Composition and thermodynamic properties of thermal plasma up to 50kK

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2007 J. Phys. D: Appl. Phys. 40 3371
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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 40 (2007) 33713385 doi:10.1088/0022-3727/40/11/018
Composition and thermodynamic
properties of thermal plasma up to 50 kK
O Coufal
Brno University of Technology, Department of Electrical Power Engineering, Technick a 8,
616 00 Brno, Czech Republic
E-mail: coufal@feec.vutbr.cz
Received 18 December 2006, in nal form 5 March 2007
Published 18 May 2007
Online at stacks.iop.org/JPhysD/40/3371
Abstract
The initial relations and the description of a method for calculating the
composition and thermodynamic properties of a closed gaseous system in
thermodynamic equilibrium at constant pressure and temperature are given.
The essence of the method consists in the minimization of the Gibbs energy
of a system in ideal state. The calculation algorithm is implemented by the
Tmdgas program in the C++ language. This program is part of the database
system TheCoufal, available to interested parties at
http://www.feec.vutbr.cz/coufal/. The method described was used to
calculate the thermodynamic properties of a system of products of the
dissociation and ionization of H
2
O. The results have been tabulated for
pressures of 1, 5 and 20 bar at temperatures ranging from ambient
temperature to 50 kK.
1. Introduction
A characteristic feature of thermal plasma is the state of
local thermodynamic equilibrium so that in the calculation of
the composition and thermodynamic properties (tmdp in the
following) of thermal plasma the method for calculating
the composition and tmdp of a closed gaseous system in
thermodynamic equilibrium at a constant temperature and
pressure can be used. We assume that temperature T is in
the interval from ambient temperature T
a
= 298.15 K to T
h
=
50 kK and pressure p [p
min
, p
max
], p
min
= 0.01 bar, p
max
=
100 bar. The temperature and pressure limits have been chosen
in agreement with the usual delimitation of thermal plasma
in view of the typical possibilities of employing the existing
plasma generators, for example, [1] and references therein.
Regarded as thermal plasma can be, for example,
a system of the products of dissociation and ionization of
a gas in which an electric arc is burning,
combustion products or combustion products with an
ionizing seed as the working gas of an MHD generator,
and
a system of the products of thermal destruction of a
substance in a gaseous medium and the products of their
reaction with this medium.
The principle of calculating the composition has been
known since 1864, when Guldberg and Waage formulated
the mass action law [2]. An impulse for the development
of calculation methods has been, above all, the possibility
of employing computers and the need to know the tmdp and
transport properties of gases at high temperatures for purposes
of modelling the phenomena in low-temperature plasma. The
calculation of tmdp is closely related to the calculation of the
composition, which is also the starting point in the calculation
of the transport properties. Proposing calculation methods
applicable at high temperatures entail specic problems not
only in connection with the calculation algorithm but also
in connection with input data for the calculation. In the
following, the initial relations and the description of a method
for calculating the composition and tmdp of a system in ideal
state are given. The calculation of composition is based on
the method of minimizing the Gibbs energy of a system,
described for the rst time in [3]. The starting relations for
designing the algorithm of tmdp calculation were published
in [4]. The description of the calculation algorithm does not
go into details because the algorithm was implemented by the
Tmdgas program in the C++ language, and starting from the
day this paper is published the source code of the program
will form part of the database system TheCoufal, which is
available at http://www.feec.vutbr.cz/coufal/ and described
in detail in [5, 6].
0022-3727/07/113371+15$30.00 2007 IOP Publishing Ltd Printed in the UK 3371
O Coufal
2. Closed system
Assume a le DATA is given, which contains standard
enthalpies of formation and standard thermodynamic functions
of individual gaseous substances. The names of these
substances form a set C(DATA) and the substances are made
up of chemical elements from a set E(DATA). C(DATA) will
be referred to as a set of compounds of a le DATA. E(DATA)
has the property that each of its elements is contained in at
least one compound in C(DATA). The subject of our interest
is thermal plasma so that the last element in E(DATA) is
electron e

. Using data from the DATA le it is possible to

calculate the equilibriumcomposition and tmdp of an arbitrary
closed system in the state of ideal gas, whose components are
substances formed by some elements from E(DATA).
A closed system S is taken to mean a pair E(S), b(S)
in which E(S) is a set of elements forming S while b(S) is
the atomic composition of the system.
The set of the components of system S
C(S) = {C
1
, C
2
, . . . , C
N
} C(DATA)
contains substances from C(DATA) that are formed by the
set of elements
E(S) = {E
1
, E
2
, . . . , E
L
} E(DATA).
The total amount of substance of elements E
j
in S is
b
j
> 0, except for e

, since thermal plasma as a whole

is electrically neutral and thus the total amount of e

is
equal to zero (b
L
= 0) in any system. An ordered L-tuple
b(S) = {b
1
, b
2
, . . . , b
L
} is the atomic composition of the
systemS. During an arbitrary process in a closed system,
the composition b(S) does not change.
Each component C
i
of system S can formally be expressed
by means of so-called constitution coefcients a
ji
as a linear
combination of elements
C
i
=
L

j=1
a
ji
E
j
. (1)
Composition n or x of system S is an ordered N-tuple
n = {n
1
, n
2
, . . . , n
N
} or x = {x
1
, x
2
, . . . , x
N
},
where n
i
or x
i
is the amount of substance or mole fraction of
the component C
i
,
x
i
=
n
i
n
, where n =
N

k=1
n
k
.
Any composition n of S must satisfy L mass balance
conditions
N

i=1
a
ji
n
i
= b
j
, j = 1, 2, . . . , L. (2)
Among these conditions, there may be some conditions
represented by a linear combination of the other conditions.
In this case the linearly dependent conditions are left out,
and the corresponding elements in E(S) are omitted. The
remaining elements will be renumbered, and we obtain a set
P(S) = {E
1
, E
2
, . . . , E
M
}, M L, P(S) E(S).
P(S) is called the atomic base of systemS. If conditions (2)
are linearly dependent, the rank of constitution matrix
A =
_
a
ji
_
, i = 1, 2, . . . , N, j = 1, 2, . . . , M, (3)
is smaller than L. The expression of component (1), balance
conditions (2) and matrix (3) depends on whether they are
referred to the set E(S) or to the atomic base P(S). The
rank of the matrix A referred to the atomic base is evidently
equal to M.
3. The Gibbs energy of system
The state of the system is determined by state parameters n,
p and T . The choice of the parameters leads to the so-called
Gibbs energy G = G(n, p, T ) [7,8]. The book [9] presents the
evidence that all tmdp of systemS are completely determined
by G(n, p, T ), and that it holds
G =
N

i=1
n
i

i
.
Hence, tmdp of the system are uniquely dened, if chemical
potentials
i
of all components of the system are dened by
functions
i
=
i
(n, p, T ). In an ideal system [8, 9]

i
(n, p, T )=

i
(T ) + RT
_
ln
p

n
+ln n
i
_
, p

=
p
p
ref
,
where

i
is chemical potential of the component C
i
C(S)
in a standard state, p
ref
is reference pressure. Potential

i
is
given by data from the DATA le, see [5].
Any macroscopic systemthat froma certain instant of time
exists in given (time independent) external conditions, will
inevitably arrive at the state of thermodynamic equilibrium,
in which no macroscopic processes and changes take place.
In the state of thermodynamic equilibrium all (macroscopic)
state parameters remain constant. Hence, for the given p
and T the state of thermodynamic equilibrium of system S
is characterized by its equilibrium composition. According
to [4, 10] the equilibrium composition minimizes the function
G(n, p, T )
RT
=
N

i=1
f
i
(n, p, T ),
where
f
i
(n, p, T ) = n
i

i
(n, p, T )
RT
.
At the given p and T the Gibbs energy G(n, p, T ) is a
convex function of n, whose minimumrefers to an equilibrium
composition. The composition satises the balance conditions
(2) and the amounts of substance n
i
, i = 1, 2, . . . , N,
of individual components must be positive [11]. The
determination of an equilibrium composition requires nding
an extreme point of the Gibbs energy on the set of compositions
which satisfy the given conditions. It is thus obvious that the
equilibrium composition of a system can only exist when the
3372
Composition and thermodynamic properties of thermal plasma
system of mass balance equations (2) has at least one solution.
This is possible only when the rank of matrix A is equal to
the rank of the extended matrix of system (2) (the theorem of
Frobenius [12]) both in the case of M = L and in the case of
L > M.
4. Calculation of equilibrium composition
The method used for the calculation of composition in the
Tmdgas program is the method of successive approximations,
presented in [3], which is extended by:
calculating the rst approximation,
introducing the so-called zero components,
changing the criterion for termination of computation,
calculating with the dominant component and
determining the temperature from which ions need to be
considered in the system.
The principle of the method presented in [3] is the method of
the Lagrange multipliers, applied to the Taylor expansion of the
Gibbs energy, withthe thirdandhigher powers beingneglected.
If n
(k)
is the kth approximation of the sought composition n,
which satises balance conditions (2), then
n
(k+1)
i
= f
i
(n
(k)
, p, T ) + n
(k)
i
_
_
u + 1 +
M

j=1

j
a
ji
_
_
, (4)
where u,
1
,
2
, . . . ,
M
is the solution of a system of M + 1
linear equations
M

=1
b

=
N

i=1
f
i
(n
(k)
, p, T ), (5)
b
j
u +
M

=1
r
j

=
N

i=1
a
ji
f
i
(n
(k)
, p, T ),
j = 1, 2, . . . , M, (6)
in which
r
j
= r
j
=
N

i=1
a
ji
a
i
n
(k)
i
, j, = 1, 2, . . . , M.
From the above relations it is obvious that in the calculation
of the composition of a system it is necessary to consider
matrix A (3) and balance conditions (2) with respect to the
atomic base P(S). In the calculation of the composition
of thermal plasma it is usual to have M = L. The case
L = M may occur at temperatures at which the systemspecies
do not dissociate, for example a system of isomers with the
same summary formula [13, 14]. In the Tmdgas program it is
therefore assumed that both matrix A and balance conditions
have been set with respect to the atomic base. If not, the
calculation is terminated by an error message.
The Tmdgas source code is written in the C++
programming language. The text of program begins with an
extensive comment, which includes a detailed description of
the structure of the inTmdgas input data le, an example of
the inTmdgas le, an example of the outTmdgas output data
le, error messages and notes on the calculation. This is why
only substantial data about the calculation method are given
below. The rst version of the Tmdgas program, which only
contained the calculation of composition, appeared as early as
1976. Since then the program has been repeatedly extended,
upgraded and used many times with success.
To set up the inTmdgas le it is of advantage to
use the above database system TheCoufal [5, 6] but
it is not a necessary condition for using the Tmdgas
program. TheCoufal includes, among other things, the
Choice program, which will create, according to the users
requirements, a substantial part of the inTmdgas le from the
data in the species le, which plays the role of the DATA le.
A drawback of the species le is that it contains data about
substances made up of only elements from E(species) =
{C, F, H, N, O, S, W, Ar, Ca, Cl, Cu, e

}, but according to
[5], an extension can be made in keeping with specic
requirements.
4.1. Calculation of the rst composition approximation
A method is proposed for calculating the rst approximation,
which makes it possible to determine a positive solution of
mass balance equations (2) for L = M. If e

P(S), then
E
M
= e

and M
neut
= M 1, else M
neut
= M. Furthermore,
we assume that the system contains M
neut
components
C
i
j
= a
ji
j
E
j
, j = 1, 2, . . . , M
neut
; a
ji
j
> 0. (7)
This means that for each element, with the exception of e

,
in the atomic base of the system there exists at least one
component represented by this element, either in atomic or
molecular form. This assumption brings no limitations since in
cases in which these components may be omitted their amounts
of substance in equilibrium composition are obtained equal to
zero. When calculating the rst approximation we distinguish
two cases.
1. e

/ P.
From here it follows that a
ji
0, b
j
> 0 for j =
1, 2, . . . , M, i = 1, 2, . . . , N. Let us denote for j =
1, 2, . . . , M
I
j
= {i | a
ji
> 0},
c
j
=

iI
j
a
ji
, (8)
g
k
= min
j=1,2,...,M
b
j
c
j
=
b
k
c
k
. (9)
Let us set n
i
= g
k
for i I
k
. From constitution matrix
A with respect to the atomic base P we leave out the kth
row and ith column for i I
k
. This reduced matrix will
be denoted as A

. The approach applies to matrix A

and
to numbers
b

j
= b
j
g
k

iI
k
a
ji
,
j = 1, 2, . . . , k 1, k + 1, . . . , M. (10)
When carrying out M repetitions, we determine all
numbers n
1
, n
2
, . . . , n
N
. The numbers are positive since
the numbers g
k
determined by (9) are positive.
3373
O Coufal
2. E
M
= e

.
From here it follows a
ji
0, b
j
> 0 for j =
1, 2, . . . , M 1, i = 1, 2, . . . , N and b
M
= 0. Let
us denote
g = min
j=1,2,...,M1
b
j
c
j
,
I
+
M
= {i | a
Mi
> 0}, (11)
I

M
= {i | a
Mi
< 0}, (12)
I
M
= I
+
M
+ I

M
,
c
+
=

iI
+
M
a
Mi
,
c

iI

M
a
Mi
,
where c
j
is dened by relation (8). Since b
M
= 0, sets
I
+
M
and I

M
are non-empty. Let us choose the number q,
0 < q < g. Let us set
n
i
=
q
2 c
+
for i I
+
M
,
n
i
=
q
2 c

for i I

M
.
In the constitution matrix Awe leave out the Mth row and
ith column for i I
M
. The matrix reduced in this way is
denoted as A

. To matrix A

and on numbers
b

j
= b
j
n
i

iI
M
a
ji
, j = 1, 2, . . . , M 1,
we apply the process described in paragraph 1 of this
subsection.
The above method does not make explicit use of
assumption (7). After each step (determination of g
k
via (9)
and n
i
= g
k
for i I
k
) we determine the amounts of substance
of all components which contain the kth element. After this
step we get
b

k
= b
k
g
k

iI
k
a
ji
= b
k
g
k
c
k
= 0
and at the same time b
j
, j = k, will be reduced to b

j
in
accordance with (10), provided there are species in the system
that in addition to element E
k
also contain element E
j
. In the
case the system contains no component (7), we may arrive at
the possibility of determining all amounts n
i
, i I
j
j = k,
while the complete amount b
j
need not be spent. The existence
of C
i
j
assures us that n
i
j
will not be determined before
distributing b
j
among the components. The non-existence of
components (7) in the inTmdgasat temperature T will showby
a warning in the outTmdgas and by the calculation continuing
for the next T .
If the occurrence of ions in the system is assumed, i.e.
E
M
= e

, then the existence of component e

in the system is
not necessary for a correct calculation of the rst composition
approximation. Only rarely, however, can we assume that
the number of free electrons in the system composition is
negligible with respect to the numbers of the other ions in the
system; it is therefore convenient to consider the component
e

in the system. The calculation without e

will be performed
in the inTmdgas but in the outTmdgas there will be warning.
4.2. Zero components and interval of occurrence
Tocalculate the compositionandtmdpof a system, the problem
of choosing the components of the system under consideration
has to be solved. By [11] the mole fraction of an arbitrary
component is in the equilibrium composition of a gaseous
system always positive. Theoretically this means that under
equilibrium composition of an arbitrary gaseous system at a
temperature T andpressure pall the knowncompounds that are
for T and p gaseous will be present in non-zero amounts. The
species known up to now amount to several millions while in
the most frequently used DATA les, i.e. in tables [15] or [8,16
18] are data for less than 2000 or 1400 species, respectively.
The equilibrium composition usually serves as the starting
point for the calculationof the tmdpandthe transport properties
of the system. The properties obtained by calculation are
only an approximation of the reality and determining their
values with great accuracy is therefore superuous. Thus it
is appropriate to choose a positive number z such that system
components with mole fraction lower than z can be neglected.
These components are called zero components.
The concept of zero component is closely associated with
concept of the interval of component occurrence. The interval
of occurrence of component C
i
C(DATA) is an interval of
temperatures
i
= [T
b
i
, T
e
i
] [T
a
, T
h
] suchthat inanarbitrary
system S containing C
i
as its component, for any pressure
p [p
min
, p
max
], and any temperature T [T
a
, T
h
]
i
, it
holds x
i
< z. The determination of the interval of occurrence
is treated in [6], where the number chosen is z = 10
12
, the
same as in this paper. It is for this z that the intervals of
occurrence are determined in the speciesle, which currently
contains data about 450 gaseous compounds. It should be
noted that the number of compounds formed by the elements
from E(species) is in [8,1518] lower than in C(species).
Let us consider an arbitrary b
j
b(S), b
j
> 0; if
e

P(S), then b
M
= 0 and j = M. In the balance
condition
a
j1
n
1
+ a
j2
n
2
+ + a
jN
n
N
= b
j
the constitution coefcients are non-negative integers and for
arbitrary i such that a
ji
> 0 we can write the condition in the
form
n
i
=
1
a
ji
_
_
b
j

N

=1, =i
a
j
n

_
_
.
If we neglect the sum on the right-hand side of this relation,
which is non-negative and lower than b
j
, then
n
i

b
j
a
ji
b
j
x
i

b
j
n
. (13)
If b
j
/n < z, then also x
i
< z and this means that all the
components containing the element E
j
are zero components.
The inequality b
j
/n < z is equivalent to the inequality
b
j
< z n. (14)
It is therefore superuous to consider the element E
j
E(S),
whose amount of substance b
j
in S satises inequality (14).
To be able to use relation (14) already when forming the system
3374
Composition and thermodynamic properties of thermal plasma
S it is necessary to limit n from below since we assume that
z is given. Let us write
b
max
= max
j = 1, 2, . . . , M
b
j
, a
max
= max
j = 1, 2, . . . , M
i = 1, 2, . . . , N
|a
ji
|.
It follows from relation (13) that in C(S) there will be a
component C
k
such that
n
k

b
max
a
max
.
For an arbitrary i it holds n n
i
, so that instead of (14) we
can limit the amount b
j
using the inequality
b
j
< z
b
max
a
max
. (15)
The element E
j
is not included in P(S) if (15) holds.
The representation of a real number in the computer is a
computer number, i.e. a nite number of bits, which inuences
the numerical process and its potentials. This fact was taken
into consideration in the design of the calculation method in
Tmdgas. By the ANSI/IEEE standard (see, for example, [19])
a real number is in double precision represented by means of
64 bits. In this representation the lowest positive number that
will be represented as non-zero is z
min
= 2
1022
.
= 10
308
.
The lowest computer number that is greater than 1 is then
1 + , where machine epsilon = 2
52
.
= 2.22 10
16
.
characterizes the precision with which numbers in the
computer can be represented. It is the minimumnumber that is
not negligible with respect to 1. For a concrete computer and
for a concrete implementation of the programming language
the values z
min
and may differ from the values given, but not
substantially, in view of the following deliberation.
It is obvious that in the course of calculation or in the
resultant composition of the system the value of the amount
of substance of a system component cannot be less than z
min
.
Omitting the C
i
component during the calculation will not
disturb the balance conditions if
a
ji
n
i
< b
j
, j = 1, 2, . . . , M
neut
, (16)
and if E
M
= e

, then it must hold simultaneously

|a
Mi
| n
i
< c
+
. (17)
It holds |a
Mi
| a
max
and we can assume {c
+
} z. If in
relation (16) we take into consideration relation (15), then from
(16) and (17) it follows that omitting the C
i
component during
the calculation will not disturb the balance conditions if
n
i
< z
0
,
where
z
0
=
z
a
max
z
m
,
z
m
=
_
min(b
max
/a
max
, 1 mol) if E
M
= e

,
b
max
/a
max
otherwise.
In double precision for z = 10
12
we have z > 10
28
.
In Tmdgas only those components are considered in the
calculation whose amount of substance does not fall during
calculation below
z
0
=
10
28
a
max
z
m
.
Although a z
0
chosen like this is z
0
z
min
, it is not appropriate
to choose z
0
too small because it is superuous, it prolongs the
calculation and, above all, it makes the calculation numerically
unstable.
To increase the clarity of the results given in outTmdgas
there is a constant z
f
= 10
18
in Tmdgas. In the composition
given in outTmdgas the amount of component C
i
is zero, if in
the calculation result is x
i
< z
f
.
4.3. Termination of the calculation
The resultant equilibrium composition n of a system S is the
limit of a sequence of successive approximations,
n = lim
k
n
(k)
,
determined with the aid of relation (4). In numerical
calculation the limit cannot be determined exactly and
therefore it is assumed that n = n
(k
0
)
. Terminating the
calculation thus consists in determining k
0
. It has been found
that the sequence
d
(k)
= max
i=1,2,...,N
|n
(k)
i
n
(k1)
i
|
n
(k)
i
, k = 2, 3, . . .
has a similar course in all cases. After several approximations
d
(k)
begins to decrease and reaches its minimum d
min
= d
(k
0
)
.
Let d
min
= d 10
o
, where 1 d < 10 and o is an integer.
For k > k
0
we have
d 10
o2
d
(k)
d 10
o+2
.
We can thus regard n
(k
0
)
as a result determined with an accuracy
of d
min
10
4
per cent.
The following criterion has been chosen in Tmdgas for
the termination of calculation. After the calculation of the
kth approximation, beginning with k = 5, the calculation
of d
(k)
is performed. If d
(k)
< 10
4
, the calculation either
terminates (if d
(k)
d
(k1)
) or it continues by determining
n
(k+1)
(if d
(k)
< d
(k1)
). If the condition d
(k)
< 10
4
is not
fullled for any k, 5 k 100, then n = n
(100)
and this result
is regarded as determined with an accuracy of d
(100)
10
4
per cent.
4.4. Calculation with dominant component
System D is a subsystem of system S, D S, if
E(D) E(S) and
the amount of substance b
j
of every element E
j
E(D)
is in D the same as in S.
Component C
i
C(D) is the dominant component if its molar
fraction in the composition of system D differs little from 1.
The accuracy of calculating the composition of system
S is worse than 1% or the matrix of the system of linear
equations (5) and (6) is singular in the calculation when there
exists a systemD S with a dominant component and E(D)
contains at least two elements different from e

. In that case
3375
O Coufal
Figure 1. Composition x of the system W . The mole fraction of the
dominant component H
2
O equals almost to one and is not plotted.
the tmdp of D are approximately the same as the properties
of the dominant component. A consequence of insufcient
calculation accuracy is a noticeable disturbance of balance
conditions (2).
A typical example of a system with dominant component
is the system W of the products of H
2
O dissociation and
ionization at lowtemperatures. Figure 1 gives the composition
of system W at temperatures of up to 700 K. The dominant
component is H
2
O. For T < 535 K the matrix of the system
of equations (5) and (6) is singular, and for 535 K T <
699 K the accuracy of the result of composition calculation
is worse than 1%. Generally, it can be said that the result
of calculating the composition of a system with dominant
component can be accepted at temperatures T T
dis
at which
the mole fraction of the largest component that is not the
dominant component is greater than 10
12
. Temperature
T
dis
depends on p and, in particular, on the dissociation
energy of the dominant component. For T < T
dis
we either
accept that the system contains only the dominant component
or the calculation must be performed with a higher than
double precision. If the system contains only the dominant
component, then its mole fraction is equal to 1. In that case
the Tmdgas program can only express the composition in
other units than 1 (e.g. in the concentration of the dominant
component). The method of setting the calculation of the
composition and tmdp of a system with dominant component
is described in the comment at the beginning of the Tmdgas
program.
4.5. Occurrence of ions in the system
The system is electrically neutral and therefore ions can be
considered in the system only at a temperature that is in
the occurrence interval of both positive and negative ions.
At low temperatures, T < T
ion
, when the proportion of
ions in the composition is insignicant, the system is usually
not neutral, the balance of electric charges in the system
is not fullled. Temperature T
ion
generally depends on the
ionization energy of components and the pressure in the system
whose composition is being determined. Figure 2 gives the
temperature dependence of mole fractions of the four most
signicant ions in system W . Considered most signicant are
Figure 2. Temperature dependence of mole fractions in W .
in this case ions whose mole fraction is greater than 10
22
at a temperature of 1400 K. The magnitude of mole fractions
in gure 2 is very small with respect to the values chosen,
z = 10
12
and z
f
= 10
18
, and the system is not electrically
neutral. Let us write (see (11) and (12))
s
+
=

iI
+
M
a
Mi
n
i
, s

iI

M
a
Mi
n
i
.
In connection with ions the procedure chosen in the Tmdgas
program was as follows:
In the calculation of composition at a temperature T ions
are considered only when T lies in the occurrence interval
of positive and negative ions.
If s
+
< z
f
, the calculation is repeated without ions.
If
|s
+
+ s

|
s
+
> z
bal
(18)
the calculation is repeated without ions.
The fullment of conditions in the two preceding points
is checked only for T < T
bal
, because for T T
bal
the
fullment of the two conditions is assumed.
z
bal
and T
bal
, similar to z
f
, are constants of the Tmdgasprogram.
The interval of the considered temperatures [T
a
, T
h
] is the sum
of three intervals: [T
a
, T
0
), [T
0
, T
ion
) and [T
ion
, T
h
]. For all the
temperatures in the rst interval we have s
+
< z
f
or relation
(18) holds. T
0
is the least temperature for which relation (18)
does not hold. In the second interval there are temperatures
for which (18) holds. For all the temperatures in the third
interval (18) does not hold. The existence of all three intervals
and their magnitudes depend on the magnitudes p, z
bal
and
T
bal
. To determine T
ion
it is necessary to choose T
bal
> T
ion
.
The magnitude of T
0
and T
ion
depends substantially on the
magnitude z
bal
. In double precision for z
bal
10
14
the third
interval is empty, and for a sufciently large z
bal
only the rst
interval is non-empty. Choosing T
bal
= 5 kK, z
bal
= 10
4
will ensure that the interval [T
ion
, T
h
] is not empty and the
mole fraction of the ion with the largest mole fraction in the
system is at temperature T
ion
smaller than z in the pressure
interval under consideration. For example, in the system W ,
for p = 1 atm, we have T
0
= 1476 K, T
ion
= 1628 K.
3376
Composition and thermodynamic properties of thermal plasma
5. Calculation of thermodynamic properties of a
system
5.1. Standard thermodynamic functions
In section 3, the equilibrium composition and the tmdp of
system S are for a given p and T determined by the values
of potentials

i
, i = 1, 2, . . . , N, of components C
i
C(S).
The values

i
(T ) can be substituted by the standard Gibbs
energy values G

i
obtained experimentally or by calculation
(see [5] or [8]). The values G

i
(T ) are either tabulated or they
can be calculated using the relation

i
(T ) = G

i
(T ) =
f
H

i,T
ref
T

i
(T ),
where
f
H

i,T
ref
is the standard molar enthalpy of formation
of component C
i
at reference temperature T
ref
, and

i
(T )
is its molar tempered Gibbs energy (according to [8]) at
reference temperature T
ref
.

i
(T ) determines further standard
thermodynamic functions (STF) of the component C
i
. In
addition to

i
we will concentrate in the following on the
standard molar thermodynamic functions: enthalpy change
H

i,T
ref
(T ) = H

i
(T ) H

i
(T
ref
), entropy S

i
(T ) and thermal
capacity C

p,i
(T ). For T
ref
= 0 K it holds
H

i,0
(T ) = T
2
d

i
(T )
dT
, (19)
S

i
(T ) =

i
(T ) +
H

i,0
(T )
T
, (20)
C

p,i
(T ) =
dH

i,0
(T )
dT
. (21)
For further application, the calculated discrete STF values are
approximated. STF are part of the inTmdgas le and they
are given by the values of dimensionless coefcients
i
,
ik
,
k = 2, 1, 0, 1, 2, 3, which determine the approximation
functions. The approximation function of

i
(T ) is
A

i
(T ) =
i
ln t +
3

k=2

ik
t
k
, t =
T
10
4
K
. (22)
The approximation of the remaining STF is determined by
relations (19)(22). The form of approximation functions
has been chosen according to [8,1618]. The method for
calculating the coefcients
i
,
ik
and the dependence of STF
on T
ref
are discussed in detail in [5]. If the user of the Tmdgas
program is going to use the species le as a data source,
then he need not be concerned with the approximation of STF
and their dependence on T
ref
. Prior to using an approximation
function other than (22) in the inTmdgas it is necessary to
modify the Tmdgas program.
5.2. Thermodynamic properties of a system
The mass of system S is
m =
N

i=1
n
i
M
i
,
Table 1. Tmdp of W for low temperatures; [h] = MJ kg
1
,
[s + RM
1
ln p

] = [c
p
] = kJ (Kkg)
1
.
T (K) h s + RM
1
ln p

c
p
300 12.320 10.493 1.8653
400 12.132 11.034 1.9029
500 11.939 11.465 1.9574
600 11.740 11.827 2.0187
700 11.535 12.143 2.0846
800 11.323 12.426 2.1533
900 11.104 12.684 2.2255
1000 10.878 12.922 2.2981
Figure 3. Pressure dependence of boiling temperature T
boi
of water.
where M
i
is the molar mass of C
i
. The system is closed and
therefore m depends on neither T nor p. The composition of
a system generally depends on p and T , n = n(p, T ). The
volume V = V(p, T ) of a system is determined using the
state equation of ideal gas V = n RT/p. The STF of system
components are functions of T ; let us write
I

i,T
ref
(T ) = [
f
H

i,T
ref
+ H

i,T
ref
(T )].
On the assumption of perfect behaviour the tmdp of the gaseous
system S are represented by
molar mass
M(p, T ) =
m
n
;
specic enthalpy
h(p, T ) =
1
m
N

i=1
n
i
I

i,T
ref
;
specic entropy
s(p, T ) =
R
M
ln
n
p

+
1
m
N

i=1
n
i
(S

i
R ln n
i
); (23)
specic heat capacity at constant pressure
c
p
(p, T ) =
h
T
=
1
m
_
N

i=1
n
i
T
I

i,T
ref
+
N

i=1
n
i
C

p,i
_
, (24)
this relation was modied using relation (21);
expansion coefcient

V
(p, T ) =
1
V
V
T
=
1
T
+
ln n
T
; (25)
3377
O Coufal
Table 2. Tmdp of W for p = 1 bar; [M] = kg kmol
1
, [h] = MJ kg
1
, [s] = [c
p,f
] = [c
p
] = kJ (Kkg)
1
, [T
V
] = [p
T
] = 1.
T (kK) M h s c
p,f
c
p
T
V
p
T
1.20 18.015 10.404 13.354 2.4387 2.4397 1.0000 1.0000
1.60 18.012 9.3724 14.094 2.6841 2.7319 1.0026 1.0001
2.00 17.963 8.1791 14.757 2.8717 3.3447 1.0316 1.0010
2.20 17.874 7.4466 15.106 2.9476 4.0482 1.0802 1.0027
2.40 17.683 6.5253 15.506 3.0126 5.2736 1.1783 1.0067
2.60 17.321 5.2831 16.002 3.0695 7.3129 1.3575 1.0146
2.80 16.699 3.5202 16.654 3.1198 10.554 1.6570 1.0291
3.00 15.729 0.9502 17.538 3.1648 15.465 2.1112 1.0535
3.20 14.369 2.8058 18.748 3.2060 22.460 2.7195 1.0895
3.40 12.686 8.1655 20.370 3.2456 31.374 3.3924 1.1341
3.60 10.889 15.363 22.424 3.2866 40.305 3.9046 1.1748
3.65 10.456 17.424 22.993 3.2974 42.066 3.9722 1.1820
3.70 10.039 19.564 23.575 3.3085 43.475 4.0074 1.1872
3.75 9.6416 21.764 24.166 3.3197 44.457 4.0082 1.1904
3.80 9.2667 24.001 24.758 3.3312 44.954 3.9739 1.1913
3.85 8.9170 26.251 25.346 3.3427 44.930 3.9057 1.1899
3.90 8.5941 28.486 25.923 3.3543 44.379 3.8066 1.1863
3.95 8.2987 30.680 26.482 3.3659 43.325 3.6808 1.1807
4.00 8.0308 32.811 27.018 3.3772 41.819 3.5336 1.1734
4.20 7.2137 40.336 28.856 3.4188 32.904 2.8477 1.1337
4.40 6.7202 45.932 30.159 3.4516 23.289 2.2194 1.0929
4.60 6.4338 49.808 31.022 3.4755 15.916 1.7676 1.0613
4.80 6.2683 52.471 31.589 3.4928 11.095 1.4776 1.0398
5.00 6.1714 54.371 31.977 3.5049 8.1530 1.2996 1.0260
5.50 6.0648 57.493 32.575 3.5260 4.9959 1.1020 1.0097
6.00 6.0300 59.722 32.964 3.5416 4.0995 1.0406 1.0042
7.00 6.0090 63.614 33.564 3.5663 3.8496 1.0140 1.0013
8.00 5.9952 67.645 34.101 3.5894 4.3233 1.0255 1.0014
9.00 5.9637 72.540 34.676 3.6224 5.6445 1.0725 1.0037
10.0 5.8897 79.395 35.396 3.7043 8.3468 1.1785 1.0097
11.0 5.7427 89.900 36.394 3.8906 13.046 1.3718 1.0219
12.0 5.4938 106.33 37.819 4.2616 20.242 1.6678 1.0423
13.0 5.1330 131.21 39.805 4.8914 29.852 2.0425 1.0706
14.0 4.6868 166.33 42.403 5.7814 40.271 2.4017 1.1011
14.5 4.4513 187.60 43.895 6.2878 44.636 2.5270 1.1136
15.0 4.2215 210.73 45.463 6.7947 47.605 2.5896 1.1220
15.2 4.1333 220.32 46.099 6.9900 48.275 2.5942 1.1239
15.5 4.0070 234.88 47.047 7.2677 48.653 2.5784 1.1250
15.7 3.9273 244.60 47.670 7.4396 48.473 2.5533 1.1246
16.0 3.8155 259.03 48.580 7.6732 47.570 2.4955 1.1223
16.5 3.6512 282.13 50.003 7.9878 44.578 2.3556 1.1145
17.0 3.5153 303.38 51.272 8.2036 40.250 2.1819 1.1033
18.0 3.3198 338.69 53.292 8.3734 30.374 1.8224 1.0773
19.0 3.2014 364.68 54.700 8.3089 22.046 1.5345 1.0544
20.0 3.1314 383.69 55.676 8.1422 16.396 1.3406 1.0378
21.0 3.0895 398.21 56.385 7.9566 12.953 1.2200 1.0267
22.0 3.0636 410.09 56.938 7.7902 11.008 1.1481 1.0195
23.0 3.0465 420.56 57.404 7.6559 10.084 1.1082 1.0150
24.0 3.0338 430.53 57.828 7.5551 9.9785 1.0920 1.0125
25.0 3.0223 440.80 58.247 7.4857 10.712 1.0976 1.0116
26.0 3.0092 452.29 58.698 7.4459 12.453 1.1277 1.0124
27.0 2.9917 466.11 59.219 7.4358 15.396 1.1865 1.0153
28.0 2.9670 483.48 59.850 7.4571 19.536 1.2744 1.0203
29.0 2.9332 505.43 60.620 7.5111 24.400 1.3811 1.0269
30.0 2.8904 532.18 61.527 7.5959 28.954 1.4830 1.0337
30.5 2.8665 547.12 62.020 7.6478 30.715 1.5228 1.0365
31.0 2.8415 562.81 62.531 7.7042 31.951 1.5510 1.0386
31.5 2.8162 578.97 63.048 7.7634 32.582 1.5657 1.0400
32.0 2.7911 595.29 63.562 7.8237 32.591 1.5664 1.0404
32.5 2.7670 611.46 64.063 7.8836 32.018 1.5540 1.0399
33.0 2.7441 627.23 64.544 7.9415 30.953 1.5303 1.0387
34.0 2.7037 656.70 65.425 8.0472 27.837 1.4603 1.0344
35.0 2.6710 682.74 66.180 8.1362 24.239 1.3784 1.0290
36.0 2.6456 705.28 66.815 8.2081 20.926 1.3013 1.0237
37.0 2.6262 724.83 67.351 8.2656 18.313 1.2384 1.0192
38.0 2.6112 742.19 67.814 8.3127 16.551 1.1931 1.0157
39.0 2.5992 758.22 68.230 8.3533 15.659 1.1656 1.0133
3378
Composition and thermodynamic properties of thermal plasma
Table 2. (Continued)
T (kK) M h s c
p,f
c
p
T
V
p
T
40.0 2.5887 773.79 68.624 8.3912 15.615 1.1557 1.0121
41.0 2.5787 789.73 69.018 8.4301 16.404 1.1626 1.0120
42.0 2.5679 806.87 69.431 8.4733 18.008 1.1860 1.0130
43.0 2.5556 826.00 69.881 8.5239 20.379 1.2250 1.0150
44.0 2.5410 847.85 70.383 8.5844 23.397 1.2773 1.0180
45.0 2.5235 872.93 70.947 8.6564 26.820 1.3384 1.0217
46.0 2.5031 901.50 71.574 8.7405 30.284 1.4014 1.0257
47.0 2.4800 933.37 72.260 8.8356 33.344 1.4577 1.0294
48.0 2.4551 967.91 72.987 8.9387 35.570 1.4989 1.0323
48.5 2.4422 985.88 73.359 8.9921 36.271 1.5119 1.0334
49.0 2.4293 1004.1 73.734 9.0459 36.670 1.5193 1.0340
49.5 2.4165 1022.5 74.107 9.0996 36.765 1.5209 1.0344
50.0 2.4040 1040.8 74.475 9.1525 36.568 1.5171 1.0343
isothermal compressibility

T
(p, T ) =
1
V
V
p
=
1
p

ln n
p
. (26)
The above relations were taken from [7, 20, 21] and
modied. Tmdp characterize the system when the pressure
or the temperature changes. The terms for the calculation
of c
p
,
V
,
T
contain partial derivatives of the composition
n(p, T ). There are two extreme possibilities of changing
p or T . The change is so slow that at any instant of
time the system composition can be regarded as equilibrium
composition. In this case the derivatives of composition are
generally different from zero and the respective tmdp are then
considered equilibrium tmdp. In the other extreme case the
change of p or T is so rapid that the composition does not
change and its derivatives with respect to p or T are equal
to zero. In this case the respective tmdp are referred to as
frozen, which is denoted by the subscript f in the symbol of
the quantity. From (24), (25) and (26) it follows
c
p,f
=
1
m
N

i=1
n
i
C

p,i
,
V,f
=
1
T
,
T,f
=
1
p
.
The above tmdp determine further tmdp of S. The
specic Gibbs energy, the internal energy and the free energy
are, respectively,
g = h T s, u = h p v, f = g p v,
where v is the specic volume
v =
V
m
=
RT
Mp
;
the equilibriumand the frozen specic heat capacity at constant
volume are
c
V
= c
p
T v

2
V

T
, c
V,f
= c
p,f

R
M
;
the equilibrium and the frozen sound velocity are
=
_
v c
p
c
V

T
,
f
=
_
p v
c
p,f
c
V,f
;
and so on. The change in the thermodynamic state of a
system can be in many cases expressed by partial differential
equations. Partial derivatives, so-called differential quotients,
can be formally written as
_
X
Y
_
Z
=
(X)
Z
(Y)
Z
,
where X, Y, Z represent some of the parameters p, T, h, s, v.
It holds
(X)
Y
= (Y)
X
.
According to [20], the differential quotients are dened by
(p)
T
= 1, (p)
h
= c
p
, (p)
s
= c
p
/T,
(p)
v
= v
V
;
(T )
h
= v (1 T
V
), (T )
s
= v
V
,
(T )
v
= v
T
;
(h)
s
= v c
p
/T, (h)
v
= v (c
V

T
+ v
V
);
(s)
v
= v c
V

T
/T.
5.3. Calculation of thermodynamic properties
The calculation of tmdp of system S at pressure p and
temperature T consists in calculating the right-hand sides
of the above formulae. For this calculation, however, it
is necessary to know the values of the potentials

i
(T ) of
all the system components, the system composition and the
composition derivatives. Potentials

i
are determined by the
values of standard enthalpies of formation
f
H

i,T
ref
and STF
of system components. The calculation of composition was
dealt with in section 4. The composition derivatives can by [4]
be determined using the following procedure.
Let n be the equilibrium composition of S for a
given p and T . Let us consider the function F =
F(n,
1
,
2
, . . . ,
M
, p, T )
F =
G(n, p, T )
RT
+
M

j=1

j
_
b
j

N

i=1
a
ji
n
i
_
.
In keeping with the method of Lagrange multipliers, n and the
multipliers
1
,
2
, . . . ,
M
must satisfythe systemof equations
3379
O Coufal
Table 3. Tmdp of W for p = 5 bar; [M] = kg kmol
1
, [h] = MJ kg
1
, [s] = [c
p,f
] = [c
p
] = kJ (Kkg)
1
, [T
V
] = [p
T
] = 1.
T (kK) M h s c
p,f
c
p
T
V
p
T
1.20 18.015 10.404 12.611 2.4387 2.4393 1.0000 1.0000
1.60 18.013 9.3748 13.349 2.6841 2.7120 1.0015 1.0000
2.00 17.985 8.2152 13.995 2.8716 3.1442 1.0182 1.0006
2.20 17.934 7.5471 14.313 2.9474 3.5722 1.0455 1.0015
2.40 17.826 6.7686 14.651 3.0124 4.2671 1.0990 1.0037
2.60 17.625 5.8141 15.032 3.0693 5.3551 1.1938 1.0078
2.80 17.284 4.5904 15.485 3.1196 6.9867 1.3484 1.0152
3.00 16.747 2.9717 16.042 3.1642 9.3352 1.5824 1.0275
3.20 15.970 0.7964 16.743 3.2037 12.581 1.9101 1.0464
3.40 14.930 2.1301 17.629 3.2386 16.863 2.3299 1.0728
3.60 13.653 6.0165 18.738 3.2699 22.148 2.8080 1.1062
3.80 12.227 11.027 20.091 3.2989 27.975 3.2642 1.1421
3.90 11.500 13.966 20.855 3.3131 30.754 3.4465 1.1585
4.00 10.790 17.166 21.665 3.3276 33.163 3.5762 1.1722
4.10 10.116 20.578 22.507 3.3425 34.964 3.6396 1.1818
4.20 9.4923 24.131 23.363 3.3578 35.938 3.6290 1.1865
4.30 8.9305 27.733 24.211 3.3737 35.950 3.5451 1.1857
4.40 8.4363 31.288 25.028 3.3898 34.982 3.3968 1.1797
4.60 7.6515 37.895 26.497 3.4214 30.652 2.9737 1.1558
4.80 7.1058 43.443 27.679 3.4502 24.733 2.5027 1.1244
5.00 6.7414 47.803 28.570 3.4735 19.004 2.0874 1.0941
5.50 6.2898 54.670 29.886 3.5129 9.7063 1.4464 1.0426
6.00 6.1282 58.445 30.545 3.5359 6.0006 1.1883 1.0196
6.50 6.0644 61.049 30.962 3.5516 4.6366 1.0871 1.0097
7.00 6.0358 63.221 31.285 3.5640 4.1378 1.0456 1.0053
8.00 6.0110 67.245 31.822 3.5847 4.0380 1.0238 1.0023
9.00 5.9911 71.495 32.322 3.6078 4.5572 1.0375 1.0024
10.0 5.9554 76.587 32.857 3.6643 5.7611 1.0831 1.0048
11.0 5.8861 83.333 33.499 3.7989 7.9139 1.1720 1.0103
12.0 5.7652 92.831 34.323 4.0844 11.312 1.3174 1.0202
13.0 5.5770 106.45 35.410 4.6078 16.172 1.5250 1.0356
14.0 5.3148 125.65 36.831 5.4320 22.446 1.7843 1.0566
15.0 4.9876 151.62 38.620 6.5443 29.541 2.0584 1.0813
16.0 4.6229 184.55 40.742 7.8058 36.051 2.2824 1.1049
16.5 4.4389 203.21 41.891 8.4131 38.457 2.3523 1.1142
17.0 4.2608 222.86 43.063 8.9560 39.966 2.3845 1.1209
17.5 4.0933 243.00 44.231 9.4041 40.419 2.3762 1.1245
18.0 3.9399 263.09 45.363 9.7368 39.785 2.3293 1.1246
18.5 3.8028 282.62 46.433 9.9447 38.165 2.2500 1.1217
19.0 3.6830 301.13 47.421 10.031 35.775 2.1473 1.1163
20.0 3.4931 333.99 49.108 9.9049 29.803 1.9119 1.1007
21.0 3.3597 360.75 50.415 9.5334 23.857 1.6881 1.0833
22.0 3.2681 382.08 51.408 9.0801 19.017 1.5074 1.0677
23.0 3.2052 399.24 52.171 8.6500 15.507 1.3739 1.0550
24.0 3.1612 413.48 52.778 8.2886 13.156 1.2806 1.0452
25.0 3.1294 425.85 53.283 8.0065 11.724 1.2182 1.0379
26.0 3.1053 437.18 53.727 7.7971 11.038 1.1802 1.0326
27.0 3.0854 448.15 54.141 7.6491 11.025 1.1628 1.0291
28.0 3.0673 459.45 54.552 7.5515 11.695 1.1652 1.0272
29.0 3.0485 471.79 54.985 7.4963 13.105 1.1879 1.0269
30.0 3.0271 485.92 55.464 7.4774 15.284 1.2318 1.0284
31.0 3.0012 502.59 56.010 7.4916 18.149 1.2949 1.0315
32.0 2.9698 522.36 56.637 7.5356 21.413 1.3701 1.0359
33.0 2.9327 545.39 57.346 7.6051 24.584 1.4451 1.0407
34.0 2.8913 571.30 58.119 7.6942 27.072 1.5048 1.0448
34.5 2.8696 585.05 58.521 7.7437 27.902 1.5247 1.0462
35.0 2.8478 599.14 58.926 7.7950 28.404 1.5366 1.0472
35.5 2.8261 613.40 59.331 7.8470 28.566 1.5402 1.0475
36.0 2.8048 627.65 59.729 7.8988 28.401 1.5356 1.0473
37.0 2.7650 655.55 60.494 7.9984 27.225 1.5054 1.0453
38.0 2.7297 681.84 61.195 8.0886 25.271 1.4554 1.0417
39.0 2.6996 705.99 61.822 8.1667 22.997 1.3966 1.0373
40.0 2.6746 727.86 62.376 8.2324 20.793 1.3384 1.0327
41.0 2.6541 747.68 62.866 8.2877 18.923 1.2873 1.0284
42.0 2.6371 765.87 63.304 8.3349 17.535 1.2468 1.0249
43.0 2.6228 782.94 63.706 8.3768 16.696 1.2185 1.0221
3380
Composition and thermodynamic properties of thermal plasma
Table 3. (Continued)
T (kK) M h s c
p,f
c
p
T
V
p
T
44.0 2.6102 799.45 64.086 8.4159 16.427 1.2031 1.0203
45.0 2.5984 815.98 64.457 8.4547 16.728 1.2004 1.0193
46.0 2.5868 833.09 64.833 8.4955 17.582 1.2101 1.0193
47.0 2.5746 851.32 65.225 8.5403 18.954 1.2315 1.0201
48.0 2.5613 871.15 65.642 8.5907 20.778 1.2632 1.0218
49.0 2.5464 892.99 66.093 8.6480 22.944 1.3030 1.0241
50.0 2.5297 917.10 66.580 8.7128 25.291 1.3475 1.0268
F/n
i
= 0 for i = 1, 2, . . . , N, and F/
j
= 0 for
j = 1, 2, . . . , M (see section 4)

i
+ ln n
i
ln n =
M

j=1

j
a
ji
, i = 1, 2, . . . , N, (27)
where

i
=

i
(p, T ) =

i
(T )
RT
+ ln p

,
and the remaining M equations are mass balance conditions
(2) for L = M. It should be noted that also in the calculation
of system composition described in section 4 the method of
Lagrange multipliers was applied but instead of the Gibbs
energy G its approximation was considered in the function F.
Let us now suppose that we want to calculate the
derivatives n
i
/X, where X is p or T and i = 1, 2, . . . , N.
By differentiating equations (27) and (2) with respect to X we
obtain
n
i
X
= n
i
_
_

i
X
+
ln n
X
+
M

j=1
a
ji

j
X
_
_
,
i = 1, 2, . . . , N, (28)
N

i=1
a
ji
n
i
X
= 0, j = 1, 2, . . . , M. (29)
By substituting (28) in (29) and after some rewriting we obtain
M linear equations for M+1 unknowns ln n/Xand

/X,
= 1, 2, . . . , M
b
j
ln n
X
+
M

=1

X
N

i=1
a
ji
a
i
n
i
=
N

i=1
a
ji
n
i

i
X
,
j = 1, 2, . . . , M. (30)
The remaining linear equation
M

=1
b

X
=
N

i=1
n
i

i
X
(31)
will be obtained by substituting (27) in the relation
ln n
X
=
1
n
N

i=1
n
i
X
.
The sought derivatives n
i
/X, i = 1, 2, . . . , N, will be
determined via solving the system of M + 1 linear equations
(30) and (31) and via substituting the solution of these
equations in relation (28). The system of equations (30) and
(31) can be set up and solved only after the calculation of
composition n.
The derivatives n
i
/X can also be calculated approxi-
mately, replacing them by the quotient of differences, if a cal-
culation of two compositions is carried out for close values of
the variable X. This method is made use of, but in addition to
the derivatives n
i
/X being determined only approximately,
this method is more demanding on calculation time.
6. Properties of W
In this section the results of calculating the tmdp of systemW
are given for T [T
a
, T
h
] and T
ref
= T
a
. Tmdp of W can be
used when modelling phenomena in water-stabilized plasma
generators [22, 23]. The set C(W ) contains 33 components:
H
3
O
+
, H
2
O
2
, H
2
O
+
2
,
H
+
3
, H
2
O, H
2
O
+
, HO
2
, HO
+
2
, HO

2
, O
3
, O
+
3
, O

3
,
H
2
, H
+
2
, H

2
, OH, OH
+
, OH

, O
2
, O
+
2
, O

2
,
e

, H, H
+
, H

, O, O
+
, O
2+
, O
3+
, O
4+
, O
5+
, O
6+
, O

.
Data about these components have been taken over from the
species le, their occurrence intervals are incident with
[T
a
, T
h
] for z = 10
12
. The species le used is an extended
and updated version of the original le, which can be viewed on
http://www.feec.vutbr.cz/coufal/. For p = 120 bar and for
T < 720 K the W is a system with dominant component H
2
O.
Table 1 gives the values of some tmdp of W for
p = 120 bar and T [T
a
, 1 kK]. The tmdp h, s+RM
1
ln p

(see (23) for n = 1 mol) and c

p
are practically independent
of p. The other tmdp depend on p provided they depend on
the molar volume v. At temperatures of up to 1 kK we have
M = 18.01528 kg kmol
1
, T
V
= p
T
= 1, and the frozen
tmdp are equal to equilibrium tmdp. Tmdp of W given in this
paper are tmdp of a gaseous system. The systemW is gaseous
at a pressure p if the system temperature T is not lower than
the boiling temperature of water T
boi
at the pressure p. The
dependence of T
boi
on p is illustrated in gure 3 and is plotted
using the data given in [21, 24].
The tmdp of W for temperatures T > 1 kK are given
in tables 24 and in gure 4. For p = 0.01, 1 bar or
p = 5, 20, 100 bar, the functions c
p
(T ),
V
(T ),
T
(T ) have 4
or 3 local maxima, respectively (see gure 4). These maxima
are conected with the changes of the amount of substance of
the systemcomponents whose proportion in the composition is
large. The rst maximumis connected with the dissociation of
H
2
O into H
2
, O
2
, OH, H and O. Further maxima are related to
the appearance of ions H
+
, O
+
, O
2+
and O
3+
. The temperatures
in tables 24 are not equidistant, they have been chosen such
that the values given in the tables represent the tabulated
functions as accurately as possible.
3381
O Coufal
Table 4. Tmdp of W for p = 20 bar; [M] = kg kmol
1
, [h] = MJ kg
1
, [s] = [c
p,f
] = [c
p
] = kJ (Kkg)
1
, [T
V
] = [p
T
] = 1.
T (kK) M h s c
p,f
c
p
T
V
p
T
1.20 18.015 10.404 11.971 2.4387 2.4391 1.0000 1.0000
1.60 18.014 9.3760 12.709 2.6841 2.7016 1.0010 1.0000
2.00 17.996 8.2338 13.345 2.8715 3.0420 1.0114 1.0004
2.20 17.964 7.5982 13.647 2.9473 3.3347 1.0282 1.0010
2.40 17.898 6.8897 13.955 3.0123 3.7807 1.0606 1.0022
2.60 17.775 6.0713 14.282 3.0694 4.4454 1.1169 1.0047
2.80 17.568 5.0923 14.645 3.1200 5.3993 1.2067 1.0090
3.00 17.245 3.8874 15.060 3.1651 6.7165 1.3407 1.0159
3.20 16.775 2.3765 15.547 3.2053 8.4709 1.5283 1.0265
3.40 16.131 0.4655 16.125 3.2407 10.728 1.7749 1.0417
3.60 15.304 1.9507 16.815 3.2715 13.525 2.0776 1.0620
3.80 14.308 4.9793 17.633 3.2982 16.838 2.4206 1.0873
4.00 13.184 8.7108 18.589 3.3213 20.516 2.7707 1.1158
4.20 11.999 13.187 19.681 3.3423 24.205 3.0776 1.1442
4.30 11.410 15.693 20.270 3.3524 25.877 3.1963 1.1569
4.40 10.837 18.355 20.882 3.3626 27.316 3.2823 1.1676
4.50 10.289 21.145 21.509 3.3730 28.430 3.3303 1.1759
4.60 9.7738 24.027 22.142 3.3836 29.138 3.3371 1.1811
4.70 9.2975 26.957 22.773 3.3947 29.383 3.3025 1.1831
4.80 8.8638 29.887 23.390 3.4062 29.141 3.2290 1.1817
4.90 8.4745 32.770 23.984 3.4177 28.428 3.1221 1.1772
5.00 8.1294 35.559 24.547 3.4292 27.297 2.9888 1.1699
5.50 6.9793 47.121 26.758 3.4822 18.556 2.1985 1.1137
6.00 6.4621 54.399 28.029 3.5190 11.169 1.6164 1.0640
6.50 6.2346 58.883 28.749 3.5425 7.2461 1.3113 1.0350
7.00 6.1293 61.993 29.211 3.5585 5.4296 1.1644 1.0198
7.50 6.0766 64.476 29.554 3.5706 4.6152 1.0934 1.0119
8.00 6.0476 66.685 29.839 3.5808 4.2735 1.0587 1.0076
9.00 6.0158 70.891 30.335 3.6007 4.2456 1.0377 1.0041
10.0 5.9894 75.356 30.805 3.6473 4.7700 1.0507 1.0040
11.0 5.9505 80.617 31.305 3.7611 5.8568 1.0917 1.0061
12.0 5.8861 87.306 31.886 4.0119 7.6537 1.1650 1.0109
13.0 5.7851 96.217 32.598 4.4906 10.324 1.2757 1.0190
14.0 5.6384 108.28 33.490 5.2827 13.962 1.4251 1.0309
15.0 5.4425 124.44 34.603 6.4290 18.492 1.6062 1.0467
16.0 5.2013 145.44 35.957 7.8723 23.553 1.8011 1.0656
17.0 4.9273 171.49 37.534 9.4215 28.421 1.9804 1.0857
18.0 4.6403 201.90 39.272 10.800 32.145 2.1096 1.1039
18.5 4.4989 218.29 40.170 11.338 33.296 2.1464 1.1114
19.0 4.3623 235.10 41.067 11.741 33.871 2.1618 1.1173
19.5 4.2328 252.06 41.948 11.997 33.851 2.1559 1.1215
20.0 4.1119 268.86 42.798 12.105 33.261 2.1301 1.1238
21.0 3.8998 300.97 44.365 11.933 30.698 2.0310 1.1234
22.0 3.7286 329.89 45.711 11.391 27.037 1.8949 1.1176
23.0 3.5946 354.98 46.827 10.681 23.165 1.7515 1.1088
24.0 3.4913 376.35 47.737 9.9555 19.677 1.6203 1.0989
25.0 3.4119 394.55 48.481 9.3069 16.841 1.5102 1.0893
26.0 3.3502 410.27 49.097 8.7704 14.700 1.4228 1.0806
27.0 3.3015 424.16 49.622 8.3501 13.198 1.3563 1.0731
28.0 3.2620 436.85 50.084 8.0333 12.262 1.3083 1.0667
29.0 3.2288 448.86 50.505 7.8036 11.842 1.2769 1.0615
30.0 3.1996 460.70 50.906 7.6434 11.915 1.2610 1.0576
31.0 3.1726 472.86 51.305 7.5403 12.486 1.2604 1.0549
32.0 3.1458 485.84 51.717 7.4837 13.561 1.2751 1.0535
33.0 3.1180 500.14 52.157 7.4652 15.122 1.3048 1.0534
34.0 3.0879 516.22 52.637 7.4791 17.089 1.3475 1.0545
35.0 3.0547 534.40 53.164 7.5202 19.300 1.3987 1.0566
36.0 3.0184 554.82 53.739 7.5834 21.510 1.4517 1.0593
37.0 2.9793 577.32 54.355 7.6634 23.434 1.4984 1.0618
38.0 2.9385 601.50 55.000 7.7540 24.811 1.5314 1.0635
39.0 2.8976 626.71 55.655 7.8487 25.475 1.5457 1.0640
40.0 2.8579 652.20 56.300 7.9416 25.396 1.5401 1.0631
41.0 2.8208 677.28 56.920 8.0286 24.674 1.5169 1.0609
42.0 2.7870 701.40 57.501 8.1074 23.498 1.4810 1.0575
43.0 2.7570 724.20 58.037 8.1768 22.088 1.4382 1.0535
44.0 2.7307 745.57 58.529 8.2372 20.651 1.3939 1.0493
45.0 2.7080 765.55 58.978 8.2895 19.350 1.3524 1.0452
3382
Composition and thermodynamic properties of thermal plasma
Table 4. (Continued)
T (kK) M h s c
p,f
c
p
T
V
p
T
46.0 2.6881 784.35 59.391 8.3355 18.298 1.3167 1.0414
47.0 2.6707 802.25 59.776 8.3769 17.567 1.2887 1.0382
48.0 2.6551 819.60 60.141 8.4156 17.196 1.2695 1.0356
49.0 2.6407 836.77 60.495 8.4534 17.199 1.2595 1.0338
50.0 2.6270 854.13 60.846 8.4919 17.576 1.2587 1.0327
7. Discussion of results
There are two groups of algorithms for calculating the
compositionandthermodynamic properties. The startingpoint
for the stoichiometric algorithms is the chemical reactions and
their equilibrium constants; these algorithms are based on the
mass action law. The non-stoichiometric algorithms start from
the fact that the Gibbs energy of a system is minimal for the
equilibrium composition of the system. It has been shown that
the two kinds of algorithm lead to the same result. The main
development of computation methods is connected with the
development of computers in the years 19401980, when it
was necessary to take into consideration the size of computer
memory and the speed of mathematical operations. Results of
the development of this period are summarized, for example,
in a reviewpaper [25] and, in particular, in monographs [4,10].
Withthe present-daylevel of computers, the capacityandspeed
of computers do not play an important role any longer. The
authors of the publication [26] do not cite any of the works
[4, 10, 25] and they regard as their own contribution even what
is given, for example, in [25, 27] and what is perfectly worked
out in [4, 10].
The calculation of composition and tmdp is usually
performed on a computer and thus the calculation result
is affected by the round-off errors and the stability of the
numerical process. It is therefore desirable to tell a correct
result froma worthless result, i.e. a result devaluedbyround-off
errors. Inthis paper, inadditiontothe descriptionof the method
of calculating the composition and tmdp of a gaseous system,
the main attention is devoted to problems of the numerical
stability of calculation and their effect on the interpretation of
calculation results.
With the exception of simple cases, the equilibrium
composition is the limit of a sequence of successive
approximations. It is therefore always necessary to deal with
determining the rst approximation and with the criterion for
terminating the calculation. The criterion for terminating
the calculation proposed in this paper provides, on the one
hand, for terminating a numerically stable calculation while
obtaining the best accuracy of the result, on the other hand,
it provides for interrupting an unstable calculation. The
method for calculating the rst approximation provides non-
zero amounts of substance of all the components considered
at the beginning of the calculation in contrast to the usually
applied method by which the majority of initial amounts
of substance is zero. Initial zero amounts of substance
make the calculation longer because there is an increase
in the number of approximations necessary for obtaining
the result. Extending the calculation time leads to an
accumulation of errors in the computer. From this viewpoint
it is not appropriate to use the calculation result for a given
Figure 4. Temperature dependence of specic heat capacities c
p,f
and c
p
for extreme pressures p
min
= 0.01 bar and p
max
= 100 bar.
p and T as the rst approximation of the calculation for
another pressure and temperature, as is mostly recommended
in the literature. According to [26], in the calculation
of the properties of system W the rst approximation is
calculated only for 10
7
K; for other lower temperatures the
rst approximation is the result for the preceding higher
temperature.
When modelling phenomena in thermal plasma, an
unfavourable effect may appear if the composition and tmdp
are not continuous functions of p and T . Continuity can only
be ensured by choosing sufciently lowvalues of the number z
(see section 4.2) and the corresponding intervals of occurrence.
The calculation of the composition of the dissociation and
ionization products of a substance is unstable at temperatures
at which the substance begins to dissociate or ionize (see
sections 4.4 and 4.5). According to section 4.5, ions in the
system W at a pressure of 1 atm can be considered from
T
ion
= 1628 K. At this temperature the most signicant ions
are H
3
O
+
and H

2
; their mole fractions are 3.909 10
14
and
3.90610
14
. The mole fraction of e

at the temperature T
ion
is 2.390 10
17
. On page 465 of [26] it is said, transition
from plasma to neutral gas is automatically performed when
concentration of free electrons is below 10
10
. In relation
to gure 1 in [26] the term concentration is usually used but
what is concerned here is evidently the mole fraction. Let
us therefore suppose that 10
10
is not the concentration but
the mole fraction; then according to the criterion in [26], at
a pressure of 1 atm there is in the system W T
ion
= 2635 K,
with the mole fraction of e

equal to 1.006 10
10
, and the
mole fractions of ions H
3
O
+
and H

2
are 5.428 10
9
and
5.310 10
9
. In table III on page 466 in [26] the Transition
Plasma to Neutral Gas is between the temperatures 703 K
and 830 K in W . Although the authors of [26] use somewhat
older sources of input data from the years 1965 and 1985 and
ignore [8, 15, 28], the large difference between the values of
T
ion
in [26] and in this paper may be due to only the numerical
3383
O Coufal
instability of the method described and applied in [26]. The
ion concentrations in the neighbourhood of the temperature
T
ion
are not large but they are important for assessing electric
conductivity and dielectric strength of a gaseous dielectric, as
is obvious, for example, from [29, 30].
A more detailed comparison of the above properties of
systemW with those published in [26] is not possible because
in [26] not the numerical values but only the values in graphs
with logarithmic scales are given. In the gures in [26] only
mole fractions are given in the composition of system W ,
which are not below 0.01.
8. Conclusion
The initial relations and a description of the method
for calculating the composition and tmdp of a closed
gaseous system in thermodynamic equilibrium at a constant
temperature and pressure were given. The method was
implemented by the Tmdgas program in the C++ language.
The basic principles andrelations of the methoddescribedwere
taken over from the literature. An original contribution of the
paper is the method for calculating the rst approximation of
system composition and a complex analysis of the numerical
process realized on computer. What follows from this
analysis is:
a criterion for terminating the calculation of system
composition,
the introduction of zero components and component
occurrence interval,
the calculation with the dominant component and
the determination of a temperature from which ions need
to be considered in a system.
The main point of the paper is the system and therefore an
original denition of system is formulated. By this denition
the system is no idealized abstract object, it starts from a
concrete DATA le of data about system components. When
preparing input data of the Tmdgas program the simplest thing
to do is to use the species le [5] instead of the DATA le. The
fact that the Tmdgas program is independent of species le
enables the user to adapt, relatively easily, the programand the
data le according to this requirements. Using the program is
simple even in cases when the user needs to obtain the tmdp of
a system without dealing in detail with the problems of their
calculation.
Strictly speaking, the above methods can only be used
on the assumption of local thermodynamic equilibrium. But
if we consider the problems associated with modelling the
kinetics of chemical reactions [31, 32], these methods are for
the time indispensable in the modelling of phenomena in low-
temperature plasma.
An example of the application of the Tmdgas programcan
be seen in the tmdp of system W as given in tables 14 and in
gure 4. The tabular form has been chosen in order to make
the results directly applicable when modelling phenomena in
the plasma of H
2
O.
Acknowledgments
This paper contains the results of research work funded
from project No 102/06/1337 of the Czech Science
Foundation.
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