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ASTM Selected Technical Papers
Hydrocarbon Analysis
By
H. M. Smith
H. M. Smith
1
U. S. Bureau of Mines
,
Bartlesville, Okla. Chairman
, ASTM Committe D-2 on Petroleum Products and Lubricants
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ISBN-10:
0-8031-6620-6
ISBN:
978-0-8031-6620-2
No. of Pages:
426
Publisher:
ASTM International
Publication date:
1965

The current status and prospective developments in the mass spectrometry of hydrocarbons is discussed in terms of (1) instrumentation and (2) analysis of hydrocarbons. The most widely used mass spectrometer is the general analytical spectrometer, which has an upper mass limit of about 600, and can be equipped to analyze gas Chromatographic fractions. High resolution, double focusing instruments which have an upper mass limit of about 2000, are being used in a rapidly expanding number of laboratories. Correlative behavior and other aspects of mass spectra are reviewed. Examples are cited to illustrate how these data are used for identification. Mass spectra were instrumental in elucidating the structure of numerous of C20–C35 isoparaffins, cycloparaffins, and alkylbenzenes. Two applications of hydrocarbon type analysis are illustrated: Compositional information for (1) an α-olefin mixture and (2) concentrates of aromatic hydrocarbons. Continued extension of the mass spectrometer appears to depend upon improved instrumentation, more efficient separation techniques, and expanded mass spectral data.

1.
Hodgson
F. N.
,
Desjardins
M.
, and
Baun
W. L.
, “
A Study of Polynuclear Aromatic Hydrocarbons Using the Vacuum Spark Mass Spectrograph
,”
Journal Physical Chemistry
 0022-3654. Vol.
67
,
1963
, pp. 1250–1253.
2.
Gohlke
R. S.
, “
Time-of-Flight Mass Spectrometry and Gas-Liquid Partition Chromatography
,”
Analytical Chemistry
 0003-2700. Vol.
31
,
1959
, pp. 535–541.
3.
McFadden
W. H.
,
Teranishi
R.
,
Black
D. R.
, and
Day
J. C.
, “
Use of Capillary Gas Chromatography with a TOF Mass Spectrometer
,” Mass Spectrometry Conference,
ASTM Committee E-14
,
New Orleans, La.
, June, 1962.
4.
Dorsey
J. A.
,
Hunt
R. H.
, and
O'Neal
M. J.
, “
Rapid-Scanning Mass Spectrometry, Continuous Analysis of Fractions from Capillary Gas Chromatography
,”
Analytical Chemistry
 0003-2700. Vol.
35
,
1963
, pp. 511–515.
5.
Brunnee
C.
,
Jenckel
L.
, and
Kronenberger
K.
, “
Continuous Mass Spectrometric Analysis of Gas Chromatographically Separated Fractions
,” Z.
Analytical Chemistry
 0003-2700. Vol.
189
,
1962
, pp. 50–74.
6.
Paul
and
Steinswedel
,
Z. Naturforschg
 0372-9516., Vol.
8a
,
1953
, p. 448.
7.
Brunnee
C.
,
Delgman
L.
, and
Kronenberger
K.
, “
The Atlas Quadrupole Mass Spectrometer
,” Eleventh Annual Conference on Mass Spectrometry and Allied Topics,
San Francisco, Cal.
, May, 1963.
8.
Clerc
R. J.
and
O'Neal
,
M. J.
 Jr.
, “
The Mass Spectrometric Analysis of Asphalt
,” A Preliminary Investigation,
Analytical Chemistry
 0003-2700. Vol.
33
,
1961
.
9.
Field
F. H.
and
Hastings
S. H.
, “
Determination of Unsaturated Hydrocarbons by Low Voltage Mass Spectrometry
,”
Analytical Chemistry
 0003-2700. Vol.
28
,
1956
, pp. 1248–1255.
10.
Wanless
G. G.
and
Glock
,
G. A.
 Jr.
, “
Simplified Mass Spectra
,” Twelfth Annual Conference on Mass Spectrometry and Allied Topics,
Montreal, Canada
, June, 1964.
11.
Steiner
B.
,
Giese
C. F.
, and
Inghram
M. G.
, “
Photoionization of Alkanes. Dissociation of Excited Molecular Ions
,”
Journal Chemical Physics
 0021-9606. Vol.
34
,
1961
, pp. 189–220.
12.
Gomer
R.
and
Inghram
M. G.
, “
Mass Spectrometric Analysis of Ions from the Field Microscope
,”
Journal Chemical Physics
 0021-9606, Vol.
22
,
1954
, pp. 1279–1280.
13.
Gomer
R.
and
Inghram
M. G.
, “
Application of Field Ionization to Mass Spectrometry
,”
Journal Am. Chemical Soc.
 0002-7863, Vol.
77
,
1955
, p. 500.
14.
Beckey
H. D.
and
Wagner
G.
, “
Analytische Anwendungsmőglichkieten des Feldionen-Massenspektrometers
,”
Zeitschrift für Analytical Chemistry
. Vol.
197
,
1963
, pp. 58–80.
15.
von Ardenne
Manfred
, “
Der Dresdner Molekűlspektrograph, ein Neuartiger Präzisions-Massenspektrograph fűr Negative Hochmolekulare Ionen
,”
Kernenergie
 0023-0642. Vol.
1
,
1958
, pp. 1029–1044.
16.
von Zahn
U.
,
Gebauer
S.
, and
Paul
W.
, “
A Quadrupole Spectrometer for Precision Mass Determinations
,” Mass Spectrometry Conference, ASTM Comnittee E-14,
New Orleans, La.
, June, 1962.
17.
Behrendt
Stefan
, “
Infrared Microspectrometer Using Molecular Beams to Monitor Capillary Gas Chromatographic Effluents
,”
Nature
 0028-0836. Vol.
201
,
1964
, p. 70.
18.
Brubaker
W. M.
,
Bell
N. W.
, and
Wiens
F. B.
, “
Quadrupole Mass Spectrometer for Atmospheric Studies in the 50- to 90-Kilometer Range
,” Twelfth Annual Conference on Mass Spectrometry and Allied Topics,
Montreal, Canada
, June, 1964.
19.
Beynon
J. H.
,
Saunders
R. A.
,
Topham
A.
, and
Williams
A. E.
, “
The Study of the Fragmentation of Long-Chain Paraffins under Electron Bombardment Using Isotopically Labeled Compounds
,” Journal
Physical Chemistry
, Vol.
35
,
1961
, pp. 114–118.
20.
O'Neal
,
M. J.
 Jr.
, and
Wier
T. P.
, “
Mass Spectrometry of Heavy Hydrocarbons
,”
Analytical Chemistry
 0003-2700. Vol.
23
,
1951
, pp. 830–843.
21.
Melpolder
F. W.
and
Brown
R. A.
,
Treatise on Analytical Chemistry
, Part I, Vol.
4
,
Interscience Publishers, Inc.
,
New York, N. J.
,
1963
, p. 2015.
22.
Levy
E. J.
,
Doyle
R. R.
,
Brown
R. A.
, and
Melpolder
F. W.
, “
Identification of Components in Paraffin Wax by High Temperature Gas Chromatography and Mass Spectrometry
,”
Analytical Chemistry
 0003-2700. Vol.
33
,
1961
, pp. 698–704.
23.
Bendoraitis
J. G.
,
Brown
B. L.
, and
Hepner
L. S.
, “
Isolation and Identification of Isoprenoids in Petroleum
,” Sixth World Petroleum Congress, Section V, Paper 15, June, 1963.
24.
Brown
R. A.
,
Skahan
D. J.
,
Cirillo
V. A.
, and
Melpolder
F. W.
, “
High Mass Spectrometry, Propylene Polymer, Alkylated Benzene, and Wax Analysis
,”
Analytical Chemistry
 0003-2700, Vol.
31
,
1959
, pp. 1531–1538.
25.
Levy
E. J.
,
Golbraith
F. J.
, and
Melpolder
F. W.
, “
Interpretive Techniques for the Determination of Paraffin Wax Composition by Mass Spectrometry and Gas Chromatography
,”
Advances in Mass Spectrometry
. Vol.
2
,
Pergamon Press, Ltd.
,
N.Y.
,
1963
, pp. 395–407.
26.
Dean
R. A.
and
Whitehead
E. V.
, “
The Occurrence of Phytane in Petroleum
,”
Tetrahedron Letters
 0040-4039. No.
21
,
1961
, pp. 768–770.
27.
Mair
B. J.
,
Krouskap
N. C.
, and
Mayer
T. J.
, “
Composition of the Branched Paraffin-Cycloparaffin Portion of the Light Gas Oil Fraction
,”
Division of Petroleum Chemistry
,
ACS Preprints
.
1962
, pp. 127–140.
28.
Cummins
J. J.
and
Robinson
W. E.
, “
Normal and Isoprenoid Hydrocarbons Isolated from Oil-Shale Bitumen
,”
Division of Petroleum Chemistry
,
ACS Preprints
.
1963
, pp. 97–103.
29.
Sharkey
,
A. G.
 Jr.
,
Wood
G.
,
Shultz
J. L.
,
Wender
I.
, and
Friedel
R. A.
, “
Analysis of Liquid Products from Coal Hydrogenation by Mass Spectrometry
,”
Fuel
 0016-2361, Vol.
38
,
1959
, pp. 315–328.
30.
Ferguson
W. C.
and
Howard
H. E.
, “
Direct Determination of Isoparaffins and n-Paraffins in Olefin-Free Gasoline by Mass Spectrometer
,”
Analytical Chemistry
 0003-2700, Vol.
30
,
1958
, pp. 314–317.
31.
Simmons
M. C.
and
Kelly
T. R.
, “
Quantitative Analysis of Complex Samples by Gas-Liquid Chromatography and Mass Spectrometry
,”
Second Gas Chromatography International Symposium
,
Academic Press
,
N. Y.
,
1961
, pp. 225–236.
32.
Meyerson
S.
,
Nevitt
T. D.
, and
Rylander
P. N.
, “
Ionization-Dissociation of Some Cycloalkanes Under Electron Impact
,”
Advances in Mass Spectrometry
, Vol.
2
,
Pergamon Press, Ltd.
,
N.Y.
,
1963
, pp. 313–336.
33.
Natalis
P.
, “
Study of Some cis and trans 1, 2-Dialkylcyclo- pentanes by Mass Spectrometry
,”
Societes Chimiques Belges Bulletin
, Vol.
66
,
1957
, pp. 5–25.
34.
Friedland
S. S.
,
Love
,
G. H.
 Jr.
,
Longman
R. T.
,
Train
K. E.
, and
O'Neal
,
M. J.
 Jr.
, “
Mass Spectra of Steroids
,”
Analytical Chemistry
 0003-2700. Vol.
31
,
1959
, pp. 169–174.
35.
Reed
R. I.
, “
Electron Impact and Molecular Dissociation. Part I. Some Steroids and Triterpenoids
,”
Chemical Society Journal
,
1958
, pp. 3432–36.
36.
Lindeman
L. P.
and
Letourneau
R. L.
, “
New Information on the Composition of Petroleum
,” Sixth World Petroleum Congress, Section V, Paper 14, June, 1963.
37.
Brown
R. A.
and
Gilliams
E.
, “
Mass Spectra of Olefins
,” Meeting of ASTM Committee E-14 on Mass Spectrometry,
New Orleans, La.
, May, 1954.
38.
Kendall
R. F.
,
Cotton
F. O.
,
Foster
N. G.
, and
Eccleston
B. H.
, “
The Mass Spectra and Analytical Correlations of C5 through C10 CODA Compounds
,” Mass Spectrometry Conference, ASTM Committee E-14,
New Orleans, La.
, June, 1962.
39.
Lindeman
L. P.
, “
Combination of Mass Spectrometer, Gas Chromatograph and Catalytic Hydrogenation for the Analysis of Olefins
,”
Division of Petroleum Chemistry
, ACS Preprints, Vol.
7
,
1962
, pp. 15–22.
40.
Melpolder
F. W.
,
Brown
R. A.
,
Young
W. S.
, and
Headington
C. E.
, “
Composition of Naphtha from Fluid Catalytic Cracking
,”
Industrial Engineering Chemistry
 0019-7866, Vol.
44
,
1952
, pp. 1142–1146.
41.
Grubb
H. M.
and
Meyerson
S.
, “
Mass Spectra of Alkylbenzenes
,”
Mass Spectrometry of Organic Ions
,
Academic Press
,
New York, N.Y.
,
1963
, pp. 453–527.
42.
Meyerson
S.
,
Applied Spectroscopy
 0003-7028, Vol.
9
,
1955
, pp. 120–130.
43.
Hood
A.
,
Clerc
R. J.
, and
O'Neal
,
M. J.
 Jr.
, “
Molecular Structure of Heavy Petroleum Compounds
,”
Journal Petroleum Inst.
, Vol.
45
,
1959
, pp. 168–173.
44.
Ford
H. T.
, “
Determination of Phenyl Position Distribution in N-Alkylbenzenes by Mass Spectrometry
,” Twelfth Annual Conference on Mass Spectrometry and Allied Topics,
Montreal, Canada
, June, 1964.
45.
Mair
B. J.
and
Martinez-Pico'
J. L.
, “
Composition of the Trinuclear Aromatic Portion of the Heavy Gas Oil and Light Lubricating Distillate
,”
Division of Petroleum Chemistry
,
ACS Preprints
,
1962
, pp. C114–C137.
46.
Beynon
J. H.
,
Mass Spectrometry and Its Application to Organic Chemistry
.
Elsevier Publishing Co.
,
Amsterdam
,
1960
, p. 261, p. 332.
47.
Barber
M.
and
Elliott
R. M.
, “
Comparison of Metastable Spectra from Single and Double Focusing Mass Spectrometers
,” Twelfth Annual Conference on Mass Spectrometry and Allied Topics,
Montreal, Canada
, June, 1964.
48.
Food Additive Petition No. 861
.
49.
Lumpkin
H. E.
, “
Analysis of a Trinuclear Aromatic Petroleum Fraction by High Resolution Mass Spectrometry
,” Twelfth Annual Conference on Mass Spectrometry and Allied Topics,
Montreal, Canada
, June, 1964.
50.
Desideri
D.
and
Biemann
K.
, “
Computer Techniques for the Fast and Facile Conversion of Line Positions to Elemental Compositions of Ions Recorded on Photographic Plates
,” Twelfth Annual Conference on Mass Spectrometry and Allied Topics,
Montreal, Canada
, June, 1964.
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