Thermodynamic and Kinetic Considerations in the Reduction of

Celestite (SrSO4) and Strontium Oxide (SrO)

Angelica B. Alvizo
College of Engineering, MSU-Iligan Institute of Technology, Tibanga, Iligan City, 9200

The thermodynamic and kinetic feasibility of reducing celestite and strontium oxide to produce
strontium sulfide and strontium metal respectively has been studied. Different reductants such as
hydrogen gas, methane gas, and carbon monoxide are considered and compared to an existing
carbothermal reduction of celestite reduction given the reactions 1, 2, 3, and 4.
SrSO4 + 2C SrS + 2CO2 [1]
SrSO4 + 4H2 SrS + 4H2 O [2]
SrSO4 + 2CH4 SrS + 2CO2 + 4H2 [3]
SrSO4 + 4CO SrS + 4CO2 [4]
For strontium oxide, the same reductants are considered and compared to an existing aluminothermic
reduction shown in reactions below.
3SrO + 2Al + BaO = 3Sr + BaO Al2 O3 [5]
2SrO + C = 2Sr + CO2 [6]
SrO + H2 = Sr + H2 O [7]
2SrO + CH4 = 2Sr + CO2 + H2 [8]
SrO + CO = Sr + CO2 [9]
At standard states, different temperatures at which the reactions proceed spontaneously are
calculated. Carbothermal reduction of celestite showed the most negative values of Gibbs energies at
temperatures greater than 286.28OC however reduction by methane gas also showed a promising
capability, reducing celestite at temperatures greater than 387.75OC. Moreover, reduction by
methane-containing gas to produce Sr metal resulted to more negative values of Gibbs energies lower
than the existing aluminothermic reduction and other reductants used. Further comparisons are made
using kinetics and enthalpy data to determine the most efficient reductant.

1. INTRODUCTION
Strontium commonly occurs in
nature, being the 15th most abundant
element on Earth, estimated to average
approximately 360 parts per million in
the Earth's crust and is found chiefly as
the sulfate mineral celestite (SrSO4) and
the carbonate strontianite (SrCO3). Of the
two, celestite occurs much more frequently
in deposits of sufficient size for mining.
However, strontium is used most often in the
carbonate form that is widely used in sugar
industry, ceramics, and electronic
applications cathode-ray tubes). It is
generally preferred due to its low cost.
Hence, having SrCO3 as the more
useful of the two common mineral, there is a
need for celestite conversion into carbonate
form. A large proportion of mined celestite
(SrSO4) is converted to the carbonate by two
processes. Either the celestite is directly
leached with sodium carbonate solution or
the celestite is roasted with coal to form the
sulfide. The latter is called the black ash
method with the reaction:
SrSO4 + 2C SrS + 2CO2
Strontium sulfide (SrS) then
undergoes water leaching using carbon
dioxide as precipitating agent to precipitate
strontium carbonate.

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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 Strontium is never found free in In air at atmospheric pressure, the
nature, it is highly reactive in air and decomposition temperature for SrSO4 is
decomposes in water to form strontium above 2,500oC as shown in Figure 1. This
hydroxide (Sr(OH)2). Its metal can be indicates that a reducing agent is necessary
obtained by electrolysis passing of electric in order to produce strontium sulfide at a
current through molten strontium chloride. lower temperature.
Nowadays, strontium is used in many Temperature, K
advanced technology applications and is 0 1000 2000 3000 4000 5000
commercially produced by reducing 10
strontium oxide with aluminum. 0.21 atm
0.01
Strontium bismuth tantalat thin films 0.00001

pO2, atm
are promising materials in ferroelectric and 1E-08
Schottky-based microelectronics 1E-11
technologies, especially for memory 1E-14
applications. Physical vapor deposition 1E-17
(PVD) techniques as magnetron sputtering, 1E-20
thermal evaporation and molecular beam Figure 1. Calculated decomposition temperatures of
epitaxy (MBE) are the most widely used SrSO4 at different oxygen partial pressures
methods for growth of these thin films. In
these techniques high purity of Sr metal is 2.2 Strontium Oxide Decomposition
used as evaporation sources and sputtering 1
SrO = Sr + 2 O2 [2.3]
targets. Furthermore, metallic strontium is
used as a "getter" in electron tubes, and as an = 142 700 24.47 () [2.4]
alloying element in aluminum alloys.
Decomposition temperature of SrO to
Sr at different partial pressures is presented
2. THERMODYNAMICS OF SrSO4 AND
in Figure 2. At atmospheric pressure, the
SrO REDUCTION
decomposition temperature of SrO is around
Calculating thermodynamic values
5,500OC which is very high. Thus reducing
before undergoing actual processes are a
agent is necessary to produce Sr metal at
convenient way of modeling reduction in
lower temperatures.
order to predict the effect and outcome of
Temperature, K
varying parameters. 0 5000 10000
100
2.1. Strontium Sulfate Decomposition 1
The decomposition of SrSO4 to SrS 0.01
0.21 atm
PO2, atm

occurs at elevated temperatures depending 0.0001

on the oxygen partial pressure in the gas 0.000001
1E-08
phase. A plot on the calculated 1E-10
decomposition temperature of SrSO4 at 1E-12
different oxygen partial pressures is 1E-14
presented in Figure 1. 1E-16
1E-18
1E-20
SrSO4 SrS + 2O2 [2.1]
Figure 2. Calculated decomposition temperatures of
= 236 140 84.04 () [2.2]
SrO at different oxygen partial pressures

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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2.3. Reduction of Strontium Sulfate
The reduction of strontium sulfate
with carbon, hydrogen gas, methane gas, and
carbon monoxide produces strontium sulfide
which can be then be easily converted
strontium sulfate have high extent at
temperatures 300OC-400 OC. For methane
reduction, same temperature range applies
using appropriate gas composition.
80000
60000

Std. Gibbs Energy, cal/mol

hydrometallurgically to the carbonate form
40000
are shown in the reactions.
20000

+ + [1] 0

= 47 160 84.3 () [2.5] -20000

-40000
+ + [2]
-60000
= 460 30.64 () [2.6] 0 200 400 600 800 1000 1200
Temperature, K
+ + + [3]
C H2 CH4 CO
= 90 680 137.2 () [2.7]
Figure 3. Gibbs Free Energies for SrSO4 Reduction
+ + [4] with C, H2, CH4, and CO at different temperatures

= 32 460 2.56 ( ) [2.8]

For equilibrium conditions, the
At standard conditions, the values of the partial pressure of oxygen and
carbothermic reduction [1] proceeds sulfur define the condensed phases that are
spontaneously at temperatures above stable during the reduction process. Phase
286.28OC which showed more negative stability fields for Sr-S-O system can be
values of Gibbs energies at higher constructed in the PO2-PS2 diagram presented
temperatures compared to other reductants. in Figure 4 and 5. The phase stability
It is then followed by methane-gas reduction diagram was constructed using reaction 2.1,
[3] proceeding spontaneously at equation 2.2 and the following reactions:
O
temperatures above 387.75 C. Reduction by
+ = + [2.9]
hydrogen gas and carbon monoxide showed
cal
exothermic systems having negative values G = 18 700 + 1.47T (mol) [3.0]
of Gibbs energies at very low temperature.
Shown in Figure 3, reduction of strontium
= + + [3.1]
sulfate using C, H2, CH4, and CO reductants cal
are compared at temperatures below melting G = 217 440 82.5T (mol) [3.2]
point of SrSO4 (1606OC) and SrS (2002OC).
The equilibrium constant for the At 1000OC, Figure 4 shows that for
carbothermic reduction [1] at temperature SrS to form from SrSO4, PO2 should be less
300OC is 2.731, 400 OC is 1286, and at 500 than 8.25 1012 . At a higher temperature
O in Figure 5, SrS is more stable and likely to
C is 123 212 1567 which indicates that the
reduction of SrSO4 by solid carbon into form from SrSO4 with PO2 < 4.68 109 .

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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 + = + [7]
10 cal
G = 83 550 11.12T (mol) [3.5]
5

0 + = + + [8]
cal
log(PS2)

G = 69 970 51.05T (mol) [3.6]

-5 SrSO (s)
4

SrS (s)
-10 + = + [9]
cal
-15 G = 75 550 4.1T (mol) [3.7]
SrO (s)
-20
-30 -25 -20 -15 -10 -5
Methane reduction [8] proceeds
0
log(PO2)
spontaneously at temperatures above
1097.45OC at standards conditions which
Figure 4. Thermodynamic Stability Diagram of
is lower compared to the existing
Sr-S-O system at 1000OC
technology of producing strontium by
aluminothermic reduction at temperatures
10 below 1294.55 OC, an exothermic reaction.
5 Only reductants methane and aluminum
are efficient enough to reduce SrO to
0
strontium metal at temperatures below the
log(PS2)

-5
SrSO (s)
melting point of SrO (2531 OC). To
4

SrS (s) produce Sr using carbon, hydrogen, and

-10
carbon monoxide as reductants proceed at
-15 SrO (s) negative values of Gibbs energies only at
-20 very high temperatures which is
-30 -25 -20 -15 -10 -5 0 uneconomic and impractical.
log(PO2) 200000

Figure 5. Thermodynamic Stability Diagram of

Std. Gibbs Energy, cal/mol

150000
Sr-S-O system at 1200OC

2.4. Reduction of Strontium Oxide 100000

50000
The reduction of strontium oxide
with aluminum, carbon, hydrogen, methane,
0
and carbon monoxide produces strontium
metal given the reactions:
-50000
0 500 1000 1500 2000 2500
+ + = + [5] Temperature, K
cal
G = 4 860 + 3.1T (mol) [3.3] delta G (Al) delta G (C) delta G (H2)

delta G (CH4) delta G (CO)

+ = + [6]
cal Figure 6. Gibbs Free Energies for SrO Reduction
G = 190 910 49.07T (mol) [3.4] with Al, C, H2, CH4, and CO at different
temperatures

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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 2.5. Heat Requirement for SrSO4 and SrO 91000
Reduction 90000
89000
To further determine the energy

H, cal
88000
efficiency of each reductant, heat required to 87000
produce SrS and Sr is calculated over a 86000
range of temperature at constant pressure 85000
expressed by the formula 84000
0 500 1000 1500
H = CpT [3.8] T, K

where Cp is the heat capacity. Figure 8. Heat Requirement Calculations using

For strontium sulfate reduction,
Figures 7 and 8 shows the graphical
presentation of heat against different
temperatures for carbon and methane
reductants respectively. In carbothermic
reduction, the largest heat requirement has a
value of 48.7 kcal and decreases at higher
temperatures corresponding to a heat
capacity of -0.225 cal/K at 498K.
An increasing heat requirement can
be observed at Figure 8 to a maximum of
90.4 kcal for the reduction of SrSO4 at
1098K using methane gas with a heat
capacity of -1.744 cal/K. Hence a higher
energy requirement is needed when using
methane gas as reductant compared to
carbon, also known as the black ash method.
49000
48500
H, cal
Methane for SrSO4 Reduction at different
Temperatures
For the production of Sr metal from
SrO using aluminum and methane, heat
requirement graphical presentations are
shown in Figures 9 and 10. The
aluminothermic reduction of exothermic
system gives off heat at a maximum of 2.5
kcal at 1050 K. A fluctuating heat
requirement can be observed in Figure 10.
The largest heat required to produce Sr from
SrO using methane has a value of 212.1 kcal
at 1298 K corresponding to a heat capacity
of 0.00966 cal/K, which makes the reductant
uneconomical to use.
-1600
-1800
-2000

-2200
48000
47500 -2400
H, cal

47000 -2600
46500 -2800
46000 1000 1100 1200 1300 1400 1500
45500
T, K
45000
44500
0 500 1000 1500 Figure 9. Heat Requirement Calculations using
T, K Aluminum for SrO Reduction at different
Figure 7. Heat Requirement Calculations using
Temperatures
Carbon for SrSO4 Reduction at different
Temperatures

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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 212150 carbothermal reduction and 90.7 kcal/mol
212100
for methane gas reduction are estimated
under Ar atmosphere.
212050
H, cal

212000 60

211950 40
20
211900
0

211850
1000 1100 1200 1300 1400
T, K
Figure 10. Heat Requirement Calculations using
Methane for SrO Reduction at different
Temperatures
3. KINETICS OF SrSO4 AND SrO
REDUCTION
The kinetics of the reduction can be
expressed by the Arrhenius equation wherein
the relationship of concentration with
temperature can be determined. As the
concentration of the reactant during the
process remains constant, the apparent
reaction rate, k is dependent on temperature.
Ea
ln = lnA RT [3.8]
where: A = pre-exponential factor
Ea = activation energy
3.1. Kinetics of Strontium Sulfate
Thermodynamic considerations of
strontium sulfate reduction have shown two
efficient reductants wherein low
temperatures are required for the production
of strontium sulfide to proceed. In Figure 11,
the natural logarithm of rate of reaction is
graphically presented against the inverse of
temperature to obtain the Arrhenius equation
[3.8]. From this equation the apparent
activation energy values of 47.2 kcal/mol for
lnk, min-1
-20
1500
-40
-60
-80
-100
0 0.001 0.002 0.003 0.004
1/T, K-1
C CH4
Figure 11. Calculated Natural Logarithm of Rate
Constants for SrSO4 Reduction at different Inverse
Temperatures
3.2. Kinetics of Strontium Oxide
For strontium oxide, aluminothermic
and methane-gas reduction are the only
efficient reductants to produce strontium
metal at viable temperatures. The kinetics of
the two reactants are considered and
presented in Figure 12.
The exothermic system of
aluminothermic reduction produced a
negative value of activation energy having
an increasing slope. This implies that at
higher temperatures, the values of rate
constant are decreasing. However, the lower
activation energy value of -4.9 kcal/mol
hence small slope, suggests that rate constant
has a low dependence on temperature
change. A controlled temperature system
during the aluminothermic process should be
observed for the reduction to proceed.
The steep slope for the methane gas
reduction expresses a high activation energy
value of 70.0 kcal/mol. This suggests a
strong dependence of rate constant which
increases with an increasing temperature.

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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 20
Table 4.2. Tabular Data for Strontium Oxide
0 Reduction to Sr
Reductant Teq, Ea, t, H,
-20 O
C kcal/ min kcal
mol
ln k

-40 Al 1295 -4.7 0.76 -2.5

-60
C 3617 - - -
H2 7240 - - -
-80 CH4 1097 70.0 1.08 212.1
-100 CO 18153 - - -
0 0.001 0.002 0.003 0.004
1/T For the production of strontium
Al CH4 metal, aluminum and methane have the
Figure 12. Calculated Natural Logarithm of Rate lowest negative values of standard Gibbs
Constants for SrO Reduction at different Inverse free energies. Though CH4 has a lower
Temperatures equilibrium temperature for spontaneous
reaction, aluminothermic reduction has a
very low energy and heat requirement, hence
4. RESULTS AND DISCUSSION
it is more preferred over methane gas. It also
has higher reaction rates. Under 1 L/min of
Table 4.1. Tabular Data for Strontium
Ar system, the reaction will proceed at 0.76
Sulfate Reduction to SrS
Reductant Teq, Ea, t, H,
mins. Therefore, for the reduction of
O
C kcal/ min kcal strontium oxide to produce strontium metal,
mol aluminothermic reduction is the most
C 286.3 47.2 2.44 48.7 practical and more preferred. The reduction
H2 -288.2 - - - however should take place in a more
CH4 387.8 90.7 2.45 90.4 temperature controlled system for the
CO -12953 - - - exothermic reaction.

5. CONCLUSIONS
Shown in Table 4.1 are the data
gathered from the thermodynamic and
Production efficiency of metals is
kinetic calculations of SrSO4 reduction to
improved when reduction temperature is low
SrS using different reductants. Carbon and
for energy costs to be minimized. Most
methane gas are thermodynamically favored
compounds however decompose at high
achieving spontaneity of the process at low
temperature thus the need for reductants to
temperatures. For the heat requirement based
change equilibrium conditions.
on H, carbothermic process gives the lower
To commercially use strontium,
value of heat needed compared to methane.
celestite should be converted to strontianite
It also has lower energy requirement. Hence
and a way to do that is to reduce celestite
for SrSO4, carbothermic reduction also
into strontium sulfide which includes
known as the black ash method is the most
pyrometallurgical process. SrS can then be
economical and practical process.
hydrometallurgically converted to SrCO3.

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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 Carbothermic reduction resulted to
more negative values of Gibbs free energies
compared to methane, hydrogen gas, and
carbon monoxide. It has a close reaction rate
with methane gas reduction but lower energy
and heat requirement.
Nowadays, pure strontium metal is
extracted to produce strontium bismuth
tantalat thin films that are promising
materials in ferroelectric and
microelectronics technologies, especially for
memory applications. Strontium can be
reduced from strontium oxide. Calculations
showed that aluminothermic and methane
reduction are thermodynamically favored.
However, due to higher reaction rates and
lower heat and energy requirement,
aluminum is more preferred.
Further experimental studies should
be conducted in order to prove and
determine the reductants capacity to reduce
SrSO4 to SrS and SrO to Sr.

6. REFERENCES

Anacleto, N. Thermodynamic
Considerations in the Reduction of Nickel
Oxide by Methane Containing Gas. (n.d.)

AZoM, (2003). Strontium (Sr) Occurrence,

Extraction, Properties and Applications of
Strontium. Retrieved from
http://www.azom.com/article.aspx?ArticleID
=1835. Accessed 04-12-17.

Mehmet B., Ahmet T., Cucurachi Y.,

Onuralp Y., (2016). Strontium Production
from Strontium Oxide Using Vacuum
Aluminothermic Process. UCTEA Chamber
of Metallurgical and Materials Engineers.

Strontium Sulfate and Strontium Oxide Reduction | Submitted to Dr. Nathaniel M. Ancleto
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