5254601.
E-mail address: kosmulsk@hermes.umcs.lublin.pl (M. Kosmulski).
0001-8686/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0001-8686(02)00083-0

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M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

Contents
1. Introduction ............................................................................................... 58
2. Experimental ..............................................................................................
3. Results .....................................................................................................
4. Discussion ..................................................................................................
References......................................................................................................

58
60
65
68

1. Introduction
Iron (hydr)oxides substantially contribute to the uptake of toxic elements in
natural mineral assemblies, even when the mass fraction of iron (hydr)oxides in
these assemblies is relatively low. The affinity of iron (hydr)oxides to anions and
cations is pH-dependent, and this can be explained in terms of pH-dependent surface
charging w14x. Namely, the surface carries a positive proton charge at pH below
the point of zero charge (PZC) and a negative proton charge at pH above the PZC.
This results in electrostatic attraction or repulsion of all ions other than protons, and
a change in pH by one or two units can enhance or depress the uptake of ions by
an order of magnitude. Thus, a serious study of the uptake of ions from solution
can hardly be imagined without knowledge of the PZC. Iron (hydr)oxides have
been used as model sorbents to examine the effects of different factors (pH,
temperature, presence of other species in solution) on the sorption process. In the
present paper, two model adsorbents are characterized and their PZC and IEP are
compared with the literature values.
The electrokinetic behavior of goethite at high ionic strengths was also studied.
NaI was selected for this study as a salt that induced a more substantial shift in the
IEP of metal oxides than any other salt.
2. Experimental
A portion of 400 cm3 of 2.5 M KOH solution was mixed with 1650 cm3 of prefiltered 0.15 M Fe(NO3)3 solution in a plastic (Nalgene) container and the mixture
was stirred vigorously. The dispersion was aged for 48 h at 80 8C. The precipitate
was then centrifuged out and re-dispersed in 0.01 mol dmy3 HNO3 solution,
centrifuged again, and this procedure was repeated 10 times, and again three times,
with MilliQ water instead of HNO3 solution. Then a few portions of the yellow
brownish precipitate were mixed together and freeze-dried. The resulting material is
referred to as goethite 25. The other portion of goethite was dried in an oven at
140 8C overnight. The resulting material is referred to as goethite 140 (although in
fact it is a goethitehematite composite).

Hyperfine interactions were determined by Mossbauer

spectroscopy (MS). Measurements were carried out at room temperature in the standard transmission geometry
using a source of 57Co in a rhodium matrix (activity of approx. 5 mCi). The isomer
shifts given below are relative to a-iron. Numerical fitting of the experimental

M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

59

Fig. 1. X-Ray diffraction spectra of goethite 25 and 140.

spectra gives the hyperfine interaction parameters, e.g. isomer shift d, quadrupole
splitting D and hyperfine magnetic field Bhf.
The potentiometric titrations of goethite dispersions (1 or 2 gy50 cm3; more
concentrated dispersions become very viscous) were carried out in a thermostated
Teflon vessel under a nitrogen atmosphere. The NaNO3 concentration was 0.001,
0.01 and 0.1 mol dmy3, and 0.1 or 0.2 mol dmy3 NaOH was the titrant. The
titration was always started at acidic pH to facilitate removal of CO2 from the
system. The electrokinetic potential was determined with Acustosizer (Matec) and
DT-1200 (Dispersion Technology) instruments at a 10% mass fraction of goethite.
The results obtained at high ionic strengths were corrected for the electrolyte
background. The dispersions were not insulated from atmospheric CO2 during the
electrokinetic measurements. The electrokinetic and potentiometric titrations were
carried out at 25 8C. NaNO3 was used to establish a constant ionic strength unless
indicated otherwise.

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M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

Fig. 2. Room-temperature Mossbauer

spectra of goethite 25 (a) and 140 (b).

3. Results
Only the goethite structure was found using X-ray diffraction in goethite 25 and
goethite 140 (Fig. 1). The signalynoise ratio was rather poor. The mass loss on
calcination at 500 8C indicated nearly stoichiometric FeOOH in both samples.

Mossbauer
spectra registered for goethite 25 and goethite 140 are presented in
Fig. 2, and the hyperfine interaction parameters calculated are summarized in Table

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61

Table 1
The calculated hyperfine interactions parameters
Sample

Bhf
(T)

d
(mm sy1)

D
(mm sy1)

G
(mm sy1)

k
(%)

Phase

Reference

Goethite 25
Goethite 140

36.9"0.1
38.3"0.1
49.6"0.1
38.1
36.0"1.5
38.0
51.9"0.1
51.7"0.1

0.34"0.01
0.35"0.01
0.36"0.01

0.13"0.01
0.13"0.01
0.11"0.01
0.27
0.24"0.05

0.27"0.02
0.23"0.03
0.23"0.03

100
65
35

Goethite
Goethite
Hematite
Goethite
Goethite
Goethite
Hematite
Hematite

This work
This work

0.45"0.01
0.37
0.38"0.01
0.34"0.01

0.09"0.01
0.09"0.01

w5x
w6x
w7x
w8x
w9x

Bhf, hyperfine field; d, isomer shift (relative to a-iron); D, quadrupole splitting; G, half-width of the
spectral lines; k, relative contribution of the component.

1. The results obtained for goethite 25 are typical for pure goethite. The results
obtained for goethite 140 reveal two phases: goethite (dotted line in Fig. 2b) and
hematite (solid line). The presence of a minor amount of hematite in well-crystallized
natural goethite has been reported w5x. The spectrum is a superposition of two
components, and their relative contributions were estimated from the area of each
sub-spectrum. The half-width of the spectral lines observed in the present study is
substantially greater than that of the calibration line (Gs0.12 mm sy1). Our XRD
study also showed poorly developed Bragg peaks, especially for goethite 140. Both
results are due to the poor crystallinity of our samples.

Fig. 3. The surface charge density of goethite 25.

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M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

Fig. 4. The surface charge density of goethite 140.

Fig. 5. The electrokinetic potential of goethite 140.

M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

Fig. 6. The electrokinetic potential of goethite 25.

Fig. 7. The electrokinetic potential of goethite 25.

63

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M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

Fig. 8. Histogram of the PZCyIEP values for iron (hydr)oxides reported in the literature. The black bars
represent the matching CIP and IEP values.

The BET surface area of goethite 25 and 140 was 40.20"0.06 and 47.05"0.23
m2 gy1, respectively (ASAP 2010).
The surface charging curves obtained at different ionic strengths intersect at pH
9.4 in both samples (Figs. 3 and 4), and this value was interpreted as the pristine
PZC values. Actually, the titration curves obtained at the ionic strengths of 0.001
and 0.01 mol dmy3 merge above pH 9.4 rather than intersect, but with 0.1 mol
dmy3 there is a distinct intersection point.
The IEP of the precipitate before freeze-drying (no salt added) was at pH 9.2
(microelectrophoresis). The z potentials of goethite 140 in 0.01 mol dmy3 NaNO3
are shown in Fig. 5. The IEP obtained by two different instruments nearly match at
pH 8.8, but they are substantially lower than the CIP (crossover point of titration
curves obtained at different ionic strengths). The z potentials of goethite 25 are
shown in Figs. 6 and 7. Fig. 6 indicates a perfect match between the common
intersection point of the charging curves (Fig. 3) and the IEP obtained by two
different instruments in 0.001 and 0.01 mol dmy3 NaNO3. The results obtained
with the Acustosizer indicate that the presence of NaI up to 0.5 mol dmy3 (only
the results for 0.1 mol dmy3 NaI are shown in Fig. 6) does not substantially shift
the IEP. The results obtained with the DT-1200 shown in Fig. 7 indicate a shift in

M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

65

Table 2
The PZC of iron (hydr)oxides as the function of hydration and the crystalline structure
Entries
Hematite, synthetic
Hematite, natural
Fe2O3 other than hematite, mixtures of
different forms or structure unknown
Goethite
FeOOH other than goethite, mixtures of
different forms or structure unknown
Fe (III) hydroxides and hydrous oxides
Total

Median

Average

Standard
deviation

62
7
22

8.1
5.4
7.2

7.82
5.64
6.89

1.17
1.56
1.51

66
14

8.4
7.25

8.32
7.27

0.89
0.77

8
8

7.99
7.8

0.69
1.23

22
193

the IEP to pH 10.8 in 0.5 mol dmy3 NaI, but a further increase in the NaI
concentration to 1 mol dmy3 shifted the IEP back to its original value.
4. Discussion

Mossbauer
spectroscopy is a very useful tool in studies of local interactions
between nuclear probes contained in the material investigated and their nearest

environment. The sensitivity of Mossbauer

spectroscopy is substantially higher than

XRD; it allows phases invisible to XRD to be revealed. Moreover, Mossbauer

spectroscopy can be used for quantitative analysis of mixtures of different phases.

Goethite a-FeOOH contains the nuclear probe 57Fe. In Mossbauer

spectroscopy
experiments, hyperfine interactions may be determined, e.g. interactions of the
electromagnetic moments of the nuclear probe with the electric and magnetic fields.
The present results indicate that XRD alone is not sufficient to exclude the presence
of hematite in aged goethite samples. Unfortunately, in many publications the
structure analysis of iron (hydr)oxides was carried out solely by means of XRD.
A literature search revealed a broad range of PZC and IEP values reported for
iron (hydr)oxides w10177x. The numerical values of PZC from these publications
are compiled elsewhere w2x, and here we only show a histogram. Fig. 8 indicates
that the PZC values obtained in the present work are higher than most of the values
reported in the literature. In order to explore the effect of the composition of the
material on the PZC, the iron (hydr)oxides were sorted into the following groups:

Synthetic hematite;
Natural hematite;
Fe2O3 other than hematite, or a mixture of different forms or structure unknown;
Goethite;
FeOOH other than goethite, or a mixture of different forms or structure unknown;
and
Iron (III) hydroxide or hydrous oxide.

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M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

Table 3
The PZC of iron (hydr)oxides as the function of the experimental method

Entries
Median
Average
Standard deviation

CIPsIEP

CIP

IEP
(classical)

IEP
(electroacoustic)

Titration
(one ionic
strength)

Total

21
8.2
8
1.05

79
8.1
7.98
0.9

69
7.9
7.58
1.51

1
9.4
9.4

24
7.85
7.63
1.34

193
8
7.8
1.23

The results of the literature survey sorted by composition are summarized in Table
2.
Apparently the effect of the degree of hydration of the sample on the PZC is
rather insignificant, namely the average and median PZC for synthetic hematite and
iron hydrous oxide and hydroxide are close to the average and median PZC in the
entire data set, and the average and median PZC for goethite are only slightly
higher. This coincidence can be explained in terms of a transformation of one or
two external atomic layers of the solid into a somewhat different structure. Probably
this surface structure (and degree of hydration) is common for different crystallographic forms representing the same chemical formula, and even for compounds of
different degrees of hydration (oxide, oxohydroxide and hydroxide). The absence
of a significant difference in PZC (median and average based on over 100 entries)
between a- and g-Al2O3, on the one hand, and between anatase and rutile on the
other w2x, are in favor of this hypothesis. The PZC of natural hematite is significantly
lower than that of other types of materials, but this result is due to the substantial
amount of silica that is found in natural hematite, as explicitly documented in many
original publications, where specific numbers (e.g. mass fraction of silica and other
impurities) are reported.
The PZC values for goethite reported in the literature are higher than those of
the other crystallographic forms of FeOOH (akageneite, lepidocrocite), mixtures of
different forms and FeOOH of unknown structure. The difference is of the order of
1.5-fold the standard deviation in each population. Thus, in contrast with the degree
of hydration, for which the effect on the PZC of iron (hydr)oxides is rather
insignificant, the structure within the same chemical formula (goethite vs. akageneite
and lepidocrocite) exercises a significant effect on the PZC. Yet, even when
compared with the data reported in the literature for goethite, our PZC and IEP
values (Figs. 37) are rather high.
The PZCyIEP of iron (hydr)oxides are sorted in Table 3 by method and the
following categories were distinguished:

Matching CIP and IEP (as in the present work for goethite 25);
CIP;
IEP (classical);
IEP (electroacoustic);
Titration (one ionic strength);

M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

67

A few less common methods (e.g. inflection point of titration curves, w22x) have
been used to determine the PZC of iron (hydr)oxides, but the results obtained with
these methods are not analyzed here. In addition, PZC values reported without
explicitly stating the experimental method w24,110,177x or experiments that did not
produce any PZCyIEP w154x were purposely ignored.
Lyklema w178x recommended a combination of potentiometric titration and
electrokinetic methods to determine the pristine PZC of materials. Namely, the PZC
and IEP shift in two opposite directions in the presence of specific adsorption of
cations or anions. Thus, matching CIP and IEP is very likely the pristine PZC of
the adsorbent. On the other hand, a lack of coincidence indicates specific adsorption.
Unfortunately, publications reporting CIP and IEP of the same sample are scarce.
Publications reporting CIP only are more numerous, but the existence of a CIP does
not prove the purity of the sample, i.e. a CIP also occurs in the presence of specific
adsorption w178x. Instead of titrations at different ionic strengths, some authors used
salt titration (at PZC, addition of inert electrolyte does not induce a change in the
pH of the dispersion), and such results are basically equivalent to the CIP and are
listed under the same category. Classical electrokinetic methods (electrophoresis,
electroosmosis) make it possible to readily determine the IEP. User-friendly equipment is available nowadays, but it takes some effort and experience to avoid
different pitfalls, e.g. related to sample preparation. For example, storage of iron
(hydr)oxide dispersion in glassware at neutral or basic pH for a few hours or days
results in a shift of the IEP to lower pH than in the original sample. Some unusually
low IEP values reported in the literature are probably due to this effect.
IEP values obtained using the electroacoustic method (as in the present study)
are listed under a separate category. On the other hand, nearly matching IEP from
electroacoustic measurements and CIP w67x is listed under matching CIP and IEP,
together with the results obtained by means of classical electrokinetic methods.
Mass titration has recently become popular as a method to determine the PZC.
In this method, the natural pH of a concentrated dispersion is identified with the
PZC. In this respect, mass titration is not very different from potentiometric titration
at one ionic strength (in which the PZC is also the natural pH of the dispersion)
and the results obtained using these two methods are combined into one group in
Table 3.
The choice of the method does not substantially affect the PZC (Table 3), i.e. a
combination of titration (the common intersection point of titration curves for
different ionic strengths is identified with the PZC) and electrokinetic measurements,
titration alone, classical electrokinetic measurements alone, and even potentiometric
titration at one ionic strength (the natural pH of a dispersion in inert electrolyte
solution is identified with the PZC) produce practically the same average and
median PZC as the entire data set. The IEP value from the electroacoustic method
is substantially higher than the IEP obtained by other methods. Interestingly, this
high value exactly matches the CIP obtained in the present work.
As discussed above, the PZC value equal to matching IEP and CIP is more
reliable than results obtained using a single method. The PZC obtained in this way

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M. Kosmulski et al. / Advances in Colloid and Interface Science 103 (2003) 5776

for iron (hydr)oxides (black bars in Fig. 8) are distributed over a rather broad range
of pH 5.59.4, but not evenly, i.e. five PZC values are concentrated in the relatively
narrow range pH 8.28.5, and six others in the range pH 99.4. These islands are
to some degree associated with specific iron (hydr)oxide minerals. For example, all
six values in the range pH 99.4 represent synthetic hematite, but a value as low
as 6.7 was also reported for the same mineral. The black bars in Fig. 8 representing
goethite (pH 7.68.5) and FeOOH other than goethite (pH 7.17.6) can only be
found over relatively narrow pH ranges.
Then again, our matching IEP and CIP for goethite 25 is substantially higher
than any other matching IEP and CIP for goethite reported in the literature. The
recent MUSIC model makes it possible to estimate the PZC of individual samples
from well-established physical quantities when the structure and contribution of
different faces to the total surface area are known. For example, Hiemstra et al. w4x
found a PZC at pH 7.5 for the (100) face of goethite, and at pH 10.7 for the (001)
and (010) faces. Then, our results may be interpreted as a relatively low contribution
from the (100) face of goethite to its total surface area.
The absence of a substantial shift in the IEP of goethite 25 in 1 mol dmy3 NaI
is rather surprising. With one exception of silica w179x, all other oxides for which z
potentials at high ionic strengths were studied using the electroacoustic method
showed a reversal of sign to positive over the entire pH range at NaI concentrations
above the critical value. The critical NaI concentrations are of the order of 0.5 mol
dmy3 for metal oxides, and as low as 0.3 mol dmy3 for hematite w180x, while for
goethite such a critical concentration is either very high or does not exist at all. In
addition, correlation of the critical concentration of NaI with the IEP (the critical
concentration is low for materials with a high pristine IEP) and the oddeven rule
(oxides of metals showing odd valence have a low critical concentration) w180x
obviously do not apply to goethite. Perhaps there is a substantial difference between
anhydrous oxides and metal oxohydroxides in the electrokinetic behavior at high
ionic strengths. A substantial difference in the mechanism of selenate binding to
hematite on the one hand and to goethite on the other w181x is another example of
individual sorption properties of these two minerals.
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