ASTM D2650-10(2021)
(Test Method)Standard Test Method for Chemical Composition of Gases by Mass Spectrometry
Standard Test Method for Chemical Composition of Gases by Mass Spectrometry
SIGNIFICANCE AND USE
5.1 A knowledge of the composition of refinery gases is useful in diagnosing the source of plant upsets, in determining the suitability of certain gas streams for use as fuel, or as feedstocks for polymerization and alkylation, and for monitoring the quality of commercial gases.
SCOPE
1.1 This test method covers the quantitative analysis of gases containing specific combinations of the following components: hydrogen; hydrocarbons with up to six carbon atoms per molecule; carbon monoxide; carbon dioxide; mercaptans with one or two carbon atoms per molecule; hydrogen sulfide; and air (nitrogen, oxygen, and argon). This test method cannot be used for the determination of constituents present in amounts less than 0.1 mole %. Dimethylbutanes are assumed absent unless specifically sought.
Note 1: Although experimental procedures described herein are uniform, calculation procedures vary with application. The following influences guide the selection of a particular calculation: qualitative mixture composition; minimum error due to components presumed absent; minimum cross interference between known components; maximum sensitivity to known components; low frequency and complexity of calibration; and type of computing machinery.
Because of these influences, a tabulation of calculation procedures recommended for stated applications is presented in Section 12 (Table 1).
Serial No. . . . . . . . . . .
7
8
9
10
11
12
13
Name or Application
Commercial
Propane
Commercial
Butane
BB Stream
(Cracked
Butanes)
Dry Gas
Cracked
Fuel Gas
Mixed Iso
and Normal
Butanes
Reformer
Make-Up
Gas
Unstabi-
lized Fuel
Gas
Component
O
P
M
O
P
M
OC
PC
M
O
P
M
O
P
M
O
P
M
OC
PC
M
Hydrogen
...
...
...
...
...
...
...
...
...
15
2
M
...
...
...
10
2
M
16
2
M
Methane
...
...
...
...
...
...
...
...
...
14
16
M
...
...
...
9
16
M
15
16
M
EthyleneE
7
26
M
...
...
...
...
...
...
12
26
M
...
...
...
...
...
...
13
26
M
Ethane
6
30
M
...
...
...
...
...
...
11
30
M
...
...
...
7
30
M
12
30
M
Propene
5
42
M
7
42
M
6
42
M
10
42
M
...
...
...
...
...
...
8
42
M
Propane
3
44
M
4
44
M
4
44
M
7
44
M
3
44
M
5
44
M
6
44
M
Butadiene
...
...
...
...
...
...
1
54
M
3
54
M
...
...
...
...
...
...
2
54
M
Butene-1
1
56
M
1
56
M
7
41
M
1
...
...
...
...
...
...
...
...
9
41
M
Butene-2
1
56
M
1
56
M
8
56
M
1
56
M
...
...
...
...
...
...
10
56
M
Isobutene
1F
F
M
1
F
F
9
39
M
1
F
...
4
43
M
...
...
...
11
39
M
Isobutane
4
43
M
5
43
M
5
43
M
8
43
M
1
58
M
6
43
M
7
43
M
n-Butane
2
58
M
2
58
M
2
58
M
4
58
M
...
...
...
2
58
M
3
58
M
Pentenes
...
...
...
6
70
M
G
70
U
9
70
M
...
...
...
3
57
M
...
70
U
Isopentane
...
...
...
3
57
M
3
57
M
5
57
M
2
57
M
4
72
M
4
57
M
n-Pentane
...
...
...
...
...
...
...
...
...
6
72
M
...
...
...
...
...
...
5
72
M
Benzene
...
...
...
...
... ...
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D2650 − 10 (Reapproved 2021)
Standard Test Method for
Chemical Composition of Gases by Mass Spectrometry
This standard is issued under the fixed designation D2650; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the quantitative analysis of
D1137 Method for Analysis of Natural Gases and Related
gases containing specific combinations of the following com-
Types of Gaseous Mixtures by the Mass Spectrometer
ponents: hydrogen; hydrocarbons with up to six carbon atoms
(Withdrawn 1981)
per molecule; carbon monoxide; carbon dioxide; mercaptans
D1247 Test Method for Sampling Manufactured Gas (With-
with one or two carbon atoms per molecule; hydrogen sulfide;
drawn 1986)
and air (nitrogen, oxygen, and argon). This test method cannot
D1265 Practice for Sampling Liquefied Petroleum (LP)
be used for the determination of constituents present in
Gases, Manual Method
amounts less than 0.1 mole %. Dimethylbutanes are assumed
D1302 Test Method for Analysis of Carbureted Water Gas
absent unless specifically sought.
by the Mass Spectrometer (Withdrawn 1967)
NOTE 1—Although experimental procedures described herein are
uniform, calculation procedures vary with application. The following
2.2 American Petroleum Institute Standards:
influences guide the selection of a particular calculation: qualitative
MPMS 14.1 Collecting and Handling of Natural Gas
mixture composition; minimum error due to components presumed
Samples for Custody Transfer
absent; minimum cross interference between known components; maxi-
2.3 Gas Producers Association Standards:
mum sensitivity to known components; low frequency and complexity of
calibration; and type of computing machinery.
GPA 2166 Obtaining Natural Gas Samples for Analysis by
Because of these influences, a tabulation of calculation procedures
Gas Chromatography
recommended for stated applications is presented in Section 12 (Table 1).
NOTE 2—This test method was developed on Consolidated Electrody-
3. Terminology
namics Corporation Type 103 Mass Spectrometers. Users of other
instruments may have to modify operating parameters and the calibration
3.1 Definitions:
procedure.
3.1.1 base peak of a compound, n—the peak used as 100 %
in computing the cracking pattern coefficient.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3.1.2 cracked gases, n—hydrocarbon gases that contain
standard.
unsaturates.
3.1.3 cracking pattern coeffıcient, n—the ratio of a peak at
1.3 This standard does not purport to address all of the
any m/e relative to its parent peak (or in some cases its base
safety concerns, if any, associated with its use. It is the
peak).
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
3.1.4 GLC, n—a gas-liquid chromatographic column that is
mine the applicability of regulatory limitations prior to use.
capable of separating the isomers of butenes, pentenes,
hexanes, and hexenes.
1.4 This international standard was developed in accor-
dance with internationally recognized principles on standard-
3.1.5 IR, n—infrared equipment capable of analyzing gases
ization established in the Decision on Principles for the
for the butene isomers.
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
1 3
This test method is under the jurisdiction of ASTM Committee D02 on The last approved version of this historical standard is referenced on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of www.astm.org.
Subcommittee D02.04.0M on Mass Spectrometry. Available from American Petroleum Institute (API), 1220 L. St., NW,
Current edition approved Jan. 1, 2021. Published February 2021. Originally Washington, DC 20005-4070, http://www.api.org.
approved in 1967. Last previous edition approved in 2015 as D2650 – 10 (2015). Available from Gas ProcessorsAssociation (GPA), 6526 E. 60th St., Tulsa, OK
DOI: 10.1520/D2650-10R21. 74145, www.gpaglobal.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D2650 − 10 (2021)
TABLE 1 Calculation Procedures for Mass Spectrometer Gas Analysis
NOTE 1—Coding of calculation procedures is as follows:
O = Order peaks are used in the calculation expressed serially from 1 to n, n being the total number of components.
P= m/e of peak used and prefix, M, if monoisotopic.
M = Method of computation
U = Unicomponent Peak Method
M = Simultaneous equations where “a” identifies the particular set of equations if more than one is used.
a
C = Chemically removed.
Residual = m/e of peak suitable as an independent check on the method.
SerialNo. 123456
B
D1302
A
Reformer
D1137
Name or Application Carbureted H -C C ,C iC
2 6 3 4 4
Natural Gas
Gas
Water Gas
C C C C
Component O P M O P M O P MO P M O P MO P M
Hydrogen . . . 6 2 M 16 2 U 17 2 M 0 . . . . .
Methane 15 16 U 7 ⁄16 M 15 16 U 16 16 M 0 . . . . .
Ethylene 13 27 M2 12 27 M 13 26 U 15 26 M 0 . . . . .
Ethane 12 30 M2 8 30 M 12 30 U 13 30 M 0 . . . . .
Propene 10 42 M2 11 42 M 8 42 M2 12 42 M 6 42 M . . M
Propane 9 29 M2 9 29 M 3 44 M1 14 29 M 9 29 M 3 29 M
Butadiene . . . 9 . . 3 . . 10 54 M 9 . M . . M
Butene-1 8 56 M2 5 56 U 9 41 M2 8 56 M 8 41 M . . M
Butene-2 8 56 M2 5 56 U 10 55 M2 8 56 M 4 56 M . . M
Isobutene 8 56 M2 5 56 U 11 56 M2 8 56 M 5 39 M . . M
Isobutane 7 43 M2 5 . . 4 M43 M1 11 43 M 7 43 M 2 43 M
n-Butane 6 58 M2 4 58 U 5 58 M1 6 58 M 2 58 M 1 58 M
Pentenes . . . 3 70 U 2 70 U 9 55 M 3 70 M . . M
Isopentane . . . 3 . . 6 M57 M1 7 57 M 1 72 M . . .
n-Pentane 4 72 M2 2 72 U 7 72 M2 5 72 M . . . . . .
Benzene . . . 2 . . 7 . . 4 78 M . . . . . .
Hexanes . . . 2 . . 7 . . . . M . . . . . .
C cyclic paraffins . . . 2 . . 7 . . 3 84 M . . . . . .
Hexanes 5 57 M2 2 . . 1 71 U 2 86 M . . . . . .
Toluene . . . 2 . . 1 . . 1 92 M . . . . . .
Hydrogen sulfide 2 34 M1 2 . . 1 . . 21 34 M . . . . . .
Carbon dioxide 11 44 M2 10 44 M 1 . C 20 44 M . . . . . .
Carbon monoxide . . . 13 12 M 1 . C 18 28 M . . . . . .
Nitrogen 14 28 M2 14 14 M 14 28 U 19 14 M . . . . . .
Air 3 32 M1 1 32 U 14 . . 22 32 M 1 32 U . . .
DD
Helium 1 4 U 1 . . 14 . . . . . . . . .
SerialNo. 7 8 9 10 11 12 13
BB Stream Dry Gas Mixed Iso Reformer Unstabi-
Commercial Commercial
Name or Application (Cracked Cracked and Normal Make-Up lized Fuel
Propane Butane
Butanes) Fuel Gas Butanes Gas Gas
C C C C
Component O P M O P M O P MO P M O P MO P M O P M
Hydrogen . . . . . . . . . 15 2 M . . . 10 2 M 16 2 M
Methane . . . . . . . . . 14 16 M . . . 9 16 M 15 16 M
E
Ethylene 7 26 M . . . . . . 12 26 M . . . . . . 13 26 M
Ethane 6 30 M . . . . . . 11 30 M . . . 7 30 M 12 30 M
Propene 5 42 M 7 42 M 6 42 M 10 42 M . . . . . . 8 42 M
Propane 3 44 M 4 44 M 4 44 M 7 44 M 3 44 M 5 44 M 6 44 M
Butadiene . . . . . . 1 54 M 3 54 M . . . . . . 2 54 M
Butene-1 1 56 M 1 56 M 7 41 M 1 . . . . . . . . 9 41 M
Butene-2 1 56 M 1 56 M 8 56 M 1 56 M . . . . . . 10 56 M
FF FF F
Isobutene 1 M1 939 M 1 . 4 43 M . . . 11 39 M
Isobutane 4 43 M 5 43 M 5 43 M 8 43 M 1 58 M 6 43 M 7 43 M
n-Butane 2 58 M 2 58 M 2 58 M 4 58 M . . . 2 58 M 3 58 M
G
Pentenes . . . 6 70 M 70 U 9 70 M . . . 3 57 M . 70 U
Isopentane . . . 3 57 M 3 57 M 5 57 M 2 57 M 4 72 M 4 57 M
n-Pentane . . . . . . . . . 6 72 M . . . . . . 5 72 M
HH
Benzene . . . . . . . . . . . . . . . . . . D
HH
Hexanes . . . . . . . . . . . . . . . . . . D
HH
C cyclic paraffins . . . . . . . . . . . . . . . . . . D
HH
Hexanes . . . . . . . . . . . . . . . . . . D
HH
Toluene . . . . . . . . . . . . . . . . . . D
I II II
Hydrogen sulfide . . . . . . . . . . C . . . C C
I II II
Carbon dioxide . . . . . . . . . . C . . . C C
Carbon monoxide . . . . . . . . . 13 28 M . . . 8 28 M 14 28 M
Nitrogen . . . . . . . . . . . . . . . . . . . . .
Air . . . . . . . . . 2 32 M . . . 1 32 M 1 32 M
I II II
Acid Gases . . . . . . . . . . C . . . C C
E
Residual 8 27 M 8 27 M 10 27 M 16 14 M 5 27 M 11 14 M 17 14 M
E
Residual 9 29 M 9 29 M 11 29 M 17 15 M 6 29 M 12 15 M 18 15 M
E
Residual . . . . . . . . . 18 27 M . . . 13 27 M 19 27 M
E
Residual . . . . . . . . . 19 29 M . . . 14 29 M 20 29 M
D2650 − 10 (2021)
TABLE 1 Continued
SerialNo. 14 15 16
Name or Application H -C Cracked Gas H -C Straight Run Gas Light Refinery Gas
2 6 2 6
Component O P M O P M O P M
Hydrogen 1 2 M 1 2 M 20 2 U
Methane 2 16 M 2 16 M 17 16 M
Ethylene 4 26 M . . . 14 26 M
Ethane 7 30 M 5 30 M 13 30 M
Propene 11 42 M . . . 12 42 M
Propane 6 29 M 4 29 M 10 29 M
Butadiene 15 54 M . . . . . .
Butane-1 . . . . . . 11 56 M
Butene-2 16 56 M . . . . . .
Isobutene . . . . . . . . .
Isobutane 12 43 M 9 43 M 9 43 M
n-Butane 18 58 M 14 58 M 8 58 M
Pentenes 21 70 M . . . 15 70 M
Isopentane 17 57 M 13 57 M 7 57 M
n-Pentane 22 72 M 18 72 M 6 72 M
Benzene . . . 19 78 M 5 78 U
Hexanes 23 84 M . . . 4 84 U
C cyclic paraffins . . . 20 84 M . . .
Hexanes . . . 17 71 M 3 86 U
Toluene . . . 21 92 M . . .
Hydrogen sulfide 9 34 M 7 34 M 1 34 U
Carbon dioxide 13 44 M 10 44 M 16 44 U
Carbon monoxide . . . . . . 18 12 U
Nitrogen 5 28 M . . . 19 28 U
Air 8 32 M 6 32 M 2 32 U
Water 3 18 M 3 18 M . . .
Cyclobutane . . . 12 56 M . . .
Cyclopentene 20 67 M . . . . . .
Pentadienes 20 67 M . . . . . .
Cyclopentane . . . 16 70 M . . .
Methylmercaptan 14 48 M 11 48 M . . .
Ethylmercaptan 19 62 M 15 62 M . . .
Residual 41 10 41 M 8 41 M . . .
Residual 14 24 14 M 22 14 M . . .
A
Method D1137.
B
Method D1302.
C
The mass spectrometer analysis for isomeric butenes is far less accurate than for the other hydrocarbon components. The inaccuracies involved in the isomeric butene
analysisbymassspectrometerrangefrom1.0to4.0mole %,dependingupontheconcentration,ranges,andextentofdriftsininstrumentcalibrations.Theseinaccuracies
will range still higher when pentenes are present in larger than 0.5 % concentrations. See Analytical Chemistry, Vol 22, 1950, p. 991; Ibid, Vol 21, 1949, p. 547; and Ibid,
Vol 21, 1949, p. 572.
D
In Method 4, butylenes and pentenes spectra are composites based on typical GLC analyses. Hexene and hexane spectra are from appropriately corrected spectra of
representative fractions.
E
Residuals GroupsA: m/e 72, 58, 57, 44, 43; Group B: m/e 56, 42, 30, 29, 14.All GroupAresidual shall be 0.2 division or less with the residual of the largest peak also
being less than 0.3 % of its total peak height. All Group B residuals shall be less than 1 % of the peak height or 0.2 division, whichever is greater.
F
Butenes are grouped if they are less than 5 %.
G
If pentenes exceed 1 %, they are determined by other means and the spectrum removed from the poly spectrum.
H
Removed from sample by distillation.
I
Chemically removed.
3.1.6 mass number or m/e value of an ion, n—the quotient 3.1.10 straight-run gases, n—hydrocarbon gases that do not
of the mass of that ion (given in atomic mass units) and its
contain unsaturates.
positive charge (number of electrons lost during ionization).
4. Summary of Test Method
3.1.7 parent peak of a compound, n—the peak at which the
m/e is equal to the sum of the atomic mass values for that
4.1 The molecular species which make up a gaseous mix-
compound. This peak is sometimes used as 100 % in comput-
ture are dissociated and ionized by electron bombardment.The
ing the cracking pattern coefficients.
positive ions of the different masses thus formed are acceler-
3.1.8 partial pressure, n—the pressure of any component in
ated in an electrostatic field and separated in a magnetic field.
the inlet system before opening the expansion bottle to leak.
The abundance of each mass present is recorded. The mixture
3.1.9 sensitivity, n—the height of any peak in the spectrum
spectrum obtained is resolved into individual constituents by
of the pure compound divided by the pressure prevailing in the
means of simultaneous equations derived from the mass
inlet system of the mass spectrometer immediately before
spectra of the pure compounds.
opening the expansion bottle to leak.
D2650 − 10 (2021)
5. Significance and Use with conventional temperature control and for laboratories that
vary the temperature of the ionization chamber to obtain
5.1 A knowledge of the composition of refinery gases is
constant patterns:
useful in diagnosing the source of plant upsets, in determining
Run Number Compound
the suitability of certain gas streams for use as fuel, or as
1 n-butane
feedstocks for polymerization and alkylation, and for monitor-
2 n-butane
ing the quality of commercial gases. 3 hydrogen
4 n-butane
5 hydrogen
6. Interferences
10.1.2 If the 43/58 and 43/29 ratios of the first two runs do
6.1 In setting up an analysis, it is possible that a constituen
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.