VTT Processes GTT Technologies: Use of For Thermochemical Calculations

Use of
for
Thermochemical Calculations
VTT Processes
GTT Technologies
2008
Use of ChemSheet for Thermochemical Calculations
•Chemsheet works as an add-in program of general

thermodynamics in Excel.
•The thermochemical programming library ChemApp is used in
combination with its application-specific thermochemical data.
•The non-ideal solution models cover concentrated aqueous
solutions, dilute and concentrated alloys, liquid slags and molten
salts, solid solutions, non-ideal gases and non-stoichiometric
systems.
•ChemSheet is straightforward and easy to use and requires no
programming skills other than normal Excel use.
Introduction 2/21
•A thermodynamic system consists of a number of phases. Phases

are divided into three groups - the gaseous phase, mixture phases,
and invariant phases.
•Phases have one or more constituents. Phase constituents have
compositions expressed as amounts of a number of components.
•A component is a system-wide entity. Usually components are
elements, but it is also possible for them to be stoichiometric
combinations of elements. For example, in an oxide system based
on calcia and silica, CaO and SiO2, may be used, as well as Ca, Si,
and O.
Definition of Terms 3/21

Two different methods are available:

•Using Global conditions of the System
•Using Streams
Using Global conditions, you merely need to set single values for
temperature and pressure, and enter incoming constituents to define
the initial composition of the system.
A stream is a means for transferring non-reacted matter to a reaction
zone. It has constant temperature and pressure, and contains one or
more constituents. When using Streams, you set the three variables:
– temperature, pressure and composition for each input stream and
set single conditions for temperature and pressure of the system
Using Initial Conditions 4/21

Target calculations are those in which certain target conditions are set, for
instance the value of a heat balance or the presence of a phase at equilibrium.
These conditions can only be satisfied when the value of some other variable, i.e.
the target variable, is adjusted accordingly:
ChemSheet is able to perform two types of target calculations:
•Extensive property target calculations
•Phase target calculations
An extension of the second type is the One-dimensional phase mapping
calculation.
NOTE Changes in extensive properties are calculated if the Streams method
is used to define the initial conditions.
A phase target calculation enables conditions to be determined for a selected
phase to be present at equilibrium (formation phase target), or the precipitation of
another, unspecified phase, from a specified mixture phase (precipitation phase
target).
Using Targets 5/21

Thermodynamic Data
ChemApp
ChemSheet
Excel Worksheet
ChemSheet Data Flow Diagram 6/21

Read
StepIndex=0
Data-file
Excel Define Name-dialog shows StepIndex=StepIndex+1

the names that are automatically
defined by ChemSheet. Update
Read Inputs Excel worksheet
Tip If you don’t like name StepIndex you
(formulas, tables,
can add a new name that refers to
StepIndex (=StepIndex) and use it. charts, ...)
Calculate Equilibrium
Write Outputs
StepIndex<StepCount
ChemSheet Code Flow Diagram 7/21

Temperature condition. Uses Temperature result. Values are

StepIndex to vary temperature from stored to H1:H12 range. The
100 to 1000 C. first two cells are reserved for
headers, which are automatic-
ally added.
ChemSheet toolbar.
Input streams temperatures,

pressures and compositions. They
may also contain formulas as in Chart for total precipitation as a function of temperature.
temperature condition The chart is linked to the I1:I12 range.
Example Application 8/21

In this case StepIndex-

variable is varied from 1 to
10. Each time it changes all
the Excel formulas and
macros are recalculated
ChemSheet Dialog 9/21

Options Dialog 10/21

1) Enter name for the stream
2) Enter formulas for the

temperature and pressure and
their units.
3) After defining a new stream you can

add any number of consti-tuents to it
with Constituents Dialog.
•Tip Formula can be a constant, contain any

mathematical operations or any Worksheet
functions or user-defined macros. It can also be
a reference to worksheet cell where the actual
value is given.
Defining Streams 11/21

1) Select variable from Option-list
2) Depending on the variable select

Phase, Constituent and Component.
3) Enter formula for the Value.
•Tip It is easier to change the value later if it is

given in a worksheet cell. So it is advised to place
those values directly on worksheet and other values
could be “hidden” inside ChemSheet.
Defining Conditions 12/21

•Enter formula that uses StepIndex and some delta value (here 100 degrees).
Use this method if the value changes gradually.
•Enter Excel worksheet function INDEX that uses StepIndex.

Use this method if the temperature changes in way that is not easy to formulate.
•Tip Instead of worksheet functions you can also use your own macros. Just remember to pass
StepIndex to it as a variable so it is called automatically every time when StepIndex changes.
Function MyFun(StepIndex as Variant) as Variant An example macro macro that returns StepIndex
MyFun = StepIndex
End Function
Using Formulas 13/21
1) Select variable from Option-list
2) Depending on the variable select Phase,

Constituent and Component.
3) Select Output range on worksheet where

to store the values for the selected variable.
NOTE Remember to include enough cells
for all calculation steps.
•Tip Using ALL as Phase, Constituent or

Component name you can output many
values at once.
NOTE Remember to include enough
columns in Output range for all the values
as each value is stored to separate column.
Defining Results 14/21

•Normally the successive calculation steps are not connected with each other.
•You can connect successive calculations steps by using “Add previous equilibrium as
stream”-option. The results from previous equilibrium are added automatically to the next
calculation.
Stream1, Stream2 Stream1, Stream2 Stream1, Stream2 Schematic example of a model with
StepIndex = 1 StepIndex = 2 StepIndex = 3 three steps and two streams. When
using “Add previous equilibrium as
stream”-option the streams should be
inputted only to the first “step”. Then
the results from the first step are
T1,p1 T2,p2 T3,p3 automatically added to subsequent
X1i X2i X3i steps.
•NOTE You have to make sure not to add streams for each calculation step as then they would be
added more than once. You should activate the constituents for each stream only at that step in which
they should be inputted.
See the Pipe.xls example
in \Samples directory and
the next slide
Using ”Add previous equilibrium as stream”-optio 15/21

n
This example uses temperature as a

target variable. Enthalpy change for
each step is calculated using heat
transfer from gas to ambient air
through pipe wall. Gas cools down as
it exchanges heat with the
surroundings. At the middle of the
pipe an additional air feed is
introduced.
Stack Pipe 16/21

Hotwall-reactor (CVD-reactor) for deposition of polycrystalline silicon by thermal decomposition
from SiHCl3-H2 gas is simulated. The silicon is deposited and grown on the surface of a disk-like
substrate that is heated by radiation through quartz glass wall.
In the model the reactor is
divided into two separate
regions: the bulk region
and the stagnant surface
region. The deposition is
assumed to be controlled
by the mass transfer from
the bulk to the surface and
the compositions of the
bulk and the surface are
assumed to be in local
equilibrium.
Hotwall-reactor 17/21
Steels contain additions of aluminium (grain
refining) and sulphur (machinability). In
both cases nozzle clogging can occur during
continous casting. Depending upon the O-
and Ca-content of the steel, one can find at
a given temperature either, solid aluminates,
aluminate + liquid oxide, liquid oxide only,
or liquid oxide + CaS-precipitate in
equilibrium with the liquid steel. A
ChemSheet model has been made that
generates two-dimensional phase diagram
where O- and Ca contents are varied at a
given temperature. The chart in figure has
been generated by doing five separate target
calculations with different O-contents to
find all the phase transitions between a
given Ca-range.
Slag Window 18/21

The properties of Pb-Ag-Sb-alloys were studied with ChemSheet. An applied phase diagram was
produced together with description of heating experiments. The range of partial melt is of interest
as the alloy is used for temperature mapping in nuclear reactors.
The phase equilibria of the ternary
Pb-Ag-Sb alloy were calculated with
0.4 and 2 weight-% Ag. The
narrowing solidus-liquidus range
with the increasing content of silver
is shown. The solidus curves (dotted
lines) for each Ag- percentage can
be traced with a single target
calculation where the activity of
liquid is set to unity and Sb-content
is the target variable. The SGTE-
data was used for the excess Gibbs
energies of the alloy.
Melting Points for Pb-Ag-Sb-Alloys 19/21

18 100
16 90
Wt % Zn, 10*Wt % Pb
14 80
12 70
60
10
50
8
40
6 30
4 20
2 10
0 0
0 20 40 60 80
time (min)
10*Pb in slag(%) Zn in slag (%) % Zn removed % Pb removed
Slag-Fuming Process for Zinc Oxide Recovery 20/21

•CHEMICAL RECOVERY CYCLES
•SOLUBILITY OF AIR GASES (O2 in bleaching liquors)
•pH & SOLUBILITY IN WET END PROCESS SOLUTIONS
•pH of PROCESS STREAMS
•OSMOTIC COEFFICIENT OF WATER
•ION EXCHANGE BETWEEN FIBERS AND FILTRATE
•DONNAN-EQUILIBRIA IN IONIC MEDIA
•HYDROMETALLURGIC LEACHING
•TiCl4-BURNER SIMULATION
•COMBUSTION MODELLING
•STACK GAS MODELS (impurities such as Hg, As, etc.)
•CVD PRODUCTION OF ULTRA-PURE SILICON
•VAPOUR PRESSURE OF Hg IN AMALGAMS
•MELTING POINTS & EUTECTICS FOR ALLOYS
•FORMATION OF ZINC FUME IN Pb-SMELTING
•TEMPERATURE & HEAT IN REACTIVE SYSTEMS
•DRYWELL MODELS FOR NUCLEAR PLANT SAFETY
•PHASE STABILITY IN STEEL-MAKING
Reference Applications 21/21

VTT Processes GTT Technologies: Use of For Thermochemical Calculations

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Use of

•Chemsheet works as an add-in program of general

•A thermodynamic system consists of a number of phases. Phases

Definition of Terms 3/21

Two different methods are available:

Using Initial Conditions 4/21

Using Targets 5/21

ChemSheet Data Flow Diagram 6/21

Excel Define Name-dialog shows StepIndex=StepIndex+1

ChemSheet Code Flow Diagram 7/21

Temperature condition. Uses Temperature result. Values are

Input streams temperatures,

Example Application 8/21

In this case StepIndex-

ChemSheet Dialog 9/21

Options Dialog 10/21

1) Enter name for the stream

2) Enter formulas for the

3) After defining a new stream you can

•Tip Formula can be a constant, contain any

Defining Streams 11/21

1) Select variable from Option-list

2) Depending on the variable select

3) Enter formula for the Value.

•Tip It is easier to change the value later if it is

Defining Conditions 12/21

•Enter Excel worksheet function INDEX that uses StepIndex.

1) Select variable from Option-list

2) Depending on the variable select Phase,

3) Select Output range on worksheet where

•Tip Using ALL as Phase, Constituent or

Defining Results 14/21

Using ”Add previous equilibrium as stream”-optio 15/21

This example uses temperature as a

Stack Pipe 16/21

Slag Window 18/21

Melting Points for Pb-Ag-Sb-Alloys 19/21

Slag-Fuming Process for Zinc Oxide Recovery 20/21

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