HSC Chemistry® 5.

0 8-1

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

8. INTRODUCTION

HSC Chemistry is designed for many different kinds of chemical reactions and
equilibrium calculations. The current version contains 14 calculation options:

1. Reaction Equations
2. Heat and Material Balances
3. Heat Loss Calculations
4. Equilibrium Compositions
5. Electrochemical Cell Equilibria
6. Formula Weights
7. Phase Stability Diagrams (Tpp- and Lpp-versions)
8. Eh - pH – Diagrams with concentration and temperature variables
9. Enthalpy, entropy, heat capacity, Gibbs-energy and Ellingham diagrams.
10. Mineralogy Iterations
11. Composition conversions
12. Water - Steam Tables and Mollier Diagrams
13. Units Conversions
14. Properties of Elements in tabular and graphical format.

The name of the program is based on the fact that all fourteen calculation options
automatically utilize the same extensive thermochemical database which contains
enthalpy (H), entropy (S) and heat capacity (Cp) data for more than 17000 chemical
compounds. This database is equivalent to more than seventeen thick data books.

The HSC Chemistry software enables the user to simulate chemical reactions and
processes on the thermochemical basis. This method does not take into account all the
necessary factors, such as rates of reactions, heat and mass transfer issues, etc. However,
in many cases a pure thermochemical approach may easily give useful and versatile
information for developing new chemical processes and improving the old ones.

Perfect simulation for all processes means that any chemical process can be designed
completely in the computer without any experimental work. This goal is, however, far in
the future, because there is no complete general theory or basic data available which
would successfully combine thermodynamics, non-ideality of solutions as well as
dynamics (kinetics) for all processes. Nearly perfect simulation may be achieved for a
single individual process step by measuring experimentally all the necessary parameters
for solution models, kinetic models, as well as for flow and heat transfer models.
However, this needs several months or years work to be able to simulate one single
process step. Quite often a fast mainframe computer is needed.

With HSC Chemistry it is possible to calculate chemical equilibria between pure

substances and the ideal and also, to some extent, non-ideal solutions. For these
calculations only enthalpy (H), entropy (S) and heat capacity (Cp) data for all prevailing
compounds or pure substances is needed. In many cases these calculation results may
simulate the real chemical reactions and processes at sufficient accuracy for the practical
applications. Important advantage is also that specification of the chemical system, data
retrieval and final calculations may be carried out in normal Intel Pentium personal
computers within few minutes.
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A. Roine June 28, 2002 02103-ORC-T

Of course, experimental work is needed to verify the results, because HSC does not take
kinetic phenomena into account. However, HSC helps to avoid expensive trial-and-error
chemistry, because it quickly and easily gives some kind of clue as to the effects of
process parameters on the reaction products and process conditions. Usually,
thermochemical calculations at least show what is physically possible and what is
impossible, which is highly valuable information when making plans for experimental
investigations.

In the thermodynamic equilibrium the rates of reactions and reverse reactions may both be
interpreted to have the same rate, ie. this state is only one special case of kinetic
phenomena. Of course, some programs are available which also take some kinetic aspects
into account. However, these are not general like thermodynamic equilibrium codes are,
ie. they are usually valid only for certain geometries and environments.

A number of solution models are available in literature to describe the non-ideality of

mixture phases. The practical problem is quite often a lack of valid data for solution
parameters. Although solution models have not been installed in the HSC Chemistry, the
non-ideality of solutions can be taken into account in the equilibrium calculations to a
certain extent by including constant activity coefficients or simple activity coefficient
formulae in the Gibbs equilibrium solver.

8.1 Invitation to new Authors

If you have a thermochemical computer program or basic thermodynamic data which may
be of more general interest, please send it to the author:

Antti Roine
Outokumpu Research Oy
P.O. Box 60
FIN-28101 PORI, FINLAND
Fax: +358 - 2 - 626 - 5310

We may also add your code to future versions of HSC Chemistry. Connection to the HSC-
database and fitting the code and user interface to HSC format can be carried out in
Outokumpu Research. Integration is easiest if the original code is written in Visual Basic,
QuickBASIC or BASIC.

The new thermodynamic data which is saved in OwnDB5.HSC database can easily be
transferred to MainDB5.HSC at Outokumpu Research.
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8.2 Physical Background of H, S, C and G

Thermochemical calculations are based on enthalpy H, entropy S, heat capacity Cp or

Gibbs energy G values for chemical species. They can all be mathematically derived from
experimental observations. The following presentation gives a brief and simplified but
illustrative idea of the thermochemical quantities and methods.

Enthalpy H: Absolute values of enthalpy H of substances cannot be measured, but

enthalpy differences between two temperatures can be determined with a calorimeter.
Heat capacity Cp at constant pressure (specific heat) can be calculated from this data using
Eq. (1).

Cp = (dH / dT)P,n [1]

Equation (1) allows the calculation of enthalpy as

T
H(T) = Hf(298.15)+  Cp dT +  Htr [2]
298.15
where Hf(298.15) is the enthalpy of formation at 298.15 K and H tr is the enthalpy of
transformation of the substance. Calorimetric measurements at different temperatures
yield the enthalpy curve of zinc shown in Fig. 2.

The enthalpy scale in Eq. 2 is fixed by defining H = 0 for the elements in their most
stable state at 25 °C and 1 bar, mainly because this is convenient for calculations at
elevated temperatures. This is called the reference state. (Another fix point could have
been H = 0 at 0 K, because the thermal motion of atoms and electrons stops completely at
this temperature.)

The ability of a chemical substance to absorb or emit heat depends on the temperature, and
therefore the curve in Fig. 2 is not linear. In addition, at phase transformation temperatures
the curve is discontinuous, because heat is needed for the phase transformations (ie. for
crystal structure changes, as well as for melting and boiling).

The enthalpy of compounds also contains their enthalpy of formation DH f from

elements. This is usually measured calorimetrically by letting pure constituent elements
react and form the compound at 298.15 K and 1 bar. The enthalpy of the compound is
therefore calculated by adding the enthalpy of formation to the experimental enthalpy
difference H(T)-H(298), see the solid line in Fig. 3.

The enthalpy values of gaseous zinc can be extrapolated to lower temperatures as shown
in Fig. 2 by the dotted line. The reference state for zinc at 25 °C and 1 bar is hexagonal
crystal. The enthalpy of gaseous zinc is 130.415 kJ/mol larger compared to solid pure zinc
at 298.15 K. This amount of heat is needed to evaporate one mole of zinc at 25 °C and 1
bar, and is called the enthalpy of formation of zinc gas from solid zinc.
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H, kJ/mol Enthalpy of Zinc Sulfide

160

140 298.15 K gas

120

100
115.311
80
130.415
60

40
liquid
20
solid 7.322
0
0
- 20
0 200 400 600 800 1000 Temperature, K 1400

Fig. 2. Enthalpy of pure zinc from 0 K to 1400 K with reference to solid, hexagonal Zn at 298.15 K.

H, kJ/mol Enthalpy of Zinc Sulfide

ZnS
100

13.389
50 298.15 K

-50

Enthalpy of Formation =
-100
-201.669 kJ/mol solid, beta

-150 solid, alfa

-200

-250
0 200 400 600 800 1000 1200 K
Temperature, 1400

Fig. 3. Enthalpy of zinc sulfide ( ). Enthalpy difference H(T)-H(298) ( ) and enthalpy of formation have
been measured by calorimeter. Note crystal structure transformation at 1293 K.
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Entropy S: Absolute entropy values can be calculated from the experimental heat capacity
values using Equation (3) and numerical integration.
T
S = S(298.15) +  (Cp / T) dT +  Htr / Ttr [3]
298.15

where S(298.15) is the standard entropy of the substance which can be calculated by
integrating Cp/T function from 0 to 298.15 Kelvins, T is temperature and H tr is enthalpy
of phase transformation at a temperature Ttr, see Fig. 4.

Entropies of crystalline substances approach zero at 0 K. This fundamental experimental

observation is compatible with the third law of thermodynamics. If entropy is understood
as a measure of disorder, the disorder reaches its minimum at absolute zero and in perfect
crystal structures.

Heat Capacity Cp: The absolute heat capacity of substances at constant pressure can be
calculated as a first derivative of the enthalpy curve in Fig. 2, using Equation (1). The heat
capacity curve is discontinuous at phase transformation temperatures, see Fig. 5. The heat
capacity values of crystalline substances in equilibrium approaches zero value at 0 K.

The temperature dependence of heat capacity at elevated temperatures cannot be predicted

theoretically by thermodynamics. A fully mathematical correlation is therefore adopted
for fitting experimental heat capacities. The Kelley equation is used throughout this
program in the following form:

Cp = A + B . 10-3 . T + C . 105 . T-2 + D . 10-6 . T2 [4]

where A, B, C and D are coefficients estimated from experimental data.

Gibbs Energy G: The mutual stability of substances (elements, compounds, ions, etc.)
cannot be compared using enthalpy, entropy or heat capacity functions solely. It must be
done using the Gibbs energy defined by Equation (5). The Gibbs energy of pure zinc has
been calculated using this equation and data in Figs. 2 and 4. The results can be seen in
Fig. 6.

G  H-T S [5]

Experimental Methods: Many experimental and theoretical methods are available for
evaluating the basic thermochemical enthalpy, entropy and heat capacity data than it is
practical to describe in this context. Usually a critical analysis of the values is based on a
thorough simultaneous cross-correlation of thermochemical data from different sources,
measurement methods (calorimetric, spectroscopic, electromotive force, solubility, etc.)
and theoretical calculations. More information of the assessment methods can be found,
for example, in the references mentioned in Chapters 32 and 33.
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S, J/(mol*K) Entropy of
200 Zinc

180 298.15 K gas

160

140 97.721

120

100 160.415
liquid
80
solid 10.571
60

40

20 41.631
0
0 200 400 600 800 1000 Temperature, K 1400

Fig. 4. Entropy of zinc calculated from the experimental heat capacity, by Eq. (3).

Cp, J/(mol*K) Heat Capacity of

35 Zinc
liquid
30 298.15 K
solid
mp = 692.7 K bp = 1180 K
25
gas
20

15
25.403
10

0
0 200 400 600 800 1000 Temperature, K 1400

Fig. 5. Heat capacity of zinc from 0 K to 1400 K calculated from calorimetric data, by Eq. (1).
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G, kJ/mol Gibbs Energy of

0 Zinc
-12.412
solid
-20 -33.841

-40 -74.825
liquid

-60
298.15 K

692.7 K
-80
gas

-100 1180 K

-120
0 200 400 600 800 1000 Temperature, K 1400

Fig. 6. Gibbs energy of zinc at 0 - 1400 K calculated from the enthalpy and entropy values using Equation
(5).

Data Format in the HSC Databases: Traditionally, experimental heat capacity values -
see Fig. 5 - have been fitted using the empirical Equation (4). The coefficients A, B, C and
D provided in HSC are valid in limited temperature ranges only. Usually the temperature
ranges are the same as the stability ranges of solid, liquid and gaseous states of the
substances.

The heat capacity coefficients can be saved in the HSC database as data sets for each
temperature range, together with the enthalpy and entropy values for formation and
transformations. The first data set contains the enthalpy of the formation H f(298.15),
standard entropy S° and the coefficients A, B, C and D for the most stable form of the
substance at room temperature. The second set contains the enthalpy and entropy of
transformation as well as the coefficients for the second temperature range, etc. For
further details, see Chapter 28.11.

Table 1 shows the thermochemical data of zinc as printed from the HSC main database.
The same enthalpy values can be found in Fig. 2, as well as the entropy values in Fig. 4.
The coefficients A, B, C and D have been derived from the experimental heat capacity
values, Fig. 5, using curve fitting and Equation (4), see Chapter 28.12.

Note that the data for gaseous substances as Zn(g) has been saved separately. Such a
selection allows, for example, equilibrium calculations with the gaseous substances also
below their boiling points.
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Species State Enthalpy Entropy Heat Capacity Cp Temperature Range
H S A B C D T1 T2
kJ/mol J/(mol*K) J/(mol*K) K K
Zn s 0.000 41.631 20.736 12.510 0.833 0.000 298.150 692.655
Zn l 7.322 10.571 31.380 0.000 0.000 0.000 692.655 1180.000
Zn(g) g 130.415 160.984 20.786 0.000 0.000 0.000 298.150 2000.000

Table 1. Thermochemical data of zinc as printed from the HSC database.

All thermochemical data required in HSC and its modules, including heat capacity,
enthalpy, entropy and Gibbs energy of the substances, can be calculated from the basic
data in its databases using Equations (1)-(11). HSC Chemistry utilizes the equations
automatically whenever needed.

Chemical Reactions: The thermodynamic enthalpy, entropy and Gibbs energy functions
for a chemical reaction are calculated as the difference between the products and reactants,
using Equations (6) - (9). The commonly needed equilibrium constant K can be calculated
using Equation (11). The physical meaning of these functions and values will be described
in more detail in Chapters 10.1 - 10.4.

Chemical reaction: aA + bB +... = cC + dD +... [6]

Enthalpy of reaction: Hr iHi(Products) - iHi(Reactants) [7]

= (c*HC + d*HD +...) - (a*HA + b*HB +...)

Entropy of reaction: Sr iSi(Products) - iSi(Reactants) [8]

= (c*SC + d*SD +...) - (a*SA + b*SB +...)

Gibbs energy of reaction: Gr SniGi(Products) - iGi(Reactants) [9]

= (c*GC + d*GD +...) - (a*GA + b*GB +...)

[C]c * [D]d * ...

Equilibrium constant: K =  [10]
[A]a * [B]b * ...

ln KGr / (-RT) [11]

where the following abbreviations have been used:

[A] = activity or partial pressure of species A, B, C, etc.
a = stoichiometric coefficient of species A in reaction
 = stoichiometric coefficient of a species in reaction (a, b, c, ...)
R = gas constant = 1.987 cal/(Kmol) = 8.314 J/(Kmol)
T = Temperature in K