Anal. Chem.
1981, 53, 88R-142R
(61L) Shimogata, M., Koyama, K., Ueda, K. Nippon Eiselgaku Zasshl(Jpn.
J . M a . ) 1980. 35(1). 172: Pest. Abstr. 1980. 13. 80-1787.
(62L) Sligh, J., Cochiane, W: P., Scott, J. Bull. Environ. Contam. Toxicol.
1979, 23(4-5), 470-4.
(63L) Stewart, T. E., Cannizzaro, R. D. Chapt. 20 In "Pesticide Analytical
Methodology", Harvey, J. Jr. and Zweig, G., Eds., ACS Symp. Ser. 136,
American Chemical Society, Washington, D.C. 1980, 367-88.
(64L) Tjan, G. H., Jansen, J. T. A. J . Assoc. Off. Anal. Chem. 1979, 62(4),
769-73.
(65L) Vasundhara, T. S., Parihar, D. B. Fresenius Z . Anal. Chem. 1979,
294(5), 408.
(66L) van Rossum, A., de Boer, F. G., Cannizzaro, R. D., van Mwrsehar, R.,
Stewart, T. E., de Wilde, P. C. Chapt. 10, in Vol. XI "Analytial Methods for
Pesticides and Plant Growth Regulators", Zweig, G. and Sherma, J, ds.,
Petroleum
R. E. Terrell
Gulf Science & Technology Corporation, Pittsburgh, Pennsylvania 15230
This is the 15th review of analytical chemistry in the pe-
troleum industry (1A-14A) sponsored by the Division of
Petroleum Chemistry of the American Chemical Society. It
covers, for the most part, papers abstracted in Chemical
Abstracts, American Petroleum Institute Refining Literature
Abstracts, and Analytical Abstracts (London) for the period
July 1978 through June 1980. One area, asphalt, spans a
4-year period from July 1976 to June 1980. The format of
the previous reviews has been followed in general. An input
concerning improvin this format or the addition or Aletion
of subsections woulf be greatly appreciated.
The assistance of D. K. Albert, Standard Oil Co. (Indiana),
Amoco Research Center, and C. A. Simpson, Mobil Research
and Development Corp., in searching the abstracts is greatly
appreciated, as is the additional screening and organization
of the 16 authors of the following 11 subsections. The pro-
duction of the review is due to their combined efforts.
CRUDE OILS
F. C. Trusell
Marathon Oil Company, Linleton, Colorado
The trend in this area toward analyses for a specific purpose
(e.g., spill identification and geochemical studies) rather than
characterization for its own sake continues unabated. Interest
in syncrudes, as indicated by the number of references, is up
sharply.
Hydrocarbons a n d Hetero Compounds. Yashina and
others used proton and 13C NMR techniques to study 22
Soviet crudes of a variety of com ositional types. The n-
R
alkane content, the degree of alip atic branching, and the
extent of substitution on aromatic compounds were all cal-
culated. Since the application of NMR is not limited by
boilin range, such studies can be carried out on heavy frac-
tions (%IB). Hajek and co-workers also studied Soviet crudes
by use of 13C NMR (36B).
Zhmykhova and Nekhamkina characterized three fractions
of Marmovichi and Ladushkino crude oils boilin above 350
OC by mass spectrometry and predicted their ehavior as
feedstocks for various refining processes (94B). Barabadze
E and co-workers determined the nature of the acids of normal
characterized the 350-500 OC fraction of Noriyskaya crude
oil by IR and UV spectroscopy, calculating the contents of
paraffins, naphthenes, and aromatic compounds (6B). Lar-
skaya and others used GC and MS, ;e arately and in com-
bination, to characterize the 200-500 arfo!(citn of Sokolwa
crude oil. They identified nearly 100 individual hydrocarbons
(49B).
Makushina and co-workers found the series o f ' 12-
methylalkanes (Cu-C30) and 13-methylalkanes (C26-C30) to
be unusually abundant in East Siberian crude oils and pro-
posed that these hydrocarbons are derived from 12,13-
88 R 0003-2700/81/0353-88R$06.00/0
Academic Press, New York 1980, pp 227-46.
(67L) Wells, D. E. Anal. Chim. Acta 1979, 104(2), 253-66.
(68L) Wlslowska, E., Kostowska, B. Chem. Anal. (Warsaw) 1979, 24(4),
707-9, Pest. Abstr. 1980, 13, 80-0560.
(69L) Wisson, M., van Hoek, C., Sauer, H. H. In Analytical Methods for
PesticMes and Plant Growth Regulators"; Zweig, G., Sherma, J., Eds.; Ac-
ademic Press: New York, 1980; Vol. XI, Chapter 8, pp 185-94.
(70L) Woolson, E. A., Aharonson, N. J. Assoc. OM.Anal. Chem. 1980,
63(3), 523-6.
(71L) Yu, T. C., Johnson, E. R., Montgomery, M. L. J . Agric. Food Chem.
1979, 27(6), 1413-4.
(72L) Zakkis, L. H. Bull. Envlron. Contam. Toxlcol. 1979, 23(3), 391-7.
(73L) Zanini, E., Barberis, E., Ronco, C. J . Agric. FoodChsm. 1980, 28(2),
464-6.
methylenetetracosanic acid in the original source material
(56B).
h
Vorob'eva and others used GC MS to characterize the
polycyclic Cl4-CZ6naphthenes o f t e 200-420 "C fraction of
Siva crude oil. They also proposed a scheme for the formation
of these compounds by the conversion of certain aliphatic
hydrocarbons (88B).
Grizzle and Coleman have reported a GC analysis for
benzene and toluene in crude oil and other fossil fuels. The
method employs two columns in series (OV-1 and TCEP), with
provisions for back-flushing heavier material. Repeatability
and accuracy are said to be f2% and f4% of the amount
present (33B). Vo-Dinh has developed a method using
room-temperature phosphorimetry for the rapid analysis of
polynuclear aromatic compounds in fossil fuels (87B).
Sultanov and others studied the content and distribution
of nitrogen compounds in Baku crudes. The highest nitrogen
content was found in the asphaltene fraction (76B). Moz-
zhelina and co-workers subjected West Surgut crude oil to acid
hydrolysis and measured the resulting amino acids. Glycine
and glutamic acid were the most abundant motein-derived
amin'o acids (55B).
Ferguson and Luke carried out a critical appraisal of flame
photometric detectors for the determination of sulfur com-
pounds. They discussed the problems of using a single FPD
for the auantitative determination of trace level sulfur com-
pounds in light naphtha, as well as using it for the qualitative
comparison of the distribution of sulfur compounds in heavier
fractions. Dual FPDs are also discussed (24B). Nuzzi and
Casalini studied the variety of thio henic com ounds in the
maltene fraction of the pentane Jeasphaltearesiduum of
Kuwait crude (58B).
Goncharov and others studied the phenols in eight West
Siberian crudes and noted the trends in total phenol con-
centration and concentrations of individual compounds with
increasing depth. They were unable to separate the effects
of age and of temperature on these trends (3UB). Nametkin
and isoprenoid alkanes in diesel fuels and kerosines from a
number of Baku and Mangyshlak crude oils (57B). Holstein
r
and Severin concentrated carbonyl com unds from crude oils
by extracting their complexes with irard-T reagent into
water. The original compounds were recovered by acid hy-
drolysis and were separated by HPLC (44B).
Brownrigg and Homing obbned total lurmnescence s
of six topped crude oils, their vacuum distillates, anc/?i%
residua and attempted to identify the principal emitting
compound classes. They attributed the dominant fluorescence
emissions to indoles and carbazoles, with weaker fluorescence
coming from benzocarbazoles and three-ring aromatics. The
0 1981 American Chemical Society
 PETROLEUM

R. E. Terrell is Senior Project Chemist.

group leader 01 the X-ray fluwescence $bo-
ratory 01 the Anaiyiical Technology DBpart-
ment 01 Guit Science and Technology Corn
pany. Pmsburgh. PA. He receive3 his B.S.
degree in chemistry t o m Drexei UnbersW.
Philadelphia, PA. He has had 20 years' ex-
perience wth anaiyiicai meLhcds using X-ray
IiUOreSCenCe speCn0icq)y and 2 years wnh
optical e m i s b n opctroscopy. Rior 10 join-
ing Gull he was a member of me Inhared
Spectroscopy Group 81 Penn %n Chemicals
Research Laboratory, Philadelphia, PA.
F. C. T~uIoII J. D. Beardrley
Marathon Oil Co. The Slandard Oil Co. (Ohio)
Littleton, CO Cleveland. OH

N. H. Fick PI. J. Lubeck C. L. Kibbv

iexaco. 1°C Marathon Od Co Gull Resedrch and Gull Research and
Beacon. NY Littleton. C o Development co. Development Co
Plttsbvrgh. PA Plnsburgh. PA

Byron Sudbir; - A
M. P. T. Bradley J L Fabec
Gulf Research and Research and Oevslopment Spectra-Physics Gull Science and
bvebpment Co Dept , CONOCO Inc. Sanla Clara. CA Technolcgy Co
Pittsburgh, PA Ponca C@. OK

J. W. Loveland .. ... ...

Laramie Energy Technology Sontech, inc. Suntech. Inc.
cenier Newtown Square. PA Newlown Square. PA
Laramie. WY

ANALYTICAL CHEMISTRY. VOL. 53, NO. 5, APRIL 1981 - 89R

PETROLEUM
observed phosphorescence was attributed to naphthalenes
(11B).
Filimonova and co-workers have compiled an extensive
literature review on the resin-asphaltene fraction of crude oils.
A large number of properties were tabulated, and a tentative
scheme for the formation and catagenic conversion of resins
and asphaltenes was proposed (25B). Gottlieb studied the
precipitation of asphaltenes from cyclohexane using n-alkanes
of various chain lengths and in varying proportions to the
cyclohexane. He has developed a stepwise precipitation of
asphaltenes accordin to molecular weight (31B). Hajek and
co-workers examinecf heavy crude oil residues by 13C Fouri-
er-transform NMR. The short relaxation time of this nucleus
in such residues permits pulse methods to be used for ob-
taining spectra without the addition of a relaxation reagent
(37B).
Syncrudes. “Analytical Chemistry of Liquid Fuel Sources.
Tar Sands, Oil Shale, Coal, and Petroleum.”, is a compilation
of 21 pa ers iven a t a symposium durin the Spring 1977
NationafAC8 Meeting (80B). Dooley an8 co-workers have
published a review paper, with many references, of methods
for characterizing syncrudes from coal (20B).
Ulanovskii and others have reviewed various solvent ex-
traction methods for fractionating coal liquids, liquid chro-
matographic procedures for further separation of the resulting
fractions, and spectroscopic and chromatographic charac-
terization of these concentrates (81B).Mair and Spitler have
proposed an improved analytical method for coal liquids. The
sample is chromatographically separated into h drocarbon
and nonhydrocarbon fractions, and the hydrocargon portion
is further separated into fractions containing saturates and
aromatics with one, two, three, and four or more rings (53B).
Paudler and Chepten studied the nitro en bases in solvent
refined coal by GC/MS. They resolvet 150 different com-
pounds and were able to identify 62 of them. They proposed
some possible ways of removing some of the highly carcino-
genic compounds (61B).
Snape and others proposed a scheme for the assignment
of 13Cchemical shifts. The scheme was used in the charac-
terization of the asphaltene and aromatic fractions of a su-
percritical gas extract of a low rank coal and on the residue
of oils obtained by hydrogenatin these fractions (73B).
Yokoyama and co-workers anal zecffractions of oil obtained
from coal hydrogenation by 13C&MR, proton NMR, and GC.
Their interpretations of the 13Cdata were enerally confirmed
by results from the other two methods (924).Dorn and others
found that elemental C and H percenta es, as well as ratios
of atomic ty es for these elements, coufd be determined in
coal liquids y! 13C FT NMR. Better agreement with con-
ventional analyses was obtained at 75 “C than at 32 “C,
suggesting that certain solutions of coaly matter may be in-
homogeneous (21B).
Yan and others re orted that polynuclear aromatic hy-
drocar%ons could be letermined in coal liquids and shales
without prior separation b dye laser excitation of Shpol’skii
effect spectra. Calibration gy standard addition was suggested
to overcome matrix effects (90B).
Jackson and others compared the compositions of 11shale
oils obtained by retorting as many different shales from the
Green River Basin of Wyoming. The types of basic nitrogen
varied significantly, but all other pro rties measured showed
little variation between samples (&By Puxbaum and Leyden
reported a simple routine method for the determination of
organic and inorganic carbon in oil shale. Small samples (2-4
mg) are heated in oxygen, and the evolved C02 is trapped in
0.02 M NaOH, where it is measured by conductance. Results
for a standard shale agreed well Hrlth the certified values (62B).
Cotter and co-workers used the Paraho shale oil plant to
determine what samples should be taken and what analyses
should be run, to monitor the composition of air, water,
product oil, and solids in, and around, a shale oil plant (17B).
Siggia and co-workers have carried out studies on the
characterization of shale oils by liquid and as chromatog-
raphy. These include separation and anafysis of the al-
kane/alkene, aromatic, and polar classes (18B,22B) and the
acidic and basic classes of compounds (79B).Rubin and others
isolated the acidic and basic fractions from shale oils, as well
as from other kinds of fossil-derived liquids, and described
the similarities and differences observed (66B).Hurtubise
and co-workers have reported a method for the isolation and
9OR ANALYTlCAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
determination of benzo[a]pyrene in shale oil. The detection
limit is approximately 1 ppm (45B).
Selucky and others separated a sample of Cold Lake bitu-
men into seven fractions by conventional methods and then
characterized each of these fractions. They concluded that
this sample resembled Athabasca bitumen but contained more
asphaltenes and less acidic and saturated components (70B).
Bunger and others compared four bitumens from Utah and
Alberta. The samples were fractionated by liquid chroma-
tography, and the fractions were analyzed by conventional
methods. Among other things, they reported these samples
resembled Wilmin on crude oil in their hydrocarbon/non-
f!
hydrocarbon distri ution (12B).
Zelenin and co-workers concentrated the oxygen-containin
compounds from a 350-400 “C cut of shale oil and studie!
their compositions by elemental analysis and IR spectroscopy
(93B).Borwitzky and Schomberg identified more than 140
polynuclear aromatic hydrocarbons from coal tar. They
suggest that coal tar is a very inexpensive, and very complete,
mixture of these compounds (IOB).Glajch and others pyro-
lyzed coal tars and etroleum pitches and characterized the
products by packefcolumn GC. They described a compu-
terized data collection system which facilitates comparisons
of samples (29B). Angelova and co-workers removed the
organic matter from bituminous rocks by extraction and by
heating. They compared the structures and functional groups
in the products from each method (3B). Urov and Listrem
extracted, and then hydrolyzed, the bitumens from shales of
the Pripyat deposit in Belorussia. The hydrolysis products
were studied by GC, TLC, and IR, and the compositions of
the hydrocarbons and carboxylic acids obtained are given
(82B).
Geochemical Studies. Larskaya and others analyzed a
series of Upper Vendian crude oils and related the differences
in composition and structure to the composition of the organic
matter from which they were formed and to the conditions
occurring during hydrocarbon formation (50B).
A study of 60 Paleozoic and Mesozoic oils, concentrating
on measuring the steranes and pentacyclic triterpanes, has
been reported. The samples were passed through a Florisil
column to remove asphaltenes. The compounds of interest
were further concentrated by silica gel chromatography and
adduction and finally detected b GC/MS. The methods
described can also be applied to se&ment extracts (7B).Bieri
and others analyzed sediments from the Atlantic outer con-
tinental shelf for polynuclear aromatic and polycyclic aliphatic
hydrocarbons at the ng/g level. They felt the PNAs were the
result of pyrogenic input. They also discussed the relevance
of (17a)-hopanes as indicators of petroleum (8B). Schaefer
and co-workers have devised a sin le-step analytical procedure
for the extraction and analysis ofhydrocarbons in rock sam-
ples. The crushed sample is placed in the flow stream of the
gas chromatograph, where the carrier gas also serves as the
stripping gas. Analysis time through C8 is 40 min (67B).
Uspenskii and others evaluated the petroleum producing
potential of rocks on the basis of the content and composition
of their organic matter. The greater the content of lipids, the
better their potential as source rocks (83B).
Schmitter and co-workers used a variety of chromatographic
techniques to separate high molecular weight carboxylic acids
from crude oils. Analyses were carried out on the resulting
concentrates by GC and GC/MS. Particular attention was
paid to the acids of the hopane series because of their im-
portance as biological markers in correlation problems (68B).
McGowan characterized the acids produced by controlled
potential oxidation of Green River oil shale kerogen with
perchloric acid (52B). Robin and Rouxhet investigated the
carbonyl and carboxyl groups in a series of kerogens from
different sources by IR spectroscopy. They described dif-
ferences in distribution and in total concentration and related
them to differences in source material and maturity (65B).
Castex analyzed some kerogens recovered from the Atlantic
Ocean in the course of the deep sea drilling project. From
their infrared spectra and their elemental composition he was
able to classify them as being from a marine, continental, or
mixed source (13B).Larter and others examined various
kerogens by pyrolysis-GC/MS and used the results to assess
the petroleum producing potential of the kerogens (51B).
Abu-Elgheit and co-workers analyzed a series of crude oils
for 14 metals by emission spectroscopy. They found that the

total metal content decreased with increasing maturity and
that ratios of certain metals were useful for roviding infor-
mation on the age and origin of the oil ( I B f :
Strand has roposed a method for the classification of
petroleums anlrock bitumens based on their IR spectra. He
demonstrated its utility by matching- petroleums
_ to their
parent bitumens (75B).- -
Oil SDills and Identification. Guiees has defined a set
of specifications for equipment to moni’tor the hydrocarbon
content of water discharged at sea. He has also described the
various types of equipment available for this task and exam-
ined in detail those instruments which met his criteria (3523).
Jones examined in less detail the analytical methods for
identifyin the source of petroleum and its products which
are spillefat sea (4713).
Higashi and co-workers used GPC with an ultraviolet de-
tector to distinguish between crude oils and several of their
refined products. In cases where the chromatograms at 254
nm were similar, better differentiation could be obtained at
280 nm (39B). The found that the GPC profiles changed
very little when cru& oil samples were artifically weathered,
while the GLC profiles changed markedly due to the loss of
light ends (41B). Ochi and Okaichi, however, found that the
GPC profile of weathered crudes differed significantly from
the respective unweathered crude, complicating identification
(59B).
Bonevski and Weber reported that crude oils could be
distinguished from one another by plotting total fluorescences
vs. temperature, using a 365-nm excitation source. While all
oils examined showed a marked decrease in fluorescence above
375 “C, their behavior below that temperature was charac-
teristic of each oil (9B). Eastwood and co-workers compared
results from room-temperature fluorescence with seven other
fluorescene or low-temperature luminescence methods for
identifying fresh and weathered oil spills. The resultin
spectra, and the instruments from which they were obtainel
are discussed (23B). Rho and Stuart described a noncom-
puterized method for producing three-dimensional repre-
sentations of fluorescence spectra. Such plots facilitate the
comparison of fluorescence data from two samples (64B).
Cheder and others discuss the use of organic marker com-
pounds, both as internal reference compounds for quantitative
determinations of pollutants and as qualitative indicators of
certain types of pollution. Examples are given of each use,
both for petroleum and for other classes of pollutants (14B).
Frame and co-workers demonstrated the use of a nitrogen
flame photometric detector in the identification of oil spills.
A concentration procedure, which also eliminates spurious
peaks from aliphatic hydrocarbons, was also described (26B).
Clark and Jurs described a technique for digitizing gas
chromatograms and then using a computerized pattern rec-
ognition routine to match oils. In a test using 80 chromato-
grams, 69 were correctly classified (15B). Utashiro and Matsuo
used a specially designed gas chromatograph with a 0.3 mm
X 10 m packed column to analyze the n-paraffins in crude oils
and heavy fuel oils recovered from the sea (84B).
Higaski and others have described their characterization
of tar balls taken from the ocean using both conventional GC
and sulfur-selective flame photometric detection (43B). They
studied the effect of weathering on the samples and attempted
to identify the sources of the tar balls (42B).
Trace Elements. Antipenko and co-workers have reviewed
the literature on the occurrences of trace elements in crude
oil and have given some correlations between the trace element
content and certain physiochemical characteristics of the oil
and its distillate fractions (4B). They also surveyed the
published methods for the separation and chracterization of
petroleum porphyrins (5B).
Giltrap and others explored spark source mass spectrometry
with electrical detection as a technique for the determination
of Al, Cr, Fe, Ni, Cu, and Sn in crude oils. It is less sensitive
than photoplate recording but is faster and more recise (233).
Gerasimova and co-workers reported that the aBdition of 3%
Tic& to deasphalted crude precipitated the major part of all
of the heteroatoms and trace elements except the sulfur
compounds. They also noted certain correlations between the
contents of various elements (27B).
Studies of vanadium and nickel, and the various forms in
which they occur, still attract considerable attention. Grizzle
and co-workers made a critical evaluation of four AA tech-
PETROLEUM
niques for these metals and reported the advantages and
short-comings of each (34B). Sebor and others have proposed
a gel ermeation method for isolating nonporphyrin com-
p o u n z of Ni and V (69B), and Stejskal and others have
developed a thermal diffusion technique for concentrating
compounds of these metals (74B). Raghaven and Agrawal
develo ed a spectrophotometric analysis for V and Ni said
to be aEle to reach trace, and ultratrace, levels (63B). Shibata
and others have described ESR studies of vanadyl complexes
at temperatures up to 435 “C. They were able to calculate
the activation energy for the interconversion of the two ob-
served forms (71B, 72B). Laktos-Szabo described the sepa-
ration, quantitative determination, and structural identifi-
cation of V and Ni porphyrins from a series of Hungarian
crude oils. The contents of these compound classes could be
related to the geochemical classification of the oils from which
they were recovered (48B).
Nonroutine Characterizations. A book,
“Chromatography in Petroleum Analysis”, describes the ap-
plication of a wide variety of chromato aphic techniques to
the analysis of petroleum and its p r o g c t s (2B).
Paczynska-Lahme and Neumann investigated the structure
of petroleum colloids by ultracentrifugation. They described
the behavior of resins and asphaltenes and the effects of each
upon certain properties of crudes and residues (60B). Weeks
and McBridge were able to correlate the ease of hydro-
processing of 10 crude oils with the amount of heteroatoms
concentrated in the . -
DreciDitates obtained from ultracentri-
fu ation (89B).
gigashi and Hagiwara studied the effect of the pore size
of the Dolvstvrene eel on the chromatomams of four different
crude oils: Differekes in the chromat&gams of the same oil,
as well as differences between oils, were observed and dis-
cussed (40B). Halasz combined a batch separation with silica
gel and a column separation on the same absorbent to char-
acterize a vacuum residuum (38B).
Torradas and others described a procedure using distillation
and column chromatography to obtain fractions from a crude
oil. These fractions were then analyzed by GC, MS, IR, and
NMR, to characterize the original crude (78B). Greenhow and
Nadjdi described a nonaqueous titration for determining the
acid compounds in strai ht-run and air-blow petroleum bi-
tumens (32B). Csikai and AI-Hobori reported the a plication
of an X-ray fluorescence analysis of sulfur and choride in
crude oil, despite the fact that the peaks from these two
elements overlap to a considerable degree (19B).
Routine Characterizations. Vercier and Mouton dis-
cussed the development and principal technical characteristics
of the new ASTM/CEN (Comite Europeen de Normalisation)
distillation assay, and some of the controversy over this me-
thod (85B,86B). Mouton and Chelveder described a rapid,
automatic distillation apparatus and compare results from it
with results from conventional distillations (54B).
Coleman and co-workers have tabulated results from the
analyses of 800 crude oils from U.S. oil fields. Each oil is
identified by field, location producing formation and age, and
producing depth (16B).Torradas and Albaiges have reported
on the composition of Amposta oil, a Spanish offshore crude
( 77B).
FUELS, GASEOUS AND LIQUID
J. D. Beardsley
The Standard Oil Company (Ohio), Cleveland, Ohio
Natural, Refinery, and Manufactured Gases. Kavan
(43C) has developed a technique for sampling gases which
consists of a pressure vessel containing argon. During transfer
into smaller vessels, no condensation of higher hydrocarbons
occurred and composition remained unchanged. A review of
as chromatographic analysis of fuel ases with 29 references
Ras been published by KO an and darkacheva (45C). Am-
erkhanov, Lychagin, and lidorova (3C) describe a chroma-
tograph with three columns for the analysis of petroleum and
hydrocarbon as mixtures. A patent has been issued to
Burrough (118) for a method and compact analyzer to de-
termine a selected gas in a gas sample. The apparatus has
a radiation source (e.g., IR) from which a modulated radiation
(at a first frequence) impinges on a flow-through sample cell.
Olacsi, Balazs, Hoffer, and Egri (64C) have standardized the
gas chromatographic analysis of natural gas with thermal
conductivity and flame ionization detectors so that C I13
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 91 R
PETROLEUM
hydrocarbons can be determined.
In the separation of isotopic methanes by gas chromatog-
raphy, Lukac (55C)has modified the surface activity of the
glass capillary column to improve the R2/t ratio (where R is
the resolution of an isotopic pair and t is the analysis time).
After the column was etched, part of the surface was covered
with a thin layer of active silica. Nitrogen plus helium were
used as the carrier gas. Capezzuto, D'Agostino, Cramarossa
and Molinari (14C) have studied the oxidation of methane
with carbon dioxide, water vapor, and oxygen in radio-fre-
quency discharges of moderate pressures. The reactor con-
sisted of a quartz tube capacitively coupled with a 35-MHz
radio-frequency generator.
Mashbits, Okhotnikov, and Khokhlov (58C)have received
a patent on the preparation of a gas sample for the chroma-
tographic analysis of impurities contained in a gas. The
process consists of passing the gas sample through a partition
chromatogra hic column which sorbed the impurities; the
c0ncentrateb)impurities were transferred to a carrier gas
stream which leads into a chromatographic analyzer. Trace
impurities in (permanent) gases and in natural gas have been
determined chromatographically by Okhotnikov, Rotin,
Khokhlov, and Yusfin (63C). An analyzer is described by
Kas rowski, Jeziorowski, Adamczyk, Niesporek, and Bytom
( 3 4 8 for determining traces of carbon dioxide, carbon mon-
oxide, and methane in gases. This analyzer is based on the
change of an electrolyte resistance in an electrolytic cell with
two electrodes. The apparatus and transistorized electronic
accessory are described in detail. Vitenberg and Tsibulskaya
(82C) have obtained a patent for the determination of trace
impurities of aromatic hydrocarbons in gases by gas chro-
matography. Thompson (80C) discussed the anomalous be-
havior of the hydrogen signal during its as chromatographic
determination in gas mixtures using a tierma1 conductivity
detector and helium carrier gas. The direction of the signal
is dependent on the hydrogen concentration in the carrier.
The determination of methanol in natural gas has been ac-
com lished by Lakeev and Vyalkina (51C) as follows:
MetRanol was absorbed from natural gas by water and the
methanol content of the aqueous solution was determined by
photocolorimetry after treatment of the solution with chro-
motropic acid.
A patent has been issued to Bakunin (6C) for the deter-
mination of trace elements in gases. The determination is
based on obtaining condensation nuclei, activation of the
nuclei (at 110-120 "C) obtaining a heated development agent
vapor (a-aminovaleric acid), mixing the gas with the devel-
oping agent, development, and enlarging of the condensation
nuclei. Mercury in natural gas has been determined by Orrit
(65C) at levels of 1to <lo0 1gHg/m3 gas. The mercury was
collected on chopped gold wire, digested in fumin nitric acid,
i?
evaporated on silicon dioxide, and measured y emission
spectrometry or X-ray fluorescence. In a method developed
by Below (7C) total sulfur in natural gas is determined con-
a
tinuously at a level down to 0.5 mg/m3. The as sample
flowing at 1.5 L / h and a t 40 mbar is passed, wit hydrogen
h
in a 1:4 vol ratio, over a platinum silica gel catalyst at 700
OC to convert sulfur compounds to ydrogen sulfide and then
into a commercial analyzer whose operating princi le involves
P
the coloration of lead acetate paper. Analysis o individual
sulfur compounds involves two glass columns, one filled with
Porapak, the other packed with 30% Triton X305 or Chro-
mosorb W-A-W-DMCS, and flame ionization and flame
photometric detectors operating in parallel. A flame photo-
metric detector has been used by Butusova, Beskova, Preo-
brazhenskaya, and Korotkova (12C)for the determination of
total sulfur in air and natural as. Air was analyzed in a glass
column packed with owderediTeflon and for natural gas the
column was replacel by a glass mixer.
Yoho (85C)has reported the results of a 36-company survey
on the measurement of the thermal energy of fuel gases. The
survey showed that combustion calorimetry is the accepted
standard method for determining heating value.
An apparatus has been developed by Simanek, Pick, and
Drabek (78C) for the calibration of industrial hygrometers
used in fuel gas production and transportation. Water is
electrolyzed and the hydro en obtained is catalytically burned
on a platinum catalyst. #he resulting water is absorbed on
magnesium perchlorate. Yagodin, Rudenko, Ivashchenko, and
Grechishnikov (84C) have determined water in gases by
92R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
measuring the discharge characteristics of a previously charged
sorbent placed in the as being studied. A method and ap-
K
paratus for continuous y monitoring the moisture content of
natural gas are described by Bozeman (9C). Karl Fischer
reagent is used as a titrant. Moore, Heidemann, and Wichert
(SOC) present a graphical method for estimating the water
content of sour natural as. The method is based on the Soave
modification of the hdiich-Kwong equation of state. Sodium
tetrachloroferrate has been used as a dehydratin agent by
Saleem, Khan, and Shahid (71C). The compouni was sup-
ported on Bioglass-2500. When it absorbed water the color
changed from yellow to brown. Methane in natural gas reacted
with the desiccant.
A water-soluble corrosion inhibitor VI, which is a mixture
of sodium salts of fatty acids and alcohols, hydrocarbons, and
nonsaponifiable oxygen-containing compounds, is introduced
into natural gas wells to prevent equi ment corrosion.
Kurtovaya, Obukhova, and Ul'yanova ( 5 0 8 have determined
the content of the inhibitor in condensate water by titration
with hydrochloric acid and in mineralized water by treating
a mixture of the water and natural gas condensate with sodium
chloride, which causes passing of the inhibitor into the hy-
drocarbon phase, and measuring its abosrbance by photoco-
lorimetry. McSpadden (56C) discussed various aspects and
methods for detecting and monitoring corrosion in the natural
gas industry.
Ragle and Cooper (67C) present methods for improving the
accuracy of the measurement of excess air in the combustion
of fuels such as natural gas and fuel oil. Users of Orsats,
washed-sample analyzers, and above-dew-point analyzers
require excess air corrections. Shimizu, Yamazoe, and Seiyama
(76C) have obtained unexpectedly high response in the de-
tection of 0.1-1.5% butylene, isobutane, propane, hydrogen,
and carbon monoxide with a calcium oxide stabilized zirconia
sensor. Several Japanese patents have been issued for gas
sensors. Ohkuma, Takahashi, Katsura, and Kaneda (62C)
have coated a gas sensor element with 1 2 layers of different
catalysts selected from platinum, palladium, and rhodium.
The use of 2 2 catalysts improves the selectivity of the sensor
toward the gases to be detected. Tin was used to prepare a
metal oxide semiconductor type combustible gas sensor by
Kusana i Kawamura, and Akiyama (49C). Katsura, Tak-
ahashi, kaneda, Hiraki, and Shiratori have obtained eight
patents for the preparation of metal oxide semiconductor type
gas sensor elements which are useful for detecting liquified
petroleum gases. A paste containing platinum and phosphorus
is coated on an iron oxide type gas sensor element (38C) and
on a tin oxide type (39C); and a slurry of platinum and
phosphorus is coated on a zinc oxide type (35C). A paste
containing rhodium and phosphorus is coated on a tin oxide
type gas sensor element (40C) and on a zine oxide type ( 4 0 0 ;
and a slurry of rhodium and phosphorus is coated on an iron
oxide type (37C). A paste containing palladium and phos-
phorus is coated on a tin oxide type gas sensor element (41C )
and on a zinc oxide t e (36C). Nitta, Kanefusa, and Hara-
dome (61C) have u s g a propane gas detector consisting of
tin(1V) oxide doped with niobium, vanadium, titanium, or
molybdenum.
Gasoline. Mose of these references dealt with analysis of
gasolines and most of the analyses were gas chromatographic.
Gaspar and Guiochon (26C) describe a computer-controlled
x
automatic gas chromatographic system equip ed with a
fluid-logic sampling gate as a sampling device. n example
is given of the analysis of a light gasoline sample on a column
coated with squalane. Gas chromatography with two columns
containing 1,2,3-tris(@-cyanethoxy)propanedeposited on a
Spherochrome support and sodium hydroxide-modified 13X
molecular sieves was used by Alekseeva, Shatilova, Slepneva,
r
and Berezovskaya ( I C ) for determining the h drocarbon
composition of strai ht-run gasolines boiling be ow 180 "C.
Schulz, Gregor et al. f74C) have developed precolumns for the
accurate capillary gas chromatographc anal sis of gasoline-
range hydrocarbons. The use of a combinedlhydrogenation
and adsorption precolumn and of a method for summarizing
the detailed results is shown for a gasoline containing ap-
proximately 40% aromatics. The quantitative analysis of
olefin-containing gasoline by capillary gas chromatography
in combination with hydrogenation and adsorption preco-
lumns is discussed by Schulz, Sedighi, Gregor, Van, and Min
(75C). The German Society for Petroleum Sciences and Coal

Chemistry (27C) describes the use of precolumns for hydro-
genation or absorption of olefins in quantitative group analysis
of olefin-containing gasoline. Fadeev, Nazarenko, Afanas'ev,
and Shteingardt (WC)have determined the gasoline content
of catalyzate from catalytic cracking by gas chromatography.
The chromatographic and distillation methods agreed.
An automated gas chromatograph is used by Clark (16C)
for the determination of paraffins, naphthenes, and aromatics
in gasoline fractions with a 200 "C FPB. Koci (44C) has
determined the paraffin and cycloparaffin composition of eight
gasolines from typical Albanian petroleum by catalytic deh-
ydrogenation of the cycloparaffins over Pt-Fe and capillary
as chromatography on sodium hydroxide-treated 13X mo-
fecular sieves. A comparison has been made by Lochmueller,
Gordon, Lawson, and Mathieu (54C) between two thermal
conductivity detectors and a flame ionization detector for use
with open tubular columns. Results are resented for analysis
of a remium grade gasoline. DiCorcia, ffampri, and Capponi
( 2 1 4 have analyzed premium grade gasoline using a gas
chromatogra hy-mass spectrometry technique on 5-m col-
umns packef with graphitized carbon black modified with
2,4,5,7-tetranitrofluorenone.Hydroxide ions generated in a
mass spectrometer by the reaction of nitrous oxide with hexane
reacted with alkylbenzenes by hydrogen abstraction but not
with saturated hydrocarbons. Sieck, Jennings, and Burke
(77C) discuss use of such a method for distinguishing samples
of liquid fuels (gasolines) from different sources. Cracked
gasolines and naphthas were studied by Sapozhnikova, Abi-
dova, Sokol'nikova, Khasanova, Cherdakova, and Nisarbaeva
(73C) using silica gel and gas-liquid chromatography. The
gas-liquid chromatographic analysis of commercial gasolines
and stocks for blending was performed by Chachulski, Czamik,
and Dettloff (15C) to test the possibility of determining octane
number and fractional composition. Dracheva and Bryan-
skaya (23C) give an equation for determining the optimum
conditions for the gas-liquid chromatographic separation of
gasoline. The direct coupling of a liquid chromatograph to
a continuous flow hydrogen nuclear magnetic resonance de-
tector has been accomplished by Haw, Glass, Hausler, Motell,
and Dorn (31C) for the analysis of petroleum fuels. Dimov
and Kovacheva ( 2 2 0 have combined the selectivity of infrared
spectrometry with the sensitivity of titrimetry and applied
it to the determination of aromatic and olefinic compounds
in gasoline. This same technique was applied to gasoline
boiling below 315 "C by Kovacheva, Dimov, and Pankova
( 4 7 0 . Kotova, Loginova, Kastorskaya, and Stryakhileva (46C)
have determined the antiknock additive (methyl tert-butyl
ether) in gasoline by titration with Mohr's salt.
A set of four nomographs is presented by Zanker (86C) to
allow the calculation of the octane number of binary blends.
Laurgeau, Espian, and Barras (53C) have developed a linear
algorithm to evaluate the octane number of both clear and
leaded asolines from their chemical compositions as deter-
%
mined y gas chromatography.
Potter (66C) has determined copper in gasoline by atomic
absorption spectrometry with electrothermal atomization and
by the lengthier spectrophotometric method (IF' 225 71). He
found no significant difference in the results obtaine by each
method. Sommer and Ohls (79C) describe a system in which
the effluent from a gas chromatographic column is fed via a
heated interface directly into an inductively coupled plasma
(ICP) burner for optical emission spectrometric analysis. The
system has been used to determine tetraethyllead in gasoline.
A method of calculation is presented by Kaegler, Lehmann,
and Baur (32C) which permits the determination of lead in
gasoline a t a level of about 0.12 g L and involves measuring
d
the Compton scattering instead o the more conventional use
of an internal standard. Lead in gasoline is determined rapidly
b Berenguer, Guinon, and de la Guardia (8C) using atomic
atsorption spectrometry on an emulsified sample.
A combination of gas chromatography and atomic absorp-
tion spectroscopy has been used by Bye, Paus, Solberg, and
Thomassen (13C) for determining tetralkylated compounds
in gasoline. Both flame and graphite furnaces were used with
the same operating conditions of the gas chromatograph.
DuPuis and Hill (24C) have analyzed gasoline for antiknock
a ents with a hydrogen atmosphere flame ionization detector
(hAFID) fitted to an Ultrabond 20 packed gas chromatograph.
HAFID and FID analyses are compared and optimum oper-
ating conditions are discussed. Tricarbonyl(methylcyc1o-
PETROLEUM
pentadieny1)manganese has been determined in gasoline by
Uden, Barnes, and DiSanzo (81C) using gas chromatography
with interfaced direct current argon plasma emission detection.
The advantages of the plasma detector are discussed.
Makabe, Ichikawa, Hashizume, Taira, Yamamoto, and
Takada (57C) have obtained a patent for the detection of
leaded gasoline in unleaded gasoline. A gasoline sample is
impregnated upon filter paper, the paper irradiated with UV
light for 3-10 min, a drop of dithizone in chloroform added,
and the absorbancy measured at 500 nm. A UV method for
the detection of the adulteration of gasolines with kerosines
has been developed by Kapmr, Kumar, Mallik, Chhibber, and
Gu ta (33C). A suspect sample had UV absorbances of >200
an8>20 a t 285 and 319 nm, respectively. A passing sample
had UV absorbances of 24 and 21 at 285 and 319 nm, re-
spectively. Adulteration by as little as 1% kerosine should
be detectable.
May and Mueller (59C) have made spectroscopic deter-
minations of the temperature and hydroxyl concentration
distributions in the combustion chambers of spark ignition
engines. Gaseous emissions, unregulated exhaust components,
and exhaust particulates were measured by Hare (30C) in
dynamometer tests over eight operating schedules and five
different fuels. A detailed description of the test program and
results is given. A simple cryogenic unit for temperature
programming from -50 "C is illustrated by deRuwe, Hein,
Schulting, and van Grondelle (20C). An example of its use
for separation of the components in car exhaust ases is given.
Brown and Kroes (1OC)describe the design a n g o eration of
metallic oxide semiconductor sensors for combusti&le gas and
vapor monitoring. These sensors have been used in the de-
termination of 50-100 ppm levels of lead-containing gasoline
in air.
Distillate Fuels. Simulated distillation by va or-phase
chromatography has been applied to petroleum prducts from
Cuban refineries by Gonzalez, Ibarra, and Perez ( 2 8 0 .
Analyses of naphtha, kerosine, jet fuel, diesel fuel, and gas
oil are discussed. Sauer, Jadamec, and Sager (72C) have
attem ted to fractionate heavy fuel oils by means of re-
versecf phase liquid chromatographic columns at different
temperatures. A review with 81 references is presented by
Lang, Sebor, Kosina, and Kusta (52C) of nuclear magnetic
resonance analysis of high molecular weight fuel samples.
Altamirano, Cortex, and Cuevas (2C) have developed a twp-
step method for the determination of n-paraffins (CB-C,,) in
kerosine by molecular sieve adsorption and gas chromato -
raphy. Jet and diesel fuels which were prepared from oil shafe
and coal syncrudes were examined by Antoine (4C) using as
chromatography. The boiling range distribution was use to
calculate various physical properties. Zrebov, Krasnaya,
B
Postnikova, and Kalinin (87C) have evaluated the reliability
of the determination of the aromatic hydrocarbon content of
jet fuels by sulfonation with sulfuric acid. They concluded
that the method was not reliable because the amount of
sulfonated aromatics depended on the concentration of sulfuric
acid. Phenols in kerosine have been separated and identified
by Rossemyr (68C) using si1 lation and gas chromato aphy.
Saint-Just and Larsen ( 7 0 6 have found a re1ationsEp be-
tween refractive index and the nitro en content of the hy-
drotreated products of a furnace oif from shale oil. Nit-
rogenous bases of straight-run and hydrotreated diesel fuels
from an Arlan crude have been separated and identified by
Baikova and Ben'kovskii et al. (5C). The separation was done
chromatographically, and the compounds were studied by IR,
UV, and mass spectrometry.
Ward ( 8 3 0 presents a review of the historical development,
performance characteristics, and applications of plasma as an
emission source for inductively coupled argon plasma spec-
troscopy. Examples are given of the multielement spectro-
metric analyses of water, liver, rocks, stainless steel, and re-
sidual fuel oil.
A spectrophotometric method using the reagent 2-
methyl-4-(2-thiozolylazo)resorcinolhas been developed by
Gonzalez Dim, Gonzalez h a s , and Garcia Montelongo ( 2 9 0
for the determination of vanadium in fuel oil. This method
is considered superior to the ASTM D 1548. Rossemyr (69C)
has made a study of the cold flow properties and the response
to a cold flow improver of some typical fuel oils. After column
chromatogra hic separation, friction and wear reducing ad-
ditives have 8,en determined by Kuehn, Stoecker, and Bor-
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 93R
PETROLEUM
mann (48C) using infrared spectrometry. Denisov, Kovalev,
Borisova, Zvereva, Englin, and Slitikova (1912)have deter-
mined antioxidants in hydrocarbon vuels uantitatively.
The sample containing the oxidation inh%itor is oxidized
with air while being heated, and the induction period is
measured. The antioxidant concentration is then determined
from a calibration graph. To determine the amount of alu-
minum compound present as a lubrication additive in mineral
oil or diesel fuel. D aev, Lozovaya, and Perveev (I7C) boiled
the sample with p e r s o r i c acid, filtered the solution, and then
titrated the diluted filtrate potentiometrically with sodium
hydroxide. A technique in which a vidicon tube is used as
a detector has been applied by Davis, Stockwell, and Pardue
(18C) to the identification and determination of quinizarin
in the eluant from a liquid chromatographic column. Quin-
izarin is sometimes added to a gas oil as a marker.
LUBRICANTS, OILS AND GREASES
N. H. Flck
Texaco Inc., Beacon, New York
Oils. The literature continues to reflect the increasing use
of combination analytical techniques to achieve preconcen-
trationlseparation and identification/quantitationof com-
ponents. Use of analytical instrumentation continues to
predominate.
Spectroscopic Techniques. Trawinski (710) described
infrared (IR) spectroscopic procedures to determine hydro-
carbon composition, content of additives, and thermal-oxi-
dation stability of lubricating oils, and also published a review
(700) on use of IR techniques for determining composition
of lubricating oils and additives. Methods for determining
olymethacrylate and succinimide additives in lubricating oils
E y qualitative and uantitative IR spectroscopy were devel-
oped by Vergos an! Stepina (730)
Belafi-Reth ( 5 0 , 6 0 ) published two papers on determi-
nation of sulfde and thiophene sulfur compounds in lube oils
by means of IR and UV spectroscopy. The sulfides were
determined by IR measurement of the sulfoxides at 1040 cm-'
after oxidation. An IR spectrometer interfaced to a computer
was used by Lynch and Brady (400) to analyze for contam-
inants in complex oil mixtures, and Hannah et al. (270) de-
scribed a technique using an IR spectrometer interfaced to
a computer to determine small amounts of additives in lube
oils. Preconcentration and se aration steps were described.
Differences could be observezbetween new and used motor
oils. The use of spectral coefficients, ratios between optical
absorbances of characteristic IR bands, for calculating the
contents of resins and paraffins-naphthenes in mineral oils
was described in a paper by Shulova (630).
Liquid Chromatography, Amos and Albaugh (10)pub-
lished a review of various chromatography techniques em-
ployed for the determination of additives in lubricating oil,
and Kajdas et al. (330) discussed at length the application
of modern instrumental methods for determining lubricant
com osition. The identification of amines in alkenylsuccin-
imigs, used as ash-free dispersants in motor oils, was in-
vestigated by Natoli and Peditto (460). Elution chroma-
tography was used for the separation, and the purified cuts
were hydrogenated followed by identification by gas chro-
matography (GC).
Separation and characterization of aromatic hydrocarbons
in mineral oils were reported by Mosescu et al. (420) who
employed elution chromatography followed by UV s ectro-
photometry of separated fractions. Kareher et al. (3407made
a study to compare methods for determining aromatic and
nonaromatic content of mineral oils boiling above 315 O C . The
three methods evaluated were ASTM D 2549-68, DIN 51
38411975,and GUD 472175, each of which is based on elution
chromatography. The application of several statistical (ndM,
ASTM D 2140, and others) and instrumental methods (IR,
UV, NMR) to structural analysis of mineral oil fractions was
reported by Grzechowiak and Sztuba (250). A method for
determining the hydrocarbon composition of petroleum oils
by combined two-stage liquid chromatography and mass
spectrometry is iven in a paper by Zakupra et al. (790).
The analysis of alkyl and aryl zinc dithiophosphate lubri-
cating oil additives was described in a paper by Fodor and
Newman (180). Li uid chromatography was combined with
infrared analysis (IF?) to obtain the alkyl to aryl ratio. Jamson
and Hillman (320) performed this analysis by using high-
94R * ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
voltage zone electrophoresis carried out on a silica gel plate
to which was applied the zinc-containing oil.
For the characterization of the saturated components of
mineral oils Szebenyi et al. (690) employed high- erformance
liquid chromatography (HPLC) followed by GE) analysis of
the separated fractions. High accuracy was reported, and only
30-70 mg of sample is required for the analysis. An HPLC
procedure utilizing a dual IR UV detector system was used
d
by Selucky et al. (570)for stu ying the composition of mineral
oils and petroleum products. Interpretations of HPLC
chromatograms are given. Majors and Johnson (410) reported
on a high-performance exclusion chromatography technique
using variable wavelength and refractive index detectors for
separating additives of molecular weight less than lo00 from
complex mixtures including lubricating oils. The analysis of
engine oils with sizeexclusion chromato aphy was described
in a paper by Wheals and Russell ( 7 6 0 y They included an
illustration of a simple circuit which provides the first-de-
rivative form of the chromatogram, thus facilitating com-
parison of chromatograms with ill-defined shoulders or in-
flections. The separation and characterization of hi h boiling
and nonboiling mineral oil products were performed %y Halasz
(260) using various HPLC techniques. He characterized the
fractions by UV and IR spectroscopy and discussed sources
of error and methods of preventing errors in liquid chroma-
tography.
The application of gel permeation chromatogra hy in re-
frigeration oil analysis was the subject of a paper y! Shiono
et al. (610),and Shiono (620) re orted on the determination
of poly(ethy1eneterephthalat.e)oEgomers in refri eration oils
by a gel permeation chromatography recedef by an ad-
sorption chromatography cleanup procefure. The evaluation
of a refrigerant-refrigerator oil-metal (Fe and Cu) system was
carried out by Enomoto et al. (140) with the aid of HPLC
and gel permeation techniques. An improved method for
measuring trace amounts of oil in diver's air sup ly was de-
scribed in a pa er by Sewell and Yee (590). T e! variable
wavelength Ufdetector used with a liquid chromatogra h
permitted a detection sensitivity of 0.2 pg. Baxa et al. ( 4 9 )
calibrated a liquid chromatograph with oil fractions of known
molecular weight and demonstrated the suitability of the
procedure for evaluation of the distillation ran e of lubricating
oil fractions. Murui and Watanabe (430) pullished a review
on the ap lications of HPLC to oils and fats anal sis.
Karleskinfet al. (350) discussed the advantage of graJent
elution HPLC on oils and fats analysis. For the determination
of amine antioxidants in high-temperature jet engine lubri-
cants Sniegoski (660) developed a uantitative thin-layer
chromatographic '(TLC) method. T l e colored spots were
measured by densitometry, and calibration graphs are given
for additive concentration range up to 1%.
Gas Chromatography and Mass Spectrometry. Anti-
oxidant additives in lube oil were anal zed with gas chro-
matography by Kononyuk et al. (370). %he analysis of syn-
thetic pentaerythritol ester oils by gas chromatogra hy-mam
trometry (GC MS) was studied by &man et al. &ID)who
i
K r m i n e d the atty acid composition of the oils after hy-
drolysis and calculation by computer of the theoretical isomer
distribution of the esterified products. These authors (820)
also analyzed trimethylol ropane-dipentaerythritol ester
synthetic lubes by GC/Mff b ut reported the separation of
isomeric trimethylolpropane esters was not successful.
However, after separation by column chromatography, a de-
tailed characterization of the complex ester s stem was pos-
sible by MS. Deo and Howard (120) used &/MS for the
analysis of commercial aryl phosphate oils used as fire-re-
tardant hydraulic fluids.
For the analysis of lube oil fractions Severin (580) discussed
photon-impact mass s ectrometry (MS) as an alternative to
field ionization MS. h i s paper also covers the use of auto-
mated fragmentography for trace impurities analysis of sat-
urated fractions. Mass spectrometry was combined with N M R
b Chadha et al. (80) to analyze three white oils obtained by
ocum treatment of lubricating oil base stocks.
Oils in t h e Environment. The characterization of pe-
troleum oils by high-speed gel permeation chromatography
with UV detector was the sub'ect of a pa er by Higashi and
P
Hagiwara (300). The method was ueefu in identifying the
source of oil spills. These authors (290) also published a
review of gel permeation, gas chromatography, and spectre

metric methods for determining oils in the environment.
Gottardi and Greiderer (240)also studied mineral oils in the
environment and reported on a method employing combina-
tion IR and fluorescence spectroscopy. The identification of
the source of a petroleum spill is based on use of a quotient
(Q) which is specific for a particular substance and is related
to the intensity of fluorescence (equal to the intensity of C-H
vibration).
Ochi and Okaichi (480)published a paper reporting on the
fluorescence spectrometric determination of oil concentrations
contained in seawater for up to a year after a refinery oil spill.
Cook et al. (100)made a comparison of methods for deter-
mining traces of oil in water, Included were the EPA reference
4
method 625 6-74-003,modifications of the EPA method, and
the Horiba CMa-200 oil monitor (solvent extraction followed
by IR at 3.5 pm). The EPA method gave the highest results
on standards prepared from soluble oil in deionized water over
the range 0-100 mg/L. Frame et al. (200)published an atlas
of gas chromatograms of petroleum and synthetic oils. In-
cluded are descriptions of analysis techniques using dual flame
ionization detectors and thermionic nitrogen-phosphorus
detectors for GC fingerprinting useful in oil pollution studies.
A review of fluorescence spectroscopic methods for oil spill
source identification, including evaluation of each method’s
utility for this purpose, was published by Frank (210).
Other Analysis Techniques. The active ingredients of
sulfonate additives were determined with dialysis techniques
by Ifcsics (310)who reported the data agreed well with those
developed by li uid chromatography. Shdiqul Alam et al.
(600) develope! a differential pulse polarographic method
which was suitable for detecting as little as 50 pM of zinc
dialkyl dithiophosphate in commercial lubricant additives.
For the determination of 2,6-di-tert-butyl-p-cresol in trans-
former oils, Foley and Kimmerle (190)used a method de-
veloped by Richards and Evans (510)which utilized pulse
voltammetry. The method was rapid, accurate to *3% and
sensitive to 10 ppm detection limit.
The determination of total acid number of lubricants and
additives was the sub’ect of a paper by Fernandez et al. (150).
These authors used a microtitrimetric procedure with a
high-frequency oscillator which was described by them in a
previous publication (160).They also reported on further
work (170)with this a paratus on determining total base
number of new and usecflubricating oils. Sharp breaks at the
end points were obtained and results were compared with
those obtained potentiometrically.
A method for the determination of chromium(V1) in syn-
thetic and mineral emulsifiable oils was developed by Neustadt
et al. (470).Separation is by TLC on alumina followed by
spectrophotometric determination a t 540 nm on the water
extracted relevant zone located by UV radiation. Lower limit
was reported as 0.09 pg/mL. Clark and MacPherson (90)
adapted the Orion NO, gas-sensing electrode to the deter-
mination of labile NOz- in unused cutting oils with a lower
detection limit of 15 pg g. The moisture content of antifreezes
d
and brake fluids was etermined with high precision by Na-
gashima and Hachiya (440)by measuring resistance while
supplying power with an ac source. For the continuous
measurement of residual concentrations (down to 0.5 ppm)
of chlorinated solvents used in dewaxing lube oils, Von der
Ohe et al. (750)described a procedure in which the solvents
are stripped by passage of air and the vapors are passed to
a measuring cell fitted with a flame ionization detector (to
measure total hydrocarbons) and a halogen detector. Aru-
tyunov et al. (20) reported on the determination of water in
petroleum oils by extracting with ethylene glycol containing
2-propanol followed by GC analysis for water in the extract.
Voloshchuk et al. (740)determined mercaptobenzothiazole
and p-hydroxydiphenylamine additives in synthetic ester oils
as a function of their optical density by photometry at 250-290
nm.
Several investigators gave their attention to detection of
trace N-nitroso compounds in petroleum metalworking
products. Smyth et al. (650)examined metalworking cooling
fluids by differential pulse polarography, GC, and thin-layer
chromatography. They found only fluids formulated to
contain high concentrations of di- and triethanolamines and
sodium nitrite contained more than 0.5 pg/mL of N-nitroso
compounds. Williams et al. (770)carried out the analysis of
cutting fluids to detect N-nitrosodiethanolamine (I) semi-
PETROLEUM
quantitatively by using a silica gel cleanup procedure followed
by TLC on a silica gel plate. Further analysis of the tri-
methylsilyl derivative of I by GC MS gave results in good
agreement with those estimated by I;, C. The initial approach
to this analysis by Kawano et al. (360)was different. These
authors first decomposed the NO - in the cuttin fluid with
urea and distilled the solvent under nitrogen. $he mixture
was then silylated and subjected to GC with FI detector or
GC/MS.
The role of spectral selectivity in determining polycyclic
aromatic hydrocarbons in oils by fluorescence detection for
liquid chromatography is discussed in a paper by Ogan et al.
(490).Their work compared two fluorescence detectors, a
broad-band-pass detector with a 350-nm cutoff filter in the
emission beam with the emission monochromator set to zero
order and a narrow-band-pass detector with the emission
s
monochromator used to select specific wavelen hs. The
advantages of each mode are discussed. The an ysis of po-
lychlorinated biphenyls in waste oils by HPLC with a re-
concentration step by column chromatography was descriL d
in a paper by Belliardo et al. (70).
Used Oil Analysis. The analysis of used oils for the
purpose of detecting contaminants, determining suitability
for continued use, and uncovering potential equipment
maintenance problems was the subject of apers by three
authors. Simley’s (640)paper was a broa&r discussion of
rograms primarily for mining machinery, while
f:t%$%ypaper was devoted more toward spectrophoto-
metric determination of trace wear metals and threshold
concentration limits for given applications. Ohls (500)covered
the use of inductively cou led plasma emission spectrometry,
including the rotrode m&, for trace wear metals in used oils.
The analyses were carried out on the oils in a direct way as
well as after ashing, and the results were compared with resulb
obtained by absorption spectrometry.
A description of the ferrographic method for wear particle
analysis was covered in detail with numerous illustrations in
two papers by Rotondi (530,540).This technique for sepa-
rating and studying particulate matter in used lubricants gives
information on the condition of such wear mechanisms as
aircraft gas turbines, gearboxes, transmissions, engines, and
hydraulic systems. Ruff (550)used this technique along with
filtration separation in his investi ation of uantitative
methods in wear debris analysis in whch he injuded simu-
lated wear debris (silica spheres, 3-pm iron particles, and
30-pm nickel particles). His pa r compared chemical analysis
and particulate analysis and Ecussed problems of particle
size resolution, lubricant dilution, particle overlap, and cali-
bration of debris recovery systems.
Properties of Oils. Sosulina et al. (670)measured the
thermal stability of lubricating oils prepared from penta-
erythritol esters by mass spectrometric determination of the
intensity of oxygen-containing radicals through the degra-
dation of the esters. A thin-film test for measurement of the
oxidation of ester-type aircraft as turbine lubricants was
developed by Cvitkovic et al. (Id).The procedure requires
only 20-200 pL of sample placed in a depression on a cata-
lytically active steel block heated in a stream of air. Analysis
by gel permeation chromatography gives information on ad-
ditive depletion and oxidized products formed. Dudukovic
and Pejovic (130)compared an extended version of the
IEC-74 method for testing the chemical stability of trans-
former oils and found it gave better precision for uninhibited
oils than did the IEC-474 method.
Bartz and Heckoetter’s (30)investigation of rapid bench
tests for estimation of the detergent-dispersant properties of
engine oils, including the Wolf test strip, PSW engine heating
test, dispersancy bench test, and HD test (Fuhrmann, 1958),
concluded that these rapid tests did not correlate with engine
tests. The mechanism and activity of deter ents-dispersants,
including succinimides, sulfonates, alkyf salicylates, and
sulfurized phenates, was the subject of a paper by Zaslavskii
et al. (800) who studied these additives in relation to their
ability to disperse carbon black labeled with ’?I’isotope in
lubricating oil. Heidemeyer (280) compared numerous
methods for injecting air into water-Containing cutting oils
for the urpose of studying their foaming behavior. Woodle
(780)Beveloped empirical equations for estimating the
characteristic factor of heavy oils from gravity in combination
with kinematic viscosity, COC flash point, or aniline point.
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 Q5R
PETROLEUM
The calculations can be easily performed on a hand calculator
having “ln” function.
Greases. Fultz (220) presented a paper describing pro-
cedures using IR and high-speed gel permeation chromatog-
raphy for identifying com onents of lubricating greases and
the MIL specification to wkch they belong. The soap content
of calcium complex greases was determined by a differential
IR spectrometric procedure by Naqvi and Biswas ( 4 5 0 ) .
Kozakova et al. (380)investigated the effects of solvent and
heating period on hydrolysis in the determination of free acids
and free bases in lubricating grease. Reverse-phase chroma-
tography was the technique employed by Gorodnicheva et al.
(230)to determine the mineral oil content of Li stearate
greases.
The compatibility of lubricating greases with elastomeric
seals, with attention to analytical tests as methods which
would not be affected by seal variability, was described in a
pa er by Verdura (720). A system for measuring the color
of rubricating greases was the subject of Sayles’ (56D)paper.
He adapted a digital-reading reflection densitometer for this
purpose and reported on its use in quality control.
Stanton (680)reported on two round robin programs to
evaluate test variables with the Falex I ring and block friction
and wear test machine. Load was found to have the pre-
dominating effect in the first program, and the second program
evaluated the effect of load on a variety of E P and non-EP
greases.
WAX
A. J. Lubeck
Marathon Oil Company, Littleton, Colorado
Only a few papers were published in the area of petroleum
waxes this review period. Of these, most dealt with finding
the most appropriate techniques to characterize waxes for
specific applications.
Harmon (5E) used gel-permeation chromatography (GPC)
and differential scannine calorimetrv to comDare and evaluate
waxes used in elastom& compounding. Hk found the data
from these tests were sufficient to enable him to select sat-
isfactory substitutes for waxes used in compounding recipes.
Sosa et al. (9E)reported on the GPC characterization of crude
paraffin waxes containing different amounts of oil. The weight
avera e and number average molecular weights were deter-
minef from a calibration graph for n-alkanes and their ratio
was found to be indicative of the broadness of the molecular
weight distribution. An electron microscope was utilized by
Szergenyi and Baumann ( 1 I E ) to examine macro- and mi-
crocrystalline waxes and fractions containing them. They
verified the selectivity of molecular sieves in separating n-
paraffins from both isoparaffins and cycloparaffins. Two
distillate waxes obtained from Ankleshwar crude oil tank
bottoms were found to be predominantly n-paraffins by
Agrawal and Joshi (1E).Their results based on physical
properties correlation, isothermal gas chromatography, proton
NMR, and 13CFourier transform NMR were all consistent
with this conclusion. Galdina et al. (3E)used hotoelectro-
colorimetry and thin-layer chromatography to letermine the
content of aromatics in oxidized and unoxidized liquid pa-
raffins separated from petroleum products by urea adduction.
Szalka and Szergenyi (IOE)published a review, with 47 ref-
erences, of the methods by which paraffins may be chemically
and physically characterized.
Mineral waxes from nonpetroleum sources were the subject
of three papers of possible interest to those working with
petroleum waxes. Bel’kevich et al. (2E) reported on the
composition of the ethanol-insoluble fraction of the tar part
of li nite wax. Preliminary separation on alumina forowed
by 1% and UV characterization established the presence of
normal and branched aliphatic hydrocarbons and oxygen-
containing compounds. Ivanova et al. (6E)separated the acids
and alcohols formed in the alkaline hydrolysis of gasoline-
extracted peat wax on an alumina column. Individual acids
and alcohols in the fractions were then determined by gas
chromatogra h . The chromium content of montan waxes
contaminate: &ring their bleachin with chromates irl the
presence of H SO4 was determined f y Maksimikhina et al.
(8E). After t i e wax sample was burned, the product was
treated with KC103, reacted with diphenylcarbazide and an-
alyzed photometrically.
96R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
Khromykh et al. (7E) reported on the filtration properties
of urea-alkane complexes formed during the dewaxin of
petroleum fractions. In a similar study, the filtration cfar-
acteristics of paraffin suspensions in dewaxing and deoiling
processes was determined by Gryaznov et al. ( 4 E ) .
ASPHALT
James R. Couper
Department of Chemical Engineering, Univershy of Arkansas, Fayettevi/k,
Arkansas 72701
During the past 4 years, the major part of the research work
has been devoted to compositional studies of asphalt. This
review is arbitrarily divided into subheadings to facilitate the
readability and location of information.
There has been a significant decline in research activity
during the past 4 years compared to the previous 2-year review
period. Most of the research is now being performed by
foreign investigators.
CHROMATOGRAPHIC METHODS
Before a chromatographic separation can be undertaken,
an initial solvent separation or preci itation step is performed.
Fractions are obtained by various cLomatographic methods,
and these fractions may be subjected to further analysis using
IR, NMR, and UV spectrometry or X-ray diffraction.
Gel Permeation Chromatography (GPC). Blanchard et.
al. (6F)obtained 23 fractions by usin a preparation-type GPC
technique from a Canadian asphalt. h e y used vapor pressure
osmometry and NMR for further analysis. NMR analysis of
some of the fractions showed that they were mainly aliphatic.
The de ee of aromaticity resent in a given fraction, though
slight, c k g e d with the morecular weight of the sample. Brule
(15F),using GPC followed by differential refractomet and
U V , noted that the polycondensed character of the asphytenes
increased with molecule size. Boduszynski (12F) gave special
attention to acidic and basic hetero compounds containing
N and 0 in the as haltenes and maltenes, noting especially
the association rog of the compounds in relation to the sta-
bility of colloidal systems in asphalts.
Kiet, Blanchard, and Malhotra (47)extended the work
reported earlier by Blanchard (6F),finding that aromaticity
and naphthenic C content of fractions with intermediate
molecular weights were low, while the paraffinic C content
was maximum. The unit molecular weight of these fractions
was 900, independent of molecular weight, indicating that the
fractions are composed of a number of linked unit sheets
rather than of a sin le, large pericondensed ring system.
Brule (I6F)used 6 P C to qualitatively and quantitatively
characterize asphalt, asphaltenes, and maltenes. The results
provide an insight into the nature of associative rocesses
involving these materials. Hall and Herron ( 3 7 8 , after a
preliminary separation with pentane, subjected each fraction
from several crudes to a preparative gel permeation chro-
mato aphic technique. A comparison of the molecular size
distriEtion was made. The found that most Kuwait maltene
molecules were small enou to diffuse into the catalyst pores
but that a substantial num%er of Kuwait al haltene molecules
were too large. The effects of size distritution on thermal
visbreaking and hydroprocessing were also discussed.
Bockrath et al. (7F) characterized coal-derived asphaltenes
by acid-base fractionation followed by GPC. Chromatography
showed a broad distribution of molecular sizes in the solvent
fractions; oil and asphaltene fractions were clearly distin-
guished despite some overlap. Schwager et al. (77F) separated
and characterized synthoil asphaltenes by usin GPC and
roton NMR spectrometry. A curve was developecfwhich may
e! used to determine approximate molecular weights of coal
liquid products. Boduszynski ( I O F ) used GPC on straight
reduced and air blown asphalt to study the change in mo-
lecular size of asphalt components. He found that the for-
mation of low-solubilit asphaltene aggregates occurred by
hydrogen bonding a n i chemical reactions during the air
blowing.
Gas Chromatography. Gas chromatograph has been
r
used to analyze tar phenols, petroleum pitch vo atiles, and
native bitumens. Bermejo et al. ( 5 0 converted the tar phenols
to trimethylsilyl ethers before subjecting them to gas chro-
matography. No column gave complete resolution of the
phenol mixtures but nearly all were suitable for analysis of
industrial mixtures. Greinke and Lewis (34F) used a com-

bination of gas chromatography and UV and mass spectros-
copy to identify volatiles from petroleum pitches in the en-
vironment, Douglas and Grantham (25F) used fingerprint
chromatography to identify hydrocarbon constituents of bi-
tumens, fossil resins, and asphalts. The fingerprints could
be related to changing depositional environments.
Inverse as chromatography (IGC) was used by Boduszyn~ki
et al. (118to study the relation between asphalt group com-
position and the retention volume of standard substances.
Tokareva et. al. (93F) used IGC to study fractions from a
Russian petroleum which included the asphaltenes, oil-resi-
nous fractions, carbenes, and carboids separated from them.
The presented the coefficients of interaction of the sorbates
u s e l as standards and the analyzed fractions. Refractive
indexes of the standards are given. He also discussed the
differing behavior of the standards and low asphaltenes,
carbenes, and other heavier fractions.
Pyrolysis gas chromatography was performed by Ramljak
e t al. (73F) on bitumens. The characteristic ratio of light
unsaturated and saturated hydrocarbons in bitumen pyroly-
zate was used to determine the maltene and asphaltene
fractions. A furnace-type microreactor was used for the py-
rolysis. The authors believed that the results obtained by
pyrolysis for asphaltene content of bitumen gave a more ac-
curate analysis than the Institute of Petroleum method.
Dubonska et al. (29F) used pyrolytic gas chromatographic
techniques to determine minute quantities of bitumen in
geology and mineral processing. Kugucheva et al. (52F) re-
ported the gas chromatographic study of a heavy pyrolysis
tar.
Liquid Chromatography. Simple liquid chromatography
was used to separate acids from asphalts as reported by
Ramljak et al. (72F). An Athabascan bitumen was submitted
to liquid chromatography followed by gas chromatography
or spectroscopy (81F). The net result of this study was a
multitude of fractions. The alkane content of the maltenes
was low, the saturated fraction was about 90% polycyclic
compound, and the aromatic fraction contained alkyl-, na-
hthenyl-, and dinaphthenylbenzenes in a 1:1.7:1.3 ratio.
I;ruwafag and Neumann (6IF)separated a bitumen from the
Kirkuk field into alkanes, mono- and bicyclic aromatic, na-
phthenic aromatic, polycyclic aromatic, and heterocyclic
compounds. The last were separated by ion exchange into
acidic, basic, and neutral compounds. The alkanes were
separated with urea, thiourea, and activated charcoal into
fractions with varying degrees of branching. Vercier et al.
(94F) developed an analytical chromatographic scheme which
uses either a “slow” or “rapid” separation procedure to sep-
arate asphaltenes and resins. This scheme is presently used
to monitor a pilot operation for upgrading residua oils.
Schwa er and Yen (78F) separated and characterized coal-
derivecf asphaltenes by using a rapid chromatographic method.
The study further used ESR to determine the nature of the
association between asphaltene molecules and concluded that
if charge-transfer interactions are present, they appear not
to be significant as binding forces between the asphaltene
molecules or nuclei.
Selucky et al. @OF) used high-pressure liquid chromatog-
raphy (HPLC) to se arate Canadian asphalts. The results
showed that in Athagasca bitumen, strai ht chained hydro-
carbons and olefins are virtually absent; Eoaever, n-alkanes
are present in a Cold Lake bitumen fraction separated by
molecular sieve adduction under the same conditions. HPLC
techniques are particularly suitable for the study of the con-
version of residua and tar sands bitumen to useful products,
according to Drushell (27F). The results of this study are
compared with compositions determined b the large scale
clay-silica el separation technique. Dark aniMcGough (23F)
used HPL!! to study the characterization of asphalt fractions.
Their results were compared with analyses by GPC.
Miscellaneous Chromatographic Methods. Gimpelevich
and Ilina (33F) used paper chromatography to study the
aromatic components of bitumens and petroleum. The me-
thod was most effective when used in conjunction with the
spectroscopic identification of aromatic hydrocarbons, espe-
cially the method of quasilinear spectra.
Bodzek et al. (14F) used laser chromatography followed by
IR and high-resolution mass spectrometry to identify hete-
rocompounds present in asphaltenes from various products
of coal hydrogenation.
PETROLEUM
Boduszynski et al. (12F) used ion-exchange and adsorption
chromatography for the separation of maltenes. Acidic and
basic fractions were both concentrated in the polar aromatic
fraction as determined by adsorption chromatography. Ki-
selev’s @OF) research was continued with identifyin the acidic
d
and basic components in petroleum- and coal- erived as-
phaltenes using ion-exchange chromatography. The acidic
fractions had more complex chemical compositions and were
characterized by using high-resolution mass spectroscopy.
McKay et al. (57F) used an n-C6HI2asphaltene prepared from
a California crude, separating it into fraction of acids, bases,
neutral compounds, saturated and aromatic hydrocarbons
using ion-exchange, coordination, and adsorption chroma-
tography. The asphaltene is a complex mixture of the most
polar and highest molecular weight compounds of the crude
oil.
Kawahara (44F) used electron capture detection gas chro-
matography as a fingerprinting technique to identify trace
organic components in spilled asphalts.
Albau h and Query (IF) used exclusion chromatography
with muftiple detectors to follow com ositional changes of
B
petroleum residuals during catalytic esulfurization.
Selucky et al. (82F)conducted a detailed analysis on a Cold
Lake Alberta asphalt using series of chromatographic sepa-
rations followed by IR, UV, NMR, and mass spectrosco y.
The composition of Cold Lake bitumen closely resembled tht
of the Athabasca bitumen except that its asphaltene content
is somewhat lower and its acidic and saturated content is
sli htly hi her.
kalasz f36F) separated vacuum residues from a Kirkuk
petroleum using extrographic means. Bockrath et al. (SF)
characterized asphaltenes isolated from a coal-derived li uid
using sequential election by solvent chromatography (SEIC).
The characterization study was used to uncover the chemical
factors that influence analytical determinations.
NMR, ESR, EPR, AA, UV, IR, AND X-RAY
METHODS
Yamada et al. (96F)reported a comparison of various
structural analyses for pitch fractions using a combination of
NMR and X-ray diffraction methods and checked b a com-
puter technique. The results obtained by the comhnation
method were in good agreement with those obtained by the
computer method. This implies that both methods are
available for the structural analysis of such carbonaceous
materials as pitch and coal extracts. Bartuska et al. (4F)
developed a sophisticated NMR technique with the goal of
providing high-resolution NMR spectra on solids with direct
applications to bitumens.
Posadov et al. (7OF) used NMR, IR, and UV to study the
structure of petroleum asphaltenes. Highly substituted two-
and three-ring aromatics in naphthenic structure were prom-
inent.
Sebor et al. (79F) used NMR spectroscopy to characterize
an asphalt-resin fraction. The aromaticity increased from
maltenes to asphalt to asphaltenes with increasing fraction
molecular weights. Structural parameters for all fractions were
tabulated. Hajek et al. (35F)analyzed heavy crude oils using
Fourier transform NMR spectroscopy. They determined the
amounts of aromatic and aliphatic carbon in heavy crude oils
containing parama netic ions (e.g., ferric iron). These ions
have an effect simifar to the addition of a reducing reagent.
Kasahara (4IF) studied the structural deterioration of as-
phalt on hot storage using hi h-resolution Nh4R. Condensed
aromatic rings appeared to %e unaffected by hot storage in
the case of aromatics and resins but the ring number increased
from 7 to 11in the case of asphaltenes. Takegami et al. (89F)
conducted a structural investi ation of asphalts and their
fractions using proton and carlon-14 NMR spectrometry.
From relative intensities of the peaks.,the -ylene chain in these
samples was deduced to be longer (Le., n > 12) than re orted
previously. Dereppe et al. (24F) developed a methozusing
carbon and proton NMR spectroscopy to derive a series of
parameters of an “average molecule” which characterize
complex multicomponent organic mixtures such as asphaltenes
and heavy petroleum products. Pearson (67F),using wide line
NMR to determine proton types in coal tar and petroleum
pitches, reported that the second moment was a measure of
aromatic protons. High-temperature proton NMR was re-
ported by Yokono et al. (99F) on ethylene-tar pitch. Pyrolysis
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 97R
PETROLEUM
depolymerization and polycondensation can be monitored by
the high-temperature technique. Podobaeva et al. (69F) used
a Samotlor crude in their structure study of asphaltenes.
Asphaltene samples were analyzed by a variety of analytical
methods, NMR, gel ermeation chromatography, mass
spectroscopy, and E S 8. Structures for fragments of as-
phaltene molecules were proposed. The effect of asphaltenes
on the conversion of bitumens by hydropyrolysis was reported
by Bunger et al. The primary analytical method to charac-
terize the asphaltenes was NMR.
An electron spin resonance (ESR) study of free radicals in
Athabasca asphaltenes was performed by Niizuma et al. ( 6 3 0 .
It was concluded that the temperature dependence of the
absorption is due to stable polycycloaromatic doublet- and
triplet-state radicals. Fuiseth et al. (32F) reported an ESR
characterization of asphaltenes formed during the aging of
coal liquids. A mechanism involving condensation of small
heteroatom-rich molecules for insolubles and asphaltenes in
the presence of ox gen was proposed.
Chernova and Cgurkerashivli (21F) used an EPR method
for studying asphaltene structure fractions of petroleum as-
phaltenes separated with the more polar solvents having higher
contents of paramagnetic centers.
Ma and Presley (56F) studied the vanadium content of
asphak using flameless atomic absorption spectroscopy. The
method can also be used for metals other than those (e.g., Cr
and Hg) lost in ashing.
Felscher ( 3 0 performed a characterization study of aro-
matic bitumen fractions with a special application of UV
spectrometry. It was possible to calculate the contribution
of naphthenic compounds to the monocyclic fraction, as well
as the mean molecular weight of the fraction.
Infrared spectroscopy was used by Filimonova et al. (31F)
on the composition and structure studies of petroleum as-
phaltenes. The asphaltenes were 50-78% aliphatic. The
aromatic portion contained three to four benzenic rings.
Milatovic et al. (58F) analyzed bitumens from Iraq using IR
spectroscopy. Their correlation may be used for the paraffin
content determination in the bitumens. Kat0 et al. (43F)
compared several structural analysis methods on pitches
starting with IR. Structural modes of each sample were
proposed on the basis of struct,ural parameters obtained by
computer calculations. Rentrop ( 7 5 0 performed IR studies
on bitumens from several countries. His results showed the
proportions of C and H in each group. IR spectroscopy was
used by Speight and Moschopedis (86F)to study quinone-type
oxy en in petroleum asphaltenes and resins. Kaibara et al.
( 3 9 b have developed a rapid spectrophotometric method for
determining asphaltenes in residual oils.
Three papers usin X-ray techniques were published in
1979. Yen et al. ( 9 8 8 studied shale oil-derived asphaltenes
combining the results from X-ray diffraction, NMR, and IR
methods. Generally, shale oil as haltene consists of a heavily
substituted linked or kata-congnsed system; the system is
small, and the substituents have an average of two or three
carbons. Schwager and Yen (78F)separated and characterized
asphaltenes from five U S . coal liquefaction processes using
X-ray scattering and ESR techniques. The X-ray studies
suggested that about four condensed aromatic sheets were
stacked on top of each other with ali hatic chains or na-
phthenic rings along the edges. The EgR studies indicated
that charge transfer interactions were not significant binding
forces between the molecules at room tem erature. Kim and
Long (49F) characterized asphaltene coloids in heavy pe-
troleum residua and liquified coals by X-ray scattering.
Apparently the basic unit of the Job0 asphaltene colloids is
a macromolecule rather than an aggregate.
MISCELLANEOUS COMPOSITION STUDIES
Chemical Methods. A number of miscellaneous chemical
separation studies were reported. Patwardhan ( 6 5 0 con-
ducted a fractionation study using different organic liquids,
e. ., chlorinated hydrocarbons, alcohols, ketones, etc. Good
sefectivity was obtained only with hexane. In another article
Patwardhan (66F) described a chemical separation method
in which hexane in the amount of 5-20 times the sample
weight was used to separate the asphaltenes. Extension of
the method to industrial fractionation is discussed. Kam’-
yanov et al. ( 4 0 precipitated as haltenes with petroleum
ether and they then were ozonized: A variety of techniques
98R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
including IR, UV, and NMR were used. The S atoms were
located in the peripheral parts of the asphaltene molecules
in the cross-linkages between separated fragments. The N
atoms were concentrated in internal parts of the asphaltene
molecules.
Ramljak et al. (72F) developed a technique for separating
free fatty acids from asphalts. A solvent-rec cling chroma-
tographic column was used. Sergienko ( 8 3 4 presented an
overview of the structure of petroleum resins and asphaltenes
in various Russian crudes.
Plyusnin et al. (68F) reported a study using titanium tet-
rachloride fractionation of petroleum asphaltene-resins dis-
solved in benzene. The number of Tic& molecules required
to complex each asphaltene molecule varied from one to two
in the first to 20 in the last fractions. The recipitate fractions
differed little in composition and molec& weight was poor,
perhaps because the complexed molecules precipitate im-
mediately, before electron-accepting titanium chloride mol-
ecules can equilibrate over donor sites with different binding
energies.
Oelert and Neumann (64F) re orted a separation and
characterization study of very hig! boiling and nonvolatile
mineral oil products using an anion exchanger activated with
NaOH. Their study reported on the roles of the various
fractions in petroleum.
Steffgen et al. (88F)developed a technique which gives
reproducible results for the determination of asphaltenes in
fuels from coal hydrogenation. Data are presented for this
method in which a large excess of entane is added to a slurry
prepared from toluene solubles angtoluene. Smith et al. (84F)
studied asphaltenes and preasphaltenes se arated from H-coal
vacuum bottoms. The results indicated &at pre-asphaltenes
consisted of 30-35% of bases stronger than water but a sub-
stantial part of the nitrogen was in structures of lower basicity.
Sulfur concentration was higher in the acidic components than
in the basic or neutral. The pre-asphaltenes appeared to be
poorer in aliphatic substituents than the asphaltenes. Vymetal
and Kulhankova (95F)separated components of the quinal-
dine fraction from coal tar by treating with aqueous urea and
crystallizing out the clathrate. Rustamov et al. (76F) de-
veloped a quantitative method of determining of calcium salts
of aliphatic sulfuric acids of asphalt. The complexing with
titanium tetrachloride to certain synthetic polymers modeling
structural fragments of asphaltenes was reported by Kho-
khlova et al. (45F). The molar enthalpies of the quinaldine
interaction with coal-derived asphaltenes and heavy oils were
used to characterize coal-liquid fractions as discussed by
Tewari et al. (9OF). Calorimetric, NMR, and elemental
analysis data were obtained by Tewari and Li (91F) by h
drogenating a Kentucky coal under different process con&
tions.
Long ( 5 3 0 stated that recent studies of asphaltenes showed
that asphaltenes are composed mainly of polar aromatics with
appreciable content of naphthene aromatics and traces of
saturates. This information and solubility theory suggested
a new definition of asphaltenes in terms of a plot of polarity
vs. molecular wei ht. Speight and Moschopedis (86F) pres-
ented a critical c&cussion of structural and compositional
studies of asphaltenes. The paper indicates the correct method
for isolating asphaltene and also the limitations of spectro-
scopic, chemical, and X-ray methods of structural analysis.
Yen (97F) discussed the structural differences between pe-
troleum- and coal-derived asphaltenes.
Thermogravimetric Methods. de Camargo and Neu-
mann (20F) reported the results of compositional studies on
bitumens using thermogravimetric, differential thermoana-
lytic, and pyrolytic gas chromatographic means. The DTA
curves were characterized by continuously increasing vapor-
ization and decomposition endothermal effects. The volatility
of bitumens was determined by DTA and pyrolytic gas
chromatography.
Primak et al. ( 7 1 0 made a thermogravimetric study of the
oxidative polycondensation of vacuum residues. The plateau
on the resulting curves corresponded to the formation of
cross-linked thermostable structures.
Fluorescence and Photocolorimetric Methods. Jacob
(38F) through the use of fluorescence techniques obtained
information which affords positive identification of the type
of bitumen in rock inclusions. Klink (51F) first separated
hydrocarbon mixtures on a silica gel column using Color

Corrector 50, 1-butylpyrene, and Sudan 111. The saturated
hydrocarbons were eluted first, then the olefins (yellow-green
fluorescence), and then the aromatics (blue fluorescence).
Brule and Druon (17F) studied the effect of blending tem-
perature and rate of cooling on the morphology and physical
roperties of bitumen binders. The morphology was examined
Ey fluorescence microscopy.
Tirak'yan et al. ( 9 2 0 developed a method for determining
photocolorimetrically in benzene the composition of as-
phaltenes. They reported that analyses took about an hour
and the precision was good. Baranova ( 3 0 proposed a
qualitative and quantitative luminescence-bituminological
analysis, finding it most suitable for testing carbonaceous
substances in rocks. General principles and applications are
discussed.
Electron Microscope Methods. Donnet and Kennel (260
performed electron microscope studies on the morphology of
two bitumens, representing the sol and gel types. The as-
phaltenes in the sol bitumen formed well-organized isolated
agglomerates, whereas the asphaltenes of the second bitumen
appeared as a continuous, unstructured network. Constan-
tinides et al. (22F) found the structures of heptane-washed
asphalts were easier to observe when the asphalt had low
paraffin content, a high dispersion coefficient, and low mo-
lecular weight ratio of asphaltenes-resins. Kim and Long
(48F)reported that they could characterize a heavy residuum
by a small angle, X-ray scattering technique which showed
that the unit detected was either a basic molecule that did
not aggregate or that the aggregates did not break up in
solution. Scanning electron microscopy was applied to the
study of asphaltenes and their thermolysis products by Re-
bagay and Mori (740. The research indicated that tem-
peratures higher than 110 "C may be required for the elim-
ination of asphaltenes from coal liquids.
Several tar sands studies were reported. Myers (62F) in
a US. Patent has roposed a method to separate the bitumen
from the tar sandy! agitation of the tar sands with a mixture
of equal parts aqueous tannic acid and 29% aqueous NH40H.
The bitumen recovery rate increased with temperature and
the separation was completed at 90-90 O C . Anderson ( Z F ) ,
in another U.S. Patent, described a hydroseparation process
for the aqueous extraction of bitumen from tar sands.
Moschopedis et al. ( 6 0 described a flocculation technique
for obtaining water-soluble aliphatic acids from Canadian Oil
Sands. This first step was followed by extraction and me-
thylation. They found it was possible to remove clay from
sludge by flocculation. Bunger et al. (19F)performed com-
position and properties studies on both Utah and Athabasca
tar sand bitumens. Thev found that the bitumens differed
significantly.
Molecular Weight Studies. Moschopedis et al. (59F)used
vapor pressure osmometry to determine the molecular weights
of asphaltenes. The data are interpreted in terms of asso-
ciation of the asphaltene units in solvents of low dielectric
constants and dissociation in solvents of high dielectric con-
stant. Data derived from viscometry methods yielded in-
consistent results.
Moschopedis et al. ( 6 0 0 performed a study using cryoscopic
methods to determine the molecular weight of asphaltenes.
The results showed pronounced variations in molecular
weights dependent upon asphaltene concentration and solvent
type.
Speight and Moschopedis (85F) in a letter to the editor of
Fuel noted that for any one method, the observed molecular
weights indicated that the asphaltenes form molecular ag-
gregates even in dilute solution, and this association is in-
fluenced by solvent polarity, asphaltene concentrations, and
the temperature of the determination.
Kiet et al. (46F)re orted on the effect of molecular weight
R
and composition on t e glass transition temperature. Masek
(55F)studied the mean molecular weight of petroleum as-
phaltenes by a light scattering technique. The concentration
of colloidally dispersed components affected the behavior of
heavy fractions during hydrocracking.
ASPHALT RHEOLOGY
Marvillet ( 5 4 0 studied the influence of asphalt composition
on its rheological properties. From the analysis of the con-
stituent hydrocarbon groups, the soft asphaltene phase shows
Newtonian behavior, but the nonvolatile maltenes have a
PETROLEUM
complex behavior at low shear rates.
The viscosity of coal liquids correlated with their asphaltene
content, with the phenol content, and with the average mo-
lecular weight of the asphaltenes. The viscosity also depended
strongly on the intermolecular association of acidic and basic
subfractions, according to Bockrath and Schweighardt (SF).
ASPHALT PAVING
Kasahara (42F)studied the physical properties and dete-
rioration characteristics on asphalts recovered after serving
as pavements. Changes in physical properties and composition
during deterioration by the thin f
ib oven test and the rolling
thin film oven test were also reported.
CATALYSTS
1. P. Debies, C. L. Kibby, J. E. Lester, and L. A. Pedersen
Gulf Research & Development Co., Pittsburgh. Pennsylvania 15230
The impact of surface science instrumentation on catalyst
characterization and research is best exemplified by the ap-
pearance of reviews such as Somorjai's (153G) on the rela-
tionship of catalysis and surface science and that of Delgass
et al. on the use of modern spectroscopies in catalysis (40G).
The list of acronyms continues to grow with low-energy
electron diffraction (LEED),photoelectron spectroscopy ( W S
or ESCA), ion scattering spectroscopy (ISS), and Au er
electron spectrosco y (AES) appearing frequently in stu ies
of catalysts. Cata&tic systems gettin the most attention
d
d
continue to be the hydrotreating ca ysts containing pre-
dominantly Ni, Co, .Mot and/or W, Fischer-Tropsch catalysts,
and the perennially mteresting supported noble metal catalysts
including bimetallics. Because of the profusion of literature
in this area, this review can only sample the advances in
catalyst studies rather than give an exhaustive review.
Elemental Analysis. Sykora and Dubsky (160G)deter-
mined the Pt content of re-forming catalysts by decom osing
the catalyst at high pressure in a solution of HC1 a n 8 H 2 0 2
at 250 "C for >14 h and then precipitating Pt with 2-
mercaptobenzothiazole. To study the Pt-support interaction
in mono- and bimetallic reforming catalysts, Putanov et al.
(133G) treated the solids with acetylacetone for 6 h and de-
termined a Pt-A1203 complex colorimetrically. Zakharov et
al. determined Pt extracted from catalysts by amperometric
titration of Pt(I1) using 10 mM Cr207- in 6-8 M H2S04 as
the titrant and a rotating Pt electrode operated at +0.4 V vs.
SCE. Ir(II1) and Fe(I1) are the only group 8 metals which
interfere (180G). A technique employing spark-source mass
spectroscopy was used to determine Pt (0.37%)and impurities
such as Ti, Si, P, Cr, Mn, Na, and Mg (1ppm to 0.05%) in
Pt/y-alumina catalysts. The results agree with those found
by atomic absorption spectrometry (AAS), X-ray fluorescence
(XRF), or spectrophotometry (127G).
Bahr and Jedras reported that 0.1 to 1.0%Re in catalysts
with or without Pt could be determined by forming a stable
complex of Rerv and thoria which has t, at 390 nm in 4-6
N HC1 in the presence of excess SnC12 (78). In the presence
of Pt, absorbance was measured at 440 nm to avoid inter-
ference. AAS was used by Sychra et al. (159G)to determine
Re in re-forming catalysts. The effect of HC1, Al, and Pt in
the AAS determination with a N20-C2Hzflame were dis-
cussed.
Toei et al. (163G) have reported the use of 5-diethyl-
amino-2-nitrophenol as complexing reagent in acidic aqueous
solution or CHCl for colorimetric determination of Pd in
catalysts. In the choroform solution, most common elements
do not interfere at <1 mM except I, Br, PtIV,Zrrv. A gravi-
metric dimethylglyoxime method and differential spectro-
photometric I- and dimethylglyoxime methods have been
compared for 8.7% Pd. Marczenko and Ransza (104G)found
that the precision of the I- and the gravimetric methods are
almost equal and better than the spectro hotometric deter-
mination with dimethylglyoxime. Lebedko and Tsypylova
(9") determined P d in catalysts by a complexometric ti-
tration with Complexon 111, in the presence of tartaric acid,
NaF, and NaOAc at pH 1.2-2. The excess Complexon was
back-titrated with Bi(N03)3. Pd value was determined with
1.5% standard deviation for 1.0% Pd. An indirect polaro-
graphic method was used by Kala urna (81G) to determine
Pd in hydrogenation catalysts. Pawas chemically displaced
by Hg at the dropping-mercury electrode in KC1 solution. For
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 99R
PETROLEUM
a 106.3-ppm solution the standard deviation was 0.09 ppm.
Goryunova (67G) measured 0.001-0.01 % Pd on ZrOz using
arc spectroscopy by comparing the P d and Zr lines produced.
A rapid radioisotope-excited energy-dispersive X-ray
fluorescence method was applied by Labrecque (97G)to de-
termine with no apparent matrix effects 0.3% to 10% Pd in
catalysts. By using a "@mI' source, Pogrebnoi and co-workers
(125G)determined Ni and Pd in zeolites, Mo in Al-Co-Mo
catalysts, and Rh in complex catalysts by X-ray spectrometry.
Relative errors were 5 and 20% for determining 2-5 and
0.2-0.3 wt% of a metal, respectively.
Several authors have dealt with the measurement of P d and
P b on autoexhaust catalysts. Minochkina et al. (11OG) re-
ported methods for determining the elements by AAS. For
concentration profiles, they mechanically removed thin layers
of the catalyst which were fused with K2S207and then dis-
solved in aqua regia. They found Pb compounds in the upper
0.1 mm film of the active layer. Pd was separately extracted
with 0.01 M phenanthroline in CHCl and the 244.8-nm line
was used to determine 0.037479% P J a t a standard deviation
of 0.0005 to 0.4% with 0.117 to 7.9% Pb. Cairns and Cookson
(27G) submitted the catalysts to proton-induced X-ray
emission (PIXE) which monitors all the elements including
impurities within the first few microns of the surface. The
technique was used in the development of a new series of
catalysts bonded to oxidation-resistant Al-containing steel.
Potter (129G) used AAS to determine Rh in Rh-Pt loaded
automotive catalyst material. The sample was digested in
H 0, H.#04, and HC1 mixture at 100 OC for 72 h. The diluted
sojutions were atomized in a graphite furnace for 9 s a t 2500
"C and analyzed a t 343.5 nm with a deuterium background
correction. Peak areas or heights could be used depending
on whether Pt was present or not. Pierre et al. (124G) used
various polarographic techniques and linear-sweep voltometry
to examine Rh"' from catalysts in 1 M KSCN. Differential
pulse polarography was favorable for Rh to 1 FM in the
presence of Pt and Pd, but not Ru".
Traces of V in catalysts were analyzed by Buenafama and
Lubkowitz (20G) using neutron activation. Sam les con-
taining Mo, Co, and small amounts of Fe, Si, S, ancfNa were
dissolved in H2S04 and 40% HF; Mo was removed by ion
exchange; and this solution was extracted with 0.02 M N -
phenylbenzohydroxamic acid in isobutyl methyl ketone. The
organic phase was irradiated 5-10 min in a thermal neutron
flux N loi2 n cm-2 s-l. NaI(T1) crystals detected the 52Vac-
tivity down to 5 ng. Bocharova and Malakhov (13G) deter-
mined VIv in Mo-V oxide catalysts by the V02+absorbance
at 770 nm in 3.5 M H2S04. For 40 mg V"/L a 10-fold excess
of Vv or Mom did not interfere a t a precision of 5%. Sembaev
et al. (244G) determined 0.5-80% V20 in catalysts containing
TiOz, V02, and Vz03by use of the IR Land at 1022 cm-' with
a precision of -3%. Astapova et al. (4G) used gas chroma-
tography to determine Cr in catalysts for CO conversion. The
dissolved sample was brought to pH 5 and extracted with
acetylacetone to remove Al, Zn, and Cu also in the catalyst.
After further treatment the Cr-acetylacetone complex was
extracted with toluene and analyzed by GLC. The limit of
detection was 1pg of Cr. Gimidzade et al. (62G)report a rapid
method for determining Mn in aluminosilicate catalysts using
carbonate melt fusion and iodate oxidation. Mn was deter-
mined at 528 nm b a calibration graph or the standard ad-
dition technique. &her components in the catalyst did not
interfere. Garnish and Fazul'zhanova (61G) ive a complex-
iometric titration method to determine Co in C!oNaY catalysts
used for toluene disproportionation. The relative error is 1 4 %
for determining 4-870 Co. EDTA complexes of Ni and Co
from hydrodesulfurization catalysts were analyzed spectro-
photometrically by Fernandez et al. (54G). They found that,
in catalysts with moderate Ni and -0.05% Co content, 0.05
mg of Co can be determined in the presence of 60 times as
much Ni with a standard deviation of 10% if adequate reagent
blanks containing Ni were used. The metals in alumina-
supported CoMo catalysts can be successfully analyzed by
X-ray fluorescence if the matrix correction equations of Hulett
and co-workers (71G) are employed with low background data
from a spectrophotometer using A K a excitation and a py-
rolytic-graphite monochromator. khaudhuri and Sen (29G)
applied an ion-exchange technique to quantitatively separate
Cu, Fe, and Zn in a low-temperature carbon monoxide con-
version catalyst; each was titrated with EDTA. This method
lOOR ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
was found to be quicker than conventional methods. AAS has
been used to analyze catalysts consisting of Cu, Cr, or Ni (10
to 40% each) as the oxide or hydroxide on silica. An acety-
lene-N20 flame was used to measure Si and Cr and air-C2H2
for Cu and Ni on silica. Coefficient of variation was -1%
for each component, (79G). Conesa Cegurra and Sorina Ruiz
(32G) report an electron spin resonance method for nonde-
structive determination of paramagnetic species; e.g., Cu(II),
on y-alumina or zeolites. Using double integration of the
spectra, results agreeing with chemical analysis were obtained
for 0.7-2.6% Cu catalysts.
Kirkbright and Taddia (90G)discuss the use of masking
agents to minimize interferences from Cu, Ni, Pd, and Pt in
the determination of As by AAS. Chlorine in catalysts was
determined by Mansour et al. using energy dispersive X-ray
fluorescence (103G). Markova et al. determined Ca in AI/
Ni/Ca catalysts by persulfate fusion followed b spectro-
photometric determination of the Ca-arsenazo complex P
v
(105G). Furmins gives a method for determinin extractable
and nonextractab e coke on catalysts (56G). Che%otarev and
Tkachev report a method for determining free and bound
water in catalysts which takes 1 h compared to the 3-5 h
required by the standard method (30G).
Structural Analysis. The section on structural analysis
deal with the use of analytical techniques to determine specific
bulk structure characteristics of different kinds of catalysts.
Srivastava et al. (157G) made thermomagnetic studies on
steam-naphtha re-forming catalyst with variations in com-
position and methods of preparation. Activity and ther-
mostability were related to the formation in situ of a well-
dispersed solid solution of Ni and Fe. Re-forming catalysts
with 0.5% Pt and 1% Gd on alumina have been studied by
ESR after each stage of preparation by Potapovich et al. The
Gd ap ears to exchange with some of the alumina hydroxyls
i n i t i d , penetrate into the support lattice durin calcination,
and interact with chloroplatinic species when the bt was added
(128G). Pt clusters on Y-zeolite cages have been probed by
X-ray absorption spectroscopy in Boudart's laboratory (60G).
A shift in the LIII edge position to higher energy and an
increase in the spectral area indicated that the Pt had become
more electron deficient. This occured when the clusters were
in the supercage, when the clusters were covered with 0, or
when multivalent cations were introduced into the zeolite. Via
and co-workers ap lied EXAFS to highly dispersed metal
81
catalysts (171G). usters of sup orted Os, Ir, and Pt were
found to have a lower average coorkation and higher thermal
disorder. Magnetic susceptibility and ESR studies were made
.to elucidate the formation and concentration of metallic Ni
in Ni/W on A1203, SO2-A1203,and B203-A1203hydrocrackin
catalysts (150G). The extent of formation of metallic Id!
depended on the support (A > SA > BA) and whether sulfur
was present. Unmuth et al. used Mossbauer spectroscopy and
XRD to characterize Fe/Ni/SiO Fischer-Tropsch catalysts
before and after reduction (1676).
ESR and thermal techniques have been used to ascertain
the structure of chromium oxides supported on alumina.
Segawa, Ishii, and Ueda (142G) studied the ESR spectra of
the oxidized and reduced catalyst combined with the activity
for dehydrogenation of isopentane and the adsorption of ox-
ygen to understand the role of oxygen-deficient sites in the
activity. They found penta- and trivalent Cr in the spectra
of the oxidized material but no pentavalent species after
reduction.
An IR spectroscopic method was used by Vorob'ev et al.
(172G) to observe that octahedrally coordinated Mo with Cb
symmetry formed along with the AI (MOO& phase of Mo on
alumina materials. Using diffuse redectance, they studied the
effect of calcination temperature on the structure of the
Mo-A1-0 system. The catal st showed a series of Mo" and
Mom structures where Movi? was identified by the charge
r
transfer band of 02-to Mas+. The catal t contained Mo tetra-
or hexacoordinated to 0 with C4 or 3" symmetry. Csuwas
assigned to A1 (MOOq)g (173G). +he structure ?f the oxidic
precursor of C?oMo/alumina hydrodesulfurization catalysts
has been the subject of study using a variety of techni ues
Apecetche and Delmon combined diffuse reflectance a n d b S
to look a t the formation of CoA1204at the expense of the
CoMo bilayer depending on calcination temperature (3G).
DeBeer and his co-workers (107G) applied laser Raman
spectroscopy to get structural information for a series of CO

and/or Mo catalysts with different degree of surface coverage.
Mo alone exhibited four species depending on loading, while
Co appeared as Co O4 and CoAlz04. Co with Mo had free
Moo3, CoMoO,, and C0Alz04structures. Erofeev et al. (5IG)
applied thermogravimetry, IR and XRD to a A1203-Co0-
Moo3 catalyst before and after sulfiding. Signifcant structural
changes were observed after sulfiding. Vanadium on spent
Co-Mo/y-Alz03 catalyst was studied by NMR and ESR
techniques. The appearance of the three forms of V was
inde endent of feed and the catalyst support type but de-
p e n g n t on the V concentration. At low levels, V02+ was
observed. As the level increased, a diamagnetic amorphous
phase was eventually dominated by VzS3-like species when
V was greater than 10 wt % (147G).
Diffuse reflectance was applied by Khasanov et al. (88G)
to Ni0-Al2O3 catalysts prepared by different methods to
determine the Ni2+and Ni3 ratio as a function of method
of preparation. Ni0-AIzO3 and NiO-SiOz methanation cat-
a1 sts were examined with IR by Bradley and Stencel (17G).
Txe spectral characteristics of the Si02 were similar to those
of linear chain silicates while the alumina spectra corresponded
to amorphous materials. Residual Coz- from the reparation
was detected. DTA of sulfided Al-Ni-Mo h y k o enation
catalysts by Irisova et al. revealed S, MoSz, MoS3, h i s , and
Ni3S4 (73G).
The structural characteristics of unsupported catalysts with
Mo have been determined by XRD, IR, ESR, reflectance, and
other techniques. Infrared emission was used by Ueno and
Bennett (166G) to study unsupported Moo3 repared b a
novel method. Binary oxide systems with Ti, &, Fe, Co, n,
or In combined with Mo at varying ratios have been studied
B for estimating catalyst crystallite sizes. A general expression
with XRD, IR, and electrical conductivity. Defect structures
assigned to solid solutions with Moo3 were observed for the
transition elements and Sn but not for In (IG, 82G). ESR
si nals were studied for V-Mo catalysts calcined in air a t 50
"8 by Sel tin et al. (143G). Two signals were associated with
f
a solid so ution of Moo3 in V 05 and V02+in V Mo08. Isaev
and Spiridonov (74G) used IR, UV, EPR, and XRD to de-
termine the coordination and oxidation states of ions in CoMo
catalysts with Mg, Bi, Fe, Ni, Cr, or Mn in some ro ortion.
A coprecipitated Ni-Mo-0 system was examinedgy ganders
by high-resolution electron microscopy before and after sul-
fiding. Crystal size, shape, and composition and support
structure were determined. Especially interestin was the
observation that the MoS, was either in a highly fispersed,
distorted form of MoSz sheets, or a coating on MoOz or Ni
sulfide crystals (140G).
A Co-V binary oxide with V/Co = 1was studied by XRD
and thermal analysis after calcination temperatures from 300
to 800 "C. As the temperature was raised, first C0304and V2OS
were the main components, then a t 600 "C a mixture of va-
nadates with Co3V207as the main component were noted
(102G). Kadenatsi et al. made UV and IR spectral studies
of Co-Cr systems used for deep oxidation of hydrocarbons.
Lattice parameters reflected the change in the ionic character
of Cr-0 compared to Co-0. Dilution of Co2+with Cr3+in-
creased the ionic nature of Co-0 while Co2+added to Cr3+
decreased that of Cr-0 bonds (80G). IR was used to study
the NiO/Cr203/M A1204catalyst system for S-resistant me-
thanation catalysts &fore and after pretreatment and reaction.
The structure of the oxide was described as NiO and MgO
dispersed in a quasi-tridimensional Cr-0-A1 network. Re-
duction and sulfidin reordered the network, altered AlO,
coordination, and reluced CrV1to Cr"' and Cr". Sulfur a
eared to be coordinated with Ni-Cr or Ni-Mg sites (1584;
!'he physicochemical properties of Bi-W-oxide catalysts were
determined with DTA, IR and XRD. Dehydration and phase
transitions were observed for binaries like Bi2(W04j3,BizW06,
and Bi WOlz. The latter compound contained high acidity
W-0-8 sites (<810 cm-') which are responsible for deep
oxidation of hydrocarbons. Partial oxidation and oxidative
ammonolysis of 1-butene and propylene occurred most readily
on a low-temperature phase of BizWOs (149G).
Lewis (IOOG)has reported that powder XRD with Cu K a
may indicate a lower zeolite content in synthetic zeolites than
is real. Loss in radiation yield can be avoided by reducing
the catalyst particle size so that each particle transmits the
X-ray intensity or b using a source like Mo K, with more
enetrating power. 8oexchanged zeolites (A, X, and Y)have
L n studied by XRD and ESR. During reduction the metallic
PETROLEUM
Co, unlike Ni, stayed e. Crystallinity and
unit cell parameters
ment in oxidation-reduction
changed single-crystal zeolites, Hass and Plath (696) studied
the transmission spectra with a microscope-spectro hotom-
B
eter. The studies were related to catalytic activlty an Ni sites
in zeolites. According to EPR work by Gull ev et al. (68G)
k
addition of dealuminated zeolite Y to an Al- o-Ni catalyst
produced more MoVand a t least two different Mo"' species
on the surface. Also, Ni reduction to the metal was faster and
occurred a t lower temperatures when zeolite was present.
Surface Composition. Brinen (19G) applied X-ray pho-
toelectron spectroscopy (XPS) to several catalyst problems
including: the surface chemistry of active HDS catalysts,
detection of promoter gradients, catalyst deactivation, poi-
soning and metals dis ersion. The applicability of Auger
electron spectroscopy &ES) and XPS to industrial catalyst
problem solving was reviewed by Bhasin (IIG). AES was
employed to study lead poisoning of a cop er catalyst and iron
B
poisoning of a palladium on alumina hy rogenation catalyst.
Scannin Auger (SAM) was employed to clarify the role of
coke in h D S catalyst deactivation.
The application of the surface spectrosco ics to quantitative
K
analysis is a sign of maturation of the tec niques. Kerkhof
and Mouijn (83G)proposed an XPS method for uantitative
2
analysis of supported catalysts. In general, goo agreement
was found between predicted and measured intensities. The
method was demonstrated for the RezO /A1203,Pt/Si02, and
fluorinated alumina systems. A m e t h d was outlined as well
relating the observed XPS intensity ratio of the dispersed
phase to the support with the size of the dispersed particles
has been derived by Fung (55G). Particle shape dictates the
functional relationship which exists between the observed
signal and particle size. Relationships have been derived for
cubic, spherical, and hemispherical particles. The expression
was used successfull to describe the sintering behavior of a
Pt/SiOz Hz reduceicatalyst. Delannay et al. (38G) have
employed analytical electron microscopy (AEM) to critically
assess the meaningfulness of metal dispersion measurements
by XPS. In the case where inhomo eneous repartition of the
active species occurs, the use of X h S intensities to monitor
dispersion becomes questionable. The authors combined
AEM and XPS to avoid misinterpretation of the XPS data.
Model HDS systems were studied during the review period
in a number of laboratories using several techniques. Jezio-
rowski and Knozinger (78G) combined Raman and UV
spectroscopies to study the interaction of 1, 3, and 8% mo-
lybdenum with y-and 7-alumina. The supports were im-
pregnated with (NH4)6M07024 a t H 6 or 11, a t which pHs
molybdenum is in the octahedral M8,0a" form or tetrahedral
MOO^^- form, respectively. The spectra indicated adsorption
occurred via the MOO z- ion. Removal of water during drying
and calcination cause%polymerization of the tetrahedral Mo
s ecies into a two-dimensional Mo-0-Mo structure. The
2 egree of polymerization is a function of molybdenum con-
centration, heat treatment, and pH. Laser Raman s ec-
troscopy was applied by Cheng and Schrader (3IG) to cEar-
acterize the formation of supported cobalt molybdate by the
dry impregnation technique. Loading levels, order of im-
pregnation, pH, and calcination conditions were monitored
during the study. Dried samples contained aggregated, dis-
torted Mo s ecies. Calcination led to Moo3 formation a t high
loadings. lddition of cobalt resulted in the formation of
CuMoO4 which su pressed formation of Moo3 until higher
loadings were reacied. The order of impre nation affected
the concentration of surface molybdates ancfthe aggregation
of surface species.
Bancroft and Hardin (8G) reported the results of a quan-
titative XPS analysis of 18 HDS catalysts. Unsatisfactory
a eement between X P S and bulk chemical composition was
ogerved for several commercial catalysts. This was attributed
to variation in preparative methods for commercial and model
laboratory catalysts. Petrakis et al. (122G) combined ESR
and XPS to examine the surface composition of calcined
evacuated and reduced 9% molybdenum on 7-alumina. MoJ
was not detected before calcination, but it was found after-
ward. For calcined and evacuated material, the MoV con-
centration decreased with increased length of treatment, but
it remained constant for reduced catalysts. XPS did not detect
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 101R
PETROLEUM
compositional variations caused by length of calcination or
evacuation but did find large composition changes between
reduced and oxidized/evacuated sam les. An experimental
method and theoretical model were &scribed by Bouwman
and Toneman (16G) for the determination of radical con-
centration profiles in spent HDS catalyst pellets by AES.
Ga'ardo et al. (57G) described an apparatus for inert transfer
of LDS catalysts from a reactor to an ESR or XPS spec-
trometer. The same authors (58G) combined XPS and diffuse
reflectance spectroscopy with previously reported AEM results
(39G)to demonstrate that molybdenum occurs on 7-A1203as
tetrahedral oxidic Mow and as MoV1in multilayers having a
bulklike MOO, or paramolybdate surrounding. Cobalt (15%)
alone on y-Al,03 was poorly dispersed and present as Co304.
Mo and Co together displayed a synergistic effect which re-
sulted in improved dispersion for both elements. As a result
of the increased dispersion CoAlzO was formed. The results
were explained in terms of a mo%el in which a bilayer of
Co-Mo is formed or CoAlz04. These same authors (59G)
characterized a Co-Mo-SiO, catalyst. They found Moo3
interacts with silica as a paramolybdate and that CoMo04 is
formed. Excess cobalt is present as Co304. Cobalt was be-
lieved to catalyze the reduction of molybdenum. Delvaux et
al. (42G) correlated the composition of a sulfided Co-Mo
catalyst with activity for hydrogenolysis, hydro enation, and
isomerization reactions. Two concentration c! omains were
found. For low Co concentrations an increase in the XPS MO
and S binding energies was observed. For concentrations
where the catalyst exhibited a strong synergy for hydrogen-
olysis and isomerization, the binding energies decreased.
Sulfur content was maximum a t this point. The formation
of a reduced species between Mo(1V) and Mo(II1) was pos-
tulated.
ESR was utilized by Khulbe et al. (89G) to determine the
concentration of electron-accepting centers in a Mo03-A1203
model HDN system. The concentration of electron acceptors
increased linearly with Moo3 concentration up to 18 wt 74
but decreased thereafter. A strong MOW)signal was observed.
Oxygen species were detected when a degassed sample was
treated with 0 or air. A mechanism was proposed to account
for formation of 02-species and the observed reversible be-
havior of 0. The concentration of electron-accepting centers
was correlated with HDN activity.
Sup orted nickel catalysts have been examined recently by
P
severa groups. Wu and Hercules (178G) combined ion
scattering spectroscopy (ISS) and XPS to characterize im-
pregnated nickel on y-alumina and silica catalysts. Nickel
showed little interaction with Si02but strong interaction with
Ali03after calcination. Unreduced Ni SiO, contained NiO.
d
At low nickel concentrations on 7 4 2 3, two forms of nickel
which interact with the su port are present. At high nickel
content a third species, Ni6, is present on alumina. Shalvoy
et al. (145G) also studied the silica-supported nickel s stem
but detected nickel silicate as well as nickel oxide. 'hickei
antigorite and nickel-supported catalysts have been charac-
terized by Vedrine et al. (170G). Materials characterized
included a lamellar clay of nickel antigorite and Ni(OHI3
impregnated on various supports. XPS showed the ease of
- -
hydrogen reduction decreased as follows: no support > TiOz
> SiO, AlzO -SiOz A1203> MgO. The Ni(OH), catalyst
showed the higkest binding energy and it was found that the
stronger the interaction of NiO with a support the closer the
energy levels came to Ni(OH)> This result was explained in
terms of modification of the electronic properties of NiO rather
than compound formation.
XPS and secondary ion mass spectrometry (SIMS) were
utilized by Ott et al. (119G) to study Fischer-Tropsch syn-
thesis over reduced Fe-Ru alloys. Both techni ues showed
1
surface enrichment of iron. The 97 Ru 3 Fe a?loy had un-
usually hi h Cz yield with selectivity to et ylene. This surface
containef50% Fe and its catalytic activity differed greatly
from middle alloys whose surface was 8040% Fe. Bonze1 and
Krebs (14G)identified the carbonaceous deposits on Fe (110)
after CO hydrogenation at atmospheric pressure. AES and
XPS distinguished three hases: a CH phase, a carbidic
hydrogen phase, and a graphic carbon. f i e CH, and carbide
were active for hydrogenation; whereas the graphitic carbon
was inactive.
Kerkhof et al. (84G) found by laser Raman spectroscopy
that rhenium on alumina is present as a tetrahedrally coor-
102R ANALYTICAL CHEMISTRY, VOL. 53, NO.5, APRIL 1981
dinated ReOi ion which is distorted by the carrier or hydroxyl
teraction occurs which results in electron density transfer from
rhenium metal to the alumina; whereas the spectra of Re/SiOz
resembled those of the metal. Reduction of Re A1 O3 at
200-300 "C was more difficult than that of ,,/Si$
resulted in reduction of some Re(VI1) to a lower oxi ation
and
state.
Parks et al. (120G) used XRD and XES to determine the
passivation mechanism of Phillips' Ni-Sb fluidized cracking
catalyst. In the catalyst, an Ni-Sb alloy forms in which an-
timony segregates to the surface and poisons neighborin
nickel atoms for h drogen chemisorption. Nickel is oisoned
by geometric blocling of sites and by alteration of erectronic
properties. The tin antimony mixed oxide oxidation catalyst
system was reported on by two groups. Cross and Pyke (34G)
combined XPS and XRD to characterize catalysts containing
0-100% tin calcined a t 300-1000 "C. Above 4 a/o (atomic
percent) antimony enrichment was observed. Catalysts con-
taining up to 60 a/o antimony showed increasing surface
enrichment with increasing calcination temperature up to lo00
"C where a surface concentration maximum occurred. Further
work suggested that =25 a/o Sb constitutes a critical surface
composition of volatile Sbz04. Arrhenius plots for the tem-
perature dependence of the equilibrium surface composition
were developed and heats of segregation derived. Roudeville
et al. (15G) used XPS to study the system for oxides con-
taining 1.5-39.7 a/o Sb calcined at 500-1100 "C. The authors
correlated catal ic activity for propylene oxidation and se-
f
lectivity for acro ein production with surface composition. The
data suggested the selective catalyst consists of an Sbz04phase
lying on a solid solution of antimony(V) in tin oxide.
Copper aluminate catalysts, for oxidation and alkane deh-
ydrogenation reactions, were studied by Ertl et al. (52G).
Copper enrichment, relative to bulk CuA1204,was observed
by XPS. A NiO promoter enhanced cop er enrichment.
el
Reduction in CO and H, at 500 "C leads to r uction of copper
but only artial reduction of NiO. Prereduced catalysts were
oxidizedy! NO or 0, at 200 "C. The original spinel structure
can be re-formed under mild conditions. This is due to the
small and highly reactive particles formed durin the redox
cycle. The low oxidation state of copper seems to %eessential
to catalytic activity. Schreifels et al. (141G) employed XPS
to characterize a series of cop er chromite catalysts. The
precalcined catalyst containel Cu(OH), and CuO. After
calcination a t 500 "C only CuO was found. In the absence
of a promoter, chrome was detected as Cr(II1) and Cr(V1). A
BaO promoter stabilized Cr(V1). The transition-metal oxi-
dation states proved to be a function of the length and tem-
perature of calcination.
Ponec (126G) has discussed the use of AES and thermal
desorption to characterize catalytic alloy surfaces. The cat-
alytic systems discussed are Pt-Pd, Pd-Ni, Pt-Au, and Ni-Cu.
Catalytic data together with surface composition data for the
Ni-Cu alloys allowed the author to draw general conclusions
with regard to the classification of catalytic reaction and
identification of factors res onsible for catalytic activity.
Rasser et al. (135G) used AE8to gain insight into the factors
involved in the enhancin action of iridium in Pt + Ir/y-AliOs
re-forming catalysts. A%S was em loyed to determine the
P
surface composition of various Pt- r alloys before and after
contact with alkanes. The influence of the Ir/Pt ratio was
determined for isomerization, cyclization, and aromatization
selectivities. In the alloys a strong Pt surface enrichment was
observed. Iridium appears to function as a carbide sup-
pressant.
Exchanged Y-Zeolite catalysts continue to be of interest.
Pedersen and Lunsford (121G)studied ruthenium in Zeolite-Y
by XPS after exposure to oxidizing and reducing environ-
ments. Ruthenium remained in the zeolite cavities after Hz
reduction or methanation as long as 0 was excluded. At
elevated temperatures the presence of 6, resulted in RUOZ
formation on the external zeolite surface. Okamoto et al.
(117G) found Rh(1) in Zeolite-Y was active for hydrogenation
and the dimerization of ethylene; whereas the metal was active
for hydrogenation of acetylene and ethylene. Rh in the zeolites
showed considerable migration, clustering, and sintering
during the activation process.

Sorption, H drogen chemisorption remains one of the
most widely useBand generally applicable measures of metal
surface area, but more situations have been found where it
is low after hi h temperature reductions. Vannice and Garten
(169C) and J a i s t n e r et al. (162G) have found that metals
supported on slightly reducible oxides such as T i 0 2 exhibit
a "stron metal-support interaction" (SMSI) when reduced
a t 500"6 (considerably higher temperatures are needed to
observe such effects on alumina supported metals).
With large uncertainties present in most methods of
characterizing supported metals, and growing interest in bi-
metallic catalysts, more than one method is usually required
to define the metal surfaces. Considerable work is being done
to compare various techniques; as always, the metal studied
most extensively is platinum. Increased hydrogen uptakes
with successive cycles, in pulsed H-O titrations on su ported
latinum, was attributed by Prasad et al. (130Gr to H
beeding from the carrier gas purification towers. They noted
(131G) that the ratio of hydrogen chemisor tion to oxygen
chemisorption to H-0 titration was 1:1:3, ingpendent of the
mean Pt crystallite size, if the hydrogen and oxygen chemi-
sorption values were obtained from hydrogen and oxy en
titers. Carballo et al. (24G) also noted that reproducibiyity
in hydrogen chemisorption on Pt/y-A1203by a flow technique
depended on thorough degassing of the catalyst with ultrapure
argon. Comparing pulsed hydrogen sorption, oxygen sorption,
H-0 titration, and 0-H titration on Pt/Al203 and Pt/Si02,
Castello (26G) concluded that H-0 titration was the most
accurate. Racaud et al. (6G) found volumetric oxygen (O/Pt
= 1) or carbon monoxide (CO/Pt = 1) chemisorption to be
most exact for supported platinum if the catalyst is not
thermally sensitive.
Turkevich et al. (165G)found good agreement between CS2
pulse poisoning and H2-02 titrations, at low metal concen-
trations, in determinin dispersions of Pt/A1203 catalysts if
a stoichiometry of S/%t = 1 was assumed. Ducarme and
Vedrine (44G) used isotopic exchange of ox gen from carbon
B
dioxide to characterize Pt/Si02 and Pt/A12 3; agreement was
satisfactory with dispersions from H-O titrations and electron
microscopy. Comparing hydrogen chemisorption and X-ray
diffraction results for platinum in zeolites, Martynyk et al.
(106G) estimated the ratio of surface Pt to Pt inside the zeolite
lattice. Burwell et al. (22G) used both hydrogen chemisorption
and X-ray diffraction line shape analysis to characterize
platinum and palladium on silica and alumina. Dispersions
could be altered over a wide range by changing the drying
calcination procedure prior to reduction. Buyonova et a l
(23G) found good agreement between hydr en chemisorption
and oxygen chemisorption on supported ir#ium. They found
thermal desorption more rapid and sensitive than static or
pulse methods. Richardson and Crump (137G) measured
nickel size distributions on silica with a magnetic granulometry
method. Narrow distributions obtained initially were
broadened by thermal treatments. Formation of a log-normal
shape above 450 "C, independent of initial distribution, was
interpreted as due to article migration. Bimodal distributions
were found a t 600 O 8 , suggesting that the support pore size
distribution affects the metal crystallite sizes.
Zakumbaeva et al. (181G) reported that increasing dis-
persion of ruthenium black increased the heat of hydrogen
adsorption. Kubicka and Kuznicka (95G) found agreement
between hydrogen adsorption, oxygen adsor tion, and H-0
titration on Ru/A12i03after correcting for aiorption on the
support. Koopman et al. (94G) found that high-temperature
treatment of RuCl3-impregnated silica with NH3 was su erior
to calcination as a pretreatment to prevent sintering &ring
reduction. Fagherazzi et al. (53G) used small-angle X-ray
scattering (SAXS),wide-angle X-ray scattering analysis of line
broadening (WAXS), and electron microscopy to study ru-
thenium, gold, or palladium on MgO, Si02, and charcoal.
SAXS data were not generally in accord with chemisorption
values for metal dispersion but gave ood values for the
support particle sizes. When SAXS can%, correctly applied,
it agrees with the other techniques and gives the metal particle
size distribution as well as average size.
Several bimetallic catalysts, with Pt as one component, have
been studied. Sinfelt and Via (14%') measured h drogen
chemisorption and X-ray diffraction lines of PtIr 2 o on
i !$ v d
A1203. Alumina gave higher dispersions. On silica, an in-
termediate line position indicates formation of PtIr clusters.
PETROLEUM
Tournayan et al. (164G) used H-0 titrations to characterize
PtIr and PtRe on y-A1203,taking advantage of reducibility
differences for oxygen on Pt vs. oxygen on Ir or Re, and
selective hydrogen sorption on Pt in the PtRe catalysts. They
found homogeneous compositions of the metal crystallites
easier to obtain in the PtRe system. Charcosset et al. (28G)
also measured CO sorption on PtRe/A1203 b IR. The extent
of alloying depended strongly on details o f trle pretreatment,
especially drying prior to reduction; they concluded that the
state of PtRe in industrial catalysts cannot be inferred from
data obtained from laboratory scale preparations. Dominguez
(43G) and Renouprez et al. (136G) used XRD, SAXS, and
X P S , magnetic measurements, and adsorption of CO, H2, and
O2 to characterize PtNi/A1203 catalysts. Oxygen sor tion
differed from hydrogen and carbon monoxide, especiaYly a t
23% Pt where neopentane isomerization activity begins
(isomerization/hydrogenolysis selectivity varies from 0 to 1
as Pt increases from 23% to 100%). Both bulk and surface
of the PtNi were homogeneous. Isomerization activity was
maximum at P w i composition, hydrogenation at P t l d i
Kharson et al. (86G) found a shift of the IR band of linearg
bound CO to lower frequencies as P b content increased in
PtPb/Si02 catalysts. A similar study of PtPd/A1203by Ouiroz
et al. (134G) also showed a shift to lower frequencies of the
IR band for linear Pt-CO and a shift to higher frequency of
the Pd-CO band with increasing Pd. These data sug est
electron donation to Pt in the PtPb and PtPd bimetalkcs.
Corro et al. (33G)investigated carbon monoxide chemisor -
tion, oxygen chemisorption, and H-O titrations on PtCo A12&
catalysts. Selective dispersion values could be obtainef; since
Co could not be titrated with oxygen while Pt could be ti-
trated. Homogeneous clusters were indicated at low Co levels
(0.1% Co, 0.9% Pt). Selective adsorption of CO on Pt and
NO on Ru, measured by IR, has been used by Gonzalez and
Ramamoorthy (66G) to distin uish exposed Pt and Ru on
PtRu/Si02 catalysts. They $0 found the CO stretching
frequency on Pt to decrease as the concentration of Ru in-
creased. A Pt&ulo composition dissociated CO at low tem-
perature. Many data are being gathered on chemisorption
using ultra-high-vacuum systems and single crystals. Somorjai
and co-workers have tabulated the surface structures of ad-
sorbed gases on solids, determined by low-ener electron
diffraction (154G),and heats of chemisorption of
N2, and C02 on metals (155G).
Ez, 02,CO,
Characterization of supported metal oxides is receiving more
attention. Weller et al. (176G) reported that oxygen chem-
isorption, to determine areas of molybdena on alumina, is more
accurate at -78 "C than a t -195 "C since the correction for
physisorbed oxygen is much smaller. Vyskocil et al. (174G)
reported a pulse method to determine oxygen chemisorption
on Co-Mo-Al203 catalysts and compared it to hydrogenation
and hydrodesulfurization activity. Lombardo, Lo Jacano, and
Hall ( I O I G ) measured the effects of poisons such as oxy en,
nitric oxide, and carbon monoxide sorption on propy ene
hydrogenation and metathesis. All poisoned hydrogenation
P
effectively at levels 100 times lower than the number of mo-
lybdenum atoms present, but they were relatively ineffective
in poisoning methathesis. A related IR study by Millman and
Hall (108G) showed that pairs of NO molecules poisoned sites
for propylene hydrogenation; it was su gested that the sites
may be Mo"' centers. Nissenbaum et .a! (113G) showed that
higher sorption capacity for CO, relative to C02and H20, was
related to higher methanol synthesis activity for Cu-ZnO-
CaO-Al203 catalysts. A combined oxygen chemisorption-EPR
study of supported vanadia (V205)catalysts was made b
Khalif et al. (85G). Heats of 0 2 - formation were 20 kcal m o l
those of 0- formation 60 kcal/mol on 1-15% V205/Mgd,and
there was a maximum in oxygen sorption with increasing V Ob
On V205/Al203,02- did not form, all sorption heats exceeied
60 kcal/mol, and O2 sorption increased re ularly with V205
concentration. A microcalorimetry study %y Della Gatta et
al. (41G)of NO sorption on a Cm/Si02 polymerization catalyst
indicated that loss of activity was associated with chan e from
sorption to give a CP(N0)2complex to that giving a &(NO)
complex. A previously reported determination of cobalt oxide
areas on Co30 / S O z catalysts, by reduction rates in carbon
monoxide, has keen extended by Mekhandzhiev and Dyakova
(108C) to include reduction rates in hydrogen.
Surface Acidity. Deeba and Hall (37G) demonstrated that
n-butylamine titrations of acid catalysts are not reliable for
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 103R
PETROLEUM
determinin acid strength distributions, since equilibrium is
not establisEed, but give the total acidity. They suggest using
irreversible chemisorption of a series of bases with differing
pK,s to obtain the distribution of acid sites of different
strengths. Janowski et al. (77G) found that the acidity of
MOO/SOz and W03/SiOz,measured by ammonia adsorption,
correiated well with activity for olefin aromatization. Nondek
e t al. (114G) found that basic sites on metal oxides could be
determined by the displacement of adsorbed benzoic acid by
acetic acid. Wierzchowski et al. (177G) measured chroma-
tographic retention volumes of ammonia and light hydro-
carbons on faujasites partially exchanged with hydrogen,
cerium, and cobalt. The steepest adsorption isotherms were
found with NaX zeolite. Retention volumes for hydrocarbons
decreased linearly with degree of H exchanged for Na. Ex-
change of polyvalent cations increased the retention volumes.
Brenner and Hucul (18Ga) pointed out that the first-order
formalism, commonly used to extract kinetic parameters from
temperature programmed desorption of gases from catalysts,
is very sensitive to experimental errors even if conditions
required for its application are met. They sug est an alter-
native technique using initial slopes of isotherm3 desorptions.
Infrared spectroscopic investi ations have been most nu-
merous in determinations of catafyst acidity, and zeolites are
the most PO ular materials for such studies. Auroux et al.
(5G) studiefthe H-ZSM-5 zeolite’s adsorption of ammonia
by IR and microcalorimetry. Compared to H-mordenite and
H-faujasite, H-ZSM-5 has a broader distribution of stron acid
sites and higher acidities, especially when made by H81 ex-
change of Na-ZSM-5 rather than NH4N03 exchange and
calcination. The most acidic sites in H-ZSM-5 were not readily
accessible to ammonia or pyridine a t room temperature.
Mirodatos et al. (111G) characterized offretite samples with
varying degrees of exchange of potassium ions by protons. IR
bands at 3550 and 3610 cm-’ grow with exchange. both are
due to acidic hydroxyl groups, but only the 3610 cm-f hydroxyl
is accessible to reactant molecules such as yridine, ammonia,
or light hydrocarbons. Bielanski et al. 5 2 G ) measured 1-
butene isomerization on NaHY zeolites and correlated it with
IR measurements of pyridine adsorption. The 3650-cm-’
hydroxyls were identified as the active centers for isomeri-
zation. Kunath and Moeller (96G) studied ammonia sorption
on calcium and ammonium-exchanged A zeolites. Both am-
monium ions and ammonium coordinated to Ca or hydro-
en-bonded to lattice oxygens were observed. Goncharuk
f65G) used pyridine pulsed poisoning of cumene dealkylation
to determine acidities of natural aluminosilicah. The number
of acid centers found was very constant despite large differ-
ences in activity. Kitaev et al. (91G) studied pyridine and
ammonia sorption on boron phosphates. Only Lewis bound
pyridine was found, but both coordinated NH3 and NH4+
formed. Phosphate hydrox 1s with 3600-3700 cm-’ stretching
frequencies were responsigle for protonation of ammonia.
Golubev et al. (64G) found that Lewis sites of alumina could
be measured by using the EPR spectrum of a substituted
piperidine base adsorbed on the alumina surface. Knozinger
and Stubner (92G) measured isobutyl alcohol adsorption
isotherms on alumina. IR showed that a carboxylate species
formed irreversibly. Irreversible sorption of coordinatively
adsorbed isobutyl alcohol also occurred, together with re-
versible sorption of weakly coordinated and hydrogen-bonded
species. The adsorbed alcohol provided hydroxyls of sufficient
acidity to isomerize cyclopropane. The free alumina was
inactive for that reaction.
Kinetics, Mechanisms, a n d Active Sites. Somorjai
(151G) reviews the use of surface spectroscopies coupled with
high-pressure reactors to identify catalyticall active sites on
B
metal catal sts. The role of steps, kinks, an coordinatively
unsaturateJsites and carbonaceous overlayers in hydrocarbon
reactions is emphasized (152G). Dwyer et al. (45G, 46G)
showed the im ortance of readsorption and secondary reac-
tions in CO hygogenation on Fe and Rh surfaces usin LEED,
8
Au er, and gas chromatography. ESCA studies by arlev et
al. T%G) of the interaction of NO with Ni surfaces reveal one
dissociated and two molecular adsorbed states. Ekerdt and
Bell (49G) used IR spectroscopy to characterize the inter-
mediates in CO/Hz reactions over silica-supported Ru. The
role of several monolayers of carbon found on the steady-state
catalyst in hydrocarbon synthesis were discussed. Vannice
determined the effect of metal-support interactions on the
104R * ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
kinetics of Hz/CO reactions over nickel (168G). Mechanisms
for the formation of isocyanate, H20,and COz from CO, H2,
and NO on silica-supported Ru were proposed by Davydov
and Bell (35G) on the basis of IR experiments. Infrared
spectroscopy was also used by Kharson and Kiperman (87G)
to study unsaturated surface species on bimetallic catalysts.
Amenomiya (2G) showed by IR that surface-bound formates
are intermediates in the water-gas shift reactions on alumina.
A number of studies have been directed toward elucidation
of the active sites on metal oxide catalysts. Iwasawa et al.
investigated the active sites for ethanol oxidation on a Mo/
Si02catalyst by XPS, photoluminescence, diffuse reflectance,
and IR s ectroscopy and chemisorption. Coordinatively un-
saturateidioxomolybdenum in a tetrahedral site is found to
be the catalytically active species (75G). Similar techniques
applied to an olefin metathesis catalyst also revealed coor-
dinatively unsaturated tetrahedral Mo to be the active site
(76G). An ESR study of electron transfer reactions between
aromatics and M0-Alz03 surfaces was conducted by Petrakis
et al. (123G). Infrared studies by Efremov et al. (47G) on
propylene and allyl bromide on a Ga-Mo oxide catalyst
showed that both are adsorbed as wallylic complexes. They
suggest MOOCH CH=CH2 as the precursor of acrolein.
Burrington and erasselli (48G) propose that propylene oxi-
dation and ammoxidation occur via an CY-Habstraction with
subsequent 0 or NH insertion. Carboxylate, formate, and
carbonate species were also identified. Da dov and Efremov
(36G) have also studied propylene and ayyl bromide inter-
mediates on CuO-MgO where a CuOCH CH-CH interme-
diate in the formation of acrolein was ogserved. h n a b e et
al. (161G) used microwave spectroscopy to study exchange
reactions of propylene with DzO or Dz over MgO-TiOz mix-
tures. In the former reaction, .-allyl carbon ion intermediates
were formed on basic sites, in the latter, isoprop 1carbenium
ions on acidic sites. Using IR and diffuse reflYection spec-
troscopy, Przheval‘skaya et al. demonstrated the existence of
a monomeric .rr-allyl nickel chloride as the active site in an
olefin oligomerization catalyst (132G).
An IR study of coking on zeolites was reported by Eisenbach
and Gallei (48G). They studied n-hexane and 1-hexene ad-
sorption on Y zeolites. A linear surface species was found a t
low temperature. Above 400 K, branching takes place and
with further heating “coke” is formed and an IR band appears
a t 1585 cm-’. Involvement of hydroxyls with frequencies a t
3640 cm-’ was shown. Also, external hydroxyls with fre-
quencies a t 3740 cm-’ are active above 500 “C, but the Ca-
(OH)+ hydroxyls (3585 cm-’) do not participate in coking.
As part of an extensive study of the relationships among
preparation, morpholo , and activity of su ported Pt cata-
R
lysts, researchers at Nor%western University ave investigated
the isotopic exchange between cyclo entane and D2 on Pt/
Si0 in which they find mechanistic cianges as the dispersion
of t i e Pt changes (72G). Another paper in this series reports
that apparent structure sensitivity in methylcyclopropane
hydrogenation over Pt/Si02 is dependent on catal st pre-
treatment conditions (118G). Barbier et al. in a studry of the
effect of metal dispersion on ethane hydrogenolysis over
Pt/Alz03found on the kinetic mechanism to be independent
of dispersion and no correlation between specific activity and
crystallite size (9G).Yang et al. on the basis of poisoning
studies, conclude that the dehydrogenation of cyclohexane
proceeds via a dual site mechanism (179G).
Kobayashi (93G) proposed a general rule to estimate re-
action mechanisms in heterogeneous catalysts from the mode
of the transient response curves of products. A method for
studying the performance of a single spherical particle with
nonuniform catalytic activity was reported by Ernst and
Daugherty (50G). Goerss et al. (63G) disclosed a gas chro-
matographic method to measure changes in catalyst activity
during use. Beskov et al. (IOG) have examined the reliabilit
x
of determination of the activity of an industrial catalyst batc
by measurement on a single sample.
Thermal Methods. Hi h-pressure DTA was used by
Hisamitsu et al. (70G)to stuiy the reactivity of HDS catalyst
containing various promoters toward organic sulfides. Nozawa
and Takayasu have used temperature programmed reduction
to study supported nickel oxide (115G) and nickel oxide-
chromia (116C) catalysts. In both cases the reducibility of
the catalyst is dependent on the method of preparation.
Brenner and Hucul (18Gb) have used temperature program-

med decomposition of W(CO)6on A1203to elucidate the re-
versible formation of subcarbonyl species. Decomposition is
dependent on the degree of hydroxylation of the surface.
Moger et al. (112G) have investigated the carbon in regen-
erated Pt catalysts. Additional hydrogen is adsorbed and
additional desorption peaks appear on catalysts containing
C deposits.
A gas chromato aphic technique was used by Rosolovskaya
et al. (139G) to &ermine diffusion coefficients of hydro-
carbons in the pores of an aluminasilicate catalyst. Surface
diffusion is an im ortant factor. Rogut and Schneider (138.G)
used an expandefVan Deemter treatment to extract effective
diffusivit coefficients from chromatographic measurements.
Lee (99Gy has shown that the single pellet chromatography
method of Smith leads to a direct determination of the dif-
fusivity, porosity and thickness of an impervious layer on the
outer surface of a catalyst pellet. Soomro and Hughes (156C)
measured thermal conductivity of porous catalyst pellets and
found lower values than theoretically predicted.
PHYSICAL PROPERTIES
Byron Sudbury
Research and Development D8partment, CONOCO Inc., Ponca City,
Oklahoma
Durin the past decade the number of literature citations
reviewefin this subsection nearly doubled from 62 to 118.
This current review notes a substantial decline in the number
of references dealing with physical properties. In particular,
interest in rheology and in distillation appears to have di-
minished significantly bringin the number of apers included
in this review to less than haff the peak n u d e r reported in
1977.
Rheology. Gyer (18H) reported that Committee D-2,
Research and Development Division VII, of ASTM in coop-
eration with several other groups, are studying factors that
influence the precision of Brookfield viscometry of automotive
lubricant fluids in order to develop a Brookfield viscometer
procedure for all automotive lubricants a t low temperature.
Round-robin tests and other information sources provided
data on friction and damping effects inherent in the viscometer
design, on thermal conditioning effects, on calibration of the
tem erature sensor and control of temperature fluctuations,
on tKe effects of test cell design, and on the effects of sample
rheology on Brookfield precision. The data were analyzed,
and estimations were performed of expected operational errors,
the precision a t each rotary speed, reproducibility, and re-
eatibility. Vidal (40H) determined the effects of initial bath
Fiquid temperature, soak time, and spindle insulation on
Brookfield viscometer measurements of low-temperature oil
viscosities; the tests showed that in an accurately controlled
liquid bath, the sample temperature can be maintained during
measurements and the soak time can be reduced to 2 h
(compared to 16 h for air bath) and that field conditions are
best simulated by cooling the sample at 1 OC/min. The
kinematic viscosity of crude oils was correlated with the ab-
solute temperature and parameters A and B by Amin and
Maddox (1H).A comparison between experimental and
calculated viscosities for fractions of several crude oils showed
that the equation represents the viscosity-temperature be-
havior of the crude oils with standard percentage errors of
<3 %, and further tests showed that the correlation represents
the viscosity behavior of the different fractions of the crude
oil with average percentage errors of less than half those of
the API method. W d e (43H) developed empirical e uations
for estimating the characterization factor of hydr-\on oils
from API gravity in combination with kinematic viscosity,
flash point, or aniline point. The equations are useful for
checking sets of tests for internal consistency, and the results
obtained from the equations based on gravity and viscosity
were comparable with those estimated from Watson-Nelson
raphs. Tewari et al. (39H) characterized the interaction
c;
getween heavy oil and asphaltene and its acid neutral and
base components in a solvent and hypothesize that hydro-
gen-bonding involving largely phenolic hydroxyl groups is
partly responsible for asphaltene-heavy oil interactions and
the viscosity increases of coal liquids.
Density. An apparatus based on a hydrostatic balance was
designed for accurate measurement (&0.01% error) of 1-2000
kg/m3 densities a t the boiling and dew points (range -200 to
+200 "C) at up to 150 bar was reported by Kleinrahm and
PETROLEUM
Wagner (23H); it may be used for measuring densities, vapor
pressures, and boiling temperatures simultaneously for ure
substances, includin hydrocarbons and refrigerants. &rit
and Laupretre (34Hf experimentally determined liquefied
natural gas component density as a function of temperature
and composition (methane, ethane, propane, iso- and n-bu-
tane, iso- and n-pentane, and N). They then used their results
to establish a correlation law to enable calculation of the
density of liquefied natural gas with a relative error of
when the components are within certain s ecified concen-
tration ranges (33H). Nemkov et al. (31H) puhshed uations
containing 90 wt % propane-butane fraction at various
7
for calculating the density of a liquefied hydrocar on gas
pressures and temperatures.
The British Standards Institution (6H) has provided
specifications for benzene and for three grades each of toluene
and of xylene; details are given for the measurement of color
and of density at 20 "C and for an acid-wash test (indicative
of the degree of refining), the determination of total S, free
S, H2S, and thiols, a test for neutrality, a determination of
residue on evaporation, and establishment of crystallization
point. The true densities of asphaltene samples were deter-
mined by Parkash et al. (35H); macropores and micropores
were recognized and their volumes excluded when the desnities
were determined by helium displacement a t 298 K. It was
thought that the pore structure is associated with the mo-
lecular structure of the as haltenes. Kanevskii et al. (21H)
reported that the standariaddition method can be used for
analysis of multicomponent mixtures by measuring the
physical properties of the mixtures before and after the ad-
ditions; examples given include the analysis of binary and
ternary organic mixtures by measuring density, refractive
index, and surface tension.
Distillation and Flash Point. An on-stream computer-
controlled gas chromatograph for analysis of interreactor
catalytic re-former products has been described by Stockinger
et al. (37H). From the data obtained from this system, cal-
culation of octane numbers, specific gravities, molecular
weights, combined H, and distillation curves can be achieved
[this system, set up to sample at various points in the reactor
system, was developed to evaluate the performance of ex-
perimental catalysts].
A simple inexpensive ap aratus for determining the flash
point (between 20 and 90 O 8 ) of corrosive mixtures employing
a battery-powered ignition source was described by Waring
and Hudson (42H); some values obtained for binary solvent
mixtures are compared with those obtained with a Pensky-
Marten apparatus and with the literature values, and agree-
ment is within f2O. A program developed for Hewlett-
Packard HP-67 and HP-97 programmable calculators per-
forms flash calculations in 1-5 min for multicomponent
mixtures with up to nine components as described by Man-
souri (27H). The equilibrium properties of the mixture are
determined from the flow rate of the feed stream, the mole
fraction of each component in the feed, and the equilibrium
constants for each component at the temperature and pressure
in the tank. Newton's iterative method is used to calculate
the rate at which the resulting vapor is withdrawn based on
an estimated rate to start the iteration and a tolerance value
for the final rate. The mole fractions in the equilibrium vapor
and liquid phases are then computed. The procedure is il-
lustrated for the flash distillation a t 600 psia and 20 O F of a
natural gas feed flowing at 1000 mol/h.
Molecular Weight. A new procedure for molecular weight
determination by vapor-phase osmometry was developed and
reported by Chung et al. (8H);this procedure eliminates the
major cause of inconsistent results usually obtained with
conventional vapor-phase osmometry techniques for raw fuel
materials. Theory and experiments with standard benzil-in-
chloroform solutions showed that vapor-phase osmometry tests
should be carried out within the rectilinear region on the
osmometer readout vs. solute concentration curves to yield
results that are independent of the solvent nature and the test
temperature. The rectilinear region can be found experi-
mentally for both calibration compounds and unknown so-
lutes. Procedure validity was demonstrated on 11 model
compounds with a variety of functional groups and of
122-1238 molecular weight. Molecular weights of two coal-
derived liquids were also determined. Dryden (12H) further
commented on this procedure.
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 105 R
PETROLEUM
The effect of silylation on the molecular weights of petro-
leum- and coal-derived asphaltenes was reported by Gould
(16H); no significant reduction in molecular weight was ob-
served upon silylation, suggesting that hydrogen bonding does
not greatly influence the observed molecular weights of the
asphaltenes near zero concentrations. Pyridine extractables
from depolymerized Bruceton coal had a number-average
molecular weight of 400, in agreement with the literature but
consisted primarily of colloidal material and polymers having
molecular weights >3000 as reported by Larsen and Choud-
hury (24H). The colloidal material was removed by ultra-
centrifugation and subjected to a second depolymerization,
to give additional soluble material; low-molecular weight
products were not obtained, so the supposed methylene-
aromatic linkages in the coal must be unreactive. The effects
of column combinations on the measurement of average
molecular weights and the molecular weight distribution in
high-performance size-exclusion chromatography were re-
ported by Mori (30H). In the polystyrenes evaluated, the
average molecular weights were not affected by the column
combination, but the ine ral molecular weight distribution
curves showed definite differences among several column sets
The most probable integral distribution curve will be obtained
from a column packed with mixed gels of different porosity;
a column combination without a gap in porosity or with many
different gel porosities is preferable. The column set should
have an exclusion limit of -10-fold the weight average mo-
lecular weight for the polymer sample.
Thermodynamics. The methods for estimating the basic
parameter (molecular weight, pseudocritical temperature and
pressure, and acentric factor) and their use in predicting the
thermodynamics, transport, and physical properties are re-
viewed by Daubert in “Characterization Parameters for Hy-
drocarbons for Physical and Thermodynamic Property
Prediction” (1OH). Manelis (26H) edited a volume titled
“Chemical Physics of Combustion and Explosion Processes.
Kinetics of Chemical Reactions”.
An isothermal titration calorimeter for excess enthalpy
measurements for volatile liquid systems was developed by
Hanson (1923; he studied the performance characteristics of
a new back-mixed flow vessel suitable for isothermal heat of
mixing calorimetry, and criteria were established for checking
the performance and selecting the optimal set of parameters
for a iven experiment. This type of mixing vessel has PO-
tenti3 for rapid and accurate determination of binary heats
of mixing; a complete binary heat of mixing curve can be
determined in 1day.
Jamieson (2OH) developed a new equation which correlates
experimental thermal conductivity as a function of temper-
ature, from the melting point up to 0.9 of the critical tem-
perature, and as a function of chemical structure, both as
individual compounds and as members of a chemical series.
The equation permits the values for other liquids of similar
structure to be estimated by interpolation with much better
accuracy than possible with purely predictive equations.
The thermal conductivity of liquid mixtures was determined
by Gaitonde et al. (14H) for a series of eight alkane/silicone
oil systems to investigate the effects of molecular character-
istics such as size and shape on thermal conductivity. The
measurements were carried out in a guarded horizontal parallel
plate apparatus suitable for tests at 15-70 “C under steady-
state conditions with an accuracy of about fl%; the thermal
conductivities of the individual liquids were also determined
and were in good agreement with published values. The size
of the molecules, as represented b the ratio of their molecular
weights, had a significant effect, {ut the shape had very little
effect. A modification of the McLaughlin equation to intro-
duce a single parameter reduces its tendency to positive errors
at hi h mole fractions and negative errors at low mole fractions
of aliane.
A thermal comparator method was developed to measure
thermal conductivity of Green River oil shales by Nottenburg
et al. (32H); predictive equations showing the variation of
thermal conductivity with temperature and shale grade are
presented, and a simple model is proposed to explain the
anisotropic effects observed in the thermal conductivity values
for heat flowing in directions parallel and perpendicular to
the shale bedding planes. Wang et al. (41“) presented an
analysis of the trends in the variation of the thermal transport
parameters with organic content (thermal diffusivity as an
106R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
example) for Green River oil shales.
A high-precision ice calorimetric system for heat capacity
measurements near the critical point capable of one part in
13000 accuracy and 10 ppm precision under calibration con-
ditions was developed by Gay (15H). Marcu and Segal(28H)
suggest a method of drawing the thermogram of a sequence
of two consecutive, partially overlapping processes of a given
order, run under nonisothermal conditions. Doulah (1IH)
gives equations for calculation of kinetic parameters from
thermal analytical data; these equations are particularly useful
in calculation of the kinetics of thermal decomposition. A
generalized rate equation is also given. A double-beam pho-
toacoustic spectrometer was designed and constructed to
permit acquisition of optical, thermal, and dimensional data
from a variety of substances including opaque materials as
reported by Blank and Wakefield (4H); powders, gels, solids,
and liquids can be analyzed directly with minimal sample
preparation.
Miscellaneous. An electron microscopic study on friction
properties of certain li uid lubricants in relation to their
structure was conducte! by Martin et al. (29H). Dwiggins
(13H) used a Bonse-Hart small-angle X-ray diffractometer
interfaced to an automated X-ray diffraction system to study
the colloidal nature of crude oil; a number of rocedures were
employed to permit detailed study of colloifs and mixtures
of colloids. Kim and Long (22H) used a Kratky small-angle
X-ray scattering apparatus to study the structure of asphaltene
colloid dispersed in heavy petroleum residua; asphaltenes from
two different crudes and from coal were characterized.
Optical microscopy was used by Cornford and Marsh (9H)
to examine the structure of metallurgical cokes in relation to
their mechanical strength. Griffiths and Marsh (17H) used
phase contrast high-resolution electron microscopy in com-
bination with optical microscopy, X-ray diffraction, and
electron diffraction to characterize structure in three heat-
treatment series of cokes prepared from petroleum pitch,
gilsonite pitch, and coal extract.
Berthold‘s patent (3H) contains information on apparatus
and methods for determining the size distribution of particles
suspended in a liquid usin moving sieves and turbidity
measurements. Bonczyk ( 5 3 evaluated the measurement of
particulate size by in situ laser-optical methods on a fuel-
pyrolyzed carbon sample. Berry discusses one manufacturer’s
aser-based particle size monitors currently on the market
(2H). Mahajan and Walker (2523) have prepared an extensive
review on densities of coals and chars, surface area, and pore
size distributions. Slettevold et al. (36H) studied the surface
area and pore distributions of retorted Colorado oil shale usin
N and C 0 2 adsorption and Hg porosimetry. Ternan an
Fuller compared various methods used to measure pore size
li
in solids (38H). Ca elle (7H) performed measurements of the
interfacial tension getween crude oil and formation water by
the spinning drop technique.
HYDROCARBONS
M. P. T. Bradley
Spectra-Physics, Santa Clara, California
As in previous years, the hydrocarbon analysis citations are
characterized by a major emphasis on gas chromatography,
although much of the reported work is somewhat repetitious.
Other chromatographic techniques, such as high-pressure
liquid chromatography and thin-layer chromatography, are
also well represented.
Several authors reported review articles ranging from a book
on manual sampling methods for liquid hydrocarbons, pub-
lished by the British Standards Institute (271) to specific
technique reviews. The British Standards manual is complete
with diagrams of sampling devices and safety precautions for
the sampling of finished products, crude oils, and intermediate
products from storage vessels, ships, barges, land vehicles, or
pipelines.
Methods of analysis of gases and light hydrocarbons by gas
chromatographic analysis were reviewed by Saha (1961) and
Mindrup (1521). The later review updates the “Atlas of Gas
Analysis by Gas Chromatography’’with 66 references classified
and cross-indexed by sample type. Numerous chromatograms,
with operating conditions, are reproduced.
Brown and Sear1 (311) reviewed the application of gas
chromatography and UV spectroscopy to the analysis of
polynuclear aromatic hydrocarbons.

Sovani and Kallyanpur (2231) reviewed thin-layer and
column chromatography methods. Analytical methods for
solid hydrocarbon mixtures were reviewed by Kuras (1311).
Ten Noever de Brauw (2321) reviewed GC-MS methods and
Wehry and Mamantov (2491) reviewed the use of matrix
isolation techniques for the analysis of individual trace organic
compounds in complex matrices, including coking plant waste
water.
As a sign of the interest in the use of noncrude oil sources,
Bartle et al. (121) provided an extensive review of paraffinic
hydrocarbons from coal.
SPECTROSCOPIC METHODS
Spectroscopic methods of analysis reported covered the full
range from infrared to UV spectroscopy, together with other
methods such as NMR and mass spectroscopy.
Hausdorff (1021) described the use of functional group
specific detectors, Startsev et al. (2251) used IR spectroscopy
at 2920 cm-’ to determine hydrocarbons in molten sulfur.
Nonlinear absorption spectroscopy was used by Radloff (1851)
for the analysis of gas mixtures. Yankov et al. (2621) used
IR to determine the composition of the light fraction of heavy
pyrolysis resins. The same technique was applied by Bakulin
et al. (71) to the determination of aromatic compounds in
reformates, gasolines, and hydrorefied ligroin-. An equation
for calculating the aromatic content as a function of the ab-
sorptivity a t 1600 cm-’ is given. Faizullina (701) used IR
spectroscopy to study the catagenic transformation of organic
matter into petroleum hydrocarbons.
The power of computerized techniques of infrared spec-
troscopy is amply demonstrated by the work of Koenig and
Kormos (1241), Von Eijk et al. (2444, Coates (454, and Dupuis
et al. (611)).
Rasmussen et al. (1881) applied principal-component
analysis techniques to the analysis of isomeric xylenes and
nonane, decane, dodecane mixtures.
Tokousbalides et al. (2351) applied matrix isolation
fluorescence and Fourier transform infrared (FTIR) spec-
troscopy to the analysis of the structural isomers of polynu-
clear hydrocarbons. Hinton et al. (1071) applied matrix iso-
lation FTIR to isomeric methylnaphthalenes and methylbi-
phenyls. Microsampling procedures for a matrix isolation
I T I R spectrometer system and its application to determining
spectra of polynuclear hydrocarbons with as little as 50-100
ng of material were reported by Hembree et al. (1041).
Dagga and Hameed (521) used ultraviolet spectroscopy for
the determination of aromatic compounds in crude oil; Ba-
lyatinskaya and Babankova (81) used H I* complexes and
ultraviolet spectroscopy at 260-279 nm to cfetermined alkynes
in the presence of alkenes. Kucherova and Yur’eva (1271)
proposed a UV spectroscopic method as an alternative to the
aniline point method for the determination of aromatic hy-
drocarbons in n-paraffins and recovered raw materials from
sulfonate production. Mosescu et al. (1561) determined mono-,
di-, tri-, and tetracyclic aromatic hydrocarbons in heavy oils;
Rusin (1941) examined coal extracts and their hydrogenation
products.
The strong interest in aromatic hydrocarbons has led to
many publications using optical techniques capable of high
sensitivity for aromatic hydrocarbons. Giering and Hornig
(891) report the use of total luminescence for the identification
and determination of hydrocarbon mixtures without prior
separation. Woo et al. (2541) used an X-ray excitation source
to develop luminescence profiles of polynuclear hydrocarbons
in coal conversion byproducts and shale and fuel oil bypro-
ducts. Zander (2631) used solid-state photoluminescence at
77 K for the determination of impurities in high-purity po-
lycyclic aromatic hydrocarbons. Vo-Dinh (2431) used a syn-
chronous luminescence technique where the excitation and
emission wavelengths are scanned simultaneously with a
constant interval. The synchronously generated spectra is
greatly simplified with, for instance, a single narrow band peak
for ethanolic naphthacene, the conventional fixed wavelength
emission and excitation spectra show three and four bands,
respectively. Some cautionary notes concerning the inter-
pretation of synchronously generated luminescence spectra
are reported by the dialog between Latz et al. (1324 and Lloyd
(137I).
Krieger et al. (126Z) used the chemiluminescence reactions
of oxygen atoms with reactive hydrocarbons to determine less
PETROLEUM
than 6 ppb of “ethylene equivalent” in automobile exhaust
gases.
Colmsjo and Stenberg (471) used low-temperature
fluorescence for the analysis of polynuclear aromatic hydro-
carbons previously se arated by high-pressure liquid chro-
9
matography. They so (481) examined the effect of tem-
perature on spectral resolution.
Brown e t al. (301) used an argon ion laser to excite
fluorescence in organic glasses containin ppb amounts of
polynuclear aromatic hydrocarbons. 4 he technique of
fluorescence line narrowing spectroscopy provided linear
calibration curves from 1 ppb to 3 ppm for pyrene and an-
thracene in glycerol-water glasses at 4.2 K by excitation with
the 364-nm argon ion laser line. Dickinson and Wehry (561)
also used an argon ion laser, coupled with time resolution to
determine 2 ng of benzo[a]pyrene in the presence of 1pg of
benzo[k] fluoranthene.
Gold et al. (901)used the SPECSOLV spectral decomposition
program to determine binary mixtures whose molecular
fluorescence spectra have overlapping bands. Ho et al. (1081)
used rank annihilation methods of quantitatively determine
one component of known identit in a mixture of unknown
compounds. Breymann (261) usdchemical techniques using
electron donors and acceptors to selectively suppress the
fluorescence of nonalternant polycyclic aromatic hydrocarbons
(suppressed by electron donors) and fused benzenoid com-
pounds (suppressed by electron acceptors).
NUCLEAR MAGNETIC RESONANCE
Bartle et al. (111) used NMR to study the structure of
fractions extracted from Turkish lignites by supercritical
toluene. They report that the average structure contains single
aromatic rings.
Sat0 et al. (2001) used chlorinated hydrocarbons and the
proton shift caused by the magnetic anisotropic effect to
determine the aromatic content of kerosines; Yamazaki et al.
(2571) used pulsed Fourier transform C-13 NMR for the
analysis of normal alkanes and substituted benzene isomers.
Alger and Pugmire (21) report s in lattice relaxation times
and nuclear Overhauser effect &ita for several compounds
which must be approximate in order to determine aromatic
compounds in coal-derived liquids. Resing et al. (1911) used
13C NMR and magic angle spinning to determine aromatic
hydrocarbons in oil shale, kerogen, shale oil, and inorganic
wastes from oil shale processing.
MASS SPECTROSCOPY
Mass spectrometric methods reported ranged from fin-
erprinting and partial quantitation of hydrocarbon mixtures
6 y means of chemical ionization mass spectrometry described
by Sieck (2171) who used the cyclohexane ion and photoion-
ization to initiate a cascade of consecutive reactions owing to
the differing ionization potentials of the hydrocarbons. By
early termination of the reaction sequence, the aromatic
content of gasolines could be partially quantitated. Niyazov
et al. (1631) studies pentacyclic hydrocarbons extracted from
petroleums that did not form thiourea adducts by mass
spectrometry. The compounds were found to be mainly
triterpanes. Shushan et al. (2161) distinguished between four
isomeric polycyclic aromatic hydrocarbons of molecular weight
228 by mass spectrometric studies of metastable ions. Levsen
et al. (1361) used field ionization mass spectrometry to de-
termine double bonds in linear alkenes. Yampol’skii (2581)
used a pyrolysis technique to eliminate 13C interference and
allow the accurate determination of deuterium in hydro-
carbons by mass spectroscopy.
Khots et al. (1211, 1221) report procedures for the quan-
titative analysis of organic compounds by correcting for mo-
lecular weight and heteroatoms. Herzschuh and Seidlitz (1051)
quantitatively measured alkanes by low-voltage electron im-
pact excitation. The results of three standard samples agreed
close1 with GLC analysis. The quantitative analysis of
compikx hydrocarbon mixtures containing htereoatoms by
means of high-resolution mass spectrometry was reported by
Polyakova et al. (1791) and Brodskii (281).
The most powerful applications of mass spectrometry are
those using mass spectroscopy combined with chromato-
graphic methods of separation. Washida et al. (2481) used
GC-MS with photoionization excitation. Although the sen-
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 * 107R
PETROLEUM
sitivity is not as great as that obtained with conventional
GC-MS with electron impact excitation, the technique gen-
erates only the parent ion and, therefore, is less susceptible
to matrix effects and can be made very selective. Francis and
Tande (771) converted alkenes into alkoxyselenium com-
pounds which were subsequently determined by GC-MS.
Randall and Wahrhaftig (1861) used a differentlly pumped
supersonic molecular beam interface to couple a mass spec-
trometer to a gas chromatograph operating with a dense gas
(20-250 atm, above but close to the critical temperature).
Under selected conditions, clustering involving the solute could
be avoided and only the mass spectra of the solute and solvent
were observed.
A newer technique than GC-MS is the coupling of mass
spectrometers to high-pressure liquid chromatographs.
Takeuchi et al. (2291) used a jet separator as an interface and
demonstrated the analysis of biphenyl, fluorene, and an-
thracene separated by a reverse-phase system with 70%
aqueous acetonitrile as eluant. Blakley et al. (201) used a laser
to evaporate the liquid chromatograph eluant and a cross-
beam technique to transport and ionize the sample. Aromatic
hydrocarbons were used as test mixtures.
Dark and McFadden (531) used HPLC and a moving belt
interface to a quadro le mass spectrometer. The system was
used to separate ancharacterize coal liquifaction products.
CHROMATOGRAPHIC TECHNIQUES
The vast majority of chromatographic references deal with
gas chromatogra hic methods of analysis. However, there is
still an appreciatle amount of work carried out by the older
techniques of column and thin-layer chromatography.
High-pressure liquid chromatography continues to grow in
use, especially for the analysis of polycyclic aromatic com-
pounds.
COLUMN CHROMATOGRAPHY
Dutkiewica et al. (621) separated polycyclic aromatic com-
pounds from c clohexane extracts by elution from an alumina
column with &ethyl ether/cyclohexane mixtures. The de-
d
tection limit ranged from 0.1 to 1 pg cm3. Czajkowski et al.
(511) tested several column materi s and determined that
Sephadex LH-20 provided the best results for the separation
of oils of 200-250 “C boiling ran e. By elution with methanol,
complete separation of mono-, 4-, and tricyclic hydrocarbons
was obtained. Rusin et al. (1951) used silica and alumina
columns for the separation of hydrocarbon fractions into broad
groups.
Fessler (761) reported on collaborative studies aimed at
selecting an alternative silica gel to that used in the fluorescent
indicator adsorption technique for hydrocarbon group analysis.
Grace chromato aphy gel Type 923 was found satisfactory.
Suggested d e t a i r for optimizing the test are also reported.
Wickramasinghe (2521) used the SARA (saturated-aro-
matic-resin-asphaltene) method of analysis. In order to study
oil pollution of seawater, it is necessary to understand the
behavior of esters in this system. The results show that the
esters, as indicated by a model compound [14C]-methylpal-
mitate, elute with the “oils”, i.e., saturated/aromatic fraction.
Schwartz (2071) described a microcolumn containing PdClz
on silicic acid for absorbing unsaturated hydrocarbons. The
method was used to quantitatively separate the saturated
components from a mixture.
THIN-LAYER CHROMATOGRAPHY
Gearin et al. (871) and Dzido and Soczewinski (641) both
examinec f the relationship and application of thin-layer
chromatography and column chromatography. Both groups
of authors DroDose that with some limitations the techniques
are intercliangeable.
Wernicke and Lassman (2511) used thin-laver chromatog-
raphy on A1203 to perform a group separation of heavy hy-
drocarbon fractions. They report that the method is more
precise and takes only 0.7 h, compared with the standard
DIN51384 method which takes 8 h. Fazylov and Narzykolov
(721) used preparative thin-layer chromatography for the
direct quantitative determination of hydrocarbon classes in
petroleum fractions.
The combination of thin-layer chromatography and
fluorescence detection is a particularily powerful technique.
108 R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
Several authors (491, 1121, 1181, 1191, 2411) applied this
combination for the determination of aromatic hydrocarbons
from a variet of sources. Hellman (1031) identified that the
fluorescence gehavior of the same polycyclic compounds were
quantitatively different on silica el F60, HPTLC material,
and on A1z03-acetylcellulose. &e stability of the model
compounds was greatest on the third material. Matsushita
(1481) used a dual band thin-layer technique for separating
and identifying individual polynuclear aromatic hydrocarbons
a t trace levels in oils.
Armstrong and McNeely (51) used micelles to perform the
separation of polycyclic aromatic hydrocarbons on Poly-
amide-6. Bancroft et al. (90 constructed novel charge-transfer
polymers, based on a picric acid substituted polyacrylic
aciddvin lbenzene resin, for the separation of aromatics from
saturated $drocarbons. The plates offer cost and stor e life
advantages over silver nitrate plates but do not comzetely
resolve complex mixtures.
CHROMATOGRAPHIC DETECTORS
As can be expected, there is still considerable interest in
new detectors for the detection of hydrocarbons followin
chromatographic separation. Christensen and May (438
evaluated several commercial HPLC detectors for selectivity
and sensitivity to polynuclear h drocarbons.
Farzane et al. (711) used a ra&ocalorimetric detector for
detecting the emittance in the combustion of hydrocarbons
and petroleum fuels.
Semiconductor detectors were reported for heavy hydro-
carbons by Gugl a et al. (971) and for low molecular weight
hydrocarbons a n i hydrogen by Hua (2130. Guglya et al. (960
also characterized a lead titanate zirconate pyroelectric de-
tector which is an order of magnitude more sensitive than a
thermal conductivity detector. A similar semiconductor de-
tector based on Fe 03,A1203,and PdClz was reported by a
Chinese group (851)
Lev (1351) reported that a fast response hot filament hy-
drocarbon gas detector is suitable for monitoring fluctuating
gas concentrations in dispersing vapor plumes. Proksch et
al. (1820 studied the response of the flame ionization detector
to hydrocarbons and perfluorocarbons. The high carbon
number perfluorocarbons showed response values similar to
those of the corresponding h drocarbons, with response ratios
close to unity and indepedent of conditions provided that
higher hydrogen flows than usual are employed.
Schwartz (2081) quantitatively analyzed hydrocarbons for
hydrogen and perdeuterated hydrocarbons by means of a
microwave plasma detector. The minimum detectable level
of hydrogen was 10 pg s-l. Driscoll et al. (591) used a com-
bination of a photoionization and a flame ionization detector
to elucidate the structure of complex mixtures.
LIQUID CHROMATOGRAPHY
High-performance liquid chromatography is increasingly
becoming the analytical method of choice for the analysis of
polycyclic aromatic hydrocarbons owing to the sensitivity,
selectivity, and speed of the technique.
Youssef and Wall (881) described silica and zirconia based
els that are modified with quaternary ammonium surfactants.
5 he columns were used for the separation of aromatic hy-
drocarbons. The effects of eluant and surfactant concentra-
tions on the retention times were discussed. Minarik et al.
(1511) examined the mechanism of separation of 58 com-
pounds on porous poly(ethanedio1 methacrylate). Gar et al.
(841) used silica gel chromatography to separate heavy aro-
matic and tars in petroleum oils.
Hunt et al. (1111) used HPLC with a variety of column
packings and solvent systems for the separation and deter-
mination of polycyclic aromatic hydrocarbons from a variety
of sources. Kamata et al. (1171) also analyzed polycyclic
aromatics, this time on Permaphase E with 1:l methanokwater
as mobile phase, By use of fluorescence detection, the system
was particularily suitable for the determination of 3,4-benz-
pyrene.
Bebris et al. (131) modified a macroporous silica and
Spherisorb S2OW by deposition of carbon formed by the
pyrolysis of benzene. Columns packed with this material were
evaluated for their selectivity in the separation of homologous
series of alkylbenzens, naphthalenes, phenols, and aromatic

acids and esters. The highest selectivities were obtained with
the highest carbon loadings.
Colin et al. (461) also examined pyrocarbon modified silica
gels and pyrocarbon modified carbon black. Better selectivity
toward polar compounds was shown by nonpolar chemically
bonded phases. It is considered that the nonspecific retention
force on these phases is adsorptive rather than dissolution in
the surface phase. Bluemer et al. (231) demonstrated the
improved group separations of polycyclic hydrocarbons from
heterocyclic N compounds on a Nucleosil-&NO2column. The
samples were taken from coal tar pitch. Mosescu et al. (1571)
separated mono-, di-, tri-, and tetracyclic compounds from
mineral oils on alumina.
Brabcova (251)and Chmielowiec and George (411) evaluated
sorbents for the analysis of polycyclic aromatic hydrocarbons.
Chernyuk et al. (381) used liquid chromatography on silica
gel with 2-propanol as eluant for the analysis of the conversion
products from C8 to cl6 paraffins on spinel catalysts. Takami
et al. (2281) also used silica gel chromatography for the sep-
aration of micro amounts of polycyclic aromatic hydrocarbons
recovered from marine sediments.
Parris (1741) described methods of separation of hydro-
phobic compounds on Zorbax ODS by using a low polarity
solvent such as tetrahydrofuran as mobile phase. The method
is a plicable to a wide variety of materials including aliphatic
antaromatic hydrocarbons and aromatic polymers.
Preparative liquid adsorption chromatography was used by
Fazylov and NarzyMov (721) for the determination of groups
of hydrocarbons from 'et fuel fractions. Radke et al. (1841)
determined the repeataiility of preparative hydrocarbon group
type determinations performed on an automated chromato-
graph.
Selective separation of unsaturated hydrocarbons, sesqui-
terpenes, methyl esters, and polynuclear hydrocarbons was
performed by Vonach and Schomberg (2451) using silver ion
complexation in the mobile phase.
Charge transfer bonded stationary phases provided suc-
cessful se aration of noncondensed and condensed aromatic
hydrocarfons accordin to Nondek et al. (1641,1651).
Mamantov et al. (1448 characterized mixtures of polycyclic
aromatic hydrocarbons by liquid chromatogra hy and matrix
isolation spectroscopy. Bluemer and ZanIer (241) used
fluorescence quenching with nitromethane as an aid to the
identification of aromatic hvdrocarbons ser>arated bv re-
versed-phase HPLC.
Chmielowiec and Sawatzky (421) examined the role of
temperature on the thermodvnamic distribution behavior of
polynuclear aromatic hydrbcarbons in a (2-18 reversed-
phase/acetonitrile system. The elution sequences of some
polynuclear aromatic hydrocarbons are reversed by temper-
ature variations, which is ascribed to domination by entropy
effects.
The use of porous polymer gels both for size exclusion
analysis and conventional reversed-phase systems was reported
by several authors includin Hanai et al. (990, Freeman and
%
Schran (780, Mori (1550, zaki et al. (1701),and Pop1 et al.
(1801).
The new development of open tubular microcapillary liquid
chromatogra hy was demonstrated by the separation of
aromatic hy&ocarbons (1061).
SUPERCRITICAL CHROMATOGRAPHY
Klesper (1231) described the particular characteristics and
advantages of this technique which is of particular interest
in the separation of high molecular weight compounds. Gouw
e t al. (921) described the use of the technique for the deter-
mination of polycyclic aromatic hydrocarbons in automobile
exhausts and refinery solid wastes. A method of interfacing
supercritical chromatography to mass spectroscopy is dis-
cussed.
The unusual gas chromatographic behavior of naphthalene,
pyrene, and phenanthrene using pressurized pentane as carrier
gas was reported by Semonian and Rogers (2101). Contrary
to theory, efficiency was independent of pressure, but the
maxima in the graphs of distribution coefficient vs. column
pressure were related to pressure-dependent physical and
chemical effects.
Ecknig and Polster (651)used supercritical COz carrier gas
and molecular sieve 5A for the separation of Cg-Cfl-alkanes.
The alkanes were rapidly eluted at a column temperature and
PETROLEUM
pressure of 140 "C and 10 MPa.
COMBINED CHROMATOGRAPHY
TECHNIQUES
Simon et al. (2181) used subtractive reaction gas chroma-
tography for the determination of dienes. The chromatogram
of the original sample was com ared with that obtained after
the dienes had been extracted gy ercolation through a silica
gel column containing maleic angydride.
Ivanenko et al. (1141) concentrated traces of nonhydro-
carbons in an ethylene polymerization solvent on alumina or
molecular sieve and analyzed the com ounds by gas chro-
matography after elution from the a i o r b e n t with water.
Beider et al. (151) used silica gel to extract alkanes from
gases used in methanol manufacture and, after extraction with
methanol-hexane, analyzed them on Apiezon L by gas chro-
matography.
Guzhova and Fadeev (981) used the fluorescent indicator
adsorption method to prepare hydrocarbon group fractions
for capillary gas chromatography.
GAS CHROMATOGRAPHY
The most widely used technique for hydrocarbon analysis
is undoubtably gas chromatography, and therefore references
tend to be repetitious with man similar separations on
identical column systems reported:
The references cited are therefore a cross-section of ref-
erence with emphasis on some of the more unusual systems.
LIGHT HYDROCARBONS
Fackrell (691) used a noncolumn technique to determine
the mean value and instantaneous value of the hydrocarbon
content of air to be determined. The pulsed sample valve
technique enabled a sample to be taken each second. A re-
finery gas analyzer was reported (331) which allows for the
analysis of hydrogen through c6+to be determined in 24 min.
The analyzer incorporates a patented hydrogen transfer
system which gives a linear response for hydrogen over the
ran e 0.01-100%.
8uevas and Guzman (501) developed a method for the
analysis of trace amounts of C3-C4 olefins in li uid petroleum
gas using a simple comparison method of csqibration.
Saha et al. (1971) used a parallel column system of
OPN/PorasilC and phenyl isocyanate/ParacilC in a dual gas
chromatograph to provide a generalized method of analysis
for 16 C1-Cs alkanes and alkenes. Schelner (2041) used ethyl
2-oxocyclopentanoate as a stationary phase for the separation
of isomeric butenes.
Saulova and Pankova (2011) determined trace impurities
a t the sub ppm level in ethylene; Seweryniak and Slonka
(2121) se arated some alkynes on UCON LB on chromosorb
P and diiutyl phthalate on C-22 firebrick.
Alkadiene and alkynes in C1-C5 fractions were determined
by the use of B,B'-oxydipropionitrile or dimethyl sulfolane
containin aqueous Na2C03as stationary phase (2111).
The ligBt hydrocarbons evolved in oil shale pyrolysis and
the effect of ox gen on their composition was studied by
Robillard et al. 6921) using a temperature programmed ap-
proach on Spherocarb.
A new stationary phase, phenyl glycidyl ether, was reported
by Lukac and Nguyen (1391) which is useful for the separation
of small amounts of c5 and c6 unsaturated compounds from
the parent n-alkanes.
UNUSUAL COLUMN CONFIGURATIONS
Rend1 et al. (1091) described the development of a dual
concentric column configuration where the inner column and
the anular space around it were packed with different ma-
terials. Use of this column system for the se aration of hy-
drocarbon/permanent gas mixtures is detailex. Willis (2531)
described the use of a porous polymer and a molecular sieve
column that could be used in a parallel, series, or series bypass
configuration in order to separate permanent gases and light
hydrocarbons.
Bertsch (181) described two-dimensional chromatographic
techniques with particular emphasis on technolo capable
of dealing with samples of extreme complexity a n c b s o trace
and ultratrace systems.
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 109 R
PETROLEUM
Hunger et al. (1101) used pulsed gas chromatography on
cobaltsodium Zeolites. An evaluation of the method showed
it to be suitable for determining total mass transport resistance
and the contributions of the two pore sizes to diffusion but
that the dependence of the diffusion coefficient on loadin
could not be determined. Berezkin (161) continued his wort
on subtractive gas chromatography with a review of the
technoloY. Explicit working details are given for a number
of examp es, together with a table listing reagents for the
removal of various components. Osis (1691) studied the
structure of the carbon skeleton of nitrogen containing com-
pounds by a hydrogenation method of reaction gas chroma-
tography.
GAS CHROMATOGRAPHIC PHASES
A great deal of attention has been paid to the use of gra-
phitized thermal black as a chromatographic medium.
Krawiec et al. (1251) studied the chromatogra hic behavior
of 65 linear or branched C2-Clo alkanes ancfalkkenes on
carbon black. Kovats indices, their variation with tempera-
ture, column capacity ratios, and adsorption enthalpies and
entropies are reported.
Felt1 et al. (751) found the the logarithm of the specific
retention volume relative to 1 g of graphitized carbon black
was a rectilinear function of carbon number for both alkanes
and alk-1-enes.
DiCorcia and Giabbai (541) demonstrated very rapid sep-
arations of C6-C9aromatics and C C5 alkanes using acked
columns containing fine particles (T85-28 pm) of CarBopack
C. Bertoni et al. (171) modified the surface of Carbopack C
H T with various stationary phases. The systems were used
to separate aromatic hydrocarbons and other samples at the
trace level.
Cicioli et al. (441) applied columns packed with PPE 20 on
gra hitized carbon black to the separation of C4-C4 hydro-
B
car ons in a single injection.
Engewald et al. (661) determined retention indices and
homomorphic factors for C9414 alkylbenzenes on graphitized
thermal carbon black.
Several authors reported on the use of other gas/solid
systems including O’Brien and Grob (1671) who studied metal
oxides and Snowden and Peake (2211) who used a KNOB-
LiN03-NaN03 eutectic for the rapid separation of saturated
“isoprenoids” and C4-Ca n-alkanes in oil shale.
Frycka (811) used cadmium chloride modified with Car-
bowax 20M; Smolkova-Keulemansova (2201) studied the re-
tention behavior of alkanes, alkenes, alcohols, and some
aromatics on a urea-hexadecane inclusion compound.
New, or rediscovered, more conventional stationary phases
ranged from asphaltenes (2311) to a series of reactive polar
polymers developed by Lukas et al. (1401-1421). Ravey (1891)
introduced the mixed bis-lactam 142-oxo yrrolidin-l-yl-
methyl)hexahydroazepin-2-oneand generate: retention data
for 26 hydrocarbons relative to 1,3-butadiene.
Parcher et al. (1721) investigated phen lmethyl-silicone
stationary phases and their use in mixed ged columns.
Sakodynskii et al. (1981) developed selective phases based
on phenylquinoxaline and “siloxarophenanthrene” in a
polymeric form. Strand and Andren (2261) synthesized some
liquid crystal phases and compared them to Dexsil 300 for
the separation of benzo[a]anthracene from chrysene. Vig-
dergauz et al. (2421) proposed classifying liquid phases not
only by the Rohrschneider indices but also with an additional
factor related to the difference in the logarithm of the re-
tention indices of m- and p-xylenes.
IDENTIFICATION OF COMPONENTS
Jaworski and Herzog (1151) identified cycloalkanes, normal
alkenes, and aromatic hydrocarbons separated on Chromosorb
101 by means of Kovats retention indices, temperature
coefficient indices, and the u parameter of the chromato-
graphic curve.
Radecki et al. (1831) derived an equation for predicting the
retention indices on nematic phases from computable par-
amters and the size of molecules of polycyclic aromatic hy-
drocarbons.
Nabivach et al. (1601) determined the Kovats retention
indices of many hydrocarbons a t 70 O C and 86 OC on a
squalane phase. Tejedor (2301) derived empirical equations
110R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
for the calculation of the retention indices of mono- and di-
alkylaromatic compounds on stationary phases with polarity
between those of squalane and Ucon 50HB-208X.
Grant and Hollis (931) used a packed, a capillary, and two
porous layer open tubular columns to verify the accuracy of
thermodynamically defied retention characteristics in linear
pro ammed-temperature gas chromatography.
&bivach et al. (1581)-1601) studied the retention indices
of aromatic hydrocarbons on squalane and of paraffinic and
aromatic hydrocarbons on tetracosane, squalane, dotriacon-
tane, and 4,4’-diisopropyldibenzybenzene. Mitra and Bhat-
tacharya (1531) applied the retention index system to solid
deposits found in a as reforming plant. Dimov and Pa w v a
(581) showed that t i e retention indices of isoalkanes i d not
depend on the McReynolds’ polarity of hydrocarbon and
methyl silicone phases.
AROMATIC HYDROCARBONS
The analysis of aromatic hydrocarbons by as chromatog-
raphy is getting as much attention as anafysis by liquid
chromatography.
Quantitative identification of aromatic hydrocarbons and
thiophenes in coker gasoline was reported by Hanna et al.
(1011). Beernaert (141) reported that as little as 0.5 ppb of
an aromatic com ound codd be determined by temperature
programmed ana&is on ES-52. The retention indices of many
compounds are also reported.
Chmela et al. (401) used poly-rn-phenyl ether, in both
packed and capillary columns for aromatic hydrocarbon
analysis. Frycka (801) selectively separated high boiling o-
lycyclic aromatic hydrocarbons on bentone-34 coated on &s
beads. Pesek and Blair (1771) used NJV-bis(2-cyanoet~yl)-
formamide and a back-flushing technique to determine C8 and
heavier alkylbenzoates in petroleum naphtha.
Pielichowski et al. (1781) used haloalkylcarbazoles, Saluste
et al. (1991) used Dexsi 300 and Shlyakov et al. (2151) used
Apiezon L to separate mono- and bicyclic arenes.
Lee et al. (1331) reported that retention indices calculated
for polycyclic aromatic compounds based on cochromato-
graphed n-alkanes as internal standards were unreliable. The
use of naphthalene, phenanthrene, chrysene, and picene gave
values that remained reproducible over several months of
extensive column usage with different temperature program
rates. The new indices are reported for 209 compounds.
Schroeder (2061) reviewed retention indices data on squa-
lane; Welsch et al. (2501)determined the retention behavior
of cotynes and octadiynes.
GENERAL GAS CHROMATOGRAPHY
Bjorseth and Eklund (191) used capill GC analysis with
simultaneous FID/EC detection to p r o y e additional iden-
tification evidence of aromatic hydrocarbons by comparin
FID/EC ratio. Blomberg et al. (221) prepared directly bondefi
phenylsilicone coated lass capillaries for the separation of
polycyclic aromatics; Eoretti and Liberti (911) evaluated a
variety of precoat rocedures for gas capillaries.
a
Johansen (1160 aescribed the use of short lass wall coated
open tubular columns for a variety of n-a1 anes including
pristane and phytane.
Kumar et al. (1301) provided details of the isothermal
analysis of naphtha on squalane; Mathews et al. (1461) sep-
arated li ht naphtha com onents on hexadicane and hexa-
decane/fielF10157 on so& lime glass.
Nygren (1661) also focused on analyses with short glass
capillaries and materially shortened fast analyses by flow
programming. The separation of Cl0-Cl8 alkanes in 3 min is
cited as an example of the technique.
Sojak and Krupcik (2221) used Carbowax 20M lass col-
umns in the solid state; Bartle et al. (101) improvefthe sep-
aration of mixtures of lacquer solvents on Carbowax 20M-2-
nitroterephthalic acid.
Tesarik et al. (2341)developed a mixed phase column 17:13
Ucon LB-55OX-tris(2-cyancethoxy)propanefor the separation
of a series of substituted na hthalenes and bi henyls.
Anoshin et al. (41) and Zawdzik (861) bot[ worked on
micropacked columns.
Many authors (1001,1501,1751,2141,1811) examined the
composition of petroleum fractions from pyrolysis gasoline
and coker gasoline. Vdarov et al. (2380 used tricresyl

phosphate for the separation of monoter enes, Grom et al.
(950 analyzed the reaction mducts of Cnabenes with tertiary
butyl hydroperoxide.
Matishev (1470, Eppert et al. (671), and Felscher (741)
determined n-alkanes. Methods for the evaluation of the
degradation of insulating oils in power transformers based on
the determination of C3 and lighter hydrocarbons were de-
tailed by Rao and Iyer (1871).
Costello and D’Amato (361) proposed that linear and
branched chain alkanes could be used as nonpolar reference
materials in gas chromatography. Kuchhal and Mallik (128Z)
used gas chromatography with n-hexane, cyclohexane, cy-
clohexene, isooctanebenzene, and methanol to study the
thermodynamics of solution in dipropionitriles.
Lukac (1381) used a parallel column system comparised of
an open tubular Apiezon L column and a packed phenyliso-
c anate Porasil C followed b s ualane on Gas Chrom P for
i i
t e sing e run separation of &-810
the as-phase radiolysis of n-pentane.
hydrocarbons formed by
Chzhkov et al. (391) used a circulation gas chromatograph
with two columns in series for the simultaneous analysis and
preparative separation of binary mixtures. They report that
the columns provide substantially better separation efficiency
than can be obtained with thermal distillation columns of the
same dimensions.
MISCELLANEOUS METHODS OF ANALYSIS
Hrubesh nlO91) described a new technique based on mi-
crowave rotational spectrometry. The computer-controlled
spectrometer can be used for the automated determination
of 10-100 ppm of hydrocarbons in air or vehicle exhaust gases.
Tsibul’skaya et al. (2371) demonstrated the ossibility of
E
determining aromatic hydrocarbons in gases y using the
equilibrium concentration in a volatile solvent under condi-
tions of changing the distribution coefficients for a microim-
purity component. The method was demonstrated to work
for benzene, toluene, and rn-xylene in vapor-air mixtures of
various humidity by determining the saturated equilibrium
amount of acetic acid absorbed into the vapor mixture by
titration with alkali.
Usmani et al. (2391) used oxidation with ammonium hex-
anitratocerate(V1) to determine milligram amounts of poly-
cyclic hydrocarbons. Phenols, amines, alcohols, and aldehydes
interfer but benzene is not oxidized.
Kazakova and Vfimtsev (1201) recisely determined ali-
phatic and aromatic alcohols in hyiocarbons by treating the
sample with 1-7 M HN03 in the presence of A1(N03)3and
then titrating the resulting solution with alkali.
The classical distillation methods are rarely reported in the
literature; however, Bligh (211) describes an improvement to
hardware for the separation of natural as com onents by
distillation. Wakselman and Bouget (2478 studiefthe nature
of the interactions between unsaturated hydrocarbons and
polar aprotic solvents. The results may be applied to ex-
tractive distillation and agree well with observations of polar
interactions.
Zimina et al. (2651) used thermal diffusion to separate
fractions of lubricating oil for further analvsis. Zhukhovitskii
et al. (2641) used chroiadistillation to conienGate impurities.
Pertsovskii and Emel’kin (1761) reported on methods to
increase the accuracy of measurement of the electrophoretic
transfer of high molecular weight hydrocarbons. The sensi-
tivity of the technique could be improved with subsequent
gas chromatographic analysis.
CATALYTIC SYSTEMS
Greco (941) reported that ethylene feedstocks could be
characterized by microscale pyrolysis gas chromatography.
The silica lined Inconel chamber used for the pyrolysis was
closely coupled to the gas chromatographic column. Results
are reported for single components of a typical feedstock.
Dyer (631) reported on the use of three Zeolite molecular
sieves for the separation and analysis of closely related system,
e.g., hydrocarbon isomers. Improved zeolite catalysts for the
synthesis of gasoline components form hydrogen/carbon
monoxide feedstocks were described by Chang et al. (371).
Slinkin et al. (2191) described a new catalyst for hydrocarbon
conversion by suspendin H,PtC& on viscose fibers. The
calcined fibers exhibited k g h activity for the conversion of
PETROLEUM
cyclic hydrocarbons to aromatics. The catalysts exhibited
strong EPR signals.
ENVIRONMENTAL
The special problems inherent in the analysis of hydro-
carbons in the environment, both air and water, were reported
by several authors. Schneider et al. (2051) used glass capillary
columns coated with aluminum oxide to determine h dro-
carbons in air at the arta per 109level. Masumov et al. 645I)
described a methof for concentrating hydrocarbons from
oxygen samples. Care must be taken to control the temper-
ature such that condensation of the gaseous oxygen is avoided.
Gamage et al. (831) reported on several new instruments
and instrumental techniques suitable for the determination
of polynuclear aromatic hydrocarbons in the work place. The
techniques reported are suitable for the characterization of
pollutants from syn-fuel operations such as tar sand and oil
shale processing.
Carsin (341) described types of sampling probes and in-
troduced a new probe designed for sampling surface oil slicks
from the sea. Experimental details are given for extracting
the oil retained in the probe filter and for its subsequent
analysis by infrared spectrophotometry.
Brown et al. (291) used a solvent/slurry extraction proce-
dure to concentrate and extract trace levels of petroleum
hydrocarbons from marine sediments.
Drozd and Novak (601)used a head space technique using
the standard addition method to determine benzene in
aqueous liquid systems. Akulinchev et al. (11) determined
the content of phenols and benzene in stratal waters as an
indicator in prospecting for natural gas. Extreme care in
handling the samples to avoid oxidation by contact with air
is required. Kudryavtseva et al. (1291) extended the analysis
of stratal waters by concentrating the hydrocarbons by
chloroform extraction.
Middleditch et al. (1491) reported that an impurity in cy-
clohexane, which is the preferred solvent for the extraction
of normal alkanes from environmental matrices, can lead to
erroneous concentrations of n-tridicane being reported. The
impurity, bicyclohexyl, is not a factor with analyses at the ppm
level but can interfere at the ppb level if conventional packed
column analysis is used.
The Proceedings of the Analytical Division of the Chemical
Society (3Z)review several papers presented that refer to the
analysis of polynuclear aromatic com ounds in food, water,
and industrial effluents. Fritz (791) 90 described a method
based on extraction and thin-layer chromatography, for the
analysis of polycyclic compounds in food, soil, and water. The
method allows the detection of 0.01 pg of benzo[a]p ene in
the presence of other polycyclic aromatic hydrocarEns.
Ogawa (1681) used liquid absorption chromatography on
silica el as a means for identifying water borne petroleum.
The efapsed time spent by the oil on the water surface was
estimated from the increase in asphalt resin content.
HYDROCARBON SOURCES
A multiple of methods were used in order to elucidate the
origin of hydrocarbon sources. Calvin (321) evaluated hy-
drocarbon-producing plants and the chemical techniques
needed for extracting the hydrocarbons. The use of these
plants to produce an energy source by photosynthesis is
discussed in detail.
Ernestova (681) proposed a method for extracting hydro-
carbons from free-flowing inorganic materials. Natusch and
Tomkins (1611) used a rapid liquid liquid extraction procedure
to isolate hydrocarbon fractions containing specific functional
groups from a complex liquid Sam le.
Several authors (171I,2591-261~reportedon the compo-
sition of hydrocarbons extracted from oil shale and used the
composition to interprete the origin of the shale and the
geological stress to which it had been exposed.
Schaefer et al. (2021,2031) described a technique based on
hydrogen stripping followed by capillary gas chromatography
to detect as little as 0.01 pbb of hydrocarbon in rock samples.
The method has been used to correlate crude oil and natural
gas accumulations with the residual hydrocarbon content of
source rocks.
Starobenets et al. (2241) examined changes in the compo-
sition of C4+ n- and isoalkanes in natural gas during migration.
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 111 R
PETROLEUM
The predominant mechanism appears to be a diffusional mass
transfer. Luks et al. (1431) developed a method of mea-
surement and prediction of the solubility of hydrocarbons in
cryogenic natural gas liquids.
Moldowan and Seifert (1541) identified head-to-head linked
isoprenoids in crude petroleum. The head-to-head linked
isoprenoids are present at a substantially higher concentration
than the head-to-tail counterparts. The same series of
head-to-head isoprenoids were discovered in crude oiis and
source rock extracts from Canada, Venezuela, the US.and
the U.S.S.R. Lekveishvili et al. (1341) used a photoinitiated
condensation with maleic anhydride to separate and identify
phenanthrenes from crude oil.
The normal paraffins in petroleum fractions were the
subject of Belgian (2401) and U S . (2561) patents. Felscher
(731) recovered n-parafins from a Romashkino bitumen.
Cracking during distillation was suggested by the data.
The hgh molecular weight fractions of Kuwait crude (1130,
Geor ian crude oils (570, and petroleum from the Siva field
(246a were analyzed by a variety of techniques.
Rodionova et al. (1931) and Diamante (711) used the
analysis of n-paraffms and the ratio of n-alkanes to na hthenes
f:
to determine the degree of metamorphism of the roc organic
matter and the preservation of the petroleum formations.
FUand Phillips (821) described a new technique for de-
termining the diffusivities of volatile hydrocarbons in semisolid
bitumen. Neumann and Kaschani (1621) reviewed the
methods of enrichment, separation, isolation, identification,
and determination of olycyclic aromatic hydrocarbons in
9
bitumens. Selucky et (2091) used a rapid chromatogrpahic
procedure for fingerprinting deasphalted bitumens.
METALS I N OILS
J. L. Fabec
Gult Science and Technology Company
An increased interest among investigators during 1980 has
been directed to the determination of metals in oils by using
inductively coupled argon plasma. In terms of total activity,
as measured by the number of papers in this review, a slight
upward trend over recent prior years is apparent. The fol-
lowing is a review of the published literature in this area.
Atomic Absorption Spectrometry (AAS). Sesaki et al.
(604 determined nickel, vanadium, and sodium in crude and
fractionated oils by dissolving the sample in a mixed solvent
and analyzing it by flameless AAS. They found (1) the best
solvent for the samples (dissolved at 60 "C) was 50% xylene,
40% MIBK, and 10% methanol, (2) the mutual interferences
of the three metals and other trace metals were eliminated
by the addition of 50-60 mg of iodine per 50 mL of sample
solution, (3) good metals agreement was obtained with the
standard Japan Petroleum Institute method for fuel oil, an
atmospheric residue, and an Arabian light crude, and (4) the
method gave better repeatability at low metals concentration.
Ivanov et al. ( 3 0 4 determined vanadium in petroleum and
ita products by combining 1 g of sample with carbon powder,
heating at 350 "C for 1 h, and adding 20 mg of NaF and a
sufficient amount of carbon powder to make a 1g weight. The
mixture is placed in the cavity of a carbon electrode and
vaporized with a 18-A ac arc. Detection is made with a sin-
gle-beam AAS. Aclibration is effected by the addition method
and results are not affected by the type of vanadium present.
After mineralization of petroleum and preparation of synthetic
mixtures, Sychra et al. (664 showed that Ni, V, Cu, Na, Ca,
Mg, and A1 do not interfere with Ni and Fe (5 pg/mL) and
V (50 pg/mL) determinations. Potential interferences were
controlled or eliminated by using proper flame conditons or
by addition of 2 mg mL of K plus 1 mg/mL of Al. They
i
confirmed their resu ts with spectrophotometry and s uare
wave polarography. The Japan Petroleum Institute 7314
evaluated test results from 34 laboratories on the analysis of
vanadium and nickel in heavy oils. An AAS solvent-dilution
techni ue was compared to the JPI method involving sulfuric
acid asting and colorimetry. The AAS method showed equal
or better precision for nickel and poorer precision for vana-
dium than the J P I method.
La Villa and Queraud (404 determined arsenic in catalytic
re-forming feedstocks by flameless AAS. The sample is treated
with 1% iodine solution and then extracted with 1% HN03.
Mg(NO& (1%Mg) is added to the extract. It is dried and
112R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
then dissolved in 1% HNO . The method of standard ad-
ditions is recommended. $he confidence interval is 95%
certainty. A rapid technique to determine low ppm levels of
Cu in petroleum products was presented by Monoiu and
Manoliu (434. Samples and standards are diluted with
white-spirit and analyzed directly by flame AAS. The relative
mean error does not exceed f l % . Whittman (734 deter-
mined calcium, magnesium, and zinc in lubricating oils and
additives by using a mixed solvent system. The sample was
mixed with 20 mL of toluene and diluted to 100 mL with
anh drous acetic acid. Results obtained by this method, by
d i n aqueous solution after ashing, and by other established
methods for 22 samples were in good agreement. A method
independent of particle size to determine molybdenum wear
metal in lubricating oils was developed by Saba and Kent
(584. The sample is added to a mixture containin H F and
HNO and shaken for 2 min before dilution wit! MIBK,
Samples containing Mo powder as large as 200 mexh were
analyzed with an accuracy of 95.5 f 2.6%. A comparison is
made between the results obtained from this procedure and
other AAS and emission techniques. Cergolj and Kunic (135)
used AAS to monitor used lubricating oils by analyzing for
ppm levels of Cu, Fe, Pb, Ag, Cr, Zn, and Mg.
Berenguer et al. ( 5 4 developed a new direct ra id method
to determine lead in gasoline by AAS after emuhfying the
sample. The lead is complexed with idoine and emulsified
in HzO with Emulsogen LBH. EtOH in added to suppress
foaming. Stable standard emulsions are prepared by using
aqueous P b (NO,),. The procedure gave a mean deviation
of 0.1-2% and a reed with the gravimetric (PbCrO,) and
volumetric (EDTI + xylenol orange) methods. Studies were
conducted by PPG Industries, Inc. (564 to determine Al, Cu,
Fe, and P b in glycol formulations.
The distribution of trace elements in various solvent-refined
coal fractions as a function of the feed coal was investi ated
by Coleman et al. (174. Solvent-refined coal (SRC! and
tetrahydrofuran soluble and insoluble SRC fractions derived
from five different feed coals were analyzed for 12 elements
via flameless AAS. Comparison of these data with previous
reported metal analyses via energy-dispersive X-ra fluores-
cence analyses of similar SRC solid products is &cussed.
Three coal liquids were separated according to effective mo-
lecular size by gel-permeation chromatography, and metal
analyses were performed on selected fractions. The possibilit
that some metals may be organically bound is considerei
Szivos et al. (674 studied the effect of HzO, EtOH, PrOH,
MeOAc, EtOAc, and MezCO on the geometry of an C2Hz-air
flame and on the AAS sensitivity by using solutions of Ag,
Cu, Fe, and Pb. They found that with organic solvents, the
rate of entry of elements was higher by the free atoms were
distributed in a large flame volume at the optimum obser-
vation height. Therefore, the increase of AAS sensitivity was
less than expected.
AAS was used by Bye et al. (114 as a specific as chro-
matograph detector. The GLC (column of 20% 8E-52 on
Chromosorb W, 125 "C, argon carrier as) effluent was led
to the atomizer of a three-slot burner kir-acetylene flame)
or to a graphite furnace. Tetramethyl- and tetraethyllead were
determined and results compared to conventional acid ex-
traction AAS determinations. Results by GLC-AAS were
86-92% of those obtained for total lead by the extraction
method. Detection limits, sensitivity, and advantages of the
interface between a li uid chromatograph and a flameless AAS
detector are describe1 by Vickrey et al. (704. The interface
device consists of a sampling valve, a dispenser, and a timing
circuit. Coanalyte addition is used. Results using this in-
terface to monitor the separation of several Se compounds (by
using Ni2+ as coanalyte) are discussed.
Yamamoto (754 presented a review with 21 references for
the determination of As, Se, and Sb by AAS. Interferences,
a review of 21 references by Mo et al. (494, and interferences
and their elimination, a review with 63 references by Chu and
Huang (154 are noteworthy of mention.
X-ray Fluorescence Spectrometry. X-ray emission
spectroscopy was used by Yasuda and Kakiyama ( 7 7 4 to
estimate the oxidation state of vanadium in samples of pe-
troleum vacuum residue and oil sand bitumen by comparison
of certain spectral parameters with those of pure V com-
pounds. Generally, most of the V was present as V4+,even
after heating samples at 450 "C for 2 h in Nz. Further heating

at lo00 "C for 1h showed gradual reduction to V3+by Hz and
H2S produced during pyrolysis. Also, a review with no ref-
erences to determine the state of V in petroleum products was
presented by Kakiyama (334.
Trace amounts of Sb, As, Bi, Cd, Co, Hg, Ni, Pb, Cu, Se,
Sn, and Zn can be determined in various matrices. Iesue and
Taroli (284 determined these metals by usin z200 mL of
water solution after (1)treating chemically, (27 forming sul-
fides, (3) collecting sulfides on cellulose powder, (4) ressing
a tablet, and (5) analyzing by X-ray fluorescence. $he cali-
bration range for each element is 0.1-2 mg and the limit of
detection is =1 I.( in the cellulose mixture. The procedure
should be applica%leto analyzing foods, petroleum d u c t s ,
P
soils, fertilizers, and waters. Trace elements in oi samples
were determined by Kubo et al. (394. They mixed wei hed
samples with standard solutions of Cr and Rh in H2S8, or
an organorhodium compound in mineral oil. Results for a
NBS fuel oil agreed with certified values. Fe, Ni, Zn, As, and
Se were determined in shale oil. Giau ue et al. ( 2 4 4 used
incoherent scatter Mo K a excitation raliation to determine
trace elements in light element matrices. The method was
evaluated by repetitive direct determinations of 22 trace el-
ements in NBS coal, orchard leaves and bovine liver, 9 ele-
ments in standard fuel oil, and 6 elements in a shale oil
standard. Comparisons are made with recommended values
and with neutron activation results. The sensitivity for most
of the elements is 2 ppm or better, and, for an analysis time
of 15 min, results are typically accurate to within &lo%.
Impurities in petroleum cokes were analyzed by Avrorina et
al. ( 3 4 . They determined Na, Mg, Al, Si, P, C1, Ca, Ti, V,
Ni, Fe, Cu, and K in seven Russian and one American pe-
troleum cokes from different refineries. Wildeman and
Heistand (724 studied trace element variations in an oil-shale
retorting operation. Seventeen trace elements were deter-
mined. Concentration ranges for these elements in shale-oil
ranged over a factor of 2, much less than they expected.
A mathematical linearization procedure using two standards
is described by Krishnan (385) to correct for matrix effects
and nonlinear detector response. This procedure is re rtedly
applicable to samples in any matrix. Claisse (16fused a
differential delta coefficient method for correction of matrix
effects by X-ray fluorescence analysis. Unknown samples are
compared to only one standard of similar type; their com-
pounds are calculated from ratios of X-ray line intensities and
equations obtained by derivation of the well-known Lochance
and Traill, Rasberry and Heinrich, and Claisse and Quintin
relations. By calculating relative intensities in the calibration
of an X-ray spectrometer, Chamberlain (144 found that ex-
tensive remeasurements on standards are eliminated. This
procedure is exemplified by the calibration of an instrument
for determining Cu, Ba, Zn, and S in oil. Nielson (525) re-
views, with 51 references, matrix correction techniques using
scatter radiation in X-ray fluorescence analysis.
A review (20 references) by Nagatani (514 includes (1)the
principle and features of energy-dispersive X-ray spectroscopy
and (2) its applications to quantitative analysis and micro-
probe analysis.
Emission Spectroscopy. Inductively coupled plasma
(ICP) was used by Merryfield and Loyd (484 to simultane-
ously determine metals in oil to the sub-ppm level. Rapid
analyses of oils for wear metals, of crudes and feedstocks, and
of process streams were possible. Instrument parameters, a
simplified preparation technique, and interferences are dis-
cussed. The advantages of this system over other emission
spectral analysis techniques were presented by Fischer (204.
Fischer (214 also presented the principles, instrumentation,
and use of ICP. Its application to metal additives in lubri-
cating oil and steel analysis is described. The instrumentation,
operating arameters, and ap lications of ICP were also
presented By Barnes ( 4 4 . AppEcations include the analysis
of metals, minerals, blood, oil, refractory oxides, organo-
phosphorus compounds, soil effluents, polymers, water, plant
tissues, and foods. A total of 337 references were cited.
Boumans (94reviewed, with 179 references, the present and
future position of ICP in analytical chemistry. Another review
with 69 references by Zimmer ( 7 8 4 covered the structure of
the plasma, injection methods, and applications.
Because of its multielement capability, element specificity,
and low detection limits, Fraley et al., (224 evaluated ICP
as a detector for high-performance liquid chromatographic
PETROLEUM
(HPLC) peaks containing specific elements. Detection limits
of 25 elements were evaluated in terms of the minimum de-
tectable concentration of the element at the chromatographic
peak maximum. ICP is compared to AAS for the detection
of HPLC peaks of Cu chelates and with UV solution ab-
sorption of Cu chelates.
Reednick ( 5 7 4 presents the advantages and capabilities
of the Spectraspan 111,a dc argon plasma (DCP), instrument.
Applications to a variety of sample types to determine ppb
levels of elements are also presented. The enhancement of
atom and ion emission in a DCP due to the addition of easily
ionized elements was studied by Johnson et al. (32J). Their
observations indicate that the enhancement effect could not
be readily explained on the basis of plasma temperature in-
creases or the classical ionization repression mechanism. They
sug ested that the enhancement may result from increases
in tRe population of metastable Ar with coincident increases
in excitation via collision with this species. This mechanism
is circumstantially supported by the present results but must
be regarded as tentative. Atomic emission analytical capa-
bilities of a DCP used in combination with an echelle spec-
trometer were evaluated by Skogerboe and Urasa (644.
Resolution capabilities, ionization interference effects, and
vaporization interference effects are presented. Comparison
of the detection capabilities of the system with those reported
for other techniques shows that they are e uivalent or superior
to those characteristic of flame AAS an% often competitive
to ICP.
The oil matrix was shown by Bib1 et al. ( 7 4 to have a
considerable effect on Fe determinations in used lubricating
oils from aircraft gas-turbine engines when analyzed by
emission spectroscopy. The size of wear particles had little
effect. For accurate analysis, the samples and standards
should have identical oil matrices. Analysis by AAS, sun les
being diluted with MIBK, gave fairly accurate results. i e r -
rography and spectrographic oil analysis enabled Yardley (764
to monitor the performances of three 90KW conveyor gear-
boxes. Four failures occurred durin this investigation. All
failures were detected by spectrograpkc oil anal is and three
by ferrography. A discussion of results i n c l u g comments
on the analyses and the basis for failure prediction.
Brinkman et al. (IO4 used flame atomic fluorescence/
emission spectrometry to determine trace metals in petroleum,
petroleum products, and alternate fuels. Instrumentation,
sampling, and detection limits for the elements analyzed are
presented. The system was applied to monitoring the loss of
various metals during the refining of a used lubricant. Goode
(254showed how methods used to obtain a calibration plot
influence chemical analysis by flame atomic emission spec-
trometry. Ex rimental data are treated by several different
methods to o k i n calibration plots, which are then used to
determine the accuracy of each method. In general, log-log
lots are more accurate than are linear plots especially at the
Righer analyte concentrations where the emission is no longer
directly proportional to concentration.
A mathematical expression was derived by Woodyard et
al. ( 7 4 4 for the emission calibration curve used in optical
emission spectroscopy. Employing a two-step preliminary
curve method, an approximation of the first derivative of the
calibration curve is formed and integrated. Problems of atom
excitation and ionization in arc and spark plasmas, spectral
line intensity, detection limits, and entry of Sam le into the
excitation source are discussed by Mandelshtam f424. Zim-
mer and Gegus (794 reviewed with 110 references, the role
of detection limits in emission spectral analysis. The opti-
mization of analytical methods in terms of obtaining error free
blackening transformations, matrix effect elimination, and the
construction of calibration curves (44references) was discussed
by Matherny (444.
Neutron Activation Analysis (NAA). Samples of crude
oil, gasoline, and fuel oil were analyzed b Block and Dams
(84 by irradiation in thermal, epithermd and fast neutron
fluxes and counting with a Ge(Lie) detector. Preparation of
organic sulfonates in oil base, detection limits and typical
concentration ranges for 23 elements, and rocedures for
f
s4Cu, 2o Hg, and 27Mgare presented.
'
avoidin interferences when measuring 80Br, BAs, lnSb, @Zn,
The method, instrumentation, and advantages of neutron
activation analysis of coal, fly ash, and fuel oils for trace
elements are described by Weaver (714. Shaw (634 reported
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 113R
PETROLEUM
the analysis of trace elements in shale oil and shale oil products
and the advantages of this technique. The greatest advantages
was no sample preparation which simplifies the process and
prevents sample contamination. Twenty-three elements were
determined. Heft and Koszykowski (274 analyzed oil-shale
retort and coal gasification products by (absolute instrumental)
NAA. This procedure depends upon the absolute measure-
ment of the disintegration rates of the nuclides produced by
neutron capture. C6&-EtOH extracts of bitumens from rocks
of a petroleum-bearing region and the rocks were studied by
Verci and Sajgo (694. The amounts of Cr, Au, Se, Co, Sc,
Mn, and Cu in rock and bitumens are given.
May and Piccot ( 4 5 4 determined As, Cd, Hg, Sb, and Se
in synthetic proteins derived from petroleum and intended
for use in animal feeds. After irradiation, the sample is
mineralized in HN03-H2S04. Various procedures are then
used to isolate these elements for counting. Levels of the
elements in the samples tested range from =7 ppb Se to 254
ppb Sb. The method was checked by application to bovine
liver.
A report by Menard ( 4 7 4 summarizes research using
californium-252 as a neutron source to analyze USAF aircraft
engine oil samples for 13 elements. The same neutron source
was employed by Lubkowitz et al. ( 4 1 4 to automatically
analyze petroleum samples for vanadium. The system design
and program are described. The unattended system can an-
alyze 48 5-10-g samples in 8 h with a detection limit of 10 ppm
f30% and accuracies of 0.2-4%.
Bergerioux and Zikovsky ( 6 4 determined 18 elements in
crude oil and heating oil from Western Canada and Venezuela
by using a small (Slowpoke) nuclear reactor. Good agreement
with accepted values was obtained for 11 elements in a NBS
standard fuel oil. Possible interfering reactions are discussed.
A review with 29 references was presented by Murakami
(504. The use of radiation from radioisotopes in analytical
chemistry and the problems associated with its use are dis-
cussed.
Miscellaneous. Sebor et al. (625) reviewed, with 146
references, the occurrence, isolation, and identification of
nickel and vanadium complexes in relation to the genesis and
industrial scale processing of petroleum.
A chromatographic process was used by Amelin et al. (2J)
to determine V on an organic ion exchanger, desorption with
an acid solution, and quantitative determination of V in the
desorbate. The analysis precision is increased by increasing
the degree of extraction of V from the petroleum. This is
accomplished by absorbing it on a complex P- and N-con-
tainingampholyte which contains an aromatic nucleus with
two phosphono groups, one of which is bound to a N atom
through an active methylene group.
Saint-Just ( 5 9 4 developed a method to determine the
vanadium content of hydrotreated petroleum residues by
visible spectroscopy. The residues are dissolved in toluene,
cyclohexane, or pyridine and the absorbance of the solution
is measured a t 550 nm. Beer's law was obeyed for 0.3-3%
(w/w) of residue. The relations between absorbance and
vanadium were not linear, but the correlation was not distorted
by interactions with the solvents. The simplicity and accuracy
of this method makes it suitable for process control applica-
tions although a specific correlation curve must be developed
for each feedstock analyzed. Tetraethylead in isooctane,
gasolines, and naphthas were analyzed by Turgel et al. (684.
The sample was decomposed with Br, free Pb was reacted with
dithizone to give red P b dithizonate, and analysis was per-
formed with spectroscopy or photocolorimetry.
Metal additives in lubricants were determined in nona-
queous medium by Altman et al. ( 1 4 using complexometric
procedures. The conditions necessary for the reaction of
additives containing Mg, Ca, Zn, Pb, or Sr (as, e.g., na-
phthenates or alkylbenzenesulfonates) with EDTA are de-
scribed. Eriochrome black T was used as indicator to titrate
for Mg2+ and Zn2+. Suitable choice of solvents and use of
elevated temperature (60 O F ) to decrease reaction time allowed
10 samples to be analyzed in 90 min with a standard deviation
of 0.8-1.9%. Problems encountered and use of masking agents
are also discussed.
114R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
The content of Al in (1)aluminum isopropylate dissolved
in PrOH and oil and (2) polyaluminostearate or poly-
aluminophenolate dissolved in oil or diesel fuel was obtained
by Dagaev et al. (184 using potentiometric titration of so-
lutions after boiling for 5 min with 0.5 M aqueous HC104 to
form Al(C104)3.The solutions studied occur in the preparation
of polyaluminoxanes, which are the main components of a
break-in additive used in engine construction, and complex
A1 lubricating greases.
Kasler and Tierney (345) described a method to determine
P in organic compounds containing transition metals by using
Fourier transform 31PNMR. Triphenyl phosphate and Cr
acetylacetonate are used as standard and relaxing agent, re-
spectively. H2S04/HC104sample di estion is used. The
results are compared to those obtainef by molybdate-vana-
date spectrophotometric method.
Trace element determinations based on laser ablation and
selectivity radiation (TABLASER) were propsed by Measures
and Kwong ( 4 6 4 as a new and reliable microultratrace
technique. Although the present sensitivity limit is in the pm
ran e im roved system design could reduce the detection
totk pp! range. An important feature of this technique is
Lt
its relative freedom from chemical matrix effects, which
suggests the possibility of a universal calibration curve for all
elements regardless of their substrate matrix. Falk ( 1 9 4
reviewed, with 13 references, the physical principles of lasers
when used for spectrochemical analyses. The detection limits
of laser sources are compared to AAS, intracavity AAS, res-
onance and nonresonance atomic fluorescence, and pho-
toionization spectrometry. A review, with 219 references, of
atomic emission spectral analysis by using lasers was presented
by Petukh et al. (554.
Quantitative or anic elemental analysis was reviewed, with
33 references, by Eel'man (234. Cavagnaro (1Wpresented
a 223-page coverage of chemical analysis techniques to de-
termine trace elements. The techniques of polarography,
spectrochemical analysis, gas chromatography, ion exchan e
separations, extractions, X-ray fluorescence analysis, and N k
and applications are covered. The anal ical chemist of (1)
8
arsenic, a review of 224 references by konieczny a n r H a h n
(654, (2) antimon , a review with 165 references by Hahn
(264, and (3) molygdenum, a review with 1122 references by
Parker (545) was presented. They discussed the properties
of each metal res ectively and the methods used to determine
them. Kiba ( 3 5 8 reviewed (29 references) the considerations
to be taken during sample preparation for trace analysis to
prevent sample contamination.
On the basis of the replies obtained from 28 countries to
a questionaire on standard reference materials, the Interna-
tional Union of Pure and Applied Chemistry (294 presented
a re ort summarizing the materials presently available, the
nee: for future materials, and the aims for future develop-
ments and the suppliers of standard materials classified into
the following sections: iron and iron base alloys, nonferrous
metals and alloys (chip or solid form), gases in metals, bio-
logical standards, environmental standards, fuels and oils,
mineral materials and oxides, high-purity substances.
A number of techniques to combust or digest organic ma-
trices for trace element determinations were presented.
(1)Knapp ( 3 7 4 used a combustion chamber attached to
a condenser and a reagent flask containing 2 mL of acid. A
conduit is tangentially attached to the combustion chamber
for the introduction of 02,The sample is laced in the com-
bustion chamber and ignited with IR raiation. The com-
bustion products are condensed and collected in the reagent
flask by reflux boiling.
(2) A combustion tube was used by Kirch and Hintzsche
(364 for organic and inorganic substances. The tube consists
of an outer reaction chamber and two inner chambers and was
designed to increase the combustion volume, thereby, de-
creasing combustion time.
(3) Schachter and Boyer (614 described a new method to
destroy organic matrices using 71% HN03 as the oxidizing
agent. The apparatus consists of a heated quartz flask, a
Soxhlet extractor, a device for varying the volume of the
Soxhlet chamber, and a cold-finger reflux consenser. Re-
coveries for several NBS standard reference materials and food
samples are reported.
(4) h inexpensive wet ashing unit was presented by Oehme
(534. The unit consists of a specially designed aluminum

block placed on a hot plate with a gas manifold and cover to
prevent contamination.
NONMETAL ELEMENTS AND COMPOUNDS
D. R. Latham
Laramie Energy Technology Center, Laramie, Wyomhg 82071
Jane V. Thomas
Wyomhg Anaw/ca/ Laboratories, Inc., Laramie, Wyoming 82070
SULFUR
The interest in sulfur in fossil fuels was evident in the large
number of papers not only describing methods for the de-
tection of sulfur and its compounds but also determining the
compounds themselves. Patterson (135K) provided a review
with 260 references, discussing methods for the separation and
determination of sulfur and sulfur compounds and the ap-
plication of these methods to analysis of air, gasoline, hy-
drocarbons, plants wool, gases, and water. Another review
with 42 references was provided by Orr (I30K) on the geo-
chemistry of sulfur as it relates to crude oil and other fossil
fuels. Analytical procedures for sulfur in coal desulfurization
products were discussed in a review article by Chakrabarti
(27K) which also contained many references.
Investigators used a wide variety of methods to study sulfur
in fossil fuels and roducts, the most popular being gas
R
chromatography wit flame photometric detectors and cou-
lometric procedures. Blanco et al. (I6K) used several methods
to determine the different forms of sulfur in oil shales, com-
pared results, and selected a method published by R. A. Mott
in 1950 for their laboratory determinations because of its
simplicity and satisfactory results. Bogorodskaya ( I 7K) re-
ported on the determination of elementary sulfur in kerogen
and rock. A rocedure for the detection of corrosive sulfur
in petroleum-{ased electrical insulatin oils was published by
the British Standards Institution ( 2 0 k ) ;the procedure uses
a well-cleaned cop er strip which is kept in contact with the
"8
oil sample at 140 for 19 h and corrosion of the strip is noted
visually. Crop er (33K) reported on an on-line sulfur analyzer
developed at {tandard Oil Co. (Indiana) which used electrical
conductivity and a ratio technique to measure weight percent
sulfur; the procedure did not require a density compensation
device since the surfur content was independent of sample
size or density.
Drushel (4IK) determined trace amounts of sulfur in pe-
troleum fractions by using a method based on hydrogenolysis
of the sample at 1125 "C and determination of the hydrogen
sulfide formed using a commercially available analyzer; results
were comparable to those obtained by a microcoulometric
method. Russian investigator Efremov (43K) proposed the
use of carbon disulfide instead of sulfur dioxide as a working
as for the isotopic analysis of sulfur using an electron-vi-
[ration spectrographic technique. Middleditch and Basile
(109K)used sulfur-34 enriched sulfur as an internal standard
to determine elemental sulfur in environmental samples by
combined gas chromatography/mass spectrometry.
Neavel and Keller (123K) applied several correction factors
to estimate the sulfur content in coal by titration of calorimeter
bomb washings; the procedure was recommended as a sub-
stitute for a separate determination of the total sulfur in coal
samples, especially where coal from a single source is routinely
analyzed. The sulfate roduced by a Parr bomb oxidation
procedure was also usefto determine sulfur in conventional
and shale oil-derived fuels by Mizisin et al. (II2K) using an
ion chromato aph; under certain condition other acid-forming
elements C O L also
~ be determined at the same time with the
ion chromatograph. A liquid lead amalgam method was de-
scribed by Yoshimura et al. ( I 7IK) in which they dissolved
the sulfur-containing com ounds in 3:l dimethylformamide-
benzene, used the liquid Ead amal am to reduce the sulfur
to hydrogen sulfide, and titrated the yead chloride formed with
a solution of EDTA in DMF; results obtained by this method
were lower than those of the bomb method because sulfate
and sulfoxides are not reduced by the amalgam.
The determination of sulfides in shale oil and distillates
was accomplished by D'Alonzo et al. (36K) by oxidizing the
sulfides to sulfoxides with sodium periodate, reducin the
sodium periodate and precipitating silver iodate, dissofvin
the precipitate in concentrated ammonium hydroxide, a n i
determining silver in the resulting solution by atomic ab-
PETROLEUM
sorption spectrophotometry. An atomic emission plasma
spectrometer with dc arc source was used by Ellerbracht et
al. (44K) to determine total sulfur in aqueous solutions; the
authors found the same sensitivity for several sulfur species
and investigated several potential chemical and spectral in-
terferences.
Chemiluminescence was used for detection of sulfur by two
groups of workers in four pa ers. Alder and Kargosha (3K)
described conditions for the &termination of total sulfur and
disulfide and polysulfide compounds in petroleum products;
they reduced the sulfur by heating with sodium or Devarda's
alloy under reflux, and the hydrogen sulfide liberated was
swept into a diffusion flame for chemiluminescent measure-
ment of the S2emission intensity. Alder and Kargosha ( 4 K )
also determined sulfur in petroleum products by combustion
followed by concentration of the sulfur dioxide in sodium
tetrachloromercurate solution and detection by cool flame
molecular emission. Traces of total sulfur in benzene were
determined by Tsebrii et al. (I65K) using a specially designed
apparatus for the reaction which liberates hydrogen sulfide;
the hydrogen suhide is absorbed and an aliquot of the solution
mixed with tetraacetoxymercurifluorescein,whose lumines-
cence is measured. The same Russian workers, Tsebrii et al.
(161K),also used the quenching effect of hydrogen sulfide on
the luminescence of fluorescein mercuric acetate to determine
total sulfur in benzene and benzene derivatives.
A photometric procedure which measured the absorbance
of methylene blue was used by Bruk et al. (22K) to determine
trace amounts of sulfur in aromatic hydrocarbons. Infrared
spectrometry was used by Beldi and Katalin (I2K) for the
determination of sulfide-type com ounds in lubricatin oils;
the oil was chromatographed on siica gel and separate8 into
saturated hydrocarbons and aromatic hydrocarbons plus sulfur
compounds.
Sulfides were determined by thin-layer chromato aphy by
Macioszczyk and Korczak (99K)following ashing of t r e sample
with metallic sodium and dissolving the residue. Sulfur
com ounds in high-boiling petroleum distillates were sepa-
r a d b y TLC on plates coated with silica gel impregnated with
mercuric acetate by Japanese investigators Kaimai and
Matsunaga (7IK);the spots were identified under 254-nm
radiation or by spraying with a palladium chloride solution
and evaluated by densitometry at 380 nm with compensation
for background a t 600 nm.
Flame photometric detectors for gas chromatography were
used in at least 10 studies of sulfur compounds in fossil fuels
and products. Below (I3K) described an apparatus for the
continuous determination of the sulfur content in natural gas
by conversion of the organic sulfur to hydro en sulfide over
a special platinum catalyst and detection b 8 C with a flame
photometric detector. Bumett et al. (BK) lscussed optimum
conditions for the chemiluminescent response of the flame-
photometric detector for a group of 11sulfur compounds; the
authors found that the detector response is proportional to
the sulfur concentration raised to the nth power and that the
compound and concentration dependencies are due to vari-
ations in n for different sulfur compounds. Butusova et al.
(24K) evaluated the use of a flame photometric detector for
the GC determination of total sulfur in natural gas and in air
using a glass mixing chamber in place of a packed column.
A flame photometric detector for the specific determination
of sulfur compounds was also described in a patent by Com-
pagnie Francaise de Raffinae S.A. (30K);the sample was f i s t
combusted and a portion of the effluent from the combustion
chamber carried to the flame photometer. Coke oven as was
analyzed by Demczak et al. (38K) for hydrogen sulfiie, car-
bonyl sulfide, sulfur dioxide, and carbon disulfide by GC on
a glass column using a flame photometric detector.
In a study of the factors influencin the formation of dia-
tomic sulfur under conditions applicabfe to flame photometric
detection, Fredriksson and Cedergren ( 5 I K ) used high-tem-
perature equilibrium calculations to show there is a maximum
in the formation of diatomic sulfur that is a function of flow
rate. Gangwal and Wagoner (53K) used a dual-flame pho-
tometric detector to relate responses of low-molecular-wei ht
sulfur compounds to area and height of the chromatographc
peaks for standard samples and coal gasifier effluent samples.
Maruyama and Kakemoto (102K) discussed the emission
responses of 2 1 sulfur compounds examined with a flame
photometric detector; the authors found that the respose to
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 115R
PETROLEUM
selected sulfur compounds was dependent on the number of
sulfur atoms in the molecule and not on its chemical structure
and that it was necessary to monitor hydrocarbons with a
flame-ionization detector for accurate measurement of the
sulfur compounds. A comparison of quenching effects in single
and dual flame photometric detectors was reported by Pat-
terson (133K) who showed the superiority of dual-flame op-
eration by determinations of sulfur in gasoline. Tsibulskii et
al. (163K) used a procedure which included equilibrium
preconcentration of the benzene and determination
of distribution coefficients GC with a flame photometric
detector to analyze for sulfur-containing impurities
in gases.
Gas chromato raphy was used by Russian investigators
Golovnya et al. k 9 K ) to study the additivity of retention
indexes of branched aliphatic sulfides for 25 compounds and
to show that deviations from additivity increase with in-
creasing polarity of the liquid stationary phase. Gas chro-
matography was also used by Kudasheva et al. (9OK) to de-
termine traces of hydrogen sulfide in ethylene by collecting
it on a column cooled with solid carbon dioxide and then
liberating the hydrogen sulfide by immersing the column in
boiling water and sweeping it into the gas chromatograph with
hydrogen.
Eight papers reported on the determination of sulfur com-
pounds by using coulometric titration for detection. Akhmetov
(1K)used direct or indirect coulometric titration with elec-
trochemically generated Cr6+to determine S2-,S03az-,and Sz.
A wide-range electrolytic titrator based on transistor elec-
tronics and a coulometric bromine sensing electrode were
developed by Austin and Moen ( I O K ) to continuously monitor
sulfur content in natural gas well sites, process gas handling,
sewage treatment, and other applications. Sulfur in gra hite
petroleum coke, or other carbonaceous material was ieter;
mined by a coulometric procedure and re orted by Benevolski
et al. (14K) and Ivanov (70K). A comkhtion-coulometric
technique for the determination of sulfur in gaseous and liquid
organic products was developed by van Grondelle et al. (60K)
using modifications to the Dohrmann microcoulometer pro-
cedure to improve performance when the sulfur contentration
is less than 1 ppm. A hydrogenation and coulometric appa-
ratus for the determination of microgram and smaller amounts
of sulfur in petroleum products was described by Kiricenkova
et al. (80K). Two easily interchangeable microcoulometric
methods for trace sulfur in hydrocarbons were discussed in
a paper b Moore et al. (113K), who compared the methods
d
over a wi e range of petroleum refinery samples; one method
was suitable for automated syringe injection, and the other
was applicable to refractory samples because it used a high-
capacity combustion tube for manual boat-inlet operation.
Muramatsu et al. (121K) determined total sulfur by decom-
posing the sample in a hydrogen stream, converting the sulfur
to hydrogen sulfide, and coulometrically measuring the
amount of hydrogen sulfide absorbed.
Titration procedures for the determination of sulfur in
organic materials are frequently used, since they are easily
automated and computerized for rapid routine analysis. For
nonroutine use the equipment required is readily available
and inexpensive. Maciak et al. (98K)described an automatic
computerized procedure which consists of combustion, transfer
of the combustion products to a titration vessel with an au-
tomatic wash, and colorimetric titration with barium per-
chlorate. A potentiometric titration procedure with lead
nitrate in methanol using a lead-sensitive electrode was dis-
cussed by Mueller et al. (118K),as was a colorimetric titration
with barium perchlorate in ethanol. Problems in the analysis
of total sulfur in crude oil by combustion and titration were
discussed in a paper by Nguyen and Tran (125K). Elemental
sulfur was determined by Puacz and Puacz (141K) by first
extracting with DMF and refluxing the extract with sodium
nitrite to oxidize the sulfur to S2OS2-; the pH was adjusted
to 5.9 and a known amount of an iodine solution added and
then titrated with As033- using starch as an indicator to
measure the amount of iodine consumed. Ammonium salts
of aryl dithiocarbamates were determined by Sharma and
Sharma (152K) using a mercurimetric titration with mercury
chloride and diphenylcarbazone as an indicator. Iodometry
employing o-diacetoxyiodobenzoate was used by Srivastava
et al. (155K) to determine mercaptans, thioureas, and organic
sulfides and disulfides. Tab0 et al. (157K)used a wet oxidation
116R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
procedure and titration with barium chloride to determine
sulfur in several organic compounds and metal complexes.
The use of X-ray fluorescence (XRF) for the determination
of sulfur was reported in four studies, one of which described
a new analyzer for sulfur in fuel oils. Masuko et al. (103K)
reported on the development and application of a nondis-
persive X-ray sulfur analyzer developed by the Rigaku Corp.
that automatically corrects errors which formerly required
time-consuming routines; the analysis of fuel oils was accom-
plished by using this instrument with calibration standards
prepared from white oil plus dibutyl disulfide. The deter-
mination of sulfur in coke was reported b Pepenin et al.
(136K) using XRF and detection by a Si(Lif semiconductor.
Schreiber (149K) reported on improvement of the XRF
analyses of sulfate by enrichment on strongly basic anion
exchange resin-loaded fiter paper and conversion of the sulfur
to barium sulfate for analysis by measurement of the higher
energy barium L/3 X-ray line instead of the sulfur K lines.
Energy dispersive k R F was used by Trovato et al. (160K) to
determine sulfur in fuel oils using a procedure that permitted
the simultaneous determination of sulfur, phosphorus, zinc,
barium, calcium, and chlorine.
Polr aphic procedures were reported in two investigations,
one of x i c h looked at elemental sulfur the other at troleum
sulfones. Korean investigators Kim and Chang &K) dis-
cussed the fadors influencing the larographic determination
of elemental sulfur in crude oil an$% petrochemical products.
The composition of four structural group classes of sulfones
obtained from seven diesel oil fractions was studied by Russian
researchers I lamova and Mazitova (69K) by polarographic
and ESR teciniques.
Thiophenic compounds in organic materials were investi-
gated by four groups of investigators. Escalier et al. ( 4 % )
used liquid and gas chromatography to separate thiophenic
compounds in naphthas; the samples were simplified by
chromatography on a silica gel column prior to identification
by gas chromato aphy/mas spectrometry. The GC retention
indexes of thiopfhe derivatives and sulfur-containing furan
and benzene compounds were determined at 130 "C on lass
columns b Golovnya et al. (58K), who also discussefthe
effects of tze interaction of the sulfur-containing compounds
with the stationary phase. Melnikova et al. (107K)described
a study of organceulfur compounds (includin alkylthiophenes,
alkyl- and cycloalkylbenzothiophenes,and diknzothiophenes)
separated by silica gel and alumina chromatography and an-
alyzed by ultraviolet, infrared, and mass spectroscopy. The
thiophenic sulfur distribution in petroleum fractions was re-
ported by Wenzel and Aiken (168K) who used gas chroma-
tography with a flame photometric detector after first sepa-
rating the fractions into thiophenes and nonthiophenes by a
catalytic procedure.
An extraction-combustion method and a vaporization-
combustion method were used by Koshida et al. (85K) to
determine free sulfur and thiosulfate. Thiourea, acetylthio-
urea, and sym-diphenylthiourea were determined gravime-
trically by precipitation of mercuric sulfide from ammoniacal
mercuric nitrate solution by Cyganski (34K).
NITROGEN
The Dumas and Kjeldahl methods (or their modifications)
for nitrogen determination were the the subject of several
papers. Brewer (1910 discussed the apparatus, reagents,
procedure, accuracy, and sources of error in the Merz mod-
ification of the Dumas method in a review paper with four
references. Hegedus Bartfai (63K) used KCIOl to eliminate
the interference of fluorine in the Dumas-Pregl method when
used to analyze for nitrogen in organic compounds containing
trifluoromethyl grou s. Silica gel was used to concentrate the
nitrogen, and an indirect combustion procedure was used to
optimize conditions for the Dumas method b Kogure et al.
(84K). In the digestion procedure for Kjeldagl nitro en de-
termination, Kawawa et al. (74K) reported the use of k&Oa
to raise the boiling point and serve as a catalyst for decom-
position, eliminatin the need for toxic metal catalysts. Morita
et al. (114K) devefoped a modified Kjeldehl method using
hydrogen peroxide as an oxidizing agent, decreasing the
amount of sulfuric acid and the time required for digestion
and eliminating the use of toxic metal catalysts. An indirect
method of determining nitrate nitrogen in organic material
was reported by Vitula (116K);total nitrogen and ammonia

lus organic nitrogen were determined, and the difference
Enitrogen.
etween the two determinations was reported as the nitrate
A review with 16 references by Koyano and Mat-
susaka (88K) provided a comparison of the Kjeldahl, Dum?,
microcoulometric titration and other methods of analysis.
Japanese workers published two papers on the determi-
nation of nitrogen in coke. Onishi et al. (128K) provided a
statistical analysis of experimental results obtained from 30
laboratories by using identical samples and identical methods
for analysis and arrived a t the conclusion that the semimicro
gasification procedure was more accurate than the semimicro
Kjeldahl or instrumental methods. Morita e t al. (116K)re-
ported on results obtained from a study of a comparison of
the semimicro Kjeldahl, semimicro gasification, and the au-
tomatic Dumas methods to establish optimum conditions for
analysis.
The use of silica gel or alumina for chromatographic sep-
arations was reported by several investigators. Holy and Lin
(66K) used an alumina column to fractionate a hydrogenated
coal liquid into a hydrocarbon fraction and two polar fractions
prior to ion-exchange resin chromatography and HPLC
analysis of the fractions obtained: all heterocyclic and many
basic nonheterocyclic nitrogen compounds had longer reten-
tion times in paired-ion chromatographic solutions than in
methanol. Silica gel, alumina, magnesia, and filter papers were
used as adsorbents by Russian investigators Kotova and
Leonov (87K) in the chromatographic separation of nitroge-
nous concentrates isolated from petroleum products; the au-
thors obtained the best se aration with paper chromatogra-
phy. Concentration roce&res for small amounts of nitrogen
compounds in petrogum fractions were developed by Morita
e t al. (115K);the authors showed that either adsorption on
silica gel a t 0.1:l adsorbate-to-silica ratio or extraction with
sulfuric acid combined with the macro Kjeldahl procedure
gave results comparable to microcoulometric analysis results.
Nomura et al. (126K) used stepwise gradient elution with
hexane and solutions of tetrahydrofuran in hexane on a silica
gel column to study distribution profiles of nitrogen com-
pounds in petroleum; their investigation demonstrated a
characteristic profile for crude and residual oil that was in-
dependent of the geological source of the oil.
Ford and Hurtubise (47K)a t the University of Wyoming
investigated the room-temperature phosphorescence of ni-
trogen heterocycles adsorbed on silica gel using luminescence,
reflectance, and infrared spectroscopy; they postulated that
benzo[flquinoline was adsorbed flatly on the surface of the
silica gel and anchored by hydrogen bonding with r electrons.
In a study of Athabasca tar sand bitumen and its hydro-
cracked products, Canadian investigators Sawatzky and
Ahmed (148K) used a modified API/US Bureau of Mines
liquid ion-exchange chromatography technique and infrared
spectrometry to show complete decarboxylation of carboxylic
acids and apparent large increase in carbazoles and indoles
during hydrocracking. Golovchin et al. (57K) used infrared
and ultraviolet spectroscopy to study nitrogen compounds
separated from a sample of the Bagdanov field petroleum by
adsorption with a cation-exchange resin; the compounds
identified were principally alkyl derivatives of pyridine,
benzopyridine, dibenzopyridine, and pyrrole.
The possible health hazards of exposure to aromatic ni-
trogen compounds from fossil fuels were investigated by Ho
et al. (65K) a t the Oak Ridge National Laboratory, using a
number of different analytical techniques including microbial
mutagenesis assay, GC/MS, IR, and NMR.
Four investigators used procedures that involved com-
bustion of the sample a t 800-1100 "C followed by chemilu-
minescence detection of the nitric oxide. Arimoto (6K) sep-
arated a broad spectrum of nitrogen compounds by gas
chromatography, oxidized at 800-850 "C, used a low-tem-
perature separation technique to remove components other
than nitrogen oxides, reduced NO2 to NO, treated with oxygen
and measured the chemiluminescence. A chemiluminescence
method was developed by Dolle et al. (40K) in which a pro-
grammed combustion at 900 "C was combined with separate
detection of nitrogen compounds pyrolyzed in helium and
oxidized in oxygen. Hardy and Knarr (62K)converted fixed
nitrogen species to nitric oxide with a platinum catalyst in
a quartz reactor tube and measured its chemiluminescence.
No interference by sulfur, phosphorus, or chlorine was ob-
served by Kurihara et al. (92K) in their determination of
PETROLEUM
nitrogen in petroleum fractions; the nitrogen-containing
fractions were oxidized a t 900 "C or greater to produce NO,
which was oxidized to NOz and ozone prior to measurement
by chemiluminescence.
Many investigators developed new instrumentation for the
analysis of nitrogen compounds. Daidoii et al. (35K) developed
a NO electrodeless dischar e lamp and used it as a light source
for the determination of B O by molecular absor tion s ec-
trometry. Deptolla and Fabinski (39K) designel a doutle-
beam infrared gas analyzer that used a fiiter to eliminate the
interferences of carbon monoxide and carbon dioxide in the
determination of NO in automobile exhaust gases. Flett (46K)
described an apparatus for determining the content of dif-
ferent isotopes of nitrogen in particulate organic matter; the
apparatus is made up of a combustion tube connected to a
nitrogen analyzer and to an emission spectrometer to deter-
mine the isotope content of the nitrogen. Automatic micro-
determination of nitrogen in difficult-to-analyze samples was
accomplished by Larina et al. (93K)with a Rapid N apparatus
that combusts the sample in 1.5 min at lo00 "C and produced
results comparable to those obtained with a Coleman Model
29 instrument. Procter (140K) described an electrochemical
apparatus for determining the concentration of nitrous oxide
in air or in exhaust from combustion; the gas is dried and
oxidized, and the NOz content is measured in an electro-
chemical cell with an active carbon anode and a platinum
cathode.
A comparison of methods of determining nitrogen in min-
eral oil using three different instruments was made by
Schuchardt (150K) who showed that the modified Dumas
method of the Carlo Erba ANA 1400 Model gave better results
than the Dohrmann Model DNlO or the Antek Model 703/
720, both of which measure py-roluminescence. Small amounts
of nitrogen in organic compounds were determined in an
apparatus described by Toelg and Werner (159K) in which
the nitrogen converted to NH4+in acid media; the NH4+.was
then oxidized to N by electrically generated hypobromite ions
and the amount of current consumed was used as a measure
of the nitrogen originally present in the sample.
Albert (2K) used a gas chromatograph with a selective
nitrogen phosphorus thermionic detector (NPTD) in parallel
with a flameionization detector to determine compound types
(pyridines, uinolines, indoles, and carbazoles) in light catalytic
cycle oil an! light vacuum gas oil; results compared favorably
with those obtained by microcoulometry or elemental anal sis
of fractions. A GC with argon as the carrier gas was usedlby
Arimoto (8K)in conjunction with a combustion tube operating
a t 800-900 "C to determine nitrogen compounds, detecting
NO with an argon ionization detector. Rubin and Bayne
(145K)described the detection of small quantities of nitrogen
compounds in a hydrocarbon matrix by as chromatography
using a rubidium-bean nitrogen-phospgorus detector. Ni-
trogen oxides in a gas were determined by Shmidel et al.
(153K) by measuring the change in ionization current as the
gas passes through an ionization chamber.
In a study of the thermal stability of nitrogen compounds,
Zamulinskii et al. (176K) used a mass spectrometer to analyze
petroleum fractions that had been decomposed by DTA a t
20-800 OC. Nitrogen compounds in li ht petroleum products
were enriched by percolation througt a column of a cation
exchanger with subsequent displacement by alcoholic po-
tassium hydroxide by investigators Rosset et al. (143K);these
enriched fractions were then separated by gas chromatogra-
phy, the nitrogen compounds detected with a Hall detector,
and the individual compounds identified by mass spectrom-
etry. Zakett et al. (175K) used mass-analyzed ion kinetic
energy spectrometry (MIKES) to identify nitrogen compounds
in coal liquids.
WATER
The determination of water in petroleum products was the
subject of one review paper (with 20 references) by Kosicki
et al. (86K) in which they compared many diverse methods
of analysis. Six papers described six different procedures for
the determination of water in a variety of materials. A Karl
Fischer method was proposed by the British Standards In-
stitution (21K)that is applicable to propylene sam les con-
taining 10 ppm water or more. Bjorkquist (15dused a
sensitive reversed-phase high-performance liquid chromato-
graphic method to detect water in both liquid and solid
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 117R
PETROLEUM
samples as well as water of crystallization. Measuring the
mutual dispersion temperature of reagents after mixing a
sample with a standard liquid that is immiscible with the
solvent is a technique described by Kurakov and Chegolya
(91K) to determine water in polar or anic solvents. Manev
and Zlatilova ( I O I K ) described a metaod to determine 1-105
ppm water in gases using an electrochemical cell of two
platinum-gauze electrodes separated by a felt wetted with a
solution of phosphorus pentoxide. A gas chromatographic
method to separate water from mixtures was developed by
Miller and Friedman (IIOK);the method was suggested for
use in the production of gasahol and in enzymatic reactions.
Japanese workers Yoshimura and Sakamoto ( I 72K) devised
a method for analyzing water in organic solvents in which
alumina or silica gel was made hydrophobic and acked in
a column and the height of sample permeation up tEe column
was compared to standards.
OXYGEN
Several widely differing methods were used to determine
oxygen in a variety of materials. Delpuech et al. (37K) applied
a nuclear magnetic resonance technique to the titration of
oxygen in benzene or hexafluorobenzene solutions; the method
is suggested for a remote control of the oxygen content in
organic solvents for oxygen pressures greater than 1 atm.
Kirsten ( 8 I K ) described a modification of a Carlo Erba ele-
mental analyzer and its use in the determination of trace
amounts of oxygen in organic compounds.
Dissolved oxygen in li uid hydrocarbons was determined
by Khamrakulov and ABramova (75K) by measuring the
potential between a gold indicator electrode and a cadmium
auxiliary electrode immersed in a supporting electrolyte that
is separated from the sample by an oxygen- ermeable PTFE
membrane; the concentration of dissolvet oxygen was de-
termined by measuring the emf of the cell and comparing the
results to samples analyzed by another method. y-photon
activation was used by Williams et al. (169K) for the deter-
mination of trace levels of oxygen in a variety of materials;
procedures for removing contamination and for radiochemial
separations are given.
The determination of oxygen in gases was the subject of
three papers. Trace amounts of oxygen in gases were de-
termined by Litsov et al. (97K) by a photometric method using
reduced Me viologen (I) adsorbed on Aerosil. Muchkaev et
al. (117K) determined oxygen in gases by isotope exchange
and emission spectrometry. Neti and Sawa (124K)described
an amperometric electrochemical measuring probe for de-
termining oxygen in automobile exhaust gases.
HALOGENS
Analysis of organic materials for halogens was reported in
more than 2 dozen papers, with the determinations of chlorine
and fluorine being the most prevalent and potentiometric
procedures having the largest number of papers published.
Heunish (64K) used a chloride-selective electrode to titrate
chlorine potentiometrically to a sharp endpoint with silver
nitrate in a solution of acetone and dilute nitric acid; the
method was applied to coal-derived distillates that had been
decomposed with sodium biphenyl in 2,2,4-trimethylpentane.
The Schoeniger combusthion method and potentiometric
titration can be used to determine lower concentrations
(0.02%) chlorine impurities in organic materials, according
to Calusaru and Domnisteanu (26K). In a study of the effect
on the potential of the fluoride selective electrode of several
solvents in mixtures with water, Gava et al. (55K) showed that
the direct potentiometric determination of fluoride is possible
in mixtures containing up to 90% methanol, 60% ethanol,
60% acetone, 30% propanol, and 10% dioxane (by volume).
A procedure for the microdetermination of organic halogens
developed by Hozumi et al. (68K) consisted of combustion
of the sample, absorption in neutral or weak acid solution,
addition of acetone, and potentiometric titration with silver
nitrate using a sodium-selective glass electrode. A potentio-
metric technique and a flow cell colorimetric technique were
described by Popp et al. (139K)for determining trace amounts
of chloride in microsamples using electrodes modified for very
small samples. Wilson and Marczewski (I70K) reported high
results obtained by a method previously described (Anal.
Abstr., 27,183, 1974) were due to interference by entrained
organic matter and that a cationic surfactant should be added
118 R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
prior to the aqueous extraction to prevent emulsion formation.
Coulometric titration methods for detection of chlorine and
bromine were described in several papers. Chu et al. (29K)
described an automatic method for the microdetermination
of chlorine and bromine using a single flask for combustion,
absorption, and coulometric titration with a silver electrode
system. A scrubber tube packed with cupric oxide wire was
strategically placed to accelerate combustion of the sample
and prevent the introduction of phosphorus in a combustion
and microcoulometric titration method proposed by Matsu-
zake and Koyano (105K);results compared favorably with
those obtained by neutron activation or X-ray fluorescence
for samples of gasoline, residual fuel oil, used lubricating oils,
phosphate ester hydraulic fluids, a cutting oil, and an insu-
lating oil. Yoshimori et al. (173K) constructed a dc amplifier
with a photocoupler for the microcoulometric titration of
chloride using a silver electrode.
A variety of other methods was used for the determination
of halogens, includin TLC and several titration rocedures.
Franc and Pour (50hdescribed a method for tge simulta-
neous detection of nitrogen, sulfur, and halogens in organic
compounds separated by pa r or thin-layer chromatogra hy;
the sample is hydro e n a t e r a n d halogens are detected gy a
blue-to-pink color caange of a strip of filter paper soaked in
2,6-dichlorophenol-indophenolsolution. Mambetkaziev et
al. (IOOK) determined chloride, bromide, and iodide by am-
perometric titration with silver nitrate solution. A rapid
spectrophotometric method for the estimation of fluoride was
proposed by Padma and Vi'ayalakshmi (131K) that was based
on the bleaching action of huoride on yellow Ce(1V) solutions
in sulfuric acid. Another rapid method for the estimation of
chlorine in lubricating oils was discussed by Ro (144K)who
determined the chlorine by pyrolysis at 900 "6, absorption
of the hydrochloric acid formed in aqueous sodium hydroxide
solution, and titration of the amount of base consumed.
An electrochemical cell for the detection and determination
of chlorine in air and gases, described by Tataria et al. (158K),
used a gold working electrode and gold or platinum black
counterelectrode. Valueva et al. (164K) determined trace
levels of fluoride in high-octane alkylates by adsorption of HF
on alumina, pyrolysis, absorption in water, and calorimetric
determination.
PHOSPHORUS
The determination of total phosphorus in or anic samples
was the subject of six papers. Arimoto ( 7 d described a
method in which the phosphorus was reduced to PH a t
600-800 "C and a flame photometric detector was used to
determine phosphorus at ppm to ppb levels. Asthana (9K)
used a decomposition technique with sulfuric acid and po-
tassium iodate a t 25 "C to form phosphates that were pre-
cipitated as ammonium molybdophosphate and determined
titrimetrically. A low-temperature ashing method followed
by spectrophotometric determination of molybdophosphate
at 725 nm was used by Narasaki et al. (122K)to determine
trace levels of phosphorus. Sliepcevic et al. (154K) determined
phosphorus in petroleum products by decomposin the sample
in a special oxygen-filled flask, treating with mol$date-N2H4
reagent, and measuring the absorbance of the molybdenum
blue at 830 nm. Vigler et al. (165K) used an electrodeless
discharge lamp in an atomic absorption spectrophotometer
with a heated-graphite atomizer to determine phosphorus at
213.6 nm. reversed- hase paper chromatogra hy was used
B
by Yuen et al. ( 1 7 4 d t o separate, identify, an estimate the
amount of a series of neutral organophosphorus compounds.
MULTIELEMENT
Several methods, especially gas chromatography and com-
bustion procedures, are particularly applicable to the deter-
mination of multiple elements in a single sample; five authors
discussed these methods for multielement anal sis in review
2
articles. A review of microcoulometric metho s, apparatus,
and techniques for the determination of sulfur, chlorine, ni-
trogen, and individual compounds containing these elements
was discussed by Killer (78K), 164 references. Barbelet ( I I K )
provided a bibliographic study of elemental analysis of heavy
petroleum fractions in a review with 145 references. The
theory, sensitivity, and precision of activation analysis of
carbon, nitrogen, and oxy en by photon nuclear reaction was
discussed by Kaneko (72fi in a review with 36 references; the

application of this method to analysis of inorganic and organic
materials was also covered.
A Perkin-Elmer Model 240 elemental analyzer for carbon,
hydrogen, and nitrogen was discussed by Cottrell and Cottrell
(31K) in a review article that covered principles of operation,
description of instrumental components, accuracy, sources of
error, and maintenance; 30 references are listed. The same
authors, Cottrell and Cottrell (32K), also discussed the
modifications of the Perkin-Elmer Model 240 elemental an-
alyzer for the determination of oxygen and sulfur in a review
article with 11references. The use of the fully automatic Carlo
Erba analyzer for carbon, hydrogen, nitrogen, and oxygen in
organic compounds is discussed by Howarth (67K) in a review
with nine references; principles of automation and combustion
are covered, as are analytical procedures, sources of error, and
maintenance.
The determination of carbon, nitrogen, and oxygen using
activation by charged particles was described by Muninov et
al. (12OK);analysis time was 1-10 min for this highly selective
and nondestructive procedure. Six U S . coals were used in
a study of the determination of oxygen and nitrogen by in-
strumental neutron activation analysis by Hamrin et al. (61K);
each sample was first submitted to either low-temperature
ashing or an acid treatment to obtain organic oxygen and
nitrogen. Nitrogen and oxygen functional groups in coal-
derived asphaltenes were determined by Schwager and Yen
(151K) by a variety of methods including silylation and NMR,
conventional elemental analysis, and infrared spectroscopy.
An apparatus that measures the difference in moisture level
or temperature between two sensing elements in two gas
streams is described by Muggli (119K);a method for deter-
mining low level (<2%) oxygen and hydrogen in gases was
also described. Chand (28K) described an apparatus for the
electrochemical analysis of gases that was used to detect ni-
trogen oxides, sulfur dioxide, oxygen, carbon monoxide,
formaldehyde, and ethanol.
Gas chromatogra hy employing both flame ionization and
flame hotometric Xetectors was used by Ogata and Miyake
(127Keto analyze sea sediments for n-paraffins and sulfur
compounds. A simple chromatographic determination of
carbon, h dro en, and nitrogen in organic compounds was
describedxy &shiev et al. (111K);the gaseous, liquid, or solid
sample was oxidized in a steel tube reactor at 800-900"C and
the products were analyzed on a 3-m by 4-mm column packed
with Polysorb-1 a t 56 "C, usin helium as the carrier gas.
Krylov et al. (89K) described atigh-vacuum gas chromato-
graph that used a second high-vacuum column connected to
the main column to improve absorption of the gases in the
anal sis of gas mixtures; the instrument em loyed a thermal
con&ctivity detector. The simultaneous Xetermination of
a mixture of low-boiling gases was accomplished by Karagezov
et al. (73K) using gas chromatography a t ambient tempera-
tures on a system combining two columns and a steel spiral
and using a thermal conductivity detector; the system was used
to separate carbon dioxide, carbon monoxide, oxygen, nitrogen,
and ethylene. Fujii (52K) reported the conditions for the
single-column simultaneous separation by temperature-pro-
grammed GC of a difficultly separable mixture of nitrogen-,
sulfur-, and oxygen-containing gases; a molecular sieve trap
was used to eliminate impurities in the carrier gas prior to
introduction into the gas chromatograph. A procedure for the
simultaneous GC determination of nitrogen, oxygen, carbon
monoxide, carbon dioxide, nitrous oxide, sulfur dioxide,
methane, ethylene, and ethane at the ppm level was reported
by Duerbeck and Niehaus (42K) who used a gas-splitting
device and two different molecular sieve columns with ul-
trasonic detectors for the analysis. Andrawes and Gibson (5K)
also used two gas chromatographic columns with a single
detector for the simultaneous determination of trace amounts
of several gases; the columns were designed to avoid overlap
of the eluting gases in the detector.
Detectors for gas chromatographic applications were devised
by three groups of investigators. Lasa et al. (94K) developed
an electron capture detector applicable to trace analysis of
electronegative compounds such as those containing chlorine,
fluorine, and oxygen; it contains a radioactive source of 10 or
20 mCi. Patterson (134K)described a glow-ionization detector
for nitrogen- and phosphorus-containing compounds. Several
commercial flame ionization detectors were com ared to one
constructed by Rusev et al. (147K) and the resuks reported;
PETROLEUM
the latter detector was modified to use a hydrogen-rich flame
for the determination of NO, NOz, sulfur dioxide, and hy-
drogen sulfide.
A chromatographic system that consists of a high-per-
formance liquid chromatograph for the detection of organo-
nitro en and organosulfur compounds was described by Fraim
(48& Callen et al. (25K) used gradient elution chromato -
raphy, infrared spectrometry, and 13C and proton N M h
techniques to investigate the nitrogen, sulfur, and oxygen
compounds of three solvent-refined coals and compared the
data with similar data obtained from an Arabian li ht vacuum
residuum. Rezl et al. (142K) described a metho8 for deter-
mining carbon, hydrogen, and nitrogen in liquid organic
samples without weighing the sample; the method was used
to analyze low-boiling liquid hydrocarbons, nitrogen com-
pounds, chlorinated hydrocarbons, and organic sulfides.
The simultaneous determination of sulfur and halogens in
organic compounds was the sub'ect of three papers. Rudnicki
and Binkowski (146K) descriLed a method in which the
sample was burned in a stream of oxygen and the combustion
products absorbed in hydrogen peroxide or sodium hydroxide
and the sulfate determined by titration with barium per-
chlorate; chloride and bromide were determined mercurime-
trically. Microgram amounts of the chloride, bromide, or
iodide and sulfur were determined simultaneously by Maz-
zeo-Farina and Mazzeo (106K)by combustion of the sample
in a Schoeniger flask, absorption of the product in a solution
of potassium hydroxide and hydrazine hydrate, titration of
the halides with mercuric perchlorate, and titration of the
sulfate with barium perchlorate. A modified Dumas-Pregl
apparatus was used by Khanzadyan and Abram an (76K) to
simultaneously determine nitrogen, fluorine, anihalogens in
organic compounds, using aliquots from a solution containing
the absorbed products of combustion of the sample.
Automatic methods for multielement analysis were reported
by many manufacturers and researchers. Kirsten (82K) de-
scribed an automatic method for the simultaneous determi-
nation of carbon, h drogen, nitrogen, and sulfur and for sulfur
alone; the methoBis based on combustion of the sample,
followed by reduction over copper or cuprous oxide at 700-800
"C and gas chromatographic separation and measurement of
the products. Merz (108K) developed automated rapid
methods for the determination of carbon, hydrogen, nitrogen,
oxygen, halogens, and sulfur in organic compounds using
combustion combined with titration or gas volumetric mea-
surements; a description of the apparatus and modifications
are given. An automatic carbon, hydrogen, and nitrogen
microanalyzer that employed a vertical reactor, an automatic
sample feeder, a collecting tube, and measurement of carbon
dioxide, water, and nitrogen by a thermal conductivity cell
was described by Fraisse et al. (49K). Kobylinska-Mazurek
and Kozlowski (83K) simultaneously determined carbon,
hydrogen, and sulfur by automated gravimetry by using
combustion mineralization in a vertical apparatus and ab-
sorbing the combusting products on either magnesium per-
chlorate, manganese dioxide, or Ascarite. An automatic an-
alyzer was also used by Pella and Colombo (135K) to si-
multaneously determine carbon, hydrogen, nitrogen, and sulfur
by combustion and gas chromatography; a thin layer of sil-
ver-coated copper selectively eliminated halogens from in-
terfering. Improvements in the reduction train of an F&M
carbon, hydrogen, nitrogen analyzer that allowed for regen-
eration of aged copper while the analyzer is operating were
discussed by Ono et al. (129K). Cabon, hydrogen, nitrogen,
oxygen, and selected heteroatoms were determined simulta-
neously by Liebman and Levy (96K)using a modular or anic
analysis system incorporating gas chromato raphy an mi-
crochemical and Fourier transform infraref spectrometry.
8
Multicomponent gas mixtures were analyzed by Bogustavskii
et al. (18K) by a spectrometric-chromatographic procedure
that consists of pulse-charging samples into the carrier gas
stream, chromatographic separation of the components, and
measuring the intensities of the emission lines produced in
a superhigh-frequency discharge. Carbon, hydrogen, sulfur,
phosphorus, halo ens, nitrogen, oxygen, and metals can be
P
determined in vo atile organic compounds by an apparatus
described by Liddle (95K) which uses an optical emission
spectrograph and a microwave-generated helium plasma.
Mass spectrometry was used for the multielement analysis
of organic materials by four research groups. Polyakova et
ANALYTICAL CHEMISlRY, VOL. 53, NO. 5, APRIL 1981 119 R
PETROLEUM
al. (138K) developed a method for the quantitative analysis
of aromatic hydrocarbons and sulfur-containing compounds
by high-resolution mass spectrometry. Khots et al. (77K)
compiled a program for the interpretation of mass spectra of
petroleum products and derived algorithms for calculation of
the monoisotopic mass spectra of complex mixtures of hy-
drocarbons and compounds containing one nitrogen atom or
up to two oxygen or sulfur atoms. The German Society for
Petroleum Sciences and Coal Chemistry (56K) published an
article on the determination of heterocyclic nitrogen and
oxygen compounds and hydrocarbons in high-boiling petro-
leum fractions by negative ion mass spectrometry and high-
resolution mass spectrometry. A static mass spectrometric
method was developed by Gardiner and Pillinger (54K) for
the determination of active gases, and suggestions were made
for the possible application of the method.
MISCELLANEOUS
An automatic potentiometric titration method was de-
scribed by Matsumura and Takashi (104K)for the titration
of quinone in carbon black with sodium borohydride and
iodine. Pink and Schaefer (137K) described a thermionic
detector for detecting organic compounds containing het-
eroatoms. A high-pressure liquid chromatography method
for the separation of sulfonated and carboxylated aromatic
compounds was discussed by Streule and Von Wattenwyl
(156K);silica gel was used as the stationary phase, and the
mobile phase was a mixture of water, ethanol, and butanol.
A carbon monoxide detector was described by Watanabe
(167K)that measured the rise in temperature resulting from
combustion of carbon monoxide in nickel oxide and selected
other metal oxides.
ANALYTICAL AND PROCESS
INSTRUMENTATION
J. W. Loveland and C. N. White
Suntech, Inc .( Newtown Square Pennsylvania
~
In this year’s review, we have modified somewhat the section
headings from those used in 1979s review (93L). For example,
we have lumped elemental analysis in with specific compounds
and compound types.
Because of the frequent reference to familiar techniques
and terminology, we are again using abbreviations to aid the
reader in his perusal of the text. Abbreviations recommended
by Chemical Abstracts will be used and are not itemized here.
Other abbreviations are as follows: AA, atomic absor tion;
IR, infrared; W, ultraviolet; MS, mass spectrometry; G8, LC,
PC, TLC, gas, liquid, a er, and thin-layer chromatography,
respectively; GCD, G 8 Jstillation; XRA, XRD, XRF, X-ray
absorption, diffraction, and fluorescence, respectively; NMR,
nuclear magnetic resonance; TC, thermal conductivity (de-
tector); FID, flame ionization detector, FPD, flame photo-
metric detector; pP, microprocessor; std. dev., standard de-
viation; vis., viscosity; psig, pounds per square inch gauge; o.d.,
i.d., outer and inner diameter; in., inch; and HC, hydro-
carbon(s); st. st., stainless steel.
In preparation of this review, increased activity was noted
in some areas and less activity in others. In the area of lab-
oratory analysis, GC is the most widely reported analytical
technique, followed by LC. No other analytical technique
accounted for very many papers. There was a notable lack
of papers on elemental analysis and computer applications.
In the process instrumentation area, there is an increasing use
of microprocessors and minicomputers for automatic control
of process GCs, MS, and other analyzers. Instrumentation
aimed at energy savings is very a parent.
The following are recommendeafor a general reading and
cover a broad spectrum of techniques and/or applications.
BROAD REVIEWS
Laboratory. A series of reviews appeared on the appli-
cation of various types of chromatography to the analysis of
various petroleum fractions and whole crudes. Camin (24L)
discussed the history of GC, LC, TLC, and PC in petroleum
analysis (79 refs). Harvey (64L) reviewed gas analysis in the
petroleum industry (59 refs). Whittemore (169L) discussed
the use of high-resolution GC for analysis of gasolines and
naphthas (11 refs). Butler (23L) discussed the theory,
methods, and applications of GCD in petroleum analysis (20
120 R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
refs). Trusell(158L) discussed the application of GC to middle
and heavy distillates, including detn. of paraffins, isoprenoids,
stearanes, triterpanes, S compds., N compds., HC types, and
used lube oils (38 refs). Suatoni (152L) reviewed the analysis
of asoline, 190-360 OC petroleum fraction, aromatic rings,
an8 pre arative sepns. using high-performance LC (13 refs).
Adlard f i L ) reviewed the analysis of heavy distillate residues
and crudes by GC. He also discussed the identification of oil
spills by GC (29 refs). Gallegos (44L) reviewed the use of
pyrolysis GC for use in analysis of HCs, petroleum residues,
coal, shale, and recent sediments (31refs). Amos (7L) reviewed
the analysis of heavy distillates, residues and crudes by LC
and supercritical fluid chromatographic techniques (29 refs).
Fisk et al. (40L) surveyed ma’or IR spectra data base
collections (including the Texas d&M University Thermo-
dynamic Research Center/API Project 44, which lists 3545
spectra of petroleum HCs and N- S-conts. compds.), various
computer search systems that may be used with these col-
lections, and the disadvantages of these systems, i.e., the only
spectral feature that can be searched is the band position (29
refs).
Gerhards (49L) analyzed sources of errors in quantitative
evaluation of 13C NMR spectra of petroleum and coal prod-
ucts. Riepe (128L) described the scope of the Institut fuer
Spektrochemie & Angewandte Spectroscopie e. V’s work in
analysis, which includes basic research, data compilation,
consultation and assistance for industrial and university
laboratories, and training. This state-supported institute has
compiled an atlas of Raman and IR spectra of about 900
substances, developed a method for purifying reference sub-
stances, and participated in specific projects for characterizing
petroleum fractions.
White et al. (16%) present a review on the chromatography
of porphyrins and metalloporphyrins and covers PC, TLC,
LC, and GC methods. There are 145 references given.
Process Analyzer. Several reviews and surveys summarize
various uses of analyzers and their employment with micro-
processors and in computer-controlled processes. The authors
see a momentum toward increased use of analyzers in the
future particularly with microprocessor-based control units
where greater reliability and less maintenance are distinct
advantages.
Jutila (7615) covered a wide variety of analyzers, such as,
GC, LC, MS, UV, IR, AA, X-ray, neutron activation, and wet
chemical analysis. The more difficult techniques to be applied
to on-line analysis are AA, neutron activation, and wet
chemical methods. In this survey, the advantages of incor-
poratin analyzers into process control loops or using them
for profuct or effluent monitoring are discussed. The oper-
ating principles, sensitivities, detection methods, sampling and
conditioning needs, and limitation of the various systems are
outlined.
Narraway (11OL)points out that the growth rate of the
analyzer market is one of the highest in the process control
instrumentation field. This is particularly true of the pe-
trochemical industry and pollution and boiler water analysis.
An example of the savings possible is given for a specific
application where an accurate thermometric method for
monitoring sulfate produced in a neutralization reaction of
an effluent permitted the use of less expensive lime and
minimized the use of caustic.
Welfare (166L)reported on the increased expenditures on
process analyzers in Western Europe which grew from about
$37 million in 1966 to $95 million in 1978 with the predom-
inant growth in the petroleum and petrochemical industries.
Reasons for this growth were a t least twofold, namely, the
increased availability of old and new types of analyzers and
the increased reliability of analyzers for both gaseous and
aqueous streams. Another aspect which has helped is the total
systems capability that many manufacturers now provide. A
typical analyzer package is illustrated for an eth lene oxide
and related sampling equipment.
8
plant which consists of five O2 analyzers, two G s, two I&,
Bailey (15L) surveyed analyzers which are pP based and
in use by large chemical and petrochemical firms. Several
analyzers discussed are Beckman Instruments’ Model 6750
GC using either FID or TC detection, Applied Automation’s
Optichrom 2100 used for on-line BTU measurement as well
as composition of natural gas streams for pipeline custody
transfer, Foxboro’s Arcas 81-P Octane Analyzer cool flame

thermal oxidation technique whose peak temperature is re-
lated to Octane Number, EG&G’s Model 911 digital humidity
analyzer, General Eastern’s (PACER) dew-/frost-point hy-
grometer, CVC’s time-of-flight MS for stack and automobile
exhaust analysis, the Thermox Air-Mizer which conserves fuel
by maintaining a safe excess air level, and Houston Atlas’
“Photorateometer” for fast readout of low levels of H2S via
optoelectronic reaction rate sensing.
Several other articles have appeared which review various
analyzers and their applications. Fuhrmann (4215) discusses
the use of GCs and optical instruments in the analysis of
chemical products and waste gases. Mukharamov et al. (106~5)
gives the technical characteristics for instruments used in
monitoring and control applications. Among those covered
are an interferometric gas analyzer for rapid detn. of C H2,
and CO, strong acid analyzers, and a salt (NaC1) in trine
analyzer. Magnetooptical converters and thermostats are also
described. Gregorowicz (51L)reviews the objectives and tasks
of the technical analyst in the control of modern roduction
processes and the need for developing test m e t h d s based on
selected chemical and physical properties and their application
for monitoring the chemical process.
Bailey (14L)reviews the use of several analyzer systems in
use for both ener y and ecology reasons. Microprocessing
units are discussetwith regards to the desi n, operation, and
special features of Beckman’s Model 6750 6 C which handles
up to 6 GCs. Other systems discussed are Teledynes’ Model
9300 IR flue gas CO and O2 analyzer which is generally in-
sensitive to spectral interference or thermal effects, the
PROMASS MS of Extranuclear Lab for fact analysis of
multicom onent streams spch as ethylene feed stocks, the
Houston /%as Model 856 total sulfur analyzer for HC streams
which depends on complete hydrodesulfurization of sulfur
compds. to H2S, Foxboro’s MIRAN 801 pP based ambient air
monitor for plant personnel safety, Taylor Instruments GC
with pressure controlled column flow switching which elim-
inates the need for internal switching valves, Uniloc’s twewire
transmitter which modulates power current for signals, and
Magna Instruments’ Model 400 corrosimeter which uses re-
sistance measurements.
ELEMENTS, COMPOUNDS, AND COMPOUND
TYPES . Specific Compounds-Other Laboratory Techniques.
This section is divided between specific compds. and type
com ds., although it is recognized that there will be some
P
over apping, since some specific com ounds enter into types
and vise versa. However, for the reafer, we try here to make
a distinction which we hope will be helpful. A few papers on
elemental analysis are also covered. No discussion on ana-
lyzers appears in this section but will be covered under the
heading of Improved Instrumentation and Techniques.
Specific Compounds-Laboratory GC Methods. Brown
(20L),using a GC, developed a new parameter for assessing
column efficiency called “the mean specific plate number”,
which is based on the arithmetical mean rather than the
geometric mean of the number of theoretical plates. The basis
for the parameter and its application to sup ort coated (SC-
OT) and wall-coated columns are discussed: Values of the
arameter are given for some n-alkanes on SE30 and squalane
ECOT columns.
Volkov et al. (164L) report that programming the flow rate
of the carrier gas produces less stationary bleeding and imposes
less strin ent requirements on thermal stability of the sta-
tionary pEase than does temp. programming. Steam can be
used as a carrier gas and the separation of n-alkanes is given
as an exam le.
Mutton 80915)used a lass column (25 m x 0.27 mm)
coated with OV-17 or 06-275 with temp. programming
(60-160 “C a t 2 “C min-’, to separate naphthalene, 10 ime-
thylnaphthalenes (DMN), biphenyl, fluorene, and other aro-
matics. An FID was used. The OV-275 column was consid-
ered to be potentially more useful for separation of the DMNs,
articularly the less volatile ones. A mixture of OV-275 and
bentone 34 looked promising in separating 1,6-from 1.7-DMN.
Butyl and dibutyl hosphates in tribut 1 phosphate-ke-
rosene mixtures were &ermined by Lee anJTing (89L)using
solvent extraction followed by GC. The mono- and dibutyl
phosphates are extracted with 1 M NaOH; the extract was
acidified with 2 M HCl and then extracted into amyl alcohol.
The two components are then treated to convert them to the
PETROLEUM
methyl derivative, i.e., dibutyl methylphosphate and butyl
dimethylphosphate prior to injection on a Carbowax 20M
column. The std. dev. for 10 ppm quantities were f1.4 and
f1.2 ppm, respectively.
Aue and Flinn (12L) discuss results obtained with a flame
photometric tin detector for GCs wherein or anotin compds.,
8
phenanthrene, and other compds. were use as carbon stds.
to define selectivity. Due to column type and detector con-
ditions, response attributed to phenanthrene was found to be
due in part to contaminants eluting close to the phenanthrene
std. and gave strong response with the FPD. The contami-
nants are believed to be sulfur-containin and are in concns.
less than 1% . Similar contamination was found in anthracene,
pyrene, and other higher mol. wt. derivatives.
Koizumi and Suzuki (85L) used a new Schiff-base-type
liquid crystal as the stationary phase to separate disubstituted
benzene derivatives. The nematic phase, 4-butyl-N-[4-(4-
methylbenzyloxy)benzylidene]aniline (I) provided excellent
separation of 0 - , m-,and p-chlorotoluene, m- and p-meth-
oxytoluene, and m-and p-dichlorobenzene. The m.p. of I is
131 “C and the transition temp. (nematic-liq.) is 147 “C. The
separations were performed a t 180 “C on 20% of I on Celite
545 HMDS.
Ohzeki and Kambara (115L)present preliminary GC data
obtained on a cation exchange resin loaded with various
quaternary ammonium ions. Resins containing benzyltri-
methyl-, benzyltriethyl-, benzyldimethyltetradecyl-, and
methyltrioctylammonium ions were compared for the sepa-
ration of the lower aliphatic HCs, benzene, toluene, and xylene.
The separation efficiencies were found to be less than those
of conventional GC columns and the HETP valves for a 2-m
column ranged from 0.14 to 0.15 cm.
Afanas’ev et al. (315)report on the use of modified porous
polymer absorbents for the separation of polar and corrosive
compds. from C2 to C HCs. Polysorb 1 was treated with an
antistatic preparation based on Sterox 920 coated with silicone
oil, phosphate ester, polyethylene glycol 2000, and poly-
ethylene glycol adipate. These stationary phases showed
shorter retention times for HCs with only a slight increase
in retention times and improved peak symmetry for polar
compds. Separations of NH3, H2S, and SO2 from water were
relatively good.
Tomkins e t al. (156L) determined benzo[a]pyrene (BaP) in
petroleum substitutes by using a combination of techniques
and were able to unambiguously detn. the compd. in the range
of 10-2-10-3 pg/g with a precision of >lo%. Ste s in the
procedure involve pretreatment to remove asp altenes,R
acid/base extraction, MezSO partition, Fluorisil column
cleanup, LC on an acetylated cellulose column and detection
of the BaP by GC, HPLC with UV detection, and fluorescence
analysis. Carbon-14 tracer techniques were used to document
recoveries.
Raverdino and Sassetti (127L) used a combination of GC
and MS to identify the positional and geometrical isomers
from Ca to C13 n-alkene mixtures from the “Olex” process.
Both capillary GC and GC-MS methods were developed for
analyzing structures with and without prior separation of the
mixture into cis-, trans-, and a-isomer fractions on a column
of alumina treated with AgN03. St. st. capillary columns (100
m X 0.25 mm) coated with DC-550 were used with a FID.
Some portions of the isomer fractims were chlorinated before
GC analysis for further confirmation. Direct GC without
derivative formation is recommended for detng. @ isomers and
direct IR for a and gcometric isomers. About 80% of the
components of the mixturz can be identified by GC after
chlorination of the alkenes and 95% by GC of the derivatives
of the products of oxidn. with Os04.
Montheard et al. (103L)determined acetylenes (alk-1-pes)
in acetic acid medium by treating the solution with ethanolic
AgNO in excess. Thesppt. formed is removed and titrated
with dH4SCN with Fe as indicator until a stable red color
is produced. The following compds. were detnd: hex-1-yne,
hept-1-yne, oct-1-yne, non-1-yne, and ethynylbenzene.
Several papers dealt with the use of HPLC for detection
and detn. of specific compds. Johnson et al. (74L) reports on
the sepn. of several fluorenes substituted with mainly N-
containing grou s at two or three different positions. Normal-
and reversed-$ase HPLC was used on columns of Partisil
10 with detection a t 254 nm. Column and elution conditions
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 121 R
PETROLEUM
are detailed, and relevant capacity ratios are provided for each
separation.
Murakami (107L)determined the retention behavior of 14
benzene derivatives using microscale HPLC on PTFE columns
(80 m X 0.5 mm) packed with LiChrosorb RP-18, RP-8, Nu-
cleosil C18, and Permaphase ODS at 30 atm. The benzene HCs
were dissolved in methanol and 0.1 pL (50 pg of solute) applied
to the column. Samples were eluted with water mixtures
(30-90%) of methanol, ethanol, 2-propanol, dioxane, or ace-
tonitrile at rates of 4 pL min-' and compds. detected by UV.
The effect of varying eluent composition and column packing
on capacity factor was studied. It was observed that a rela-
tionship existed between lo capacity factor and log molarity
of organic solvent in the efuant.
Dimitrova (32L) used HPLC to separate cis-trans isomers
of unsaturated HCs using a A NO3-impregnatedsilica gel (10
pm). A 40 cm X 0.3-0.4 cm i.d column of Li Chrosorb Si 100
with a 10% loading of A NO give complete resolution of
cis-trans isomers of C to 8 afkenes. The mobile phase was
a 0.5% solution of MkK idkeptane. Some isomers of alka-
dienes and trienes were also separated.
Specific Compounds-Metals/Laboratory Methods.
Koizumi et al. (84L)used a combination of techniques, HPLC,
high-temp. furnace, and a Zeeman AA spectrometer for an-
al zing organometallic compds. The method was applied to
T 6 L in NBS petroleum stds. with a recovery of 97.6% bein
obtained at a 190-ng level and eliminated interference in P i
and Cd detns. in the presence of the chlorides of Mg, Cu, and
Ca. The general technique is to take fractions obtained by
HPLC and decompose them in a special furnace using a
tantalum sample cup. The atomized metal and vapors are
swept into the spectrophotometer by a stream of Ar.
Windsor and Denton ( I 71L) used an inductively coupled
plasma detector for the elemental analysis of GC effluents and
compared the response to other type detectors. In general,
detection'limits, linear dynamic range and selectivity were
comparable to FPD, argon, and low-pressure He microwave-
excited plasma detectors. The detector was used for detng.
tetramethyltin in a mixture containing benzene, toluene, and
p-xylene.
Bertrand et al. (16L) discussed the detn. of Pb in lube oils
down to 5 ng of Pb with an accuracy of *6%. The Pb is
present as Pb naphthenate enriched in various natural isotopes
of Pb. The sample is di ested in acid. Pb from the resulting
aq. soln. is electroplatefonto a Pt anode, and the Pb on the
anode surface determined by means of second ion MS using
an ion microprobe mass analyzer. This p r o x e s data on the
relative amount of each mass number component in the
sample. Quantitation is obtained by adding to the sample a
known amount of a std. Pb compd. with an isotopic compo-
sition different from that of the sample.
Type Compounds-Laboratory GC Methods. Sojak et
al. (14.55) used GC studies on the retention characteristics of
various unsaturated HCs to determine the effect of slight
structural differences. Data obtained from five classes of
unsaturated aliphatic and substituted aromatics and other
compds. containing 0 and C1 led to the conclusion that re-
tention anomalies are associated with molecular structures
on which the possibility of a ring conformation exists between
a propyl group and the *-electron system of the remainder
of the molecule. The propyl grou anomaly is evident from
P
a lower retention index, a low PO arity, and a lower b.p.
Johansen (76L) reports on an improved GC analysis of
a-olefins. He used an all-glass system including columns
coated with OS 138 rather than st. st. columns to obtain
improved separation. Still better separation of a-olefins was
obtained with glass open-tubular columns coated with nitro-
terephthalic acid-modified Carbowax 20M stationary phase.
Polynuclear aromatics (PNA) separations were reviewed
by Zielinski and Janini (174L). While it is impossible to cover
all oints of a review article, it should be pointed out that these
aut\ors felt that improved separation of PNAs usin nematic
fi
liquid crystal as the stationary phase is possible.. owever,
some precautions must be observed to provide good results.
Schulz (138L)describes the development of GC methods
for improved sepn. of gasoline components, particularly
asolines contg. olefins where capillary columns and preco-
Pumns for the reaction of reversible or irreversible sepn. of
groups are used. Olefins and aromatics are absorbed b om-
plexation with AgN03 on Sterchamol while satd. H d are
122R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
unimpeded and thermally desorbed later for capillary sepn.
Small branched olefins require the lowest adsor tion temp.,
Le., C5 olefins are completely adsorbed at -75 "8, while long
chain n-alkenes are most strongly bound, with 1-octene, for
example, requiring 200 "C or more for desorption. Olefin
recoveries, except terminal olefins having branched vinyl C
atoms which undergo double bond displacement, are close to
100%.
Other work on olefin separations was reported by Lukac
and Nguyen (94L)where the C5 and c6 unsaturated compds.
were separated from their parent satd. compds. A stationary
phase of phenyl glycidyl ether was used and the retention
indices of the C5olefins and two of the dienes were calculated.
Sandra et al. (135L)shows the versatility of glass ca illary
columns in which the stationary phases were polyox et!ylene
2.
glycols with mol. wt. ranging from 1 X lo5to 5 X 10 Normal
sepns. are obtained with the more common classes of organic
compds. with little tailing. Sepns. are made with high effi-
ciency and over a wide temp. range of 50-300 "C. The columns
have been used to separate various compds. in the classes of
alkanes, amines, fatty acid methyl esters, organochlorine in-
secticides, and other type compds.
Poznyak et al. (121L)used a flow-through UV detector for
detecting olefins eminating from GC columns. The method
depended on the measurement of excess O3 at 254 nm after
reaction with the olefin. Reliable detection depends on
maximum conversion of olefins to ozonides. Conditions which
gave good results were: sample volume, 3 pL; reaction cell
length, 2.5 cm; flow rate of O& mixture (25 pM O&, 1.5 mL
min-'; and carrier flow rate, 1.5 mL min-'.
Dahlmann et al. (3015)determined retention indices for a
series of compds. in five classes of compds. including: + m e a ,
alkenes, aromatics, alcohols, and esters. Three different
columns (2 m X 2.7 mm) were used: (1)1.5% Apiezon L on
Chromosorb G AW-DMCS (80-100 mesh); (2) 5% OV-25 on
Gas Chrom Q (100-120 mesh); (3) 5% of Silar 5 CP on Gas
Chrm Q (100-120 mesh). Columns were temp. programmed
from 25 to 250 "C at 10 OC min-' with Nz as carrier, and
detection was by FID. Correlation between several physical
properties such as b.p., mol. wt., density, and retention indices
were made. Use of the best combinations permitted calcu-
lations close to observed retention indices.
Carson et al. (26L) determined the GC relative molar re-
sponse (RMR) of C5-C8paraffins on a 10 ft. X 0.25 in. column
acked with 10% Carbowax 20M on 60 80 mesh Chromosorb
! i
at 125 "C with a TC detector. Two b ends, each containin
68 components were added to benzene which was also use!
as the standard. The data showed that within the aliphatic
and cyclic HCs there exists a fixed RMR unit difference of
about 16 RMR units in a homologous series. It is to be ex-
pected that a similar unit difference in RMR will be found
for other homologous series.
Type Compounds-Other Laboratory Methods. Several
publications reported on the use of HPLC methods for the
sepn. of com ound types. Ageev et al. (4L) used columns of
hydroxylatecfsilica gel to separate monoalkf and plymethyl
derivatives of benzene with hexane as t e mo ile phase.
Retention results were studied as a function of mol. structure
and the free energy of adsorption. Retention times increased
with the no. of methyl groups and they decreased with the
length of the alkyl chains.
Selucky et al. (140L)used HPLC as a means to fingerprint
crudes and etroleum products. The system used silica gel
packing ancfheptane as eluant with UV and RI as detectors
to determine HC com d. classes in crudes, their relative
distributions, and the !.p. distribution of the saturates in
10-12 min. Heavy crudes took about 18 min. to complete. A
combination of GC and HPLC on mixtures of aromatics in-
dicate that mono- and diaromatics and often di- and tri-
aromatics can be differentiated from alk 1 and cyclo alkyl-
A
aromatics, The combination of GC and PLC wag used to
fingerprint samples of automotive and aviation gasohm, lube
oils, and other refinery stream products.
Parris (I17L) used IR to detect LC eluants in separating
saturated triglycerides, . k e a ((26 thro h c ), and 5 alkenes
(Clothrough C1J. Studes were performa wig a st. st. column
(25 cm X 4.6 mm) packed with Zorbax ODS with a DuPont
IR detector and a 254-nm fixed-wavelength photometer.
Mobile phases used were mixtures of acetonitrile, tetra-
hydrofuran, and CHZCl2.The system's sensitivity with glycerol

tributyrate was -200 ng. Good separations are obtained by
matching the IR absorbance of the initial and final mobile
phase solvents.
Colin and Guiochon (28L) performed reversed-phase LC
to determine selectivity for homologous series of n-alkanes,
n-alkylbenzenes, and n-methyl esters. Columns were packed
with LiChrosorb R P 8, R P 18, pyrocarbon (Spherosil XOB),
and Partisil ODs. Column peak capacity was found to be
pro ortional to the resolution. Separations obtained mainly
wit{ branched chained alcohol series indicate that carbon
adsorbants are more selective than chemically bonded phases.
The correlations may be useful for predicting retention se-
quence.
Antipenko et al. (IOL)by selective bromination of por-
phyrins with HBr indicate the method’s use for direct de-
termination of the open positions in por hyrins. By MS
analysis of the brominated products of vana&lporphyrin (VP),
concentrates from two crudes showed that 57-70% of the
porphyrins contained one to three bromine atoms, which
corresponds to nonsubstituted P-position in the pyrrolic rings
of the original VPs. Compounds with zero, one, or two open
positions in pyrrolic rings formed continuous homologous
series.
Schmitter et al. (137L) analyzed for carboxylic acids in
crudes by a combination of techniques including GC, LC,
electron impact MS, and chemical ionization MS. The acids
were extracted from the crude on a column of KOH treated
silica gel and then converted to their methyl esters and pu-
rified on a similar column followed by thin-layer chroma-
tography and urea-adduct methods. Fractions were obtained
containing straight chain, branched chain, and cyclic esters.
The straight chain esters were further separated by GC on
a column (18 m X 0.5 mm) coated with OV-101 and temp.
programmed (4 “C min-’) from 100 to 300 “C. The other
fractions were separated and identified by GC-MS methods.
Grushova et al. (57L) used the relative chromatographic
polarity parameter (P)as a tool for the rapid evaluation of
the extraction characteristics of binary solvent mixtures.
Ethylene glycols or sulfolane were mixed in varyin propor-
tions with N-methylcaprolactam, N-methylpyrrolifone, me-
thylcellosolve cyanoethylate, or tetrahydrofurfuryl cyano-
ethylate and then used as the stationary phases in GC sepa-
ration of a std. 1:l benzeneln-hexane mix a t 30 “C. The
calculated P valves were correlated with extraction selectivity
coef. (p) and the distribution coef. ( K )of the solvent mixtures
measured in direct extraction experiments. As P increased
for the solvents, p increased linearly while K decreased. High
extraction efficiencies were observed when P > 80% while
when P was between 70 and 80%, the combination of selec-
tivity and solvent power was maximized.
Gallegos (43L)analyzed organic mixtures by metastable ion
methods using a double-focusing MS. Metastable transition
s ectra can be used in two ways by MS; one uses a single ion
gtection while the second uses mass ratio and intensity in-
formation. The latter approach was used to analyze alkane,
alkene, and cycloalkane isomers as well as HC mixtures.
PHYSICAL PROPERTIES
Laboratory. Stuckey (15115)used two different approaches
to obtain wt. response factors of GC detectors for GC
“simulated” distn. (GCD) of crudes (TCD) and refined pe-
k t
troleum streamsT(FID), basedEon the chemical $ nature of $the
samples. Am empirical approach was used with crudes and
a statistical approach was applied to the refined petroleum
streams. Results showed that a common response factor
should not be applied; response factors are needed for each
data point or temp. An equation was developed which relates
the response factor to the UOP characterization factor and
the b.pt. GCD data can be converted to wt. % and/or vol. %
by using response factors. GCD can be used as a quality
control method and as an inexpensive crude assay tool and
provides a rapid method of defining product distribution on
a very small sam le.
da Silva et al. 6 I L ) described the use of GC to determine
the solubility of gases in liquids a t ressures from 760 mm
to 10-20 mm. The gas is equilibrate! with the solvent at the
desired temp. and pressure for 24 h in a cell consisting of two
connecting vessels with a volume ratio of 5:1000, and a GC
analysis of the liquid is then carried out. Method precision
is 3%. The solubility of 0 2 and NO in n-hexane, acetonitrile,
PETROLEUM
and other solvents showed good agreement with lit. values.
In the first of two papers, van Kasteren and Zeldenrust
(159L)discussed the design and evaluation of a flow colo-
rimeter which can measure enthalpy-temp. relationships for
small amounts of condensable gase at 100-300 K and up to
70 bars with an accuracy of about 1% . This device can also
handle two-phase gas/liquid systems and operates a t a con-
stant pressure over the entire temp. range independently of
the vapor pressure of the gas mixt. Performance was tested
on pure CH4 under supercritical and critical conditions. In
the second paper, van Kasteren and Zeldenrust (160L)com-
piled exptl. results by using their flow colorimeter and com-
pared these with predictions based on a modified Redlich-
Kwong (MRK) equation of state. The heat capacities and
enthalpies of the pure forms of the ma’or components u s u d
occurring in natural gas (CH4,CzH6,C3k8,N2)were measured:
These exptl. data were used to improve the predictions of an
MRK-based computer program. Cooling curves of binary
mixts.of these components and of two multicomponent mixts.
of Nz with C1-C5 and C1-C3 alkanes a t 110-270 K were then
determined with the computer program. The predicted data
were in fair agreement with exptl. except for the liquid-phase
heat capacities of the CzHs/Nzand C3H*/N2 binaries, which
were much lower than exptl., roably because of a liquid-liquid
phase sepn. at low temps. #mall amounts of He (0.3%) in-
creased the liquid-phase heat capacity of a multicomponent
mixt. but not that of pure CH., or Nz. Karaiskakis et al. (77L)
used GC to determine the enthalpy and entropy of adsorption
of pentane, hexane, heptane, cyclo ntane, cyclohexane, and
cycloheptane on Al 0 modified witr4-20% of an alkali halide
(five chlorides a n d d a F , NaBr, and NaI). The entropy and
enthalpy varied widely. Two new parameters calculated in
terms of the thermodynamic compensation effect, ~LT,
L, provided a better characterization of adsorption t an en-
and
thalpy and entropy. The only necessary condition for a
compensation effect to occur is that the mean values of he
coordinates for the various intersection points of the relevant
straight line lies within a small range. Disking et al. (33L)
developed criteria for evaluating the thermal oxidative stability
of oils using chromatography, differential thermal analysis,
and differential thermo avimetric analysis. Unfortunately,
only the title of this articg was translated for the abstract used
as B basis for this review.
Process Analyzers. Many of the following physical
property analyzers have been discussed in previous reviews
and will be mentioned briefly here to update applications and
improve instrumentation. In one article (124L),the Totco
purity analyzer is discussed. This analyzer determines purity
based on freezing point determinations for liquids freezin
between -40 and 100 “C. The analysis cycle of 12-18 min s t d
permits continuous open or closed-loop monitoring of pro-
cesses and has been used in US., Europe, and Japan. Com-
mon chemicals which are monitored are p-xylene, styrene,
benzene, p-dichlorobenzene, phenol, and acetic acid. Another
device designed to continuously monitor jet fuel freeze points
is the Totco freeze point analyzer. The unit operates over the
range of -65 to -15 “C and is used on distillation columns or
blenders to keep the product within specification.
The Home Instruments’ Distillar on-line analyzer (125L)
carries out a standard distillation test in 20 min and follows
the ASTM D-86 test closely. It w i l l record on a re
a chosen
? distillation! point normally S tested by A
methods. The basic components of the analyzer are: flask,
heater, condenser, calibrated receiver of st. st., temperatures
sensing element, a 100-mL charge burette, and electrical and
pneumatic components for automatic operation including
.
filling, flushing, and drainin The analyzer is air purged. Six
models are available depensing on requirements of the user.
Walko (16.55) discusses a new gas and liquid densitometer
of the insertion type useful on process fluids, slurries, and
LNG. The vibration-element sensor is enclosed in a
“Minitube” and the coils are arranged outside the tube and
enclosed. Floating faces on the transducer act as axial loading
plates and compensate for the liquid pressure inside the tube.
The system can be used a t cryrogenic or high temp., but pH
should be above 5 in pipelines and tanks. Prototypes were
accurate to within 0.1% in LNG tests. Other uses are to detect
oil-water interfaces and determine oil-water ratios. Solartron
also makes a version that when calibrated with Argon w i l l give
ethylene density to within 0.2 % .
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 123R
PETROLEUM
Williams (170~5) also discusses a density analyzer, but the
principle is based on the adsorption of high-energy y-rays.
The same unit can be used for level measurement as well as
the density of liquids or the amount of solids in slurries. The
Paper provides tips on nuclear gauging including: safety,
icensing, source decay, and factors affecting density gauging,
such as: stratification, air bubbles, vibration, corrosion, and
temp. These and other factors to be considered in applying
the technique to slurries, sewage sludge, interface detection,
and level auging are also discussed.
Morris &04L) has collected comments from manufacturers
of prolems encountered with sensing interface levels and
whether CLP provides possibilities for improved measurement.
Emulsion layers usually provide problems for most interface
levels, as do interfaces with motion. Several other aspects of
sensing interface levels are discussed too numerous to mention
here.
IMPROVED INSTRUMENTS AND
TECHNIQUES
Laboratory-GC Methods. About half of all references
in this section deal with some aspect of gas chromatography.
Soroka (147L) used a statistical techni ue known as target
factor analysis (TFA) to study the fo(howing: gas-liquid
chromatography data matrix involving 49 solvents (alkanes,
alkenes, alkyl halides, monomeric solvents); 6 matrices from
McReynolds' compilation (ketones, aldehydes, carbonyls, and
mixed functions1 grou 9); gas-solid chromatographic data
involving retention in&xes (alkyl and aromatic solutes and
ionic forms of Amberlite A 15 and Chromosorb P); and the
analysis of an ion exchan e problem. A com uter program
(FACTANAL)facilitates appfication of TFA to tiese problems
Hirsch et al. (68L)used correspondence factor analysis (CFA)
to identify the major influences on the behavior of satd. and
unsatd. HCs in gas-solid chromatography on ion exchangers
in different cationic forms, using stationary phases prepared
from sulfonated Porapak Q ethylvinylbenzene/divinylbenzene
copolymer. CFA shows that ion exchangers in the Ag', Nil+,
Zn2+,and Cd2+forms have different selectivities for unsatd.
HCs. Steric hindrance of this selectivity occurs with the larger
cations, such as Ag+. The H', K', Na+, and T1+ forms are
practically nonselective relative to the unsulfonated copolymer
matrix.
Gangwal et al. (46L)discussed the reliability and limitations
of pulse chromatography in evaluatin properties of flow
systems. They used theor. analysis an8 adsorption experi-
ments with pulses of CHI and C2HG on silica gel to evaluate
the technique for determining the axial dispersion coefficient,
adsorption equil. constant, chemisorption rate constant, mass
transfer coefficients, effective and surface diffusivity, reaction
rate constants and the Kubin-Kucera adsorption model.
Experimental reproducibility was good. The validity of the
model was confirmed by the agreement between experimental
and predicted effects of velocity, particle size, temp., and bed
length on model parameters. Results on pore diffusivity and
adsorption equil. constant were in good agreement with lit-
erature values obtained by other techniques. Pulse chroma-
tography was unsuitable for determining the rate constant of
physisorption and the mass transfer coefficient. A total of
50 references are given.
Norris (113L)discussed the applications of analytical
chromatography in petroleum technology and lubrication. The
first of two papers cover history, theory, columns, and packings
for adsorption, partition, and exclusion systems, prepn. of
samples, control of conditions, and the hydrocarbon skeletons
of interest in petroleum chemistry. Also discussed were PC
and TLC and their applications in the analysis of additives
in lube oils and greases. In the second paper, Norris (114L)
continues his discussion, covering the behavior of H2 in GC
columns, sepn. of wide-boiling range samples, programmed
temp. GC, the capillary column, and automatic GC analysis.
Also discussed is the application of GC to use! engine oil anal.,
detg. oil vis., gasoline analysis, and identification of ur.knowns
from a library of reference spectra. The article also dlscusses
the development of high-performance of LC, reversed hase
chromatography, and size-exclusion chromatography. &am-
p l e ~of applications of LC to motor oils and gasolines are given.
Laurgeau and Barras (88L) showed that two samples in-
'ected simultaneously into a GC column is pseudorandom
Binary sequence from different sampling devices yield output
124R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
data that can be analyzed by decorrelation techniques into
separate chromato rams. The basic theory and exptl. pro-
grams are discusse! and illustrated by sepns. of the compo-
nents of propane-butane mixts.
A number of papers appeared on GC columns and column
techniques. Rooney (131L)discussed the advantages of glass
capillary columns in the analysis of petroleum products on
a 60-m column coated with SP-2100 with flame ionization
detection. Hz, He, and N2 carrier gases were compared. The
lower vis. of H resulted in shorter analysis times. Brander
(19L)describe8 a new glass capillary system for the Varian
Model 3700 GC. The use of glass inserts in the capillary
injector permits direct, split, and splitless modes of operation
without removal of the capillary column. Branching of the
column is facilitated by using ferrules. Good retention time
repeatability is obtained because of the thermostated pneu-
matic system and precise column oven tem . control. The
system was tested on a mixt. of Cllto CS H&. Anderson et
al. (8L) described a novel dual glass-capillary system. The
two columns, each in its own oven, are connected by a heated
transfer l i e , permitting the use of optimum stationary phase
polarity, thus improving selectivity. The use of flow circuits
allows changes in the direction of the column effluent. The
transfer line can serve as an intermediate trap. The design
and modification of the system are described and operatin
parameters are discussed. Chromatograms of standarf
arylalkane mix$. are given to illustrate possible sepns. Evrard
et al. (37L)described a sampling system using heated sample
phials and a packed precolumn for high-temp. isothermal
capillary GC. The sample is diluted with 0.1 or 0.2 mL of
volatile solvent placed in the phial and the phial placed in
a loading chamber. N2 is used to purge the system, the phial
is heated, and the vapors are condensed on a precolumn
packed with OV-1 (1-12%) on Gas-Chrom Q (80-100 mesh)
and operated in the back-flush mode. The substances to be
analyzed are then transferred via a wall-coated capillary trap
to a capillary column for analysis. The device is controlled
by a programmable electromechanical processor. Mixts. of
n-alkanes (C14-CM)have been analyzed with a precolumn (at
100 "C) contg. 12% OV-1 and a 25-m analytical column (at
242 "C) wall-coated with OV-101. Blanks are free of ghost
peaks when thermally prestripped phials are used.
Sharp (143L)presented a practical guide to the use of
wall-coated open-tubular glass capillary columns in lab GC
which should facilitate setup and operation of such columns
by ersons unfamiliar with their use. Sample introduction
anfdetection (FID) are discussed, and the prepn. and in-
stallation of com. lass capillaries are described in detail.
Applications descri%edbriefly include the analysis of petro-
leum fractions. Grob et al. (55L) discussed the principles and
basic techni ue of deactivating glass capillary columns by
silylation. T%e glass is leached with HC1 and pure si1 latin
agent (hexamethyldisilamne or tetramethyldiphenyldisiLe7
drawn into the column to about 7% of its total length and
flushed through the column with carrier gas. When the liquid
has been displaced, the column is evacuated, sealed, heated
slowly to 400 OC, and held at this temp. for about 3 h. The
column is then cooled and flushed successively with CBHBCH3,
CH30H, and E g o . The column may then be coated with an
appropriate stationary phase. Factors influencing column
performance are discussed. The sepn. of test mixts. of HCs,
carboxylic acids, and drugs is illustrated. Badings et al. (13L)
described the prepn. of wall-coated open-tubular capillary
columns after surface roughening using amorphous silica. The
capillary is leached and treated with a plug of dil. sodium
silicate soln. to deposit a small amount of amorphous silica
even1 on the inner surface, and finally b a stream of HC1
K
gas. detailed procedure is given for stab&ing deactivating,
and finally coating the roughened surface. Performance data
are iven for several columns so prepared, including sepns.
of afkanes on Carbowax 20M.
Toth (157L) compared the sepn. efficiency of packed steel
or glass capillary GC columns having roughened or smooth
internal surfaces with different stationary phases at 50 and
100 "C for various paraffinic and aromatic HC mixtures.
Important parameters are peak resolution per unit lenkth,
effective number of plates per unit length, rate of formatlons
of effective plate number, type of column, the stationary phase,
and the partition ratio. A total of 19 references are given.
Orav et al. (116L)studied the GC sepn. of Clo to Clz alkene

cis-trans isomers at 60 to 80 "C on st. st. capillary columns
(0.25 mm x 100 m) coated with 1,2,3-tris(2-cyanoethoxy)-
propane. The retention indexes and their temp. increments
and structural increments were correlated with the structure
of the isomers. Results were compared with those obtained
on columns coated with less polar stationary phases. Galli
et al. (45L) described an efficiently cooled on-column injector
which isolates the end of the column from the oven temper-
ature, eliminating "discrimination" of compounds in a given
sample. Coolin is achieved by a stream of air entering the
f
area of the capi lary fitting and flowing alon the outside of
d
the capillary into the oven. Problems cause by insufficient
cooling are discussed, and the efficiency of the s stem is
illustrated by using test mixtures of alkanes (C18-8a). No
band broadening occurs because of the cold spot at the column
inlet.
Lafosse and Durand (87L) studied squalane, 1,3,5-tri-
cyanopentane and mixts. of these two compds. as stationary
phases on Gas-Chrom Q (80-100 mesh) in st. st. columns (0.125
in. outside diam.) for GC separation of compds. having widely
different polarity such as HCs, alcohols, haloalkanes, nitro-
alkanes, heterocyclics, etc. The mixed supports were prepared
by either by coating the support with a mixed soln. of the two
phases or by mixing supports coated with the single phase.
The two methods of preparing mixed phases gave equivalent
results. Separation was carried out a t 60 "C with N as a
carrier gas and FID. Retention vols. are tabulated and con-
clusions drawn about the interaction of the solutes with the
nitrile groups as an aid in selecting stationary phases for GC.
Nawrocki et al. (111L)studied the sepn. properties of poly-
[Cu(II) di-n-hexylphosphinate] as a GC column packing for
homologous series, isomers, and compds. with close b.ps. The
sepn. of impurities in a-methylstyrene was used as an example
of contamination analysis. Pscheidl et al. (126L)discussed
elimination of the effects of the solid sup ort (Porolith) on
the GC stationary solvent phase. A Cu capiary tube was used
without a solid support, and the support was treated in various
ways to eliminate its effect. The stationary liquid hase used
B
was 1,l-diphenylethane, and the sepn. was Carrie out using
cyclohexane, cyclohexene, and CsH6. The analysis is related
to the hydrogenation of cyclohexene.
Blyuss et al. (17L) showed that the se n. efficiency of GC
systems with parallel multiple columns is getter than for those
systems using sequential operation of columns. Examples are
iven with Polysorb and mol. sieve columns for the sepn. of
f I 2 , 0 2 , N2, CH?, C02, and C2H6. Pretorius et al. (122L)
discussed optimization of GC resolution of multicomponent
mixts, using temp. variation of series-coupled columns. One
column was packed with Chromosorb coated with 4% of
OV-101, the other with Chromosorb coated with 4% of Silar
5. Each column was placed in a separate oven, and the col-
umns were connected in series, N2 carrier gas was used with
FID. A mixture of acetophenone, benzyl alcohol, and dode-
cane was used. The temp. of the OV-101 column was held
a t 80 "C and the temp. of the other column was varied. The
relative retention values of the solutes can be dramatically
changed and elution order can be reversed.
Zhukhovitskii et al. (173L) described the technique of
"limiting chromadistillation". In this technique, before sepn.
is carried out, the GC column is wetted with a component of
volatility significantly greater than that of the sam le com-
ponents. The technique is illustrated by data on tRe sepn.
of a mixt. of C6 to C9 alkanes, using a column (100 cm X 0.3
cm) filled with glass spheres (0.7 mm) and operated a t 21 "C
with He as a carrier (flow rate at column exit = 18 mL/min).
Matsuoka et al. (97L)described the use of short precolumns
contg. hydrogenation catalysts in a GC between the injector
and a squalane-coated capillary column using H as a carrier
gas. A com lete hydrogenation catalyst was used to establish
the skeletafstructures of C to C8 HCs, and an intermediate
catalyst was used to cause double-bond migration in unsatd.
compds. This technique ermitted detn. of retention times
of several unsatd. compg. with the use of only a few std.
samples. Variation in the precolumn temp. gave the ther-
modynamically predicted changes in the ratio of hydrogenated
and nonhydrogenated products. Thus 0.5% Pd on A1203a t
180 "C gave complete hydrogenation, and at 270 "C and above
six-membered rings were increasingly dehydrogenated to yield
the corresponding aromatic compds., but aliphatic corn ds.
remained in the reduced form. A 250-mg sample of P l o n
PETROLEUM
Chromosorb at 100 OC gave complete reduction of very small
samples (0.02 HL)with no side reactions; 10 mg of catalyst
gave partial hydrogenation and double bond migration (1pL
sample).
Gaspar et al. (47L) described a computer-controlled auto-
matic GC which used a fluid logic gate as the sampling device
for introducing the sample as a narrow band a few ms wide.
Difficult sepns. (e.g., a light asoline) can be made in a few
seconds using short open-tub& columns (< 1m) with narrow
i.d. (< 100 km).
Ferguson and Luke (39L) gave a critical appraisal of the
FPD in petroleum analysis. Experience was summarized
under the headin s inequality of response, quenching of S
k
response and lac of sensitivity and under three topics:
analysis of individual S compds. in the 15" to 65 "C cut of
crude oils, the S fingerprint of crude oils, the evaluation of
a dual-flame detector. Wenzel(167L) summarized questions
and answers (discussed at ACS short courses) concerning the
Melpar FPD GC detector. These include causes for a decrease
in sensitivity for S, deterioration of the photomultiplier tube
as a cause of loss of sensitivity with time, prevention of FPD
solvent flame-out, and prevention of S chemiluminescence
quenching by eluting HCs.
Stockwell (149L) described automatic analysis by using
hybrid chromatographic systems to provide unique identifi-
cation of certain components. Such systems include GC-co-
lorimetry, N-selective detectors, chemiluminescence detectors
linked to specific catalytic reactors, and vidicon or linear-
diodearray spectrometers used with LC. Applications include
detn. of components of gas oil. Phillips and Goldan (119L)
discussed the enhancement of electron capture detector (ECD)
sensitivity to nonelectron-attaching compds. by addn. of N2O
to the carrier gas. In the GC se n. of H2, COz, and CHI on
Porapak Q and Mol Sieve 5Ae!t addn. of N20 to the N2
carrier gas produced a large increase in the sensitivity of the
ECD to these compds. with no detectable change in peak
width, eak shape, or retention time. This enhanced response
is attriEuted to the reaction of these compds. with 0- to form
stable negative ions, which interrupts the normal steady-state
reaction sequence. At a signal to noise ratio of 2, the minimum
detectable limits of these compds. is about 1X molecules.
The as-yet-unpublished detn. of pg quantities of C2H,through
C6H14 and other org. compds. is noted.
Schwarz et al. (139L) described on oscillating slit mechanism
for detg. H isoto ratios in a microwave induced plasma. HCs
(nondeuteraterperdeuterated, or partially deuterated)
emerging from a GC (using He carrier gas) were subjected to
a low-pressure microwave discharge, which fragmented the
compds. and generated intense atomic emissions. These
signals were led to a monochromator provided with an os-
cillating exit slit so that the H and 2H signals passed alter-
nately to the photomultiplier, the output of which was resolved
by two lock-in amplifiers. The ratio of the two signals and
H/2H in the mixts. was rectilinear over more than 1 order of
magnitude. The method was also applied to isoto e diln.
analysis, where perdeuterated naphthalene was adfed to a
water sample cont traces of naphthalene and benzene and
the HCs were e x t t into an org. solvent for analysis. Hen-
neberg et al. (65L) described an open-split interface for
high-performance GC-MS which has a glass restriction and
is provided with a flow of scaven er gas. With a small sca-
venger flow, dead-volume tailing of%rge peaks is avoided; with
a large flow, peaks that would otherwise be too large are
diluted. The system was tested for alkanes and various polar
mixts. and was found to have no effect on the quality of the
chromatogram. At higher temps., adsorption was a limitin
factor. Pt capillaries were inferior to glass. D'Orazio (34157
used a Raman multichannel spectrometer as a detector for
a GC using a column (0.25 mm X 15 m) coated with OV-101.
The GC effluent was passed through the focus of an Ar+ laser
beam in a Raman spectrometer system and the beam was
directed to the entrance slit of a single grating monochromator
and via an objective to a 500-channel array detector. Con-
ditions for detg. benzene were established and the detection
limit for toluene in acetone was detd. The sepn. efficiency
for fractions of cyclohexane and benzene was measured, and
0-and m-xylene in a mixt. with toluene, benzene, and acetone,
were readily identified.
Ecknig and Polster (355) studied the elution of n- and
isoalkanes from mol. sieve 5A with supercritical C02 as a
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 125R
PETROLEUM
mobile phase, in the ranges from 0.5 to 20 MPa and from room
temp. to 200 "C. n-Alkanes up to Cl4 can be sepd. individually
and those up to Cm as a group from isoalkanes by appropriate
selection of temp. and pressure.
Several pa ers dealt with sam le introduction into the GC.
Kennard ancfLaskowski (80L) Bescribed the use of a hot air
to heat samples in a Hewlett-Packard 7671 A autosampler.
g e gun is fitted to the sampler tray to heat samples awaiting
injection. This permits injection of waxy or viscous samples
with the instrument in the automatic mode. The s stem
incorporates a device to prevent overheating. Grog and
Heukom (56L) discussed the influence of the syringe needle
on the precision and accuracy of vaporizing GC injections,
usin a C9-C4 alkane test mixt. and stream splitting on a
capiflary column. The discrimination of the high boiling
components in the injector is mainly due to a selective elution
of the sample out of the syringe needle. Different methods
of handling the syringe needle were tested, and the discrim-
ination is uantitated and correlated with the material left
in the neehe. The Sam le should be pulled back into the
barrel of the syringe a n f t h e needle allowed to warm up in
the injector before the sample is transferred into it. Solvent
flush may be preferred for com onents sensitive to the hot
metal surface of the needle. fonchik and Walker (146L)
described an inlet (for capillary GC for trace analyses) con-
sisting of an 11.4 cm long glass-lined st. st. tube for direct
injection of the sample without purging on venting into a
Varian 3700 GC. n-Hexane (99% pure) analyzed on a
Squalane support-coated o en tubular (SCOT) column gave
a 1 ppm cyclopentane pea!. Analysis of a C -c13 mixt. of
n-alkanes on an OV-l7/SCOT column with the Jirect in'ection
inlet and with a com. available splitter inlet showed little
difference in column efficiency between the two inlets. The
direct inlet is also useful for wide-boiling range mixts. and
thermally labile compds. since a high injection port temp. is
not required. A c,-c16 n-alkane mixt. was sepd. with an
in'ection port temp. of 150-250 "C, compared with the 300
"dinlet temp. required with a splitter inlet. Tejedor (154L)
also described direct injection into capillary columns for trace
analysis using identification by MS. No resolution loss or
excessive loss of peak symmetry was observed, and the method
can be used routinely without column deterioration or effi-
ciency loss. The method was studied by using a st. st. column
(0.25 mm X 50 m) wit UCON 50 HB2000 to separate a mixt.
of n-hexane, methylcyclohexane, cyclohexane, iso-PrOAc,
2-pentanone, and 4-Me-2-pentanone in CSz soln. Kitamura
and Seko (82L)also discussed GC trace analysis for separating
a trace component which appears as a shoulder on the tail of
the main sample component peak. A dual-column system was
used and the sample contg. the impurity was injected into one
column, a reference being injected into the second column
under conditions so that the tail of the reference peak coin-
cides with the tail of the principal component peak. A timin
device is used to permit the reference material to be injecte
at a fixed time after the injection of the sam le so that peak
d the fillin device and the method of filling the column was
time-matching can be achieved. By use of a Zifference signal
from the detector, only the impurity peak will appear in the
chromatogram. By use of a 2-m sample column of P6-15008
and a 1.5-m reference column packed with DNP and C H8 as
reference, benzene contg. 1 ppm PhMe was separates.
Andersson and Ericsson (9L) determined the mean time-
temp. rofile in a sample subjected to pyrolysis GC in order
to estatlish whether it is ossible to equate the temp. of the
E
pyrolyzer with that of t e sample being pyrolyzed. The
degradation of cis-1,4-polybutadienewas studied by sequential
pyrolysis. By use of measured rates of degradation for dif-
ferent amounts of sample, determination of the temp. de-
pendence of the degradation rate from an Arrhenius plot, and
combination of exptl. results with theor. derived expressions,
the time-temp. profiles of different amts. of sample could be
calculated. Choosing the a propriate pyrolysis conditions of
sample thickness, time, anftemp. of the sample is nearly the
same as that of the pyrolyzer. Zizin and Makov (175L) de-
signed two units for the thermochromatographic (Tg) variant
of GC analysis using water as heat exchange medium. Temp.
ranges of 0-100 "C or 0-150 "C (under higher pressure) are
available. The method changes the temp. gradient of the
column and ives better sepn. coefficients than conventional
methods as femonstrated by sepn. of aromatic HCs. The TG
effect and the effect of temp. programming are discussed.
126R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
Liquid Chromatography. A number of papers were
published in the field of LC. Hirata and Novotny (67L)found
that packed capillary columns of the reversed-phase type for
LC provide the high efficiencies needed to resolve complex
mixts. Small volume samplin and detection are design
problems that must be solved. direct method of sampling
is demonstrated that compares favorably with splitting in-
jection. Two step-wise gradient elution techniques were de-
veloped for these columns. With small volume UV and
spectrofluorometric detectors, a standard mixt. of toluene,
naphthalene, fluorene, anthracene, pyrene, chrysene, and
benzo[e]pyrene was separated. The method was then applied
to polyaromatic fractions from coal tar.
Freeman and Schram (4115) derived in numerical form a
sin le expression relating liquid gel permeation with alkane
mo!. size (L) including the conformational coefficient (ZJ.
L = 3.26 + 0.0358MW - 0.202i. The value Z i is constant
for each structural isomer group. Values of Zi for the following
alkane series are tabulated n-alkane, 2-Me, 3-Me, 4-Me, 3-Et,
4-Et, 2,2-Me22,3-Mez 3,3-Mez. Hennion et al. (66L)studied
the influence of the number and length of alkyl chains on
chromato raphic roperties of hydrocarbonaceous bonded
phases. {arious Jkyltrichlorosilanes (C Cl8) were bonded
to porous silica and the products were s f r y packed in LC
columns (4.8 mm X 15 cm). For octodecyltrichlorosilane at
111"C, 18 h were required to achieve max. C content in the
packing. Higher temps. gave greater loading more ra idly.
Capacity factors for a series of polycyclic aromatic H d and
henols increased exponentially with the C content of the C18
rionded phase up to 15%. The selectivity factors also in-
creased with C content and column efficiency was max. at
about 14.5% C. For bonded phases with different alkyl chain
lengths, the capacity factor for hydrocarbons increased ex-
ponentially with chain length; for phenols this increase was
rectilinear. Increasing the polarity of the mobile phase (0 to
30% H 2 0 in CHBOH) increased exponentially the capacity
ratios for the HCs and the selectivity factors. For best results,
a Clgbonded phase with a coverage of about 2 pmol m-3 should
be used.
Hammers et al. (61L)discussed the standarization and
determination of selectivity of octadecylsilylsilica in LC. The
adsorbent was prepared by treating Merckosorb Si 60 with
trichlorooctadecylsilane (surface coverage 1.64 pmol m-2 and
was acked into a column (2.1 mm X 25 cm). Retention data
R
on t e column were measured for a range of mono- and di-
substituted benzenes, polycyclic aromatic HCs, and substi-
tuted hexanes and cyclohexanes. The eluents were hexane,
hexane-CH Clz (137), and CH C12. Factors affectin retention
were consi8ered mathematicdl , Ageev et al. (5Lf prepared
columns for LC with sepn. efgciencies of 20000 to 40000
theoretical lates/m (chromatograph Tsvet 304). The ad-
sorbents (siica gel S-3, Silochrome S-80 and S-120, were
fractionated by sedimentation in HzO. The construction of
describecf The efficiency was tested by using mixts. of c6&,
phenanthrene, PhN02,and Ph NH. Tables give the number
of theoretical plates for the sorbents, their different particle
sizes, and application procedures for different samples.
Hammers et al. (62L)investigated the adsorptive ro erties
of N-2-cyanoethyl-N-methylaminosilica (CNA-&car for a
large number of mono- and disubstituted benzenes and some
unsubstituted polycyclic aromatic HCs when CNA-silica was
used for LC with hexane, CHzCl , or he~ane-CH~C!~ (13:7)
as mobile phase at 25 and 43.5 "6 The results are discussed
in relation to the adsorption mechanism and are compared
with those obtained on ODS-silica.
Kostyla et al. (86L)used chemically modified solid poly-
meric supports contg. specific functional groups for the sepn.
v d or concn. and detection of selective classes of org. com ds.
via LC, Pyrrolidone on vinyl modified silica was u s e l to
separate aromatic compds., an organomercurial group on
agarose to separate mercaptans, and the diazonium func-
tionality on a solid supporting resin for separating phenols
and arom. amines. Use of the supports for chromatographic
sepn. was discussed.
Halasz (6015)described a procedure for fractionating vac-
uum residues from several crude oils (Boscan, Safaniya) by
LC. The following were discussed briefly: nature and pre-
treatment of column packing, water content of heptane,
eluting solvents, column capacity, accuracy, and repeatability

of the method. The method does not apply to gas oil and other
light petroleum fractions since 90% of these oils eluted in the
first two fractions.
Semonian et al. (141L)described the use of positive pressure
columns for solvent cleanu or LC. The formation of gas
bubbles, the loss of solvent gy evaporation and the contam-
ination by H 0 vapor that occurs when gravity-feed columns
are used can 'be minimized by using a closed system in which
the solvent itself provides a protective gas cover. A column
of silica gel having a stopcock (at its lower end) leading to a
receiver was connected a t its upper end to the solvent res-
ervoir. The reservoir was connected via a T to a vent and to
a mercury vessel for regulating the pressure. The equipment
was used to purify pentdne.
Joecker and Smink (72L) discussed the selection of the
optimum system and detectors for the detection of aromatic
substances via LC. Schick and Huber (136L) patented.an
amperometric sensor for LC using metal oxide hydroxide
electrodes. The working electrode consists of a transition-
metal substrate having a surface layer of a multivalent ox-
idelhydroxide of the metal in which the anionic vacancies in
the coating are partially filled with halide or sulfide ions.
Applications include the detn. of mono- and polyhydroxy
aliphatic and aromatic compds., aromatic and aliphatic amines
and thiols, and H 2 0 Lower detection limits for glucose at
a Cu oxide-hydroxi%e working electtode were 100-500 pg.
Vidrine and Mattson (163L)described a practical real-time
Fourier transform IR detector for LC. Sample flow cell de-
tection with automatic solvent subtraction is used and de-
tection of 500 ng of injected paraffin oil was demonstrated.
Results from LC runs were used to illustrate system capability.
IR s ectra can be acquired simultaneously. Vidrine (162L)
B
use subtractive techniques in interpreting on-line Fourier-
transfor IR spectra of LC column eluates to permit the
identification of o-xylene in a chromatographically incomplete
sepn. of a com. rn-xylene contg. small amounts of p - and
o-xylene and the identification of CC14 and toluene as con-
taminants in an incompletely resolved chromatogram of
polystyrene.
Li and Arrington (9OL) used a dual-wavelength spectro-
photometer as a high-resolution, high-precision, high-selec-
tivity detector to overcome peak overlapping and provide
quantitative sepn. of a mixt. of polycyclic HCs via LC. The
sepn. was carried out by using a column packed with
pBondapak CI8 at 37 "C with 74% CH30H as the mobile
phase. Positive identification of the HCs was assisted by (1)
computer-simulated chromatograms from chromatographic
and spectral data obtained under different conditions and (2)
use of equations derived from the transient absorbance during
elution and from the difference in absorbance a t the two
wavelengths. Stoveken and Vitali (150L)discussed in detail
the general principles of LC with a spectroscopic detector and
applications to HC sepns. They used Perkin-Elmer's Series
2 and Series 3 LC with: (1) the Model LC-55 variable-
wavelength UV detector fitted with an accessory for recording
the spectra, (2) the Model Lc-15 fixed wavelength UV de-
tector, (3) the Model LC-lo00 fluorescence detector. Examples
of spectra include tert-butylbenzene, benzene, toluene,
ethylbenzene, and isopropylbenzene.
Colin et al. (29L)described the construction and perform-
ance of an improved differential refractometer detector for
LC. Design modifications over conventional RI detectors
include the following: (1)symmetrical design and small focal
lengths; (2) placing the double prism in a parallel li ht beam
P
making it less sensitive to vibrations; (3) a cod-source
light-emitting diode (G& TIL 31) emitting at about 940 nm
with a bandwidth of 45 nm minimizes base-line shift by re-
ducing differential heating of the two cells by the source; (4)
designing the cell block for easy removal and thus simpler
maintenance; (5) small cell volume which reduces band
broadening. The detector has a time constant of 24 ms and
a linear dynamic range of 27 OOO. The equipment is compared
with a Waters R 401 detector. Under optimum conditions
1 pm of benzene in heptane can be detected.
Fallick and Rausch (38L)described the radial compression
technique for packing LC columns with small particle size
packings which permits the reproducible formation of a ho-
mogeneous bed and eliminates wall effects. Performance of
this packing technique and the LC system thus obtained is
illustrated with the sepn. of arom. HCs and other org. compds.
PETROLEUM
Mills et al. (IO1L) described the use of a general purpose
microcomputer for flexible automation of LC. Hardware was
constructed from a set of ready-made circuit boards. Control
programs were written in assembly language and the data-
handling program in CORAL 66. The system had facilities for
automatic repetitive sampling (coeff. of variation of 1%) and
means for implementing rinse and purge routines. A data-
processing algorithm ensured quantitative results even for
poorly resolved peaks. Chromato ams for six arom. HCs are
f
given. Majors (96L)discussed app 'cation of the Varian Model
5000 (microprocewor-based LC with CRT display) to the sepn.
of polystyrene oligomers, using the 3-solvent capabilities of
the unit. The advantage of the units' automatic loop valve
in monitoring the course of a chemical reaction is also dis-
cussed.
In addition to GC and LC, a number of other analytical
techniques were covered. Adrian (2L) reviewed the prepn.
of samples for IR spectroscopy by means of suspension in
paraffin oils and their derivatives. Miyashita et al. (102L)
developed an automated quant. IR system by coupling an IR
spectrophotometer and an on-line minicomputer. A least-
squares polynominal of degree two was used to calculate the
smoothed transmittance in real time. After a sample was
measured, solvent com ensated transmittance data for
quantitative detn. were oEtained. This system is suitable for
programmed wavenumber scanning control because of the high
wavenumber reproducibility of the spectrophotometer. Three
isomeric xylenes were detd. precisely with this system.
Grasselli (5015) described the development of analytical
methodology and the application of various analytical tech-
niques to analyze a deposit in a gasoline tank truck (IR
spectroscopy), structural analysis of a Co molybdate-on-alu-
mina hydrodesulfuriation catalyst (Raman spectroscopy), and
an engine valve deposit that was suspected of being a motor
oil additive (complex IR spectroscopic scheme).
Kekedy and Kormos (79L) reviewed the roperties and
B
a plications of a semiconductor electrode base on SnOz. This
e6ctrode consists of a layer (1-2 pm) of SnO, coated on glass,
which has high conductance. Electrochemically it behaves
similarly to a Pt electrode but can be used over a wider po-
tential range (2300 mV). This electrode has been used as the
working electrode in potentiometry, chronopotentiometry,
coulometry, and stripping anal sis. I t also forms the basis
of electrochemical sensors for 60,0, acetone, or HCs.
Kawala et al. (7815)discussed the use of molecular distn.
for analytical and preparative sepn. of high-boiling petroleum
fractions. Preliminary single-stage sepn. of less volatile com-
ponents and further sepn. of more volatile components into
narrow-boiling fractions using a multistage unit were used to
separate the atm. residue of Romashkino oil. Zygmunt and
Staszewski ( I 16L) described the use of Na 4-chloromercuri-
benzenesulfonate (I) in ethanediol-H20 (1:l)to extract and
concentrate RSH from petroleum HCs. In the extn., I forms
mercaptides with RSH; the extracted mercaptides are then
regenerated by treating the extract with aq. 3.8% thioacet-
amide and are removed by extn. with hexane or hexane-
benzene (91)with recoveries from 96 to 99%. This procedure
might be used as a preliminary to the GC detn. of individual
thiols in gasoline cuts.
Jenkins (71L)discussed the use of XRF (energy-or
wavelength-dispersive) to provide a reasonably complete
elemental analysis which in turn is used to greatly simplify
phase analysis by powder XRD. Computer 'search-matchin
of data can be improved considerably where both positive an8
negative elemental information are available. Application of
combined XRD-XRF for routine phase analysis of leaded
asoline engine deposits and airborne particulates is described.
Instrumentation is discussed.
Arkenbout (11L) reviewed the advantages of continuous
fractional crystallization for the sepn. and purification of org.
compds. from theor. and ractical standpoints. Applications
include the sepn. of xyEne isomers and thiophene from
benzene and the purification of benzene. Several lab-scale
devices are described and scale-up to pilot plant scale is
mentioned.
Nechitailo (I12L) described the development of thermal
analysis (TA) and its application to petroleum chemistr
characterized Soviet and foreign TA equipment, and m a l l
an extensive lit. review. Potential a plications and results
of TA analysis were discussed for H8compos. of crude oils,
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 127R
PETROLEUM
melting temps. and purity of HCs, phase diagrams of mixts.
of n-paraffins, thermal stability and structure of adducts of
urea and thiourea with n-paraffins and isoprenoid HCs,
characteristics of lubricants and mechanism of their oxidation,
various synthetic lube additives, greases and soap thickeners,
petroleum asphaltenes and resins, prepn., compos., and props.
of catalysts, and physical and chem. processes in polymers,
108 references.
Tittarelli (155L) reported on recent trends, developments,
and Petroleum Industry applications in flameless AA spec-
troscopy, as given in the jointly held 20th Colloquim S ec-
troscopicum Internationale and the 7th International 8on-
ference on AA (Prague 8-30 to 9-3-77). The following are
discussed: mechanisms of atomization and of the loss of
atomic vapor in the atomizers; results of de Galen’s study of
the Perkin-Elmer HGA-2100 and Varian-Techtron CRA-90
atomizers which showed that current efficiencies and sensi-
tivities could be improved considerably; methods of correcting
for background absorption (including FM continuous light
and echelle-grating monochromators) to permit the analysis
of concentrated solns. and eliminate noise from the light source
and flame. Also discussed extensively is a U S . oil company
trace metals project (Anal. Chem. 1974) which described
methods for Mn, Hg, Cd, and Be in petroleum products.
Lukasiewicz (95L)described the use of relatively transparent
flames produced with N20/H2in AA for direct analysis of
petrochemical and petroleum products for trace nonrefractory
elements without prior sample diln. The analysis of gasoline
indicated that litle N 2 0 band absorption remains when mass
transport of organic solvent to the flame is high. Correlations
between the decrease in absorption of N20/H2flame at 205.2
nm and the following were found: (1)the amount of C de-
livered to the flame gasoline, isooctane, acetone, methyl iso-
butyl ketone, and 2-propanol; (2) the product of the b.p. and
heat of vaporization at the b.p. for relatively nonpolar solvents
such as isooctane, cyclohexane, benzene, acetone, toluene,
methyl isobutyl ketone, xylene, and several alcohols and n-
alkanes. Robinson (129L)discussed the potential difficulties
in using carbon atomizers in AA, includin factors affecting
the rate of atomization and background a%sorption and de-
tection and correction. Detection limits for 34 elements are
given. The use of gas ((20,)lasers in studying volatile organic
compds. is also considered, and applications are discussed.
Detection limits with a prototype instrument are <1pg for
vinyl chloride, ethylene, and propylene, 16 references.
Severin (142L) studied existing MS methods and the de-
velopment of new methods for the analysis of complex mixts.
Electron impact spectra were obtained for model compds. in
the aromatic, naphthenic-aromatic, naphthenic, and paraffinic
compd. classes and for cyclic 0-,and N- and S-compds. and
were used to develop “clastograms”. The latter showed that
ionization potential differences can be used to determine
quantitatively traces of heterocompds. in sat. fractions. Ap-
plication of the photon impact method to a satd. lube oil
fraction (up to 500 mol. wt.) showed many fewer fragment ions
than did the electron impact method. Photon impact should
provide an alternative to field ionization. The photon spectra
of C4-CI4 n-alkanes at 50-500 “C showed a temp.-dependent
behavior favorable to analysis. An analytical MS was modified
to permit simultaneous use of both the electron and photon
methods, including interfacing a computer to the MS. Albers
(6L)used high-resolution MS to determine N- and 0-contg.
heterocom ds. in high-boiling petroleum fractions, using a
Varian MifT 731. Preliminary measurements of vacuum
distillates gave a resolution of m / A m = 35000 sufficient to
distinguish heterocompds. with one or two N and 0 atoms
from each other and from HCs but not for distinguishing S
compds. Spectra of the basis fraction of a Kurkuk vacuum
distillate showed the presence of mainly HCs, compds. with
one N and compds. with one N plus one 0 atom. The degree
of condensation approximated that of pyrene. A small amt.
of alkyl-substituted pyridines appeared among the N compds.
which had degrees of condensation of acridine or higher.
Shibata (144L)described an ESR study of vanadyl com-
lexes (VC) in various carbonaceous materials up to 435 OC.
!‘he ESR spectra were clearly correlated with the charac-
teristics of mesophase formation during carbonization of such
materials as petroleum residue from Vanezuelan (650 ppm
V), Wafra (120 ppm V) and Taching reduced crudes, various
coal-tar pitches, a hydrogenated coal oil, and Gilsonite pitches.
128R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
Samples contg. no V were doped with a vanadyl porphyrin
complex to 300 ppm V. The temp. of appearance of isotropic
ESR spectra of VCs was used to classify the samples into two
groups. This classification was completely consistent with
classificationsbased on the activation energies for VC rotations
and on the properties of the mesophase structures of cokes
derived from the samples.
Process Analyzers: GC. The use of pP or computer
controlled GCs is now well documented as one of the most
highly used on-line analyzers in the petroleum and petro-
chemical industry. A pP based GC can usually handle from
one to four or six GCs and several streams per GC simulta-
neously. A com uter-controlled system may handle four to
sixteen GCs wit! each GC handling several streams. There
is, however, a limit on the total combination of compounds,
streams, and GCs. Whether one uses a pP GC system or the
larger computer system is a decision that must be made on
the basis of the needs of the user.
Systems now available because of their computing and
memory capabilities not only provide composition information
as did the analogue type GCs but now can provide gravity,
as well as BTU outputs, thus providing the equivalent of three
analyzers in one.
McCoy (99L)discusses the added capabilities of pP-based
programmers. Among those mentioned are control of multiple
analyzers, time-based scheduling of events, self-diagnostics
and alarming, stored program$, and arithmatical computations
with printout capabilities. The use of such a system on a
natural gas pipe-line is described where the programmer
controlled two GCs, calculated composition, BTU, specific
gravity and sulfur content, and running averages and printed
out the results on two printers.
Gay (48L)surveyed process GCs controlled by microcom-
puters for interfacing with the main process control loop of
a plant. This England based survey covered units supplied
by Foxboro-Arcas, Applied Automation, Beckman, Pye Un-
icam, and Taylor Servormex. Stockinger et al. (148L)de-
veloped an on-line computer-controlled GC for observing
composition changes in a catalytic re-former pilot plant to
evaluate catalysts. The chromatographic system consisted
of four high-resolution columns in two temperature zones and
two FIDs. Temp. and flow programming were used to op-
timize peak resolution. Up to 280 compds. were identified
in some wide boiling range products. Properties, such as Oct.
No. sp. gr., mol. wt., and v.p. were calculated.
Griffin and Webb (52L, 53L) indicate the usefulness of
process GCs with other instrumentation including computers
as a means for optimizing the balance between energy input
and process yield and product quality. Processes, such as
distillation, catalytic cracking, ammonia, and ethylene pro-
duction are covered.
Other Analyzers: LC, MS, IR. LC as a process analyzer
is in its early stages of application. There will no doubt be
further development work in this area where other techniques
cannot be used successfully. Mowery (105L),for example,
reports on preliminary laboratory studies aimed a t process
control applications. In most cases, these studies are on
streams containing unstable or reactive compounds and
phenolic type materials. Examples are given on the use of
silica gel column with aqueous mobile phases.
Poddar et al. (12OL)relates an LC application that auto-
matically samples a batch process for making butadiene-
styrene rubber. The analyzer calculates mol. wt. distribution
in 20 min compared with 3.5 h by manual methods. Other
uses include detn. of ethyl derivatives of toluene for distillation
control, analyzing chlorinated phenols, acetophenone, catechol,
hydroquinone, and measuring antioxidant levels in several
products.
An article (7015)describes a pP controlled DuPont Model
850 with precise pumping rates, crude elution gradient ca-
pability, and programmed control of solvent composition,
analysis time, column temperature, and detector sensitivity.
The reproducibility is about 0.3%, includin separations with
E
complex gradients. Detection limits are t e range of nano-
to picograms. The pP keyboard permits change of operating
parameters without interrupting the analysis.
On-line MS has only recently become a commercially viable
technique. This is due primarily to cost reductions and
availability of the minicomputer for handling the lar e amount
of data involved. I believe it can be said that MS d continue

to increase in use because of its fast response and capability
to handle many compds. simultaneously and its ability to cover
the ppm range and, in some cases, ppb range. Even though
its cost is still relatively high compared to GC and other
analyzers, its versatility is such that it can and will replace
some of the more conventional analyzers in the near future.
Rothstein (133L)covers the basic functions and components
of an on-line MS, the ionization process, interpretation of the
spectral data to obtain concentrations directly for each com-
ponent in the sample, and the calibration of the MS.
Tailliez (153L) discusses the use of a time-of-flight MS
which permits simultaneous determination of up to 16 com-
pounds or se uentially a much greater number of compounds.
Accuracy is h o u t f 2 % with less than 1s response time over
the concentration range of 5 ppm to 100% in gas mixtures.
With some decrease in accuracy the response time can be
reduced to 0.01 s. Sampling rates as low as 0.0001 cm3/s can
be used. An obvious advantage is to detn. unstable inter-
mediates in process reactions.
Zamaria (172L) describes the “PROMASS” on-line MS
which is a computer-controlled quadrupole MS designed as
a rugged, automatic multicomponent gas analyzer. Program-
ming permits the system to search and measure specific
compounds for a given gas stream. It provides automatic
calibration, pushbutton startup and shutdown, status warning,
and disorder indicators. Detection ranges for most gases is
lo00 ppm to 100%. A five-component sample of roughly equal
concentrations with normalization requires 0.2 s. One par-
ticular use has been in ethylene oxide production where the
MS determines C2, 02,HC1, and C12 u to 500 ppm silulta-
neously and quickly. Generally, two G8s are needed for this
analysis.
Other MS applications have been reported (2%). Both Dow
Chemical Co. and Perkin-Elmer Corp. are using a prototype
single MGA-1200-PDP 11/40 combination in closed-loop
control of six reactors. Results by the MGA-1200 kept the
carbon balance between 99.5 and 100.5% with readings in 25
s. Over 9 months, only four calibrations were required. By
GC and O2analyzers, the carbon balance ranged from 98 to
102% and required 6 min.
Kocak and Wilks (83L) gives a review of IR analyzers for
on-line streams in process industries. A flow-through IR
reflectance sample cell for concentrations of 0.1-100% is
considered using a single-beam with a dual filter differential
method to counter background interferences. Another ap-
proach is the MIR or multiple internal reflection technique
in which the IR radiation is reflected inside the crystal and
refracted partly back to the sample. As a result, as the sample
flows past the crystal it absorbs IR energy proportional to the
concentration and barring interferences greater sensitivities
can be expected. Lositskii and Rylov (91L)present a review
covering single-beam and double-beam IR and opticoacoustic
analyzers for gases and air. Muraki et al. (108L) have de-
veloped a modified IR gas analyzer that uses two beams from
a single sourve, one passes through a reference circuit, the
other through a test circuit and both are alternately inter-
rupted by a chopper. In the path of one beam are a concave
mirror, a temp. compensating cell, the sample cell, a second
concave mirror, a wavelength band filter, and one side of a
detector. In the other beam are a concave mirror, an aperture,
an airtight interference cell with adjustable length for cali-
bration, a second concave mirror, a filter wavelength band
which includes most of the transmitted wavelen h band of
P
the fiist filter, and the other side of the detector. he N-fiied
detector is temp. controlled and has a window for each en-
tering beam and a common light sensor. The test and ref-
erence beams each alternately entering the detector provides
a signal. An example of an application is having C2H4in the
compensating cell when NO is detd. in the test gas.
Jones and Reed (75L) have used a near-IR analyzer to
analyze for ppm to percentage concns. of H20in ethylene
dichloride. The optical system uses a quartz-iodine source
lamp for 1000-3000-nm emission, a collimating lens, sample
cell, rotating disk with interference filters for two different
wavelengths, and a detector. The system is used also for detng.
acetic acid in esterification batch operations. Productivity
was increased by 6% while saving on steam.
Process Analyzers: Process Energy Conservation. As
part of the overall energy conservation program of industry,
analyzers along with the use of computers make a substantial
PETROLEUM
contribution to the energy goals. Buford et al. (22L)discusses
the instrumentation of 16 fractionation towers in which a
computer-operated GC system was used as part of a digital
control system. The system included 27 analyzers sampling
33 streams. Preliminary finding indicated savings of close to
$460000 on steam alone. Other information pertinent to the
success of the s stem was discussed, such as: training of
personnel, t r e n i displays of process variables, and other
control-related items.
Hachmuth and Griffin (59L)cover the use of control sys-
tems including analyzers and computers to im rove gas plant
energy efficiency for maximum recovery of and C3 while
producing on-spec. liquids and residue gas. On-line analysis
of the demethanizer product by GC provides a C1/Cp ratio
output which is used to adjust the temperature set point. Acid
content of the feed gas is analyzed and the output used to
adjust the flow of amine used to remove the acid gases.
Griffin et al. (54L) look to be 1980s for highly efficient
process heaters, propose computer control of flue gas 02,
control of flux densities, hence flame patterns, and control
of SO3 dew point. The trend will be toward large single
burners with mechanical draft equipment and com uterized
flame failure s stems to monitor safe start up and sRutdown.
An interrupteipilot and a UV detector will be needed for gas
fuel and an intermittent pilot which with two IR detectors
for the main burner and pilot flame.
A total energy measurement system is described by Rosko
and Haas (132L) that provides both energy content as well
as total flow and energy as primary outputs and real specific
gravity, gas composition, and flow and energy as secondary
outputs. The ENCAL I1 system combines three subsystems,
namely, flow measurement by orifice technique, a process GC
for composition, and a microcomputer for system control and
calculations. Other features include complete power fail
automatic recovery, autodiagnostics, self-calibration of G 4
every 24 h or a t operator’s selected interval, summation of up
to 6 m with flow switching to optimize flow measurement, and
capacity for digital transmission of results to a host computer.
Kennedy (81L)outlines the instrumentation and process
control principles in the design of a new petroleum refinery.
Examples of analyzers used to optimize operations are octane
analyzer for reformate, GC for distillation, and a multistream
O2 analyzer for fuel-air ration control.
Analyzers: Techniques, Sampling, Sensors. A new
DuPont Model 560 moisture analyzer was used (123L)to solve
an analyzer chloride corrosion problem on the H2 recycle
stream of a catalytic re-former. The newer model, while still
using the same basic vibrational fre uency change of a hy-
groscopically sensitized quartz c r y s d as in the older model,
provides a longer drying cycle to reduce corrosion. In addition,
the wet and dr samples are alternately passed through the
sensor while d e reference crystal remains sealed. A p P
processes data and provides a digital display and output
compatible with computer processing.
McWhorter (IOOL)emphasizes the need for proper heat
tracing of analyzer sample lines particularly on those va or
samples having dew points above ambient temperature. o n e
recommendation is to use prefabricated steam-traced bundles
with special attention to steam pressure, tubing bundle, slope
of lines, steam traps placements, steam supply points, and
maintenance. Nothing is proposed on the use of electrical heat
trace which, while more expensive, have some advantages over
steam tracing.
Lovelace (92L)addresses the design considerations of
sampling systems and provides a checklist of hazards (toxic,
flammable, etc.), physical conditions, materials of construction
and installation procedures to be considered. Also covered
are sample enclosures, and shielding for operations. The
o ration and advantages of indirect line sampler devices are
E considered. Types of systems discussed are sampling pl
double three-port valves, piston ram-t e valves, S a m 3
YK
syringes, and sample chambers, along wit commercial sam-
pling devices.
Hara (63L) discusses the manufacture of a special semi-
conductor gas sensor element prepared from SiOz and metal
oxide semiconductor particles. The sensor showed good mech.
strength, long service life, and high sensitivity for hydrocarbon
gases, such as propane. The element has two Pt electrodes
imbedded in the sensor and when a potential is applied be-
tween the electrodes, the potential changes as the resistance
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 129R
PETROLEUM
changes due to the presence of the gas.
Patrushev et al. (118L)present a review of work done in
an experimental lab in East Europe on the development and
use of solid-electrolyte gas analyzers of the electrochemical
type for gases, air and waste water.
Bond (18L)presents a discussion on the use of fiber optics
as an alternative to convential wire cables for transmission
of control and measurement signals and data within process
plants. Advantages are very wide band width, immunity from
electromagnetic disturbance, and safety in hazardous areas
and small chance of tapping. Uses are given of purely optical
transducers for measuring levels, flow rate, temperature,
pressure, and strain. The application of one such optic system
in a major oil company is used, as an example, where pulses
are transmitted up to 150 m and all electronics are outside
the hazardous area. We see the use of fiber optics as a new
and useful tool in the near future as costs are reduced and
installation and patching procedures are simplified.
On a more state-of-the art level, one article (27L) describes
the use of Analog Devices Inc's desktop Macsym I1 computer
for collecting rocess signals, such as come from thermocou-
ples, flow antpressure transducers, and GCs. The system
uses a version of the BASIC computer language and is de-
signed for pilot plant use but can be extended to entire process
plants. The system monitors and controls several operations
through keyboard instruction and presents data as graphs or
stores it for later review. Both analog and digital signals from
sensors can be handled via card-type modules.
Pollution Analysis and Instrumentation. The literature
is replete with papers dealing with pollution methods ermane
to the petroleum and related industries. It woulf be im-
possible to discuss all such methods many of which would be
covered in reviews on air pollution and water analysis in this
journal. For this review we will mention some work done with
methods and techniques not routinely used. No references
to process analyzers will be made in this section.
Guillemin et al. (58L) describe a GC technique for ppm
pollutants in which the carrier gas is a mixture of steam and
N2. An FID is used, and columns are packed with various
grades of spherosil. Good separations were obtained with
symmetrical peaks for mixtures of C1-C4 alkanes and alkenes,
C1-C6 alcohols, and various ketones plus a mixture of several
chlorinated HCs at ppm levels. The detection limit for vinyl
chloride was 5 ppb. The particular advantage we see in the
method as described is that it can be used directly on water
samples as well as air and process samples.
Etz and Blaha (36L)discussed critical measurement aspects
of Raman microprobe analysis, including instrument design
and s atial resolution, laser-induced sample heating and
optidbreakdown, effects due to the chem. chemical reactivity
of microparticles, laser-induced fluorescence, and low-signal
measurements. Limitations and counterremedies are de-
scribed. Spectra given include polynuclear aromatic HCs and
various microparticles and airborne dusts.
Brown et al. (21L) report on the development of a rapid
field test for detectin oil in sediments. The sample, mixed
with NaZSO4,is stirref with hexane, the extract concentrated,
and an aliquot placed on a strip of Gelman ITLC SA paper.
A chromatogram is developed via the ascending technique for
2.5 cm with a benzene-light naphtha mix. After drying, the
chromatogram is viewed under UV radiation and compared
with a standard. A ositive indication is a bright blue
fluorescence and the,d%ection limit is 2 pg of oil.
van Loon (161L)used a combination of GC separation and
AA detection for monitoring metals in the environment and
roducts. For example, Zn alkyls and ar 1 compds. in lu-
Ericating oils, Pb alkyls in gasoline and air, 8 r in liquified coal
and shale, and Mn as the cyclopentadienyl Mn tricarbonyl
were determined by GC/AA. Much of the study dealt with
techniques for interfacing the AA as a detector to the GC
columns under different analysis conditions.
Rohbock and Mueller (13015)describe an apparatus for the
measurement of alkyl-lead compounds in air. The air sample
passes through a glass fiber filter. Then the TEL is concen-
trated by adsorption on a 5% Apiezon L on Chromosorb W
AW in a st. st. U-tube at -193 "C. Upon heating of the U-tube
to 130 "C, the TEL is desorbed and determination by AA with
the use of raphite furnace at 2400 "C. For a 200-L sample
of air, the fetection limit for P b is 1ng m-3 and relative error
is about 10%.
130R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
May (98L) provides a listing of several applications of
neutron activation analysis in chemical and pollution fields.
Examples are given, such as: analysis of precious metals,
nuclear graphite and hydrocarbons, control of pollution of
water and seawater, analysis of food, hair, and atmospheric
dust.
Rutherford et al. (134L) describes an "in vitro" enzyme
inhibition method for screening petroleum effluents. The
extent of inhibition by a simulated petroleum effluent con-
taining expected contaminants at the maxium level was de-
termined. A preincubation mixture containing 10 pL of glu-
cose 6-phosphate dehydrogenase (I) and 1mL of the simulated
effluent made from 10 mg of NH4C1, 0.25 mg of KzCrO 10
mg of No. 2 fuel oil, 0.1 mg of phenol, 0.17 mg of Na2S.9&0,
20 mg of Kaolinite, and 1 L of HzO (soln A) was kept a t 23
"C for 30 min. To a 10-pL aliquot of solution A was added
1mL of solution I reaction mixture containing 1mM NADP'
and 1mM glucose 6-phos hate in 0.05 M Tris-HC1 buffer (pH
8.1),and the rate of pro&ction of NADPH (11) a t 23 "C was
determination spectrophotometrically. Comparison of the rate
of formation of I1 between soln A and no soln A gave the
percentage inhibition. The main thrust here is that enzyme
inhibition may be a useful screening tool for degree of con-
tamination of refinin effluents.
Imamura and Fu'ii 69L) determined toluene, ethylbenzene,
and xylenes a t ppb levels in ambient air by GC/MS tech-
niques. Samples were injected directly by means of a PTFE
sample loop onto a glass column (1.5 m X o mm) packed with
10% of Bentone 34-DDP (1:l)on Chromosorb W AW (60-80
mesh) and operated at 50-60 "C with He as carrier gas (30
mL min-'). The effluent was coupled directly to a MS op-
erated a t 70 eV. The mass fragments were continuously
monitored at mle 91. Detection limits observed were 2-4 ppb.
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(78D) Woodle, R. A., NLGI(Nat. Lubric. Grease Inst.) Spokesman, 42, 412
(19791
\ . - . - I .
(79D) Zakupra, V. A., Kozak, V. A., Kolosova, E. V., Vykhrestyuk, N. I.,
Khim. Tekhnol. Top/. Masel, (3) 58 (1979).
(80D) Zasiavskii, Y. S.,Morozova, I.A,, Bondarenko, A. P., Dorovskaya, S.
V., Shreerova, R. N., Darmenko, V. S.,Maslov, L. L., Tr.-Vses. Nauchno-
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WAX
(1E) Agrawal, K. M., Joshi, G. C., J . Appl. Chem. Biotechnol, 28, 718
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(2E) Bel'kevich, P. I.,Zubko, S. V., Yurkevich, E. A., Vestsi Akad. Navuk
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(3E) Gaidina, L. V., Igonin, P. G., Svitkln, V. V., Sergeeva, L. M., Butyakina,
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ASPHALT
(1F) Albaugh, E. W. and R. C. Query, Anal. Cbem., 48, (1976).
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PETROLEUM
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 PETROLEUM
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CATALYSTS
(IG) Adzhamov, K. Yu, Agaguseinova. M. M., Khanmamedova, A. K., Akha-
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(5G) Auroux, A., Bolls, V., Wierzchowski, P., Gravelie, P., Vedrine, J., J.
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(6G) Baucaud, R., Blanchard, G., Charcosset, H., Tournayan, L., React. Ki-
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(7G) Bahr, H., and Jedras, C., Chem. Anal. (Warsaw), 23, 1031 (1978).
(8G) Bancroft, G. M., Hardin, A. H., Anal. Chem., 57, 2102 (1979).
(9G) Barbier, J., Morales, A., Maurel, R., Bull. SOC. Chim. Fr., (1-2, Pt. I),
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(10G) Beskov, V. S., Naumov, Yu. 6.. Kinet. Katal., 79, 1307 (1978).
(11G) Bhasin, M. M., 72nd AIChE Ann. Meet. frepr. 23 (a), 16 (1979)
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(14G) Bonzel, H P., Krebs, H. J., Surf. Sci., 97, 499 (1980).
(15G) Boudeville, Y., Figueras, F.. J. Catal., 58, 52 (1979).
(16G) Bouwman, R., Toneman, L. H., J. Catal., 67. 146 (1980).
(17G) Bradley, E. B., Stencei, J. M., Appl. Spectrosc., 32, 496 (1978).
(18G) (a) Brenner, A,, Hucul, D., J. Cafal., 5 6 , 134 (1979); (b) Brenner, A,,
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(19G) Brinen, J. S., "Electron Spectroscopy in Catalyst Research", Applied
Surface Analysis, ASTM STP 699, Barr, T. L., Davis, L. E., Eds., Ameri-
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(20G) Buenafama, H. D., Lubkowitz, J. A,, Anal. Chim. Acta, 96, 285
(1978).
(21G) Burrington, J. D., Grasselli. R. K.. J. Catal., 59, 79 (1979).
(22G) Burwell, R., Butt, J., Cohen, J., Sashital. S., Uchijima, T., Henmann, J.,
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(23G) Buyanova, N., Zapreeva, O., Karnaukov, A,, Kinet. Katal., 79, 1196
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(24G) Carballo. L., Serrano, C., Wolf, E., Carberry, J., J. Catal., 52, 507
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(33G) Corro, G., Maubert, A., Gomez, R., N o w . J. Chim., 3 , 755 (1979).
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(45G) Dwyer, D. J., Somwjai, G. A,, J. Catal., 56, 249 (1979).
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(47G) Fhemov, A. A., Tkhy, I . , Davydov, A. A,, Kine?. Katal. 20, 154,
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(48G) Eisenbach, D., Gallei, E., J. Catal., 56, 377 (1979).
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(55G) Fung, S. C., J. Catal., 58, 454 (1979).
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Pharmaceuticals and Related Drugs
R. K. Gllpln’
Department of Chemistry, Kent State University, Kent, Ohio 44242
L. A. Pachla‘ and J. S. Ranweiler
Research Division, McNeil Pharmaceutical, Spring House, Pennsylvania 19477
The current review surveys pharmaceutical analysis and
related methodology that has appeared in Analytical Ab-
stracts or Chemical Abstracts from July 1978 to June 1980.
Although an excess of 800 entries have been cited, these cover
only a small percentage of the work reported during the time
period of the review. An attempt has been made to report
only those references that have appeared to be significant and
have been published in easily accessible journals.
The past format of the review has been modified in ac-
cordance with the comments received during the Analytical
Chemistry Reader Survey conducted in 1979. Changes which
have been made include a reduction in the number of refer-
ences cited, addition of a narrative section, and elimination
of potential overlaps between this review and the Clinical
Chemistry Review by not citing articles which have dealth with
the analysis of pharmaceutical compounds in biological ma-
trices.
The review has been divided into 10 major sections: Gen-
eral, Alkaloids, Antibiotics, Inorganics, Nitrogen- and Oxy-
gen-Containing Compounds, Steroids, Sulfur-Containing
Compounds, Vitamins, Techniques, and Miscellaneous. Most
of the major sections have been divided further into subsec-
tions.
GENERAL
Subjects for books and reviews have included: current
aspects of pharmaceutical analysis ( I , 7), Vol. 8 of a collective
series concerned with individual compounds and their ana-
lytical profiles ( 2 ) ,and a comprehensive semiannual report
which contained over 1800 references ( 3 ) . During this time,
“The International Pharmacopoeia” (12) and a pocket text-
book of pharmaceutical analysis arranged by subject have been
published (13). The topic of “com uter assisted synthetic
analysis” also has been consideref ( 4 . -In addition, the
analytical methods found in the European Pharmacopoeia I11
and the German Pharmacopoeia 8 have been compared (5).
Other reviews have been concerned with glycosides and al-
kaloids (6) and illicit drugs (8). Summaries of papers pres-
ented at general meetings (IO,11)and a brief paper dealing
with the analytical characteristics of several drugs (9) also have
been published.
In the preparation of the current manuscript general papers
and reviews directed toward individual classes of compounds
have been listed and discussed under one of the remaining
sections by subject.
ALKALOIDS
During the period of this review, many aspects of the
analysis of alkaloids have been considered. Topics of sepa-
ration and detection enhancement have received considerable
Current address: Warner-Lambert Co., Ann Arbor, MI.
142 R 0003-2700/81/0353-142R$06.00/0
--.
A3
(175L) Zirin, V. G., Makov, pJ. I., Z a v d . Lab., 45, 1082 (1979); C . A . , 92,
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(1979).
attention. Liquid chromatography has been used to separate
16 compounds from 8 different groups (1A). Additionally, the
solvent composition effect of various water/methanol systems
on the reversed-phase selectivity of several alkaloids has been
studied (10A). Development of a capacitance-conductance
detector and its application to HPLC analysis have been
described (3A). Postcolumn derivatization for the improved
detection of alkaloids in normal-phase liquid chromatography
has been discussed (6A). Also, various as ects of thin-la er
chromatography have been considered. Tfese have incluJed
the use of optical brighteners for detection enhancement (4A),
extraction of solutes from plates using supercritical gases
(12A),separation of toxic alkaloids on metal-salt-impregnated
plates (9A),and a review on identifyin narcotic drugs (11A).
The separation of some pharmaceutic&y important alkaloids
using zirconium antimonate impregnated paper has been
reported (7A). In addition, nonchromatographic procedures
have received attention. General aspects of colorimetric
analysis using several metallic acids for the determination of
important alkaloids have been discussed @A). Kinetic energy
spectrometry has been used for the direct quantitation of
alkaloids in whole plant materials (5A). Various alkaloids have
been determined by enzymic inhibition enthalpimetry (2A).
Cinchona. A modified nonaqueous titration procedure has
been com ared with the USP nonaqueous titration procedure
and founa to be comparable in specificity and reliability for
the determination of quinidine sulfate in tablets. However,
the USP method has shown greater variability (13A). A rapid
liquid chromatographic estimation of dihydroquinidine con-
tamination in quinidine raw materials has been published
(14A).
Ergot. HPLC methods for the analysis of various ergot
alkaloids using an NH2 column (26A) and columns packed
with porous polystyrene modified with hydroxymethyl groups
(27A) have been reported. Ergot alkaloids have been sepa-
rated by using both silica and CIScolumns (25A). Irradiation
of the HPLC effluent with a high-pressure lamp has been
employed to identify ergot compounds by monitoring de-
creases in their fluorescence (22A). The linear relationship
between fluorodensitometric signal and concentration has been
examined. Theoretical vs. experimental data for far vs. near
side TLC scanning have been reported for several ergot al-
kaloids (21A). An automated fluorometric ion-pair method
which permits 20 determinations/h has been developed (17A).
The physical properties as well as chemic4 stability of various
hydrated ergot alkaloid preparations have been studied (15A).
Analytical procedures have been reviewed for the determi-
nation of bromocriptine methanesulfonate (16A). A method
a
based upon classical column chromato raphy with fluoro-
metric detection has been reported for t e determination of
methyler onovine and ergonovine maleate in tablets and in-
jectables (%A). Ergonovine also has been quantitated by using
reversed-phase HPLC conditions (23A). Solvent-dependent
0 1981 American Chemical Society