See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/226684481

The Role of Intermediates in the Process of Red

Ferric Pigment Manufacture from FeSO4⋅7H2O

Article in Hyperfine Interactions · February 2002

DOI: 10.1023/A:1021259432720

CITATIONS READS

7 53

5 authors, including:

Radek Zboril M. Mashlan

Palacký University of Olomouc Palacký University of Olomouc
326 PUBLICATIONS 7,609 CITATIONS 101 PUBLICATIONS 845 CITATIONS

SEE PROFILE SEE PROFILE

Dimitrios Petridis Petr Pikal

National Center for Scientific Research De… Precheza
124 PUBLICATIONS 4,358 CITATIONS 9 PUBLICATIONS 35 CITATIONS

SEE PROFILE SEE PROFILE

Available from: M. Mashlan

Retrieved on: 20 July 2016
 Hyperfine Interactions 139/140: 437–445, 2002.
437
© 2002 Kluwer Academic Publishers. Printed in the Netherlands.

The Role of Intermediates in the Process of Red

Ferric Pigment Manufacture from FeSO4·7H2O

RADEK ZBORIL1, MIROSLAV MASHLAN1, DIMITRIS PETRIDIS2,

DAGMAR KRAUSOVA1 and PETR PIKAL3
1 Departments of Experimental Physics, Inorganic and Physical Chemistry, Palacky University,
Svobody 26, 771 46 Olomouc, Czech Republic
2 Institute of Materials Sciences, NCSR “Demokritos”, Athens 15310, Greece
3 Research Department, PRECHEZA, 750 62 Prerov, Czech Republic

Abstract. One method of industrial manufacture of red ferric pigments is based on the thermal
decomposition of FeSO4 ·7H2 O into α-Fe2 O3 (copperas red). The difficult reproducibility of the color
quality of the final pigment is the main problem of this process. One of the factors that can influence
the pigment color is contamination by some of the intermediates formed during the transformation
process. The identification of two groups of intermediates is the basic result of an extensive lab-
oratory investigation carried out using 57 Fe Mössbauer spectroscopy and X-ray powder diffraction
(XRD). The first group of intermediates includes sulfato-phases as FeSO4 ·H2 O, FeSO4 , Fe(OH)SO4 ,
Fe2 O(SO4 )2 , Fe2 O(SO4 )2 ·xH2 O x∈(0, 1), and Fe2 (SO4 )3 . Thermally metastable polymorphs of
iron(III) oxide, β-Fe2 O3 , γ -Fe2 O3 and ε-Fe2 O3 , represent the other group. Mössbauer characteri-
zation of all intermediate products is given. A significant influence of β-Fe2 O3 on the pigment color
was found.

Key words: FeSO4 ·7H2 O, thermal decomposition, intermediate, Mössbauer spectroscopy, red pig-
ment, iron oxide.

1. Introduction

The thermal decomposition of FeSO4 ·7H2 O (copperas) in an oxidizing atmosphere

is one of the age-long and most complicated problems of solid-state chemistry.
Many authors [1–13] investigated the different stages of this controversial process
and referred to different iron compounds as intermediates. Apart from higher hy-
drates, FeSO4 ·H2 O is the main Fe2+ phase that can be transformed by both oxidiz-
ing and dehydrating routes [1–8, 11]. The majority of authors regard Fe(OH)SO4
as the primary oxidation product [1–12]. Fe2 (SO4 )3 [7–12] and oxysulfates as
Fe2 O(SO4)2 [1–10], Fe12 O3 (SO4 )15 [9], Fe14 O3 (SO4 )18 [12] or Fe2 O2 SO4 [13]
were suggested as possible intermediates of secondary high-temperature decom-
position stages. Respecting the structure of the final product, only the formation of
the thermally stable hexagonal α-Fe2 O3 is mentioned in the literature.
438 R. ZBORIL ET AL.

In this work we present results of a Mössbauer spectroscopy and XRD study

focused on the identification of solid conversion intermediates and explanation of
their formation mechanism.

2. Experimental
As the thermally treated starting material, FeSO4 ·7H2 O (Sigma-Aldrich) was used.
Four stepwise-identified main intermediates were prepared in pure forms and their
thermal behavior was studied separately. Thermal dehydration of suitable commer-
cial hydrates in a nitrogen atmosphere was used for the preparation of FeSO4·H2 O
(from FeSO4·7H2 O at 120◦ C), FeSO4 (from FeSO4 ·7H2 O at 270◦ C) and Fe2 (SO4 )3
(from Fe2 (SO4 )3 ·5H2 O at 200◦ C). Fe(OH)SO4 was synthesized by air oxidation of
FeSO4 ·7H2 O at 250◦ C. The thermal treatment of samples was carried out in air
under isothermal conditions, at various temperatures (150–700◦ C). Each sulfato-
intermediate was heated at appropriate temperature for different periods of time
(1–70 hours) to examine objectively its transformation mechanism.
The transmission Mössbauer spectra were collected using a Mössbauer spec-
trometer in constant acceleration mode. The measurements were carried out using
a 57 Co(Rh) source, in the temperature range of 4.1–300 K. Phase compositions of
samples were monitored by XRD using θ–2θ conventional equipment (SEIFERT-
FPM, Germany) with Cu-Kα wavelength. The individual phases were identified
by means of a PDF2 database [14]. Re-emission visible spectra were measured in
the wavelength range of 400–750 nm using an UltraScan XE instrument. Particle
size distribution was determined by the dynamic light scattering method (DLS)
using Zeta Potential Analyzer Zeta Plus (Brookhaven Instr. Corp., USA). Standard
chemical, elemental and X-ray fluorescence (XRF) analyses were performed to
assess the chemical composition of some intermediates.

3. Identified intermediates, Mössbauer characterization and mechanism of

formation
Five main conversion stages proceeding in the temperature range of 100–700◦ C
were investigated.
FeSO4 ·H2 O was identified as a dominant phase of the initial dehydrating stage
occurring at temperatures under 150◦ C. Oxidizing and dehydrating tendencies are
typical for the thermal behavior of iron(II) sulfate monohydrate that transforms
through the routes. Fe(OH)SO4 and FeSO4 were detected as primary products of
individual routes. The third conversion stage consists in the thermal oxidation of
anhydrous iron(II) sulfate and it starts at temperatures above 300◦ C. Fe2 (SO4 )3
and superparamagnetic nanoparticles of γ -Fe2 O3 were observed in oxidation prod-
ucts. Other stage – decomposition of Fe(OH)SO4 is connected with the existence
of two transformation ways. At lower temperature (450◦ C), Fe(OH)SO4 under-
goes gradual dehydration into Fe2 O(SO4 )2 through metastable intermediate
RED FERRIC PIGMENT MANUFACTURE FROM FeSO4 ·7H2 O 439

Scheme 1. The solid-state transformations occurring during the thermal decomposition of

FeSO4 ·7H2 O in air.

Fe2 O(SO4)2 ·xH2 O, where x ∈ (0, 1). At higher temperatures, the other way in-
cluding one-step dehydration into Fe2 (SO4 )3 and α-Fe2 O3 occurs. The last stage
involves the desulfurization of Fe2 O(SO4 )2 and Fe2 (SO4 )3 at temperatures above
500◦ C. Oxysulfate converts straight into α-Fe2 O3 , Fe2 (SO4 )3 decomposes prefer-
ably into γ -Fe2 O3 nanoparticles and/or β-Fe2 O3 depending on the selected heating
temperature. Thermally metastable cubic spinel modifications of iron(III) oxide,
gamma and beta undergo the thermally induced structural change into α-Fe2 O3 .
β-Fe2 O3 transforms directly while ultrasmall particles of γ -Fe2 O3 transform
through orthorhombic ε-Fe2 O3 . Identified intermediates and their room temper-
ature (RT) Mössbauer parameters are summarized in Table I. Scheme 1 illustrates
the main transformation steps during the thermal decomposition of FeSO4 ·7H2 O
to the final α-Fe2 O3 .
We did not identify any unusual oxysulfates (Fe12 O3 (SO4 )15 [9], Fe14 O3 (SO4 )18
[12], Fe2 O2 SO4 [13]) mentioned in the literature. The possibility of the forma-
tion of debatable Fe2 O(SO4 )2 from FeSO4 ·H2 O [4], FeSO4 [1, 2, 4, 5, 9, 12]
or Fe2 (SO4)3 [6] was disproved. On the other hand, the two-step dehydration of
 440

Table I. Numbers of XRD cards from PDF 2 database and the values of RT Mössbauer parameters of intermediates identified during the thermal
decomposition of FeSO4 · 7H2 O in air

Intermediate Number RT Mössbauer parameters RT Mössbauer parameters

of XRD (this work) (literature)
card ISFe QS B ISFe QS B Ref.
[mm/s] [mm/s] [T] [mm/s] [mm/s] [T]

FeSO4 ·H2 O 45-1365 1.26 2.71 – 1.25 ÷ 1.29 2.67 ÷ 2.71 – [3, 8, 15]
FeSO4 33-0682 1.25 3.03 – 1.24 ÷ 1.29 2.94 ÷ 3.05 – [8, 15]
Fe(OH)SO4 21-0428 0.44 1.44 – 0.42 ÷ 0.44 1.42 ÷ 1.47 – [1, 3, 4, 15]
Fe2 O(SO4 )2 · xH2 O, 21-0928 0.43 0.91 – x x x [x]
x ∈ (0, 1)
Fe2 O(SO4 )2 x 0.45 0.47 – 0.47 0.44 – [3]
Fe2 (SO4 )3 33-0679 0.50 – – 0.50 ÷ 0.55 – – [8, 15–17]
γ -Fe2 O3 – 39-1346 0.37 0.80 ÷ 1.20 – 0.33 ÷ 0.36 0.76 ÷ 1.0 – [18–21]
nanoparticles
β-Fe2 O3 – d site 39-0238 0.36 0.69 – 0.36 0.69 – [16, 17]
b site 0.37 0.90 – 0.37 0.90 –
ε-Fe2 O3 – Fe1 site 16-0653 0.37 −0.05 45.4 0.39 −0.06 45.2 [22]
Fe2 site 0.38 −0.20 45.2 0.37 −0.19 45.0
Fe3 site 0.36 0.00 39.1 0.38 0.00 39.5
Fe4 site 0.20 −0.14 26.1 0.21 −0.07 26.2
ISFe – isomer shift related to metallic iron, QS – quadrupole splitting, B – magnetic induction, [x] – no literary data.
R. ZBORIL ET AL.
RED FERRIC PIGMENT MANUFACTURE FROM FeSO4 ·7H2 O 441

Figure 1. RT Mössbauer spectra (a) Fe(OH)SO4 heated at 450◦ C for 70 hours, (b) Fe2 O(SO4 )2
heated at 500◦ C for 1 hour.

Fe(OH)SO4 culminating by the formation of just Fe2 O(SO4)2 was isolated for the
first time. Likewise, the formation of β-Fe2 O3 , γ -Fe2 O3 and ε-Fe2 O3 polymorphs
during the multistage conversion of FeSO4 ·7H2 O was not reported up to now. Let
us discuss the features and mechanism of formation of these phases.
Fe2 O(SO4 )2 is formed as the product of the gradual dehydration of Fe(OH)SO4
at minimum transformation temperature (450◦ C). It is the only Fe3+ intermediate
that remains magnetically disordered at 4.1 K. The dehydration of Fe(OH)SO4
proceeds through hydrated oxysulfate as an intermediate (see Figure 1(a)). RT
Mössbauer spectra of all basic sulfates (Fe(OH)SO4 , Fe2 O(SO4 )2 ·xH2 O and
Fe2 O(SO4)2 ) show approximately the same value of the isomer shift. The de-
creasing values of the quadrupole splitting parameter (see Table I) indicate that
dehydration is accompanied by the gradual increase in symmetry of the iron en-
vironment. The complete transformation of Fe(OH)SO4 at 450◦ C allowed us to
perform complex chemical, elemental and XRF analyses (determination of iron
and sulfur content). These confirmed that the chemical composition of the product
442 R. ZBORIL ET AL.

corresponds to the formula of Fe2 O(SO4 )2 . An X-ray diffraction pattern could not
be assigned to any of the tabled phases, although many line positions corresponded
to the phase with formula Fe12 S11 O51 (number of card from PDF 2 database: 21-
0923, probably the mixture of Fe2 O(SO4 )2 and Fe2 O3 with the molar ratio 11/1).
The study of the decomposition mechanism of Fe2 O(SO4 )2 at 500◦ C proved that
it transforms straight to α-Fe2 O3 (see Figure 1(b)). It is evident that the separate
study of the transformation of Fe(OH)SO4 brought the elucidation of the role of
debatable Fe2 O(SO4)2 in the process of thermal conversion of copperas.
The formation of nanoparticles of cubic spinel γ -Fe2 O3 (maghemite) was ob-
served during two of the investigated solid-state reactions, thermal oxidation of
FeSO4 and conversion of Fe2 (SO4)3 (preferentially at lower temperature of about
530◦ C). In the room temperature Mössbauer spectra, a broad superparamagnetic
doublet with a quadrupole splitting distribution indicates the presence of parti-
cles generally smaller than 10 nm [18–21]. Isomer shift parameters were about
0.37 mm/s in both cases. Values of the full width at half maximum (FWHM)
varied depending on the particle size distribution. At low temperature Mössbauer
measurements, the superparamagnetic doublet splits into two hyperfine magnetic
field distributions with unequal isomer shifts corresponding to two sites of fer-
ric ions in the spinel structure of maghemite. The found quadrupole shift values,
near 0 mm/s in both sites, are characteristic just for maghemite [21]. γ -Fe2 O3
nanoparticles, after their formation, undergo a thermally induced structural change
into hexagonal α-Fe2 O3 through ε-Fe2 O3 . This two-steps transformation mecha-
nism is another evidence confirming the primary formation of γ -Fe2 O3 because
an epsilon-polymorph is produced exclusively as the intermediate of the phase
transition of maghemite nanoparticles to hematite [22]. RT Mössbauer spectrum in
Figure 2 demonstrates the successive transformation of maghemite nanoparticles
during thermal conversion of Fe2 (SO4 )3 .
Orthorhombic ε-Fe2 O3 shows several intermediate structural features between
γ -Fe2 O3 and α-Fe2 O3 . In the structure of this polymorph there are four non-equival-
ent Fe3+ positions, three octahedral (Fe1 , Fe2 , Fe3 ) and one tetrahedral (Fe4 ) [22].
The high values of FWHM (∼0.7 mm/s) observed for sextets corresponding to
ε-Fe2 O3 reflect the lower degree of the structural ordering.
β-Fe2 O3 is the other cubic polymorph of iron(III) oxide, in addition to
γ -Fe2 O3 , that forms during the thermal decomposition of Fe2 (SO4 )3 , at higher
temperatures of about 600◦ C. This rare form of Fe2 O3 has a body-centered cubic
structure with two non-equivalent octahedral sites of Fe3+ . The mechanism and
kinetics of β-Fe2 O3 formation from iron(III) sulfate are described in our previous
work [16].

4. Influence of β-Fe2 O3 on the color quality of iron(III) oxide

β-Fe2 O3 is the thermally most stable intermediate that was identified in several
samples of industrially manufactured pigment. Thus β-Fe2 O3 can be regarded as
RED FERRIC PIGMENT MANUFACTURE FROM FeSO4 ·7H2 O 443

Figure 2. The room temperature Mössbauer spectrum of a sample prepared by heating Fe2 (SO4 )3
at 530◦ C for 6 hours.

Figure 3. Differential re-emission spectra of Fe2 O3 with various phase composition.

the main contamination phase that can debase the color quality of copperas red
pigment (α-Fe2 O3 ) produced from FeSO4 ·7H2 O. The influence of beta modifi-
cation on the color of iron(III) oxide was studied using Mössbauer spectroscopy
(qualitative and quantitative phase analysis) and re-emission spectroscopy (color
quality measurement). β-Fe2 O3 can be present in the final industrial product only
as an admixture. Therefore, it’s “color effect” was investigated in samples with
444 R. ZBORIL ET AL.

minority percentage (<50%) of this structural form. The initial mixture of α- and
β-Fe2 O3 (α/(α + β) = 59%) was prepared by the thermal treatment of Fe2 (SO4 )3
at 600◦ C for 2 hours. This mixture was heated at 600◦ C for different times to
transform partially β-Fe2 O3 into α-Fe2 O3 . Thus samples with a higher percentage
of α-Fe2 O3 (α/(α + β) = 72, 77, 86, and 97%) were prepared. The re-emission
spectrum of the initial mixture was subtracted from the spectra of other samples;
these differential re-emission visible spectra are shown in Figure 3.
The particle size distributions of all samples were very similar and values of the
mean particle diameter ranged from 420 nm to 450 nm. Therefore, the differences
observed in re-emission spectra can be explained just by the β-Fe2 O3 influence.

5. Conclusions
A new model of the thermal decomposition of FeSO4 ·7H2 O in air was suggested.
Fe2 O(SO4)2 and Fe2 (SO4 )3 were identified as the products of the dehydration–
oxidation stage taking place at temperatures up to 500◦ C. High-temperature desul-
furization of both ferric sulfato-phases is associated with the formation of four
(α, β, γ , ε) Fe2 O3 polymorphs. β-Fe2 O3 as the thermally most stable intermediate
can significantly influence the color of the final red pigment (α-Fe2 O3 ).

Acknowledgements
Financial support from the Grant Agency of The Czech Republic under Projects
202/00/0982, 202/00/D091, from program KONTAKT under Project ME 351
(2000) and through a NATO Linkage grant HTECH LG 973515 is gratefully ac-
knowledged.

References
1. Neto, K. S. and Garg, V. K., J. Inorg. Nucl. Chem. 37 (1975), 2287.
2. Soroka, P. I., Parkhomenko, V. D., Belous, V. P. and Parkhomenko, N. V., Zh. Prikl. Khim. 53
(1980), 1725.
3. Bristoti, A., Kunrath, J. I., Viccaro, P. J. and Bergter, L., J. Inorg. Nucl. Chem. 37 (1975), 1149.
4. Pelovski, Y., Petkova, V. and Nikolov, S., Thermochim. Acta 274 (1996), 273.
5. Gallagher, P. K., Johnson, D. W. and Schrey, F., J. Am. Ceram. Soc. 53 (1970), 666.
6. Pelovski, Y. and Petkova, V., J. Therm. Anal. 49 (1997), 1227.
7. Swamy, M. S. R., Prasad, T. P. and Sant, B. R., J. Therm. Anal. 16 (1979), 471.
8. Vertes, A. and Zsoldos, B., Acta Chim. Acad. Sci. Hungar. 6 (1970), 261.
9. Kamel, A. H., Sawires, Z., Khalifa, H., Saleh, S. A. and Abdallah, A. M., J. Appl. Chem.
Biotechnol. 22 (1972), 591.
10. Swamy, M. S. R. and Prasad, T. P., J. Therm. Anal. 20 (1981), 107.
11. Margulis, E. V., Shokarev, M. M., Savtchenko, L. A., Kopylov, N. I. and Bejsekeeva, L. I., Zh.
Neorg. Khim. 16 (1971), 734.
12. Ismail, H. M., Zaki, M. I., Hussein, A. M. and Magar, M. N., Powder Technol. 63 (1990), 87.
13. Lorant, B., Z. Analyt. Chem. 219 (1966), 256.
14. Powder Diffraction File 1997, International Center for Diffraction Data, Pennsylvania, USA.
RED FERRIC PIGMENT MANUFACTURE FROM FeSO4 ·7H2 O 445

15. Zboril, R., Mashlan, M. and Krausova, D., Czech. J. Phys. 51 (2001), 719.
16. Zboril, R., Mashlan, M., Krausova, D. and Pikal, P., Hyp. Interact. 121–122 (1999), 497.
17. Zboril, R., Mashlan, M. and Krausova, D., In: M. Miglierini and D. Petridis (eds), Mössbauer
Spectroscopy in Materials Science, Kluwer Academic Publishers, Dordrecht, 1999, p. 49.
18. Pascal, C., Pascal, J. L., Favier, F., Elidrissi Moubtassim, M. L. and Payen, C., Chem. Mater.
11 (1999), 141.
19. Liu, T., Guo, L., Tao, Y., Wang, Y. B. and Wang, W. D., Nanostruct. Mater. 11 (1999), 487.
20. Iijima, S., Nomura, A., Mizukami, F., Shin, S. and Mizutani, F., J. Radioanal. Nucl. Chem. 239
(1999), 297.
21. de Bakker, P. M. A., de Grave, E., Vandenberghe, R. E. and Bowen, L. H., Hyp. Interact. 54
(1990), 493.
22. Tronc, E., Chanéac, C. and Jolivet, J. P., J. Solid State Chem. 139 (1998), 93.