HSC Chemistry® 5.

0 14 - 1

A. Roine June 28, 2002 02103-ORC-T

14. HSC EQUILIBRIUM MODULE SAMPLES
Contents of an Input File for GIBBS Program
§Copper Smelting at 1300 C ' Heading
1 ' 0 = results to screen, 1= results to file
6 4 0 3 3 2 1 ' Elements, phases, inv. phases, and
' ^ number of components / phase 1., etc.
'N2(g) ' 2.00 0.00 0.00 0.00 0.00 0.00 ' stoichiomet.
'O2(g) ' 0.00 2.00 0.00 0.00 0.00 0.00 ' matrix
'SO2(g) ' 0.00 2.00 1.00 0.00 0.00 0.00
'*2FeO*SiO2(l) ' 0.00 4.00 0.00 2.00 1.00 0.00
'SiO2(l) ' 0.00 2.00 0.00 0.00 1.00 0.00
'Cu2O(l) ' 0.00 1.00 0.00 0.00 0.00 2.00
'Cu2S ' 0.00 0.00 1.00 0.00 0.00 2.00
'FeS ' 0.00 0.00 1.00 1.00 0.00 0.00
'Cu ' 0.00 0.00 0.00 0.00 0.00 1.00
4
1573.150 ' Equilibrium temperature (K)
0.000000E+00 1.916105E+02 3 ' H, S, number of temperature intervals
2.919177E+01 -1.121312E-03 0.000000E+00 4.091976E-06 0.000000E+00 0.000000E+00
400.000 0.000000E+00 ' ^ A, B, C, D, E, F (J/(mol*K))
2.255176E+01 1.320889E-02 3.129632E+05 -3.389040E-06 0.000000E+00 0.000000E+00
1600.000 0.000000E+00 ' Temperature (K), H (J/mol)
3.684012E+01 2.594080E-04 -5.478948E+06 0.000000E+00 0.000000E+00 0.000000E+00
0.000000E+00 2.051470E+02 1 ' H (J/mol), S (J/(mol*K)), ()
3.132312E+01 3.893657E-03 -3.105337E+05 -3.349854E-07 0.000000E+00 0.000000E+00
-2.968130E+05 2.482210E+02 3
1.734500E+01 7.922700E-02 2.646000E+05 -4.563100E-05 0.000000E+00 0.000000E+00
700.000 0.000000E+00
5.164756E+01 6.297887E-03 -2.158751E+06 -1.367747E-06 0.000000E+00 0.000000E+00
2000.000 0.000000E+00
6.665800E+01 -4.478000E-03 -1.128930E+07 8.430000E-07 0.000000E+00 0.000000E+00
-1.458188E+06 9.729792E+01 1
2.405800E+02 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-9.275245E+05 9.310607E+00 1
8.577200E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-1.302203E+05 9.640145E+01 1
9.991399E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-8.117000E+04 1.161520E+02 4
4.793800E+01 9.717300E-02 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
376.000 3.619000E+03
1.184100E+02 -5.818200E-02 7.920001E+04 2.231700E-05 0.000000E+00 0.000000E+00
720.000 1.172000E+03
8.372372E+01 -1.253259E-03 2.450114E+05 -6.180060E-07 0.000000E+00 0.000000E+00
1400.000 1.284500E+04
8.966300E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-1.016710E+05 6.032100E+01 4
-2.732690E+02 7.791840E-01 8.124200E+06 0.000000E+00 0.000000E+00 0.000000E+00
411.000 1.665000E+03
7.235800E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
598.000 3.970000E+02
9.458400E+01 -8.366901E-02 1.411000E+05 4.794300E-05 0.000000E+00 0.000000E+00
1465.000 3.246400E+04
6.255100E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
0.000000E+00 3.316400E+01 2
4.057800E+01 -1.132500E-02 -3.284000E+05 9.800000E-06 0.000000E+00 0.000000E+00
1358.000 1.313800E+04
3.284400E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
5 1 2 5 7 8 ' Raw materials, and their serial numbers
298.150 298.150 298.150 298.150 298.150
2 ' ^ Temperatures of the raw materials (K)
13 ' Number of equilibria to be calculated
3 3 3 2 2 ' 2 = constant input amount, 3 = increases
1.0000000E-03 1.8850000E+00 ' Amount of raw material 1., step (mol)
1.0000000E-03 5.0000000E-01 ' Amount of raw material 2., step (mol)
1.0000000E-03 1.2500000E-01 ' Amount of raw material 5., step (mol)
1.0000000E+00 ' Amount of raw material 7. (mol)
2.0000000E+00 ' Amount of raw material 8. (mol)
10 ' Exit
' 9 = Activity Coefficients if values other than 1

Input File for SOLGASMIX Program (Amounts in moles)

 HSC Chemistry® 5.0 14 - 2

A. Roine June 28, 2002 02103-ORC-T

§Copper Smelting at 1300 C ' Heading
0 ' 0 = mole mode, 1= gram mode
6 4 1 3 3 2 ' Elements, phases, inv. phases, and
' ^ number of components / phase 1., etc.
'N2(g) ' 2.00 0.00 0.00 0.00 0.00 0.00 ' stoichiomet.
'O2(g) ' 0.00 2.00 0.00 0.00 0.00 0.00 ' matrix
'SO2(g) ' 0.00 2.00 1.00 0.00 0.00 0.00
'*2FeO*SiO2(l) ' 0.00 4.00 0.00 2.00 1.00 0.00
'SiO2(l) ' 0.00 2.00 0.00 0.00 1.00 0.00
'Cu2O(l) ' 0.00 1.00 0.00 0.00 0.00 2.00
'Cu2S ' 0.00 0.00 1.00 0.00 0.00 2.00
'FeS ' 0.00 0.00 1.00 1.00 0.00 0.00
'Cu ' 0.00 0.00 0.00 0.00 0.00 1.00
4
1573.150 ' Equilibrium temperature (K)
0.000000E+00 1.916105E+02 3 ' H, S, number of temperature intervals
2.919177E+01 -1.121312E-03 0.000000E+00 4.091976E-06 0.000000E+00 0.000000E+00
400.000 0.000000E+00 ' ^ A, B, C, D, E, F (J/(mol*K))
2.255176E+01 1.320889E-02 3.129632E+05 -3.389040E-06 0.000000E+00 0.000000E+00
1600.000 0.000000E+00 ' Temperature (K), H (J/mol)
3.684012E+01 2.594080E-04 -5.478948E+06 0.000000E+00 0.000000E+00 0.000000E+00
0.000000E+00 2.051470E+02 1 ' H (J/mol), S (J/(mol*K)), ()
3.132312E+01 3.893657E-03 -3.105337E+05 -3.349854E-07 0.000000E+00 0.000000E+00
-2.968130E+05 2.482210E+02 3
1.734500E+01 7.922700E-02 2.646000E+05 -4.563100E-05 0.000000E+00 0.000000E+00
700.000 0.000000E+00
5.164756E+01 6.297887E-03 -2.158751E+06 -1.367747E-06 0.000000E+00 0.000000E+00
2000.000 0.000000E+00
6.665800E+01 -4.478000E-03 -1.128930E+07 8.430000E-07 0.000000E+00 0.000000E+00
-1.458188E+06 9.729792E+01 1
2.405800E+02 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-9.275245E+05 9.310607E+00 1
8.577200E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-1.302203E+05 9.640145E+01 1
9.991399E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-8.117000E+04 1.161520E+02 4
4.793800E+01 9.717300E-02 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
376.000 3.619000E+03
1.184100E+02 -5.818200E-02 7.920001E+04 2.231700E-05 0.000000E+00 0.000000E+00
720.000 1.172000E+03
8.372372E+01 -1.253259E-03 2.450114E+05 -6.180060E-07 0.000000E+00 0.000000E+00
1400.000 1.284500E+04
8.966300E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-1.016710E+05 6.032100E+01 4
-2.732690E+02 7.791840E-01 8.124200E+06 0.000000E+00 0.000000E+00 0.000000E+00
411.000 1.665000E+03
7.235800E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
598.000 3.970000E+02
9.458400E+01 -8.366901E-02 1.411000E+05 4.794300E-05 0.000000E+00 0.000000E+00
1465.000 3.246400E+04
6.255100E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
0.000000E+00 3.316400E+01 2
4.057800E+01 -1.132500E-02 -3.284000E+05 9.800000E-06 0.000000E+00 0.000000E+00
1358.000 1.313800E+04
3.284400E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
5 1 2 5 7 8 ' Raw materials, and their row numbers in the stoichiometry matrix
298.150 298.150 298.150 298.150 298.150
2 ' ^ Temperatures of the raw materials (K)
13 ' Number of equilibria to be calculated
3 3 3 2 2 ' 2 = constant input amount, 3 = increases
1.0000000E-03 1.8850000E+00 ' Amount of raw material 1., step (mol)
1.0000000E-03 5.0000000E-01 ' Amount of raw material 2., step (mol)
1.0000000E-03 1.2500000E-01 ' Amount of raw material 5., step (mol)
1.0000000E+00 ' Amount of raw material 7. (mol)
2.0000000E+00 ' Amount of raw material 8. (mol)
10 ' Exit
 HSC Chemistry® 5.0 14 - 3

A. Roine June 28, 2002 02103-ORC-T

Input File for SOLGASMIX (Input amounts in grams)
§Copper Smelting at 1300 C ' Heading
1 ' 0 = mole mode, 1= gram mode
6 4 1 3 3 2 ' Elements, phases, inv. phases, and number of components / phase 1...
'N2(g) ' 2.00 0.00 0.00 0.00 0.00 0.00 ' stoichiomet.
'O2(g) ' 0.00 2.00 0.00 0.00 0.00 0.00 ' matrix
'SO2(g) ' 0.00 2.00 1.00 0.00 0.00 0.00
'*2FeO*SiO2(l) ' 0.00 4.00 0.00 2.00 1.00 0.00
'SiO2(l) ' 0.00 2.00 0.00 0.00 1.00 0.00
'Cu2O(l) ' 0.00 1.00 0.00 0.00 0.00 2.00
'Cu2S ' 0.00 0.00 1.00 0.00 0.00 2.00
'FeS ' 0.00 0.00 1.00 1.00 0.00 0.00
'Cu ' 0.00 0.00 0.00 0.00 0.00 1.00
14.007 ' N Mol. Weight g/mol
15.999 ' O
32.060 ' S
55.847 ' Fe
28.086 ' Si
63.546 ' Cu
4
1573.150 ' Equilibrium temperature (K)
0.000000E+00 1.916105E+02 3 ' H, S, number of temperature intervals
2.919177E+01 -1.121312E-03 0.000000E+00 4.091976E-06 0.000000E+00 0.000000E+00
400.000 0.000000E+00 ' ^ A, B, C, D, E, F (J/(mol*K))
2.255176E+01 1.320889E-02 3.129632E+05 -3.389040E-06 0.000000E+00 0.000000E+00
1600.000 0.000000E+00 ' Temperature (K), H (J/mol)
3.684012E+01 2.594080E-04 -5.478948E+06 0.000000E+00 0.000000E+00 0.000000E+00
0.000000E+00 2.051470E+02 1 ' H (J/mol), S (J/(mol*K)), ()
3.132312E+01 3.893657E-03 -3.105337E+05 -3.349854E-07 0.000000E+00 0.000000E+00
-2.968130E+05 2.482210E+02 3
1.734500E+01 7.922700E-02 2.646000E+05 -4.563100E-05 0.000000E+00 0.000000E+00
700.000 0.000000E+00
5.164756E+01 6.297887E-03 -2.158751E+06 -1.367747E-06 0.000000E+00 0.000000E+00
2000.000 0.000000E+00
6.665800E+01 -4.478000E-03 -1.128930E+07 8.430000E-07 0.000000E+00 0.000000E+00
-1.458188E+06 9.729792E+01 1
2.405800E+02 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-9.275245E+05 9.310607E+00 1
8.577200E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-1.302203E+05 9.640145E+01 1
9.991399E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-8.117000E+04 1.161520E+02 4
4.793800E+01 9.717300E-02 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
376.000 3.619000E+03
1.184100E+02 -5.818200E-02 7.920001E+04 2.231700E-05 0.000000E+00 0.000000E+00
720.000 1.172000E+03
8.372372E+01 -1.253259E-03 2.450114E+05 -6.180060E-07 0.000000E+00 0.000000E+00
1400.000 1.284500E+04
8.966300E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
-1.016710E+05 6.032100E+01 4
-2.732690E+02 7.791840E-01 8.124200E+06 0.000000E+00 0.000000E+00 0.000000E+00
411.000 1.665000E+03
7.235800E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
598.000 3.970000E+02
9.458400E+01 -8.366901E-02 1.411000E+05 4.794300E-05 0.000000E+00 0.000000E+00
1465.000 3.246400E+04
6.255100E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
0.000000E+00 3.316400E+01 2
4.057800E+01 -1.132500E-02 -3.284000E+05 9.800000E-06 0.000000E+00 0.000000E+00
1358.000 1.313800E+04
3.284400E+01 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00 0.000000E+00
5 1 2 5 7 8 ' Raw materials, and their row numbers in the stoichiometry matrix
298.150 298.150 298.150 298.150 298.150
2 ' ^ Temperatures of the raw materials (K)
13 ' Number of equilibria to be calculated
3 3 3 2 2 ' 2 = constant input amount, 3 = increases
2.8013401E-02 5.2805256E+01 ' Amount of raw material 1., step (g)
3.1998802E-02 1.5999400E+01 ' Amount of raw material 2., step (g)
6.0084306E-02 7.5105376E+00 ' Amount of raw material 5., step (g)
1.5915201E+02 ' Amount of raw material 7. (g)
1.7581400E+02 ' Amount of raw material 8. (g)
10 ' Exit
 HSC Chemistry® 5.0 14 - 4

A. Roine June 28, 2002 02103-ORC-T

Case 1: Hydration of Magnesia Chrome Bricks
Magnesia chrome bricks are widely used as a lining material in pyrometallurgical
applications because of their stability in process conditions. However, at room
temperatures they easily react with moisture and crumble due to hydration reactions. HSC
software can be used to estimate the lowest temperature, which must be exceeded to
prevent such reactions and to specify these reactions.
Magnesia chrome bricks contain magnesium, chromium, iron and oxygen. All species,
which contain these elements and hydrogen, can easily be collected to the Equilibrium
module from the database. The following ideas were used to specify the system (Fig 2):
- Metallic substances were removed, as they are not needed in these conditions.
- Gas species (16) were inserted in the gas phase.
- Other species (25) were assumed to exist as pure substances (invariant phases),
because of the low temperatures where molten mixtures do not exist.
- MgO, Cr2O3 and Fe2O3 raw materials were added according to their amount in
the brick: MgO 60, Cr2O3 18 and Fe2O3 14 kg.
- Water gas was added to the gas phase. The amount was set slightly higher than
needed to hydrate all species in the brick.
- A small amount of nitrogen was added to the gas phase.
The results of the calculations are shown in Fig. 1. This diagram shows that hydration of
the bricks is possible if the temperature of the lining is lower than 270 °C. Hydration
damage is caused only due to the formation of magnesium hydroxide; the chromium and
iron do not take part in hydration reactions. Magnesium oxide (periclase) forms the
matrix of the brick, therefore hydration of magnesium oxide crumbles the whole
construction.

Figure 1. Calculation results for hydration of magnesia chrome brick.

 HSC Chemistry® 5.0 14 - 5

A. Roine June 28, 2002 02103-ORC-T

Hydration of Magnesia Chromite Brick

File Format: GIBBS C:\Hsc5\Gibbs\Ankrom01.igi
Pure Substances in the Last Phase YES
Increase Temperature 101 Steps Criss-Cobble On
Temperature Range: 1000.000 0.000 C
Pressure Range: 1.000 1.000 bar

SPECIES Temper. Amount Amount Step Step Activity

Formula C kmol % kmol % Coeff.
PHASE 1: 5.000 100.000
N2(g) 25.000 1.000 20.000 1.000
H2O(g) 25.000 4.000 80.000 1.000
H2(g) 25.000 1.000
O2(g) 25.000 1.000
Cr(g) 25.000 1.000
CrO(g) 25.000 1.000
CrO2(g) 25.000 1.000
CrO3(g) 25.000 1.000
Fe(g) 25.000 1.000
FeO(g) 25.000 1.000
Fe(OH)2(g) 25.000 1.000
Mg(g) 25.000 1.000
Mg2(g) 25.000 1.000
MgH(g) 25.000 1.000
MgO(g) 25.000 1.000
MgOH(g) 25.000 1.000
Mg(OH)2(g) 25.000 1.000
PURE SUBSTANCES: 1.695 100.000
Cr2FeO4 25.000 1.000
Cr2MgO4 25.000 1.000
CrO2 25.000 1.000
CrO3 25.000 1.000
Cr2O3 25.000 0.118 6.988 1.000
Cr5O12 25.000 1.000
Cr8O21 25.000 1.000
Cr(OH)2 25.000 1.000
Cr(OH)3 25.000 1.000
Fe2MgO4 25.000 1.000
Fe0.945O 25.000 1.000
Fe0.947O 25.000 1.000
FeO 25.000 1.000
FeO1.056 25.000 1.000
Fe2O3 25.000 0.088 5.173 1.000
Fe3O4 25.000 1.000
Fe(OH)2 25.000 1.000
Fe(OH)3 25.000 1.000
Fe2O3*H2O 25.000 1.000
H2O 25.000 1.000
MgCr2O3 25.000 1.000
MgFe2O4 25.000 1.000
MgO 25.000 1.489 87.839 1.000
MgO2 25.000 1.000
Mg(OH)2 25.000 1.000

Figure 2. Specification of phases and species in the Magnesia Chrome brick example.
 HSC Chemistry® 5.0 14 - 6

A. Roine June 28, 2002 02103-ORC-T

Case 2: Ammonia Synthesis (by Panu Talonen)
Ammonia was expensive to produce before the current process, which uses high pressure
and iron catalyst, was invented. The synthesis is usually made at temperature of 370 –
540 °C. The effect of pressure on the ammonia formation can easily be evaluated with
HSC Equilibrium module. The formation reaction can be written as follows:
N2(g) + 3 H2(g) -> 2NH3(g)
The number of gas moles decreases in this reaction and therefore high pressure may be
assumed to favor the synthesis. The equilibrium calculation may be carried out as
described in Chapter 13. The chemical system specification and other calculation
parameters are shown in Fig. 2. The calculations are carried out by increasing the
pressure from 0.001 to 1000 bar at a constant temperature of 480 °C.
The calculated results are shown in Fig. 3. It is easy to see that at normal 1 bar pressure it
is quite impossible to produce high amounts of ammonia. It also seems that synthesis
should be done at the highest possible pressure. However, modern ammonia plants
operate at about 150 bar pressure for economic reasons. The ammonia is condensed from
the gas mixture and the unreacted hydrogen and nitrogen are recycled back to the reactor.

Figure 3. Calculation results for ammonia synthesis example.

 HSC Chemistry® 5.0 14 - 7

A. Roine June 28, 2002 02103-ORC-T

Ammonia Synthesis at 480 °C
File Format: GIBBS C:\Hsc5\Gibbs\Ammonia.igi
Pure Substances in the Last Phase YES
Increase Pressure 51 Steps Criss-Cobble On
Temperature Range: 480.000 480.000 C
Pressure Range: 0.001 1000.001 bar

SPECIES Temper. Amount Amount Step Step Activity

Formula C kmol % kmol % Coeff.
PHASE 1: 4.001 100.000
H(g) 25.000 1.000
H2(g) 25.000 3.000 74.981 1.000
HN3(g) 25.000 1.000
N(g) 25.000 1.000
N2(g) 25.000 1.001 25.019 1.000
N3(g) 25.000 1.000
NH(g) 25.000 1.000
NH2(g) 25.000 1.000
NH3(g) 25.000 1.000
N2H2(g) 25.000 1.000
N2H4(g) 25.000 1.000
N3H(g) 25.000 1.000
NH(H3)2(g) 25.000 1.000
PURE SUBSTANCES:
NH4N3 25.000 1.000

Figure 4. Specification of phases and species in ammonia synthesis example.

 HSC Chemistry® 5.0 14 - 8

A. Roine June 28, 2002 02103-ORC-T

Case 3: Decomposition of MgCl2*6H2O
All compounds will decompose if the temperature is high enough. Especially substances
with combined water will decompose at quite low temperatures. The decomposition
temperatures may be found from many different handbooks, but they may also be
calculated with the HSC Equilibrium module if the basic data is available in the HSC
database. Magnesium chloride forms a MgCl 2*6H2O compound which decomposes
according to the reaction:
MgCl2*6H2O -> MgCl2*4H2O + 2H2O(g)
MgCl2*4H2O -> MgCl2*2H2O + 2H2O(g), etc.
The decomposition temperature as well as the decomposition vapor pressure may be
calculated using the chemical system specification shown in Fig. 5. The user must specify
all possible condensed phases as well as a gas phase. Please note: A) Small nitrogen
amount stabilize the gas phase, B) small Cl 2(g) and O2(g) amounts shift the material
balance out from stoichiometric one and C) Mg(g) allows magnesium to enter the gas
phase also.
The results of the calculations are shown in Figs. 6 and 7. The decomposition seems to
start at 100 °C, see Fig. 6. The vapor composition is drawn in Fig. 7 by selecting the
Equilibrium Composition option. This diagram shows that the vapor pressure of water is
0.67 bar at 175 °C and 1 bar total pressure. To calculate vapor pressure at higher
temperatures, the total pressure must be increased, for example, to 10 bar.
Decomposition of MgCl2*6H2O at 1 bar
File Format: GIBBS C:\Hsc5\Gibbs\Mgcl2.igi
Pure Substances in the Last Phase YES
Increase Temperature 81 Steps Criss-Cobble On
Temperature Range: 0.000 400.000 C
Pressure Range: 1.000 1.000 bar

SPECIES Temper. Amount Amount Step Step Activity

Formula C kmol % kmol % Coeff.
PHASE 1: 0.100 100.000
N2(g) 25.000 0.100 99.980 1.000
Cl2(g) 25.000 0.000 0.010 1.000
HCl(g) 25.000 1.000
H2O(g) 25.000 1.000
O2(g) 25.000 0.000 0.010 1.000
H2(g) 25.000 1.000
Mg(g) 25.000 1.000
PURE SUBSTANCES: 1.000 100.000
MgCl2*6H2O 25.000 1.000 100.000 1.000
MgCl2*4H2O 25.000 1.000
MgCl2*2H2O 25.000 1.000
MgCl2*H2O 25.000 1.000
MgCl2 25.000 1.000
Mg(OH)Cl 25.000 1.000
MgO 25.000 1.000
H2O 25.000 1.000

Figure 5. Specification of phases and species in MgCl2*6H2O example.

 HSC Chemistry® 5.0 14 - 9

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Figure 6. Calculation results for MgCl2*6H2O decomposition example.

Figure 7. Vapor composition at a total pressure of 1 bar.

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Case 4: Decomposition of FeSO4*7H2O (by Ben Karlemo)
Thermal decomposition of a chemical compound will sometimes give valuable
information of its behaviour in a real chemical process. This evaluation may be carried
out with the HSC Equilibrium module and with a thermo-gravimetric analyzer. These
evaluations have been made in this example for FeSO 4*7H2O. The chemical system
specifications for the HSC equilibrium module are shown in Fig. 8. Please note (see
Chapter 13.4): A) The small amount of nitrogen stabilizes the gas phase, B) the small
amount 1E-5 kmol of O2(g) shifts the material balance away from the stoichiometric one,
C) Fe(g) allows iron to enter the gas phase also, and D) Solgasmix routine has been used.
The results are shown in Fig. 9.
The hydrates gradually decompose at 50 to 200 °C and sulfates at 400 to 650 °C.
Hematite will reduce to magnetite at 1250 °C. These results may be used to explain the
experimental thermo-gravimetric results shown in Fig. 10. The TG curve shows the actual
weight change and the DSC curve shows the enthalpy change compared to the reference
test.

Decomposition of FeSO4*7H2O at 1 bar

File Format: GIBBS C:\Hsc5\Gibbs\Feso4.igi
Pure Substances in the Last Phase YES
Increase Temperature 100 Steps Criss-Cobble On
Temperature Range: 0.000 1600.038 C
Pressure Range: 1.000 1.000 bar

SPECIES Temper. Amount Amount Step Step Activity

Formula C kmol % kmol % Coeff.
PHASE 1: 0.004 100.000
N2(g) 25.000 0.004 99.990 1.000
O2(g) 25.000 0.000 0.010 1.000
SO2(g) 25.000 1.000
S2(g) 25.000 1.000
H2S(g) 25.000 1.000
H2O(g) 25.000 1.000
H2(g) 25.000 1.000
Fe(g) 25.000 1.000
PURE SUBSTANCES: 0.360 100.000
FeSO4*7H2O 25.000 0.360 100.000 1.000
FeSO4*4H2O 25.000 1.000
FeSO4*H2O 25.000 1.000
Fe2(SO4)3 25.000 1.000
FeSO4 25.000 1.000
FeO*OH 25.000 1.000
FeO 25.000 1.000
Fe2O3 25.000 1.000
Fe3O4 25.000 1.000
H2O 25.000 1.000

Figure 8. The specification of phases and species for the equilibrium calculations.
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Figure 9. The result of the calculated decomposition of FeSO 4*7H2O.

The theoretical and experimental weight change curves are compared in Fig. 11, which is
calculated in MS Excel. Both curves are in quite good correlation with each other. The
decomposition occurs at slightly higher temperatures in the experimental results than in
the calculated ones, but this may be explained by some kinetic effects. The final weight
of the sample was nearly the same in the experimental and theoretical results at high
temperatures. The decomposition reactions may also be verified by comparing the
analyzed and the calculated gas composition with each other.
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Figure 10. Results of FeSO4*7H2O run on NETSCH TG-DSC analyzer under nitrogen
atmosphere showing TG and DSC curves. Heating rate was 5 °C/min.

Figure 11. The comparison of the measured and calculated mass change of FeSO 4*7H2O.
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Case 5: Alkali circulation in Blast Furnace (by Riku Sarkkinen)
Alkali metals tend to enrich in the iron blast furnace. The alkali content in raw materials
(pellets, sinter and coke) is not so high, but they evaporate at the bottom part of the
furnace (~1500 °C) and do not exit with the products (slag, iron) easily. Neither do they
exit with the process gas, which goes upward, because the temperature is quite low at the
top of the furnace (~100 °C). This problem may be evaluated with the HSC Equilibrium
module.
The chemical system specification is shown in Fig. 13. The raw material amounts are
based on the following assumptions: Coke ash analysis (main components): SiO 2 53, CaO
3, MgO 2, and Al2O3 27 wt %. Process gas is formed by air reaction with coke, the main
components in the gas phase are CO(g), CO2(g) and N2(g). The alkali elements are K and
Na. The calculations are carried out as described in Chapter 13 by increasing the
temperature from 500 to 2000 °C. Iron has not been taken into account because the alkali
circulation occurs above the liquid iron zone. Equilibrium calculations were made as
described in Chapter 13.
The calculation results are shown in Fig. 12. At high temperatures almost all the sodium
and most of the potassium seems to be in elemental form in the gas phase. These gas
species flow with the main process gases upward where cold charge materials decrease
the temperature and alkalis react with the slag components. The reaction products are
mainly sodium and potassium carbonates, sodium silicates and potassium alumina
silicates. These solid compounds flow downwards with the blast furnace charge materials
to the high temperature zone at the bottom of the furnace, where the alkali components
vaporize again, which leads to the alkali circulation.

Figure 12. Equilibrium results of alkalis and slag components as a function of

temperature.
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File Format: GIBBS C:\Hsc5\Gibbs\Alkal1.igi
Pure Substances in the Last Phase YES
Increase Temperature 200 Steps Criss-Cobble On
Temperature Range: 500.000 2000.062 C
Pressure Range: 1.000 1.000 bar

SPECIES Temper. Amount Amount Step Step Activity

Formula C kmol % kmol % Coeff.
PHASE 1: 197000.000 100.000
AlO(g) 25.000 1.000
CO(g) 25.000 1.000
CO2(g) 25.000 1.000
Ca(g) 25.000 1.000
K(g) 25.000 4000.000 2.030 1.000
K2(g) 25.000 1.000
K2CO3(g) 25.000 1.000
KNa(g) 25.000 1.000
KO(g) 25.000 1.000
Mg(g) 25.000 1.000
MgO(g) 25.000 1.000
N2(g) 25.000 150000.000 76.142 1.000
Na(g) 25.000 3000.000 1.523 1.000
Na2(g) 25.000 1.000
NaO(g) 25.000 1.000
O(g) 25.000 1.000
O2(g) 25.000 40000.000 20.305 1.000
SiO(g) 25.000 1.000
PHASE 2: 1417.000 100.000
AlO 25.000 1.000
Al2O3 25.000 300.000 21.171 1.000
Al2O3*SiO2(D) 25.000 1.000
Ca2Al2SiO7 25.000 1.000
Ca3Al2Si3O12 25.000 1.000
CaO 25.000 60.000 4.234 1.000
Ca2SiO4(A) 25.000 1.000
KAlO2 25.000 1.000
KAlSiO4 25.000 1.000
K2CO3 25.000 1.000
K2O 25.000 1.000
K2O*Al2O3*2SiO2 25.000 1.000
K2O*SiO2 25.000 1.000
K2O*2SiO2 25.000 1.000
MgO 25.000 57.000 4.023 1.000
MgSiO3 25.000 1.000
Na2CO3 25.000 1.000
Na2O 25.000 1.000
Na2O*Al2O3 25.000 1.000
*2Na2O*SiO2 25.000 1.000
Na2SiO3 25.000 1.000
SiO2 25.000 1000.000 70.572 1.000
PHASE 3:
Al 25.000 1.000
Ca 25.000 1.000
K 25.000 1.000
Mg 25.000 1.000
Na 25.000 1.000
Si 25.000 1.000
PURE SUBSTANCES: 70000.000 100.000
C 25.000 70000.000 100.000 1.000
Al4C3 25.000 1.000
Na2C2 25.000 1.000
SiC 25.000 1.000

Figure 13. Specification of phases and species in the Blast Furnace example.