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Software and databases for thermodynamic calculations

CHAPTER 6

SOFTWARE AND DATABASES FOR


THERMODYNAMIC CALCULATIONS

As indicated by the previous chapters, for efficient thermodynamic


calculation and plotting of different types of diagrams it is
necessary to carry out complicated calculations but, in particular,
have the required number of data of sufficient quality at our
disposal. This is greatly helped by the application of powerful
computers and the internet.
The literature describes a large number of algorithms including
thermodynamic or thermochemical calculations, including databases
for calculating phase composition, equilibrium diagrams, chemical
reactions, thermal equilibria, solubilities, complex chemical equilibria,
chemical modelling, etc. [1, 2]. However, many efficient algorithms
operate with non-compatible databases and, therefore, in parallel.
A problem in this case is obviously the protection of copyright and,
on the other hand, the relatively high price of these program
facilities. A quote for unification on the basis of compatible data
sets was made by Bale and Eriksson [3] and at present there are
several very large database systems enabling calculations and
modelling of thermodynamic processes in hydrometallurgy, although
each system has its specific features. The most important fact from
this viewpoint is the existence of the concept of integrated databases
brought into life by the Scientific Group Thermodata Europe SGTE.
The integrated thermochemical database (ITD) is the defined as a
system offering large thermochemical data banks and powerful
programming enabling equilibrium thermodynamic calculations typical
of complex chemical equilibria and calculations of phase diagrams
in multicomponent multiphase systems.
SGTE is a consortium of seven west European organisations
concerned with the development and operation of thermochemical
databases in the form in which they can be used widely, although
the majority of the existing program facilities are incompatible. At
present, the integrated database SGTE contains the data on

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Hydrometallurgy

approximately 3000 compounds, of these 2000 condensed phases,


1000 gaseous compounds and 500 substances in the ion form for
aqueous solutions [4].
It is not possible to list all the existing database systems nor the
program facilities that are available. They are almost all of the
commercial nature and their price very often controls their
application and extent of use. On the other hand, new systems are
being continuously developed. that is why as an example, attention
will be given to several well known systems which may greatly help
the thermodynamic calculation and other tasks in hydrometallurgy.
FactSage © [5] is one of the largest fully integrated database
computer systems for chemical thermodynamics in the world. In
this form, the system appeared in 2001 after merger with all the
systems F*A*C*T and ChemSage/SolGasMix, which were
developed over a period of almost 20 years in Umeå, Sweden
Montreal, Canada and Aachen, Germany [6, 7].
The FactSage © program package operates on a PC under the
Windows system and consists of a complex of information,
databases, calculation and manipulation modules enabling work with
a large number of pure substances and also substances in the ion
state and species. At the present time, the system utilises several
hundreds of industrial, governmental and academic institutions in the
area of material science, pyrometallurgy, hydrometallurgy,
electrometallurgy, corrosion, glass industry, ceramics, geology,
combustion processes, etc. [8].
Figure 6.1 shows the areas of application of FactSage program
package, version 5.3, in the year 2005.
From the viewpoint of hydrometallurgy, it is possible to calculate
the equilibria in the solutions, E–pH and species diagrams, apply
with the Debye–Hückel limiting law, model diluted and concentrated
aqueous solutions on the basis of the Pitzer model, model aqueous
solutions at high pressures and temperatures, apply the Helgeson
model to diluted aqueous solutions, etc.,
In addition to the possibility of purchasing program package,
either as a single or multiple licence, the researcher can work
directly on the Internet where individual applications are free of
charge otherwise a fee must be paid.
Figure 6.2 shows the possibilities of working with FactSage on
the Internet, Fig. 6.3 and Fig. 6.4 show examples of the results.
Another relatively widely used system is HSC [10] which,
however, is far smaller and designed for individual work on a PC.
Its name comes from working with enthalpy (H), entropy (S) and

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Software and databases for thermodynamic calculations

Fig. 6.1. Menu of the FactSage program package.

Fig. 6.2. Operation of the Fact-Web system on the Internet.

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Hydrometallurgy

EpH-Web diagram
Cu-H2O, 298.15 K
m = 1 e-6

1.6
1.4
1.2
1
.8 CuO2[2-]
Cu[2+]
.6 Cu(OH) 2(S)
E(volts)

.4
.2 Cu[+]
0 Cu2 O(s)
-.2
-.4 Cu(s)
-.6
-.8
-1
-1.2
-2 0 2 4 6 8 10 12 14 16

pH

EpH-Web diagram
Fe-H2O, 298.15 K
m = 1e-6

1.6
Fe[3+]
1.4
1.2
1 Fe zO3 (S)
.8
.6
E (volts)

.4
.2 Fe[2+]
0
-.2
-.4
FeOH[+]
-.6 Fe3 O4(S)
-.8 Fe(OHz)(S)
Fe(S)
-1
-1.2
-2 0 2 4 6 8 10 12 14 16
pH

Fig. 6.3. Pourbaix diagrams of the Cu–H 2 O and Fe–H 2 O system obtained using the
Fact-Web [9].

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Software and databases for thermodynamic calculations

Al–Mg

700

600 Liquid
Temperature (°C)
500
FCC_A1
AlMg_GAMMA HCP_A3
400

Al30Mg23
300

200

Al140Mg89
100

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mole Mg/(Al+Mg)
KCl - Ni Cl 2

1000
B Sal HlIquid
1 bar

800 B Sal Hliquid + HICI(S)


Temperature (°C)

600
B Sal Hlquid + KCI(S)

400
KHICI(S)

200

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
mole NiCl 1/(KCl+NiCl2 )

KNO2 - KOH

404°
400

337° ESal Hlquid


Temperature (°C)

300 ESal Hlquid + KO H(s2)

335° 0.706 249°


KNO(s2) + ESal Hlquid 0.638 225° ESal Hlquid + KO H(s)
217° 0.303
200
K2(OH)(NO)(s)

130°

100
KNO (s) + K(OH)(NO2 )(s)

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
mole KOH/(KNO3+KOH)

Fig. 6.4. Phase diagrams obtained using the Fact-Web [9].

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Hydrometallurgy

thermal capacity (C). The current version HSC 6.1 operates under
Windows ® . The system was developed by Outokumpu Research
Centre in Pori, Finland, in 1981 and has been greatly changed since
then. The version of the program 5.11 has 14 application
possibilities, Fig. 6.5, of which the application most important for
hydrometallurgy is the calculation of reaction equations, material
and heat balance, calculation of equilibrium compositions,
electrochemical equilibria, plotting and displaying E–pH diagrams,
plotting of species diagrams, etc.
At the present time, the database contains data on approximately
17,000 chemical substances. The entire system is organised in
modules enabling independent activities. They are:
• equilibrium module;
• module of the mass/enthalpy equilibrium;
• Excel module enabling easy operations with calculations and
imaging;
• tabulation and drawing thermodynamic parameters of the
individual components;
• calculation of mineralogy and elemental composition;

Fig. 6.5. Menu of HSC software, version 5.11.

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Software and databases for thermodynamic calculations

• depicting the data from the database;


• conversions between the units.
The E–pH diagrams presented in Chapter 5 were designed and
drawn by the HSC program, version 5.11.
The database system MTDATA – Metallurgical and Thermo-
chemical Data Service [11] was developed and operated by the
National Physics Laboratory, Harwell Laboratory, England, which
is a member of SGTE. The development of the program started in
1971, with the most marked development possible only with the
development of personal computers. Although this large system is
designed mainly for high temperature systems, it may also be used
for equilibrium calculations for multicomponent multiphase systems,
calculation and graphical imaging of thermodynamic functions for
pure substances, calculation and graphical imaging of
thermodynamic functions in solutions, calculations and graphical
imaging of binary and ternary phase diagrams, calculation of phase
interfaces and crystallisation routes in multicomponent systems,
calculation of the regions of stability and calculation and graphical
imaging of E–pH diagrams, Fig. 6.6.
The METSIM software [12] (Metallurgical Simulations) is a
system of programs for solving complex chemical, metallurgical and
environmental processes, developed and distributed by the
international consortium PROWARE [13]. The system is suitable for
calculating the mass and energy equilibria and optimisation of
engineering calculations, and is used for modelling and also
production processes, such as waste processing, processing of ore
minerals, dressing flowsheets, hydrometallurgy, pyrometallurgy, coal
processing, heap leaching, etc.
A suitable example is the calculation of material equilibrium in
heap leaching where it is necessary to consider the chemical
reactions, precipitation and evaporation, the content of actual solid
reagents and water, drainage and logistics. The model is not
designed for the steady state and forms the time dependences of
individual yield curves during leaching. It may also be used for
comparing the control strategies, the effect of changes of the key
parameters and the effect seasonal changes.
Figure 6.7 shows the simulated situation and Fig. 6.8 its output
GWB (Geochemist’s Workbench ® ) [14] is a set of interactive
programs for solving the equilibrium in the aqueous phase, and
offers facilities for calculations in environmental protection and
improvement of environment, oil industry and economical geology.
The following tasks can be solved in metallurgy:

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Hydrometallurgy

14

37
3 14
1 17
28

6
12 22
6 12
Eh/V

0
36 12
35 42
33 28
16
33

32 33
29
-1 32
19 20
29

1 18
34
1

0 2 4 6 8 10 12 14
pH
Fig. 6.6. E–pH diagram of the Fe–S–H2O system at 200 °C, calculated by the MTDATA
system.

1
COPPER HEAP LEACH EXAMPLE
17 33
18
2 19 22

27
24
26 64 21
28
29
60
65

Fig. 6.7. Flow diagram of copper heap leaching in created by METSIM software.

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Software and databases for thermodynamic calculations

Fig. 6.8 Outputs of copper heat leaching simulation.

• chemical reaction equilibria;


• formation of E–pH and activity diagrams;
• calculation of species in the solution and gas fugacity;
• model sorption of ions and formation of complexes at the
interface, etc.
Figures 6.9–6.11 show examples of the output of the GWB
software for hydrometallurgy.

-10
Scorodite
H3 AsO4
-20
Log f O2 (g)

-30 -
H2AsO 4

-- ---
-40 HAsO4 AsO4
As(OH)3

-50 -
As(OH) 4
Orpiment
-
-60 AsO2 OH
Realger Arsenopyrite

0 2 4 6 8 10 12 14
pH

Fig. 6.9. Diagram of the As–Fe–S–H 2O system at 100°C generated by GWB software.

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Hydrometallurgy

-10
CuOH+ Malachile
-20 ++
Cu

log f O2 (aq)
-30

-40
Caprice
-
CuCl 2
-50

-60
Copper
-70

60°C
-80
0 2 4 6 8 10 12 14
pH

Fig. 6.10. Redox–pH diagram. Effect of chlorides on the formation of copper complexes
at 60°C at f CO2 = 1.

200
Clinozoisite
Margarite Prehnite

Diaspore
150

Clinoptil-Ca
T (°°C)

100
Muscovite
Gibbsite

Clinoptil-K

50

Kaolinite Mordenite-K
0
-4 -3 -2
log a SiO2 (aq)

Fig. 6.11 Diagram of the stability of aluminosilicate in the presence of SiO 2 in the
temperature range 0–200°C.

Of course, there are large numbers of other powerful or less


powerful computer systems or software used for thermodynamic
and thermochemical calculations in hydrometallurgy. The most
important part of the discussed programs are the databases which
of course determine the price of these programs. In many cases it
is possible to obtain partially or even completely comparable results,

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Software and databases for thermodynamic calculations

Table 6.1. Price list of several programs and databases for hydrometallurgical applications

S y s te m Pric e

Pro g ra m D a ta ba s e S ing le us e r M ultilic e nc e Univ e rs itie s

$6000

FAC T FAC T $15000

S GTE $8500

HS C $595 $7000 $3500

C HEMS HEET $2695 $3995 $1395 / 2095

MTDATA (fo r
£600
a q ue o us so lutio ns)

a c c o rd ing to a c c o rd ing to
METS IM
a gre e me nt a gre e me nt

GW B $ 9 9 . 0 0 ha nd b o o k $799.00 + $399.00 $599.00

may be less comfortably, also on considerably cheaper products. In


any case, the application of integrated thermochemical databases
ITD in connected with the computer network is most promising.
Table 6.1 shows the input data on the prices of the previously
mentioned program facilities in spring of 2005.

References
1. Havlík T., Kammel R.: Chemické listy, 89, 1995, 603–610.
2. STN Database Catalog – the world premier on-line service for sci-tech in-
formation, FIZ Karlsruhe, January 2003.
3. Bale Ch.W., Eriksson G.: Canadian Metallurgical Quarterly, 29, 2, 1990,
105–132
4. http://www.sgte.org/
5. Bale Ch.W. a kol.: FactSage thermochemical software and databases, Calphad,
26, 2, 2002, 189–228
6. Thermfact/CRCT (Montreal, Canada) http://www.crct.polymtl.ca
7. GTT-Technologies (Aachen, Germany) http://www.gtt-technologies.de
8. http://www.esm-software.com/
9. http://www.factsage.com/
10. Roine A.: HSC Chemistry for Windows, Outokumpu, ver. 5.0, 2002
11. Davies R.H. a kol: MTDATA – Thermodynamic and phase equilibrium software
from the National Physical Laboratory, Calphad, 26, 2, 2002, 229–271
12. Swanson V.N.: Modelling heap leach operations with METSIM, In: Recent
Trends In Heap Leaching Conference, Bendigo, Victoria, Australia, 27–29
September 1994
13. http://members.ozemail.com.au/~ozmetsim/met2/http://www.rockware.com/
catalog/pages/gwb

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