Chemical Geology 231 (2006) 288 – 299

www.elsevier.com/locate/chemgeo

Structural characterization and chemical reactivity of synthetic

Mn-goethites and hematites
Mariana Alvarez a,1 , Elsa H. Rueda a,⁎, Elsa E. Sileo b
a
Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
b
INQUIMAE, Dpto. de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires,
Pabellón II, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina
Received 30 November 2005; accepted 1 February 2006

Abstract

Several goethites were obtained through the hydrolysis at 60 °C of Fe(III) solutions containing variable amounts of Mn(II) ions.
The obtained samples were thermally treated at temperatures ranging from 180 to 310 °C until the complete phase transformation
to hematite was achieved. The effect of Mn in the dehydroxylation process was investigated using X-ray diffraction (XRD) and the
Rietveld refinement of XRD data together with scanning electron microscopy (SEM), differential thermogravimetric analysis
(DTA) and Fourier transform infrared spectroscopy (FTIR). In all cases, the formed hematites retained the acicular shape of the
precursor goethite. The dehydroxylation temperature increased with the increase of the Mn content in the parent goethite. The cell
parameters of both phases decreased with the thermal treatment, however the decrease in the goethite b-parameter was more
pronounced. This fact could be attributed to the distortion in the goethite structure by the presence of manganese. The band shifts in
the FT-IR spectra of the goethites with different Mn substitution were analysed. The intensities of the hydroxyl vibrations were
indicative of the degree of dehydroxylation.
The chemical reactivity of all the samples, before and after the thermal treatment, was also studied. The kinetic experiments
were carried out at 40 °C in 4 mol dm− 3 HCl. The acid dissolution of all Mn-goethites showed a congruent behavior indicative of a
homogeneous distribution of Mn in the goethite crystals, this trend was not observed in the formed hematites presenting a high Mn
content. The dissolution rate in goethites increased with the increase of Mn content, the opposite effect was observed in the
corresponding hematites. The activation energy in both phases was also obtained and indicated that the Mn substitution produces
an opposite effect on goethite- and hematite-phases. Different kinetic laws were applied in order to explain the dissolution behavior,
but the modified first-order Kabai equation described the dissolution data best.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Mn-goethite; Thermal transformation; Mn-hematite; Rietveld refinement; Acid dissolution

1. Introduction due to the wide interest in the technological applications

Several studies involving different aspects of the
dehydration of goethite to hematite have been performed
⁎ Corresponding author. Tel.: +54 291 4595159.
E-mail address: ehrueda@criba.edu.ar (E.H. Rueda).
1
Tel.: +54 291 4595159.
0009-2541/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2006.02.003
of iron oxides. A common method of hematite formation
is the thermal dehydration of goethite; this has been
the focus of a relative large number of studies (Derie
et al., 1976; Klissurski and Bluskov, 1980; Mendelovici
et al., 1982; Goñi-Elizalde and García-Clavel, 1988;
Schwertmann and Cornell, 1991; Pomiès et al., 1999).
The final product of the thermal dehydration is α-Fe2O3,
 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
whose properties depend on the temperature, treatment
conditions, and the crystallinity of the goethite (Derie et
al., 1976; Klissurski and Bluskov, 1980; Goñi-Elizalde
and García-Clavel, 1988). Dehydration of goethite in-
volves removal of hydrogen and one quarter of the
oxygen, without disturbing the network of remaining
oxygen, and atomic rearrangement of Fe3+ to form
hematite: 2 α-FeOOH → α-Fe2O3 + H2O. Two different
mechanisms have been suggested: direct dehydration of
goethite to hematite without an intermediate phase
(Watari et al., 1983; Goss, 1987), and the formation of
an intermediate product during dehydration where in the
inhomogeneous dehydration process, the crystal devel-
ops separate ‘donor’ and ‘acceptor’ regions (Ball and
Taylor, 1961; Lima-de-Faria, 1963).
Although most work on the goethite dehydroxylation
has focused on non-substituted goethite (Ruan et al.,
2001), natural goethite often contains appreciable quan-
tities of aluminum ion substituting Fe. This substitution
may affect the dehydroxylation temperature (Jonas and
Solymar, 1970; Fey and Dixon, 1981; Ruan and Gilkes,
1995a). Others cations such as Cr, Ge, Ni, Co and Mn
may also substitute Fe in natural goethite (Schwertmann
and Lathman, 1986; Bernstein and Waychunas, 1987;
Trolard et al., 1995).
Chemical dissolution of iron oxides has been studied
for a long time in analysis of natural and synthetic
mixtures, material chemistry, and technology (Blesa et
al., 1994; Cornell and Schwertmann, 1996). In general,
the solubility of iron oxides in pure water is extremely
low (Schwertmann, 1991); however, dissolution of Fe
oxides is promoted by strong acids and by reducing and
complexing agents.
Dissolution of iron oxides containing foreign ions
that replace Fe has also received attention. The mech-
anisms of dissolution of pure and Al-substituted, syn-
thetic and natural goethite in HCl solutions are well
understood (Surana and Warren, 1969; Cornell et al.,
1974, 1975, 1976; Schwertmann, 1984a; Cornell and
Schindler, 1987). Lim-Nuñez and Gilkes (1987) and
Alvarez et al. (2005) showed that transition metals-
substituted goethites dissolve in acidic media at rates
different from that of pure goethite. Wells et al. (2001)
investigated the influence of metal substitution on the
dissolution rate and kinetics of dissolution in 1 mol dm− 3
HCl of Al-, Mn- and Ni-susbtituted hematites. In all
cases, dissolution kinetics have been used to interpret
the release mechanism of cations included in goethite
and hematite; so, the acid dissolution provides evidence
of the uniformity of incorporation of Fe and metals in
these minerals. Iron and metal analysis of sequential
extracts during the dissolution of samples can provide
289
information regarding the distribution of the foreign
metal within the structure of the iron oxide. If Fe and
associated metals dissolve at identical rates, then it is
reasonable to assume that the metal is uniformly dis-
tributed throughout the iron oxide crystals. Conversely,
if Fe and the metal show quite different patterns of
dissolution, then it is unlikely that the two elements are
present in a single mineral of uniform composition
(Sidhu et al., 1981; Singh and Gilkes, 1992).
The aim of this work is to provide information about
the effects of Mn substitution on the thermal transfor-
mation of goethite to hematite achieved at different
temperatures. For that, the structural changes of the two
phases are analysed using the Rietveld refinement of
XRD powder data. The effect of the Mn incorporation
on the dissolution behavior in acidic media of all the
formed solids is also investigated.
2. Materials and methods
Manganese goethites were synthesized from the
Fe(III)-system using a method described elsewhere
(Sileo et al., 2001). Ferrihydrites were precipitated by
adding a 2 mol dm− 3 NaOH to different solutions
containing variable quantities of Fe(III) and Mn(II)
nitrates. The final ratio OH− / (Fe + Mn) and the total
(Fe + Mn) concentration in all samples were 13.16 and
0.53 mol dm− 3, respectively. The precipitates obtained,
were washed twice with double-distilled water and
centrifuged. After this treatment, the samples were aged
for 21 d at 60 °C in closed polyethylene flasks con-
taining 0.3 mol dm− 3 NaOH. Initial mole ratios
χMn = Mn / (Mn + Fe) were 0.00, 0.03, 0.07 and 0.10
(samples named S0_60 °C to S3_60 °C, respectively). After
aging, the materials were washed with double-distilled
water until the conductivity of the filtrated solution was
b 5 μS. The remaining solids were dried at 40 °C and
gently crushed. Then, the samples were oxalate-ex-
tracted in order to remove remaining ferrihydrite from
their surfaces.
Sub-samples of Mn-substituted goethites were heated
in a glass furnace with temperature control within ± 2 °C
for 2 h at temperatures ranging from 180 to 310 °C
to evaluate the degree of transformation goethite →
hematite.
The level of Mn incorporation was calculated from
the composition of the oxalate-extracts. Metal contents
in the goethites were determined on 20 mg of each
sample dissolved in 6 mol dm− 3 HCl at 60–80 °C, using
a GBC Model B-932 flame atomic absorption spectrom-
eter. Differential thermal analyses (DTA) were carried
out in a DTA-50 Shimadzu analyzer. Approximately
290 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299

Table 1 ultrasonic treatment and a drop of suspension was placed

Chemical composition for the samples synthesized at 60 °C onto a metallic support. SEM images were obtained from
Sample(1) χMn (preparative) χMn (experimental) a Phillips SEM 515 equipment operated at 30 keV.
S0_60 °C 0.00 0.0 Fourier Transform infrared absorption (FTIR) spec-
S1_60 °C 0.03 0.025 ± 0.005 tra, between 400 and 4000 cm− 1 with 2 cm− 1 resolution,
S2_60 °C 0.07 0.067 ± 0.001 were obtained using a Nicolet 510P FT-IR spectrometer.
S3_60 °C 0.10 0.083 ± 0.002
The samples were dispersed in KBr disks (1%).
(1)
Subscript indicates different Mn level and synthesis temperature. Dissolution kinetics were measured at 40 °C. 50 mg
of each sample was suspended in 50 cm3 of 4 mol dm− 3
5 mg of sample was heated in flowing air to 500 °C at HCl and sealed in a cylindrical beaker provided with a
10 °C min− 1. thermostat water jacket. The suspension was magneti-
X-ray diffraction patterns were recorded in a Siemens cally stirred throughout the experiment. Sample aliquots
D5000 diffractometer using the Cu Kα radiation at (1 cm3) were withdrawn at predetermined intervals and
40 kV, and 30 mA. Divergence, scattered, and receiving filtered immediately through 0.22 μm membrane filters.
radiation slits were 1°, 1°, and 0.2 mm, respectively. A The solution to solid weight ratio (1000 : 1) used in this
curved graphite-monochromator was used. Data were work is in line with previous dissolution studies that
collected in the 19.000° ≤ 2θ ≤ 140.000° range, with used ratios in the range 250–2000 : 1 to ensure that the
variable scanning steps in the range 0.030° to 0.020° dissolution was independent of the solution to sample
and different counting times. The step width of each run ratio (Cornell et al., 1974; Sidhu et al., 1981; Lim-Nuñez
assured a minimum of about 12 intensity points for the and Gilkes, 1987). Determinations of dissolved Fe and
narrower peaks. The data were analysed by the Rietveld
refinement method (Rietveld, 1969) using the General
Structure Analysis System (Larson and Von Dreele,
1994). The Thompson–Cox–Hasting pseudo-Voigt
function (Thompson et al., 1987) with the microstrain
broadening description of Stephens (1999) was used for
fitting the peak profiles. A linear interpolation function
was employed for fitting the background signal. Cell
parameters, peak displacement, full width at half
maximum, microstrain broadening, scale factor, and
positional parameters for all atoms were refined. The
isotropic thermal parameters were fixed at the values
measured for goethite (Szytula et al., 1968) and hematite
(Maslen et al., 1994) single-crystals.
Specimens for scanning electronic microscopy
(SEM) were dispersed in double-distilled water with

Fig. 1. DTA profiles for the samples Si_60 °C. Mn contents are indicated Fig. 2. XRD of samples (a) S0 and (b) S3 heated at different
in Table 1. temperatures.
 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 291

In addition, a splitting of the dehydroxylation endo-

thermic peak is observed. A double DTA peak due to
dehydroxylation of pure goethite to hematite has been
found by Derie et al. (1976) and Schwertmann (1984b).
Derie et al. (1976) suggested that the hematite shell
formed around goethite crystals retards the dehydration
of the core, while Murad reported that ground natural
highly crystalline goethite shows a double peak.
Schwertmann (1984b) also reported a double peak in
the dehydroxylation of well-crystallized α-FeOOH that
was attributed to an intermediate goethite with a slightly
higher dehydroxylation temperature generated during
heating. In Al-substituted goethite the double peak was
interpreted by the difference in the dehydroxylation
temperatures of Al–OH and Fe–OH groups (Fey and
Dixon, 1981). However, these explanations for a double
peak cannot be used to explain the multiple peaks
observed here. Instead polycrystallinity and lattice dis-
tortions and defects may be responsible for the peak
broadening. The presence of Mn in goethite weakens
and broadens this endothermic feature.
The XRD patterns (Fig. 2) obtained after heating the
samples at different temperatures show that goethite is
completely transformed to hematite from 260 to 310 °C
as the χMn value increases from 0 to 0.083 mol/mol.

3.2. Crystal morphology

Fig. 3. Scanning electron micrographs (×20,000) of samples

Fig. 3 shows SEM micrographs for sample S2 at three
(a) S2_60 °C and (b) S2_310 °C. different heating temperatures. The starting goethite
crystals prepared at 60 °C are acicular and this
Mn amounts were determined by atomic absorption morphology is retained on thermal treatment at 220
spectroscopy.
To determine activation energy (Ea), dissolution Table 2
kinetics were measured at three temperatures (40, 50 Agreement factors for the refinements
and 60 °C). Sample(1) R(2)
wp R(3)
exp GofF(4) RBragg Composition (%)
All kinetic experiments were carried out in duplicate Goethite Hematite
or triplicate and the coefficient of variation was b 0.08. S0_60 °C 10.50 7.24 1.4 4.21 100.0 0.0
S1_60 °C 10.50 7.27 1.4 3.78 100.0 0.0
3. Results and discussion S2_60 °C 10.60 7.00 1.5 3.67 100.0 0.0
S3_60 °C 8.98 6.95 1.3 2.91 100.0 0.0
S0_220 °C 11.18 8.88 1.50 7.55 58.6(8) 41.4(8)
3.1. Mn content, DTA and XRD
S1_220 °C 9.15 7.18 1.38 3.91 61.4(4) 38.6(4)
S2_220 °C 8.83 6.67 1.49 3.51 68.1(4) 31.9(4)
Table 1 shows that the Mn content in the series S3_220 °C 11.08 8.60 1.18 5.15 71.4(3) 28.6(3)
increases with the increase of Mn (II) in the initial S0_260 °C 9.07 7.13 1.42 4.96 0.0 100.0
solution. S1_260 °C 9.35 7.27 1.51 4.01 0.0 100.0
S2_260 °C 9.92 7.50 1.57 3.83 30.4(8) 69.6(8)
The main endothermic DTA peak (Fig. 1) for the
S3_260 °C 11.63 9.19 1.55 9.46 35.9(7) 64.1(7)
dehydroxylation is displaced from 267 to 294 °C as the S2_310 °C 13.81 10.42 1.40 8.88 0.0 100.0
Mn content increases from χMn = 0 to 0.083. The same S3_310 °C 12.47 9.93 1.36 6.04 0.0 100.0
trend was observed for Al-(Fey and Dixon, 1981; Lim- (1)
Subscript indicates dehydroxylation temperature; (2)Rwp: weighed
Nuñez, 1985; Ruan and Gilkes, 1995a) and Cr- sum of residuals of the least square fit of the Rietveld refinement;
(3)
substituted goethites (Sileo et al., 2004). Rexp: value statistically expected; (4)GofF: Rwp / Rexp.
292 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299

transformation of goethite to hematite was observed in

Fig. 4. Weight (%) of hematite from S0 to S3 heated at different
temperatures between 60 and 310 °C.
and 310 °C. The same feature was also observed by
Cornell and Schwertmann (1996), Pomiès et al. (1999)
and González et al. (2000).
3.3. Hematite / goethite ratio and unit cell dimensions
during dehydroxylation
Table 2 collects the parameters that describe the
quality of the Rietveld simulation and the proportion of
goethite and hematite in the samples. Reliability factors
are in the range Rwp ≡ 8.83–13.81; RB ≡ 2.91–9.46;
GofF values are reasonably adequate, between 1.30 and
1.57.
Since the thermal treatment of samples S0 to S3 at 60
and 180 °C renders only goethite, only refinement data
for 60 °C is presented. Partial dehydroxylation at 220 °C
is occurred in all samples, and in samples S2 and S3 at
260 °C. For each temperature the higher goethite content
is found in samples with higher χMn values. Complete
S0_260 °C and in S1_260 °C. At 310 °C only hematite was
present in all compositions (Fig. 4). The data confirm
that Mn-substitution in goethite raises the dehydroxyla-
tion temperature.
The cell parameters obtained by the Rietveld refine-
ment are shown in Table 3.
Although Fe(III) and Mn(III) have similar ionic
radii, the electronic configuration of Mn(III), a d4 ion,
presents a tetragonally distorted rather than a symmet-
rical octahedral coordination sphere that does not
arrange as easily into the structure of goethite as does
Fe(III). This is reflected in the increase in the b
parameter as the level of Mn substitution for samples
synthesized at 60 °C increases and a decrease in the a
and c parameters (Sileo et al., 2001). These changes in
cell parameters confirm the oxidation of Mn(II) to Mn
(III) and the isostructural Mn-for-Fe substitution.
Fig. 5 shows the evolution of the cell parameters of
goethite and hematite vs. temperature for S2 and S3
samples.
A systematic decrease in the a and c parameters of
Mn-goethite on thermal treatment takes place in both
samples; b parameter shows the same decreasing trend,
but in the temperature range 60–220 °C this change is
more pronounced in sample S3. At 260 °C both samples
reach practically the same value for this parameter. This
behavior of the b dimension may be related to the
migration of cations and rearrangement of oxygen
packing over the temperature range of dehydroxylation
used in this study. Similar trend is observed in Al-
goethites (Ruan and Gilkes, 1995a). It is important to
emphasize that the Mn distribution within the goethite
and hematite crystals could not be determined. Gasser et

Table 3
Unit cell parameters for the samples
Sample Goethite Hematite
3
a (nm) b (nm) c (nm) Vol (nm ) a = b (nm) c (nm) Vol (nm3)
S0_60 °C 0.46172(5) 0.99548(10) 0.30242(3) 0.13901(2) – – –
S1_60 °C 0.46113(2) 0.99573(5) 0.30217(1) 0.13875(1) – – –
S2_60 °C 0.46051(1) 0.99698(2) 0.30197(1) 0.13864(1) – – –
S3_60 °C 0.45990(1) 0.99837(1) 0.30165(1) 0.13851(1) – – –
S0_220 °C 0.46114(9) 0.99774(7) 0.30051(4) 0.13827(4) 0.50519(63) 1.37576(262) 0.30408(99)
S1_220 °C 0.46060(10) 0.99791(12) 0.29902(5) 0.13744(3) 0.50553(20) 1.37905(70) 0.30521(16)
S2_220 °C 0.46066(9) 0.99686(12) 0.29819(5) 0.13693(3) 0.50632(11) 1.37893(179) 0.30615(39)
S3_220 °C 0.45945(5) 0.99540(8) 0.29762(2) 0.13611(2) 0.50481(25) 1.38673(72) 0.30604(24)
S0_260 °C – – – – 0.50390(2) 1.37624(13) 0.30263(3)
S1_260 °C – – – – 0.50373(5) 1.37583(20) 0.30233(7)
S2_260 °C 0.45588(18) 0.99546(38) 0.29418(13) 0.13350(5) 0.50467(5) 1.37375(37) 0.30300(8)
S3_260 °C 0.45832(10) 0.99559(18) 0.29465(4) 0.13444(4) 0.50312(4) 1.37499(21) 0.30142(5)
S2_310 °C – – – – 0.50333(2) 1.37537(18) 0.30176(4)
S3_310 °C – – – – 0.50308(4) 1.37535(16) 0.30145(6)
 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 293

Fig. 5. Cell parameters vs. temperature for S2 (○) and S3 (■): (a), (b), (c) goethite phase, and (d), (e) hematite phase.

al. (1999) found a Mn zoning in goethite, which may
partly explain inhomogeneous transformation of ferri-
hydrite to goethite. This behavior could also occur in the
topotatic goethite–hematite phase transformation in the
presence of Mn.
The a and c parameters of hematite decrease as the
temperature of the treatment is raised from 220 to
260 °C. Similar trends were reported for pure hematites
and Al-hematites obtained from thermal transformation
of the corresponding goethites (Ruan and Gilkes, 1995a;
Ruan et al., 2001).
3.4. FT-IR spectra
In the FT-IR spectra (Fig. 6) structural OH of
goethite causes the absorption at 3140 cm− 1, the
hydroxyl stretching region, and the two bands at
∼890 and 795 cm− 1 correspond to OH deformation
and water bending modes (Cambier, 1986). The
intensity of the band at 3140 cm− decreased as the
1
Mn content increased shifting to lower energy values and
disappeared in all the samples after heating at 260 °C.
The same trend in intensity is found in the bands
294 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
Fig. 6. Infrared spectra of samples (a) S0, (b) S1, (c) S2 and (d) S3, and its dehydroxylated products obtained from heating goethite between 180 and
310 °C for 2 h.
corresponding to the OH deformation and water bending
modes.
After heating at 220 °C all samples show a band at
∼3400 cm− 1, together with the weak absorption at
∼1620 cm− 1, attributed to ‘loosely bound water’, which
are indicative of hydroxyl in hematite. The spectra show
that the hematites, formed by thermal dehydroxylation
of goethite, inherited some structural OH expressed by
Fe2−x / 3(OH)xO3−x. Wolska and Szajda (1985) reported
the bands near 3400, 950 and 630 cm− 1 as OH unit
vibrations in “hydrohematite”.
The presence of goethite detected by XRD in
samples S2 and S3 only could be supported by FT-IR
spectra of S2. In samples S2_310 °C and S3_310 °C, the
spectra show characteristic bands of “hydrohematite”,
and no bands of goethite are detected. These results
agree with XRD patterns.
3.5. Dissolution curves
The representative plots of Fe released at 40 °C in
4 mol dm− 3 HCl vs. time for the prepared Mn-goethites
and the totally thermal transformed Mn-hematites are
shown in Fig. 7.
Dissolution curves for goethite show nearly linear
shapes in the range of time studied in this work
(Fig. 7a), whereas the curves for the samples S0_260 °C,
S1_260 °C, S2_310 °C and S3_310 °C, where the unique
phase is hematite, show deceleratory shapes (Fig. 7b).
As shown in the Fig. 7, dissolution rates are similar for
S0_60 °C and S1_60 °C and then increase with Mn content
(S0_60 °C ≈ S1_60 °C b S2_60 °C b S3_60 °C), whereas the
opposite effect was observed with the increase of Mn
substitution in the hematite samples. These latter re-
sults agreed with those presented by Wells et al. (2001).
The dissolution rate per gram of oxide was calculated
from the initial nearly linear region of the dissolution
curves (Table 4).
The initial dissolution rates in Table 4 indicate that
non-substituted hematite (S0_260 °C) dissolved about 90
times faster than the corresponding goethite (S0_60 °C).
In the case of substituted samples, hematite with higher
Mn content (S3_310 °C) dissolved only about 5 times
faster than the corresponding Mn-goethite (S3_60 °C).
Then, Mn substitution reduced the dissolution rate of
hematite, but increased the dissolution rate of goethite.
The increase in k0 values detected in the mixed
goethite–hematite samples compared to that of pure
 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 295

goethite may be explained by the development of Table 4

micropores and structural disorder formed during the Initial dissolution rate (k0) for goethites as affected by Mn substitution
and heating
phase transformation (Naono and Fujiwara, 1980; Goss,
Sample Mol% Mn Hm (1) k0 (mmol Fe g R2
1987; Ruan and Gilkes, 1995b). This process involves
Hm þ Gt oxide− 1 min− 1)
an increase of the surface density of sites susceptible to
acid attack (Watari et al., 1979, 1983; Cornell and S0_60 °C 0 0 0.01037 0.999
S0_180 °C 0 0.01333 0.998
Giovanoli, 1993). At the beginning of dehydroxylation
S0_220 °C 0.414 0.06492 0.966
only a departure of this trend is observed in sample S3. S0_260 °C 1 0.92904 0.997
This behavior will be discussed below. S1_60 °C 2.5 0 0.01386 0.999
S1_180 °C 0 0.02684 0.999
3.6. Congruency of dissolution of Fe and Mn S1_220 °C 0.386 0.09770 0.952
S1_260 °C 1 0.57086 0.991
S2_60 °C 6.7 0 0.01627 0.998
Plots of fraction of Mn versus fraction of Fe S2_180 °C 0 0.02056 0.997
dissolved during dissolution provide an indirect mea- S2_220 °C 0.319 0.07227 0.953
sure of the distribution of Mn within the crystals of S2_260 °C 0.696 0.21034 0.980
goethite and hematite. Dissolution data for Fe and Mn S2_310 °C 1 0.16701 0.998
S3_60 °C 8.3 0 0.02562 0.999
S3_180 °C 0 0.01771 0.974
S3_220 °C 0.286 0.08515 0.969
S3_260 °C 0.641 0.08688 0.998
S3_310 °C 1 0.13368 0.998
(1)
Hm: hematite; Gt.: goethite.

for Mn-substituted goethite and corresponding hematite

are shown in Fig. 8a) and b), respectively.
The data for Mn-substituted goethites (Fig. 8a) is
well described by a line of slope = 1, indicating that
Mn3+ and Fe3+ were uniformly distributed within the
crystal structure of goethite, and that dissolution was
congruent. In contrast, a withdrawal of congruency was
observed for Mn-substituted hematites (Fig. 8b). The
convex χMn : χFe curve for hematite S1_260 °C indicates
that, after the thermal transformation, Mn tends to be
more concentrated towards the surface of the hematite
particles. The opposite trend is observed in S2_310 °C,
which presents a concave curve. In spite of this rather
erratic behavior, it suggests an inhomogeneous Mn
distribution in the hematite phase after thermal treat-
ment, being this effect more significant in samples with
low Mn content. Further studies concerning the crystal
analysis and Mn distribution should be carried out in
order to achieve a better understanding of this process.

3.7. Effect of dissolution temperature–activation energy

The activation energy (Ea) for the dissolution process

Fig. 7. Representative dissolution curves for synthetic goethites (a) and
corresponding hematites (b) expressed as mmoles of Fe released per
gram oxide in 4 mol dm− 3 HCl at 40 °C vs. time, as affected by Mn
substitution (Mn content, as mol%: S0 = 0; S1 = 2.5; S2 = 6.7; S3 = 8.3).
was obtained for goethite and hematite phases in samples
S0 (χMn = 0) and S2 (χMn = 0.067), using the Arrhenius
equation, with R2 values ≥ 0.98, (data not shown). The
dissolution rate (k) values were obtained from the slopes
of initial nearly linear regions of the dissolution curves
measured at 40, 50 and 60 °C. The calculated Ea value
296 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
Fig. 8. Plot of χMn dissolved vs. χFe dissolved in 4 mol dm− 3 HCl for
(a) Mn-substituted goethites, and (b) Mn-substituted hematites.
for pure goethite (S0_60 °C) is 149.6 kJ mol− 1, while the
value for pure hematite (S0_260 °C) is 85.6 kJ mol− 1. In
the case of the substituted goethite, the Ea value en-
countered for S2_60 °C (90.1 kJ mol− 1) is smaller than
the value calculated for S0_60 °C, this fact may be
ascribed to the presence of weaker Mn–O bonds com-
pared to the only Fe–O bonds present in pure goethite
(Schwertmann, 1991).
The comparison between goethite and hematite with
the same χMn value (S2_60 °C and S2_310 °C) shows Ea
values of 90.1 and 91.0 kJ mol− 1, respectively. The
latter value is in agreement with the Ea values reported
by Wells et al. (2001) for hematite synthesized with
6.3 mol% Mn substitution (84.1 kJ mol− 1). As can be
seen from the Ea results, Mn substitution produces op-
posite effects in the stabilization of goethite and hema-
tite against proton attack.
3.8. Dissolution kinetics
Dissolution data at 40 °C, for all samples were fitted
to several kinetic laws, such as the quadratic, the
Avrami–Erofejev and the Kabai laws (Cornell and
Schwertmann, 1996). The best description of the kinetic
behavior was found using the Kabai law.
The coefficients obtained fitting the data with the
α
Kabai equation (Kabai, 1973), χFe = 1 − e−(kt) , are listed
in Table 5. Here, χFe is the fraction of Fe dissolved at
time t and α is a constant value. For α N 1 the curve is
sigmoidal in shape, for α b 1 the curve is deceleratory.
The dissolution rate constant, k, was obtained from plots
of ln[ln{1 / (1 − χFe)}] vs. lnt, where ln[ln{1 / (1 − χFe)}]
is the log-transform linearized form of the Kabai
equation.
As can be seen, the dissolution of Mn-substituted
goethites synthesized at 60 °C is well described by the
Kabai equation.
For some but not all samples consisting of goethite
and hematite, v.g. all the samples heated at 220 °C, two
intercepting straight lines were required to achieve a
better fit. The break between the two lines may represent
the point at which most hematite has dissolved so that
continuing a slower dissolution of goethite determines
the slope of the second line.
The same behavior is also detected in samples
S2_180 °C and S3_180 °C, where Mn-goethite is the unique
phase present. This effect is in line with a clear decrease
of the intensity of the low water bending bands, at
∼1650 and ∼1790 cm− 1, with the Mn substitution (Fig.
9). However, we found that the presence of Mn in the
goethite structure retards the complete transformation to
hematite, as shown by XRD, IR and DTA analysis.
The good fit of the data found for goethite / hematite
mixtures at 260 °C to single lines is difficult to explain.
Although more than one phase is present, there is no
assurance of the Mn distribution in each phase, so a
compensating effect could justify this good fit. The d4
electron configuration of Mn3+ undergoes a large static
Jahn–Teller distortion in octahedral coordination and
this effect may limit the substitution of Mn in hematite.
The results obtained by Singh et al. (2000) agree with
those of Cornell and Giovanoli (1987) who showed that
quantities ≤ 5 mol% Mn can be incorporated in the
hematite structure. Any additional Mn is either adsorbed
or precipitated as a separate phase. Since the Jahn–
Teller effect limits the solubility of Mn in hematite, a
non-uniformity Mn distribution between both phases is
possible.
The effect of Mn incorporation in the stability of the
goethite and hematite phases is reflected in the variation of
the k values obtained from the Kabai law. In all cases, k
shows a significant increase with the total phase transfor-
mation of goethite to hematite; however, this increase is
smaller with the higher Mn content. For example, k derived
 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 297

Table 5
Coefficients for the Kabai equation for samples dissolved at 40 °C
Sample Mol% Mn Hm (1) Linear part n α k (min− 1 × 103) R2
Hm þ Gt
S0_60 °C 0 0 – 7 1.217 1.98 0.994
S0_180 °C 0 – 9 1.282 1.70 0.996
S0_220 °C 0.414 I 11 0.298 0.11 0.997
II 5 0.772 1.61 0.996
S0_260 °C 1 – 9 1.130 81.36 0.991
S1_60 °C 2.5 0 – 7 1.617 3.63 0.999
S1_180 °C 0 – 6 1.189 3.86 0.997
S1_220 °C 0.386 I 8 0.412 7.71 0.989
II 4 1.351 7.80 0.991
S1_260 °C 1 – 10 0.867 54.57 0.999
S2_60 °C 6.7 0 – 9 1.395 2.42 0.997
S2_180 °C 0 I 6 1.139 1.75 0.997
II 3 1.955 2.15 0.978
S2_220 °C 0.319 I 8 0.388 6.42 0.995
II 4 1.064 7.96 0.997
S2_260 °C 0.696 – 12 0.759 23.30 0.997
S2_310 °C 1 – 10 0.926 31.37 0.992
S3_60 °C 8.3 0 – 9 1.016 3.63 0.993
S3_180 °C 0 I 5 0.822 1.53 0.995
II 5 1.722 3.76 0.998
S3_220 °C 0.286 I 7 0.533 8.24 0.993
II 4 1.032 7.30 0.994
S3_260 °C 0.641 – 12 0.784 14.56 0.998
S3_310 °C 1 – 10 1.156 14.37 0.992
(1)
Hm: hematite; Gt: goethite.

from Kabai equation is 1.98×103 min− 1 for pure goethite
(S0_60 °C), and 8.14 × 104 min− 1 for pure hematite
(S0_260 °C), while for S3_60 °C k value is 3.63×103 and
1.44 × 104 min− 1 for S3_310 °C. These results are in
accordance with k0 values observed in Table 4.
4. Conclusions
A series of goethites with increasing Mn content were
synthesized by forced hydrolysis with base addition, and
Fig. 9. FTIR spectra from samples S0_180 °C to S3_180 °C in the region of
the water bending bands (1600–1900 cm− 1).
thermically treated at different temperatures. The degree
of transformation could be evaluated in function of
changes in the cell parameters of all samples, and their
chemical reactivity in an acidic media.
Crystals of Mn-substituted goethite retain the acicular
shape after transformation to hematite at 310 °C. The
temperature of transformation decreases as the Mn con-
tent increases. In the same way, the Mn substitution in
goethite raises the dehydroxylation temperature.
The cell parameters of both goethite and hematite
decrease with the thermal treatment. However, the be-
havior of the b parameter in Mn-goethite is more erratic.
In agreement with XRD results, IR spectra support
the assumption that Mn retards the dehydroxylation of
goethite solid phase to form hematite.
The results of this study confirm that Mn-substituted
goethite is thermally more stable than non-substituted
goethite. The same effect was observed in Al-goethite.
The acid dissolution of all Mn-goethites is congruent,
but not for all Mn-hematites. The major diversion from
this tendency is observed in hematites with higher Mn
content.
The increasing Mn substitution in goethite raises the
dissolution rate, while the opposite effect was observed
for the corresponding Mn-hematites obtained from heat-
ing goethite.
298 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
Mn substitution produces opposite effects in activa-
tion energy for acid dissolution in both goethite and
hematite phases.
Dissolution of pure and Mn-substituted goethites and
hematites, and samples containing a mixture of both
phases in 4 mol dm− 3 HCl can be well explained by the
modified first-order Kabai equation. Data for samples
treated at 180 and 220 °C conform to two straight lines
whereas a single line provided a satisfactory description
of dissolution of the remaining samples.
Further studies such as high resolution TEM should
be carried out in order to elucidate how Mn distribution
in each phase influences the reactivity of these samples.
Acknowledgements
This work has been partially supported by SGCyT
(PGI: 24/005), Universidad Nacional del Sur, Bahía
Blanca, Argentina and grant from Universidad de
Buenos Aires (X168), Argentina. The authors are grate-
ful to the anonymous reviewers for constructive com-
ments that enhanced the clarity of this manuscript. [DR]
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