Petroleum
J. M. FRASER
Union Oil Company of California, Brea, Calif. 92521
This is the thirteenth review of analytical chemistry in the
petroleum industry (1A-12A) sponsored by the Division of
Petroleum Chemistry of the American Chemical Society. Its
objective is to cover the most important and relevant publi-
cations appearing essentially in 1974 and 1975. Specifically,
it covers the papers abstracted in Chemical Abstracts, in the
American Petroleum Institute Refining Literature Abstracts,
and in Analytical Abstracts (London) for the period of July
1974 through June 1976. Thus this review begins where the
previous one ended and the general format of previous issues
is being continued.
References conform to the Chemical Abstracts “Guide for
Abbreviating Periodical Titles.” In addition, when a reference
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
publication might not be readily available, the abstract journal
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has been appended to that for the original source. The ab-
Crude Oils
F. C. Trusell
Marathon Oil Company, Littleton, Colo.
Sampling. Sampling is often the weakest link in crude oil
analysis. The Reservoir Fluids Group of the Chambre Syn-
dicate de la Recherche et de la Production du Petrole et du
Gaz Naturel has recommended procedures for obtaining either
surface or bottom-hole samples (81B).
Hydrocarbons. Urazgaliev et al. determined the distri-
bution of n-paraffins in 20° and 50° cuts of Mangyshlak pe-
troleum boiling below 510°. They tabulated the physical
property data from these fractions and proposed an expla-
nation of the observed pour properties of the oil based on the
crystallizing properties of its constituents (95B).
Abidova et al. distilled Uzbekistan oils into five fractions
boiling below 200° and determined the individual aromatic
hydrocarbons in them by GC. Oils from deeper strata con-
tained substantially more aromatics than shallower oils (2B).
Kasamatsu analyzed the diaromatic fractions of three low-
sulfur Southeast Asia crudes and six high-sulfur Middle East
crudes by GC and by IR spectroscopy, and found 2-monoalkyl
naphthalenes, and naphthalenes with one methyl group on
each ring were more abundant in the low-sulfur oils (52B).
Zhurba et al. employed GC and MS to determine the hy-
drocarbon-type distributions in the 140-180° and 180-240°
fractions of several eastern Ukrainian crude oils, and related
their findings to the ages of the containing formations (103B).
Kuklinskii and Pushkina have developed a formula for de-
termining adamantane in crude oils based on the IR absorb-
tivity of a key CH group vibration, and used it in the analysis
of 34 USSR crudes. They found the importance of adaman-
tane structures falls sharply in fractions boiling above 300 °C
(60B). Garmasheva analyzed the oils from the bitumen frac-
tions of Pripyat Basin crudes. He identified tetralins, indanes,
benzonaphthenes, dibenzonaphthenes, and tricyclic naph-
thenes, and determined the number of carbon atoms in
paraffinic chains to ranges from 6 to 20 (29B).
Guseva and Chernova separated asphaltenes from several
samples of recent sediments by extraction with CHCI3 and
with EtOH-CgHe- The asphaltenes were studied by x-ray
diffraction, and though they were in the initial stage of di-
agenesis, they already had aromatic structures similar to those
of asphaltenes extracted from crude oils. The asphaltenes
ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
breviations C.A., A.P.I.A., and A.A. are used to identify the
abstract journals cited above. These abbreviations are fol-
lowed by the volume number, the abstract number, and the
year.
The abstract searching was done by J. F. Hickerson, Exxon
Co., U.S.A.; R. W. King, Sun Oil Company; C. A. Simpson,
Mobil Research and Development Corp.; and J. M. Fraser,
Union Oil Co. of California. The collected abstracts were then
screened and organized by subjects. Each collection of ab-
stracts was then additionally reviewed, screened, and orga-
nized by fourteen authors of the eleven subjects or subsections
which follow. The generous assistance of the abstractors and
of the authors, many of whom have contributed to previous
reviews, is very much appreciated and the production of this
review is due to their combined efforts.
extracted with EtOH-CeHe were more highly branched than
those extracted with CHCI3 (37B).
Heterocompounds. Drobot and Presnova determined the
amount, composition, and distribution of the main types of
sulfur compounds from selected crudes of the Sikerian Plat-
form (24B). Numanov et al. employed catalytic micro-hy-
drodesulfurization, followed by MS analysis to determine the
structures of sulfides in two crude oils from south central Asia.
Mono- and bicyclic sulfides accounted for 78-84% of the total
sulfides in the samples examined (73B). Numanov and co-
workers characterized other high sulfur (5.0-6.2% S) crudes
from the same general area and found mercaptans and sulfides
the predominant sulfur compounds in those fractions boiling
below 200°, but disulfides predominated in those fractions
boiling over 200° (74B). Khaitbaev et al. analyzed the sulfur
compounds from petroleums of this area and confirmed the
above findings, but added more detailed data (54B).
Akhmedova attempted to establish a relationship between
S, N, and silica gel resin content, and also between their con-
tent and depth of occurrence and specific gravity of some
Azerbaidzhán crudes. However, the correlations were not close
as might be hoped (3B).
Orr studied changes in sulfur content and in sulfur isotope
ratios with thermal maturation, using the Big Horn Basin
(Wyo.) Paleozoic oils. In addition to the trends usually ob-
served, he noted that during thermal maturation in high
temperature (>80-120°) reservoirs with sulfate present,
nonmicrobial sulfate reduction may take place with negligible
isotopic fractionation (75B). Ho et al. determined the classes
of sulfur compounds in 78 crude oils from many of the world’s
major fields. Oils abundant in unstable compounds, such as
nonthiophenic sulfides and benzothiophenes, were classed as
immature. Those containing more of the stable dibenzothio-
phenes were classed as mature, while a third group of inter-
mediate distributions was termed altered (44B).
Gusinskaya et al. separated the nitrogen bases from a series
of Sakhalin crudes by ion-exchange and adsorption chroma-
tography, and used IR and NMR spectroscopy to determine
their general structure (38B). Brodskii and co-workers con-
tinued this study, showing that pyridine derivatives consti-
tuted 18-30% of the basic extract, quinoline derivatives 50-
60%, and acridine-benzoquinolines 12-20%. Most of the
heteroaromatic cores were present as cata- or peri-condensed
systems with one to three naphthenic rings. The majority of
substituted species had one relatively long alkyl chain and
several methyl or ethyl groups ( ). Sevast’yanova et al.
determined the ratio of basic-to-total nitrogen in 29 Ukrainian
crude oils, and the distribution of primary, secondary, and
tertiary amines in each sample (88B).
. 231 R
 Fingerprinting and Spill Source Identification. The
number of papers dealing with this topic has increased sub-
stantially since the last review, and a wide variety of analytical
techniques has been brought to bear on the problem. Bentz
recently reviewed the techniques used by U.S. agencies for oil
spill identification (9B). Brown, Lynch, and co-workers have
thoroughly explored the use of IR spectroscopy, on both fresh
and weathered crudes, for matching source to spill (12B-14B,
68 B). Kawahara and Yang applied discriminant analysis to
IR data to group oils together (53B).
Lukens characterized spilled oils by neutron activation
analysis, developing a pattern for the distribution of trace
elements. He achieved unambiguous identification in the
majority of cases (67B). Anbar et al. devised a technique for
producing arrays of hundreds of microcones on a porous
substrate for obtaining field ionization mass spectra of crude
oils. The spectra, consisting primarily of unfragmented mo-
lecular ions, differentiate between samples by showing the
relative abundance of the sum of the isomers at each mass
(SB).
Zafiriou and co-workers devised a simple GC method for
matching spills to suspected sources, and tested it on samples
from Portland and New York Harbor. They claim the validity
of the method is only slightly affected by weathering. The rate
of successful correlations was 100% if there were eight or fewer
candidate oils, but dropped to 50% for 14 oils, and to 27% for
22 oils (102B). Garza and Muth used GC separation followed
by dual response detection, FID for hydrocarbons and FPD
for sulfur compounds, as the basis for matching spills to
sources (30B). Ilardi identified two spilled oils by GC of se-
lected distillate fractions coupled with the quantitative de-
termination of V and Ni in the distillation residue (46B).
Jackson and co-workers developed a GC method for finger-
printing crude oils and condensates using only the 232-316°
fraction, and demonstrated its utility on a number of Aus-
tralian crudes and condensates (48B).
Wilson et al. analyzed six crude oils, using a variety of an-
alytical techniques, to evaluate the methods as means of
identifying oil spill sources. They found GC, AA, and the de-
termination of S and of N to be the most useful (99B). Lie-
berman artificially weathered crude oils and distillate frac-
tions, and then analyzed the weathered and unweathered
samples by GC, low- and high-voltage MS, emission and x-ray
spectroscopy, and the Kjeldahl technique. Several of the de-
rived indices were sufficiently unaffected by the simulated
weathering to allow discrimination between like and unlike
pairs of oils (66B).
Green and O’Haver compared electronic differentiation of
luminescence with respect to time and mechanical wavelength
modulation and found the first method simpler in practice.
It also gave better resolution of minor spectral features and
permitted better fingerprinting of crude oils (32B). John and
Soutar elucidated the influences of solvent, wavelength in-
crement, concentration, temperature, and frequency bandpass
on the spectra of oils obtained by synchronous excitation
spectrofluorimetry, and concluded that this technique, when
combined with conventional fluorimetry, showed promise as
a tool for identifying oil spills (50B).
Pattern recognition techniques have been applied to the
problems of recognizing the sources of oil spills. Clark and Jurs
used them with 87 to 100% success in classifying crude oils on
the basis of fingerprint gas chromatograms (16B), while
Duewer et al. applied them to elemental compositions as de-
termined by neutron activation analysis (25B).
Geochemical Studies. Gubnitskii and co-workers analyzed
crude oils from 93 wells, representing 11 fields of the Baltic
region, measuring physical properties, sulfur content, hy-
drocarbon type distribution, and gasoline yield. High as-
phaltene and resin contents of some oils were attributed to
secondary loss of light hydrocarbons. The light fractions were
low in aromatics, believed to be the result of water washing
in the lower formations (33B). They also determined the
concentrations of a few individual hydrocarbons in several
samples and noted that, as the reservoir temperature in-
creased, the ratios of n-hexane to its isomers and of cyclo-
hexane to methylcyclopentane also increased (34B).
The most thorough investigation of using the ratios of in-
dividual hydrocarbons for showing similarities between crude
oils was carried out by Erdman and Morris. They coupled such
measurements with determinations of the carbon isotope
232 R · ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
ratios of the topped crude and of its saturate, aromatic, and
asphaltic fractions, the n-alkane distribution, and the odd-
even preference to show wehther or not two samples have been
derived from a common source (26B).
Isaev and Danilov analyzed 48 petroleums from 26 deposits
of the Middle Volga region and found the following trends
with decreasing age of the reservoir rocks: an increase in the
contents of n -paraffins, isoprenoids, Cg and Cs aromatics, and
substituted cyclanes at the expense of mono- and unsubsti-
tuted rings. The content of mono-substituted alkanes de-
creases (47B). Davydov et al. examined 64 samples from this
region and were able to distinguish compositional changes
during thermal maturation from those brought about by lat-
eral migration and low temperature processes. The former was
significant in this region only at depths below 2000 m (20B).
Danilov and Isaev determined the distributions of n-paraffins
in the ligroine-kerosene fractions of oils from 28 fields, and
noted the trends observed with increasing depth (19B). Bo-
gomolov and Chikhacheva removed the n-paraffins from 26
petroleums of different compositions and origins by urea
adduction. They used both the absolute amounts of n-par-
affins and their distributions in different fractions for genetic
classification of the samples (10B).
Vyshemirskii et al. measured the carbon isotope ratios of
101 petroleums and 105 bitumenoids from western Siberia and
classified their findings according to geologic age and whether
the sample had been formed where found, or whether it had
migrated into its present location, and tabulated their ob-
servations (97B). Alekseev and co-workers studied the effects
of adsorption by rocks and of diffusion processes on the carbon
isotope ratios and hydrocarbon compositions of 21 Mesozoic
petroleums, and attributed observed differences to changes
brought about by migration of some of the oils through rocks
of low permeability ( 4B). Yakovets and Sibokon found they
could distinguish oils of sapropelic origin from those of humic
origin. Oil from sapropelic sources contained more Cn-Cia
n-alkanes and high molecular weight isoprenoids, while oils
from humic sources contained more isoalkanes, and more
pristane then phytane (100B).
Smirnova analyzed the <200° fractions from nine petro-
leums by GC and IR, and explained the changes observed in
the amount of alkanes, naphthenes, cyclohexane derivatives,
and the isoalkanes with increasing depth of burial (90B).
Ashirov and co-workers determined the distribution of hy-
drocarbon group-types in the 150-300° fractions of various
petroleums from the Kuibyshev region and showed that
though these oils had been derived from a common source,
their compositions differed because of their different histories
(7B). Abidova et al. analyzed the gasoline fractions of petro-
leums from western Tashla, showing their results in plots of
the number of substituents on benzene rings as a function of
the weight percent in the overall fraction. Changes in the total
aromatic content were ascribed to adsorption of these com-
pounds during migration (IB). Kam’yanov and co-workers
determined the concentrations of the Cg-Cg aromatics in the
<200° fractions of petroleums and condensates from the
Turkmen SSR, and were able to correlate the relative distri-
butions of these compounds with the petroleum type (paraf-
finic vs. naphthenic) (51B). Ermolkin et al. determined the
concentrations of individual hydrocarbons in various petro-
leums and used the results to predict the compositions of
condensates and petroleums in undrilled structures (27B).
Williams characterized 187 oil samples from 107 fields in
the Williston Basin by GC, IR, carbon isotope ratio, and op-
tical rotation, and showed the oils could be divided into three
major genetic types. He emphasized the importance of
employing a variety of techniques for this type of study
(98B).
Kuklinskii et al. separated and measured the n- and iso-
paraffins, naphthenes, and aromatics in 50° fractions in the
200-450° cuts of various petroleums. They found that the
amounts of paraffins and monocyclic naphthenes increased
with depth, as did the ratios of normal-to-isoparaffins and of
naphthenes-to-aromatics (61B). Kontorovich has reviewed
the uses of various modern analytical techniques for corre-
lating crude oils as to their genetic type and for recognizing
changes due to differing histories (58B).
Isoprenoid hydrocarbons are of considerable interest to
petroleum geochemists, as the distribution of these com-
pounds can be used to establish genetic relationships between
James M. Fraser is manager of the analyt-
ical research group of the Union Oil Com-
pany of California Research Department,
Brea, Calif. He received his B.S. degree in
chemistry from the University of Wisconsin
in 1953, and his Ph.D. degree from there in
physical chemistry in 1957. At that time he
joined the pure Oil Company Research De-
partment in Crystal Lake, III. He was director
of the analytical division of the Pure Oil
Company Research Department at the time
of the merger of The Pure Oil Company into
Union Oil Company of California in 1965. He
is a member of the ACS, SAS, and of sev-
eral ASTM committees.
F. C. Trusell J. D. Beardsley
Marathon Oil Company The Standard Oil Co. (Ohio)
Littleton, Colo. Cleveland, Ohio

N. H. Pick
Texaco, Inc. D. R. Cushman
J. W. Schick
Beacon, N. Y. Mobil Research and
Mobil Research and
Development Corp.
Paulsboro, N.J. Development Corp. J. R. Couper
Paulsboro, N.J. Department of Chemical
Engineering
University of Arkansas
Fayetteville, Ark.

J. Freel
Gulf Research &
Development Co. N. W. Lambert
Pittsburgh, Fa. Union Oil Co. of Calif. . P. T. Bradley R. E.Terrell
Research Department The Standard Oil Co. (Ohio) Gulf Research and Development
Brea, Calif. Cleveland, Ohio Co.
Pittsburgh, Pa.

J. W. Loveland C. N. White
Suntech, Inc. Suntech, Inc.
Newtown Square, Pa. Newtown Square, Pa.
W. E. Haines D. R. Latham
Laramie Energy Research Laramie Energy Research
Center Center
Energy Research and Energy Research and
Development Administration Development Administration
Laramie, Wyo. Laramie, Wyo.

ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977 · 233 R

 oils, and because their presence is taken as strong evidence for
the biogenic origin of petroleum. Gurko and Stepina deter-
mined the distributions of these compounds in petroleums
from the Baltic Sea region (36B), while Solodkov et al. carried
out their studies on oils and condensates of the Turkmen SSR
(91B, 92B). The finding of both groups showed that the
amount of isoprenoid hydrocarbons generally increased with
increasing temperature (depth). Kharchuk cautioned that
isoprenoid hydrocarbons, especially phytane and its higher
homologues, may not be reliable indicators of the biogenic
origin of petroleum because of the inability of GC columns to
adequately separate these compounds from isomers of similar
boiling point (55B). Haug and Curry examined a seep residue
from Costa Rica and, in addition to the regular Cíe and C18-20
isoprenoids, positively identified the regular C21 and C23-25
homologues, and tentatively identified the regular C26, C28,
and C30 compounds (40B).
The steranes and triterpanes are also thought to be bio-
logical markers. As they are higher boiling, and less easily
concentrated, than the isoprenoids, they have not been as
intensely studied. Pym et al. described a separation and
concentration scheme for triterpanes, and used it to finger-
print eight crude oils (79B). Ushakova and co-workers found
six definite triterpane structures in a concentrate of Baku oil
obtained by adsorption chromatography on activated charcoal
with n-hexane and cyclohexane as eluents. GC/MS was em-
ployed for the detection (96B). Pustil’nikova et al. separated
dearomatized 450-500 °C cuts into 10 fractions by thermal
diffusion and analyzed each by capillary GC. Identification
of steranes and triterpanes was made by comparisons with
standards prepared by hydrogenation of the appropriate ke-
tone or alcohol (78B). Mulheirn and Ryback employed optical
rotatory dispersion and high resolution NMR to determine
the nature and sterochemistry of the steranes in oils from the
Green River Shale, and on that basis suggest algae as the
source organisms (72J3).
The porphyrins have also attracted the attention of petro-
leum geochemists because of their relationship to living
matter. Shulova and Graizer have tabulated the ratios of V
and Ni porphyrins and their distribution in crude oils from
different USSR regions, and have discussed their relation to
genetic crude types (89B). Zil’bermints et al. measured the
V porphyrin contents of crude oils, and found that they in-
creased with depth, and were related to the contents of S and
of asphaltenes (104B). Serebrennikova and co-workers con-
centrated the V porphyrins from a large number of western
Siberian petroleums and by MS analysis determined them to
be homologues of alkyl, cycloalkyl, and bicycloalkyl porphy-
rins with C6-C26 alkyl substituents (87B). Sedymova et al.
concentrated Ni and V porphyrins from some bitumenoids
of western Siberia by chloroform extraction. The distribution
of these compounds was found to be related to the rock type,
tar and asphaltene content, and the concentration of carbonyl
groups (86B). Azizov et al. carried out a similar study of oils
from the Tadzhik Depression, but correlated porphyrin con-
tent with the amounts of S and N present (8S).
Didyk and co-workers determined the types and distribu-
tion of porphyrins in a Venezuelan crude, utilizing TLC to
separate fractions containing a high concentration of single
molecular weight species, and examining these to determine
the extent of alkylation (21B). Moghadam and Raisszadeh
concentrated the porphyrins from crude oils and found their
concentration increased rapidly with depth, and was greater
in asphalt base crudes than in paraffinic base crudes. They
also studied the thermal stability of the vanadyl porphyrins
(70B).
Mozzhelina and Titov analyzed crudes from the Tomoskoi
Oblast and found peptides in the polar extracts, particularly
in the fractions containing metal porphyrin complexes, ana
postulated a relation between the two (7IB).
Shale Oils. Pulsed NMR (69B), thermal analysis (80B),
laser pyrolysis-GC (39B), and conventional pyrolysis (64B)
have all been proposed as replacements of the Fisher assay for
estimating the potential oil yield from oil shales.
Scrima and co-workers obtained thermograms and chro-
matograms from Green River oil shale indicating that the
bitumen separated by controlled heating is identical to that
obtained by solvent extraction (85B). Cummins et al. analyzed
the benzene-soluble products from oil shade heated to simulate
in situ processing conditions. Normal alkanes were formed at
234 R · ANALYTICAL CHEIDISTRY, VOL. 49, NO. 5, APRIL 1977
150-350°, though at 250° branched and cyclic alkanes were
the main products and contained isoprenoid, sterane, and
triterpane structures. The polar resins had a high concen-
tration of acidic material (18B). Poulson et al. have reported
on the composition of a synthetic crude oil prepared by hy-
drogenation of the IBP-3500, 350-550°, 550-850°, and 850°+
fractions (77B).
Robinson and Cook, emphasizing the distribution of n-
alkanes and isoprenoid compounds, and the aromaticity of the
kerogen, noted numerous compositional differences in the
organic matter from Green River Shale and related these
differences to depth of burial, and to differences in source
material and environmental conditions (82B). Klesment and
co-workers characterized the tars from Estonian oil shales by
TLC and GC and found high concentrations of C13, C15, and
C17 n-alkanes, and C12, C14, and Cíe n-alkenes. They thermally
decomposed the kerogen in the presence of Se and obtained
a product rich in C5 to C17 alkanes which they attributed to
the fatty acids of plankton, the presumed precursors of the
kerogen (57B). Yen proposed a structural model of Green
River kerogen based on x-ray diffraction. He sees it as a 3-
dimensional, multimembered, saturated carbon skeleton, and
is able to account for extractable steroid, terpenoid, and iso-
prenoid subunits (101B).
Metals and Salts. Khomutnikov and Pichuzhkin proposed
determining the salt content of water-in-oil emulsions by
stirring the sample with a nonionic surfactant to invert the
emulsion and titrating the chloride ion to a conductometric
endpoint with AgNOs or Hg(NÜ3)2 (56B).
Gleim and co-workers found that the Mo content of oil
decreased with depth, and postulated this was due to deeper
oils being less accessible to bacteria (31B). Flegontova et al.
determined the concentrations of 11 metals in 53 Mangyshlak
petroleums, and used changes in various ratios to trace mi-
gration paths. Low V/Ni ratios were found in oils of low S
content, while high values of V and Ni were due to high as-
phaltene and tar contents in some wells, and to contact with
formation waters in other wells (28B). Hitchon and co-workers
determined the concentrations of 22 trace elements in 88 crude
oils from Alberta by neutron activation, and selected 11 for
factor analysis. The contents of these elements were found to
be controlled by maturation processes rather than by migra-
tion processes (43B). Chinenova and co-workers combined
EPR with electron spectrographic methods to study the
paramagnetic metals and metalloporphyrins in the bitumi-
noids of rocks of different ages and discussed the observed
differences in terms of differences in geochemical origin
(15B).
Non-Routine Characterizations. Coste separated and
analyzed the oil and water phases of two crude oil emulsions.
He found naphthenic acids, amines, asphaltenes, and metal-
loporphyrin concentrated in the oil phase, and interpreted this
as indicating that they take part in stabilizing the emulsions
(17B). Petrov and Shtof carried out an IR study of the struc-
ture of petroleum emulsion stabilizers, with emphasis on the
asphaltenes and resins (76B).
Kurbskii and co-workers precipitated the asphaltenes from
16 crudes and bitumens and used them as liquid phases for
the GLC separation of a set of standard compounds. They
were able to relate the retention volumes of these compounds
to the degree of metamorphism of the parent petroleums
(62B). Roots and Speight studied the relation between resins
and asphaltenes in petroleums of various ages and found that,
in general, the amounts of the two classes paralleled one an-
other. The asphaltenes had lower H/C ratios and more het-
eroatoms than resins, and tended to be larger with more
complex ring systems (59B). Antipenko and Titov compared
the physical and chemical properties of asphaltenes extracted
by polar solvents with those of the unextracted, nonpolar as-
phaltenes, and found the polar ones to be higher in their C and
N contents, and lower in H, S, O, V, and free radicals (6B).
Using ultrafiltration and ultracentrifugation, Hombach
separated high molecular weight structures (mol wt > 100 000)
from distillation residua which gave IR and ESR spectra
similar to those of the asphaltenes of low- and medium-rank
coals (45B).
Kurokawa and Rondo distilled Rhafji atmospheric residue
into seven fractions, the heaviest with an end point corre-
sponding to 733 °C, and a residuum. Each fraction was char-
acterized as to its n- and isoparaffin, naphthene, and aromatic
contents, and they determined that the ratio of saturates to
aromatics in each fraction differed little from that of the
original residue (63B).
Satter-Zade et al. carried out spectropolarometric studies
on Bibieibat (83B) and Ramany (84B) crude oils, and noted
that optical activity, after passing through a minimum in the
kerosene fractions, increased with increasing boiling point,
and was higher for the saturate fractions than for the aro-
matics.
Jackson et al. compared simulated TBP curves from GC
using a 10-m capillary column with conventional TBP curves,
and found the agreement to be excellent. Differences were
easily explicable (49B). Levy et al. describe the modification
of the injection port of a GC which facilitates the examination
of tars and other viscous and/or high boiling samples (65B).
API Research Project 60 has continued to be a source of new
methods for analyzing the heavy ends (370-535 °C) of crude
oil, and of data concerning the composition of this fraction in
a world-wide series of representative crudes (22B, 23B, 41B,
42B, 93B, 94B).
Routine Characterizations. As in previous review periods,
there has been a great number of reports dealing with the
routine characterization of crude oils by conventional meth-
ods. One in particular stands out for its general interest,
compiling data from 94 representative crudes from around the
world (35B).
Fuels, Gaseous and Liquid
J. D. Beardsley
The Standard Oil Co. (Ohio) Cleveland, Ohio
Natural, Refinery, and Manufactured Gases. Cardwell
(19C) lists the compositions of natural gases of the United
States, Canada, Indonesia, and the United Kingdom for 1972
with emphasis on helium. Routine analysis and related source
data for 278 United States natural gas samples from wells and
pipelines are tabulated for 1973 by Moore (76C). Analyses
were made by mass spectrometer and a special helium ana-
lyzer. He (77C) also tabulates for 1974 the analyses and related
source data for 352 natural gas samples from gas and oil wells
and pipelines in 18 states and five foreign countries.
A procedure and apparatus for the preparation of natural
gas samples for C isotope determination by mass spectrometry
are described by Nesmelova and Sokolov (86C). Stufkens and
Bogaard (122C) analyze natural gas by means of gas chro-
matography, using one, single, temperature-programmed
column and two detectors (TCD and FID) in series. From the
composition, the calorific value can be calculated without any
systematic error. A comparison of calculated and measured
calorific values of natural gases was made for six Algerian and
North Sea natural gas samples by White, Cross, et al. (129C).
The calculated values were at least as precise as those obtained
by calorimetry and the average difference between the two
methods was 2.87 BTU/ft3.
A discussion by Lambert and Juren (63C) covers the com-
positions of typical U.K. natural gases, properties, and im-
purities; and natural gas processing including removal of hy-
drocarbon liquids, water, hydrogen sulfide, carbon dioxide,
and nitrogen and the recovery of ethane and heavier hydro-
carbons. Jones (50C) defines gas quality in terms of acceptable
standards for internal corrosion control; i.e., H2S, CO2,02; and
water vapor contents, temperature, and free liquid content.
Methods of analysis for the corrosive agents are described.
Turowska and Pruszynska (124C) determine down to ap-
proximately 1 ppm of CO2 by gas chromatography. The sep-
arated constituents are passed through a column packed with
firebrick covered with a nickel catalyst. At 350 °C the CO2 is
reduced to methane. The content of CO2 is calculated by
comparison of peak areas for the sample and for standard
mixtures of methane with CO2. The theory and technique of
colorimetric analysis of fuel gases for impurities such as sulfur
compounds, nitrogen oxides, acetylene, phenols, hydrogen
cyanide, and others, in total 20 different determinations, is
reviewed by Vlckova and Kavan (127C). Afanas’ev, Denisova,
ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
Lomovtseva, et al. (1C) have determined microimpurities of
hydrogen sulfide in a natural gas flow by gas chromatogra-
phy.
The chromatographic determination of water contents of
approximately 1 ppm in natural gas has been achieved by
Yusfin, Okhotnikov, Rotin, et al. (134C). Water contents of
40 to 200 ppm in natural gas are determined by Davies (26C)
using a modified Karl Fischer titration apparatus. The
method was tested on standard water mixtures and agreed
well with gravimetric, P2O5, and dew point procedures. The
method is free from interference by light hydrocarbons and
methanol. Gokhberg and Ovchinnikova (39C) make a direct
chromatographic determination of moisture in natural gas
mixtures.
Trace amounts of tetrahydrothiophen odorant in natural
gas are determined by gas chromatography by Demczak,
Gawlik, and Kegel (27C). Gas chromatography is used by
Kavan (55C) to determine the odorants dimethyl sulfide and
tetrahydrothiophene in natural gas. The impurities of these
odorants plus 14 other compounds have been studied. Knight
and Yerma (56C) have developed a simple low cost field test
for mercaptan odorants in natural gas. A metered amount of
gas is bubbled through a disposable reagent tube containing
.ZV-ethylmaleimide and the red-pink color intensity of the
product is compared with a standard color chart calibrated
in parts per million of mercaptan.
A procedure has been developed by Skorik, Zalkin, and
Konyukhov (116C) for a gas chromatographic analysis of a
mixture of flue gases from high sulfur natural gas using a single
apparatus. Koroleva, Moroz, Khazanov, and Baranovskii
(60C) use two gas chromatographs simultaneously to analyze
the combustion products from natural gas.
Properties of liquefied natural gas are calculated by Nanjo,
Harado, Ono, and Saito (83C). Lyle, Burghard, and Lawler
(69C) have developed an instrument to measure the corrosi-
vity of liquefied petroleum gas bv means of the increase in
electrical resistance of thin (500-A) copper film deposited on
a glass slide as tarnish products forms. The results are quan-
titative in contrast to the ASTM D 1838 test which gives only
qualitative results.
The composition of gas from the catalytic cracking of vac-
uum gas oil has been studied, using capillary gas chromatog-
raphy, by Alymova, Lulova, and Kuz’mina (4C). The method
is suitable for all refinery gases. Optyczne (89C) has patented
an apparatus for the automatic monitoring of the presence of
methane in air.
Aviation Fuels. Shelton (112C) tabulates analytical data
for 104 samples of JP-4 and JP-5 military fuels and Jet A, A-l,
and B commercial fuels from 15 companies. Correlation
equations for calculating hydrogen content and heat of com-
bustion on jet fuels have been evaluated by Angello (9C).
Petrovic, Bogojevic, and Vitorovic (94C) contend that de-
termining the temperature at which 90% of the jet fuels are
distilled is a better method for evaluating as compared to
quality control based on determining the temperature at the
end of the distillation.
The resins present in jet fuel from different USSR crudes
were separated by adsorption on alumina and desorbed with
methanol and acetic acid by Englin, Alekseeva, Sashevskii,
et al. (28C). The varying content and composition of these
resins have an important influence on the anti-wear properties
and thermal stability of the fuels. Imhof and Worm (47C) have
patented a device and method for determining the alcohol
content of jet fuel. The alcohol is determined by a color reac-
tion with an 8-hydroxyquinoline ester of vanadic acid
(H3PO4). Gel permeation chromatography has been used by
Hillman, Paul, and Cobbold (45C) to determine dilinoleic acid
and acid phosphate ester in aviation fuels.
Taylor (123C) has investigated the effect of trace impurity
sulfur compounds on the rate of deposit formation in deoxy-
genated jet fuel. The results confirm that the ability of rig-
orous deoxygenation per se to suppress the deposit formation
process depends on the type and level of the trace impurity
sulfur compounds which are present in the fuel. The Coordi-
nating Research Council (24C) reports that the use of the
Alcor Inc. Mark 8A light reflectance instrument for measuring
the deposits on JFTOT tubes shows promise that the Jet Fuel
Thermal Oxidation Test will replace the ASTM-CRC Fuel
Coker as the standard test for determining the oxidative sta-
bility of jet fuel.
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