=
r
( ) x
, (3)
ISO/CD 207652
ISO 2011 All rights reserved 5
and the inverse reduced (dimensionless) mixture temperature t is given by
t =
T x
T
r
( )
, (4)
where
r
and T
r
are reducing functions for the mixture density and mixture temperature (see 4.2.7)
depending on the molar composition of the mixture only.
The residual part o
r
of the reduced Helmholtz free energy is given by
) , , ( ) , , ( ) , , (
r r
o
r
x x x t o o t o o t o o A + = . (5)
In this equation, the first term on the righthand side o
r
o
describes the contribution of the residual parts of the
reduced Helmholtz free energy of the pure substance equations of state, which are multiplied by the mole
fraction of the corresponding substance and linearly combined using the reduced mixture variables o and t
(see equation (8)). The second term Ao
r
is the departure function, which is the summation over all binary
specific and generalized departure functions developed for the respective binary mixtures (see equation (10)).
4.2.4 The reduced Helmholtz free energy of the ideal gas
The reduced Helmholtz free energy o
o
represents the properties of the idealgas mixture at a given mixture
density , temperature T, and molar composition xx according to
 
=
+ =
N
i
i i i
x T x x T
1
o
o
o
ln ) , ( ) , , ( o o . (6)
In this equation, the term
i i
x x ln is the contribution from the entropy of mixing, and o
o
oi
(, T ) is the
dimensionless form of the Helmholtz free energy in the idealgas state of component i as given by
) , (
o
o
T
i
o =


.

\

+


.

\

+ + +


.

\

=

6 , 4
, c o
, o
o
, o
, c o
3 , o
, c o
2 , o
o
1 , o
, c
sinh ln ln ln
k
i
k i k i
i
i
i
i i
i
T
T
n
T
T
n
T
T
n n
R
R
0
(
(
(


.

\

= 7 , 5
, c o
, o
o
, o
cosh ln
k
i
k i k i
T
T
n 0 , (7)
where
c,i
and T
c,i
are the critical parameters of the pure components (see Annex C). The values of the coefficients
n
o
oi,k
and the parameters 0
o
oi,k
for all 21 components are given in Annex B.
NOTE 1 The method prescribed is taken without change from the method prescribed in Part 1 of this International
Standard. The user should however be aware of significant differences that result inevitably from the change in definition
of inverse reduced temperature t between Part 1 and Part 2.
NOTE 2 R = 8.314 472 Jmol
1
K
1
is the current, internationally accepted standard for the molar gas constant [4].
Equation (7) results from the integration of the equations for the idealgas heat capacities taken from [5], where a different
molar gas constant was used than the one adopted in the mixture model presented here. The ratio R
*
/R with R
*
=8.314 51
Jmol
1
K
1
takes into account this difference and therefore leads to the exact solution of the original equations for the
idealgas heat capacity.
ISO/CD 207652
6 ISO 2011 All rights reserved
4.2.5 The pure substance contribution to the residual part of the reduced Helmholtz free energy
The contribution of the residual parts of the reduced Helmholtz free energy of the pure substance equations of
state o
r
o
to the residual part of the reduced Helmholtz free energy of the mixture is
=
=
N
i
i i
x x
1
r
o
r
o
) , ( ) , , ( t o o t o o , (8)
where
o
r
oi
(o, t) is the residual part of the reduced Helmholtz free energy of component i (i.e., the residual part of the
respective pure substance equation of state listed in table 2) and is given by
+
+ =
=
+ =
i i
i
k i
k i k i
i
k i k i
K K
K k
c
t d
k i
K
k
t d
i,k i
e n n
, Exp , Pol
, Pol
, o
, o , o
, Pol
, o , o
1
, o
1
o
r
o
) , (
o
t o t o t o o . (9)
The equations for o
r
oi
use the same basic structure as further detailed in Annex D.2. The values of the
coefficients n
oi,k
and the exponents d
oi,k
, t
oi,k
and c
oi,k
for all 21 components are given in Annex D.2.2.
4.2.6 The departure function contribution to the residual part of the reduced Helmholtz free energy
The purpose of the departure function is to further improve the accuracy of the mixture model in the
description of thermodynamic properties in addition to fitting the parameters of the reducing functions (see
4.2.7) when sufficiently accurate experimental data are available to characterize the properties of the mixture.
The departure function Ao
r
of the multicomponent mixture is the double summation over all binary specific
and generalized departure functions developed for the binary subsystems and is given by
= + =
A = A
1
1 1
r r
) , , ( ) , , (
N
i
N
i j
ij
x x t o o t o o (10)
with
) , ( ) , , (
r r
t o o t o o
ij ij j i ij
F x x x = A . (11)
In this equation, the function o
r
ij
(o, t) is the part of the departure function Ao
r
ij
(o, t, xx ) that depends only on
the reduced mixture variables o and t, as given by
( ) ( )
+
+ =
=
+
=
ij ij
ij
k ij k ij k ij k ij k ij k ij
ij
k ij k ij
K K
K k
t d
k ij
K
k
t d
k ij ij
e n
n
, Exp , Pol
, Pol
, ,
2
, , , ,
, Pol
, ,
1
,
1
,
r
) , (
o  c o q
t o
t o t o o
,
(12)
Where
o
r
ij
(o, t) was developed either for a specific binary mixture (a binary specific departure function with binary
specific coefficients, exponents, and parameters) or for a group of binary mixtures (generalized departure
function with a uniform structure for the group of binary mixtures).
ISO/CD 207652
ISO 2011 All rights reserved 7
(a) Binary specific departure functions
Binary specific departure functions were developed for the binary mixtures of methane with nitrogen, carbon
dioxide, ethane, propane, and hydrogen, and of nitrogen with carbon dioxide and ethane. For a binary
specific departure function, the adjustable factor F
ij
in equation (11) equals unity.
(b) Generalized departure functions
A generalized departure function was developed for the binary mixtures of methane with nbutane and
isobutane, of ethane with propane, nbutane, and isobutane, of propane with nbutane and isobutane, and of
nbutane with isobutane. For each mixture in the group of generalized binary mixtures, the parameter F
ij
is
fitted to the corresponding binary specific data (except for the binary system methanenbutane, where F
ij
equals unity).
(c) No departure functions
For all of the remaining binary mixtures, no departure function was developed, and F
ij
equals zero, i.e.,
Ao
r
ij
(o, t, xx ) equals zero. For most of these mixtures, however, the parameters of the reducing functions for
density and temperature were fitted to selected experimental data (see 4.2.7 and 6.2).
The values of the coefficients n
ij,k
, the exponents d
ij,k
and t
ij,k
, and the parameters q
ij,k
, c
ij,k
, 
ij,k
, and
ij,k
for all
binary specific and generalized departure functions considered in the mixture model described here are given
in annex D.3, Table D.4. The nonzero F
ij
parameters are listed in Table D.5.
NOTE Compared to the reducing functions for density and temperature, the departure function is in general of minor
importance for the residual behavior of the mixture since it only describes an additional small residual deviation to the real
mixture behavior. The development of such a function was, however, necessary to fulfill the high demands on the
accuracy of the mixture model presented here in the description of the thermodynamic properties of natural gases and
other mixtures.
4.2.7 Reducing functions
The reduced mixture variables o and t are calculated from equations (3) and (4) by means of the
compositiondependent reducing functions for the mixture density and temperature
= =


.

\

+
+
+
=
N
i
N
j j i j i ij v
j i
ij v ij v j i
x x
x x
x x
x
1 1
3
3 / 1
, c
3 / 1
, c
2
,
, ,
r
1 1
8
1
) (
1


(13)
( )
= =
+
+
=
N
i
N
j
j i
j i ij T
j i
ij T ij T j i
T T
x x
x x
x x x T
1 1
, c , c
2
,
, , r
5 . 0
) (

 . (14)
These functions are based on quadratic mixing rules and are reasonably connected to physically wellfounded
mixing rules. The binary parameters 
v,ij
and
v,ij
in equation (13) and 
T,ij
and
T,ij
in equation (14) are fitted
to data for binary mixtures. The values of the binary parameters for all binary mixtures are listed in table E.1
of Annex E. The critical parameters
c,i
and T
c,i
of the pure components are given in Annex C. In equations
(13) and (14), 
ij
=1/
ji
and
ij
=
ji
.
NOTE The binary parameters of equations (13) and (14) were fitted based on the deviations between the behavior of
the real mixture and the one resulting from ideal combining rules for the critical parameters of the pure components. In
those cases where sufficient experimental data are not available, the parameters of equations (13) and (14) are either set
to unity or modified (calculated) in such a manner that the critical parameters of the pure components are combined in a
different way, which proved to be more suitable for certain binary subsystems (see also Annex E.1).
4.3 Thermodynamic properties derived from the Helmholtz free energy
ISO/CD 207652
8 ISO 2011 All rights reserved
4.3.1 Background
The thermodynamic properties in the homogeneous gas, liquid, and supercritical regions of a mixture are
related to derivatives of the Helmholtz free energy with respect to the reduced mixture variables o and t, as
summarized in the following section (see table 1). All of the thermodynamic properties may be written
explicitly in terms of the reduced Helmholtz free energy o and various derivatives thereof. The required
derivatives o
t
, o
tt
, o
o
, o
oo
, and o
ot
are defined as follows:
x , o
t
t
o
o

.

\

c
c
=
x ,
2
2
o
tt
t
o
o


.

\

c
c
=
x , t
o
o
o
o

.

\

c
c
=
x ,
2
2
t
oo
o
o
o


.

\

c
c
=
x
x
,
,
o
t
ot
o
o
t
o


.

\


.

\

c
c
c
c
= (15)
Each derivative is the sum of an idealgas part (see Annex B) and a residual part (see Annex D). The
following substitutions help to simplify the appearance of the relevant relationships:
r 2 r 2
,
2
1
2 1 2
) (
oo o oo o
t
o
o o o o o o o o
o
o o
o + + = + =


.

\

c
c
=
i
x
(16)
r r
,
2
2
1
ot o ot o
o
o
o o t o o o o t o o
t
o o
t
t o + = =


.

\


.

\

c
c
=
i
x
(17)
Detailed expressions for o
t
, o
tt
, o
o
, o
oo
, o
ot
, o
1
, and o
2
can be found in Annexes B and D.
NOTE In addition to the derivatives of o with respect to the reduced mixture variables o and t, composition
derivatives of o and of the reducing functions for density and temperature are required for the calculation of vaporliquid
equilibrium (VLE) properties as described in Part 3 of this International Standard.
4.3.2 Relations for the calculation of thermodynamic properties in the homogeneous region
The relations between common thermodynamic properties and the reduced Helmholtz free energy o and its
derivatives are summarized in table 1. The first column of this table defines the thermodynamic properties.
The second column gives their relation to the reduced Helmholtz free energy o of the mixture. In equations
(23), (25), (26), (28), (29), and (31), the basic expressions for the properties s, h, c
p
, w,
JT
, and k have been
additionally transformed, such that values of properties already derived can be used to simplify the
subsequent calculations. This approach is useful for applications where several or all of the thermodynamic
properties are to be determined.
In equations (22) to (27), the relations for the thermodynamic properties represent the molar quantities (i.e.,
quantity per mole, lower case symbols). Specific quantities (i.e., quantity per kilogram, represented normally
by upper case symbols) are obtained by dividing the molar variables (e.g., v, u, s, h, g, c
v
, and c
p
) by the molar
mass M.
The molar mass M of the mixture is derived from the composition x
i
and the molar masses M
i
of the pure
substances as follows
=
=
N
i
i i
M x x M
1
) ( (18)
The massbased density D is given by
M D = (19)
NOTE 1 Values of the molar masses M
i
of the pure substances are given in Annex C and are taken from [6]; these
values are not identical with those given in ISO 207651 and ISO 6976:1995 [7]. However, they are identical with the most
ISO/CD 207652
ISO 2011 All rights reserved 9
recent values adopted by the international community of metrologists. In these equations, R is the molar gas constant;
consequently R/M is the specific gas constant.
NOTE 2 See Annex B.1 for information on reference states for enthalpy and entropy.
Table 1 Definitions of common thermodynamic properties and their relation to the reduced
Helmholtz free energy o.
Property and definition Relation to o and its derivatives
Pressure
( )
x T
v a x T p
,
) , , ( c c =
r
1
) , , (
RT
x p
oo
t o
+ =
(20)
Compression factor
( ) RT p x T Z / ) , , ( =
r
1 ) , , (
x Z oo t o + =
(21)
Internal energy
Ts a x T u + = ) , , ( t
o t
t o
=
RT
x u ) , , (
(22)
Entropy
( )
x v
T a x T s
,
) , , ( c c =
o
t
o t
t o
=
R
x s ) , , (
o =
RT
u
(23)
Isochoric heat capacity
( )
x v
v
T u x T c
,
) , , ( c c = tt
o t
t o
2
) , , (
=
R
x c
v
(24)
Enthalpy
pv u x p T h + = ) , , ( t
o t oo
t o
o
+ + =
r
1
) , , (
RT
x h
Z
RT
u
+ =
(25)
Isobaric heat capacity
( )
x p
p
T h x p T c
,
) , , ( c c =
1
2 2
) , , (
o
o
tt
o t
t o 2
+ =
R
x c
p
1
2
2
o
o
+ =
RT
v
c
(26)
Gibbs free energy
Ts h x p T g = ) , , (
o oo
t o
o
+ + =
r
1
) , , (
RT
x g
(27)
Speed of sound
( )( )
x s
p M x p T w
,
1 ) , , ( c c =
tt
o t
o
o
t o
2
2
2
2
1
) , , (
=
RT
M x w
k Z =
(28)
Joulethomson coefficient
( )
x h
p T x p T
,
JT
) , , ( c c =
( )
1
2
2
2 1
JT
2
o o t o
o o
tt
= R


.

\

= 1
1
2
o
o
p
c
R
(29)
Isothermal throttling coefficient
( )
x T
T
p h x p T
,
) , , ( c c o =
1
2
1
o
o
o =
T
(30)
Isentropic exponent
( )( )
x s
v p p v x p T
,
) , , ( c c k =


.

\

=
1
2
2
2
r
1
1
o o t
o
oo
o
k
tt
o
v
p
c
c
Z
1
o
=
(31)
Second virial coefficient
( )
x T
Z x T B
,
0
lim ) , ( c c
=
r
0
r
lim ) (
o
o t
o
= B (32)
Third virial coefficient
x T
Z x T C
,
2 2
0
lim
2
1
) , (

.

\

=
c c
r 2
r
0
lim ) (
oo
o t
o
= C (33)
ISO/CD 207652
10 ISO 2011 All rights reserved
5 Method of calculation
5.1 Input variables
The method presented in this standard internally uses reduced density, inverse reduced temperature, and
molar composition as the input variables. The actual allowable input variables are either
(a) Molar density , temperature T , and molar composition x , or
(b) Absolute pressure p, temperature T , and molar composition x .
If the massbased density D is available as input, then is obtained directly as =D/M, where ) (x M is the
molar mass given by equation (18). For given values of the molar density , temperature T, and molar
composition x , the reduced mixture variables o and t can be calculated from equations (3) and (4) using the
reducing functions for density and temperature given by equations (13) and (14).
More often, however, absolute pressure, temperature, and molar composition are available as the input
variables. In consequence, it is usually necessary to first evaluate the reduced density o and the inverse
reduced temperature t from the available inputs. The conversion from temperature to inverse reduced
temperature is given by equation (4). Section 5.2 explains how to obtain the reduced density given pressure
and temperature.
The composition in mole fractions is required for the following 21 components: methane, nitrogen, carbon
dioxide, ethane, propane, nbutane, isobutane (2methylpropane), npentane, isopentane (2methylbutane), n
hexane, nheptane, noctane, nnonane, ndecane, hydrogen, oxygen, carbon monoxide, water, hydrogen
sulfide, helium, and argon. For natural gases and similar (multicomponent) mixtures, the allowable ranges of
mole fraction are defined in 6.3. The sum of all mole fractions shall be unity.
NOTE 1 If the sum of all mole fractions is not unity within the limit of analytical resolution, then the composition is either
faulty or incomplete. The user should not proceed until the source of this problem has been identified and eliminated.
NOTE 2 If the mole fractions of heptanes, octanes, nonanes, and decanes are unknown, then the use of a composite
C6+ fraction may be acceptable. For VLE calculations (including dew points), this simplification is not acceptable since
even small amounts of heptanes, octanes, nonanes, decanes, and higher hydrocarbons have a significant influence on the
phase behavior of the mixture. The user should carry out a sensitivity analysis in order to test whether a particular
approximation of this type degrades the result.
NOTE 3 Composition given in volume or mass fractions will need to be converted to mole fractions using the method
given in ISO 14912 [8].
5.2 Conversion from pressure to reduced density
Combination of the relations for the reduced mixture variables o and t (equations (3) and (4)) and equation
(21) results in the following expression
p
x RT x
Z x x
t
o
o t o o o t
o
r r
r
( ) ( )
( , , ) ( , , ) = = + 1 , (34)
where
= + = =


.

\

+


.

\

=


.

\

=
1
1 1
r
1
r
o
,
r
r
) , (
) , (
) , , (
N
i
N
i j
ij
ij j i
N
i
i
i
x
F x x x x
t
t t
o
co
t o co
co
t o co
co
co
t o o . (35)
If the input variables are available as pressure, inverse reduced temperature, and molar composition, equation
(34) may be solved for the reduced molar density o. The derivatives of o o t
o
r
i
( , ) with respect to o and the
ISO/CD 207652
ISO 2011 All rights reserved 11
coefficients n
oi,k
and the exponents d
oi,k
, t
oi,k
, and c
oi,k
involved (see equation (9)) are given in Annex D.2. The
derivatives of ) , (
r
t o o
ij
with respect to o and the coefficients n
ij,k
, the exponents d
ij,k
and t
ij,k
, and the
parameters F
ij
, q
ij,k
, c
ij,k
, 
ij,k
, and
ij,k
involved (see equations (11) and (12)) are given in Annex D.3.
Information on the reducing functions is given in annex E.
The solution of equation (34) may be obtained by any suitable numerical method but, in practice, a standard
form of equationofstate densitysearch algorithm may be the most convenient and satisfactory. Such
algorithms usually use an initial estimate of the density (e.g., the idealgas approximation for low density
gaseous states) and proceed to calculate the pressure p. In an iterative procedure the value of o is changed
in order to find the final reduced density o, which reproduces the known value of p to within a preestablished
level of agreement. A suitable criterion in the present case is that the pressure calculated from the iteratively
determined reduced density o shall reproduce the input value of p at least to within 1 part in 10
6
.
5.3 Implementation
Once the independent variables reduced density o, inverse reduced temperature t, and molar composition x
of the mixture are known, the reduced Helmholtz free energy and the other thermodynamic properties (see
table 1) can be calculated. Equation (2) formulates the reduced Helmholtz free energy as o=o
o
+o
r
. The
relations for the idealgas part o
o
are given in equations (6) and (7). The relations for the residual part o
r
,
which is formulated as a function of the reduced density o, the inverse reduced temperature t, and the molar
composition x , are specified in equations (5) and (8) to (12) so as to give the following expression for o:
= =



.

\

+


.

\

+ + +


.

\

=
N
i k
i
k i k i
i
i
i
i i
i
i
T
T
n
T
T
n
T
T
n n
R
R
x x
1 6 , 4
, c o
, o
o
, o
, c o
3 , o
, c o
2 , o
o
1 , o
, c
sinh ln ln ln ) , , ( 0
t o o
(
(
(


.

\

= 7 , 5
, c o
, o
o
, o
cosh ln
k
i
k i k i
T
T
n 0
=
+
N
i
i i
x x
1
ln
=
+
+ =
= (
(
+ +
N
i
K K
K k
c
t d
k i
K
k
t d
oi,k i
i i
i
k i
k i k i
i
k i k i
e n n x
1 1
, o
1
, Exp , Pol
, Pol
, o
, o , o
, Pol
, o , o o
t o t o (36)
( ) ( )
= + =
+
+ =
= (
(
+ +
1
1 1 1
,
1
,
, Exp , Pol
, Pol
, ,
2
, , , ,
, Pol
, ,
N
i
N
i j
K K
K k
t d
k ij
K
k
t d
k ij ij j i
ij ij
ij
k ij k ij k ij k ij k ij k ij
ij
k ij k ij
e n n F x x
o  c o q
t o t o
For all 21 components, the values of the coefficients n
o
oi,k
and the parameters 0
o
oi,k
of the idealgas part of the
reduced Helmholtz free energy are given in Annex B. The values of the coefficients n
oi,k
and exponents d
oi,k
,
t
oi,k
, and c
oi,k
in the contribution to the residual parts of the pure substance equations of state are listed in
Annex D. The values of the coefficients n
ij,k
, the exponents d
ij,k
and t
ij,k
, and the parameters F
ij
, q
ij,k
, c
ij,k
, 
ij,k
,
and
ij,k
in the departure functions for all relevant binary mixtures are given in Annex D as well.
Derivatives of o with respect to the reduced mixture variables o and t that are needed for the calculation of the
various thermodynamic properties may be obtained from Annexes B and D. Annex B lists the derivatives of
the idealgas part of the reduced Helmholtz free energy, a
o
, with respect to the reduced density and inverse
reduced temperature of the mixture. Derivatives of the contribution of the residual parts of the pure substance
equations of state to the reduced residual Helmholtz free energy of the mixture, a
r
, with respect to the reduced
mixture variables o and t may be obtained from Annex D. Derivatives of the contribution of the departure
functions for binary mixtures to a
r
with respect to the reduced mixture variables o and t are given in Annex D
as well.
6 Ranges of application
ISO/CD 207652
12 ISO 2011 All rights reserved
6.1 Pure gases
The temperature and pressure ranges of validity for the pure fluid equations of state are listed in table 2. For
these ranges, the equations have been tested with experimental data. The lower temperatures correspond to
the triple point temperatures of the substances. For the main components, the equations have been tested for
temperatures up to at least 600 K and pressures up to 300 MPa. For the secondary alkanes, the equations
have been tested for temperatures up to 500 K and pressures up to at least 35 MPa. For the other secondary
components the temperatures range up to at least 400 K (water up to 1273 K) and pressures range up to at
least 100 MPa. The extrapolation to temperatures and pressures far beyond the listed (tested) ranges of
validity yields reasonable results.
Table 2 Validity range and references for the 21 components in the mixture model
a
Pure substance Reference Tested range of validity Number
of terms Temperature Pressure
T/K p
max
/MPa
Main components
Methane Klimeck (2000) [9] 90 623 300 24
Nitrogen Klimeck (2000) [9] 63 700 300 24
Carbon dioxide Klimeck (2000) [9] 90
b
900 300 22
Ethane Klimeck (2000) [9] 90 623 300 24
Secondary alkanes
Propane Span & Wagner (2003) [10] 85 623 100 12
nButane Span & Wagner (2003) [10] 134 693 70 12
Isobutane Span & Wagner (2003) [10] 113 573 35 12
nPentane Span & Wagner (2003) [10] 143 573 70 12
Isopentane Lemmon & Span (2006) [11] 112 500 35 12
nHexane Span & Wagner (2003) [10] 177 548 100 12
nHeptane Span & Wagner (2003) [10] 182 523 100 12
nOctane Span & Wagner (2003) [10] 216 548 100 12
nNonane Lemmon & Span (2006) [11] 219 600 800 12
nDecane Lemmon & Span (2006) [11] 243 675 800 12
Other secondary components
Hydrogen
c
Kunz et al. (2007) [1] 14 700 300 14
Oxygen Span & Wagner (2003) [10] 54 500
e
100 12
Carbon monoxide Lemmon & Span (2006) [11] 68 400 100 12
Water Kunz et al. (2007) [1] 273 1273 100 16
Helium
d
Kunz et al. (2007) [1] 2.2 573 100 12
Argon Span & Wagner (2003) [10] 83 520 100 12
Hydrogen Sulfide Lemmon & Span (2006) [11] 187 760 170 12
a
The tabulated references correspond to the equations for the residual part of the Helmholtz free energy of the
pure substances. The equations for the isobaric heat capacity in the idealgas state from [5] were used to
derive the Helmholtz free energy of the ideal gas for all components.
b
The equation can be extrapolated from the triplepoint temperature 216 K down to 90 K.
c
Represents equilibrium hydrogen.
d
Represents helium4. The lower temperature limit of the equation of state is the helium I to helium II transition
point.
e
The upper limit of oxygen has been increased to 500 K based on recent validation of the equation of state.
ISO/CD 207652
ISO 2011 All rights reserved 13
6.2 Binary mixtures
Table 3 summarizes the available data for volumetric and caloric properties of all binary mixtures considered
in this method. Almost half of the total number of data points are from those 15 mixtures for which binary
specific or generalized departure functions have been developed. The majority of the data (approximately
65%) describe the pT relation, approximately 25% are vaporliquid equilibrium, and about 9% are caloric
properties.
(a) Specific departure functions
Table 4 lists the binary mixtures for which either binary specific or generalized departure functions have been
developed because sufficiently accurate and extensive data are available. Binary specific departure functions
are given for the binary mixtures of methane with nitrogen, carbon dioxide, ethane, propane, and hydrogen,
and of nitrogen with carbon dioxide and ethane (see also figure 2).
The temperature range of the experimental data used to test the equations developed for the binary mixtures
covers approximately 80 K to 700 K at pressures up to 70 MPa and more (e.g., 100 MPa for methanecarbon
dioxide and 750 MPa for methanenitrogen). The composition ranges from nearly 0 to 1 for all mixtures listed
above; see [2] for further details.
(b) Generalized departure functions
A generalized departure function was developed for eight binary mixtures of secondary alkanes (see table 4).
The generalized departure function is used for the binary mixtures of methane with nbutane and isobutane,
ethane with propane, nbutane, and isobutane, propane with nbutane and isobutane, and nbutane with
isobutane.
Aside from experimental data for these binary mixtures, selected volumetric and caloric properties for the well
measured binary alkane mixtures methaneethane and methanepropane were also used for the
development of the generalized departure function for secondary binary alkane mixtures. The final structure
of the generalized departure function is almost completely based on accurate and comprehensive data sets
for the three binary systems methaneethane, methanepropane, and methanenbutane, with more than
6,200 selected data points used (about 1,000 data points for the methanenbutane binary system). The
temperature range of the experimental data used to test the equations developed for the secondary binary
alkane mixtures covers roughly 95 K to 600 K at pressures up to 35 MPa (70 MPa for methanenbutane).
The composition ranges from nearly 0 to 1 for all mixtures listed above; see [2] for further details.
(c) No departure functions
For all of the remaining binary mixtures, no departure function was developed (see figure 2). The
corresponding binary mixtures are either characterized by limited data, which do not permit the development
of binary specific or generalized departure functions, or are of minor importance for the description of the
thermodynamic properties of (multicomponent) natural gases due to the small mole fractions of the respective
components. Fitting the parameters of the reducing functions for density and temperature to selected
experimental data is sufficient and yields accurate results for most of the binary mixtures. In those cases
where sufficient experimental data are not available, the parameters of the reducing functions for density and
temperature are either set to unity or modified (calculated) in such a manner that the critical parameters of the
pure components are combined in a different way, which proved to be more suitable for certain binary
subsystems (see also Annex E.1).
For the temperature, pressure, and composition ranges covered by the experimental data used to test the
equations developed for the binary mixtures without a departure function, i.e., by adjusting the reducing
functions for density and temperature only, see [2].
ISO/CD 207652
14 ISO 2011 All rights reserved
Table 3 Summary of the available data for volumetric and caloric properties of binary mixtures
Data type Number of data
points
Temperature
ranges
Pressure ranges Composition
ranges
c,d
total
a
used
b
T/K p/MPa x
Density 51442 30252 66.9 800 0.00 1027 0.00 1.00
Isochoric heat capacity 1236 625 101 345 67.1
902
0.01 0.84
Speed of sound 2819 1805 157 450 0.00 1971 0.01 0.96
Isobaric heat capacity 1072 490 100 424 0.00 52.9 0.09 0.93
Enthalpy differences 1804 198 107 525 0.00 18.4 0.05 0.90
Excess molar enthalpy 177 20 221 373 0.8 15.0 0.01 0.98
Saturated liquid density
e
460 119 95.0 394 0.03 22.1 0.00 1.00
VLE data 20161 6350 15.5 700 0.00 422 0.00 1.00
Total 79171 39859 15.5 800 0.00 1971 0.00 1.00
a Number of available data points used in testing the GERG2008 equation of state.
b Number of data points selected for the development of the GERG2008 equation of state.
c Mole fractions of the second component of the binary mixture, i.e., component B of mixture AB.
Values of 0.00 and 1.00 result from a mixture composition close to a pure component.
d The composition range for VLE data corresponds to bubble point compositions.
e Listed separately due to a different data format. Saturated liquid (and vapour) densities may also be
tabulated as ordinary pT or VLE data.
Density in kgm
3
instead of pressure.
Table 4 List of the binary mixtures for which binary specific and generalized departure functions
were developed
Binary mixture Type of departure function Number of terms Type of terms
a
MethaneNitrogen binary specific 9 P (2), E (7)
MethaneCarbon dioxide binary specific 6 P (3), E (3)
MethaneEthane binary specific 12 P (2), E (10)
MethanePropane binary specific 9 P (5), E (4)
MethanenButane generalized 10 P
MethaneIsobutane generalized 10 P
MethaneHydrogen binary specific 4 P
NitrogenCarbon dioxide binary specific 6 P (2), E (4)
NitrogenEthane binary specific 6 P (3), E (3)
EthanePropane generalized 10 P
EthanenButane generalized 10 P
EthaneIsobutane generalized 10 P
PropanenButane generalized 10 P
PropaneIsobutane generalized 10 P
nButaneIsobutane generalized 10 P
a
P indicates polynomial terms, and E indicates the exponential terms composed of a polynomial and
exponential expression according to equation (12). The numbers in parentheses indicate the respective
number of terms K
pol
and K
exp
.
ISO/CD 207652
ISO 2011 All rights reserved 15
Figure 2 Overview of the 210 binary combinations that result from the 21 natural gas components
for the development of the GERG2008 equation of state. The diagram shows the different
formulations developed for the binary mixtures.
6.3 Range of validity for natural gases
The method described in this part of ISO 20765 applies to the calculation of thermodynamic properties of
natural gases and similar mixtures in the homogeneous (singlephase) region (gas, liquid, and dense fluid) for
normal and extended ranges of application. The ranges of validity in this part is defined as follows.
Pressure and temperature ranges
The relevant ranges of pressure and temperature are given in table 5. The method described in this part of
the standard applies strictly to mixtures in a homogeneous state (gas, liquid, and dense fluid).
Table 5 Normal ranges of application
Pressure (absolute) 0 < p / MPa s 35
Temperature 90 s T / K s 450
Composition ranges
Pipeline quality natural gas is taken as a natural (or similar) gas with mole fractions of the various components
that fall within the ranges given in the third column of table 6. The method described in ISO 207651 applies
only to pipeline quality natural gases for those ranges of pressure and temperature within which transmission
and distribution operations normally take place. The method given in this standard also applies to these
conditions as well as an expanded composition range of natural gas as given in the fourth column of table 6.
Accurate and extensive experimental data sets are available within the composition ranges listed in the table
below and have been used to validate the quality of the method presented here (see 7.4). Possible trace
components of natural gases, and details of how to deal with these, are discussed in Annex F. This method is
7
.
1
0
D
e
v
e
l
o
p
m
e
n
t
o
f
t
h
e
D
i
f
f
e
r
e
n
t
B
i
n
a
r
y
E
q
u
a
t
i
o
n
s
o
f
S
t
a
t
e
.
.
.
1
6
7
ISO/CD 207652
16 ISO 2011 All rights reserved
not applicable where the total of all trace components exceeds 0.000 5 mole fraction.
Beyond the expanded quality range is the extended composition range that covers the full composition range
for all mixture components, i.e., from 0 to 1. Due to the limited data situation, results obtained for multi
component mixtures in the extended range of validity should be carefully assessed. The method can be used
for temperatures above 700 K and pressures above 70 MPa. However, due to the limited data situation it is
difficult to estimate the uncertainty of the method (see 7).
Table 6 Mole fraction ranges for components of expanded and pipeline quality natural gas
Mole fraction for
i Component Pipeline quality range Expanded quality range
1 Methane 0.7 s x
CH4
s 1.00 0.3 s x
CH4
s 1.00
2 Nitrogen 0 s x
N2
s 0.20 0 s x
N2
s 0.55
3 Carbon dioxide 0 s x
CO2
s 0.20 0 s x
CO2
s 0.30
4 Ethane 0 s x
C2H6
s 0.10 0 s x
C2H6
s 0.25
5 Propane 0 s x
C3H8
s 0.035 0 s x
C3H8
s 0.14
6 + 7
nButane + Isobutane
a
0 s x
C4H10
s 0.015 0 s x
C4H10
s 0.06
8 + 9
nPentane + Isopentane
a
0 s x
C5H12
s 0.005 0 s x
C5H12
s 0.005
10 nHexane 0 s x
C6H14
s 0.001 0 s x
C6H14
s 0.002
11 nHeptane 0 s x
C7H16
s 0.000 5 0 s x
C7H16
s 0.001
12 + 13 + 14
Octane+Nonane+Decane
a
0 s x
C8+
s 0.000 5 0 s x
C8+
s 0.000 5
15 Hydrogen 0 s
x
H2
s 0.10 0 s
x
H2
s 0.40
16 Oxygen 0 s
x
O2
s 0.000 2 0 s
x
O2
s 0.02
17 Carbon monoxide 0 s x
CO
s 0.03 0 s x
CO
s 0.13
18 Water 0 s x
H2O
s 0.000 15 0 s x
H2O
s 0.000 2
19 Hydrogen sulfide 0 s x
H2S
s 0.000 2 0 s x
H2S
s 0.27
20 Helium 0 s x
He
s 0.005 0 s x
He
s 0.005
21 Argon 0 s x
Ar
s 0.000 2 0 s x
Ar
s 0.000 5
a
Indicates the sum of the mole fractions of the components may not exceed the specified value.
NOTE 1 The method described in this part of the standard is applicable even for the individual pure components wi th
high accuracy (i.e., to within experimental uncertainty). For this application, the tested ranges of validity for temperature
and pressure is given in table 2.
NOTE 2 The accurate description of the thermodynamic properties of multicomponent mixtures by the GERG2008
equation of state is based on the accurate and wideranging equations of the binary subsystems, which were developed
with experimental data that generally cover the entire composition range. Therefore, it can be expected that even multi 
component natural gases of very unusual composition will be accurately described.
ISO/CD 207652
ISO 2011 All rights reserved 17
7 Uncertainty of the equation of state
7.1 Background
When ranges of uncertainties are given, the upper uncertainty value should be used unless further
comparisons are made with the information given in the technical report to verify that the lower uncertainty
value is valid for a particular application. The uncertainty in this document has a 95% confidence level
(coverage factor k = 2).
7.2 Uncertainty for pure gases
7.2.1 Natural gas main components
The estimated uncertainties in calculated density and speed of sound for the natural gas main components
methane, nitrogen, carbon dioxide, and ethane are summarized in table 8. For methane, more details are
given in figures 3 and 4; details for nitrogen, carbon dioxide, and ethane are given in [1]. The estimated
uncertainties in gas phase density and speed of sound range from 0.03% to 0.05% over wide ranges of
temperature (e.g., up to 450 K) and at pressures up to 30 MPa. In the liquid phase at pressures up to
30 MPa, the estimated uncertainties in density range from 0.05% to 0.1%. At higher temperatures or
pressures, the estimated uncertainties in calculated speed of sound are generally higher than in calculated
density because of less accurate data.
7.2.2 Secondary alkanes
The estimated uncertainties in calculated density, speed of sound, and isobaric heat capacity for the
secondary alkanes propane, nbutane, isobutane, npentane, isopentane, nhexane, nheptane, noctane, n
nonane, and ndecane are summarized in table 9. For calculated densities, uncertainties of 0.2% were
estimated, whereas calculations of speed of sound and isobaric heat capacity have estimated uncertainties
between 1% and 2%.
ISO/CD 207652
18 ISO 2011 All rights reserved
Table 8 Uncertainties of the equations of state for the natural gas main components methane,
nitrogen, carbon dioxide, and ethane with regard to different thermodynamic properties.
Density Speed of sound
Gas phase
a
p 30 MPa
p > 30 MPa
c
0.03% 0.05%
0.1% 0.5%
0.03% 0.05%
b
0.5%
d
Liquid phase
p 30 MPa
p > 30 MPa
c
0.05% 0.1%
0.5%
f
0.5% 1.5%
e
1.5%
g
Saturated liquid
0.05%
h
Saturated vapor 0.05%
a
for temperatures up to 450 K; uncertainties at higher temperatures are given in figures 3 and 4 for methane and in [2] for
nitrogen, carbon dioxide, and ethane.
b
This uncertainty range is not valid over the entire temperature and pressure ranges specified in the table; further details
are given in figure 4 for methane and in [2] for nitrogen, carbon dioxide, and ethane.
c
States at pressures p > 100 MPa are not included in the table due to their limited technical relevance, but can be
obtained from figures 3 and 4 for methane and from [2] for nitrogen, carbon dioxide, and ethane.
d
for methane; (1 2)% for nitrogen, (0.5 1)% for carbon dioxide, and 2% for ethane; see [2].
e
for methane; 1% (p 20 MPa) for nitrogen, (0.5 1)% for carbon dioxide, and (1 2)% for ethane; see [2].
f
for methane, nitrogen, and ethane; 1% for carbon dioxide.
g
for methane; 2% (p > 20 MPa) for nitrogen, (0.5 1)% for carbon dioxide, and 2% for ethane; see [2].
h
for methane, nitrogen, and carbon dixoide; 0.1% for ethane.
Table 9 Uncertainties of the equations of state for propane, nbutane, isobutane, npentane,
isopentane, nhexane, nheptane, noctane, nnonane, ndecane, hydrogen sulfide, oxygen,
and argon for various thermodynamic properties
Pressure range Uncertainty in
( , ) T p w T p ( , ) c T p
p
( , ) ) (
s
T p ' ( ) T '' ( ) T
p 30 MPa
a
0.2%
b
(1 2)%
c
(1 2)%
c
0.2%
d
0.2%
0.4%
d,e
p > 30 MPa
f
0.5% 2% 2%
a
Larger uncertainties exist in the extended critical region.
b
In the extended critical region, Ap p / is used instead of A / .
c
1% at gaseous and gaslike supercritical states, 2% at liquid and liquidlike supercritical states.
d
Larger relative uncertainties may result for small vapor pressures and their corresponding saturated vapor
densities.
e
Combination of the uncertainties of the gas densities and vapor pressures; experimental data of this accuracy
are available for only a few substances.
f
States at pressures p > 100 MPa are not included due to their limited technical relevance.
ISO/CD 207652
ISO 2011 All rights reserved 19
Figure 3 Uncertainty diagram for densities of methane calculated from the GERG2008 equation of
state.
Figure 4 Uncertainty diagram for speeds of sound of methane calculated from the GERG2008
equation of state.
ISO/CD 207652
20 ISO 2011 All rights reserved
7.2.3 Other secondary components
For oxygen and argon, the estimated uncertainties in calculated density, speed of sound, and isobaric heat
capacity are as stated in table 9 for the secondary alkanes.
The estimated uncertainties in calculated density for the other secondary components, namely hydrogen,
carbon monoxide, hydrogen sulfide, and helium, at supercritical temperatures and for pressures up to 30 MPa
are less than 0.2% and at higher pressures less than 0.5%. In general, higher uncertainties may occur in the
liquid phase and for other thermodynamic properties.
For hydrogen at temperatures above 270 K and pressures up to 30 MPa, the uncertainty in calculated density
is less than 0.1%. At pressures above 30 MPa, the uncertainty in density is slightly higher, approximately
(0.2 0.3)%. The equations for hydrogen and helium are designed to be valid at low (absolute) temperatures,
which occur in their sub and supercritical regions. This is of particular importance for the mixture model
presented here since for pure substances the reduced temperature range 1.2 T/T
c
1.8 corresponds to the
region where the highest accuracy in the description of thermodynamic properties of typical natural gases is
demanded.
For water, calculated liquid densities and vapor pressures have an estimated uncertainty of 0.2%. Other
properties have higher uncertainties as detailed in the technical report.
7.3 Uncertainty for binary mixtures
The most accurate binary mixture data were used for the development of the GERG2008 equation of state.
However, in regions where these data are not available, less accurate data were also taken into account for
the development and assessment of the equation. Experimental data for multicomponent mixtures were
used for the validation of the quality of the equation only. The total uncertainties of the most accurate
experimental binary and multicomponent mixture data with respect to selected thermodynamic properties are
listed in table 10. The tabulated values represent the lowest uncertainties possible that can be achieved by
the mixture model presented here. The corresponding experimental results are based on modern
measurement techniques, which fulfill present quality standards. They are characterized by uncertainties
equal to or below the lowest values listed in table 10. In contrast to the experimental uncertainties given for
pure fluid properties measured using stateoftheart techniques, the experimental uncertainties estimated for
the properties of mixtures measured with the same apparatuses are, in general, higher due to the significant
contribution of the uncertainty in the mixture composition.
Over wide ranges of temperature, pressure, and composition, the uncertainties tabulated below are mostly
valid for those binary systems where binary specific departure functions were developed, see 6.2 and table 4.
Due to limited experimental data (e.g., accurate speed of sound measurements are available for only a few
binary systems), the uncertainties are partly valid for the remaining binary mixtures, including those binary
systems for which a generalized departure function was developed, see 6.2 and [1].
General estimates of the uncertainties of the GERG2008 equation of state in the description of selected
thermodynamic properties are given in table 11. The different binary mixtures are distinguished by adjusted
reducing functions and a binary specific departure function, adjusted reducing functions and a generalized
departure function, or only adjusted reducing functions (without a departure function) to describe the mixtures.
Uncertainty values are given for different pressures, temperatures, and (approximate) reduced temperature
ranges.
ISO/CD 207652
ISO 2011 All rights reserved 21
Table 10 Relative experimental uncertainties of the most accurate binary and multicomponent mixture data
Data type Property Relative uncertainty
Density (gas phase) A s (0.05 0.1)%
Density (liquid phase) A
s (0.1 0.3)%
Isochoric heat capacity
v v
c c A
s (1 2)%
Speed of sound (gas phase) Aw w s (0.05 0.1)%
Isobaric heat capacity
Ac c
p p
s (1 2)%
Enthalpy differences (gas phase) A A A h h ( )
s (0.2 0.5)%
Saturated liquid density A ' ' s (0.1 0.2)%
VLE data
A p p
s s
s (1 3)%
NOTE Ah indicates a difference between two state points, h(T
2
,p
2
)h(T
1
,p
1
).
From table 11 it is evident that binary systems with a binary specific departure function generally have the
lowest uncertainty for the different properties as compared to the other binary systems with either a
generalized departure function or only modified reducing parameters. Gas phase densities and speeds of
sound have uncertainties of 0.1% for binary mixtures with a binary specific departure function. The relative
uncertainty in isobaric and isochoric heat capacity is estimated to be less than (1 2)% in the homogeneous
gas, liquid, and supercritical regions independent of the type of developed binary equation.
Table 11 Uncertainty of the GERG2008 equation of state in the description of selected volumetric
and caloric properties of different binary mixtures
a
Mixture region
b
Adjusted reducing functions with a
Only adjusted reducing
functions (no departure
function)
binary specific
departure function
generalized
departure function
Gas phase 0 30 MPa
1.2 s T/T
r
s 1.4
A
s 0.1%
A
s (0.1 0.2)%
A
s (0.5 1)%
Gas phase 0 30 MPa
1.4 s T/T
r
s 2.2
A
s 0.1%
A
s 0.1%
A
s (0.3 0.5)%
Gas phase 0 20 MPa
1.2 s T/T
r
s 1.4
Aw
w
s 0.1%
Aw
w
s 0.5%
Aw
w
s 1%
Gas phase 0 20 MPa
1.4 s T/T
r
s 2.2
Aw
w
s 0.1%
Aw
w
s 0.3%
Aw
w
s 0.5%
Saturated liquid state
100 K T 140 K
A '
'
s
(0.1 0.2)%
A '
'
s
(0.2 0.5)%
A '
'
s
(0.5 1)%
Liquid phase 0 40 MPa
T/T
r
s 0.7
A
s (0.1 0.3)%
A
s (0.2 0.5)%
A
s (0.5 1)%
a
The relative uncertainty in isobaric and isochoric heat capacity is estimated to be less than (1 2)%
in the homogeneous gas, liquid, and supercritical regions independent of the type of binary equation.
b
For a typical natural gas, temperatures of 250 K, 300 K, and 350 K correspond to reduced
temperatures T T x
r
( ) =1 t of about 1.3, 1.5, and 1.8, respectively.
ISO/CD 207652
22 ISO 2011 All rights reserved
7.4 Uncertainty for natural gases
The GERG2008 widerange equation of state for natural gases and other (multicomponent and binary)
mixtures, consisting of the components listed in table 6, is valid in the gas phase, in the liquid phase, in the
supercritical region, and for vaporliquid equilibrium states. For natural gases and similar mixtures, a normal
range of validity and an extended range of validity were defined. The extrapolation to temperatures and
pressures even far beyond the extended range of validity yields reasonable results. The estimated
uncertainties for the different ranges of validity, as described below, are based on the representation of the
available experimental data for various thermodynamic properties of natural gases and other multicomponent
mixtures by the GERG2008 equation of state as summarized in table 12.
In general, there are no restrictions in the composition range of binary and multicomponent mixtures. But,
since the estimated uncertainty of the GERG2008 equation of state is based on the experimental data used
for the development and evaluation of the equation, the uncertainty is mostly unknown for composition ranges
not covered by experimental data. The data situation allows for wellfounded uncertainty estimates only for
selected properties and parts of the fluid surface.
Most of the available experimental data for multicomponent mixtures describe the p)T relation of natural
gases and similar mixtures in the gas phase. The majority of these data cover the temperature range 270 K
T 350 K at pressures up to 30 MPa [1,2] and were measured for pipeline quality natural gas. There are a
number of additional experimental data available that define the composition range of wider quality natural gas,
e.g., measurements on rich natural gases with comparatively high content of carbon dioxide, ethane, propane,
and nbutane; see table 6 for the composition ranges defined for pipeline quality and expanded quality natural
gases. As mentioned in 6.3, pipeline quality natural gases are a subset of the expanded quality natural gases.
Table 12 Summary of the available data for volumetric and caloric properties of natural gases and
other multicomponent mixtures
Data type
a
Number of
data points
Covered ranges Maximum
number of
components
Temperature Pressure
T/K p/MPa
Density 21769 91.0 573 0.03 99.9 18
Speed of sound 1337 213 414 0.00 70.0 13
Isobaric heat capacity 325 105 350 0.5 30.0 8
Enthalpy differences 1166 105 422 0.2 16.5 10
Saturated liquid density 124 105 251 0.04 3.2 8
VLE data 2284 77.8 450 0.1 27.6 4
Total 27005 77.8 573 0.00 99.9 18
a
Further data not included in table 12 were used to validate the quality of the GERG2008 equation of state,
e.g., recent dewpoint measurements for a number of different natural gases and other multicomponent
mixtures, see [2].
7.4.1 Uncertainty in the normal and expanded ranges of validity of natural gas
The normal range of validity of natural gas covers the temperature range 90 K T 450 K for pressures up to
35 MPa, see 6.3, table 5. This range corresponds to the use of the equation in both standard and advanced
technical applications using natural gases and similar mixtures, e.g., pipeline transport, natural gas storage,
and improved processes with liquefied natural gas. Estimated uncertainties for the composition subsets
pipeline quality natural gas and expanded quality natural gas are summarized in table 13.
ISO/CD 207652
ISO 2011 All rights reserved 23
Table 13 Uncertainty of the GERG2008 equation of state in the description of selected volumetric
and caloric properties of pipeline quality and expanded quality natural gases
Pipeline quality natural gas
Temperature region Pressure region Uncertainty
Density, gas phase 250 K s T s 450 K p s 35 MPa
s
A
0.1%
Density, liquid phase 100 K s T s 140 K p s 40 MPa
s
A
(0.1 0.5)%
Saturated liquid density 100 K s T s 140 K
s
'
' A
(0.1 0.3)%
Speed of sound, gas phase 250 K s T s 270 K p s 12 MPa Aw
w
s 0.1%
270 K s T s 450 K p s 20 MPa Aw
w
s 0.1%
250 K s T s 270 K
250 K s T s 450 K
12 s p s 20 MPa
20 s p s 30 MPa
Aw
w
s (0.2 0.3)%
Enthalpy differences, gas
phase
250 K s T s 350 K p s 20 MPa
s
A
A A
h
h) (
(0.2 0.5)%
Enthalpy differences, liquid
phase
s
A
A A
h
h) (
(0.5 1.0)%
Isobaric/isochoric heat capacity, gas and liquid phases
p
p
c
c A
or ~
A
v
v
c
c
(1 2)%
Expanded range
a
Molar mass
Pressure region
Uncertainty
Density, gas phase M 26 kgkmol
1
p s 30 MPa
s
A
0.1%
M > 26 kgkmol
1
p s 30 MPa
s
A
(0.1 0.3)%
b
a
For rich natural gases, i.e., for natural gas mixtures that contain comparatively large
amounts of carbon dioxide, ethane, propane, and further secondary alkanes, the
tested temperature range is as follows: 280 K s T s 350 K.
b
For mixtures with molar masses M > 30 kgkmol
1
and compositions within the limits
stated in table 6, the upper uncertainty value in density is estimated to be 0.5%.
Pipeline quality natural gas
Density data in the gas phase for pipeline quality natural gases are described by the equation with an
uncertainty of A / 0.1% (over the temperature range 250 K T 450 K and for pressures up to 35 MPa).
The uncertainty in speed of sound is likewise less than 0.1%. However, due to limited experimental data, this
uncertainty is restricted to pressures below 20 MPa; at temperatures below 270 K it is restricted to pressures
below 12 MPa. The most accurate liquid or saturated liquid density data are described within 0.1% to 0.3%,
which is in agreement with the estimated experimental uncertainty of the measurements.
Expanded quality natural gas
This quality range of natural gases comprises a wider composition range than given by the pipeline quality
natural gases. The wider composition range is almost identical to the composition range covered by the
available experimental natural gas and similar multicomponent mixture data, including several data sets for
natural gases containing synthetic mixtures, ternary mixtures of natural gas main components, and rich
ISO/CD 207652
24 ISO 2011 All rights reserved
natural gases. Rich natural gases contain large amounts of carbon dioxide (up to 0.20 mole fraction), ethane
(up to 0.18), propane (up to 0.14), nbutane (up to 0.06), npentane (0.005), and nhexane (0.002).
For mixtures that fall within the wider composition range defined in table 6, the estimated uncertainty in gas
phase density is 0.1% for molar masses M 26 kgkmol
1
; see equation (18) for the calculation of the molar
mass from the given mixture composition. For mixtures with molar masses M > 26 kgkmol
1
, the uncertainty
in gas phase density is 0.1% to 0.3%. For other thermodynamic properties, wellfounded estimates of
uncertainty cannot be given due to the limited data situation.
NOTE 1 For rich natural gases, the lower temperature limit is increased because dew point temperatures are
considerably higher for these types of mixtures, which contain comparatively large amounts of carbon dioxide, ethane,
propane, and the further secondary alkanes.
NOTE 2 Within the mole fraction limits defined for pipeline quality natural gas, the molar mass of any mi xture will
always be lower than 26 kgkmol
1
.
Uncertainty in the extended range of validity, and calculation of properties beyond this range
The extended range of validity covers temperatures of 60 K T 700 K and pressures up to 70 MPa. The
uncertainty of the equation in gas phase density at temperatures and pressures outside the normal range of
validity is roughly estimated to be (0.2 0.5)%. For certain mixtures, the extended range of validity covers
temperatures of T > 700 K and pressures of p > 70 MPa. For example, the equation accurately describes gas
phase density data of air to within (0.1 0.2)% at temperatures up to 900 K and pressures up to 90 MPa.
For other thermodynamic properties, wellfounded estimates of uncertainty cannot be given due to the limited
data situation outside the normal range of validity. However, the estimates given for the pure substance
equations and for the different binary systems give some clue as to what may be expected with respect to the
description of other thermodynamic properties in the extended range of validity.
When larger uncertainties are acceptable, tests have shown that the equation can be reasonably used outside
the extended range of validity. For example, density data (frequently of questionable and low accuracy
outside the extended range of validity) for certain binary mixtures are described to within (0.5 1)% at
pressures up to 100 MPa and more.
7.5 Uncertainties in other properties
An estimate of the uncertainty Az of the equation of state in any property z other than the density and not
explicitly listed above, such as JouleThomson coefficient or isentropic exponent, can be obtained by
calculating
z z T x
1 1
= ( , , ) (37)
and
z z T x
2 2
= ( , , ) (38)
with
2 1
= + A , (39)
where A is the absolute uncertainty in density for given values of
1
, T, and x . Then, the absolute
uncertainty in the property z corresponds to the difference
Az z z =
2 1
. (40)
This value most likely under estimates the uncertainty in the property.
7.6 Impact of uncertainties of input variables
The user should recognize that uncertainties in the input variables, usually pressure, temperature and
composition by mole fractions, will have additional effects upon the uncertainty of any calculated result. The
uncertainties given so far for calculated results in 7 assume the input data are exact. In any particular
ISO/CD 207652
ISO 2011 All rights reserved 25
application where the additional uncertainty may be of importance the user should carry out sensitivity tests to
determine its magnitude. Varying the input variables may do this.
8 Reporting of results
When reported in accordance with the units given in Annex A, results for the thermodynamic properties shall
be quoted with rounding to the number of digits after the decimal point as given in table 14. The report shall
identify the temperature, pressure (or density), and detailed composition to which the results refer. The
method of calculation used shall be identified by reference to ISO 207652 Natural gas Calculation of
thermodynamic properties.
For the validation of calculations and for subsequent calculations based on thermodynamic properties
obtained using this standard it may be appropriate to carry extra digits (see example calculations in Annex G).
Table 14 Reporting of results
Symbol Property Units Decimal places
Z Compression factor  4
Molar density kmol/m
3
3
D Massbased density kg/m
3
2
p Pressure MPa 3
u Molar internal energy kJ/kmol 0
U Specific internal energy kJ/kg 1
h Molar enthalpy kJ/kmol 0
H Specific enthalpy kJ/kg 1
s Molar entropy kJ/(kmolK) 2
S Specific entropy kJ/(kgK) 3
g Molar Gibbs free energy kJ/kmol 0
G Specific Gibbs free energy kJ/kg 1
c
v
Molar isochoric heat capacity kJ/(kmolK) 2
C
v
Specific isochoric heat capacity kJ/(kgK) 3
c
p
Molar isobaric heat capacity kJ/(kmolK) 2
C
p
Specific isobaric heat capacity kJ/(kgK) 3
JouleThomson coefficient K/MPa 2
T
Isothermal throttling coefficient 10
3
m
3
/kmol 2
k Isentropic exponent  2
w Speed of sound m/s 1
B Second virial coefficient 10
3
m
3
/kmol 4
C Third virial coefficient 10
6
m
6
/kmol
2
4
ISO/CD 207652
26 ISO 2011 All rights reserved
Annex A
(normative)
Symbols and units
Symbol Meaning Source of values Units
a Molar Helmholtz free energy equation (1) kJ/kmol
B Second virial coefficient equation (32) m
3
/kmol
c Density exponent equation (9) 
c
p
Molar isobaric heat capacity equation (26) kJ/(kmolK)
c
v
Molar isochoric heat capacity equation (24) kJ/(kmolK)
C Third virial coefficient equation (33) m
6
/kmol
2
C
v
Specific isochoric heat capacity table 14 kJ/(kgK)
C
p
Specific isobaric heat capacity table 14 kJ/(kgK)
d Density exponent equation (9) 
D Massbased density equation (19) kg/m
3
F Mixture parameter equation (11) 
g Molar Gibbs free energy equation (27) kJ/kmol
h Molar enthalpy equation (25) kJ/kmol
H Specific enthalpy table 14 kJ/kg
i Serial number equation (6) 
j Serial number equation (10) 
k Coverage factor Scope 
k Serial number equation (7) 
K Number of terms equation (9) 
M Molar mass equation (18) kg/kmol
n Coefficient equation (7) 
N Number of components in the mixture equation (6) 
p Pressure equation (20) MPa
R Molar gas constant, R = 8.314 472, [4] equation (7) kJ/(kmolK)
R* Molar gas constant, R*= 8.314 51, used in [5] equation (7) kJ/(kmolK)
s Molar entropy equation (23) kJ/(kmolK)
S Specific entropy table 14 kJ/(kgK)
t Temperature exponent equation (9) 
T Temperature in K (ITS90) equation (1) K
u Molar internal energy equation (22) kJ/kmol
U Specific internal energy table 14 kJ/kg
ISO/CD 207652
ISO 2011 All rights reserved 27
v Molar volume equation (20) m
3
/kmol
w Speed of sound equation (28) m/s
x Mole fraction equation (6) 
xx Molar composition (vector of mole fractions) equation (1) 
z Any property equation (37) 
Z Compression factor equation (21) 
Greek Symbols
o Reduced molar Helmholtz free energy, o= a/(RT) equation (2) 
 Parameter equation (12) 

T
Parameter equation (14) 

V
Parameter equation (13) 
Parameter equation (12) 
T
Parameter equation (14) 
V
Parameter equation (13) 
o Reduced density, o= /
r
equation (2) 
o
T
Isothermal throttling coefficient equation (30) m/kmol
c Parameter equation (12) 
c Partial derivative equation (15) 
Ao Departure function for the reduced molar Helmholtz
free energy equation (5) 
q Parameter equation (12) 
0 Parameter equation (7) 
k Isentropic exponent equation (31) 
JT
JouleThomson coefficient equation (29) K/MPa
Molar density equation (1) kmol/m
3
t Inverse reduced temperature, t=T
r
/T equation (2) 
Inferior indices
c At the critical point equation (7) 
Exp Exponential term equation (9) 
i Serial number equation (6) 
j Serial number equation (10) 
k Serial number equation (7) 
o Property of the pure substance equation (5) 
Pol Polynomial term equation (9) 
r Reducing property equation (3) 
s At saturation (phase equilibrium) table 9 
o Partial derivative with respect to o equation (15) 
t Partial derivative with respect to t equation (15) 
ISO/CD 207652
28 ISO 2011 All rights reserved
0 Reference state, T
0
= 298.15 K, p
0
= 0.101325 MPa equation (B.4) 
Superior indices
o Idealgas state equation (1) 
r Residual part equation (1) 
' Saturated liquid state table 9 
" Saturated vapor state table 9 
ISO/CD 207652
ISO 2011 All rights reserved 29
Annex B
(normative)
The reduced Helmholtz free energy of the ideal gas
B.1 Calculation of the reduced Helmholtz free energy of the ideal gas
For a pure component, the Helmholtz free energy of the ideal gas is given by
) , ( ) ( ) , ( T Ts RT T h T a
o o o
= . (B.1)
For the ideal gas, the enthalpy h
o
is a function of temperature only, whereas the entropy s
o
depends on
temperature and density. Both properties can be expressed in terms of the idealgas isobaric heat capacity c
o
p
as follows:
o
0
o o
0
d ) ( h T c T h
T
T
p
+ =
}
, (B.2)
o
0
o
0
o
o
ln d ) , (
0
s R T
T
R c
T s
T
T
p
+


.

\

=
}
. (B.3)
When the above expressions for h
o
(T) and s
o
(,T) are inserted into equation (B.1), one obtains
(
(
+


.

\

+ =
} }
o
0
o
0
o
o
0
o o
ln d d ) , (
0 0
s R T
T
R c
T RT h T c T a
T
T
p
T
T
p
, (B.4)
where all variables with the subscript 0 refer to an arbitrary reference state. The reference state of zero
enthalpy and zero entropy is here adopted at T
0
= 298.15 K and p
0
= 0.101 325 MPa for the ideal gas. The
integration constants h
o
0
and s
o
0
are then determined so as to conform to this definition. The reference density
o
0
is given by
o
0
=p
0
/(RT
0
).
In order to obtain an explicit equation for a
o
(,T), an equation for the idealgas isobaric heat capacity c
o
p
is
needed. The idealgas isobaric heat capacity may be written as follows [2]
= =




.

\


.

\

+




.

\


.

\

+ + =
7 , 5
2
c o
c o
o
6 , 4
2
c o
c o
o o
3
o
cosh sinh
1
k
k
k
k
k
k
k
k
p
T
T
T
T
n
T
T
T
T
n n
R
c
0
0
0
0
. (B.5)
The values of the coefficients n
0
k
and parameters 0
0
k
of equation (B.5) are given in table B.1.
NOTE The equation for the idealgas isobaric heat capacity is taken from [5] and given as a function of the temperature
T. The values resulting from the parameter product 0
o
k
T
c
(for k = 4 to 7) are in agreement with the original
ISO/CD 207652
30 ISO 2011 All rights reserved
parameters D
O
, F
O
, H
O
, and J
O
, respectively, and the coefficients n
o
k
(for k = 4 to 7) have identical values as the
coefficients C
O
, E
O
, G
O
, and I
O
, respectively. The coefficient n
o
3
=B
o
1.
For a mixture at a given mixture density , temperature T, and molar composition x , the reduced Helmholtz
free energy of the ideal gas is given as follows:
 
=
+ =
N
i
i i i
x T x x T
1
o
o
o
ln ) , ( ) , , ( o o . (B.6)
In this equation, o
o
oi
(, T ) is the dimensionless form of the Helmholtz free energy in the idealgas state of
component i as given by
) , (
o
o
T
i
o =


.

\

+


.

\

+ + +


.

\

=

6 , 4
,
, ,
,
3 ,
,
2 , 1 ,
,
sinh ln ln ln
k
i
k i k i
i
i
i
i i
i
T
T
n
T
T
n
T
T
n n
R
R
c o
o
o
o
c o
o
c o
o
o
o
c
0
(
(
(

.

\

= 7 , 5
, c
o
, o
o
, o
cosh ln
k
i
k i k i
T
T
n 0 , (B.7)
and the term
i i
x x ln accounts for the entropy of mixing of the idealgas mixture.
NOTE To indicate a pure substance as a component in a mixture, the inferior indices o (referring to pure substance)
and i (referring to the considered component) are introduced.
It is important to observe that in equation (B.6) o
o
is a function of the molar density , the temperature T, and
the molar composition x , where is the molar density of the real mixture (i.e., not the molar density of the
ideal gas). If the input variables are the absolute pressure p, the temperature T and the molar composition x ,
may be calculated from the input variables as described in 5.
B.2 Derivatives of the reduced Helmholtz free energy of the ideal gas
For some of the thermodynamic properties, the calculation requires first and second partial derivatives of the
reduced Helmholtz free energy of the ideal gas o
o
=o
o
(, T , x ) (equation (B.6)) with respect to the reduced
mixture density o or inverse reduced mixture temperature t. The relevant mathematical expressions are as
follows:
( )
o
o
o
t
o
1
1
o
, c
r
,
o
o
*
r
,
/
o
=
=


.

\

c
c
=


.

\

c
c
=
N
i
T
i
i
x
R
R
i c
i
x (B.8)
( )
2
*
2
r
,
1
1
2
o 2
2
, c
r
,
2
o 2
o
/
o
o
o
o
t
oo
R
R
N
i
T
i
i
x
i c
i
x =



.

\

c
c
=


.

\

c
c
=
=


.

\

(B.9)
( ) ( )
0
/ /
1
o 2
r
, c
, c
r
o 2
o
, ,
o
=


.

\

c c
c
=


.

\

c c
c
=
=
N
i
i
i
i
x
T T T
T
x
i c i c
i
o
t o
o
o
ot
(B.10)
ISO/CD 207652
ISO 2011 All rights reserved 31
( )
=


.

\

c
c
=


.

\

c
c
=
N
i
i
i
x
T T T
T
x
i c
i
1
o
r
, c
,
o
o
/
,
o
o
t
o
t
o
o (B.11)
( )
(
(
(
(
(
(


.

\



.

\

+ + =


.

\

c
c
= =

7 , 5
, c o
, o
o
, o
o
, o
6 , 4
, c o
, o
o
, o o
, o
, c
o
3 , o
o
2 , o
o
tanh
tanh
/
,
o
k
i
k i k i k i
k
i
k i
k i
k i
i
i i
T
T
n
T
T
n
T
T
n n
R
R
T T
i c
i
0 0
0
0
o
(B.12)
( )
=



.

\

c
c
=


.

\

c
c
=


.

\
 N
i
i
i
x
T T
T
T
x
i c
i
1
2
o 2
2
r
, c
,
2
o 2
o
/
,
o
o
tt
o
t
o
o (B.13)
( )
(
(
(
(
(
(
(
(



.

\



.

\


.

\




.

\



.

\


.

\




.

\

=



.

\

c
c
= =

7 , 5
2
, c o
, o
2
o
, o
o
, o
6 , 4
2
, c o
, o
2
o
, o
o
, o
2
, c
o
3 , o
2
o 2
cosh sinh
/
,
o
k
i
k i
k i
k i
k
i
k i
k i
k i
i
i
T
T
n
T
T
n
T
T
n
R
R
T T
i c
i
0
0
0
0
o
(B.14)
ISO/CD 207652
32 ISO 2011 All rights reserved
Table B.1 Values of the coefficients and parameters in equation (B.7) for the 21 components
a
k n
i k o
o
,
0
o
o
i k ,
k n
i k o
o
,
0
o
o
i k ,
Methane
1 19.597508817 5 0.00460 0.936220902
2 83.959667892 6 8.74432 5.577233895
3 3.00088 7 4.46921 5.722644361
4 0.76315 4.306474465
Nitrogen
1 11.083407489 5 0.14660 5.393067706
2 22.202102428 6 0.90066 13.788988208
3 2.50031 7
4 0.13732 5.251822620
Carbon dioxide
1 11.925152758 5 1.06044 2.844425476
2 16.118762264 6 2.03366 1.589964364
3 2.50002 7 0.01393 1.121596090
4 2.04452 3.022758166
Ethane
1 24.675437527 5 1.23722 0.731306621
2 77.425313760 6 13.1974 3.378007481
3 3.00263 7 6.01989 3.508721939
4 4.33939 1.831882406
Propane
1 31.602908195 5 3.19700 0.543210978
2 84.463284382 6 19.1921 2.583146083
3 3.02939 7 8.37267 2.777773271
4 6.60569 1.297521801
nButane
1 20.884168790 5 6.89406 0.431957660
2 91.638478026 6 24.4618 4.502440459
3 3.33944 7 14.7824 2.124516319
4 9.44893 1.101487798
ISO/CD 207652
ISO 2011 All rights reserved 33
Isobutane
1 20.413726078 5 5.25156 0.485556021
2 94.467620036 6 25.1423 4.671261865
3 3.06714 7 16.1388 2.191583480
4 8.97575 1.074673199
nPentane
1 14.536611217 5 21.8360 1.789520971
2 89.919548319 6 33.4032 3.777411113
3 3.0 7
4 8.95043 0.380391739
Isopentane
1 15.449907693 5 20.1101 1.977271641
2 101.298172792 6 33.1688 4.169371131
3 3 7
4 11.7618 0.635392636
nHexane
1 14.345969349 5 26.8142 1.691951873
2 96.165722367 6 38.6164 3.596924107
3 3.0 7
4 11.6977 0.359036667
nHeptane
1 15.063786601 5 30.4707 1.548136560
2 97.345252349 6 43.5561 3.259326458
3 3.0 7
4 13.7266 0.314348398
nOctane
1 15.864687161 5 33.8029 1.431644769
2 97.370667555 6 48.1731 2.973845992
3 3.0 7
4 15.6865 0.279143540
nNonane
1 16.313913248 5 38.12350 1.370586158
2 102.160247463 6 53.34150 2.848860483
3 3.0 7
4 18.02410 0.263819696
ISO/CD 207652
34 ISO 2011 All rights reserved
nDecane
1 15.870791919 5 43.49310 1.353835195
2 108.858547525 6 58.36570 2.833479035
3 3.0 7
4 21.00690 0.267034159
Hydrogen
1 13.796443393 5 0.45444 9.847634830
2 175.864487294 6 1.56039 49.765290750
3 1.47906 7 1.37560 50.367279301
4 0.95806 6.891654113
Oxygen
1 10.001843586 5 1.01334 7.223325463
2 14.996095135 6
3 2.50146 7
4 1.07558 14.461722565
Carbon monoxide
1 10.813340744 5 0.00493 5.305158133
2 19.834733959 6
3 2.50055 7
4 1.02865 11.675075301
Hydrogen Sulfide
1 9.336197742 5 1.00243 2.270653980
2 16.266508995 6
3 3.0 7
4 3.11942 4.914580541
Water
1 8.203520690 5 0.98763 1.763895929
2 11.996306443 6 3.06904 3.874803739
3 3.00392 7
4 0.01059 0.415386589
Helium
1 13.628409737 3 1.5
2 143.470759602
Argon
1 8.316631500 3 1.5
2 4.946502600
a
The values of the coefficients and parameters are also valid for equation (7).
ISO/CD 207652
ISO 2011 All rights reserved 35
Annex C
(normative)
Values of critical parameters and molar masses of the pure components
Table C.1 Critical parameters and molar masses of the 21 components
Component Formula
c,i
/(moldm
3
) T
i c,
/K M
i
/(gmol
1
)
a
Methane CH
4
10.139342719 190.564 16.04246
Nitrogen N
2
11.1839 126.192 28.0134
Carbon dioxide CO
2
10.624978698 304.1282 44.0095
Ethane C
2
H
6
6.870854540 305.322 30.06904
Propane C
3
H
8
5.000043088 369.825 44.09562
nButane nC
4
H
10
3.920016792 425.125 58.1222
Isobutane iC
4
H
10
3.860142940 407.817 58.1222
nPentane nC
5
H
12
3.215577588 469.7 72.14878
Isopentane iC
5
H
12
3.271 460.35 72.14878
nHexane nC
6
H
14
2.705877875 507.82 86.17536
nHeptane nC
7
H
16
2.315324434 540.13 100.20194
nOctane nC
8
H
18
2.056404127 569.32 114.22852
nNonane nC
9
H
20
1.81 594.55 128.2551
nDecane nC
10
H
22
1.64 617.7 142.28168
Hydrogen H
2
14.94 33.19 2.01588
Oxygen O
2
13.63 154.595 31.9988
Carbon monoxide CO 10.85 132.86 28.0101
Water H
2
O 17.873716090 647.096 18.01528
Hydrogen sulfide H
2
S 10.19 373.1 34.08088
Helium He 17.399 5.1953 4.002602
Argon Ar 13.407429659 150.687 39.948
a
According to IUPAC Technical Report (2006) [6].
ISO/CD 207652
36 ISO 2011 All rights reserved
Annex D
(normative)
The residual part of the reduced Helmholtz free energy
D.1 Calculation of the residual part of the reduced Helmholtz free energy
The residual part o
r
of the reduced Helmholtz free energy o of the mixture is given by
) , , ( ) , , ( ) , , ( x x x t o o t o o t o o
r r
o
r
A + = , (D.1)
where
=
=
N
i
i i
x x
1
) , ( ) , , ( t o o t o o
r
o
r
o
(D.2)
and
= + =
= A
1
1 1
r r
) , ( ) , , (
N
i
N
i j
ij ij j i
F x x x t o o t o o . (D.3)
In equation (D.1), the first term on the righthand side, o
r
o
(o, t, x ), describes the contribution of the residual
parts of the reduced Helmholtz free energy of the pure substance equations of state, which are multiplied by
the mole fraction of the corresponding substance and linearly combined using the reduced variables o and t
of the mixture, to the residual part of the reduced Helmholtz free energy of the mixture. The second term is the
departure function, Ao
r
(o, t, x ), which is the summation over all binary specific and generalized departure
functions. The variables o and t are the reduced mixture density and inverse reduced mixture temperature,
respectively, as given by
o
=
r
( ) x
(D.4)
and
t =
T x
T
r
( )
, (D.5)
where
r
and T
r
are reducing functions for the mixture density and mixture temperature depending on the
molar composition of the mixture only (see 4.2.7 and Annex E.1).
D.1.1 Derivatives of the residual part of the reduced Helmholtz free energy
The derivatives of the residual part o
r
(o, t, x ) of the reduced Helmholtz free energy o of the mixture with
respect to the reduced mixture variables o and t are as follows:
ISO/CD 207652
ISO 2011 All rights reserved 37
= + = =




.

\

c
c
+



.

\

c
c
=



.

\

c
c
=
1
1 1
r
1
r
o
,
r
r
N
i
N
i j
ij
ij j i
N
i
i
i
x
F x x x
t
t
t
o o
o
o
o
o
o
o (D.6)
= + = =




.

\

c
c
+



.

\

c
c
=



.

\

c
c
=
1
1 1
2
r 2
1
2
r
o
2
,
2
r 2
r
N
i
N
i j
ij
ij j i
N
i
i
i
x
F x x x
t
t
t
oo
o
o
o
o
o
o
o (D.7)
= + = =




.

\

c c
c
+



.

\

c c
c
=



.

\

c
c
=
1
1 1
r 2
1
r
o
2
r 2
r
N
i
N
i j
ij
ij j i
N
i
i
i
x
F x x x
t o
o
t o
o
ct o
o
o
ot
(D.8)
= + = =




.

\

c
c
+



.

\

c
c
=



.

\

c
c
=
1
1 1
r
1
r
o
,
r
r
N
i
N
i j
ij
ij j i
N
i
i
i
x
F x x x
o
o
o
t t
o
t
o
t
o
o (D.9)
= + = =




.

\

c
c
+



.

\

c
c
=



.

\

c
c
=
1
1 1
2
r 2
1
2
r
o
2
,
2
r 2
r
N
i
N
i j
ij
ij j i
N
i
i
i
x
F x x x
o
o
o
tt
t
o
t
o
t
o
o (D.10)
D.2 Calculation of the pure substance contribution to the residual part of the
reduced Helmholtz free energy
The contribution of the residual parts of the reduced Helmholtz free energy of the pure substance equations of
state o
r
o
to the residual part of the reduced Helmholtz free energy of the mixture is given by equation (D.2),
where the residual part of the reduced Helmholtz free energy of component i, o
r
oi
(o, t), (i.e., the residual part
of the respective pure substance equation of state) is given by
+
+ =
=
+ =
i i
i
k i
k i k i
i
k i k i
K K
K k
c
t d
k i
K
k
t d
i,k i
e n n
, ,
,
,
, ,
,
, ,
1
,
1
) , (
Exp Pol
Pol
o
o o
Pol
o o
o o
r
o
o
t o t o t o o . (D.11)
For each of the pure substances, the equations for o
r
oi
use the same basic structure, however, the number of
terms differ. For the main components, the equations consist of 24 terms for methane, nitrogen, and ethane
and of 22 terms for carbon dioxide. For the secondary alkanes and the other secondary components (oxygen,
carbon monoxide, helium, hydrogen sulfide, and argon), 12 terms are used, while the equations for hydrogen
and water consist of 14 and 16 terms, respectively. The values of the coefficients n
oi,k
and exponents d
oi,k
, t
oi,k
,
and c
oi,k
for the 21 components are given in Annex D.2.2.
D.2.1 Derivatives of
) , (
r
o
t o o
i
with respect to the reduced mixture variables
The derivatives of the residual part of the reduced Helmholtz free energy of component i, o
r
oi
(o, t), (equation
(D.11)) with respect to the reduced mixture variables o and t are as follows:
ISO/CD 207652
38 ISO 2011 All rights reserved
+
+ =


.

\



.

\

+
=



.

\

c
c
i i
i
k i k i k i k i
i
k i k i
K K
K k
c t c
k i k i
d
k i
K
k
t d
k i k i
i
c d n
d n
, Exp , Pol
, Pol
, o , o , o , o
, Pol
, o , o
1
, o , o
1
, o
1
1
, o , o
r
o
exp o t o o
t o
o
o
t
(D.12)
+
+ =


.

\



.

\



.

\



.

\

+

.

\

=



.

\

c
c
i i
i
k i k i k i k i k i k i
i
k i k i
K K
K k
c t c
k i
c
k i k i
c
k i k i
d
k i
K
k
t d
k i k i k i
i
c c d c d n
d d n
, Exp , Pol
, Pol
, o , o , o , o , o , o
, Pol
, o , o
1
2
, o , o , o , o , o
2
, o
1
2
, o , o , o
2
r
o
2
exp 1
1
o t o o o o
t o
o
o
t
(D.13)
+
+ =
=


.

\



.

\

+
=



.

\

c c
c
i i
i
k i k i k i k i
i
k i k i
K K
K k
c t c
k i k i
d
k i k i
K
k
t d
k i k i k i
i
c d t n
t d n
, Exp , Pol
, Pol
, o , o , o , o
, Pol
, o , o
1
1
, o , o
1
, o , o
1
1 1
, o , o , o
r
o
2
exp o t o o
t o
t o
o
(D.14)
+
+ =


.

\

+
=



.

\

i i
i
k i k i k i
i
k i k i
K K
K k
c t d
k i k i
K
k
t d
k i k i
i
t n
t n
, Exp , Pol
, Pol
, o , o , o
, Pol
, o , o
1
1
, o , o
1
1
, o , o
r
o
exp o t o
t o
ct
co
o
(D.15)
+
+ =


.

\


.

\

+

.

\

=



.

\

c
c
i i
i
k i k i k i
i
k i k i
K K
K k
c t d
k i k i k i
K
k
t d
k i k i k i
i
t t n
t t n
, Exp , Pol
, Pol
, o , o , o
, Pol
, o , o
1
2
, o , o , o
1
2
, o , o , o
2
r
o
2
exp 1
1
o t o
t o
t
o
o
(D.16)
ISO/CD 207652
ISO 2011 All rights reserved 39
D.2.2 Coefficients and exponents of ) , (
r
o
t o o
i
Table D.1 Values of the coefficients and exponents in equation (D.11) for methane, nitrogen, and ethane
a,b
.
k n
i k o ,
n
i k o ,
n
i k o ,
Methane Nitrogen Ethane
1 0.57335704239162 0.59889711801201 0.63596780450714
2 0.1676068752373010
1
0.1694155748073110
1
0.1737798178545910
1
3 0.23405291834916 0.24579736191718 0.28914060926272
4 0.21947376343441 0.23722456755175 0.33714276845694
5 0.1636920140412810
1
0.1795491871514110
1
0.2240596469956110
1
6 0.1500440638928010
1
0.1459287572021510
1
0.1571542488691310
1
7 0.9899048949291810
1
0.10008065936206 0.11450634253745
8 0.58382770929055 0.73157115385532 0.1061204937974510
1
9 0.74786867560390 0.88372272336366 0.1285522443942310
1
10 0.30033302857974 0.31887660246708 0.39414630777652
11 0.20985543806568 0.20766491728799 0.31390924682041
12 0.1859015113306110
1
0.1937931545415810
1
0.2159227711724710
1
13 0.15782558339049 0.16936641554983 0.21723666564905
14 0.12716735220791 0.13546846041701 0.28999574439489
15 0.3201974389434610
1
0.3306671209530710
1
0.42321173025732
16 0.6804972936453610
1
0.6069081701855710
1
0.4643410025926010
1
17 0.2429141285373610
1
0.1279754829287110
1
0.13138398329741
18 0.5144045163944410
2
0.5874366410729910
2
0.1149285036436810
1
19 0.1908494973353210
1
0.1845195197196910
1
0.3338768842990910
1
20 0.5522967724129110
2
0.4722662204247210
2
0.1518317158364410
1
21 0.4419739297608510
2
0.5202407968059910
2
0.4761080564765710
2
22 0.4006141670842910
1
0.4356350595663510
1
0.4691716627788510
1
23 0.3375208590757510
1
0.3625169075093910
1
0.3940175580464910
1
24 0.2512765821335710
2
0.2897402686654310
2
0.3256995624761110
2
k c
i k o ,
d
i k o ,
t
i k o ,
k c
i k o ,
d
i k o ,
t
i k o ,
1 1 0.125 13 2 2 4.5
2 1 1.125 14 2 3 4.75
3 2 0.375 15 2 3 5
4 2 1.125 16 2 4 4
5 4 0.625 17 2 4 4.5
6 4 1.5 18 3 2 7.5
7 1 1 0.625 19 3 3 14
8 1 1 2.625 20 3 4 11.5
9 1 1 2.75 21 6 5 26
10 1 2 2.125 22 6 6 28
11 1 3 2 23 6 6 30
12 1 6 1.75 24 6 7 16
a
The values of the coefficients and exponents are also valid for equation (9).
b
K
Pol,i
= 6, K
Exp,i
= 18.
ISO/CD 207652
40 ISO 2011 All rights reserved
Table D.2 Values of the coefficients and exponents in equation (D.11) for propane, nbutane,
isobutane, npentane, isopentane, nhexane, nheptane, noctane, nnonane, n
decane, oxygen, carbon monoxide, hydrogen sulfide, and argon
ac
.
k n
i k o ,
n
i k o ,
n
i k o ,
Propane nButane Isobutane
1 0.1040397310735810
1
0.1062627741145510
1
0.1042933158910010
1
2 0.2831840408140310
1
0.2862095182835010
1
0.2818427254889210
1
3 0.84393809606294 0.88738233403777 0.86176232397850
4 0.7655959185002310
1
0.12570581155345 0.10613619452487
5 0.9469737305728010
1
0.10286308708106 0.9861574930213410
1
6 0.2479647549700610
3
0.2535804060265410
3
0.2394820868232210
3
7 0.27743760422870 0.32325200233982 0.30330004856950
8 0.4384600064837710
1
0.3795076105743210
1
0.4159815613509910
1
9 0.26991064784350 0.32534802014452 0.29991937470058
10 0.6931341308986010
1
0.7905096905101110
1
0.8036934276410910
1
11 0.2963214598165310
1
0.2063672054777510
1
0.2976137325115110
1
12 0.1404012675138010
1
0.5705380933475010
2
0.1305963030314010
1
nPentane Isopentane nHexane
1 0.1096864309800110
1
0.1101753196664410
1
0.1055323801366110
1
2 0.2998888829806110
1
0.3008236853198010
1
0.2612061589062910
1
3 0.99516886799212 0.99411904271336 0.76613882967260
4 0.16170708558539 0.14008636562629 0.29770320622459
5 0.11334460072775 0.11193995351286 0.11879907733358
6 0.2676059515074810
3
0.2954804254123010
3
0.2792286106261710
3
7 0.40979881986931 0.36370108598133 0.46347589844105
8 0.4087642308307510
1
0.4823608348829310
1
0.1143319698029710
1
9 0.38169482469447 0.35100280270615 0.48256968738131
10 0.10931956843993 0.10185043812047 0.9375055892465910
1
11 0.3207322332799010
1
0.3524260178545410
1
0.6727324715599410
2
12 0.1687701621697510
1
0.1975679759988810
1
0.5114158358542810
2
nHeptane nOctane nNonane
1 0.1054374764526210
1
0.1072254487563310
1
0.11151x10
1
2 0.2650068150614410
1
0.2463295117200310
1
0.27020x10
1
3 0.81730047827543 0.65386674054928 0.83416
4 0.30451391253428 0.36324974085628 0.38828
5 0.12253868710800 0.12713269626764 0.13760
6 0.2726647274392810
3
0.3071357277793010
3
0.28185x10
3
7 0.49865825681670 0.52656856987540 0.62037
8 0.7143281508417610
3
0.1936286285765310
1
0.15847x10
1
9 0.54236895525450 0.58939426849155 0.61726
10 0.13801821610756 0.14069963991934 0.15043
11 0.6159528738001110
2
0.7896633050003610
2
0.12982x10
1
12 0.4860251039302210
3
0.3303659796810910
2
0.44325x10
2
ISO/CD 207652
ISO 2011 All rights reserved 41
nDecane Oxygen Carbon monoxide
1 0.1046110
1
0.88878286369701 0.92310041400851
2 0.2480710
1
0.2487943331214810
1
0.2488584520580010
1
3 0.74372 0.59750190775886 0.58095213783396
4 0.52579 0.9650181706188110
2
0.2885916439465410
1
5 0.15315 0.7197042871277010
1
0.7025625727654410
1
6 0.3286510
3
0.2233744300019510
3
0.2168704326948810
3
7 0.84178 0.18558686391474 0.13758331015182
8 0.5542410
1
0.3812936803576010
1
0.5150111634346610
1
9 0.73555 0.15352245383006 0.14865357483379
10 0.18507 0.2672681491091910
1
0.3885710088681010
1
11 0.2077510
1
0.2567529867712710
1
0.2910043394894310
1
12 0.1233510
1
0.9571430212366810
2
0.1415568446627910
1
Hydrogen Sulfide Argon
1 0.87641 0.85095714803969
2 0.2036710
1
0.2400322294348010
1
3 0.21634 0.54127841476466
4 0.5019910
1
0.1691977069253810
1
5 0.6699410
1
0.6882596501903510
1
6 0.1907610
3
0.2142803281533810
3
7 0.20227 0.17429895321992
8 0.4534810
2
0.3365449560419410
1
9 0.22230 0.13526799857691
10 0.3471410
1
0.1638735079155210
1
11 0.1488510
1
0.2498766685147510
1
12 0.7415410
2
0.8876920481570910
2
k c
i k o ,
d
i k o ,
t
i k o ,
k c
i k o ,
d
i k o ,
t
i k o ,
1 1 0.25 7 1 2 0.625
2 1 1.125 8 1 5 1.75
3 1 1.5 9 2 1 3.625
4 2 1.375 10 2 4 3.625
5 3 0.25 11 3 3 14.5
6 7 0.875 12 3 4 12
a
The values of the coefficients and exponents are also valid for equation (9).
b
K
Pol,i
= 6, K
Exp,i
= 6.
c
For the simultaneously optimized equations of state of Span and Wagner (2003) [10], the old molar
gas constant R
*
was substituted with the recent one R without conversion. This has nearly no effect
on the quality of the equations of state (page 104 of [2]).
ISO/CD 207652
42 ISO 2011 All rights reserved
Table D.3 Values of the coefficients and exponents in equation (D.11) for carbon dioxide,
hydrogen, water, and helium
a
.
k c
i k o ,
d
i k o ,
t
i k o ,
n
i k o ,
Carbon dioxide
b
1 1 0 0.52646564804653
2 1 1.25 0.1499572504259210
1
3 2 1.625 0.27329786733782
4 3 0.375 0.12949500022786
5 1 3 0.375 0.15404088341841
6 1 3 1.375 0.58186950946814
7 1 4 1.125 0.18022494838296
8 1 5 1.375 0.9538990407281210
1
9 1 6 0.125 0.8048681931767910
2
10 1 6 1.625 0.3554775127309010
1
11 2 1 3.75 0.28079014882405
12 2 4 3.5 0.8243589008167710
1
13 3 1 7.5 0.1083242797900610
1
14 3 1 8 0.6707399316109710
2
15 3 3 6 0.4682790760052410
2
16 3 3 16 0.2835991183217710
1
17 3 4 11 0.1950017474409810
1
18 5 5 24 0.21609137507166
19 5 5 26 0.43772794926972
20 5 5 28 0.22130790113593
21 6 5 24 0.1519018995733110
1
22 6 5 26 0.1538094895330010
1
Hydrogen
c
1 1 0.5 0.5357992845125210
1
2 1 0.625 0.6205025253059510
1
3 2 0.375 0.13830241327086
4 2 0.625 0.7139795489612910
1
5 4 1.125 0.1547405395973310
1
6 1 1 2.625 0.14976806405771
7 1 5 0 0.2636872398845110
1
8 1 5 0.25 0.5668130315606610
1
9 1 5 1.375 0.6006395803043610
1
10 2 1 4 0.45043942027132
11 2 1 4.25 0.42478840244500
12 3 2 5 0.2199764082713910
1
13 3 5 8 0.1049952137453010
1
14 5 1 8 0.2895590286681610
2
ISO/CD 207652
ISO 2011 All rights reserved 43
Table D.3 (continued)
k c
i k o ,
d
i k o ,
t
i k o ,
n
i k o ,
Water
d
1 1 0.5 0.82728408749586
2 1 1.25 0.1860222041658410
1
3 1 1.875 0.1119900961374410
1
4 2 0.125 0.15635753976056
5 2 1.5 0.87375844859025
6 3 1 0.36674403715731
7 4 0.75 0.5398789343243610
1
8 1 1 1.5 0.1095769021449910
1
9 1 5 0.625 0.5321303782856310
1
10 1 5 2.625 0.1305053393082510
1
11 2 1 5 0.41079520434476
12 2 2 4 0.14637443344120
13 2 4 4.5 0.5572683862371910
1
14 3 4 3 0.1120177414380010
1
15 5 1 4 0.6606275806809910
2
16 5 1 6 0.4691852200453810
2
Helium
e
1 1 0 0.45579024006737
2 1 0.125 0.1251639075492510
1
3 1 0.75 0.1543823165062110
1
4 4 1 0.2046748970722110
1
5 1 1 0.75 0.34476212380781
6 1 3 2.625 0.2085845951278710
1
7 1 5 0.125 0.1622741471177810
1
8 1 5 1.25 0.5747181820089210
1
9 1 5 2 0.1946241643071510
1
10 2 2 1 0.3329568012302010
1
11 3 1 4.5 0.1086357737236710
1
12 3 2 5 0.2217336524595410
1
a
The values of the coefficients and exponents are also valid for equation (9).
b
K
Pol,i
= 4, K
Exp,i
= 18.
c
K
Pol,i
= 5, K
Exp,i
= 9.
d
K
Pol,i
= 7, K
Exp,i
= 9.
e
K
Pol,i
= 4, K
Exp,i
= 8.
ISO/CD 207652
44 ISO 2011 All rights reserved
D.3 Calculation of the departure function contribution to the residual part of the
reduced Helmholtz free energy
The purpose of the departure function is to further improve the accuracy of the mixture model in the
description of thermodynamic properties in cases where fitting the parameters of the reducing functions for
density and temperature (see Annex E) to accurate experimental data is not sufficient. The departure function
Ao
r
of the multicomponent mixture is the double summation over all binary specific and generalized departure
functions developed for the binary subsystems and is given by
= + =
A = A
1
1 1
r r
) , , ( ) , , (
N
i
N
i j
ij
x x t o o t o o (D.17)
with
) , ( ) , , (
r r
t o o t o o
ij ij j i ij
F x x x = A . (D.18)
In this equation, the function o
r
ij
(o, t) is the part of the departure function Ao
r
ij
(o, t, x ) that depends only on
the reduced mixture variables o and t, as given by
( ) ( )
+
+ =
=
+ =
ij ij
ij
k ij k ij k ij k ij k ij k ij
ij
k ij k ij
K K
K k
t d
k ij
K
k
t d
k ij ij
e n n
, Exp , Pol
, Pol
, ,
2
, , , ,
, Pol
, ,
1
,
1
,
r
) , (
o  c o q
t o t o t o o , (D.19)
where o
r
ij
(o, t) was developed either for a specific binary mixture (a binary specific departure function
with binary specific coefficients, exponents, and parameters) or for a group of binary mixtures (generalized
departure function with a uniform structure for the group of binary mixtures).
The values of the coefficients n
ij,k
, the exponents d
ij,k
and t
ij,k
, and the parameters q
ij,k
, c
ij,k
, 
ij,k
, and
ij,k
in
equation (D.19) for all binary specific and generalized departure functions considered in the mixture model are
given in table D.4. The values of the nonzero F
ij
parameters in equation (D.18) are listed in table D.5.
D.3.1 Binary specific departure functions
Binary specific departure functions were developed for the binary mixtures of methane with nitrogen, carbon
dioxide, ethane, propane, and hydrogen, and of nitrogen with carbon dioxide and ethane. For a binary specific
departure function, the adjustable factor F
ij
in equation (D.18) equals unity.
D.3.2 Generalised departure functions
A generalized departure function was developed for the binary mixtures of methane with nbutane and
isobutane, of ethane with propane, nbutane, and isobutane, of propane with nbutane and isobutane, and of
nbutane with isobutane. For each mixture in the group of generalized binary mixtures, the parameter F
ij
is
fitted to the corresponding binary specific data (except for the binary system methanenbutane, where F
ij
equals unity).
D.3.3 No departure functions
For all of the remaining binary mixtures, no departure function was developed, and F
ij
equals zero, i.e.,
Ao
r
ij
(o, t, x ) equals zero. For most of these mixtures, however, the parameters of the reducing functions for
density and temperature are fitted to selected experimental data (see Annex E).
ISO/CD 207652
ISO 2011 All rights reserved 45
D.3.4 Derivatives of ) , (
r
t o o
ij
with respect to the reduced mixture variables o and t .
The derivatives of the function o
r
ij
(o, t) (equation D.19) with respect to the reduced mixture variables o and t
are as follows:
+
+ =
=
(
(
(

.

\




.

\


.

\


.

\

+
=




.

\

c
c
ij ij
ij
k ij k ij
ij
k ij k ij
K K
K k
k ij k ij k ij
k ij
k ij k ij k ij k ij
t d
k ij
K
k
t d
k ij k ij
ij
d
n
d n
, Exp , Pol
, Pol
, ,
, Pol
, ,
1
, , ,
,
, ,
2
, , ,
1
1
, ,
r
2 exp  c o q
o
o  c o q t o
t o
o
o
t
(D.20)
( ) ( ) ( ) ( )
(
(


.

\

+
+ = =
+ 
.

\

=




.

\

c
c
k ij
k ij
k ij k ij k ij
k ij
k ij k ij k ij k ij
d d
ij ij
ij
k ij k ij
ij
k ij k ij
K K
K k
t d
k ij
K
k
t d
k ij k ij k ij
ij
n d d n
, 2
,
2
, , ,
,
, ,
2
, ,
2 2 exp
, Exp , Pol
, Pol
, ,
, Pol
, ,
1
,
1
2
, , ,
2
r 2
1
q
o
 c o q
o
o  c o q
t o t o
o
o
t (D.21)
( ) ( ) ( ) ( )
(
+
+ =
=
+ =




.

\

c c
c
k ij k ij k ij
k ij
k ij k ij k ij k ij
d
ij ij
ij
k ij k ij
ij
k ij k ij
K K
K k
t d
k ij k ij
K
k
t d
k ij k ij k ij
ij
t n t d n
, , ,
,
, ,
2
, ,
2 exp
, Exp , Pol
, Pol
, ,
, Pol
, ,
1
1
, ,
1
1 1
, , ,
r 2
 c o q
o
o  c o q
t o t o
t o
o
(D.22)
+
+ =



.

\


.

\


.

\

+
=




.

\

c
c
ij ij
ij
k ij k ij
ij
k ij k ij
K K
K k
k ij k ij k ij k ij
t d
k ij k ij
K
k
t d
k ij k ij
ij
t n
t n
, Exp , Pol
, Pol
, ,
, Pol
, ,
1
, ,
2
, ,
1
, ,
1
1
, ,
r
exp o  c o q t o
t o
t
o
o
(D.23)
+
+ =



.

\


.

\


.

\


.

\

+

.

\

=




.

\

c
c
ij ij
ij
k ij k ij
ij
k ij k ij
K K
K k
k ij k ij k ij k ij
t d
k ij k ij k ij
K
k
t d
k ij k ij k ij
ij
t t n
t t n
, Exp , Pol
, Pol
, ,
, Pol
, ,
1
, ,
2
, ,
2
, , ,
1
2
, , ,
2
r 2
exp 1
1
o  c o q t o
t o
t
o
o
(D.24)
ISO/CD 207652
46 ISO 2011 All rights reserved
D.3.5 Coefficients, exponents, and parameters for the departure functions
Table D.4 Values of the coefficients, exponents, and parameters in equation (D.19) for the
binary specific and generalized departure functions
a
.
k d
ij k ,
t
ij k ,
n
ij k ,
q
ij k ,
c
ij k ,
k ij ,

ij k ,
MethaneNitrogen
b
1 1 0 0.9803898551733510
2
2 4 1.85 0.4248727014300510
3
3 1 7.85 0.3480021457614210
1
1 0.5 1 0.5
4 2 5.4 0.13333813013896 1 0.5 1 0.5
5 2 0 0.1199369497462710
1
0.25 0.5 2.5 0.5
6 2 0.75 0.6924337977516810
1
0 0.5 3 0.5
7 2 2.8 0.31022508148249 0 0.5 3 0.5
8 2 4.45 0.24495491753226 0 0.5 3 0.5
9 3 4.25 0.22369816716981 0 0.5 3 0.5
MethaneCarbon dioxide
c
1 1 2.6 0.10859387354942
2 2 1.95 0.8022857672738910
1
3 3 0 0.9330398511571710
2
4 1 3.95 0.4098927400584810
1
1 0.5 1 0.5
5 2 7.95 0.24338019772494 0.5 0.5 2 0.5
6 3 8 0.23855347281124 0 0.5 3 0.5
MethaneEthane
d
1 3 0.65 0.8092605029874610
3
2 4 1.55 0.7538192508005910
3
3 1 3.1 0.4161876889121910
1
1 0.5 1 0.5
4 2 5.9 0.23452173681569 1 0.5 1 0.5
5 2 7.05 0.14003840584586 1 0.5 1 0.5
6 2 3.35 0.6328174480773810
1
0.875 0.5 1.25 0.5
7 2 1.2 0.3466042584880910
1
0.75 0.5 1.5 0.5
8 2 5.8 0.23918747334251 0.5 0.5 2 0.5
9 2 2.7 0.1985525506689110
2
0 0.5 3 0.5
10 3 0.45 0.6177774617155510
1
0 0.5 3 0.5
11 3 0.55 0.6957535827110510
1
0 0.5 3 0.5
12 3 1.95 0.1063018530638810
1
0 0.5 3 0.5
ISO/CD 207652
ISO 2011 All rights reserved 47
Table D.4 (continued)
k d
ij k ,
t
ij k ,
n
ij k ,
q
ij k ,
c
ij k ,
k ij ,

ij k ,
MethanePropane
e
1 3 1.85 0.1374642995857610
1
2 3 3.95 0.7442501212955210
2
3 4 0 0.4551660021368510
2
4 4 1.85 0.5454660335023710
2
5 4 3.85 0.2368201682447110
2
6 1 5.25 0.18007763721438 0.25 0.5 0.75 0.5
7 1 3.85 0.44773942932486 0.25 0.5 1 0.5
8 1 0.2 0.1932737488820010
1
0 0.5 2 0.5
9 2 6.5 0.30632197804624 0 0.5 3 0.5
NitrogenCarbon dioxide
f
1 2 1.85 0.28661625028399
2 3 1.4 0.10919833861247
3 1 3.2 0.1137403208227010
1
0.25 0.5 0.75 0.5
4 1 2.5 0.76580544237358 0.25 0.5 1 0.5
5 1 8 0.4263800092681910
2
0 0.5 2 0.5
6 2 3.75 0.17673538204534 0 0.5 3 0.5
NitrogenEthane
g
1 2 0 0.47376518126608
2 2 0.05 0.48961193461001
3 3 0 0.5701106209053510
2
4 1 3.65 0.19966820041320 1 0.5 1 0.5
5 2 4.9 0.69411103101723 1 0.5 1 0.5
6 2 4.45 0.69226192739021 0.875 0.5 1.25 0.5
MethaneHydrogen
h
1 1 2 0.25157134971934
2 3 1 0.6220384111198310
2
3 3 1.75 0.8885031518439610
1
4 4 1.4 0.3559221257323910
1
ISO/CD 207652
48 ISO 2011 All rights reserved
Table D.4 (continued)
k d
ij k ,
t
ij k ,
n
ij k ,
q
ij k ,
c
ij k ,
k ij ,

ij k ,
MethanenButane, MethaneIsobutane, EthanePropane, EthanenButane,
EthaneIsobutane, PropanenButane, PropaneIsobutane, and nButaneIsobutane
i
1 1 1 0.2557477684411810
1
2 1 1.55 0.7984635713635310
1
3 1 1.7 0.4785913146580610
1
4 2 0.25 0.73265392369587
5 2 1.35 0.1380547134531210
1
6 3 0 0.28349603476365
7 3 1.25 0.49087385940425
8 4 0 0.10291888921447
9 4 0.7 0.11836314681968
10 4 5.4 0.5552738572194310
4
a
The values of the coefficients, exponents, and parameters are also valid for equation (12).
b
K
Pol,ij
= 2, K
Exp,ij
= 7.
f
K
Pol,ij
= 2, K
Exp,ij
= 4.
c
K
Pol,ij
= 3, K
Exp,ij
= 3.
g
K
Pol,ij
= 3, K
Exp,ij
= 3.
d
K
Pol,ij
= 2, K
Exp,ij
= 10.
h
K
Pol,ij
= 4, K
Exp,ij
= 0.
e
K
Pol,ij
= 5, K
Exp,ij
= 4.
i
K
Pol,ij
= 10, K
Exp,ij
= 0.
Table D.5 Values of the nonzero F
ij
parameters in equation (D.18) for the binary specific and
generalized departure functions
a,b
.
Mixture ij
F
ij
MethaneNitrogen 1
MethaneCarbon dioxide 1
MethaneEthane 1
MethanePropane 1
MethanenButane 1
MethaneIsobutane 0.771035405688
MethaneHydrogen 1
NitrogenCarbon dioxide 1
NitrogenEthane 1
EthanePropane 0.130424765150
EthanenButane 0.281570073085
EthaneIsobutane 0.260632376098
PropanenButane
0.31257260048910
1
PropaneIsobutane
0.55160977102410
1
nButaneIsobutane
0.55124029300910
1
ISO/CD 207652
ISO 2011 All rights reserved 49
a
The values of the F
ij
parameters are also valid for equation (11).
b
The F
ij
parameters equal zero for all other binary combinations.
ISO/CD 207652
50 ISO 2011 All rights reserved
Annex E
(normative)
The reducing functions for density and temperature
E.1 Calculation of the reducing functions for density and temperature
The compositiondependent reducing functions are used to calculate the reduced mixture variables o and t
(i.e., dimensionless mixture density and temperature, respectively) according to
o
=
r
( ) x
(E.1)
and
t =
T x
T
r
( )
. (E.2)
The reducing functions for density and temperature can be written as
= =


.

\

+
+
+
=
N
i
N
j j i j i ij v
j i
ij v ij v j i
x x
x x
x x
x
1 1
3
3 / 1
, c
3 / 1
, c
2
,
, ,
r
1 1
8
1
) (
1


(E.3)
and
( )
= =
+
+
=
N
i
N
j
j i
j i ij T
j i
ij T ij T j i
T T
x x
x x
x x x T
1 1
, c , c
2
,
, , r
5 . 0
) (

 , (E.4)
with 
v,ij
= 1/
v,ji
,
v,ij
=
v,jj
, 
T,ij
= 1/
T,ji
, and
T,ij
=
T,ji
. These functions are based on quadratic mixing rules and
with that they are reasonably connected to physically wellfounded mixing rules. The binary parameters of
equations (E.3) and (E.4) consider the deviation between the behavior of the real mixture and the one
resulting from the ideal combining rules for the critical parameters of the pure components.
The values of the binary parameters 
v,ij
,
v,ij
, 
T,ij
, and
T,ij
in equations (E.3) and (E.4) for all binary mixtures
are listed in table E.1. The critical parameters
c,i
and T
c,i
of the pure components are given in Annex C.
E.1.1 Binary parameters for mixtures with no or very poor experimental data
The binary parameters 
v,ij
and
v,ij
in equation (E.3) and 
T,ij
and
T,ij
in equation (E.4) are fitted to
experimental data for binary mixtures. In those cases where sufficient experimental data are not available, the
parameters of equations (E.3) and (E.4) are either set to unity or modified (calculated) in such a manner that
the critical parameters of the pure components are combined in a different way, which proved to be more
suitable for certain binary subsystems. For example, for binary hydrocarbon mixtures for which no data or only
few or very poor data are available, 
v,ij
and 
T,ij
are set to one, and the binary parameters
v,ij
and
T,ij
are
calculated from the following conversions:
ISO/CD 207652
ISO 2011 All rights reserved 51
3
3 / 1
,
3 / 1
,
, ,
,
1 1
1 1
4


.

\

+


.

\

+
=
j i
j i
ij v
c c
c c
and
( )
( )
5 . 0
, ,
, ,
,
2
1
j i
j i
ij T
T T
T T
c c
c c
+
= . (E.5)
In this way, the original Lorentz and Berthelot combining rules for the critical parameters of the pure
components in equations (E.3) and (E.4) are substituted by the arithmetic mean of the critical parameters. The
use of different combining rules is superfluous when data are used to adjust the binary parameters.
Table E.1 Values of the binary parameters in equations (E.3) and (E.4) for the reducing
functions for density and temperature.
Mixture ij 
v ij ,
v ij ,

T ij ,
T ij ,
CH
4
N
2
0.998721377 1.013950311 0.998098830 0.979273013
CH
4
CO
2
0.999518072 1.002806594 1.022624490 0.975665369
CH
4
C
2
H
6
0.997547866 1.006617867 0.996336508 1.049707697
CH
4
C
3
H
8
1.004827070 1.038470657 0.989680305 1.098655531
CH
4
nC
4
H
10
0.979105972 1.045375122 0.994174910 1.171607691
CH
4
iC
4
H
10
1.011240388 1.054319053 0.980315756 1.161117729
CH
4
nC
5
H
12
0.948330120 1.124508039 0.992127525 1.249173968
CH
4
iC
5
H
12
1.0 1.343685343 1.0 1.188899743
CH
4
nC
6
H
14
0.958015294 1.052643846 0.981844797 1.330570181
CH
4
nC
7
H
16
0.962050831 1.156655935 0.977431529 1.379850328
CH
4
nC
8
H
18
0.994740603 1.116549372 0.957473785 1.449245409
CH
4
nC
9
H
20
1.002852287 1.141895355 0.947716769 1.528532478
CH
4
nC
10
H
22
1.033086292 1.146089637 0.937777823 1.568231489
CH
4
H
2
1.0 1.018702573 1.0 1.352643115
CH
4
O
2
1.0 1.0 1.0 0.950000000
CH
4
CO 0.997340772 1.006102927 0.987411732 0.987473033
CH
4
H
2
O 1.012783169 1.585018334 1.063333913 0.775810513
CH
4
H
2
S 1.012599087 1.040161207 1.011090031 0.961155729
CH
4
He 1.0 0.881405683 1.0 3.159776855
CH
4
Ar 1.034630259 1.014678542 0.990954281 0.989843388
N
2
CO
2
0.977794634 1.047578256 1.005894529 1.107654104
N
2
C
2
H
6
0.978880168 1.042352891 1.007671428 1.098650964
N
2
C
3
H
8
0.974424681 1.081025408 1.002677329 1.201264026
N
2
nC
4
H
10
0.996082610 1.146949309 0.994515234 1.304886838
N
2
iC
4
H
10
0.986415830 1.100576129 0.992868130 1.284462634
N
2
nC
5
H
12
1.0 1.078877166 1.0 1.419029041
N
2
iC
5
H
12
1.0 1.154135439 1.0 1.381770770
N
2
nC
6
H
14
1.0 1.195952177 1.0 1.472607971
N
2
nC
7
H
16
1.0 1.404554090 1.0 1.520975334
N
2
nC
8
H
18
1.0 1.186067025 1.0 1.733280051
ISO/CD 207652
52 ISO 2011 All rights reserved
N
2
nC
9
H
20
1.0 1.100405929 0.956379450 1.749119996
N
2
nC
10
H
22
1.0 1.0 0.957934447 1.822157123
N
2
H
2
0.972532065 0.970115357 0.946134337 1.175696583
N
2
O
2
0.999521770 0.997082328 0.997190589 0.995157044
N
2
CO 1.0 1.008690943 1.0 0.993425388
N
2
H
2
O 1.0 1.094749685 1.0 0.968808467
N
2
H
2
S 0.910394249 1.256844157 1.004692366 0.960174200
N
2
He 0.969501055 0.932629867 0.692868765 1.471831580
N
2
Ar 1.004166412 1.002212182 0.999069843 0.990034831
CO
2
C
2
H
6
1.002525718 1.032876701 1.013871147 0.900949530
CO
2
C
3
H
8
0.996898004 1.047596298 1.033620538 0.908772477
CO
2
nC
4
H
10
1.174760923 1.222437324 1.018171004 0.911498231
CO
2
iC
4
H
10
1.076551882 1.081909003 1.023339824 0.929982936
CO
2
nC
5
H
12
1.024311498 1.068406078 1.027000795 0.979217302
CO
2
iC
5
H
12
1.060793104 1.116793198 1.019180957 0.961218039
CO
2
nC
6
H
14
1.0 0.851343711 1.0 1.038675574
CO
2
nC
7
H
16
1.205469976 1.164585914 1.011806317 1.046169823
CO
2
nC
8
H
18
1.026169373 1.104043935 1.029690780 1.074455386
CO
2
nC
9
H
20
1.0 0.973386152 1.007688620 1.140671202
CO
2
nC
10
H
22
1.000151132 1.183394668 1.020028790 1.145512213
CO
2
H
2
0.904142159 1.152792550 0.942320195 1.782924792
CO
2
O
2
1.0 1.0 1.0 1.0
CO
2
CO 1.0 1.0 1.0 1.0
CO
2
H
2
O 0.949055959 1.542328793 0.997372205 0.775453996
CO
2
H
2
S 0.906630564 1.024085837 1.016034583 0.926018880
CO
2
He 0.846647561 0.864141549 0.768377630 3.207456948
CO
2
Ar 1.008392428 1.029205465 0.996512863 1.050971635
C
2
H
6
C
3
H
8
0.997607277 1.003034720 0.996199694 1.014730190
C
2
H
6
nC
4
H
10
0.999157205 1.006179146 0.999130554 1.034832749
C
2
H
6
iC
4
H
10
1.0 1.006616886 1.0 1.033283811
C
2
H
6
nC
5
H
12
0.993851009 1.026085655 0.998688946 1.066665676
C
2
H
6
iC
5
H
12
a
1.0 1.045439935 1.0 1.021150247
C
2
H
6
nC
6
H
14
1.0 1.169701102 1.0 1.092177796
C
2
H
6
nC
7
H
16
1.0 1.057666085 1.0 1.134532014
C
2
H
6
nC
8
H
18
1.007469726 1.071917985 0.984068272 1.168636194
C
2
H
6
nC
9
H
20
a
1.0 1.143534730 1.0 1.056033030
C
2
H
6
nC
10
H
22
0.995676258 1.098361281 0.970918061 1.237191558
C
2
H
6
H
2
0.925367171 1.106072040 0.932969831 1.902008495
C
2
H
6
O
2
1.0 1.0 1.0 1.0
C
2
H
6
CO 1.0 1.201417898 1.0 1.069224728
C
2
H
6
H
2
O 1.0 1.0 1.0 1.0
C
2
H
6
H
2
S 1.010817909 1.030988277 0.990197354 0.902736660
C
2
H
6
He 1.0 1.0 1.0 1.0
C
2
H
6
Ar 1.0 1.0 1.0 1.0
ISO/CD 207652
ISO 2011 All rights reserved 53
C
3
H
8
nC
4
H
10
0.999795868 1.003264179 1.000310289 1.007392782
C
3
H
8
iC
4
H
10
0.999243146 1.001156119 0.998012298 1.005250774
C
3
H
8
nC
5
H
12
1.044919431 1.019921513 0.996484021 1.008344412
C
3
H
8
iC
5
H
12
1.040459289 0.999432118 0.994364425 1.003269500
C
3
H
8
nC
6
H
14
1.0 1.057872566 1.0 1.025657518
C
3
H
8
nC
7
H
16
1.0 1.079648053 1.0 1.050044169
C
3
H
8
nC
8
H
18
1.0 1.102764612 1.0 1.063694129
C
3
H
8
nC
9
H
20
1.0 1.199769134 1.0 1.109973833
C
3
H
8
nC
10
H
22
0.984104227 1.053040574 0.985331233 1.140905252
C
3
H
8
H
2
1.0 1.074006110 1.0 2.308215191
C
3
H
8
O
2
1.0 1.0 1.0 1.0
C
3
H
8
CO 1.0 1.108143673 1.0 1.197564208
C
3
H
8
H
2
O 1.0 1.011759763 1.0 0.600340961
C
3
H
8
H
2
S 0.936811219 1.010593999 0.992573556 0.905829247
C
3
H
8
He 1.0 1.0 1.0 1.0
C
3
H
8
Ar 1.0 1.0 1.0 1.0
nC
4
H
10
iC
4
H
10
1.000880464 1.000414440 1.000077547 1.001432824
nC
4
H
10
nC
5
H
12
1.0 1.018159650 1.0 1.002143640
nC
4
H
10
iC
5
H
12
a
1.0 1.002728434 1.0 1.000792201
nC
4
H
10
nC
6
H
14
1.0 1.034995284 1.0 1.009157060
nC
4
H
10
nC
7
H
16
1.0 1.019174227 1.0 1.021283378
nC
4
H
10
nC
8
H
18
1.0 1.046905515 1.0 1.033180106
nC
4
H
10
nC
9
H
20
a
1.0 1.049219137 1.0 1.014096448
nC
4
H
10
nC
10
H
22
0.976951968 1.027845529 0.993688386 1.076466918
nC
4
H
10
H
2
1.0 1.232939523 1.0 2.509259945
nC
4
H
10
O
2
1.0 1.0 1.0 1.0
nC
4
H
10
CO
a
1.0 1.084740904 1.0 1.173916162
nC
4
H
10
H
2
O 1.0 1.223638763 1.0 0.615512682
nC
4
H
10
H
2
S 0.908113163 1.033366041 0.985962886 0.926156602
nC
4
H
10
He 1.0 1.0 1.0 1.0
nC
4
H
10
Ar 1.0 1.214638734 1.0 1.245039498
iC
4
H
10
nC
5
H
12
a
1.0 1.002779804 1.0 1.002495889
iC
4
H
10
iC
5
H
12
a
1.0 1.002284353 1.0 1.001835788
iC
4
H
10
nC
6
H
14
a
1.0 1.010493989 1.0 1.006018054
iC
4
H
10
nC
7
H
16
a
1.0 1.021668316 1.0 1.009885760
iC
4
H
10
nC
8
H
18
a
1.0 1.032807063 1.0 1.013945424
iC
4
H
10
nC
9
H
20
a
1.0 1.047298475 1.0 1.017817492
iC
4
H
10
nC
10
H
22
a
1.0 1.060243344 1.0 1.021624748
iC
4
H
10
H
2
a
1.0 1.147595688 1.0 1.895305393
iC
4
H
10
O
2
1.0 1.0 1.0 1.0
iC
4
H
10
CO
a
1.0 1.087272232 1.0 1.161390082
iC
4
H
10
H
2
O 1.0 1.0 1.0 1.0
iC
4
H
10
H
2
S 1.012994431 0.988591117 0.974550548 0.937130844
ISO/CD 207652
54 ISO 2011 All rights reserved
iC
4
H
10
He 1.0 1.0 1.0 1.0
iC
4
H
10
Ar 1.0 1.0 1.0 1.0
nC
5
H
12
iC
5
H
12
a
1.0 1.000024335 1.0 1.000050537
nC
5
H
12
nC
6
H
14
a
1.0 1.002480637 1.0 1.000761237
nC
5
H
12
nC
7
H
16
a
1.0 1.008972412 1.0 1.002441051
nC
5
H
12
nC
8
H
18
1.0 1.069223964 1.0 1.016422347
nC
5
H
12
nC
9
H
20
1.0 1.034910633 1.0 1.103421755
nC
5
H
12
nC
10
H
22
1.0 1.016370338 1.0 1.049035838
nC
5
H
12
H
2
a
1.0 1.188334783 1.0 2.013859174
nC
5
H
12
O
2
1.0 1.0 1.0 1.0
nC
5
H
12
CO
a
1.0 1.119954454 1.0 1.206043295
nC
5
H
12
H
2
O 1.0 0.956677310 1.0 0.447666011
nC
5
H
12
H
2
S 0.984613203 1.076539234 0.962006651 0.959065662
nC
5
H
12
He 1.0 1.0 1.0 1.0
nC
5
H
12
Ar 1.0 1.0 1.0 1.0
iC
5
H
12
nC
6
H
14
a
1.0 1.002995876 1.0 1.001204174
iC
5
H
12
nC
7
H
16
a
1.0 1.009928206 1.0 1.003194615
iC
5
H
12
nC
8
H
18
a
1.0 1.017880545 1.0 1.005647480
iC
5
H
12
nC
9
H
20
a
1.0 1.028994325 1.0 1.008191499
iC
5
H
12
nC
10
H
22
a
1.0 1.039372957 1.0 1.010825138
iC
5
H
12
H
2
a
1.0 1.184340443 1.0 1.996386669
iC
5
H
12
O
2
1.0 1.0 1.0 1.0
iC
5
H
12
CO
a
1.0 1.116694577 1.0 1.199326059
iC
5
H
12
H
2
O 1.0 1.0 1.0 1.0
iC
5
H
12
H
2
S 1.0 0.835763343 1.0 0.982651529
iC
5
H
12
He 1.0 1.0 1.0 1.0
iC
5
H
12
Ar 1.0 1.0 1.0 1.0
nC
6
H
14
nC
7
H
16
1.0 1.001508227 1.0 0.999762786
nC
6
H
14
nC
8
H
18
a
1.0 1.006268954 1.0 1.001633952
nC
6
H
14
nC
9
H
20
1.0 1.020761680 1.0 1.055369591
nC
6
H
14
nC
10
H
22
1.001516371 1.013511439 0.997641010 1.028939539
nC
6
H
14
H
2
1.0 1.243461678 1.0 3.021197546
nC
6
H
14
O
2
1.0 1.0 1.0 1.0
nC
6
H
14
CO
a
1.0 1.155145836 1.0 1.233272781
nC
6
H
14
H
2
O 1.0 1.170217596 1.0 0.569681333
nC
6
H
14
H
2
S 0.754473958 1.339283552 0.985891113 0.956075596
nC
6
H
14
He 1.0 1.0 1.0 1.0
nC
6
H
14
Ar 1.0 1.0 1.0 1.0
nC
7
H
16
nC
8
H
18
1.0 1.006767176 1.0 0.998793111
nC
7
H
16
nC
9
H
20
1.0 1.001370076 1.0 1.001150096
nC
7
H
16
nC
10
H
22
1.0 1.002972346 1.0 1.002229938
nC
7
H
16
H
2
1.0 1.159131722 1.0 3.169143057
ISO/CD 207652
ISO 2011 All rights reserved 55
nC
7
H
16
O
2
1.0 1.0 1.0 1.0
nC
7
H
16
CO
a
1.0 1.190354273 1.0 1.256123503
nC
7
H
16
H
2
O 1.0 1.0 1.0 1.0
nC
7
H
16
H
2
S 0.828967164 1.087956749 0.988937417 1.013453092
nC
7
H
16
He 1.0 1.0 1.0 1.0
nC
7
H
16
Ar 1.0 1.0 1.0 1.0
nC
8
H
18
nC
9
H
20
a
1.0 1.001357085 1.0 1.000235044
nC
8
H
18
nC
10
H
22
1.0 1.002553544 1.0 1.007186267
nC
8
H
18
H
2
a
1.0 1.305249405 1.0 2.191555216
nC
8
H
18
O
2
1.0 1.0 1.0 1.0
nC
8
H
18
CO
a
1.0 1.219206702 1.0 1.276565536
nC
8
H
18
H
2
O 1.0 0.599484191 1.0 0.662072469
nC
8
H
18
H
2
S 1.0 1.0 1.0 1.0
nC
8
H
18
He 1.0 1.0 1.0 1.0
nC
8
H
18
Ar 1.0 1.0 1.0 1.0
nC
9
H
20
nC
10
H
22
a
1.0 1.000810520 1.0 1.000182392
nC
9
H
20
H
2
a
1.0 1.342647661 1.0 2.234354040
nC
9
H
20
O
2
1.0 1.0 1.0 1.0
nC
9
H
20
CO
a
1.0 1.252151449 1.0 1.294070556
nC
9
H
20
H
2
O 1.0 1.0 1.0 1.0
nC
9
H
20
H
2
S 1.0 1.082905109 1.0 1.086557826
nC
9
H
20
He 1.0 1.0 1.0 1.0
nC
9
H
20
Ar 1.0 1.0 1.0 1.0
nC
10
H
22
H
2
1.695358382 1.120233729 1.064818089 3.786003724
nC
10
H
22
O
2
1.0 1.0 1.0 1.0
nC
10
H
22
CO 1.0 0.870184960 1.049594632 1.803567587
nC
10
H
22
H
2
O 1.0 0.551405318 0.897162268 0.740416402
nC
10
H
22
H
2
S 0.975187766 1.171714677 0.973091413 1.103693489
nC
10
H
22
He 1.0 1.0 1.0 1.0
nC
10
H
22
Ar 1.0 1.0 1.0 1.0
H
2
O
2
1.0 1.0 1.0 1.0
H
2
CO 1.0 1.121416201 1.0 1.377504607
H
2
H
2
O 1.0 1.0 1.0 1.0
H
2
H
2
S 1.0 1.0 1.0 1.0
H
2
He 1.0 1.0 1.0 1.0
H
2
Ar 1.0 1.0 1.0 1.0
O
2
CO 1.0 1.0 1.0 1.0
O
2
H
2
O 1.0 1.143174289 1.0 0.964767932
O
2
H
2
S 1.0 1.0 1.0 1.0
O
2
He 1.0 1.0 1.0 1.0
O
2
Ar 0.999746847 0.993907223 1.000023103 0.990430423
ISO/CD 207652
56 ISO 2011 All rights reserved
COH
2
O 1.0 1.0 1.0 1.0
COH
2
S 0.795660392 1.101731308 1.025536736 1.022749748
COHe 1.0 1.0 1.0 1.0
COAr 1.0 1.159720623 1.0 0.954215746
H
2
OH
2
S 1.0 1.014832832 1.0 0.940587083
H
2
OHe 1.0 1.0 1.0 1.0
H
2
OAr 1.0 1.038993495 1.0 1.070941866
H
2
SHe 1.0 1.0 1.0 1.0
H
2
SAr 1.0 1.0 1.0 1.0
HeAr 1.0 1.0 1.0 1.0
a
The values of the binary parameters
v ij ,
and
T ij ,
were calculated from equation (E.5).
ISO/CD 207652
ISO 2011 All rights reserved 57
Annex F
(informative)
Assignment of trace components
In order to calculate, with the use of the method described in this part of ISO 20765, the thermodynamic
properties of a natural gas or similar mixture that contains trace amounts of one or more components that do
not appear in table 6, it is necessary to assign each trace component to one of the 21 major and minor
components for which the GERG2008 equation of state was developed. Recommendations for appropriate
assignments are given in table F.1.
Each recommendation is based on an assessment of which substance is likely to give the best overall
compromise of accuracy for the complete set of thermodynamic properties. The factors taken into account in
this assessment include molar mass, critical temperature, and critical volume. Because, however, no single
assignment is likely to be equally satisfactory for all properties, it is not unreasonable that the user may prefer
an alternative assignment for a particular application in which, for example, only a single property is needed.
For this reason the recommendations are not normative. Implementations of the method that include
assignments for trace components need to be carefully documented in this respect.
NOTE The additional components given in table F.1 are the same as those included in ISO 6976 [7].
Table F.1 Assignment of trace components
trace component formula recommended assignment
2,2dimethylpropane (neopentane) C
5
H
12
npentane
2methylpentane C
6
H
14
nhexane
3methylpentane C
6
H
14
nhexane
2,2dimethylbutane C
6
H
14
nhexane
2,3dimethylbutane C
6
H
14
nhexane
ethylene (ethene) C
2
H
4
ethane
propylene (propene) C
3
H
6
propane
1butene C
4
H
8
nbutane
cis2butene C
4
H
8
nbutane
trans2butene C
4
H
8
nbutane
2methylpropene C
4
H
8
nbutane
1pentene C
5
H
10
npentane
propadiene C
3
H
4
propane
1,2butadiene C
4
H
6
nbutane
1,3butadiene C
4
H
6
nbutane
ISO/CD 207652
58 ISO 2011 All rights reserved
acetylene (ethyne) C
2
H
2
ethane
cyclopentane C
5
H
10
npentane
methylcyclopentane C
6
H
12
nhexane
ethylcyclopentane C
7
H
14
nheptane
cyclohexane C
6
H
12
nhexane
methylcyclohexane C
7
H
14
nheptane
ethylcyclohexane C
8
H
16
noctane
benzene C
6
H
6
npentane
toluene (methylbenzene) C
7
H
8
nhexane
ethylbenzene C
8
H
10
nheptane
oxylene C
8
H
10
nheptane
all other C6 hydrocarbons nhexane
all other C7 hydrocarbons nheptane
all other C8 hydrocarbons noctane
all other C9 hydrocarbons nnonane
all other C10 hydrocarbons ndecane
all higher hydrocarbons ndecane
methanol (methyl alcohol) CH
3
OH ethane
methanethiol (methyl mercaptan) CH
3
SH propane
ammonia NH
3
methane
hydrogen cyanide HCN ethane
carbonyl sulfide (carbon oxysulfide) COS nbutane
carbon disulfide CS
2
npentane
sulfur dioxide SO
2
nbutane
nitrous oxide N
2
O carbon dioxide
neon Ne argon
krypton Kr argon
xenon Xe argon
ISO/CD 207652
ISO 2011 All rights reserved 59
Annex G
(informative)
Examples
The following examples are provided for the purpose of software validation.
Table G.1 Gas analysis by mole fraction
Component Gas 1 Gas 2 Gas 3 Gas 4 Gas 5 Gas 6
1 Methane 0.796 0.650 0.720 0.550
2 Nitrogen 0.100 0.065 0.010 0.25
3 Carbon dioxide 0.010 0.190 0.010 0.15
4 Ethane 0.057 0.010 0.150
5 Propane 0.020 0.010 0.010 0.100 0.10
6 nButane 0.005 0.010 0.010 0.10
7 isoButane 0.005 0.010 0.010 0.10
8 nPentane 0.002 0.010 0.010 0.10
9 isoPentane 0.002 0.010 0.010 0.10
10 nHexane 0.001 0.010 0.020 0.10
11 nHeptane 0.001 0.020 0.010 0.10
12 nOctane 0.001 0.010 0.10
13 nNonane 0.10
14 nDecane 0.05
15 Hydrogen 0.200 0.10
16 Oxygen 0.010 0.049 999 0.10
17 Carbon monoxide 0.010 0.100 0.10
18 Water 0.000 001 0.05
19 Hydrogen sulfide 0.10
20 Helium 0.005 0.10
ISO/CD 207652
60 ISO 2011 All rights reserved
21 Argon 0.10
Total 1.000 1.000 1.000 1.000 1.000 1.000
ISO/CD 207652
ISO 2011 All rights reserved 61
Table G.2 Calculations
Gas 1 M = 19.778 kg/kmol
T p D Z U H S Cv Cp w
K MPa kg/m kJ/kg kJ/kg kJ/(kgK) kJ/(kgK) kJ/(kgK) m/s K/MPa
180.00 10.000 389.18 0.33956 587.21 561.52 3.8341 1.6233 3.3622 796.80 0.0080269
220.00 10.000 267.65 0.40397 438.06 400.70 3.0329 1.6813 5.0560 427.36 1.8447
200.00 20.000 380.27 0.62552 548.37 495.77 3.6247 1.6149 3.1519 826.44 0.052377
250.00 20.000 283.04 0.67232 399.28 328.61 2.8802 1.6215 3.4875 568.65 0.77140
305.00 3.0000 24.835 0.94211 123.61 2.8081 1.0611 1.5553 2.1284 394.93 4.5112
350.00 10.000 74.667 0.91021 88.582 45.346 1.3808 1.7043 2.5065 430.98 2.6236
Gas 2 M = 26.843 kg/kmol
T p D Z U H S Cv Cp w
K MPa kg/m kJ/kg kJ/kg kJ/(kgK) kJ/(kgK) kJ/(kgK) m/s K/MPa
180.00 13.000 548.61 0.42502 476.13 452.44 2.7551 1.3262 2.4027 945.53 0.28327
220.00 11.000 452.06 0.35708 372.89 348.55 2.2159 1.3850 2.8949 615.88 0.26965
250.00 20.000 425.35 0.60721 318.05 271.03 1.9729 1.4023 2.7340 615.09 0.26645
350.00 20.000 226.57 0.81426 77.691 10.583 1.0241 1.5242 2.6216 414.60 1.6170
355.00 3.0000 28.743 0.94921 31.065 135.44 0.15609 1.4383 1.8513 357.41 4.0492
400.00 10.000 88.041 0.91676 67.533 181.12 0.38181 1.5813 2.1613 383.33 2.4644
Gas 3 M = 24.295 kg/kmol
T p D Z U H S Cv Cp w
K MPa kg/m kJ/kg kJ/kg kJ/(kgK) kJ/(kgK) kJ/(kgK) m/s K/MPa
150.00 10.000 504.68 0.38600 625.94 606.13 3.5589 1.6072 2.6157 1267.9 0.46108
200.00 10.000 431.60 0.33852 492.03 468.86 2.7711 1.6072 2.9153 889.61 0.17932
250.00 20.000 376.46 0.62095 371.21 318.08 2.2087 1.6569 3.0291 731.32 0.072674
300.00 20.000 289.77 0.67228 227.15 158.13 1.6264 1.7557 3.3290 523.24 0.83762
ISO/CD 207652
62 ISO 2011 All rights reserved
380.00 5.0000 41.741 0.92111 90.218 210.00 0.16124 1.8869 2.4301 378.29 3.5788
400.00 10.000 82.020 0.89066 99.474 221.40 0.34656 1.9839 2.6995 392.34 2.6674
Gas 4
M = 18.037 kg/kmol
T p D Z U H S Cv Cp w
K MPa kg/m kJ/kg kJ/kg kJ/(kgK) kJ/(kgK) kJ/(kgK) m/s K/MPa
180.00 25.000 378.94 0.79511 587.57 521.60 3.9519 1.6680 3.1028 849.32 0.15640
220.00 25.000 307.84 0.80081 474.55 393.33 3.3091 1.6573 3.2831 660.80 0.27099
240.00 1.7000 16.192 0.94898 240.28 135.30 1.2079 1.5070 2.0930 371.93 5.5554
260.00 25.000 242.33 0.86078 365.93 262.76 2.7635 1.6780 3.1984 564.69 0.69309
300.00 10.000 80.581 0.89738 193.05 68.950 1.7100 1.6729 2.5985 425.19 2.6008
400.00 10.000 54.907 0.98774 1.9610 184.09 0.98174 1.8988 2.5469 495.53 1.3589
Gas 5
M = 27.610 kg/kmol
T p D Z U H S Cv Cp w
K MPa kg/m kJ/kg kJ/kg kJ/(kgK) kJ/(kgK) kJ/(kgK) m/s K/MPa
150.00 30.000 704.83 0.94229 353.11 310.55 2.4550 0.89982 1.7205 713.43 0.26388
200.00 25.000 502.27 0.82643 269.63 219.85 1.8878 0.84706 1.8818 485.49 0.41958
250.00 20.000 299.16 0.88802 188.56 121.70 1.3922 0.81223 1.6418 391.32 1.3328
300.00 15.000 172.80 0.96087 123.76 36.952 1.0017 0.79210 1.3398 387.22 1.5610
350.00 10.000 95.443 0.99409 69.179 35.595 0.65788 0.78914 1.1995 401.08 1.4409
400.00 5.0000 41.380 1.0031 19.179 101.65 0.27250 0.79492 1.1359 416.75 1.2625
Gas 6
M = 81.365 kg/kmol
T p D Z U H S Cv Cp w
K MPa kg/m kJ/kg kJ/kg kJ/(kgK) kJ/(kgK) kJ/(kgK) m/s K/MPa
180.00 10.000 758.08 0.71716 302.28 289.09 0.47202 1.4744 1.9300 1603.4 0.54381
250.00 10.000 699.02 0.55998 163.58 149.27 0.18277 1.6214 2.0839 1283.4 0.48029
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ISO 2011 All rights reserved 63
300.00 25.000 671.21 1.2150 63.863 26.617 0.54977 1.7870 2.2353 1184.5 0.43573
400.00 5.0000 549.38 0.22266 196.06 205.16 1.3054 2.1625 2.7652 645.44 0.091974
450.00 0.50000 11.811 0.92057 557.91 600.24 2.3202 2.2505 2.4030 203.37 11.662
500.00 2.0000 52.175 0.75024 648.58 686.91 2.3827 2.5111 2.8942 176.26 11.031
ISO/CD 207652
64 ISO 2011 All rights reserved
Bibliography
[1] KUNZ, O. and WAGNER, W., The GERG2008 WideRange Equation of State for Natural Gases and
Other Mixtures, to be published.
[2] KUNZ, O., KLIMECK, R., WAGNER, W., and JAESCHKE, M., The GERG2004 WideRange Equation of
State for Natural Gases and Other Mixtures: GERG Technical Monograph 15 and Fortschr.Ber. VDI,
Reihe 6, Nr. 557, VDI Verlag, Dsseldorf, 2007.
[3] STARLING, K. E. and SAVIDGE, J. L., Compressibility Factors of Natural Gas and Other Related
Hydrocarbon Gases. American Gas Association, Transmission Measurement Committee Report No. 8,
Second Edition, Arlington, Virginia, 1992, and Errata No. 1, 1994.
[4] MOHR, P. J., TAYLOR, B. N., and NEWELL, D. B., CODATA recommended values of the fundamental
physical constants: 2006, J. Phys. Chem. Ref. Data, 37, 11871284, 2008.
[5] JAESCHKE, M. and SCHLEY, P. , Idealgas thermodynamic properties for naturalgas applications. Int. J.
Thermophysics, 16, 13811392, 1995.
[6] WIESER, M. E., Atomic weights of the elements 2005 (IUPAC Technical Report). Pure Appl. Chem., 78,
20512066, 2006.
[7] ISO 6976, Natural gas Calculation of calorific values, density, relative density and Wobbe index from
composition.
[8] ISO 14912, Gas analysis Conversion of gas mixture composition data.
[9] KLIMECK, R., Entwicklung einer Fundamentalgleichung fr Erdgase fr das Gas und Flssigkeitsgebiet
sowie das Phasengleichgewicht. Dissertation, Fakultt fr Maschinenbau, RuhrUniversitt Bochum,
2000.
[10] SPAN, R. and WAGNER, W., Equations of state for technical applications. II. Results for nonpolar fluids,
Int. J. Thermophysics, 24, 41109, 2003.
[11] LEMMON, E. W. AND SPAN, R., Short fundamental equations of state for 20 industrial fluids. J. Chem. Eng.
Data, 51, 785850, 2006.
ISO/CD 207652
ISO 2011 All rights reserved 65
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