ISSN 0967-0912, Steel in Translation, 2007, Vol. 37, No. 4, pp. 336–338. © Allerton Press, Inc., 2007.

Original Russian Text © V.A. Gorbachev, V.M. Abzalov, B.P. Yur’ev, 2007, published in “Izvestiya VUZ. Chernaya Metallurgiya,” 2007, No. 4, pp. 27–30.

Conversion of Magnetite to Hematite in Iron-Ore Pellets

V. A. Gorbachev, V. M. Abzalov, and B. P. Yur’ev
Ural State Technical University

DOI: 10.3103/S0967091207040031

The oxidation of magnetite in pellets consists of a
series of successive transformations. As yet, the mech-
anism of these transformations and the influence
exerted by various factors remain to be fully under-
stood, as a result not only of the complexity of the het-
erogeneous oxidation process but also of the lack of a
unified approach. On the one hand, some of the initial
data are omitted from consideration, thereby hindering
the comparison and generalization of results obtained
in different conditions; on the other, the presence of
several models of pellet oxidation gives rise to different
and often contradictory approaches to their description.
It is very important to determine the kinetic stage of
the process, when the oxidation rate is limited by the
chemical reaction. We need to establish here which pro-
cesses are in fact part of the chemical conversion of
magnetite to hematite. Even in the very early period of
magnetite oxidation
2Fe 3 O 4 + 0.5O 2 = 3Fe 2 O 3 ,
at the nucleation stage, which is beyond the reach of
existing experimental methods, there is ionic redistri-
bution, i.e., a diffusion process. Moreover, oxygen
adsorption at the magnetite surface determines the con-
centration gradient of iron and oxygen ions and hence
their diffusion. Thus, in the reaction zone, diffusion is
always present; only its mechanism may change.
Another noteworthy aspect is the analysis of the
kinetic features of the direct reaction in Eq. (1). Without
discussing the discrepancy between experimental val-
ues of the constants obtained by different authors,
which is natural when numerous factors influence the
process, we should note the impossibility of describing
the reaction over a broad temperature range (400–
1350°C, say) by means of a single empirical or other
model.
Consider the structure of the reagent (Fe3O4) and
product (Fe2O3). Magnetite has a crystalline structure
of the type of spinel MgAl2O4. The oxygen ions form
cubic dense packing, which may be represented by a
series of layers ABCABC. The iron ions are of different
valency: one third are divalent, and two thirds are triva-
lent. Altogether, there are eight divalent cations and six-
teen trivalent cations in the elementary cell. The alter-
nation of oxygen layers with crystallographic indices
(111) and iron layers is depicted in Fig. 1.
It is evident that the distribution of iron ions
between the oxygen planes (111) is inhomogeneous.
Thus, if there is one iron plane (although dense) in one
gap, in the next there will be three: one consisting of
iron ions in octahedral coordination and two of iron
ions in tetrahedral coordination.
The presence of cations distorts the close packing of
the oxygen ions. Thus, in ideal oxygen packing, the
parameter corresponding to the elementary cell is
0.75 nm. In fact, this parameter is 0.839 nm in magne-
tite and corresponds to the case when the ions—spheres
of the upper layer—partially emerge from the holes of
the adjacent layer. The distance between the oxygen
planes (111) in magnetite is 0.242 nm [1].
Ferrous oxide Fe2O3 has a crystal lattice of corun-
dum type (α-Al2O3). The oxygen ions form a hexagonal
close packing, which is usually represented by an alter-
(1) nation of layers of types A and B, i.e., ABABAB. As in
the case of magnetite, the iron ions between these oxy-
gen planes partially distort the packing of oxygen ions,
as a result of which the elementary cell of α-Fe2O3 is
usually shown in rhombohedral syngony. Note that,
(a)
(b)
Fig. 1. Alternation of oxygen (—) and iron (---, –·–) layers
of hematite (a) and magnetite (b) lattices.

336
 CONVERSION OF MAGNETITE TO HEMATITE IN IRON-ORE PELLETS 337

despite the distortion of the oxygen planes (111), prac- (b)

tically the maximum close packing is observed; this is O2
important in analyzing the diffusion of cations and Fe2O3
anions. Between the oxygen planes, there are layers of
iron ions, occupying two thirds of the available octahe- Fe2O3 Oads
dral vacancies (Fig. 1). The formula of the hematite
may be slightly nonstoichiometric (x is around 0.01 in
the formula Fe2 + xO3 [1]); the excess iron ions are at Fe3+ Fe3+
forbidden points, thereby creating potential centers of Fe3O4 Fe3+ Fe3O4
magnetite nucleation. (a)
Consider the conversion of the magnetite lattice to
Fig. 2. Oxidation of magnetite.
the hematite lattice. This transformation is accompanied
by change in both the oxygen and iron sublattices: the
packing of the oxygen sublattice changes: ABCABC
ABABAB, i.e., face-centered packing is replaced by planes, and diffusion of iron ions away from the solid–
hexagonal close packing. In the iron sublattice, there gas boundary. The most significant difference between
are more significant changes: besides the 12% decrease the dissociation mechanism and the oxidation mecha-
in the concentration of iron ions, one third change their nism is in the crystal-chemical deformation and hence
valency (to three) and change from an octagonal to a in the stress state. However, in the temperature range
tetragonal distribution (Fig. 1). where dissociation develops, the stress state that
appears relaxes by plastic deformation at rates consid-
Thus, in the oxidation of magnetite, restructuring of erably exceeding the rate of diffusional mass transfer,
the oxygen sublattice simply requires shift to the direc- and hence these differences may be disregarded. As a
tion (211) in the (111) plane; no change in oxygen con- result, oxidation and dissociation may be regarded as a
centration is required. The restructuring of the iron sub- process with the same mechanism, whose direction
lattice is more significant: the cations are redistributed, depends on the thermodynamic conditions of the exper-
with change in their concentration; in other words, dif- iment.
fusional processes occur. This analysis indicates that
iron-ion diffusion in magnetite predominates over oxy- As a first approximation, we consider the simplest
gen mass transfer in the solid phase. More accurate kinetic analysis of the transformation in Eq. (1). Sup-
quantitative estimates of the interaction energy of struc- pose that the reaction rate v of Eq. (1) is equal to the
tural defects call for examination of the specialized lit- difference in rates of the direct (v→) and inverse (v←)
erature [2]. However, the interface between the new reactions: v = v→ – v←. Then, in accordance with the
(Fe3O4) and old (Fe2O3) oxide phases is a dislocation approach in [3], we may write
wall in the oxygen sublattice and determines the path of
accelerated cation diffusion. The oxidation process is v = K 1 Fθ – K 2 F ( 1 – θ ), (2)
illustrated in Fig. 2a, where the transport of iron ions
occurs along the phase boundary and is determined by where K1 and K2 are the rate constants of the direct and
the laws of surface diffusion. inverse reactions; F is the reaction surface; θ is the
degree of surface filling with adsorbent
As the reaction proceeds, the product (hematite)
layer covers the whole surface of the reagent (magne- θ = ap/ ( 1 + ap ); (3)
tite), and transport of Fe2+ ions will occur along the
hematite grain boundaries (Fig. 2b). For example, with p is the partial gas (oxygen) pressure; a is the adsorp-
increase in temperature, the basic component in the cat- tion coefficient.
ionic flux will be due to bulk diffusion in hematite.
Thus, analysis of the experimental data regarding the Taking account of Eq. (3), Eq. (2) may be written in
switch from a kinetic to a diffusional mechanism (or the form
vice versa) with change in activation of the process may ap 1
be based on the velocity (and activation energy) of a v = K 1 F --------------- – K 2 F ---------------. (4)
diffusional flux associated with oxidation of the magne- 1 + ap 1 + ap
tite. Obviously, the proposed oxidation mechanism For small partial oxygen pressures, ap
1. Taking
may also be applied to the analysis of hematite reduc- into account that K2 = K1aP (P is the dissociation
tion and dissociation. index), we may then write
Without considering the reduction process, which
has already been adequately studied, we may note some v = K 1 Fap – K 1 FaP,
key features of dissociation. In terms of its mechanism,
dissociation differs from oxidation in that it is an or
inverse process characterized by dismantling of hema-
tite’s oxygen sublattice, relative shift of the (111) v = K 1 Fa ( p – P ). (5)

STEEL IN TRANSLATION Vol. 37 No. 4 2007