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By Authority Of

THE UNITED STATES OF AMERICA

Legally Binding Document


By the Authority Vested By Part 5 of the United States Code 552(a) and
Part 1 of the Code of Regulations 51 the attached document has been duly
INCORPORATED BY REFERENCE and shall be considered legally
binding upon all citizens and residents of the United States of America.
HEED THIS NOTICE: Criminal penalties may apply for noncompliance.

e
Document Name: ASTM D3588: Standard Practice for Calculating Heat
CFR Section(s):
Standards Body:

Value, Compressibility Factor, and Relative Density


(Specific Gravity) of Gaseous Fuels
40 CFR 75, Appendix F
American Society for Testing and Materials

Official Incorporator:
THE EXECUTIVE DIRECTOR

OFFICE OF THE FEDERAL REGISTER


WASHINGTON, D.C.

~~l~

Designation: D 3588 - 98

Standard Practice for

Calculating Heat Value, Compressibility Factor, and Relative


Density of Gaseous Fuels 1
This standard is issued under the fixed designation D 3588; the nwnber immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A nwnber in parentheses indicates the year of last reapproval. A
superscript epsilon (E) indicates an editorial change since the last revision or reapproval.

D 2650 Test Method for Chemical Composition of Gases by


Mass Spectrometry6
2.2 GPA Standards:
GPA 2145 Physical Constants for the Paraffin Hydrocarbons
and Other Components in Natural Gas 7
GPA Standard 2166 Methods of Obtaining Natural Gas
Samples for Analysis by Gas Chromatography7
GPA 2172 Calculation of Gross Heating Value, Relative
Density, and Compressibility Factor for Natural Gas
Mixtures from Compositional Analysis7 ,g
GPA Standard 2261 Method of Analysis for Natural Gas and
Similar Gaseous Mixtures by Gas Chromatography7
GPA Technical Publication TP-17 Table of Physical Properties of Hydrocarbons for Extended Analysis of Natural
Gases7
GPSA Data Book, Fig. 23-2, Physical Constants7
2.3 TRC Document:
TRC Thermodynamic Tables-Hydrocarbons9
2.4 ANSI Standard:
ANSI Z 132.1-1969: Base Conditions of Pressure and
Temperature for the Volumetric Measurement of Natural
GaslO,ll

1. Scope

1.1 This practice covers procedures for calculating heating


value, relative density, and compressibility factor at base
conditions (14.696 psia and 60F (15.6C) for natural gas
mixtures from compositional analysis. 2 It applies to all common types of utility gaseous fuels, for example, dry natural gas,
reformed gas, oil gas (both high and low Btu), propane-air,
carbureted water gas, coke oven gas, and retort coal gas, for
which suitable methods of analysis as described in Section 6
are available. Calculation procedures for other base conditions
are given.
1.2 The values stated in inch-pound units are to be regarded
as the standard. The SI units given in parentheses are for
information only.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its lise. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2. Referenced Documents
2.1 ASTM Standards:
D 1717 Methods for Analysis of Commercial ButaneButene Mixtures and Isobutylene by Gas Chromatography 3
D 1945 Test Method for Analysis of Natural Gas by Gas
Chromatography 4
D 1946 Practice for Analysis of Reformed Gas by Gas
Chromatography 4
D 2163 Test Method for Analysis of Liquefied Petroleum
(LP) Gases and Propane Concentrates by Gas Chromatography 5

3. Terminology
3.1 Definitions:
3.1.1 British thermal unit-the defined International Tables
British thermal unit (Btu).
3.1.1.1 Discussion-The defining relationships are:
1 Btuolb- I = 2.326 J og-I (exact)
1 lb = 453.592 37 g (exact)
By these relationships, 1 Btu = 1 055.055 85262 J (exact). For
most purposes, the value (rounded) 1 Btu = 1055.056 J is
adequate.
3.1.2 compressibility factor (z)-the ratio of the actual

1 This practice is under the jwisdiction of ASTM Committee D-3 on Gaseous


Fuels and is the direct responsibility of Subcommittee D03.03 on Determination of
Heating Value and Relative Density of Gaseous Fuels.
Current edition approved May 10, 1998. Published April 1999. Originally
published as D 3588 - 98.
2 A more rigorous calculation of Z(T,P) at both base conditions and higher
pressures can be made using the calculation procedures in "Compressibility :md
Super Compressibility for Natural Gas and Other Hydrocarbon Gases," American
Gas Association Transmission Measurement Committee Report 8, AGA Cat. No.
XQ1285, 1985, AGA, 1515 Wilson Blvd., Arlington, VA 22209.
3 Discontinued, see 1983 Annual Book of ASTM Standards, Vol 05.01.
4 Annual Book of ASTM Standards, Vol 05.05.
S Annual Book of ASTM Standards, Vol 05.01.

Annual Book of ASTM Standards, Vol 05.02.


Available from Gas Processors Association, 6526 E. 60th, Tulsa, OK 74145.
B A program in either BASIC or FORTRAN suitable for running on computers,
available from the Gas Processors Association, has been found satisfactory for this
purpose.
9 Available from Thermodynamics Research Center, The Texas A&M University,
College Station, TX 77843-3111.
10 Available from the American National Standards Institute, II W. 42nd St.,
13th Floor, New York, NY 10036.
11 Supporting data are available from ASTM Headquarters. Request RR:D031007.
6

76

~~r~ 03588
volume of a given mass of gas at a specified temperature and
pressure to its volume calculated from the ideal gas law under
the same conditions.
3.1.3 gross heating value-the amount of energy transferred
as heat from the complete, ideal combustion of the gas with air,
at standard temperature, in which all the water formed by the
reaction condenses to liquid. The values for the pure gases
appear in GPA Standard 2145, which is revised annually. If the
gross heating value has a volumetric rather than a mass or
molar basis, a base pressure must also be specified.
3.1.4 net heating value-,-the amount of energy transferred
as heat from the total, ideal combustion of the gas at standard
temperature in which all the water formed by the reaction
remains in the vapor state. Condensation of any "spectator"
water does not contribute to the net heating value. If the net
heating value has a volumetric rather than a mass or molar
basis, base pressure must also be specified.
3.1.5 relative density-the ratio of the density of the gaseous fuel, under observed conditions of temperature and
pressure, to the density of dry air (of normal carbon dioxide
content) at the same temperature and pressure.
3.1.6 standard cubic foot of gas-the amount of gas that
occupies 1 fe (0.028 m3 ) at a temperature of 60F (15.6C)
under a given base pressure and either saturated with water
vapor (wet) or free of water vapor (dry) as specified (see ANSI
Z 132.1.). In this practice, calculations have been made at
14.696 psia and 60F (15.6C), because the yearly update of
GPA 2145 by the Thermodynamics Research Center, on which
these calculations are based, are given for this base pressure.
Conversions to other base conditions should be made at the end
of the calculation to reduce roundoff errors.
3.1.7 standard temperature (USA}-600P (15.6C).
3.2 Symbols:
3.2.1 Nomenclature:
3.2.1.1 B-second virial coefficient for gas mixture
3.2.1.2 ~ -summation factor for calculating real gas
correction (alternate method)
3.2.1.3 (cor)-corrected for water content
3.2.1.4 (dry)-value on water-free ba.sis
3.2.1.5 d-density for gas relative to the density of air.
3.2.1,6 id-ideal relative density or relative molar mass,
that is, molar mass of gas relative to molar mass of air
.
3.2.1.7 Gid-molar mass ratio
3.2.1.8 H~~ -gross heating value per .unit mass
3.2.1.9 H~d -gross heating value per unit volume
3.2.1.10 H~d ~gross heating value per unit IT).ole .
3.2.1.P h~ -net heating value per unit mass
3.2.1.12 h~d -net heating value per unit volume
3.2.1.13 h~d -net heating value per unit mole
3.2.1.14 a, b, c-in Eq 1,integers required to balance the .
equation: C, carbon; H, hydrogen; S, sulfur; 0, oxygen
3.2.1.15 (id}~ideal gas state
3.2.1.16 (l}-iiquid phase
3.2.1.17 M-molar mass
3.2.1.18 m-mass flow rate
3.2.1.19 n-number of components
3.2.1.20 P-pressure in absolute units (psia)

77

3.2.1.21 Qid-ideal energy per unit time released as heat


upon"combustion
"
3.2.1.22 R-gas constant, 10.7316 pSia.fe/(lb mol oR) in this
practice (based upon R = 8.31448 J/(mol-K))
3.2.1.23 (sat)-denotes saturation value
3.2.1.24 T-absolute temperature, OR = 0p+ 459.67 or K =
C + 273.15
3.2.1.25 (T, P}-value dependent upon temperature and
pressure
3.2.1.26 V-gas volumetric flow rate
3.2.1.27 x-mole fraction
.
3.2.1.28 Z-gas compressibility factor repeatability of property
3.2.1.29 S-repeatability of property
3.2.1.30 p-density in mass per unit volume
3.2.1.31 LJ=l -:-property summed for Components 1
through n, where n represents the total number of components
in the mixture
3.2.2 Superscripts:
3.2.2.1 id-ideal gas value,
3.2.2.2.l-liquid
3.2.2.3 a-value at saturation (vapor pressure)
3.2.2.4 '-reproducibility
3.2.3 Subscripts:
3.2.3.1 a-value for air
3.2.3.2 a-relative number of atoms of carbon in Eq 1
3.2.3.3 b-relative number of atoms of hydrogen in Eq 1
3.2.3.4 c-relative nurriber of atoms of sulfur in Eq 1
"
3.2.3.5 j-property for component j .
3.2.3.6 ii-nan-ideal gas property for component i
3.2.3.7 ij-non-ideal gas property for mixture of i and j
3.2.3.8 jj-non-ideal gas property for component j
3.2.3.9 w-valuefor water
3.2.3.10 I-property for Component 1
3.2.3.11 2-property for Component 2
4. Summary of Practice
4.1 The ideal gas heating value 'and ideal gas relative
density at base conditions (14.696 psia and 60 0 P (5.6C)) are
calculated from the molar composition and the respective ideal
gas values for th~ components; these ~alues are then adjusted
by means of a calculated compressibility factor.
S. Significance and Use
5.1 The heating value is a measure, of the suitability of a
pure gas or a gas mixture for use as a fuel; it indicates the
amount of energy that can be obtained as heat by burning ~ unit
of gas. For use as heating agents, the relative merits of gases
from different sources and having different compositions can
be compared readily on the basis of their heating vall).es,
Therefore, the heating value is used as a parameter for
determining the price of gas in custody transfer. It is also an
essential factor in calculating the efficiencies of energy cone'
version devices such as gas-fired turbines. The heating v,alues
of a gas depend not only upon the terriperature and pressure, ,
but also upon the degree of saturation with water vapor.
However, some calorimetric methods for measuring heating
values are based upon the gas being saturated with water at the
specified conditions.

~~r~D3588
7. Calculation-Ideal Gas Values; Ideal Heating Value

5.2 The relative density (specific gravity) of a gas quantifies


the density of the gas as compared with that of air under the
same conditions;

7.1 An ideal combustion reaction in general terms fat fuel


and air in the ideal gas state is:

6. Methods of Analysis'
6.1 Determine the molar composition of the gas in accordance with any ASTM or GPA method that yields the complete
composition, exclu,siv.e of water, but including all other components present in amounts of 0.1 % or more, in terms of
components or groups of components listed in Table L At l~ast
98 % of the sample must be reported as individual components
(that is, not more than a total of 2 % reported as groups of
components such as butanes, pentanes, hexanes, butenes, and
so forth). Any group used must be one of those listed in Table
1 for which average val~es appear. The,following tyst methods
are applicable to this' pr.act~ce when appropriate for the sample
undertest: Test Methods D 1717, D '1945; D 2163,and D 2650.

+ (a + b/4 + c)O;(id) = aC02(id) + (h/2)H 20

CaHbsc (id)

(id or I)

+ cS02(id)

(I)

where id denotes the ideal gas state and I denotes liquid


phase. The ideal net heating value results when all the water
remains in the ideal gas state. The ideal gross heating value
results when all the water fonned by the reaction condenses to
liquid: For water, the reduction frorriH2 0(id) to H2 0(l)is H~
- H~ , the ideal enthalpy of vaporization, which is somewhat
larger than the enthalpy of vaporization H~ - F1~' .
7.1.1 Because the gross hea:tirt~ '~alue re~ults from an ideal
combustion r~aqion, ideal ,gas relationships apply. T'he jdeal
gross heating vah~e per unit mass for a mIxture, H;~ is:

TABLE 1 Properties of Natural Gas Components at 60F and 14.696 psia A


Ideal Gross Heating ValueD
Compound

Formula

Molar Mass,
Iblbmor 'B

Molar Mass,
Ratio, GldC

Hdn ,

Hid

Btulbm- 1

m'

Ideal Net Heating 'value

Hd'
v ,
Btu.

H%,

Hydrogen
Helium
Water
Carbon monoxide
Ntlrogen
Oxygen
Hydrogen sulfide
Argon
Carbon dioxide

H2
He
H2O
CO
N2
O2
H2S
Ar
CO 2

2.0159
4.0026
18.0153
28.010
28.0134
31.9988
34.08
39,.948
44.010

0.06960
0.13820
0.62202
0.96711
0.96723
1.1048
1.1767
1.3793
1.5196

kJ mor '
286.20
0
44.409
282.9
0
0
562.4
0
0

Air

28.9625

1.0000

Methane
Ethane
Propane

n-Pentane
n-Hexane
n-Heptane
n-Odtane
n-Nonane
n-Decane

CH.
C2He
C3 Ha
C.H1Q
C.H1Q
CS H'2
CS H'2
CaH ,
97 H '6
CSH,S
C9 H20 '
C1O H22

16.043
30.070
44.097
58.123
58.123
72.150 .
72.150
86.177
100.204
114:231
128.258
142.285

0.55392
1.0382
1.5226
2.0068
2.0068
2.4912
2.4912
2.9755
3.4598
3.9441
4.4284
4.9127

891.63
1562.06
2220.99
2870.45
2879.63
3531.5
3535.8
4198.1
4857.2
5515.9
6175.9
6834.9

23891
22333
21653
21232
21300
21043
21085
20943
20839
20759
20701
20651

1010.0
1769.7
2516.1
3251.9
3262.3
4000.9
4008.9
4755.9
5502.5
6248.9
6996.5
7742.9

802.71
1428.83
2043.3
2648.4
2657.6
3265.0
3269.3
3887.2
4501.9
5116.2
5731.8
6346.4

Neopentane
2-Methylpentane
3-Methylpentane
2,2-Dimethylbutane
2,3-Dimethylbutane
Cyclopropane
Cyclobutane
Cycl9pentane
Cyclohexane
Ethyne (acetylene)
Ethene (ethylene)
Propene (propylene)
Benzene

CSH'2
CeH ,
CeH ,
CeH ,
CeH ,
C3 He
C.Hs
CS H'0
CaH'2
C2H2
C2H.
C3 Ha
CaHa

72.015
86.177
86.177
86.177
86.177
42.081
56.108
70.134
84:161
26.038
28.054
42.081
78.114

2.4912'
2.9755
2.9755
2:9755:
2.9755
1.4529
1.9373
2-4215
2.9059
0.8990
0.9686
1.4529
2.6971

3517.27
4190.43
4193.03
4180.63
4188.41
2092.78
2747.08
3322.04
3955.84
1301.32
1412.06
2059.35
3202.74

20958
20905
20918
20856
20895
21381
21049
20364
20208
21487
21640
21039
18177

3985
4747
4750
4736
4745
2371
2747
3764
4482
1474
1600
2333
3742

3879.6
3882:2
3869.8
3877.5
1959:6:
2569.4
3100.0
3689.4
1256.9
1323.2
1926.1
3169.5

C.H '0
CS H.12
. CeH,
C.Hs
,CS H1O

58.123
72.150
86.177
56.108
70.134

2.0068
2.49~ 2
2.9755
1.9372
2.4215

2875
3534
4190
2716
3375

21266
21056
20904
20811
20691

3257
4003
4747
3077
3824

2653
3267
3879
2538
3153

~Butane

n-Butane
~Pentane

Butanes (ave)
Pentanes (ave)
Hexanes (ave)
Butenes(ave)
Pentenes (ayet:

61022
0
1059.8
4342
0
0
7094.2
0
0
0

ft"3

324.2
0
50.312
320.5
0
0
637.1
0
0
0

kJ mor '
241.79
0
0
282.9
0
0
517.99
0
0
0

~250.8

Hdm'

Btulbm'
51566
0
0
4342
0
0
6534
0
0
0
21511
20429
19922
19590
19658
19456
19481
19393
19315
19256
19213
19176

h~
Btu

it"

Summation
Factor, bl ,
psia- '

273.93
0
0
320.5
0
0
586.8
0
0

0
0
0.0623
0.0053
0.0044
0.0073
0.0253
0.0071
0:0197

0.0050

909.4
1618.7
2314.9
300P.4
3010.8
3699.0
3703.9
4403.9
5100.3
5796.2
6493.6
7189.9

0.0116
0.0239
0.0344
0.0458
0.0478
0.0581
0.0631
0.0802
0.0944
0.1137
0.1331
0.1538

19371
"19355
19367
19306
19344
20020
19688
19003
18847
20753
20278
19678
17444

3683
4395
4398
4384
4393
2220
2911
3512
4180
1424
1499
2182
3591

0.021
0.020
0.033
0.069

19623
19469
19353
19450
19328

3006
3702
4395
2876
3572

0.046
0.062
0.080
0.046
0.060

0.080
0.080
0.080
0.080

'.,

AThis table is consistent with j3PA 2145-89, but ij is necessary to use, the val.ues from the most recent edition of GPA 2145 for custody transfer calculations.
B1984 Atomic W:eights: C= 14,011, H = 1.00794, 0 =: 15.~994, N = 14.0067, S = 32.06.
cMolai mass ratio is the ratio o'flhe m'olar mass of the gas to that of air.
DSased upon ideal reaction;] the entry for water represents the iotal enthalpy of vaporization.
EComposilion from: F. E. Jones, J. Res. Nat. Bur. Stand., Vol. 83,419, 1978.

78

~~r~ D 3588
II

H'm'd

II'

'LJ
" x,M.T-l 'd ,I 'LJ
" x,M,
= j=1
'
1'=1 't'~J,

(2)

j'A.,r.r..l!I,J

where: Xj is the mole fraction of Componentj;Mj is the iliohir


mass of Component j from Table 1, and n is the total number
of components.
7.1.2 H;~J is the pure component, ideal gross heating value
per unit mass for Component j (at 60F (15.6C) in Table 1).
Values of H~~ are independent of pressure, but, they vary with
temperafure. '
7.2 Ideal Gas Density
7.2.1 The ideal gas density, pid, is:,
, pid = (PIR1)

j=!

xM, = MPIRT

'(3)

,")

where B jj is the second virial coefficient for Component j and


is the second cross virial coeffici~nt for Components i andj.
The second virial coefficients are flIDctibns of temperature. Eq
9 can be used with Eq 10 for calculation of the compressibility
factor for the various pressure bases, but it is not accurate at
pressures greater than two atmospheres. Special treatmeI)"t is
not required for H2 and He at mole fractions up to 0.01.
Calculations can be made with Bjj = 0 for hydrogen and
helium.
7.5.2 Eq 9 and Eq 10 for calculation of Z(T,P) for a gas
mixture are rigorous but require considerably calculations and
information that is not always available. An alternative, ap, proximate expressio~ for Z(T,P) that is, more convenient for
hand calculations is:
Bij

.M is the molar mass of therpixture,i::

where;

(11)

II

M= j=!
~xM,
, ..)

(4)

where f3 jj = BjJRT and~ is the summation factor for


Componentj. ValuesofVJ3jj ai"60F (l5.6C>C) appear in Table
2. The method based upon Eq lLhas been adopted for this
practice.
7.6 Real Gas Density:
7.6.1 The real gas densityp' at a specific temperature and
"
pressure is: ,

P is the base pressure in absolute units (psia), R is the gas

constant, 10.7316 pSiaJe/(lb moloR) in this practice, based


upon R = 8.31448 J/(molK), T is the base temperature in
absolute units (OR = of + 459.67). Values of the ideal gas
density at 60F (15.6C) and 14.696 psia are in GPA Standard
2145.
7.3 Ideal Relative Density:
7.3.1 The ideal relative density i d is:

'p = pidlz '

'.
(12)
pid and Z are evaluated' ~t'the same te~Penit1ire and

where:
pressure.
7.7 Real Relative Density:
7.7.1 The realre!ativedensity, di~:,

II

id

_j

= j~ xA = 2: x#/Ma = MIMa

(5)

where: Ma is the molar mass of air. The ideal relative density


is the molar mass ratio.
7.4 Gross Heating' Value per,unit Volume:'
7.4.1 Multiplication of the' gross heating value pet unit mass
by the ideal gas density provides the gross heatillg value per
unit volUme; H~d:
,j

Hid = pid Hid =


v,

Xfiid,

" ".

(6)

v.;.

',Ii~~'iS th~ pure component gross h~ad~g value per unit


vol ume for COIJ.1ponent j at' specified tempei:atu~e' and pressure
(60F (l5.6C) ,and 14.696.psia in.Table 1, ideal gas values).
,.7.4.2 Conversion of valuesin Table .1 to diff((rent pressUr~
bases results from multiplying by the' pressure ratio,:,
'
, H~ (P) = H~d (P ~ ~4.696) X PII4.696

,.

J',

i'.

. ,

, 4:1 = p/Pa '= MZa'lM.2 '

""n

1'=1

~'

.'

":.'''-:. ,';
'

(13)'

. :' r~ : ';.

7.8 Real H eating Value-The real heating value is pot given


by division of the ideal heating value by the compressibility
factor. Real gas heating. vill ues differ from the iaeal gas values
by less than one partin 10 4 at 14.696psia, which is of the' order
of the accuracy of the'heating vaJ.ues;~; .:.,
.
7.9 Gross Heating Value oj Water Wet Gas:
7.9.1 If the gas cQntains water as a cqmponent but the
compositional analysis is ,on a dry basis, it is necessary to
adjust the mole fractions to refleci: the presence of water. The
corrected mole fractions are:: "
4cor) = x/I -xw)

(14)

(7)

; ,The mole fraction of watercari range from zero up to the


saturated :value. ;rpe ,~aturated valu,e for xlV i~,assumi!1g
Raoult's Law:

'(8)

(15)

),where p is the real gas density in rnass per unit volume. At


conditions near ambient;, the tmncated virial equation of state
satisfactorily represents the \7ohimetric behavior of'mitural gas:'
, ,,'
Z (~,P)T 1, + SPIRT' ' .
" '
, (9.)

where: R~ is:,th~ vapor press~of wat~r (0.256 36 psia at


e?0F (15;6C)):'
,
.
7.9.2 Technically, water has a gross heating value,the ide,al
enthalpy of condensation. If only the water that is fanned
during the combustion condenses; then the heat released upon
combustion of a wetgaswith'dry air becomes:

Real 'Gas Values~ompressi~ility Factor;


;, 7.5; 1 The compressibility factor is:

\7.5

Z (T,p)=.'pid Ip = (MPIR1)lp

. whereB is the second virial coefficient for tI1~ gas imxture.


,
The second virial cm;fficient for a mixture is:'
;

(16)
11

':Forwater7satnratedgas, Xw at 60 o P(15.6 C) is 0;256 3f>IPb


wherePb:is the baSe pressure. Eq16 is'adequate for custody
transfer applications as 'a matter ofdefini.tion'. However, this'

II: -,.

= ;;::;11'=1
~~;,xJ3"
I

(1.0)

I)

79

~~f~ D 3588
TABLE 2 Example Calculations of Gas Properties at 60F and 14.696 psia (Gas Analysis on Dry Basis)A
id
NOTE I-Division of Hv by Z does not'give a real gas heating value but rather an ideal gas heating value per real cubic feet. Any digits carried beyond
1 part in 1000 are not significant but only allieviate roundoff error. Although CO2 hflS a carbon/atom, its ex = 0 because it is not part of the ~uel fOJ.;nula
C",Hf3 S' Y ' .
'.

Compound
Methane
~thane

Propane
i-Sutane
n-Butane
i-Pentane
n-Pentane
Hexane
Helium
Nitrogen
Carbon dioxide
Summation
AXw

x,

01,

13,

'Y,'

Hvf1

0.8302
0.0745
0.0439
0.0083
0.0108
0.0031
0.0025
0.0030
0.0003
0.0032
0.0202

1
2
3
4
4
5
5
6
0
0
0

4
6
8.
10
10
12
12
14
0
0
0

0
0
0
0
0
0
0
0
0
0
0

1010.0
1769.7
2516.1
3251.9
3262.3
4000,9
4008.9
4755.9
0
0
0

'G~

b,

0.55392
1.03820
1.52260
2.00680
2.00680
2.49120
2.49120
2.97550
0.13820
0.96723
1.51960

1.0000

= (0.25636)/14.696

0.0116
0.0239
0.0344
0.. 0458
0.0478
0.0581
0.0631
0.0802

0.0044
0.0197

xf'i.,

x,l3,

Xtii

x,HJ/ .

G7

x,b, .

0.8302
0.1490
0.1317
0.0332
0.0432
0.0155
0.0125
0.0180
0
0
0

3.3208
0.4470
0.3512
0.0830
0.1080
0.0372
0.03
0.0420
0
0
0

0
0
0
0
0
0
0
0
0
0
0

838.5
131.8
110.5
27.0
35.2
12.4
10.0
14,3
0
0
0

0.4599
0.0773
0.0668
0.0167
0.0217
0.0077
0.0062
0.Op89
0.0000
0.0031
0.0307

0.00963
0.001 78
iO.001 51
0.00038
0.00052
0.00018
0.00016
0.00024
0.00000
0.00001
0.00040

1.2333

4.4192

1179.7

0.6991

0.01481

x,

= 0.0174

G'd (dry gas) = 0.6991


Z (dry gas) = 1 - [0.014 81f(14.696) = 0.9968
Z (dry air) = 1 - [0.0050]2(14.696) = 0.9996
G (dry gas, dry air) = 0.6991 (0.9996)/0.9968 = 0.7011
G (dry gas, sat air) = 0.6991(0.9995)/0.9968 = 0.7010
HVd (dry gas, dry air) = 1179.7 Btult""
HVd (sat gas, dry air) = 1179.7(0.9826) = 1159.1 Btulr3
1- Xw = 0.9826
G'd (sat gas) = 0.6991(0.9826) + 0.0174(0.622 02) = 0.6978
Z (sat gas) = 1 - [0.9826(0.01481) + 0.0174(0.0623)]2(14.696) = 0.9964
Z (sat air) = 1 - [0.9826(0.0050) + 0.0174(O.0623)f(14.696) = 0.9995
G (sat gas, dry air) = 0.6978(0.9996)/0.9964 = 0.7001
G (sat gas, sat air) = 0.6978(0.9995)/0.9964 = 0.7000
{HVdlZ}(dry gas, dry air) = 1179.7/0.9968 = 1183.5 Btun-3
{HVdIZ} (sat gas, dry air) = 1159.1/(0.9964) = 1163.3 Btun-3

8. Precision

equation does not accurately'describe the effect of water upon


the heating value. Appendix Xl contains a rigorous examination of,the effect of water.
7.10 Calculation of the Ideal Energy Released as Heat:
7.10.1 When multiplied by the gas flow rate, the ideal gross
heating value provides the ideal energy released as heat upon
combustion, Qid ,an ideal gas property:

8.1 The properties reported in this practice derive from


experimental enthalpy of combustion measurements which, in
general, are accurate to I part in 1000. The extra digits that
appear in the accompanying tables alleviate prob~ems associated with roundoff errors and internal consistency, but they are
not significant.
8.2 The values of properties in this practice are those that
appear in GPA Standard. 21'72-5>7, Fig. 23-2 of the GPSA
Engineering Data Book, GPA TP-17, and the TRC Thermodynamic Tables-Hydrocarbons. GPA Standard 2145 is updated
annually and the varues in that standard should be used in all
calculations.

(17)

where mis the mass flow rate. For an ideal gas, the mass flow
rate is related to the volumetric flow rate, yid , by:
(18)

and
(19)

NOTE 2-Three sources of error must be considered: errors in heating


values of the components, errors in the calculated compressibility factor,
and errors in the composition. The uncertainty' (twice the standard
deviation) of the ideal gas heating values for components should be
0.03 %. Such errors affect the bias and the agreement between calculated
and mel\sured heating values, but they do not affect the precision. Erro;rin
the calculated cpmpressibility factor varies with the composition of the
gas, but fpr natural gas, this error should be less than 0.03 % and
negligible ~ompal'ed to enors adslng fro~ uncertainty in composition. In
this practice, the errors in the heating valUes of the components and the
calcul~ted compressipility factor, ,2'1 are neglected. The precision of the
method is related to the repeatability and reproducibility of the analysis.
An example appears in Table 3.
.
,

7.10.2 The ideal gas flow rate is related to the real gas flow
rate by:

y;d = VIZ

(20)

where V is the real gas volumetric flow rate and Z(T,P) is the
real gas compressibility factor at the same T and P. Hence,
combining Eq 19 and Eq 20 gives:
Qid '"

H~ VIZ (T,P)

(21)

NOTE I-The ideal etiergy released per unit time' as heat upon combustion, Qid ,can be calculated using the mass flow rate (Eq 17), the ideal
gas flow rate (Eq I9),'or'the reill gas flow rate' (Eq 21), but is always an
ideal gas property. Division of H~d by the gas compressibility factor Z(T;P)
does not produce a real gas heating value but only allows calculation, of
Qid \.Ising the real gas flow rate rather than the,ideal gas flow rate.

NOTE 3-It is essential to include all components in the gas sample that
appear with mole fractions greater than or equal to 0.001 in the analysis.
Some routine analyses do not detelmine compounds such as I-Ie and H 2 S,
but these compounds are important to the calculations.

80

ij~r~ 03588
TABLE ~ Example Calculations of Gas Propertiesat60F and 14.696 psia(Gas Analysis on Wet Basis)A

I-Division of Hv id by Z does not give a real gas heating value but rather an ideal gas heating value per real cubic feet. Any digits carried beyond
1 part in' lOQO are not significant but only allieviateroundoff error. AlthOl1gh CO2 has a carbon atom, its ct = 0 because it is not part of'the fuel 'formula
CCl.Hf!,S'Y'
NOTE

x,

Compound

0.8157
0.0732

Methane
Ethane
Propane
i-Butane
n-Butane
i-Pentane
n-Pentane
Hexane
Helium
Nitrogen
Carbon dioxide
Water

0..0198
0..0174

Summation

1.0.0.0.0

AG/~ (sat gas)

.0.0431
.0.0.082
0 ..01.06
0 ..0.03.0
0.0.025
0.0.029
0.0.0.03
0.0031

[3,

"II

Hv'f'

GIfI
,

b,

Xfi,

x,[3,

XN,

4
6
8

0
0
0

.0
.0
.0
.0
.0
.0
.0
.0

0.55392
1.03820
1.52260
2.00680
2.00680
2.49120
2.49120

0.0116
0.0239
0.0344

1.0

1010.0
1769.7
2516.1
3251.9
3262.3
4000.9
4008.9
4755.9
0
0

3.2629
0.4392
0.3451
0.0816

0.0478
0.0581
0.0631

0.8157
0.1464
0.1294
0.0326
0.0424
0.0152
0.0123

2.9755.0
0.1382.0

0.08.02
.0
0.0044

.0

0.96723
1.51'960

0
0
0
0
0
0
0
0
0
0

50.3

0.622.02

ell

1
2'
3
4
4
5
5
6
0
0
0
0

10
12
12
14
0
0
0
0

.0.0458

0..0197
0..0623

1.2118

x,G;d

Xibi

823.9
129.5

0.4518 '
0.0760

1.08.5

.0 ..0657
.0 ..0164
.0 ..0213
.0 ..0076
.0 ..0061
.0 ..0088

O'

.0.9

0 ..0.030
.0 ..0302
.0 ..0108

4.3421

1.16.0.0

.0.6977

0.0366
0.0295
0.0413
0
0

0
0
0
0

26.5
34.6
12.2
9.8
14.0
0
0
0

0.1.061

0..0177

x, H0

0.00946

0.0.01 75
.0.0.0148
.0 ..0.0.0 37
.0 ..0.0.0 51
O.O()(j 18

.0 ..0.0015
.0 ..0.0024

.0
0.0.0039
0 ..0.01 09
0.D1564

= .0.6977,

Z (sat gas) = 1 - [0.015 64]2(14.696) = 0.9964


Z (dry air) = 1 - [0 ..005.0]2(14.696) = 0.9996
G (sat gas, dry air) = 0.6977(.0.9996)/0.9964 = 0.6999
Hvd.(sat gas, dry air) = 1160.0 - 0.9 =c 1159.1 Btuft--3
Z (sat air)
1 ~ [0.9826(0 ..050) + 0.0174(0.0623)]2(14.696) = 0.9995
'
. G (sat gas, sat air) = 0.6977(0.9995)10.9964 = 0.6999
{HvdlZ}(sat ga~, dry air) = 1159.1/(0.9~64) = 1163.3 Btuft--3 .

\""

. 8.3 Repeatability:
.
.8.3.1 If all the components are analyzed and the results are
normalized, then the repeatability of the heating value l SH is:
8H
. --'-d =
, ; H'

1 /I
id
id-.
2
~2 ~ [(H -H )8~.J

(H' )

j=!

(22)

J.

l'

8.3.2 If the resu1tsof the analysis are made to ,Sllrll to 1.0' by


calculating the methalle mole fraction as the difference between 1.0 and the sum of the ',mOle fractio l1s. of the other
components, then
8H
Hid =

'1

/I

id'

(Hidh~[Hj 8;j]

2'"

Component j. TJ.1ediff.erences be~ween he~til).g value$ cal~u


lated from succ,essivepairs of ~alysis performecU)r t11e spine
operator using the same Sample of gasanclthe same instrUment
~hould exceed 2SH in only: 5.% of the tests whf?J.:l ~llis ,taken
as one standwd deviation.. , , .
. . ' ,'.
"."

..::

(23)

,.:

, ;

! , '.

~'.

'.

:' ,

',:.,

,I

8.4 Reproducibility~Thereproducibility SH' is Q<,J;~qulated


from Eq 22 andEq 23 usingSx'J' the, .reprodu~ibility;0f thei
method of analysis for Compound j. The ditferencebetween
heating values"calculated.from analysis obtained in different,
laboratories is expected to exceedSH' for only 5 %.of the
analyses.
.'. ,'.J

where SXj is the repeatability of the method of analysis for

,(.

;"

c.

','

A,PPENDIXES
'. (Nonmandatory Information) ,

Xl. EFFECT OF WATER UPON THE HEATING VALUE

Xl. 1 Custody transfer of natmal gas uses a simple pricing


equation that st~tes that the cost of gas is the rate of energy
released upon combustion multiplied by the price of gas per
energy unit multiplied by the time or accOlllting. period. The
rate of energy released upon combustion'is the product of the
heating value of the gas and the flow rate of the gas. The flow
rate of the gas requires knowledge of the compressibility factor
and the relative density of the gas. All three custody transfer
properties (heating value, compressibility factor, and relative
density) can be calculated from the composition given pure
component property tables. The equations for calculating the
properties of dry natural gas are well known, but this appendix
also presents an account of the effects of water contained in the

.'

gas arid in the air used to'bi.lffi the gas.


Xl.2 The heating value of a natural gas is the absolute
value of its enthalpy of combustion in an ideal combustion
reaction. The heating value is, therefore,' an ideal gas property
that can be calculated unambiguously from tables of pure
component values and it has no pressure dependence.
X1.3 An ideal combustion reaction with fuel and air in the
ideal gas state and the possibility of water in the fuel and air is:

+ (ex + [3/4 + 'Y)(I + e)OzCid)


+ 0.043 83(ct + [3/4 + 'Y)(l + e)Ar (i(l)
(Xl.1)
+ [0.001 62(ct + [3/4 + 'Y)(l + e) + xJ(l- xN - xc)]C0zCid)
CaH~S-iid)

~~f~ D 3588
!A~LE
I

Composition,

, Compound

Xj

0.8302
0.0745
0.0439
0.0083
0.0108
0.0031
0.0025
0.0030
0.0003
0.0032
0.0202

Methane
Ethane
Propane
Isobutane
Butane
Isopentane
Pentane
Hexane
Helium
Nitrogen
Carbon dioxide
Total

T.OoOO

X1.1 Example Calcl,I.lation of Pre.cision


Repeatability

H:"- H,,~
Btu,ft-3

169.7
-590.0
-1336.4
-2072.2
-2082.6
-2821.2
-2829.2
-3576.2
1179.7
1179.7
1179.7

ax!

ax'] ,

0.0010
0.0002
0.0002
0.0001
0.0002
0.0001
0.0001
0.0001
0.0001
0.0001
0.0002

0.029
0.014
0.071
0.043
0.173
0.080
0.080
0.128
0.014
0.014
0.056

0.0020
0.0004
0.0004
0.0002
0.0004
0.0002
0.0002
0.0002 .
0.0002
0.0002
0.0004

+ [3.728 73(a + 1314 + 1')(1 + e) + xN 1 (l-xN -xc)]Nz{id) + (n~

+ n~)HzO (id)
= [a

+ 0.001

62(a

+ 1314 + 1')(1 + e) + xd(1- xN -

Rep(oducibilily

[( H:(BtufI-3)2
- H~ )ax~2

D.702

[( H~ - H~)ax'l
(Btu'W3 )2'

0.115
0.056'
0.286
0.171
0.694
0.318
0.320
0.512
0.056
0.056
0.223
2.807

= water.

The quantity Hw (id) - Hw(l) is the ideal enthalpy of


vaporization for water.

xc)]COz{id)

+ n~H20 (id) + n~H20 (1) + I'SOz{id)

X1.5 It is possible to calcu,!ate a real ga~ heating value


rather than using a hypothetical. state,. but the calculations are
tedious, the numerical values are negligibly different, and the
mathematical simplicity of the defining equation is lost. It is
customary in the gas industry to use gross heating value for
most calculations, So for the remainder of this appendix, the
term "heating value;' refers to the gross value.

+ [3.728 73(a + 1314 + 1')(1 + e)

+ xJ(I-xN -xd]Niid)
+ 0.043 83(a + 1314 + 1')(1 + e)Ar(id) + (a + 1314 + I')e02(id)
where: <Y, 13, and 'Y are stoichiometric coefficients, E is the
fraction excess air, the composition of ,iir is assumed to be that
of Table XI.I ,n~ and the moles of water contained in the gas,
n~ ate the moles of water contained in the air,
are the moles
of water contained in the product gastnixture, n~ are the moles
of gas that actually condense, Xc is the mole fraction of CO 2 in
the gas, arid xN is the mole fraction of N2 in the gas. If air has
been injected into the gas, it is assumed that the effect is
accounted fat in the excess fraction E. Fuel gas mixtures would
have non-integer values of <Y, 13 and 'Y.

n:

X1.6 Eq 7 in Section 7 provides the recipe to convert lhe


heating value from one base pressure to another. Note thal
when using Eq 7, Hv id should be Calculat~d using the values
from Taple 1 before converting the pressure; the individual
values in Table I should not be converted. Conversion to
another temperature is more complicated. Heating value data
exist at 25C based upon ~e reaction:

X1.4 It is customary to define hypothetical reference states


for the water formed by the reaction denoted by Eq I (as
opposed to "spectator" water that enters the reaction carried by
the gas or air). If we assume that the water formed in the
reaction remains in the ideal gas state, the heating value is
termed "net." If we assume that the water formed in the
reaction condenses totally to the liquid state, the heating value
is termed "gross." The gross heating value is greater than the
net heating value by the ideal enthalpy of vaporization for
water:

CaH~Spd)

+ (a + 13/4 + 'Y)02(id) = aC0z{id) + (13/2)HzO (I)


+ "IS0z(id)
(XU)

XI.7 The experiments use pure oxygen and are corrected to


. stoichiometric proportions. It is necessary to correct the sensible heat effects to arrive at a different temperature:
Hn id (1)

= Hnid (25) +

fil"7' dd - L dd]dT
P

(XI.4)

where:

c; = aC;'co, + (13/2)C~~H,o + I'C;'so,


L c; = C;'caH,s, + (a + 13/4 + "I)C;'o,

~
r

heating value (gross) - heating value (net) = H.. (id) - Hw (l)


(X 1.2)

where:
H
enthalpy,
I = liquid state, and

(X 1.5)

(XI.6)

and: C~ is the ideal specific heat at constant pressure, r


denotes reactants and r' denotes products.

82

';'\':

~~f~ 03588
. X2. ACCOUNTING FOR: WATER
.

)(2.1 If the gas contains ~ater (or must be assumed to be


saturated) but the compositional analysis is on a dry basis, it is
necessary to adjust the mole fractions to account for the fact
that water has displaced SOme gas, -thus lowering the heating
value. The mole fraction of water in the gas results from the
definition of relative humidity:
(X2.1)

(Based upon one mole of the fuel Ca Hf3S'/) where kg is the


relative humidity of the gas, p~ is the vapor pressure of water, -and nw denotes moles of water. For saturated gas kg is tmity.
Rearranging Eq X2.1 gives the moles of water:
nw

= xj( 1 -

x,')

(X2.2)

11 nJ 1+
= x{

and the heating value becomes:


(X2.4)

where water is not included in the N components of the


summation. If the compositional analysis determines x.v and
water is included in the N components of the summation:
=

(X2.6)

n::,J[ 4.77418(0: + (3/4+ ,,)(1 + e) + n~] '= hap;,;P

(X2.7)

= 4.77418(0: + (3/4 + ,,)(1 + e)WP;';P)/(l- hap;,;P)

n~./ {o: +" + (XN + xc)l(1 ~xN,...,~d + (IX


+3.72873(1 + e)
n~v =

+- 0.04383(1

X ,livid
l

+(3/4 +,,)[0.00162(1(X2.8)
+ e)

+ ~) + e] + n~} = P;';P

{o: + " + (xN + xc)l(1- XN - xd + (0: + (3/4 + ,,)[0.001 62(1

+ e)

(X2.S)

(3/2 +

nf. +

n~ - n~.

(X2.9)

where: ka is the relative humidity of the air. Eq X2.6 and Eq


X2.7 are reformulations of Eq X2.1 to reflect inlet conditions.
Eq X2.S reflects Eq X2.1 for the saturated product gas (it must
be saturated before any water can condense). Eq X2.9 is a
water balance: [3/2 are the moles of water formed by the
reaction, n~ + n~ are the moles of water that enter with the gas
and air,
are the moles of water that saturate the product gas,
and n~ are the moles of water that condense. Therefore, the
complete correction for the effect of water on heating value is:

n:

~ x~vet liv~d_

;;:::1

n~

nf,/[l + (XN + xd/(l- XN '- xd +' nf.] = f,8p;,;p


nf. = (hBP':}P)/[(l-xN -xd(1-,hKP;';P)

n;. =
X)(1-X,.) ] = (1- xw)xi
(X2.3)

livid

-al cuIate nwg , nwa , nv -' and nw'


I
w

+3.72873(1 + e) + 0.043 83(1 + e) + e]}(P;';P)/(l- P;';P)

The corrected mole fractions then become:


xi(cor) = x{

,"

H: = H~d CEq X2.4 or Eq X2.S) + (hgp~jP)/(1 -xn -xc)(l - hgp;,;P)


(X2.10)

X2.2 It is necessary to remove the effect of water because,


although water has a heating value, it is only a condensation
effect. Water carried by wet gas (spectator water) does not
actually condense, and only water formed in the reaction
contributes to heating value.

+ 4.774 18(0: + (3/4 + ,,)(1 + e)WP;';P)I(l- hap;,;P) - [0: + "

+ (xn -xc)
(1-xn-xJ + (0: + (3/4 + ,,)(3.77418 + 4.77418 e)]
X (P;';P)/(l- P~)}H:~]

X2.4 Depending upon the relative humidities of the gas and


air, the observed heating value can be greater or smaller than
that calculated using Eq X2.4 or Eq X2.5. A humidity of air
exists for each gas above which HV id is greater than that
calculated by Eq X2.4 or Eq X2.S. That critical value depends
upon the gas composition, the humidity of the gas, and the
amount of excess air. For pure, dry methane with no excess air,
ka = 0.793 45.

X2.3 Accounting for water in the above manner is sufficient


for defined custody transfer conditions, but when trying to
model actual situations, the question becomes much more
complicated. It is obvious that all of the reaction water actually
cannot condense because in a situation in which both gas and
air are dry some of the reaction water saturates the product
gases and the remainder condenses. It is possible to account for
these effects in a general manner. To do so, it is necessary to

X3. REAL GAS PROPERTIES

X3.1 In principal, we have enough information to convert


the heating value to a real gas property (it is not necessary to
do so for relative density because the molar mass ratio, G id, is
the desired property). This is simply a matter of evaluating the
integral:

Hn_Hn id

f~{[ (~~)1. - [(~~)JJdP

aH)
(av)
( av T = V- T aT p

dB = 2 RF7r
dB
B- TdT

(X3.2)

where V is the molar volume. The temperature dependence


of b must be defined, but in the custody transfer region it is
easy to do so. The products and reactants again correspond to
Eq X1.3.

(X3.1)

X3.2 While it is obviously possible to make the required


calculations to convert the heating value into a real gas

where:
83

~~f~ D 3588
base conditions, to have all the water formed in the reaction be
either all gas or all liquid; some of the water formed is in each
state. Thus, if the definition is of a hypothetical state, using a
hypothetical real gas rather than an ideal gas state adds nothing
but complexity.

property, it serves no custody transfer purpose to do so. As we


have seen, the cost equation is unchanged; the calculations
while obvious are tedious. Hv is slightly different from HV id
because the base pressure is low; the likelihood of having all
the information required to use Eq X3.1 is remote. The heating
value is defined in a hypothetical state. It is not possible, at

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