REAL for Windows

Computer modeling of complex chemical

equilibrium at high pressure and temperature

Version 3.0 User's Guide

 1983-2001, Belov G.V.

Moscow
CONTENTS
CONTENTS ........................................................................................................................................................... 1

INTRODUCTION ................................................................................................................................................. 2

ALGORITHM ....................................................................................................................................................... 3

EQUATION OF STATE ....................................................................................................................................... 4

ENVIRONMENT .................................................................................................................................................. 5
SPEED BUTTONS ................................................................................................................................................... 5
EQUILIBRIUM SPECIFICATION ................................................................................................................................ 6
SOURCE COMPOSITION.......................................................................................................................................... 7
SUBSTANCES ........................................................................................................................................................ 8
RESULTS OF CALCULATIONS ................................................................................................................................. 8
ANALYSIS ........................................................................................................................................................... 11
SETTINGS............................................................................................................................................................ 12
VISUAL ANALYSIS, PLOTTING CHARTS................................................................................................... 13

WARNINGS......................................................................................................................................................... 14

NONEQUILIBRIUM CONSIDERATIONS ..................................................................................................... 14

THE DATABASE ON THE SOURCE COMPONENTS ................................................................................. 15

GENERAL ASSUMPTIONS CONCERNING COMBUSTION ..................................................................... 16

ROCKET PERFORMANCE CHARACTERISTICS ...................................................................................... 17

"FROZEN" AND "EQUILIBRIUM" PARAMETERS .................................................................................. 17

HOW TO ...? ........................................................................................................................................................ 18

REFERENCES .................................................................................................................................................... 21

1
Introduction
This manual contains information about REAL - a general thermodynamics code,
intended for computer simulation of chemical equilibrium in the complex chemically reacting
systems at high temperature (up to 6000 K) and high pressure (up to 600-800 MPa). The
software makes it possible to find chemical and phase composition of an arbitrary system at
assigned conditions. It also allows calculation of thermodynamic and thermophysical
properties.
REAL is derived from an older version of ASTRA - well known in Russia a computer
program, [1], used for calculation of equilibrium characteristics, chemical and phase
composition of arbitrary thermodynamic systems.
The algorithm of the program is based on the fundamental thermodynamic principle of
entropy maximum. Such an approach provides a possibility of a generalized description of any
high-temperature system, using the fundamental laws of thermodynamics only. The method,
algorithm and computer code are original and were worked out in Moscow State Technical
University and Glushko Thermocenter of the Russian Academy of Sciences, [1,2,3].
Only two thermodynamic parameters and mass content of chemical elements in the
system are to be assigned to find equilibrium composition and related properties of the
system. Any pair of the six equilibrium parameters may be assigned:
p - pressure, T - temperature, V - volume, H - enthalpy, S - entropy, U - internal energy.
Calculation of the adiabatic expansion parameters down to given pressure or volume is
possible too. Modeling is possible for partially non-equilibrium systems.
To accomplish the computer simulation the researcher can choose one of the following
equations of state (EOS):
• ideal gas EOS;
• virial EOS (with three coefficients);
• EOS proposed by V.I. Nedostup, [5].
REAL allows to determine
• theoretical rocket performance for both equilibrium and frozen compositions during
expansion (velocity of flow, specific impulse, throat characteristics, an area ratio
etc.), freezing temperature can be varied;
• powder characteristics (powder force, covolume);
• equilibrium and frozen sound velocity;
• transport properties of the combustion products (dynamic viscosity coefficient,
thermal conductivity);
• partially equilibrium composition with assigned concentrations of several
compounds;
• heat of combustion at V = const (in equilibrium and frozen assumptions).
REAL allows to plot curves on the screen, thus visualizing the results of modeling.
In order to facilitate the tedious procedure of input source species formulae it is
possible to use the database of the source components, which contains chemical formula of
the component, its heat of formation, brief name for a quick search and full name.
Thermodynamic properties of individual species are stored in a database. The database
contains information about thermodynamic, thermochemical and thermophysical properties of
2500 species made up by 79 chemical elements. The main body of the database consists of the
information from [6-11]. The database welcomes improvement and expansion. Special service
software (ASTD) is available for the interactive access to database information: contents
review, extraction of properties of the species given, new data insertion or verification. ASTD
is shipped separately!

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 Limits. Condensed substances can form only single-component nondiluting phases.
REAL can handle up to 600 reaction products, made up by up to 20 chemical elements,
including about 50 single condensed substances. Current working matrix dimension is
70 = 6 + M + R, where M - number of elements in the system, R - number of phases.
The most distinguishing feature of REAL is its ability to take into consideration
intermolecular forces of the gas species, significant at high pressures. This ability makes it
possible to calculate equilibrium thermodynamic properties including values of such fuel
characteristics as impulse, powder force and the chemical composition of combustion
products more reliably than in ideal gas assumption.
Now two versions of REAL - for DOS and for Windows are available. DOS version
requires approximately 1 Mbyte disk memory and 580 Kbyte RAM. Windows version needs
about 2 Mbyte disk memory and 4 Mbyte RAM.

Algorithm
An object of examination in present work is a thermodynamic system that interacts
with environment by means of heat and material exchange. We will consider the
thermodynamic equilibrium as some final state of a thermodynamic system insulated from the
external medium, i.e., there exists thermal, mechanical and chemical equilibrium in each point
of the system and there are no flows. In practice, the requirement of insulation means that the
processes leading to equilibrium occur faster than the changes on the system’s boundaries
(external change of pressure, temperature and chemical composition, etc.) take place. We will
suppose also that the system contains only one gas phase and several single-component
condensed phases.
From the second law of thermodynamics, it follows that entropy of insulated system
achieves maximum at the state of equilibrium. As it was already mentioned, any part of
equilibrium system might be treated as insulated from the external influence, so, to find the
equilibrium parameters of the system it is necessary to detect the coordinates of constrained
maximum of entropy. In other words, finding out such values of concentrations of substances
ni is necessary that maximize the function S(U, V, n) subject to the constraints, imposed by the
laws of mass and energy conservation and the fact that concentrations of substances cannot be
negative.
To find out the unknown concentration values we use Lagrange multipliers method.
Lagrange function in our case is
L = S + (U 0 − U (T ,V , n))lU + ( H 0 − H (T ,V , n))lH + ( S 0 − S (T ,V , n))lS +
c N

 ( aji ni − bj)lj + ( pV − R0Tng Z )lV + ( P1 − a1)lP1 + ( P2 − a 2)lP2,

j =1 i =1

here U0, H0, S0 - equilibrium values of internal energy, enthalpy and entropy respectively, li -
Lagrange multipliers, p, T, V - equilibrium values of pressure, temperature and volume, ng -
number of moles of the gas phase, R0 - universal gas constant, Z - coefficient that takes into
consideration real properties of the gas phase, P1, P2 - thermodynamic parameters that define
equilibrium, a1, a2 - numerical values of these parameters, c - total number of elements plus
electroneutrality equation, N - total number of substances in the system, aji - quantity of atoms
of element j in substance i, bj - abundance of element j in the system.
Equations for U0, H0, S0 and chemical potentials of the gas substances include items
that take into consideration intermolecular forces (residual items).
General set of equations is obtained by differentiating L by all independent variables,
taking into consideration constraints, and equating the result to zero. It includes six equations

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for the thermodynamic parameters, c equations of the elemental abundance, and r equations
for condensed substances (r - quantity of condensed phases).
The resulting set of equations is a nonlinear one. To find the solution, we fulfill the
following sequence of steps:
1. calculate equilibrium composition in ideal gas assumption (all residual items have zero
values, Z = 1) using Newton-Raphson method;
2. calculate values of residual items and Z value with the use of results of the previous step; if
volume is not assigned, then before the residual items calculation find volume, matching
selected real gas EOS;
3. find solution in real gas assumption, using calculated values of residual items, the
algorithm of calculations is the same as in step 1;
4. if relative difference between results of two successive steps is less than given value 0,
then stop calculation process, else go to step 2.
Steps 1. - 4. allow to accomplish computer modeling of the thermodynamic system in
real gas assumption as quick as possible, using all advantages of the perfect algorithm of
calculation equilibrium parameters in ideal gas assumption [1].

Equation of state
REAL allows to use three equations of state for the gas phase in calculations:
- ideal gas EOS
p =  *R0 * T,
where  - density, R0 - universal gas constant;
- virial EOS
p =  *R0 * T(1 + B *  + C * 2),
where B, C - virial coefficients;
- EOS, proposed by V.I.Nedostup
p =  *R0 * T[1 + B(T0) *  / (1 -  / 0)],
where T0 = T/(1 -  / 0), 0 - density at zero temperature, B(T0) - second virial coefficient.
The last two equations of state adequately describe gas phase behavior up to pressure
values 600 - 800 MPa. This limitation is conventional one, because sometimes calculations
may be carried out at higher pressure values. Indeed for Nedostup EOS upper limit is defined
by the relation /0, which must be less than 0.9. Virial EOS has not an exact upper
boundary, and evaluating its reliability at pressures higher than 600 MPa or at low
temperatures is difficult. From theory it follows, that virial EOS is valid if density value is
lower than critical one. However, the latter is usually unknown for complex mixtures of
combustion products. Being compared, these two EOS display the same p() dependence up
to pressure 300 MPa ( = 0.2 g/cc).
Usually, at higher density Nedostup EOS shows more rapid growth of pressure than
virial EOS. It can be explained by the fact that at high density three coefficients in virial EOS
cannot adequately describe gas phase behavior, and fourth and fifth coefficients need to be
used. We think that using virial EOS is reasonable if p < 600 MPa and T > 1000 K. For lower
temperature values or higher pressure values we recommend Nedostup EOS. We consider it
very useful for the researcher to have at disposal two real gas EOS for study of the high
pressure systems.

4
Environment
The source information for the calculations and the results of calculations are placed
on the pages of a "Notebook", Fig. 1. To select necessary page just click on the tab in the
bottom of the notebook or press [Alt/Num], where Num - figure from 1 to 5.
Page one ("Equilibrium specification") is intended for the input of parameters, which
specify equilibrium and their values. The components, which form the source system, and
their amounts are to be typed in the table "Source components".
Page two ("Substances") displays list of substances, selected from the database
according to the source components. If no source component is specified, the list is empty.
One can expel some substances from the system of even assign concentration for some
substances if he has reasons for that.
Page three ("Results") displays results of calculations (if there are any). Results cannot
be edited. If necessary, a quick search for a given string can be accomplished.
Page four ("Analysis") is intended for detailed examination of the results obtained.
Page five ("Settings") allows modifying additional parameters, which define equation
of state, mode of calculation, units of parameters in the file of results, template options and
values.

Speed buttons
Speed buttons are located on the panel in the upper part of the window. They allow
carrying out file operations, starting calculation, view information about the elemental
composition and total enthalpy of the system, etc.

Fig. 1

5
 Open - opens an existing file. Action of this button depends on the number of the page
opened. For pages 1), 2) and 4) this button allows to open data file, for page 3) - open file of
results, and for page 5) - a configuration file.
New - creates a new file. For pages 1), 2) and 4) this button allows to create a new
data file, for page 5) - a new configuration file.
Save - saves file. For pages 1), 2) and 4) this button allows to save data file, for page
5) it allows to save the configuration file.
SaveAs - allows choosing the name of the file. For pages 1), 2) and 4) this button
allows to save data file, for page 5) it allows to save the configuration file.
Delete - allows deleting a data file and all related files (file of results, etc.);
Info - displays information about concentrations of the elements, enthalpy value, sum
of mass fractions, and Oxidizer/Fuel ratio;
Run - starts calculations;
About - displays About window;
Help - shows help;
Exit - allows quitting REAL.

Equilibrium specification
The necessary information for the calculation includes (see Fig. 1):
◼ parameters, that define equilibrium and their values ,
◼ source composition of the thermodynamic system.
To start calculations click button "Run" (or press [Alt/R]).
Results of calculations are placed on page 3) "Results".
The first and second parameters that specify equilibrium can be selected from the
combo boxes under heading "Parameters". To do this, click the left mouse button on the
arrow and select the parameter from the list (if necessary). The drop-down list contains six
parameters:
p - pressure,
T - temperature,
V - volume,
H - enthalpy,
S - entropy,
U - internal energy.
The first combo box contains an additional parameter - Template, which allows
carrying out some routine calculations: calculation of impulse, calculation of powder force
and calculation of the heat of combustion at constant volume.
If necessary, calculation of the adiabatic expansion parameters down to given pressure,
area ratio fa/fthroat or up to given volume can be accomplished. To select adiabatic expansion
parameter (Pa -pressure, Va – volume, Fa/Fthroat – area ratio), click the left mouse button
on the arrow of the third combo box in "Parameters" column and select parameter. To cancel
this option (clear the field), select the blank line from the drop-down list.
Values of parameters that specify equilibrium are to be typed in edit fields under
heading "Values of parameters". One can type a single value or several values (not more than
10) or use step calculations. If several values of parameters are typed, they must be separated
by space, like
10 24.5 123.12
If step calculations are planned, only two values must be present in the list - the first
value and the last value. In that case, calculations will be accomplished in a stepwise mode,

6
starting from the first value, then first value plus step, then previous value plus step, etc.,
while resulting value is less than the last value.
Step value is a number that define the increment (or the decrement if negative) of the
parameter in stepwise calculations. Step value is either positive or negative value.
Units of parameter values (J or cal, MPa or atm, K or C, cub.m/kg or cub. dm/kg) can
be selected by means of three combo boxes under heading "Units of parameters". Click the
left mouse button on the arrow of an appropriate combo box and select the unit necessary.
REAL checks the typed values and tries to prevent random errors, such as negative
temperature or entropy. Hence, it is reasonable to assign parameters first and then type their
values.
If “Template” option was selected, all edit fields must be empty, because template
calculations use predefined values of parameters (see Settings for details). Template mode
calculations are available for
- Specific Impulse calculation (chamber pressure, fuel ehthalpy and exit pressure
given);
- Powder Force calculation (combustion pressure and fuel internal energy are given);
- Heat of Combustion calculation (Specific Volume and fuel internal energy are
given.
“Task name” - an optional parameter. It may be used for some additional comment,
which will be placed into the output file before the results of calculations.

Source composition
Besides the equilibrium parameters, it is necessary to assign elemental composition of
the system, that is to specify how many grams or kilograms of each source component are put
into system. Therefore, here it is just necessary to type into the table "Source components" the
source components' formulas and mass fraction of each component in the system. The total
sum of mass fractions needs not be 1 or 100. The program will calculate elemental
concentrations per 1 kg of the system.
REAL is supplied with a database of source components, the use of which can
significantly simplify a tedious task of typing long formulas (see Source Components
Database). Double click the left mouse button in the table “Source Composition” (Fig. 1) to
select component from the Source Components Database (Fig. 6). “Formula” field in the
selected row must be empty!
It is possible to type enthalpy of the source components in the table "Source
components". In that case total enthalpy of the system will be calculated and may be used as
value(s) of the parameter that defines equilibrium, if the parameter is enthalpy or internal
energy. This possibility is useful for combustion examination.
When typing formulae of components in this window one should use traditional
notation of periodic table of the elements - capital letters of the formula should be written as
capital, and small letters should be written as small as small. The numbers in the formula may
be whole numbers of decimals.
Examples:
CO2, MgH, Al2O3, N53.91 O14.48.
The chemical formulas written in this window are not connected with the substances
formulas in the database. The only thing program needs to know is which elements and in
what quantity are present in the thermodynamic system.
Mass fractions of the source components may be set also as a list of values, separated
by space (Variable Source Components Variant):
1 3 5.5 10.3

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Number of values in the list must be the same for all components in the table, or the list must
contain only one value, which will be constant, while other values change.
Total number of values in the list must not exceed 10!

Another useful feature is stepwise calculation with variable concentration of one or

several source components. To use it, one must specify two concentration values in column
"Mass fraction" (the first and the last) and type the step value in column "Step".
If more than one source component has several values of concentrations then all values
will be changed simultaneously, that is if Component 1 has concentration values (1 3) and
Component 2 - (5.5 1.5), first calculation will be accomplished for Component 1 = 1,
Component 2 = 5.5; second calculation: Component 1 = 3, Component 2 = 1.5. The same is
true for the stepwise calculations.
If both parameter and source composition are variable, the first is changed parameter
value and then source composition value.
In a problem where one of the assigned thermodynamic parameters is enthalpy H or
internal energy U, the enthalpy value computed from values in the "Source components" table
may be assigned to H or U. Then the appropriate parameter value must have zero value. In
calculations instead of zero the parameter value will be used, computed as
X =  Hi * MPi /  MPi
where
Hi - enthalpy of i-th source component,
MPi - mass fraction of i-th source component.
The summation is accomplished for all the source components.

Substances
Page "Substances" (Fig. 2) allows selecting substances, which will be included into
thermodynamic system being modeled. If one does not have special ideas about composition,
selecting all substances from the list is reasonable (default setting).
Buttons to the right side of the page are
“Select All” - selects all substances,
“Unselect All” - cancels selection of all substances,
“Show selected” - shows only selected substances, then changes the caption to “Show
All”,
“Reread” - reads the list of substances from database again.
The column “No” shows ordinal number of the substance.
Column “Mark” shows selection (“*” - selected).
Column “Phase” shows the phase state of the substance (gas or condensed).
Column “Formula" displays formulae of the substances.
Column “Fixed mol.” is used in order to type the known or supposed values of
concentrations (non-equilibrium feature). See also Nonequilibrium considerations.
To select the substance click the left mouse button in field “Mark” near the formula.
Field “Formula Search” allows incremental search of substances in the list by given
formula or its fragment.

Results of calculations
Results of calculations are saved in a file with the same name as data file name and
extension .txt. It is usual ASCII file, and one can look it through or edit or print using any text
editor.

8
 The structure of the file of results for each variant is as follows. In the upper part the
variant name and the date of calculations are written, then stands information about EOS used.
Below are written values of the two assigned thermodynamic parameters and content of
chemical elements per 1 kg of the system. Then go Oxidizer/Fuel ration and Oxygen balance.

Fig. 2

Oxidizer/Fuel ratio is computed as

 =  Vi[ El ]i / Vi[ El ]i ,
Oxidizers Fuels
[El] i - content of the chemical elements in the system, Vi - coefficient (see below).
Oxidizers and their coefficients Vi: F, Cl, Br, I - 1; O - 2.
Fuels and their coefficients Vi: H, Na, Li, K - 1; Mg, Ca, Ba - 2; Al, Fe, B - 3; C, S, Ti,
Si, Sn - 4.
Part of the table under heading "Equilibrium parameters" (Fig.3) contains the
following information:
p - pressure,
T - temperature,
V - volume (V is the sum of volumes of the gas phase and all condensed phases),
S - entropy,
H - enthalpy,
U - internal energy,
M - total number of moles in the system,

9
 Fig. 3
Vg - gas phase volume,
Rg - gas constant,
a" - equilibrium sound velocity,
k" - equilibrium adiabatic exponent,
Cp", Cv" - equilibrium values of heat capacity at constant pressure and volume
respectively;
Mu - dynamic viscosity coefficient,
Lt - thermal conductivity,
Lt" - full thermal conductivity,
Mcond - mass fraction of all condensed substances.
In the lower part of the table, the equilibrium composition is written. At the bottom of the
table there is written information about "frozen" values of Cp - heat capacity at constant
pressure, Cp/Cv, a - sound velocity, k - adiabatic exponent. Some special parameters are
written here too:
FP - "powder force",
Cov - covolume,
PP - "powder potential",
where
FP = Rg * T;
Cov = V - FP/p;
PP = Cv * T.
If necessary (see Settings) rocket performance characteristics are placed into the output file.

10
Analysis
A general outline of the page is displayed on Fig. 4.
Here it is necessary to select X-value (“Parameter” or “Concentration”) and Y-
value(s) (“Concentration” or “Parameter”) to extract corresponding values into the table or
to plot curves.
Selection of the X-value can be accomplished by the left mouse button clicking on a
necessary item.
Selection of the Y-value(s) is accomplished by left mouse button clicking in “Mark”
column against the necessary item(s). Second click here removes the selection. Up to ten rows
can be marked simultaneously.
Default selection for X-value is the first item!
Button “View As Table” allows viewing values of the selected items in a table.
Button “Plot the Chart” allows plotting the curves for the selected items (Y-values) as
function(s) of the selected X-value.

Fig. 4
List “Parameter” contains
p - pressure,
T - temperature,
V - volume,
S - entropy,
H - enthalpy,
U - internal energy,
...........................................................

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 list of elements in the system (in square brackets),
list of source components (formulas).
The last two items allow finding out influence of elemental composition and source
component quantities upon resulting equilibrium parameters of thermodynamic system being
investigated.
List “Concentration” contains formulas of substances included into the system.
NOTE! One should remember which parameters were variable in calculations, because
if two or more parameters were varied, sometimes the resulting chart may be a rather
confusing one. The same is true for the substances included into the system. In brief, if one is
planning to accomplish the graphic analysis, only one parameter may be varied.

Settings
Page “Settings” (Fig. 5) contains several radio groups and the template edit fields.
Here one can set up specific demands for the procedure of calculations and output of the
results.
Group “Output Units” allows selecting two kinds of units for the parameters
presentation in the file of results.
The group “Concentration Units” allows selecting units of concentration in the output
file. Mole parts are calculated only for the gas substances, mole parts for condensed
substances are zero or one. Mass fractions are calculated with respect to all substances in the
system.
The group “Equation of State” allows selecting an EOS for the gas phase.
Group “Composition” allows writing in the file of results only substances,
concentration of which is more, than prescribed in “Cut-off value” edit field.
Group “Results” permits to reduce the quantity of the output information into the text
file (no composition, only three thermodynamic parameters (pressure, temperature, volume)
and Cp”/Cv” ratio).
Group “Template” allows selecting kinds of template calculations among
- Specific Impulse Calculations,
- Powder Force Calculations,
- Heat of Combustion Calculations.
The group “Specific Options” contains several check boxes, which allow or prohibit
- print ideal gas results, if real gas EOS is used in calculations,
- include gas ions into the system,
- calculate throat parameters for rocket performance calculation,
- calculate equilibrium sound velocity, viscosity coefficient and thermal conductivity
coefficient,
- calculate parameters of adiabatic expansion in “frozen” mode, freezing temperature
is defined by value in “Freezing Point” edit field,
- check the total sum of mass fractions of the source components and ask for
confirmation to continue calculations.
The panel “Template Values” contains several edit fields that define the default
parameters for
- Specific Impulse Calculations,
- Powder Force Calculations,
- Heat of Combustion Calculations.
Values H = 0 or U = 0 mean, that in calculations instead of zero will be used total
enthalpy value from the table (see Source Components).

12
 Fig. 5
“Cut-off value” - contains minimum concentration value (mile/kg), which restricts the
output of equilibrium composition into the file of results, if radio button “PrDom” was
selected.
“p(atm)” - specifies external atmospheric pressure, which is used for the specific
impulse calculation.
“Freezing Point” - this is the temperature value, below which combustion products
composition in adiabatic expansion process remains fixed, only phase transitions are allowed.
Button “Highlight color” allows changing the highlight color of the edit fields.
Button “Font color” allows changing the font color in the selected edit fields.
All the settings may be saved in the configuration file real.cfg and will be valid for this
data set and all other data sets in a current directory until they are changed again.

Visual analysis, plotting charts

This window contains a chart and the following buttons - “Log(X)”, “Log(Y)”,
“Print”, “Edit”.
“Log(X)” and “Log(Y)” buttons allow to change scales for X-axis and Y-axis
respectively. These buttons are enabled only when all values on the axis are positive.
“Print” button allows to print the image of the chart area.
“Edit” button provides access to details of the chart (fonts, colors, axis scale, axis
formats, change title, foot, legend, a general outlook of the chart etc.).
To the right side of the chart, there are the label(s), which serve as alternative
(movable) legend. This label(s) may be dragged to any position on the chart using standard
drag-drop technique (press the left mouse button on a label, move a label to the new location

13
and release the button). After resizing or scale changing this label(s) returns to original place.
The captions of the labels may be edited. To call the edit window just click the right mouse
button.
Internal part of the chart (between the axis) may be moved to any direction by pressing
right mouse button on it and mouse moving. The chart may also be zoomed by pressing left
mouse button on the corner of the area and mouse moving. The appearing rectangle will
define the zooming area. To restore the original chart, try the same procedure so that the
mouse cursor (with pressed left button) leaves internal chart area through the left margin or
upper margin.

Warnings
The program analyses and controls all the input information and if something is wrong,
the message will appear on the screen. Some troubles can arise during the preparations for the
calculations:
- total number of species found in the database for given chemical elements is more
than 600;
- dimension of working matrix is more than 70 (system contains too many chemical
elements) - in this and previous cases you are to lessen the number of elements.
Maximum number of iterations allowed is 100. If the calculation process fails to
converge, a corresponding message will appear. Calculations are carried out until maximum
relative error (eps) is more than 10-6.
There are three main situations when calculation process fails.
1. Assigned values of thermodynamic parameters cannot be obtained in reality for
given thermodynamic system.
2. In rare cases, when temperature is not assigned, REAL fails to find the exact
solution because the equilibrium temperature is located near the phase transition point. In this
situation only approximate solution can be found, and after 100 iterations program asks for
confirmation if the current results should be accepted. We recommend accepting the results
and then carrying out a reverse calculation. For example, if direct calculation was carried out
for given p0 and H0, the reverse calculation should be fulfilled for T and p0, where T -
calculated temperature. Then compare enthalpy values from direct (H0) and reverse
calculations. If the difference is not significant, the results of direct calculation can be
regarded as reliable ones.
3. Given pressure is too high or temperature is too low, and the items that take into
consideration intermolecular forces become unrealistic. In this case, none of the two real gas
equation of state can be applied.

Nonequilibrium considerations
See also Substances.
REAL does not take into account the kinetics of the chemical reactions. However, it
provides the possibility to put some constraints on the equilibrium model. Here they are:
1. include some species into the thermodynamic model - is useful when very small
number of species is allowed to form the system;
2. exclude some species from the calculation process that means inhibition of some
chemical reactions;
3. one may assign the fixed concentrations for some species (if one knows these
concentrations from experiments or other sources).

14
The database on the source components
One can get access the database on source components by double clicking the left
mouse button in the table “Source Composition” (Fig. 1), (active row in column “Formula”
of the table must be empty).

Fig. 6
The window for work with the source components database is shown at fig. 6.
There are three tables in the window. The upper left table contains description of
classes. The database is structured for comfortable use. All substances are divided into nine
conditional classes:
1 - Polymers;
2 - Plasticizers;
3 - Explosive fillers;
4 - Fuels;
5 - Oxidizers;
6 - Stabilizers of chemical stability;
7 - Technological additives;
8 - Burning-rate catalysts;
9 - Others.
To show all components irrespective of their class, check the check box “All classes”.
When it is unchecked, only components from active class are displayed.
The lower table contains information about components:
◼ Formula;
◼ Brief name of component;

15
 ◼ Enthalpy of formation at 298.15 K (kJ/kg);
◼ Full name of species,
◼ Molecular mass (g).
Finally, the top right table contains most frequently used data (FUD). Information from
main (lower) table may be transferred into FUD table by pressing “Copy to FUD” button.
Main table and table FUD are independent, i.e. if the data are modified or deleted in one table,
they are not influenced in the other table.
To insert information from the database into "Source components" table, select the
component in one the tables (main or FUD) and press the button "Select". Press "Close" if you
do not want to select any item.
One may edit information about components in either in main table or in FUD table.
To do that in main table, press “Edit” button. To insert the new record press button “Insert”,
to delete selected record – press button “Delete”. Information in FUD table is edited in place.
To move the cursor from field to field in the table use [Tab] - forward,
[Shift/Tab] - back. [Ctrl/Home] - go to the first record, [Ctrl/End] - go to the last record.
The search is performed in an active column down from the current position in a mode
“find the nearest match”, i.e., the program tries to find the first matching text in the active
column.
Button “Find” allows continuing the search of the substring in the active column
down from current position in a mode “find the nearest match”.
If necessary, one can change enthalpy units (J or cal, mole or kg). To do that, click left
mouse button on the arrow of combo box "Enthalpy units" and select appropriate units. After
that, all enthalpy values will be recalculated.
The information may be sorted by formula, by brief name, by full name and by
enthalpy. Use combo box “Order by” to that aim.
Molecular mass is calculated automatically from the component formula, so the
formula must be typed, when new component is added!
Source Components Database, which contains information about formulas and
enthalpies of formation for more than 300 substances, is intended for use with REAL.
Information about components is stored in files CLASS.XXX, COMPONS.XXX,
FUD.XXX, which are located in directory COMPONENTS.

General assumptions concerning combustion

The calculation of thermodynamic and other parameters is based on the following
assumptions: one-dimensional form of the continuity, energy and momentum equations;
complete combustion; adiabatic combustion; zero velocity in the combustion chamber;
homogeneous mixing. For equilibrium expansion, composition is assumed to attain
equilibrium instantaneously during expansion. For frozen expansion, composition is assumed
to remain fixed at the combustion composition starting from predefined freezing temperature.
Computation of equilibrium composition and corresponding thermodynamic parameters
for the combustion at constant pressure or volume is based on an assumption that no heat loss
occurs during combustion process. Therefore, in case of the constant pressure combustion
enthalpy of products remains constant and equals to the enthalpy of reactants. When the
combustion occurs in a closed vessel (volume is constant) internal energy of combustion
products remains constant.
Taking into account the thermodynamic relation
U = H - pV
One can conclude that for the solid or liquid reactants U  H, as pV at atmospheric pressure
and the room temperature is negligibly small.

16
 Value of enthalpy (or internal energy) of reactants can be calculated by formula
X =  Hi  MPi /  MPi ,
i i
where
Hi - enthalpy of i-th source component (reactant) in initial state - usually p = 1 at, T =
298 K, so Hi  Hf(298)i,
MPi - mass fraction of i-th source component.

Rocket performance characteristics

Velocity of flow Wa
Wa = 2 ( H 2 * − Ha ) ,
H2* - enthalpy of the flow in the combustion chamber, Ha - current enthalpy of the flow.
Specific impulse (vacuum) Ivac
Ivac = Wa + pa f 'a = Wa + pa f a / m ,
pa - current pressure, fa - flow area, m  - unit mass flow rate.
Specific impulse (atmosphere) Iatm
Iatm = Wa + ( pa − ph ) f 'a = Wa + ( pa − ph ) f a / m ,
ph - ambient pressure.
Area per unit mass flow rate f’a
f 'a = f a / m .
Characteristic velocity 
 = p2* f 'throat = p2* f throat / m
,
p2* - chamber pressure, fthroat - throat area.
Coefficient of thrust K
K = I(vac) / 
Area ratio
fa / fthroat. .
Mach number M
M = Wa / a,
a - local sound velocity.

"Frozen" and "Equilibrium" parameters.

As it was already mentioned REAL calculates equilibrium and frozen values of sound
velocity, heat capacities and adiabatic exponent. These terms (“frozen” and “equilibrium”) are
not very good, but they are used in practice. Sometimes the questions arise what is the
difference and which value is more valid. Indeed the four parameters Cp, Cv, k and sound
velocity a are the derivatives:
Cp = (H / T ) p ;
Cv = (U / T )V ;
k = (H / U ) S ;
a = (p / ) S ,
where  is density ( = 1/V).
Values of these derivatives may be computed using one of the two assumptions.
1) "Frozen" assumption, implies that the variation of T (or U, or ) does not cause the change
of the chemical composition, i.e. all possible chemical reactions are frozen.
"Frozen" values of Cp and Cv are computed as

17
Cp =  Cpini ,
Cv =  Cvini ,
where Cpi and Cvi are the heat capacities of individual species, ni - equilibrium mole numbers.
In ideal gas assumption
k = Cp/Cv;
a = kngR 0T ,
ng - the sum of mole numbers of the gas species, R0 - universal gas constant.
2) "Equilibrium" assumption, implies that with the variation of T (or U, or ) the chemical
composition changes, i.e., all chemical reactions are possible. To better understand the nature
of "equilibrium" parameters let us consider an approximate algorithm of their calculation
(REAL do not use this algorithm):
to compute "equilibrium" values of Cp and Cv one should
a) accomplish the usual calculation at assigned parameters (say p= 0.1 MPa, T=700 K),
b) accomplish the same calculation but with p=0.1 MPa, T=701 K,
c) Cp" = H/T = H/1,
Cv" = U/T = U/1,
where H and U are the differences of parameters from the calculations b) and a), i.e. the
derivatives can be computed numerically.
The similar algorithm may be used for the calculation of sound velocity a", (V+V, S)
computation should be used as b) step, S and V are taken from step a). Of course, if T or V
are too large the results will be wrong.
The algorithm of the calculations of equilibrium sound velocity, heat capacities and
adiabatic exponent used in REAL has been developed by Prof. B.G. Trusov for the ideal gas.
This algorithm was modified to take into account the real properties of the gas phase.
In some cases, the difference between frozen and equilibrium values may be rather
significant. Of course, the question arises: which assumption is true? Unfortunately, it is
impossible to give the definite answer for an arbitrary system. It depends mostly on the
temperature of the system and the ratio of chemical reactions velocities and the flow velocity.
One can say that at high temperatures the equilibrium assumption is more reasonable.
However, in general case it is the task of the user to decide which assumption is valid. More
extensive theory may be found in books on thermodynamics of the rocket engines or the gas
dynamics of the reacting flows, see [12, 13] for example.

How to ...?
1) ...specify chemical composition of the propellant.
To assign chemical composition of the propellant type the chemical formulae of the
components of the propellant and their mass fractions into corresponding fields of the table
“Source Composition” (page 1 of the "Notebook"). Total sum of the mass fractions need not
be equal to 1 or 100.
2) ...calculate the adiabatic flame temperature at constant pressure (combustion
chamber).
In this case, the equilibrium is specified by given pressure and enthalpy. To assign
equilibrium parameters for the calculation, select “p” as the first parameter and “H” as the
second one from the corresponding combo boxes (page 1 of the "Notebook"), type the
pressure value (in MPa or atm) in the first line on the first page, e.g.,
300
then type the enthalpy value (in kJ/kg or kcal/kg) in the second line, e.g.,

18
 -3520
Then select the proper units in “Units of parameters” combo boxes by the right mouse button
clicking in corresponding fields. Specify composition of the propellant and click “Run” to
start calculations. Select page 3 (“Results”) to view the results.
3) ...calculate the combustion pressure in a closed vessel (bomb).
In this case, the equilibrium is specified by given specific volume and internal energy.
Specific volume can be computed as
V = v/m,
where v - volume of the vessel, m - mass of the propellant (powder). As one can easily notice
V = 1/D, where D - loading density. Internal energy of liquid or solid propellant usually equals
to its enthalpy.
To assign equilibrium parameters for the calculation, select “V” as the first parameter
and “U” as the second one from the corresponding combo boxes (page 1 of the "Notebook"),
type the value of the specific volume (in cub.m/kg or cub.dm/kg) in the first line, e.g.,
0.02
then type the internal energy value (in kJ/kg or kcal/kg) in the second line, e.g.,
-2200
Then select the proper units in “Units of parameters” combo boxes by the right mouse button
clicking in corresponding fields.
The combustion pressure in a closed bomb is usually high enough, so real gas equation
of state should be used in calculations. To pick out a proper equation of state find, item
“Equation of state” on page 5 (“Settings”) and select the virial one (if not selected yet).
Specify composition of the propellant and click “Run” to start calculations. Select
page 3 (“Results”) to view the results.
4) ...calculate the impulse of the propellant.
To assign equilibrium parameters for the calculation, select “p” as the first parameter
and “H” as the second one from the corresponding combo boxes (page 1 of the "Notebook"),
type values of pressure (p) and enthalpy (H) of the system in the first and the second lines,
e.g.,
7
-2140
Then select pressure (Pa) or volume (Va) from the combo box in the third line as a parameter
that specifies characteristics of adiabatic expansion, and in the corresponding edit field type
the value, e.g.,
0.1
Default units for pressure and enthalpy are MPa and kJ/kg. One may change units in
“Units of parameters” combo boxes.
Specify composition of the propellant and click “Run” to start calculations. Select
page 3 (“Results”) to view the results.
5) ...calculate powder force.
To assign equilibrium parameters for the calculation, select “p” as the first parameter
and “U” as the second one from the corresponding combo boxes (page 1 of the "Notebook"),
type values of pressure (p) and internal energy (U) of the system in the first and the second
lines, e.g.,
300
-2481
In that case, the third line is not filled. Default units for pressure and internal energy are MPa
and kJ/kg. One may change units in “Units of parameters” combo boxes.

19
 Specify composition of the propellant and click “Run” to start calculations. Select
page 3 (“Results”) to view the results.
6) ...calculate the enthalpy of the combustion products.
Calculation of the enthalpy of the combustion products is possible if values of any pair
of parameters from the list (p, T, V, S, U) are known. Let us consider the case of known
pressure and temperature. Select “p” as the first parameter and “T” as the second one from the
corresponding combo boxes (page 1 of the "Notebook"), type values of pressure (p) and
temperature (T) of the system in the first and the second lines, e.g.,
0.1
298
Specify composition of the propellant and click “Run” to start calculations. Select
page 3 (“Results”) to view the results.
7) ...use in calculation only selected species.
If one wants to perform calculation with some constrained set of species, select page 2
(“List of Substances”) and remove the undesirable species by clicking the left mouse button
in the corresponding cells of “Mark” column, so that blank spaces were left there (will be
included into the system modeled). Now if one clicks “Run” only those species marked with
‘*’ will be taken into consideration.
8) ...fix concentrations of some species.
If one knows from experiment or any other source the concentrations of some species
in the combustion products, he can correct the results of calculations by setting these
concentrations. To do that, open page 2 (“List of Substances”) and type the known
concentrations of species in the corresponding cells of the column “Fixed mol.” (in mole/kg).
Now if one clicks “Run” the calculation will be performed with the use of this information.
9) ...set and change template parameters.
To set or change template parameters, open page 5 (“Settings”), find the group
“Template Values”. The group contains seven items that specify parameters of the
equilibrium as follows
Specific Impulse Calculation of
p = 4 MPa, H = 0 kJ/kg, Pa=0.1 MPa
Powder Force Calculation
p = 300 MPa, U = 0 kJ/kg
Heat of Combustion Calculation
V = 0.01 cub.m/kg U = 0 kJ/kg
Now type new values of the parameters (if necessary). When one presses the button
“Save”, these new template parameters will be saved in the configuration file real.cfg and
will be valid for this data set and all other data sets in a current directory until they are
changed again. In calculations instead of zero values for H and U will be used parameter
value, computed as
X =  Hi  MPi /  MPi ,
i i

where
Hi - enthalpy of i-th source component,
MPi - mass fraction of i-th source component.

20
References
1. Primenenie EVM dlia termodinamicheskih raschetov meatallurgicheskih processov //
G.B. Siniarev, N.A. Vatolin, B.G. Trusov et al. - M.: Nauka, 1982.- 263p.
2. Belov G.V. Termodinamichesky analiz produktov sgoraniia pri vysokih davleniiah //
Vestnik MGTU.-1993.-No.2.-P.43-46.
3. Belov G.V. Raschet parametrov ravnovesnogo sostoiania mnogocomponentnyh
sistem s ispolzovaniem uravnenia sostoiania realnogo gaza//Izv. vuzov.
Mashinostroenie.-1985.-No.5.-P.69-72.
4. Belov G.V. Thermodynamic analysis of combustion products at high pressure and
temperature. Propellants, Explosives, Pyrotechnics. v.23, No 2, pp. 86-89, 1998.
5. Nedostup V.I., Gal'kevich E.P. New equation of state for real gases. Dokl. Akad.
Nauk SSSR.-1978.-No.2A.-P.179-182.
6. Thermodynamic Properties of Individual Substances. Fourth Edition/Ed. by L.V.
Gurvich, I.V. Veitz, Ch.B. Alcock, v.1. N.Y.: Hemisphere Publishing Corp., 1989.
7. JANAF Thermochemical tables: 3-rd edition. NSRDS-NBS - Washington: US
Gov.Print. Office, 1985.
8. Schick H.L. Thermodynamics of certain refractory compounds. v.1-2. - N.-Y.-
London: Acad.Press, 1966.
9. Barin J., Knacke O. Thermochemical properties of inorganic substances. - Berlin:
Springer-Verlag, 1973, 1977.
10. Fundamental properties of inorganic fluorides. Reference book. (in Russian), Ed. by
N.P.Galkin, Moscow, Atomizdat, 1975.
11. Bolgar A.S., Turtchanin A.G., Phesenko V.V. Thermodynamic properties of
carbides (in Russian).- Kiev, Naukova Dumka,1973.
12. Gordon S., McBride B.J. Computer Program for Calculation of Complex Chemical
Equilibrium Composition, Rocket Performance, Incident and Reflected Shocks and
Chapman-Jouget detonations. NASA, 1971, SP-273.
13. Alemasov V.E., Dregalin A.F., Tishin A.P. et al. Thermodynamic and
Thermophysical Properties of Combustion Products. Moscow, 1971.

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