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Kinetics and mechanism of formation of MoO2 by

solid state reaction between MoS2 and MoO3

I. Wilkomirsky & E. Sáez

To cite this article: I. Wilkomirsky & E. Sáez (2019): Kinetics and mechanism of formation of
MoO2 by solid state reaction between MoS2 and MoO3, Canadian Metallurgical Quarterly, DOI:
10.1080/00084433.2019.1653541

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CANADIAN METALLURGICAL QUARTERLY
https://doi.org/10.1080/00084433.2019.1653541

Kinetics and mechanism of formation of MoO2 by solid state reaction between

MoS2 and MoO3
I. Wilkomirskya and E. Sáezb
a
Department of Metallurgical Engineering, University of Concepción, Concepción, Chile; bCaletones Smelter, El Teniente Division of CODELCO,
Rancagua, Chile

ABSTRACT ARTICLE HISTORY

The kinetics and mechanism of the solid state reaction between MoS2 and MoO3 to form MoO2 Received 16 May 2018
under nitrogen atmosphere between 723 and 973 K were studied using bulk mixed samples, Accepted 5 August 2019
mixed compressed pellets and pure MoS2 and MoO3 pellets with one face in contact. The results
KEYWORDS
show that for the bulk samples, the reaction reaches a maximum conversion of 67.3% at 923 K Kinetics; mechanism of
in 75 min, while for compressed samples conversion under similar conditions reaches 96.1% in formation; molybdenum
75 min, which reflects the effect of the physical conditions of both types of experiments on the dioxide
reaction kinetics. The calculated activation energy values for both experimental conditions are
consistent, with an average value of −44.2 ± 1.9 kJ, which is in the range of diffusion-controlled
solid state reactions. For the samples with one face in contact, above 923 K the results appear to
indicate that solid state molecular diffusion of both MoS2 and MoO3 in opposite directions in the
newly formed MoO2 crystal structure could take place, with estimated diffusion coefficients of
MoS2 in MoO2 and MoO3 in MoO2 at 923 K of 1.08 × 10−6 and 7.78 × 10−6cm2 s−1, and at 973 K
of 10−5 and 1.13 × 10−5 cm2 s−1, respectively.

RÉSUMÉ
On a étudié la cinétique et le mécanisme de réaction à l’état solide entre MoS2 et MoO3 pour former
le MoO2 sous une atmosphère d’azote entre 723 et 973 K à l’aide d’échantillons bruts mélangés, de
boulettes comprimées mélangées et de boulettes pures de MoS2 et de MoO3 avec une face en
contact.
Les résultats montrent que pour les échantillons bruts, la réaction atteint une conversion
maximale de 67.3% à 923 K en 75 min, alors que pour les échantillons comprimés, la conversion
dans des conditions similaires atteignait 96.1% en 75 min, ce qui reflète l’effet des conditions
physiques des deux genres d’expériences sur la cinétique de réaction. Les valeurs d’énergie
d’activation calculées pour les deux conditions expérimentales sont cohérentes, avec une valeur
moyenne de –44.2 ± 1.9 kJ, qui se situe dans la gamme des réactions à l’état solide, contrôlées
par diffusion.
Pour les échantillons avec une face en contact, au-dessus de 923 K, les résultats semblent
indiquer que la diffusion moléculaire à l’état solide du MoS2 et du MoO3, dans des directions
opposées dans la structure cristalline de MoO2 nouvellement formée, pourrait se produire, avec
des coefficients de diffusion estimés du MoS2 dans le MoO2 et du MoO3 dans le MoO2 à 923 K
de 1.08 × 10−6 et de 7.78 × 10−6 cm2/sec, et à 973 K de 10−5 et 1.13 × 10−5 cm2/sec, respectivement.

1. Molybdenum sulphides and oxides

but they are highly unstable and decompose to MoS2
Four molybdenum sulphides are known: Mo3S4, Mo2S3, and oxygen.
MoS2 and MoS3. Mo3S4 sulphide is formed from aqueous Several molybdenum oxides with oxidation states
solutions and decomposes above about 120°C to MoO3- between 2 and 6 have been identified, most of them
·nH2O and sulphur. The trisulphide MoS3 generally con- non-stoichiometric, with only two (dioxide MoO2 and
tains an excess of sulphur as MoS3+x, in which x = 0–0.7. trioxide MoO3) being stoichiometric, stable compounds.
When heated in an inert atmosphere between 527 and Several others such as Mo5O12, Mo3O8, Mo2O5, Mo4O11
573 K it decomposes to MoS2 and sulphur. Molybdenite and Mo9O26 have been found in small amounts in mul-
(MoS2) decomposes to Mo2S3 and gaseous sulphur tiple-hearth roasters and appear to be solid solutions of
under neutral atmosphere above 1673 K. Two molyb- MoO2 and MoO3 in different proportions. Another
denum oxysulphides are known: MoO2S and MoOS2, oxide is the so-called ‘molybdenum blue,’ which is an

CONTACT I. Wilkomirsky [email protected]

© 2019 Canadian Institute of Mining, Metallurgy and Petroleum
2 I. WILKOMIRSKY AND E. SÁEZ

amorphous, water soluble compound apparently formed

by several oxides.
Figure 1 shows the Kellogg’s Mo–S–O stability phases
diagram at 883 K, which is the average roasting tempera-
ture used in industry. Under industrial roasting con-
ditions, the trioxide MoO3 is the only stable compound.
Commercially, molybdenite is the only important sul-
phide, and is produced from molybdenite ores as a by-
product of the copper industry. Molybdenite concen-
trates, with over 45% Mo as MoS2, are oxidised (roasted)
in air at 873–893 K to molybdenum trioxide in multiple-
hearth furnaces. The main oxidation reactions can be
written as follows: Figure 2. Typical concentration profiles of MoS2, MoO2 and
MoO3 in a multiple-hearth molybdenite concentrate roaster [7].
MoS2(s) + 3.5O2(g) = MoO3(s) + 2SO2(g) (1)

MoS2(s) + 3O2(g) = MoO2(s) + 2SO2(g) (2) MoO2 has more molybdenum per unit mass
(74.99 wt-%) than MoO3 (66.65 wt-%); therefore, it is
2MoO2(s) + O2(g) = 2MoO3(s) (3) more convenient as a steel addition or for producing fer-
romolybdenum alloys or molybdenum metal or salts.
Another important reaction that occurs during roast- Although the overall oxidation kinetics of MoS2 to
ing is the solid state reaction between molybdenite and MoO3 have been studied by Ammann et al. [1], Wilko-
the trioxide: mirsky et al. [2], Marin et al. [3], Utigard [4] and
Wang et al. [10], the kinetics and mechanisms of
MoS2(s) + 6MoO3(s) = 7MoO2(s) + 2SO2(g) (4)
MoO2 formation by reaction (4) are not well understood.
This reaction, together with reaction (2), appears to The formation of molybdenum dioxide by the reaction
play a significant role in industrial operations, since between MoS2 and MoO3 was first identified and studied
during roasting the amount of MoO2 formed can by Zelikman et al. [5], who described the basic kinetics of
account for up to 80% of the total mass in the roaster. formation from bulk samples of MoS2 and MoO3, but
In Figure 2 a typical concentration profile of MoS2, did not report an activation energy value. The presence
MoO2 and MoO3 in an industrial roasting furnace is of MoO2 was later identified in a continuous pilot roaster
shown, where the significant amount of MoO2 formed by Coudurier et al. [6] and its occurrence in an industrial
in the middle hearths can be observed. operation was confirmed by Huggins et al. [7], who
reported up to 85 wt-% MoO2 in the middle-lower
hearth of a roaster.
Saez [8] studied this reaction and the mechanisms
involved at laboratory scale, in apparently the most com-
prehensive study carried out to date. Whang et al. [9]
also recently studied this solid state reaction, although
no kinetic data was reported. They found that complete
conversion of stoichiometric blends of MoS2 and MoO3
to MoO2 can be obtained at 973 K.
Lessard et al. [11] proposed producing MoO2 by reac-
tion of MoS2 with MoO3, and further oxidation of some
of the MoO2 to MoO3 to be recirculated to the MoO2
production reaction. Those authors analysed thermody-
namically the reactions involved and ran several tests,
obtaining MoO2 with 0.02–0.05 wt-%S. Further pilot
tests were proposed to scale up the concept to industrial
scale.
Thermodynamically, the oxidation of MoS2 to
Figure 1. Kellogg’s stability phases diagram of the Mo–S–O sys- MoO2 or MoO3 as competing reactions per mole of
tem at 883 K. oxygen according to reactions (1) and (2) indicate
 CANADIAN METALLURGICAL QUARTERLY 3

(1) Kinetic studies with bulk, mixed, powdered samples

of pure MoS2 and pure MoO3.
(2) Kinetic studies with compressed pellets made of
mixed, pure MoS2 and pure MoO3.
(3) Kinetic studies with individual compressed pellets of
pure MoS2 and pellets of pure MoO3 with one face in
contact.

Experimental conditions for all three types of exper-

iments are given in Table 1.
In all three experiment types, the atmosphere used
was 1.5 L min−1 of nitrogen with less than 0.001% oxy-
gen, with a total pressure of one atmosphere. The maxi-
Figure 3. Standard free energy of reactions that take place mum content of SO2 in the off gases was about 2.6 vol.-
during roasting of molybdenite concentrates. %. The equipment used was a 5-cm diameter SS 316
tube, a horizontal tubular electric furnace and 10-
cu.cm rectangular alumina crucibles. The temperature
that the oxidation to MoO2 has a lowest negative was controlled between ±4°C by a type K thermocouple
standard free energy of reaction, as seen in Figure coupled to an automatic temperature controller.
3. At 883 K the formation of MoO2 by reaction (2) The initial molybdenite concentrate has the compo-
has a value of ΔG° = −261.1 KJ per mole of oxygen, sition given in Table 2. Prior to the study, the kinetics
while for the same conditions formation of MoO3 by concentrate was purified by sulphation with pure sul-
reaction (1) has a value of ΔG° = −190.8 KJ per mole phuric acid (96%) at 160°C for 6 h. with a concentrate/
of oxygen. acid mass ratio = 1/1 in an agitated glass reactor. The
The solid state reaction (4) between MoS2 and MoO3 pulp was then leached with water at 10% solid at 50°C
at 883 K has a value of ΔG° = −210.9 KJ per mole of for 2 h, filtered and washed thoroughly with hot water
MoS2. Under industrial roasting conditions, this reaction to remove the soluble metals. Removal of copper was
is virtually independent of the gaseous phase compo- more than 92%, with molybdenite dissolution of less
sition, since the equilibrium partial pressure of SO2 is than 1%. The purified concentrate has the chemical com-
0.33 atm, far from the gaseous phase composition in position also given in Table 2.
the roasters of 0.015–0.020 atm of SO2. These conditions The particle size of the purified concentrate is shown
indicate that only the MoO3 oxide is the stable phase in in Table 3.
the industrial roaster, as indicated by the Kellogg’s dia-
gram in Figure 1; therefore, reaction (4) should take
Table 1. Experimental conditions used in the three experiment
place in parallel with reaction (2) to form MoO2.
types.
Although the stable oxide under roasting conditions is 1. Bulk, blended MoS2 + MoO3 powders.
the trioxide, it cannot coexist with MoS2. This combined Mixing time: 2 h in a blender at 30 RPM.
mechanism of formation of MoO2 through reactions (2) MoS2/MoO3 ratio: 1/6 (stoichiometric)
Particle size (both MoO3 and MoS2): −270 mesh ASTM
and (4) could explain the very large fraction of this oxide Weight of each mixed sample: 10–12 g
in the middle hearths of the roaster. Reaction time: 0–75 min
Temperature range: 723–923 K
Oxidation of MoO2 to MoO3 has the lowest stan- 2. Compressed pellet samples of blended MoS2+MoO3 powders
dard free energy of reaction per mole of oxygen Mixing time: 2 h in a blender at 30 rev min−1
MoS2/MoO3 ratio: 1/6 (stoichiometric)
throughout the roasting temperature range; therefore, Particle size (both MoS2 and MoO3) = −270 mesh ASTM
it should proceed only when the concentration of Compacting pressure: 4000 lb/sq.in
MoS2 is very low, as also indicated by the curves of Weight of each pellet: 10–13 g
Reaction time: 0–135 min
Figure 2. Temperature range: 823–923 K.
3. Compressed individual pellets of pure MoS2 and pure MoO3
MoS2/MoO3 weight ratio of pellets: 1/6 (stoichiometric)
Particle size (both MoS2 and MoO3) = −270 mesh ASTM
2. Experiments Compacting pressure: 4000 lb/sq.in
Compacting pressure of both pellets (in contact): 4000 lb/sq.in
In order to study the kinetics and mechanism of the solid Weight of each individual pellet: 5–6 g
state formation of MoO2 from MoS2 and MoO3, three Reaction time: 120 min
Temperature range: 823–973 K
different kinds of experiments were performed:
4 I. WILKOMIRSKY AND E. SÁEZ

Table 2. Chemical composition of molybdenite concentrate used (wt-%)

Element Mo S Fe Cu K Na SiO2 MoS2
Initial concentrate 55.98 37.28 0.62 0.12 – – 6.05 93.24
Purified concentrate 56.83 37.86 0.14 <0.01 <0.01 <0.01 5.10 94.71

Table 3. Particle size analysis of purified molybdenite 3. Results and discussion

concentrate.
Mesh ASTM Wt-% retained % accumulated
3.1 Kinetics tests with bulk samples
−100 0.0 0.0 Twenty-five tests at 723, 773, 823, 873 and 923 K with
100/150 3.1 3.1
150/200 7.0 10.1 mixed, bulk samples of MoS2 and MoO3 were performed
200/270 16.3 26.4 under the conditions given in Table 1. The results
270/400 66.2 92.6
+400 7.4 100.0 obtained are shown in Table 5 and Figure 4.
In Figure 4 the strong influence of temperature on the
extent of reaction (4) is shown. It can be observed that
below 873 K the reaction is slow, while at 923 it becomes
The MoO3 used was prepared by roasting the purified fast up to nearly 35% conversion to MoO2. Above this
molybdenite concentrate in air at 620°C for 6 h in an value, a much slower increase in conversion to MoO2
electric muffle. The calcine was disaggregated and can be observed, possibly due to the progressively thicker
screened to 100% −270 mesh ASTM. The composition layer of MoO2 formed between the remaining particles of
of the roasted product is shown in Table 4. reactants, increasing the diffusion resistance of both
The only significant impurity in both the molyb- MoS2 and MoO3 through the newly formed MoO2.
denum concentrate and the trioxide was silica, with The maximum conversion to MoO2 at 923 K of 68%
5.10 and 6.1 wt-%, respectively. can be compared with the maximum conversion to
The determination of the three phases present (MoS2, MoO2 obtained in a multiple-hearth industrial furnace
MoO2 and MoO3) was based on the fact that MoO3 is of nearly 80% of MoO2 (Figure 2), where bulk powdery
highly soluble in ammonium hydroxide solutions, conditions also prevail. The higher conversion obtained
while MoO2 and MoS2 are insoluble; therefore, reacted in industrial operations compared with the present
samples were first leached at 20°C with 0.5 M NH4OH results could be due to the continuous blending effect
solutions for 30 min. The solid residue was then leached produced by the rotating arms along the furnace, while
with 0.5 M H2SO4 solutions at 50°C for 30 min to dis- the tests done in this study used a static bed.
solve the MoO2, since MoS2 is insoluble in acid under
these conditions. The samples were also analysed by 3.2 Kinetics tests with compressed pellets
DRX.
Twenty-four individual tests were carried out with com-
pressed pellets of blended MoS2 and MoO3 at 823, 873
and 923 K under the conditions given in Table 1. The
Table 4. Chemical composition of the molybdenite trioxide used results obtained are given in Table 6.
(wt-%).
Conversion to MoO2 as a function of time is also
Element Mo S Fe Cu SiO2 MoO3
shown in Figure 5, where the higher conversion to
62.50 0.012 0.16 <0.01 6.10 93.77
MoO2 achieved in these tests compared with the bulk

Table 5. MoO2 formation from bulk, mixed samples of MoS2 + MoO3 as a function of time and temperature (wt-% of MoO2 formed).
Time (min) 5 10 15 20 25 30 35 40 45 55 60 70 75
723 K
2.6 − 3.1 − − 4.6 − 5.2 − − 4.5 − −
773 K
3.8 – 4.6 − − 5.3 − 6.0 − − 6.8 − −
823 K
− 6.2 − 8.1 − − 11.8 − 13.0 − 12.6 − −
873 K
− 11.3 − − 23.9 − − 31.2 − 34.8 − 36.1 −
923 K
− 38.5 − − 52.2 − − − 63.2 − 65.5 − 67.3
 CANADIAN METALLURGICAL QUARTERLY 5

Then,
ln (kr /ko ) = ln kr – ln ko = –E/RT (9)
By taking the derivate of both sides with respect to (1/T )
it can be written then:
d ln rMoO2
= −E/RT (10)
dt
It is assumed that the extent of the initial contact
between MoS2 and MoO3 is constant for all specimens
in the separate series of reactions. Then, a plot of
ln rMoO2 versus 1/T is expected to yield a straight line
from the slope of which the activation energy E can be
determined.
From Figures 4 and 5 the specific rate constants of
reaction (4) were calculated by drawing the tangents to
the kinetic curves from time zero, values which were
Figure 4. Conversion of MoS2 + MoO3 to MoO2 as a function of
used to calculate the rate of formation of MoO2 and
time and temperature for blended bulk samples.
therefore kr, which was used to draw the Arrhenius
plot for both bulk and compressed samples. The results
samples conversion for the same temperature and reac- are shown in Figure 6.
tion time is evident. For example, at 923 K for the com- The slopes of both data are in good agreement, with a
pressed samples conversion reaches over 95% in about calculated average activation energy of −44.2 ± 1.9 kJ
60 min, while for the bulk samples conversion under (−10.6 ± 0.5 kcal). This value is in the range of diffu-
the same conditions reaches only 67%. sion-controlled solid-state reactions and has not been
From reaction (4), it can be written: previously determined.
rMoO3 rMoO2 rSO2
rMoS2 = − =− = (5)
6 7 2
or 3.3 Kinetics test with compressed pure pellets with
7 7 one face in contact
rMoS2 = − TMoO3 = −7rMoS2 = rSO2 (6)
6 2 For the compressed pellets of pure MoS2 and pure
Then, the kinetic expression for the formation of MoO3, four tests were performed at 823, 873, 923 and
MoO2 would be: 973 K for 120 min under the conditions given in Table
1. The reacted samples were cooled rapidly under nitro-
dMoO2 7 dMoO3 dMoS2 gen, cut into thin slices of ±0.5–0.7 mm and ground in a
rMoS2 = − =− = −7
dt 6 dt dt hand mortar for chemical and DRX analysis. The chemi-
7 dSO2 cal analysis has an estimated error of ±10% due to the
= = kr CMoS
n
Cm
2 MoO3
(7)
2 dt small samples obtained and the difficulty of cutting
Where for a diffusion-controlled reaction n and m are thin sample slices from the reacted pellets.
zero. The resulting equation can be expressed by the The results obtained are shown in Figures 8–11 and
Arrhenius law: Table 7 and indicate that above 873 K, molecular diffu-
sion of MoO3 and MoS2 into the crystal structure of
rMoO2 = kr = ko exp −(E/RT) (8) the newly formed MoO2 appears to become significant.

Table 6. MoO2 formation from compressed samples of MoS2 + MoO3 as a function of time and temperature (wt-% of MoO2 formed).
Time (min) 5 15 20 25 30 35 40 45 50 55 60 65 75 95 100 105 125 130 135
823 K
− 32.1 38.1 − − 52.2 − − 59.2 − − 65.0 − 74.3 − − 75.6 − −
873 K
− 34.2 42.8 48.1 − − 53.2 − − 60.6 − 68.3 − − 80.2 − − 83.8 −
923 K
21.6 − 54.7 74.6 79.9 − − 91.6 − − 95.6 − 96.1 − − 96.2 − − 96.0
6 I. WILKOMIRSKY AND E. SÁEZ

Figure 5. Conversion of MoS2 + MoO3 to MoO2 as a function of

time and temperature for compressed pellets.

The reaction between MoS2 and MoO3 could start at Figure 7. SEM of the MoS2–MoO2–MoO3 reaction interface at
923 K showing the large crystals of MoO2 formed between
the pellet interface, followed by the diffusion of either MoS2 (left) and MoO3 (right).
MoS2 and/or MoO3 through the newly formed MoO2
layer. Figure 7 shows a SEM of the reacted interface,
where crystals of MoO2, MoS2 and MoO3 can be seen. 10), an effect that is more pronounced at 973 K, (Figure
These phases were also identified by DRX. 11) a condition under which nearly 20% of MoS2 has
In the 823–873°K temperature range, MoO2 for- diffused into the total mass of MoO3 + MoO2 + MoS2
mation is restricted mainly to the MoS2–MoO3 interface, at 2-mm depth. Since no MoO3 can coexist with MoS2
as seen in Figures 8 and 9. Since the volumetric molar beyond the initial reaction interface, the concentration
ratio between MoS2 and MoO3 is 33.34/30.68 and the profiles indicate that MoS2 and MoO3 could have
molar ratio for reaction (4) is 1/6, most of the mass diffused separately and unidirectionally in opposite
reduction due to the chemical reaction is concentrated directions into the MoO2 crystalline structure.
in the MoO3 pellet. The molecular diffusion coefficient could be estimated
At 923 K the concentration profile shows a small by assuming that for transient unidirectional diffusion of
diffusion of MoS2 into the newly formed MoO2 (Figure MoS2 in MoO2 and MoO3 in MoO2, Fick’s second law
represents the phenomena.
A different diffusion mechanism could involve the
slow diffusion of the large S−4 ions and the faster diffu-
sion of the smaller Mo+6 cations in the MoO2 crystals,
while the MoO3 molecules should remain essentially
stationary, maintaining their electroneutrality (one
mole of MoS2 reacts with 6 moles of MoO3). In this
case, the diffusion of the S−4 ions could control the over-
all reaction. The formation and evolution of the gaseous
SO2 should be very rapid and not participate in the over-
all control of the process.
By assuming molecular diffusion, the concentration of
MoS2 in MoO2 and MoO3 in MoO2 as a function of time
can therefore be expressed as:


∂CMoS2 ∂ ∂CMoS2
= DMoS2 −MoO2 (11)
∂t ∂x ∂x


∂CMoO3 ∂ ∂CMoO3
= DMoO3 −MoO2 (12)
∂t ∂x ∂x

Figure 6. Arrhenius plot for the solid state reaction between The molecular diffusion coefficients of both MoS2 and
MoS2 and MoO3 for bulk samples and compressed pellets. MoO3 in MoO2 can then be estimated by applying the
 CANADIAN METALLURGICAL QUARTERLY 7

Figure 8. Concentration profiles of MoO2, MoS2 and MoO3 at 823 K (compressed pellets with one face in contact).

Matano-Boltzmann expression: By applying Equations (13) and (14) for an arbitrary

 MoS2 distance of 2 mm from the Matano interface and the cor-
1 ∂x responding concentrations of MoS2 and MoO3, as well as
DMoS2 −MoO2 = − xdCMoS2 (13)
2t ∂CMoS2 CMoS◦
graphic integration of Figures 10 and 11, the molecular
2

 CMoO diffusion coefficients, which are given in Table 8 and

1 ∂x 3
Figure 12, were estimated. These values are in the
DMoO3 −MoO2 = − xdCMoO3 (14)
2t ∂CMoO3 CMoO
o range of solid state diffusion and could represent the
3

Figure 9. Concentration profiles of MoO2, MoS2 and MoO3 at 873 K (compressed pellets with one face in contact).
8 I. WILKOMIRSKY AND E. SÁEZ

Figure 10. Concentration profiles of MoO2, MoS2 and MoO3 at 923 (compressed pellets with one face in contact).

solid state molecular diffusion of MoS2 and MoO3 in Conclusions

opposite directions in the crystal structure of the newly
The kinetics and mechanism of the solid state reaction
formed MoO2.
between MoS2 and MoO3 to form MoO2 under nitro-
From Figures 9–11, MoO2 formation by solid state
gen atmosphere between 723and 973 K were studied
diffusion at 823, 873, 823 and 973 K for a 120-min reac-
using bulk mixed samples, mixed compressed pellets
tion time was also calculated. The results are shown in
and pure MoS2 and MoO3 pellets with one face in
Figure 13, where the exponential form of MoO2 for-
contact.
mation with temperature can be observed.

Figure 11. Concentration profiles of MoO2, MoS2 and MoO3 at 973 (compressed pellets with one face in contact).
 CANADIAN METALLURGICAL QUARTERLY 9

Table 7. Chemical composition of compressed pellets with one face in contact.

Compound Distance from reacting interface (mm) (closest distance)
(wt-%) 3 2 1 0 −1 −2 −3 −4 −5 −6 −7 −8
823 K
MoS2 98.1 96.0 46.2 – 0.3 0 0 0 0 0 0 0
MoO3 0 0.6 4.92 – 98.0 >99 >99 >99 >99 >99 >99 >99
MoO2 0 0.8 7.3 – 0.9 <0.1 0 0 0 0 0 0
873 K
MoS2 – 98.0 55.1 1.8 – – 0.1 – – 0
MoO3 – 0.8 32.3 97.3 – – >99 – – >99
MoO2 0.2 12.2 1.9 – – 0 – – 0
923 K
MoS2 >99 – 25.6 4.8 – – 0.2 – – – 0
MoO3 2.8 – 57.6 78.0 – – 93.1 – – – >99
MoO2 0 – 15.2 22.3 – – 16.7 – – – 0
973 K
MoS2 – 81.3 – – – 16.1 – – – 4.8 – 0
MoO3 – 20.0 – – – 49.9 – – – 82.2 – 94.3
MoO2 – 0 – – – 38.1 – – – 17.9 – 6.8

Table 8. Estimated values of the molecular solid diffusion

coefficients of MoS2 in MoO2 and MoO2 in MoO3 (±10%).
Temperature (K) 923 973
DMoS2–MoO2 (cm2 s−1) 1.08 × 10−6 1.00 × 10−5
DMoS2–MoO2 (cm2 s−1) 7.78 × 10−6 1.13 × 10−5

The results show that for the bulk samples, the reac-
tion reaches a maximum conversion of 67.3% at 923 K
in 75 min, while for the compressed samples conversion
under similar conditions reaches 96.1%, which indicates
the influence of the physical characteristics of both types
of experiments on the diffusion coefficient of MoS2 and/
or MoO3 through the newly formed MoO2 crystal layer.
The calculated activation energy values for both exper-
imental conditions are consistent, with an average Figure 13. Formation of MoO2 from MoS2 and MoO3 pellets as a
value of −44.2 ± 1.9 kJ, which is in the range of diffu- function of temperature for a 2-h reaction time.
sion-controlled reactions. No other value has been
reported in the literature for this reaction.
For the samples with one face in contact, above 923 K
molecular solid diffusion of both MoS2 and MoO3 in
opposite directions in the newly formed MoO2 crystal
structure appears to take place, with estimated molecular
diffusion coefficients of MoS2 in MoO2 and MoO3 in
MoO2 at 973 K of 10−5 and 1.13 × 10−5 cm2 s−1, and at
923 K of 1.08 × 10−6 and 7.78 × 10−6 cm2 s−1,
respectively.

Disclosure statement
No potential conflict of interest was reported by the authors.

Notes on contributors
I. Wilkomirsky is Professor of Extractive Metallurgy at the
University of Concepcion, Chile. He holds a B.in Chemical
Figure 12. Estimated coefficients of MoS2 in MoO2 and MoO3 in Engr. from this University, a M.Sc.in Metallurgy from Color-
MoO2 at 873 and 923 K. ado School of Mines and Ph.D. from UBC also in Metallurgy.
10 I. WILKOMIRSKY AND E. SÁEZ

He authored and co-authored over one hundred technical and [6] Coudurier L, Wilkomirsky I, Morizot G. Molybdenite
scientific papers and three books on the subject. roasting and rehenium volatilization in a multiple-
E. Sáez graduate as Metallurgical Engineer from the University hearth furnace. Trans Inst Min Met. 1970;79(Sec):
of Concepcion in 1989 and works in El Teniente Division of 34–40.
Codelco, Chile. [7] Huggins DK, Bryan FA, McHugh LF, et al. Fundamental
investigations on molybdenite hearth roasting. Paper
presented at XVI CIM Annual Meeting, Vancouver;
References Aug 1977.
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