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se/std-18918

Natural gas - Calculation of calorific Naturgas - Beräkning av värmevärde,

values, density, relative density and densitet, relativ densitet och Wobbe-
Wobbe index from composition index baserat på gassamman-
sättningen

This Swedish Standard consists of the English ver- Denna standard utgörs av den engelska versionen av
sion of the International Standard ISO 6976:1995. den internationella standarden ISO 6976:1995.
Swedish Standards corresponding to documents re- Motsvarigheten och aktualiteten i svensk standard
ferred to in this Standard are listed in ”Catalogue of till de publikationer som omnämns i denna standard
Swedish Standards”, annually issued by SIS. The framgår av ”Katalog över svensk standard”, som år-
Catalogue lists, with reference number and year of ligen ges ut av SIS. I katalogen redovisas internatio-
Swedish approval, International and European nella och europeiska standarder som fastställts som
Standards approved as Swedish Standards as well as svenska standarder och övriga gällande svenska
other Swedish Standards. standarder.
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Natural gas — Calculation of calorific values, density,

relative density and Wobbe index from composition

1 Scope synonymous with “calorific value”; “specific gravity” is

synonymous with “relative density”; “Wobbe number” is
synonymous with “Wobbe index”; “compressibility factor”
is synonymous with “compression factor”.
This International Standard specifies methods for the
3 If the composition of the gas is known by volume frac-
calculation of the superior calorific value, inferior tions these must be converted to mole fractions (see
calorific value, density, relative density and Wobbe annex C). Note, however, that the derived mole fractions
index of dry natural gases, natural gas substitutes and will have uncertainties greater than those of the original
other combustible gaseous fuels, when the compo- volume fractions.
sition of the gas by mole fraction is known. The
methods provide a means of calculating the proper- 4 For the purposes of this International Standard, the sum
ties of the gas mixture at commonly used metric ref- of the mole fractions used must be unity to the nearest
erence conditions. 0,000 1, and all components with mole fractions greater
than 0,00005 must be accounted for.
The methods of calculation require values for various 5 For the calorific value calculated on a volumetric basis,
physical properties of the pure components; these there are limitations on the amounts of components other
values are provided in tables and their sources are than methane which may be present. It is impossible to be
identified. definitive on this matter, but the following guidelines may
be useful:
Methods are given for estimating the precision of
calculated properties. N 2 should not be present in amounts exceeding 0,3
mole fraction;
The methods of calculation of the values of properties
CO 2 and C2H 6 should each not exceed 0,15 mole frac-
on either a molar or mass basis are applicable to any tion;
dry natural gas, natural gas substitute or other
combustible fuel which is normally gaseous. For the no other component should exceed 0,05 mole fraction.
calculation of the values of properties on a volumetric
basis, the methods are restricted to gases consisting Given these limits, the expected trueness of the calculation
preponderantly of methane (not less than 0,5 mole is within 0,1 %.
fraction).
6 The effects of water vapour on the calorific value, either
Examples of calculations are given in annex D for the directly measured or calculated, are discussed in annex F.
recommended methods of calculation.
7 For the methods of calculation described to be valid, the
NOTES gas must be above its hydrocarbon dew-point at the pre-
scribed reference conditions.
1 The symbols used in this International Standard, to-
gether with their meanings, are given in annex A. 8 The values of basic physical property data are subject to
revision as more accurate values become available from
2 The qualifiers “higher”, “upper”, “total” and “gross” authoritative sources.
are, for the purposes of this International Standard, syn-
onymous with “superior”; likewise, “lower” and “net” are
synonymous with “inferior”. The term “heating value” is
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2 Definitions On molar, mass and volumetric bases, the inferior

calorific value is designated respectively as
For the purposes of this International Standard, the
following definitions apply.
2.3 density The mass of a gas sample divided by
its volume at specified conditions of pressure and
2.1 superior calorific value: The amount of heat temperature.
which would be released by the complete combustion
in air of a specified quantity of gas, in such a way that 2.4 relative density: The density of a gas divided
the pressure p1 at which the reaction takes place re- by the density of dry air of standard composition (see
mains constant, and all the products of combustion annex B) at the same specified conditions of pressure
are returned to the same specified temperature t 1 a s and temperature, The term ideal relative density ap-
that of the reactants, all of these products being in the plies when both gas and air are considered as fluids
gaseous state except for water formed by com- which obey the ideal gas law (see 2.7); the term real
bustion, which is condensed to the liquid state at t 1 . relative density applies when both gas and air are
considered as real fluids.
Where the quantity of gas is specified on a molar ba-
sis, the calorific value is designated as 2.5 Wobbe index: The superior calorific value on a
mass basis the calorific value is designated as volumetric basis at specified reference conditions,
divided by the square root of the relative density at
the same specified metering reference conditions.
Where the quantity of gas is specified on a volumetric
basis, the calorific value is designated as 2.6 enthalpy of transformation: The enthalpy of
are the gas volume transformation of a substance from state A to state
(metering) reference conditions (see figure 1). B is thermodynamic terminology for the amount of
heat release which accompanies the transformation
2.2 inferior calorific value: The amount of heat between states. A positive heat release is taken by
which would be released by the complete combustion convention to be a numerically identical negative
in air of a specified quantity of gas, in such a way that enthalpy increment. The quantities enthalpy of com-
the pressure p, at which the reaction takes place re- bustion and enthalpy of vaporization therefore have
mains constant, and all the products of combustion meanings which should be contextually self-evident;
are returned to the same specified temperature t1 a s the term enthalpic correction refers to the (molar)
that of the reactants, all of these products being in the enthalpy of transformation between the ideal and real
gaseous state. states of a gas.

Figure 1 — Calorific value on a volumetric basis — Metering and combustion reference conditions
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2.7 ideal gas and real gas: An ideal gas is one sponding mole fraction, all the terms then being
which obeys the ideal gas law: added together to obtain the “mole fraction average”
of the property for the ideal-gas mixture. Values on a
volumetric basis are then converted to values for the
real-gas state by applying a volumetric correction fac-
where
tor.
is the absolute pressure; NOTE 10 An enthalpic correction factor which is also, in
principle, required in calorific value calculations is deemed
is the thermodynamic temperature;
to be negligible in all relevant cases.
is the volume per mole of gas;
In clause 10, values are given for the physical
is the molar gas constant, in coherent properties of the pure components of natural gas on
units. molar, mass and volumetric bases for the commonly
used reference conditions. Examples of calculations
No real gas obeys this law. For real gases, equation are given in annex D.
(1) must be rewritten as
... 4 Behaviour of ideal and real gases

where Z(T,p) is a variable, often close to unity, and is 4.1 Enthalpy of combustion
known as the compression factor (see 2.8 and E.2).
The most fundamental physical quantities required in
2.8 compression factor: The actual (real) volume the calculation of calorific values from first principles
of a given mass of gas at a specified pressure and are the ideal-gas (standard) molar enthalpies of com-
temperature divided by its volume, under the same bustion for the component gases of the mixture.
conditions, as calculated from the ideal gas law. These quantities are complex functions of tempera-
ture; thus, the values required depend upon the
2.9 combustion reference conditions: The speci- combustion reference temperature t1 . For practical
fied temperature t 1 and pressure p 1. These are the reasons, it is not intended that the user himself car-
conditions at which the fuel is notionally burned (see ries out calculations which give the appropriate values
figure 1). at any arbitrary combustion reference temperature.
Instead, tabulations are given for the temperatures
2.10 metering reference conditions: The specified t1 = 25 °C, 20 °C, 15 °C and 0 °C. In clause E.1 the
temperature t2 and pressure p 2. These are the con- derivations of the values tabulated are discussed; the
ditions at which the amount of fuel to be burned is important point is that all four values for any sub-
notionally determined; there is no a priori reason for stance are mutually consistent in a thermodynamic
these to be the same as the combustion reference sense.
conditions (see figure 1).
For the calorific value (on any of the three possible
NOTE 9 A range of reference conditions is in use bases), a so-called enthalpic correction is, in principle,
throughout the world; appropriate data for the principal sets required in order to convert the ideal-gas enthalpy of
of metric reference conditions are given in tables in this
combustion for the gas mixture to a value appropriate
International Standard.
to the real gas. This, however, is generally small
enough to be negligible. A discussion justifying such
2.11 dry natural gas: Gas which does not contain
neglect is given in clause E.3.
water vapour at a mole fraction greater than 0,000 05.

4.2 Calculation of compression factor

3 Principle
For the volumetric-basis calorific value, a second real-
Methods are provided for the calculation of the gas correction is required to account for the deviation
calorific values, density, relative density and Wobbe of the gas from volumetric ideality, and this is gener-
index of any dry natural gas, natural gas substitute or ally not negligible. This correction is also required in
other combustible gaseous fuel from a known com- the calculation of density, relative density and, by im-
position. These methods use equations in which, for plication, Wobbe index. Clause E.2 gives the back-
all individual molecular species of the gas mixture, the ground to the way in which corrections for volumetric
values of ideal-gas thermophysical properties (which non-ideality should be applied, discusses the princi-
are given) are weighted in accordance with the corre- ples involved, and justifies the simplifications em-
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ployed which enable tractable calculations to be made have been derived from the 25 °C values in accord-
without necessitating machine computation. ante with the methods described in clause E. 1.

Such corrections for volumetric non-ideality are made NOTES

using the compression factor Zmix. The formulation to
11 Values of are independent of pressure; conse-
be used for Zmix at the metering reference conditions,
quently the combustion reference pressure p 1 is irrelevant
as required for the calculations described in clauses for the ideal-gas case and is omitted from the nomenclature
5 to 9, is (equation E.17): adopted.

12 The ideal-gas calorific value on a molar basis of a gas

or gas mixture is defined in this International Standard as a
positive number. The values given in table 3 are numerically
equal to the standard molar enthalpies of combustion,
where the summation is taken over all N components which are, however, conventionally expressed as negative
quantities (see 2.6).
of the mixture. Values of the so-called summation
factor are given in table 2 (clause 10) at the
three metering reference conditions of common in- 5.2 Real gas
terest, for all of the components of natural gas and
substitute natural gas considered in this International For the purposes of this International Standard the
Standard. Values are also given for all pure component real-gas calorific value on a molar basis is taken as
compression factors (or hypothetical compression numerically equal to the corresponding ideal-gas
factors) Z j, from which the bj's have generally been value.
derived using the relationship bj = 1 – Zj. Any user re-
quiring greater detail should consult clause E.2. NOTE 13 A rigorous approach to the calculation of the
real-gas calorific value on a molar basis from the ideal-gas
value would require the calculation of an enthalpic cor-
rection (see 4.1 ) for the mixture. In practice, this correction
5 Calculation of calorific value on a is very small for typical natural gases, and can usually be
molar basis neglected with resultant errors not exceeding 50 J·mol -1
(approximately 0,005 %) (see clause E.3),

5.1 Ideal gas

6 Calculation of calorific value on a mass
The ideal-gas calorific value on a molar basis, at a basis
temperature t1, of a mixture of known composition is
calculated from the equation
6.1 Ideal gas

The ideal-gas calorific value on a mass basis, at a

temperature t1, of a mixture of known composition is
calculated from the equation
where

is the ideal molar calorific value of the

mixture (either superior or inferior);

is the ideal molar calorific value of com- where

ponent j (either superior or inferior);
is the molar mass of the mixture, and is
is the mole fraction of component j. calculated from the equation

Numerical values of for t 1 = 25 °C are given in

table 3 (clause 10); the values for are taken
from the original literature sources cited in annex M,
and the values for derived using the accepted
value of the standard enthalpy of vaporization of water being the mole fraction of
at 25 °C (see annex B). component j;

Values for for other temperatures (t 1 = 20 °C, being the molar mass of com-
15 °C and 0 °C) are also given in table 3; these values ponent j;
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is the ideal calorific value on a mass basis

of the mixture (either superior or inferior).

Table 1 (clause 10) lists values of the molar mass for

all components considered in this International Stan-
dard.

Use of equations (5) and (6) represents the definitive The use of equation (8) represents the definitive
method for calculating An alternative method uses method for calculating An alternative method uses
the equation the equation

where is the ideal calorific value on a mass ba- is the ideal calorific value on a
volumetric basis of component j (either superior or
sis of component (either superior or inferior).
inferior).
For convenience, values of for four values
For convenience, values of for a variety of com-
of t 1 (25 °C, 20 °C, 15 °C and 0 °C) are given in
bustion and metering reference conditions are given
table 4 (clause 10), in order that the user may avoid
in table 5 (clause 10), in order that the user may avoid
the necessity of using values of as the starting
the necessity of using values of as the starting
point of a calculation.
point of a calculation.
Numerical values obtained from either method will be
Numerical values obtained from either method will be
concordant to within 0,01 MJ·kg-1, which is within
concordant to within 0,01 MJ·m-3, which is within
the limits of significance for the current state-of-the-
the limits of significance for the current state-of-the-
art.
art.

6.2 Real gas 7.2 Real gas

For the purposes of this International Standard, the The real-gas calorific value on a volumetric basis, for
real-gas calorific value on a mass basis is taken as combustion at temperature t1 and pressure p 1 of a gas
numerically equal to the corresponding ideal-gas mixture metered at a temperature t 2 and pressure p 2
value. is calculated from the equation

NOTE 14 See 5.2 for clarification and justification.

7 Calculation of calorific value on a where

volumetric basis is the real-gas calorific value on a
volumetric basis (either superior
or inferior);
7.1 Ideal gas
is the compression factor at the
The ideal-gas calorific value on a volumetric basis, for metering reference conditions.
a combustion temperature t 1, of a mixture of known
composition, metered at a temperature t2 and press- The compression factor Zm i x( t 2,p 2) is calculated from
ure p2, is calculated from the equation ecuation (3), using values of the summation factor
given for individual pure substances in table 2
(clause 10).

NOTE 15 See 5.2 for clarification and justification of the

where practical approach to real-gas calorific values. Since no
enthalpic correction is made to the ideal-gas calorific value
is the ideal calorific value on a on a volumetric basis in this calculation, the combustion
volumetric basis of the mixture reference pressure p 1 is irrelevant and is omitted from the
(either superior or inferior); nomenclature adopted.
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8 Calculation of relative density, densit 8.2 Real gas

and Wobbe index

The relative density of the real gas is calculated from

the equation

8.1 Ideal gas

The relative density of the ideal gas is independent

of any reference state, and is calculated from the where
equation
is the relative density of the real gas;
(11)
is the compression factor of the gas;

is the compression factor of dry air of

where standard composition.

is the relative density of the ideal gas; The compression factor is calculated from
ecuation (3), using values of the summation factor
is the molar mass of component j;
given for individual pure substances in table 2
is the molar mass of dry air of standard (clause 10). The compression factor Za i r(t,p) is given
composition. in clause B.3 as

Z air 273,1 5 K, 101,325 kPa) = 0,99941

Table 1 (clause 10) lists values of molar mass. Clause
B.3 gives the composition of standard air the derived Z air (288,15 K, 101,325 kPa) = 0,99958
value for Mair is 28,962 6 kg·kmol-1..
Z air (293,15 K, 101,325 kPa) = 0,99963
The density of the ideal gas depends upon its tem-
perature t and pressure p, and is calculated from The density of the real gas is calculated from the
equation

where
where p(t,p) is the density of the real gas.
is the density of the ideal gas;
The Wobbe index of the real gas is calculated from
is the molar gas constant the equation

see clause B.1);

(=t+273,15) is the absolute tempera-

ture, in kelvins.
where
The Wobbe index of the ideal gas is calculated from
the equation is the Wobbe index of the real gas;

is calculated as described in 7.2.

NOTE 16 Some care in the use of units is required for the

calculations described in this subclause, particularly for cal-
where culations of density. With R expressed in joules per mole
kelvin, p in kilopascals and M in kilograms per kilomole, the
is the Wobbe index of the ideal gas; value of p is obtained automatically in kilograms per cubic
metre, the preferred SI unit.
is calculated as described in 7.1.
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9 Accuracy is the value of the physical property

calculated from the ith analysis of the
gas;
9.1 Precision
is the arithmetic mean of n values of

9.1.1 Repeatability and reproducibility

NOTE 17 For definitions of repeatability and
reproducibility, their interpretation in terms of the stan-
The precision of a calculated physical property value,
dard deviation of the population of values as given b
which results solely from random errors in the ana-
equation (17), and for the origin of the factor
lytical procedures, may be expressed in terms of re- therein, see for example reference [26] in annex M.
peatability and/or reproducibility, where these are
defined as follows. b) By combining, in an appropriate manner, the re-
peatability or reproducibility of the concentration
Repeatability: The value below which the absol- of each component in the gas analysis; the ap-
ute difference between a pair of successive test propriate combination formulae are given in 9.1,2
results obtained using the same method, on and 9.1.3 (for the derivation of these equations,
identical test material, by the same operator, using see annex H).
the same apparatus, in the same laboratory, within
a short interval of time, may be expected to lie NOTE 18 The equivalence of a) and b) in Practice as op-
with a specified probability. In the absence of posed to principle is open to discussion. This is because the
other indications, the probability is 95 %. statistical link between the methods assumes that the re-
peatedly measured analytical values are distributed in a
Reproducibility: The value below which the ab- Gaussian (normal) fashion for each component concen-
solute difference between two single test results tration, and that this is also the case for the set of calculated
obtained using the same method, on identical test physical property values. Experience has shown that these
criteria are not usually met, especially for small data sets
material, by different operators, using different
and/or sets containing outliers.
apparatus, in different laboratories, may be ex-
pected to lie with a specified probability. In the
absence of other indications, the probability is
9570. 9.1.2 Estimation of repeatability

The latter quantity is usually significantly larger than The repeatability AH, at a 95 %. confidence level, of
the former. Each measure of the precision of a calcu- the calorific value H may be calculated either from
lated physical property depends only upon the pre- equation (17) (with Y replaced by H), or directly from
cision of the analytical data. the analytical data, using the appropriate expression,
as follows:
The general concepts of repeatability and
reproducibility may be applied not only to physical
a) When all components except methane are analy-
properties calculated from compositional analyses,
sed, the methane (j = 1) concentration being cal-
but also to each component concentration in the
culated by difference, then
analyses from which the properties are derived. Con-
sequently, the repeatability or reproducibility of a
physical property value may actually be obtained in
either of two apparently equivalent ways, viz.

a) By direct application of the above definitions to

repeated calculations of the physical property in
question, i.e. from the equation
is the repeatability of the calculated
ideal-gas calorific value (molar or volu-
metric basis) for the mixture;

is the repeatability of the mole fraction

of component j in the mixture of N
components;

is either the repeatability or is the ideal-gas calorific value of com-

reproducibility of Y, as appropriate; ponent j;
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is the ideal-gas calorific value of NOTE 19 The contribution of the repeatability of the
methane. calculated compression factor Z to the overall repeatability
of the calorific value on a volumetric basis is small, and
is therefore ignored in the above formulation; likewise, the
b) When all components including methane are
contribution of AZ to the overall repeatability of the real-
analysed, then gas density, of the real-gas relative density and
real-gas Wobbe index is also ignored.

9.1.3 Estimation of reproducibility

where, although is calculated using the nor-

malized mole fractions is the repeatability values, relative density, density and Wobbe index may
of the mole fraction of component j in the mixture be calculated by means of the equations (18) to (24)
of N components before normalization is carried inclusive, provided that the in equations
out. (18), (19), (22) and (23) are now identified as the ap-
propriate reproducibilities of the mole fractions xj. The
The repeatability of the relative density and reproducibilities may also be determined from the
of the density may be calculated from the fol- calculation of times the standard deviation of
lowing equations, respectively: the population of calculated values of H, d, p or W,
using equation (17), where the analyses of compo-
sitions have been carried out in accordance with the
definition of reproducibility given in 9.1.1.

9.2 Trueness
where is the repeatability of the mean molar
mass M of the natural gas, given by Observations of the precision of analytical data cannot
be regarded as carrying any implication for the
— for case a): trueness of those data; it is entirely possible to
achieve excellent precision at the same time as very
bad trueness.

The absolute trueness of a calculated physical

property value of a natural gas mixture may be con-
— For case b): sidered as resulting from the combination of three in-
dependent sources of systematic error, viz.

a) uncertainties in the basic data given in tables 1 to

5;

b) bias in the method of calculation which uses

where Mj is the molar mass of component j. these data;

The repeatability of the Wobbe index may be c) uncertainties (as distinct from random impre-
calculated from the equation cision) in the analytical data used as input to the
method.

In practice, it is difficult to make calculations of

trueness due to the lack of adequate information; for
example, reference back to original sources of basic
As for the calorific value, the repeatabilities data often reveals information concerning precision
may also be determined by calculation of only (see, in this context, the discussion of methane
the standard deviation of a set of calculated property given in annex G), and the same is often true for
values [i.e., from equation (17) with Y replaced by A-f, analytical data. In addition, a rigorous approach would
d, p or W, as appropriate] where the compositional provide an absolute uncertainty, whereas what is of-
analyses have been carried out in accordance with the ten required in practice is an estimate of the uncer-
definition of repeatability given in 9.1.1. However, the tainty of a physical property value relative to some
provision given in note 18 to 9.1.1 still applies. datum point. For example, calorific values are often
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referenced to the calorific value of pure methane; and possibly in the future, when the accuracy of
consequently any uncertainty in the assumed calorific natural gas analysis has improved), a more rigorous
value of methane does not contribute to the relative approach, based on a), b) and c), may be necessary.
uncertainty of the calorific value of a natural gas, or to
the difference between the calorific values of two 9.3 Expression of results
different natural gases.
The number of significant figures which are given for
Experience has shown that the relative uncertainties the value of each property should reflect the expected
of the physical property values considered herein will accuracy of calculation of the property in question.
be most strongly influenced by uncertainties in the Even in the case of a “perfect” analysis, the results
analytical data, and that contributions from uncer- of calculations for mixtures should be reported to no
tainties in basic data and bias in the method of calcu- better than the following levels of significance.
lation will be very small. The contributions from the
basic data are expected to be less than 0,05 % and Calorific value — molar basis: 0,01 kJ·mol- 1
from bias in the method of calculation to be less than — mass basis: 0,01 MJ·kg-1
0,015 %. These contributions may be neglected when — volumetric basis: 0,01 MJ·m-3
compared to the uncertainty in the analytical data
from the analysis of a typical natural gas mixture Relative density: 0,0001
containing 12 to 20 components. Density: 0,0001 kg·m -3
Wobbe index: 0,01 MJ·m -3
For those cases where the contributions from uncer-
tainties in the basic data and from bias in the method However, attention must be paid to whether the ana-
of calculation are significant when compared with the lytical data do in fact justify quoting to this level of
analytical uncertainty (for example, for the high accu- supposed significance and, if not, the number of sig-
racy analysis of mixtures of only a few components, nificant figures quoted should be reduced accordingly.