Petroleum
F. D. Tuemmler, Shell Development Co., Emeryville, Calif.
is theninth in the series of
This
reviews of analytical chemistry as
used in the petroleum industry (7A, 8A,
28A-27A), sponsored by the Petroleum
Division of the American Chemical
Society. It covers essentially the years
1966 and 1967, or rather the papers ab-
stracted in Chemical Abstracts (Analyt-
ical and Petroleum Sections), in the
American Petroleum Institute Refining
Literature Abstracts, in the Journal of the
Institute of Petroleum, and in Analytical
Abstracts (London) for the period from
July 1966 through June 1968. Gener-
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ally, those papers published in 1968 and
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abstracted have been set aside for the
next in this series of reviews.
Organization of the Review. In
organizing the papers into subject
classifications, each was associated
with a class of products. Inasmuch
as many analyses by a given technique
or by competitive techniques would
be scattered throughout the review,
some papers were classified by compo-
nent or by property measured to simplify
location of the more closely related ma-
terial. Thus, it was necessary to decide
under which category to place a given
paper. Some readers will no doubt have
preferred that we had classified many
papers differently, and in these cases we
ask their tolerance.
References. Because references
were selected from four abstract jour-
nals, journal abbreviations differed.
Further, during this time period,
Chemical Abstracts “Guide for Abbre-
viating Periodical Titles” was revised
(September 1966). All references were
altered to conform with this guide, and
to eliminate redundant reference items
for the sake of compactness. As a
further aid, in those cases where the
referenced publication might not be
readily available, the abstract journal
reference has been appended to that for
the original source; to identify these ab-
stract references, the abbreviations CA,
API, JIP, and AA were used to identify,
in order, the journals listed in the first
paragraph. These abbreviations are
followed by the proper volume number,
then by the abstract number.
General Reviews. While nearly all
of the papers included in this review
concern a restricted subject, there are
a few which deal with general dis-
cussions of specific analytical pro-
cesses or the application of a variety
of analytical techniques to the ex-
amination of a variety of petroleum
products or process streams.
For the first time in a considerable
number of years, Kerenyi (17A) re-
152 R · ANALYTICAL CHEMISTRY
viewed recent advances in analytical
distillation (101 references). Caigneau
(5A) looked at the progress in mass
spectrometry over the past 10 years,
while St. George et al. (41 A) and Lump-
kin (28A) listed the variations of mass
spectrometric applications in the petro-
leum and petrochemical industries
Reed (39A, 37 references) covers theory,
design, abbreviations, and resolutions.
The use of X-ray spectrographic analysis
of liquids and solutions has been de-
scribed by Gunn (10A, 36 references),
Kajikawa et al. (14A, 46 references), and
Magin (29A). Infrared spectrometry
has been reviewed by Shimazu (40A,
59 references) and Whetsel (46A, 10
references). The use of nuclear mag-
netic resonance in fuel science has been
described by Rao et al. (37A, 10 refer-
ences) and Yamamoto (48A, 26 ref-
erences). Gas chromatography as a
tool for the analysis of petroleum,
petroleum gases, and petrochemical pro-
cesses has been reviewed by Tagiev
(42A) and Moghadam (30A). Killer
et al. (19A) described the application of
thin-layer chromatography to a variety
of products (54 references). Barras et
al. (1A, 20 references) reviewed the basic
principles of atomic absorption; Mostyn
(32A, 28 references) reviewed the use
of this technique as applied to fuels
and lubricants. Gray (9A) and Per-
dijon (84A) reviewed the principle of
analysis based on thermal, fast-neutron
activation.
Boreham et al. (3A, 42 references)
summarized the use of all the above
analytical processes and, in addition,
included electrophoresis, flame photom-
etry, and polarography as used in re-
search and control in the gas and petro-
leum industries. Keil (16A) concen-
trated on physical chemical methods
such as electrochemistry, thermody-
namics, and absorption and emission
spectrometric techniques.
Methods Coordination. Of par-
ticular interest during this review
period is the appearance of several
papers concerned with the integra-
tion and coordination of new tech-
niques. These indicate the most
efficient combinations of methods for
analyzing a given class of materials
for the information required, and are
concerned mostly with the newer
methods described above. Lawrey
(20A) made this comparison for gaso-
line and blended fuels. Powell (86A, 26
references) did not deal with any particu-
lar product class. Texaco (31 A, 33 ref-
erences) provided a searching look at
the analysis of lubricants. Jenkins,
et al. (12A) looked at the redundancy of
specification tests. Although this paper
concerns itself with gasoline specifica-
tions, the principles of mathematical
correlations and choice of the most sen-
sitive are applicable to other products.
Data Handling. The use of com-
puters in handling analytical data is
rapidly expanding and the increase
in papers on such usage during this
review period comes as no surprise.
Karau et al. (16A) described the Gulf
administrative computer system for
compiling analytical data and prepar-
ing control reports for optimizing use of
work space and analytical personnel;
Harding et al. (11A) described a com-
parable system. Ogle (33A) described
problems relating analytical and com-
puter analytical instrument coupled
- -
hardware systems. A coupled gas
chromatograph, an integrator system,
and teletypewriters for monitoring and
recording results as used in a dozen or
more companies have been described
(4A).
Tunnicliff (43A) detailed a sophisti-
cated general Fortran program for in-
terpreting and reporting results of emis-
sion spectrographic analyses. LeFeuvre
et al. (21 A), Wellington et al. (44A),
and Williams et al. (47A) described
means of operation and logging and
computing data from an engine test
laboratory; a comparable system in-
stalled in England has also been de-
scribed (13A).
Automated Control. The automati-
zation of analytical test methods
used for plant control continues and
as it applies to specific procedures is
described in detail later in this re-
view. Kienitz et al. (18A) discussed the
problem in a general way; Bassalert (2A)
directed his review to petroleum product
quality control. Wherry (45A) de-
scribed the roll of chromatographs in
meeting some demanding refinery con-
trol needs.
Standardization. Rather (38 A),
president of the American Society for
Testing Materials, has ably described
the general relationship of technical,
professional, and trade associations
in the standardization held. The
intended role of the Institute of
Petroleum in this field is outlined by
Pohl (35A). A necessary feature of a
standardized method is a statement of
its precision when applied in several
laboratories; Fritz (6A) evaluated the
problem of developing necessary data
from which such precision can be esti-
mated.
Crude Oils
G. W. Ruth
Marathon Oil Co., Littleton, Colo.
McAuliffe (21B) described an im-
proved method and apparatus for sepa-
rating hydrocarbon constituents from
samples so the hydrocarbons may be
quantitatively analyzed. The method
consists of establishing a vacuum of at
least 0.1 mm mercury and flowing a
liquid sample into the vacuum chamber
after it has been closed. A portion of
the gas evolved is collected and analyzed
for hydrocarbons.
A rapid method for drying samples of
crude oil was proposed by Linderman
and Tsesarskaya (19B). Synthetic
sodium-A zeolite was used as the dehy-
drating agent. Oil samples containing
2% moisture were completely dehy-
drated at up to 200 rn’l/hr. Regenera-
tion time for the zeolite was reasonably
short.
A rapid method for crude oil evalua-
tion without distillation was developed
by Gay lor and Jones (HB). The
method consists of six tests on the whole
crude oil—i.e., gas chromatography,
condensed aromatics by polarography,
pentane insolubles by ASTM D 893,
specific gravity by hydrometer, sulfur
content by X-ray fluorescence, and
nitrogen content by a Kjeldahl proce-
dure. The six tests, along with multiple
regression equations that were derived,
give the yields and qualities of all frac-
tions through asphalt.
Triems and Heinze (34B) reported a
method using elution chromatography
combined with other information to
classify crude oils. The procedure is
applied to analysis of crudes from which
asphaltenes and the fractions boiling
below 200 °C have been removed. The
deasphalted topped residues are sub-
sequently eluted by isooctane, benzene,
and acetone. By comparing the group
analysis thus obtained with the sulfur,
asphaltene, paraffin, and naphtha con-
tent and density, a crude oil can be
characterized effectively. Crudes from
10 regions were examined.
Attempts were made by Bene and
Louis (4-B) to characterize crude oils by
nuclear magnetic resonance. The pro-
ton nmr spectra of CH2 and CH3 peaks
of several alkanes were correlated with
chain length and termination. Amount
and degree of branching of alkanes,
amount of cycloalkanes, and presence of
aromatic and methylated aromatic
hydrocarbons were determined in several
crudes. A more involved analytical
procedure whereby nuclear magnetic
resonance, gas chromatography, and
mass spectrometry were used was re-
ported by Boulet et al. (8B). The pro-
cedure consists of gas chromatographic
analysis of - ß compounds, mass
spectrometry and gas chromatographic
analysis of the C7-Cs compounds, and
division of the remainder of the crude
into several fractions by distillation fol-
lowed by separation of each fraction by
liquid chromatography. Aromatic com-
pounds are further analyzed by nmr.
Both Bene and Boulet made compari-
sons among several crudes of different
origins.
Smith and Hale (32B) summarized
several methods of crude oil character-
ization. Routine analyses data were
used as a basis in all cases. A similar
survey covering the standard tests per-
formed in French refineries and used in
the analysis of crude oils was reported by
Henrion and Picard (16B). Specifica-
tions required, along with numerous ex-
amples for each property taken from the
crude oils usually processed in France,
are given.
A French committee on research and
production of petroleum and natural gas
(29B) proposed standard methods for
rapidly determining the main charac-
teristics of crude oils. Methods were
proposed for measuring the C1-C5 hy-
drocarbons by gas chromatography, for
identifying crude oils by uv spectro-
photometry, for evaluating surface-
active agents as crude oil demulsifiers,
and for measuring the hydrocarbons
present in water by ir spectrophotom-
etry.
A review of the uses of modern phys-
icochemical and analytical methods for
determining the geochemical features of
petroleum oils was compiled by Podklet-
nov (26B). The review concentrated
on methods associated with the carbohy-
drate composition of oils. The methods
surveyed were: gas-liquid chroma-
tography, mass spectrometry, optical
spectrometry, and combinations of these
methods.
Coleman et al. (10B) used gas-liquid
chromatography to identify naturally
occurring cyclic sulfides in a crude oil
distillate boiling from 111 to 150 °C.
Isothermal distillation, vacuum frac-
tionation, and chromatographic separa-
tions on alumina gel were used to con-
centrate the cyclic sulfides. The re-
sulting sulfide-containing fractions were
then analyzed by gas-liquid chroma-
tography. Eighteen species were identi-
fied by their retention times, by micro-
desulfurization, and by ir spectra.
Gas chromatography was also used by
Guichard-Loudet and Follain (1SB) to
determine light hydrocarbons in crude
oil. Results were compared with those
of distillation tests, and satisfactory
agreement was obtained except for
ethane.
Brunnock (9B) reported separation
and distribution of normal paraffins from
petroleum heavy distillates by a com-
bination of molecular sieve adsorption
and gas chromatography. In this pro-
cedure, distillate fractions are dewaxed
and the n-paraffins present in the wax
are selectively adsorbed by heating a
solution of the wax in benzene under
reflux with molecular sieve pellets. The
sieve structure is then destroyed with
hydrofluoric acid, and the liberated 71-
paraffins are determined by gas-liquid
chromatography. The method was ap-
plied to contrasting waxy crude oil from
Libya and Nigeria.
A rapid method for determining the
asphaltene content in crude oil was de-
veloped by Biktasheva (7B). Solutions
of crudes, 1%, in petroleum ether and in
o-oxylenol were prepared and electrical
conductivity of the solutions was mea-
sured. In the first solvent, only the
resins were soluble; in the second, resins
and asphaltenes were soluble. By use
of the difference in conductivity of the
two solutions and a calibration curve,
the amount of asphaltene was deter-
mined. Analysis time was 10 minutes
and accuracy was 0.3%.
Another procedure for the determina-
tion of asphaltene in crudes was re-
ported by Neumann et al. (24B). As-
phaltenes were first determined by pre-
cipitation from crude oil followed by six-
stage ultrafiltration. The most satis-
factory results were obtained using ethyl
acetate in the precipitation step, then
extracting the precipitant with pentane.
Carbon-13 nuclear magnetic resonance
spectrometry was used by Friedel and
Retcofsky (12B) to detect and deter-
mine aromatic carbon atoms in a Ponca
City crude petroleum. An aromaticity
of 0.15 was found for this petroleum.
Aromaticity values obtained from the
tests agreed with those obtained by
proton magnetic resonance and mass
spectrometry. Seevers (30B) analyzed
the subsurface waters of oil fields for the
aromatic compounds present. Their
presence and qualities are determined by
conversion to phenols by irradiation,
followed by colorimetric determinaii n
of the phenol content.
Jordan and Carel (18B) reported a
rapid semiqualitative method for de-
termining the halogenated hydrocarbons
content of crude oils. The equipment
is completely portable and can be used
for field testing, as well as in the labora-
tory. The procedure consists of a dis-
tillation step requiring 6 to 8 min to
separate the halogenated hydrocarbons,
followed by a modified version of Feigl’s
spot test in which colored complexes are
formed and compared with standards.
Detection limits for various halogenated
hydrocarbons are given.
Starting temperatures for paraffin
crystallization in several crude oils were
determined by a densimetric method
developed by Abramov and Kovalev
(IB). A comparison of the results ob-
tained by this procedure and the results
obtained by a refractometric method is
given. Mikhal’kov (22B) concluded
that the starting temperature for paraf-
VOL. 41, NO. 5, APRIL 1969 · 153 R
fin crystallization cannot be accurately
determined under crude oil production
conditions owing to the absence of
chemical equilibrium in the crude oil
during its recovery and trasnportation.
This conclusion was drawn from data
obtained by optical and ultrasonic
methods.
Prikhod’ko (S8B) proposed a method
using a modified Vigner-Kelly type
sedimentometer for dispersion analysis
of petroleum emulsions. The apparatus
consists of a glass sedimentation tube
350 mm long connected to an apparatus
maintaining a constant level in the tube,
and a measurement capillary tube 2.5
mm in diameter. Equations giving
distribution of the particles according to
their size are given.
Moore et al. (SSB) applied atomic
absorption spectrometry to trace anal-
yses of petroleum. Cu, Ni, Zn, and Pb
were determined at concentrations < 1
ppm. A liquefied petroleum gas Was
used as fuel in an all-aluminum burner.
By use of a standard addition technique,
high precision and accuracy were
achieved.
A nondestructive activation analysis
of crude oils for arsenic to 1 ppb was re-
ported by Veal (S6B). The arsenic is
determined without destruction of the
sample, and gamma-ray spectrometry is
used to measure the 0.56 MeV gamma
ray from As76. Cu. Zn, Na, Ni, and Br
need not be separated but can be deter-
mined simultaneously.
Augsten (SB) described an apparatus
and procedure for flame photometric
determination of alkali and alkali earth
metals in nonprocessed petroleum, while
Popescu et al. (S7B) reported a technique
for the direct determination of traces of
sodium in crude oil cuts by flame pho-
tometry. Sodium content is determined
by direct atomization of the liquid into
the flame of a Zeiss-Jena type III pho-
tometer. For cuts covering light and
medium distillate, 1 to 3 ppm sodium
can be determined with a relative error
of about 10%.
Calcium and magnesium were deter-
mined in the filtrate of drilling mud by a
complexometric method proposed by
Wydra (S8B). The sample is titrated
with EDTA at pH 12 using one indicator
to determine calcium. The titration is
then carried out at pH 10 using a differ-
ent indicator to determine total calcium
and magnesium. Magnesium is cal-
culated by difference.
Gates and Caraway (1SB) also de-
scribed a method for determining calcium
and magnesium, along with barium,
strontium, and iron in oil well scale.
Carbon disulfide was used to remove the
oil and water and the scale was then dis-
solved in concentrated hydrochloric acid.
Ba, Ca, Sr, Mg, and Fe were then deter-
mined by flame photometry, the method
of additions being used. Sulfate and
phosphate were determined colorimetri-
154 R · ANALYTICAL CHEMISTRY
cally and carbonate was determined
volumetrically. The analysis was rapid
and reasonably accurate, although iron
and magnesium interfered with each
other.
Several methods for determination of
vanadium appeared in the literature
during the past year. Some methods
used similar techniques, but each is
different to some degree. A sensitive
colorimetric determination for 0.15 to
10 ppm vanadium in petroleum using 10
g or less of sample was reported by Mac-
Millan and Samuel (SOB). The method
makes use of the fact that hema-
toxylin gives a pink color with vanadium
in 6N to 7N orthophosphoric acid with
an absorbance peak at about 520 to 523
mg. Results obtained from the analy-
sis of six crude oil samples are given.
Steinke (SSB) described a photomet-
ric method for the determination of 1 to
5 ppm of vanadium in oil fractions with
4-(2-pyridylazo)resorcinol. An accu-
racy of ±0.4 was reported.
4 -
Methooxybenzothiohydroxamic
acid was used by Skorko-Trybula (SIB)
to determine 10-3 to 10~5% of vanadium
in crude oil and petroleum products.
In 6N hydrochloric acid medium, V4+
with this reagent forms a green complex
which is easily extracted with CHCI3 and
the higher alcohols. Interference by
iron, molybdenum, and niobium can be
prevented by a preliminary extraction
with tributyl phosphate, and titanium is
extracted with benzoylphenylhydroxyl-
amine, vanadium being maintained in
the V4+ state. No interference occurs
if the concentration of these metals is
lower than that of vanadium.
A spectrographic analysis for deter-
mining vanadium and nickel in oil ash
was reported by Petho (S5B). The
crude oils were purified and dehydrated
by centrifuging, then dissolved in the
presence of concentrated sulfuric acid.
Ash was mixed with silicon dioxide con-
taining 1% cobalt reference standard.
The mixture was then combined with
spectral-quality graphite powder.
Less than 1 ppm nickel and vanadium
in petroleum stock can be determined
accurately by a method proposed by
Bergmann and Ehrhardt (5B). The
metals are concentrated on a disk of
cation exchange paper and then deter-
mined by X-ray fluorescence. Analysis
time was 4 hr, and the relative error is 5
to 10% at 0.1 to 1.0 ppm nickel or
vanadium. No interelement effect be-
tween nickel, vanadium, and iron was
noticed.
Alternating-current polarography was
used by Ishii and Musba (17B) to deter-
mine vanadium in petroleum. The
method was rapid and simple and no
interferences rvere noted.
Veal (S7B) described a method of pre-
paring internal standards for determina-
tion of vanadium by thermal neutron
activation. Standards were prepared
by uniformly dispersing a known amount
of solid internal standard in polyethylene
pellets and then fabricating into sample
bottles.
A method was also described for the
determination of vanadium in crude oil.
Neutron activation analysis was used by
Vajta et al. (SSB). Determinations
were made on several Hungarian crudes
and on a few Russian crudes. The
amount of vanadium carried over in dis-
tilling the various petroleum fractions
was also determined by this method.
Finally, a procedure for the extraction
and determination of vanadium has been
proposed by Biechler and Jordan (6B).
Samples containing 4 to 150 ppm vana-
dium were dissolved in acid, V4+ was
oxidized to Vs+, and the vanadium was
then extracted as vanadium tungsto-
phosphate. The complex is measured
colorimetrically. Interference of Mo,
Cr, Fe, and W was at a minimum.
A mass spectrometric characterization
of petroporphyrins was carried out by
Baker (3B). Asphaltenes were pre-
pared in the standard way by precipita-
tion from the crude petroleum with
pentane. Petroporphins were prepared
by extraction from the asphaltenes with
methanesulfonic acid, then recovered by
extraction with methylene chloride and
purified by chromatography. Data ob-
tained showed that up to 12 homologs
of the deoxophyllo and etio series may
be present in a Gaussian-type distribu-
tion with a band width of three to five
methylene groups. High resolution
mass spectrometry indicated the pres-
ence of only alkyl porphyrins with no
oxygen functional groups, but chromato-
graphic separation of the petroporphy-
rins confirmed the presence of etio and
phyllo series and a small amount of
rhodo series porphyrins.
The geochemical significance of trace
metals in petroleum and their relation-
ship to the porphyrins and asphaltenes
was discussed by Colombo (11B).
Their determination by neutron activa-
tion and their use in investigating the
origin, migration, and evaluation of
petroleum was also discussed.
Engine Fuels
K. L. Shull and J. D. Beardsley
The Standard Oil Co. (Ohio), Cleveland,
Ohio
Phillips Petroleum Co. (S9C) studied
a modification of the Reid vapor pressure
method in which the air-liquid ratio was
increased from 4:1 to 25:1 and the test
temperature was raised from 100 to
130 °F. These test conditions corre-
lated best with direct vapor-liquid ratio
measurements at 120, 140, and 160 °F.
This modification was also suitable for
characterizing motor fuels with regard
to hot-weather acceleration performance
in automobiles.
Perry (88C) described the gas chro-
matographic determination of dibromo-
ethane in gasolines, which involved the
use of an electron capture detector.
This ionic detector was much more
sensitive to dibromoethane than to other
gasoline components.
The results of two experimental pro-
grams on evaporation losses from motor
vehicles were reported by the Coordinat-
ing Research Council (17C, 49C).
Six methods of determining total fuel
lost from the carburetor (cold trapping,
air cup, bag enclosure, fuel-line reser-
voir, syringe, and API gravity) and
three methods of determining losses
from the fuel tank (cold trapping, char-
coal trapping, and air cup) were studied,
as well as procedures for the calculation
of carburetor and tank losses and the
amount of tank losses.
Fagley and Nunez (21C) determined
the components of exhaust gas by using
nondispersive infrared and polarographic
analyzers to measure fuel-air ratios.
Bentur et al. (5C) established that kero-
sine contamination of 83-octane gasoline
from 0.5% upward can be determined
by semimicro paper chromatography.
This application was extended to cata-
lytically reformed and 91-octane gasoline
by Babitz and Rocker (4C).
A simple bench apparatus was de-
veloped by Johnstone and Dimitroff
(29C) to test gasolines for deposit-
forming characteristics; this apparatus
closely simulates the engine intake sys-
tem. The tendency of motor fuels to
form engine deposits causing preignition
was evaluated by Aronov et al. (SC);
benzene was specified for burning off
these deposits. The ignition properties
of the deposits were evaluated by the
preignition number, which is the ratio of
the number of ignitions caused by the
sample fuel and by the standard fuel,
respectively. Wagner and Bryan (48C)
determined chlorine, bromine, and lead
in automotive combustion deposits by
an X-ray spectrographic analysis with-
out calibration curves; they used an
inert dilution method.
Ma and Moore (S6C) investigated
preignition and knock properties of
fuels prepared from various blends of
benzene and n-heptane. They used
three parallel experimental techniques:
autoignition in a tubular reactor; auto-
ignition in a motored engine; and knock
resistance in a firing engine.
Clark et al. (12C) developed optimal
equations for predicting road octane
numbers of European gasolines from the
motor or research octane number of the
whole fuel plus either the distribution
octane number of the delta research
octane number. Their most significant
finding was that measurement of the
front-end octane is essential for optimum
prediction. In addition, they obtained
a single equation which predicted road
octane numbers of both grades of gaso-
lines from their research and delta re-
search octane numbers, lead contents,
and API gravities (18C).
Chassis dynamometer and field tests
carried out by Ingamells et al. (28C)
demonstrated that effects of tempera-
ture and absolute humidity on octane
number requirement are linear, but
those of altitude are nonlinear. These
effects should be taken into account in
the prediction of octane number require-
ments for car populations in specific
localities.
The Journal of the Institute of Petro-
leum (30C) reported findings of a study
on maintenance and equipment for CFR
engines which was sponsored by the
Institute. This study recommended a
400-ml buret for blending reference fuels
and a method for determining valve stem
clearances which involves a micrometer
and special plug gauges. Motor (LP)
octane numbers determined for indi-
vidual [LPG components were used by
ASTM Committee D-2 to develop an
octane calculation method for LPG fuels
of known composition; Boldt (7C) de-
scribed the work of this committee.
Churshukov et al. (11C) evaluated the
corrosive action of fuels and the effec-
tiveness of anticorrosive additives. A
steel or bronze plate was weighed, then
immersed in the fuel sample for 4 hr at
constant temperature and maximum
moisture content; the plate was cleaned
to remove corrosion products, and
weighed again. An apparatus for mea-
surement of changes in potential in a
flowing hydrocarbon fuel was described
by Lamouche (34C). Tararyshkin and
Chechkina (45C) determined the pres-
sure of saturated vapor of hydrocarbon
fuels using a variation of the well known
static method for determination of vapor
pressure at elevated temperatures based
on application of a glass tensiometer. A
detailed description of a method and
apparatus for determining the volatility
of hydrocarbon fuels at low pressures
was given by Tararyshkin (44C) Kus-
ter and Comery (33C) used refractive
index to determine water-soluble ad-
ditives in liquid hydrocarbon fuels. An
apparatus for determination of low
boiling material in diesel fuel, motor oil,
etc. was patented by Lohrmann et al.
(35C). Hazes produced in petroleum
fractions (boiling range, 300 to 482 °F)
were studied by Hermanie and van der
Waarden (24C). Rybakov et al. (42C)
visually determined the particle size
distribution of impurities in such petro-
leum products as motor and jet fuels.
Dyatlov (19C) described an apparatus
for fractional distillation of fuels at high
pressures which was used to determine
the volatility of aviation fuels. The
Coordinating Research Council (16C)
recommended techniques for measuring
vapor pressure, oxygen content, specific
heat, energy content, bulk modulus, co-
efficient of expansion, and viscosity; these
properties were considered to be critical
for supersonic transport fuels. A rocking
autoclave in which heat resistance of
fuels is examined under conditions simu-
lating those of fuel tanks in a flying air-
plane was described in detail by Alekse-
eva and Ivanov (1C). The Coordinat-
ing Research Council (15C) evaluated
a modification of the standard ASTM-
CRC fuel coker which can be used to
measure high temperature stability of
fuels for advanced aircraft gas turbine
engines. Zengel (52C) compared visual
results obtained with the ASTM-CRC
fuel coker and results obtained with a
Minex heat exchanger in determination
of thermal stability of hydrocarbon fuels.
Whisman and Ward (50C) reported a 5-
ml bomb and method which shows
promise of permitting precise measure-
ment of labeled fuel components that con-
tribute to deposits during thermal stress-
ing. Three test methods were de-
veloped and evaluated for separation and
measurement of radioactivity contrib-
uted to deposits and gums by selected
fuel components.
A method and apparatus for maintain-
ing a minimum concentration of ethane
and lighter components in transferring
liquefied petroleum gas were described
by Smith (43C). Hooper et al. (26C)
determined oily residues (in the lubricat-
ing oil range) in liquefied petroleum gas
by a methyl ethyl ketone-sodium bisul-
fate method. Reinhardt et al. (40C)
described a gas chromatographic proce-
dure for trace substances in fuel gases
which utilizes an argon ionization de-
tector and two columns. A photomet-
ric comparator was used by Dasgupta
and Dey (18C) for the determination of
dust in fuel oil. Risch (41C) used
electrochemical testing to determine if a
fuel oil contained sufficient inhibitor.
An experimental study by Versino et al.
(47C) of six fuel oils with viscosities of
3.5° to 21.5° Engler at 50 °C showed
that better dewaxing of fuel oils would
eliminate bottoms problems especially
in low capacity equipment. Boyer (9C)
reported that naphtha was tested as a
fuel for steam production in the Nantes-
Chevire power plant of Electricite de
France in an attempt to alleviate air
pollution. Yuhara and Kato (SIC)
studied the influence of suspended parti-
cles on rheological properties of residual
fuel oil using a rotational viscometer.
Kouzel (SIC) presented a chart which
permits rapid estimation of the true boil-
ing point (JBP) cut point for an ASTM D
86 end point when the 30% TBP tem-
perature and the 30 to 90% TBP slope are
known. Fluorescent indicators for chro-
matographic determination of aromatic
and olefinic component in light petroleum
s
products were prepared by Kurchatkina
et al. (S2C). The amount of gasoline in
lube oil was determined by Alvey (2C)
VOL. 41, NO. 5, APRIL 1969 · 155 R
with an apparatus consisting of a heated
funnel attached to a calibrated capillary.
Borisov et al. (8C) described an ap-
paratus for determination of the amount
of gas dissolved in liquid fuels or in
water. The principal part of the ap-
paratus is an elastic membrane by which
pressure in the measuring buret can be
made equal to external pressure. Van
Horn (46C) developed a correlation for
low temperature vapor-liquid equilibria
of light hydrocarbons in hydrocarbon
solvents from chromatographic measure-
ment of equilibrium constants. Panels
of sniffers were used by Humble to deter-
mine odor of petroleum products ranging
from naphthas used in dry cleaning fluid
to solvents used in making cooking oils,
margarine, and peanut butter, reported
Hydrocarbon Processing (27C).
Burgoyne et al. (IOC) explained the
significance of open and closed flash
points. An ideal closed flash point can
be defined for a liquid by reference to
the lower flammability limit of its vapor
in air; if temperature of a liquid exceeds
its closed flash point, concentration of
vapor near the liquid surface exceeds the
lower flammability limit and the vapor
can be ignited near the surface. The
open flash point is an arbitrary quantity
which does not relate to any specific
hazard.
Blanchard and Goucher (6C) in-
vestigated the mechanism of microbio-
logical contamination of jet fuel and
developed techniques for detection of
this contamination. Hazzard (23C) de-
scribed two sampling procedures, the
nutrient media, and the procedure for
culturing microorganisms on filter mem-
branes for detection of microorganisms
in petroleum products. Hill et al. (25C)
presented a method for making up petri
plates for estimation of microorganisms
in petroleum products; this method
yielded consistently high recoveries of
organisms from oil emulsions with good
replication of results.
A new laboratory test for predicting
the low temperature operability of diesel
fuels was developed by Coley et al.
(14C); the new method involves mea-
surement of the flow limiting tempera-
ture when a small quantity of fuel is
filtered through a fine gauge assembly
mounted in an ASTM pour point jar.
Engel and Ticac (20C) discussed labo-
ratory procedures for predicting low
temperature operability of diesel fuels
such as the filter test proposed in (14C)
and the modified Enjay fluidity test.
The test apparatus and procedure for
measurement of the filter choking pro-
pensity of diesel fuels were described by
Onion (37C). Gutman et al. (22C)
studied the titration for acidity in diesel
fuels and kerosines using the indicator
intrazine yellow; correct results were
obtained when the end point was taken
at the color transition from yellow to
blue instead of from yellow to green.
156 R · ANALYTICAL CHEMISTRY
Lubricants, Oils,
and Greases
F. M. Roberts
Texaco, Inc., Beacon, N. Y.
Oils. A technical conference on
methods for evaluating antiwear and
extreme pressure (EP) properties of
lubricants was sponsored by the
Academy of Science of the USSR and
reported by Fuks (35D). Vichard and
Godet (101D) reported on an analysis
of wear machines in which it was found
that the Shell four-ball, Bartel IFE, and
Timken testing rigs should not be used
for fundamental research on wear prop-
erties.
Sayles (90D) presented a review on
the development of the four-ball EP
tester. An automated four-ball testing
machine was described by Frenkel and
Grivstov (34D). Bartz and Goettner
(10D) made a systematic study of the
variables in evaluating automotive gear
oils with the four-ball machine, and
Bartz (9D) used this machine to in-
vestigate 33 oils to generalize corrosion
and load results for different classes of
oils. Appeldoorn and Royle (4D) sub-
stituted ceramic balls for steel balls to
obtain better repeatability and shorter
tests.
A comparison of the procedures and
applications of the IAE, Ryder, and
FZG gear oil tests was made by Lechner
and Seitzinger (63D). A cooperative
program was carried out by the Insti-
tute of Petroleum Gear Lubricant Rig
Tests Subpanel and the Deutsche Gesell-
schaft fuer Mineraloelwissenschaft und
Kohlechemie to investigate correlation
between IAE and FZF test machines.
Correlation was good when tooth-tip
sliding velocities were similar (50D).
Niemann and Assmann (80D) reported
that 10 years experience with the FZG
gear test rig shows the test classifies
lubricants clearly with respect to load-
carrying and wear.
An analytical investigation by Mc-
Cain and Alsandor (68D) showed that
important factors in gear lubrication are
oil jet orientation, oil velocity, and use of
disengaging lubrication. Harris (4SD)
reported an analytical method to pre-
dict skidding in high speed roller bear-
ings and to evaluate corrective measures.
Darling and Isherwood (22D) described
apparatus for determining antiscuffing
properties of marine turbine oils and
for testing machine-type failures of
turbine thrust blocks. Jonach and
Baker (47D) discussed laboratory and
shipboard testing of selected diesel
cylinder lubricants.
Weaver (102D) used a radiotracer
technique to measure the antiwear per-
formance of hydraulic fluids. A method
for determining critical temperature
for the appearance of a boundary oil
film was developed by Klimov and
Kichkin (57D). Gansheimer (36D) de-
scribed a press-fit test which, on the
basis of 16 year’s experience, provides a
rapid, exact, and simple evaluation of
lubricants operating at low speeds and
high pressures. Kellermann and Tur-
lach (54D) developed a simple apparatus
to measure the relative coefficient of
friction at high contact pressures, as in
wire drawing, and to provide for control
of surface quality of wire.
A variety of engine tests for determin-
ing oil quality have been described and
Sandulescu (87D) presented a review of
the latest methods used in the U.S.A.,
Great Britain, Europe, U.S.S.R., and
Romania. The Petter-W-1 test was
shown by Pallay et al. (81D) to cor-
relate well with standard engine tests,
and to be faster and less expensive.
The test didn’t show much differentia-
tion between high detergent premium
oils. The Coordinating Research Coun-
cil reported results of a study of a new
crankcase ventilation system to im-
prove L-38 oxidation test results (16D)
and recommended new reference oils
for studying oil oxidation characteristics
in the CLR oil test engine (17D). In
cooperation with the Army Engine,
Fuels, and Lubricants Group, a useful
engine test technique for predicting fuel
and lubricant compatability was de-
veloped (18D). Zarubin et al. (104D)
reported evaluation of new PZV-60
units for evaluating detergent properties
of oils according to Gost 57 26. Levrague
et al. (64D) discussed use of a super-
charged Petter AV diesel engine to cover
the ever-increasing bmep and thermal
loads of modem diesel engines. Saxe
et al. (89D) used a water-cooled one-
cylinder diesel engine for testing motor
oils. Baist (6D) modified the MWM
test A by changing the cylinder liner,
coolant, and fuel to permit testing oils
of S-l and higher classes. Dysart (26D)
reported use of a modified Cooper-
Bessemer/Lufkin GSC engine for pre-
dicting deposit formation in two-cycle,
spark-ignited gas engines.
Laboratory bench tests for determin-
ing oil quality include a device described
by Kyuregyan (62D) for evaluating de-
tergent properties of motor oils. Var-
nish deposits formed on a heated alu-
minum bushing in contact with a ro-
tating steel shaft were the basis for
evaluation. Forbes and Wood (3SD)
mixed synthetic sludge precursors with
oil, then treated the heated mixture with
gases containing oxides of nitrogen.
Resulting sludge deposits were rated to
assess the oil’s detergency qualities.
Assmann and Janouchova (5D) de-
veloped an apparatus for determining
oxidation stability of oils for self-
saturating lubricated bearings. Kaye
and Seager (53D) used dielectric con-
stant measurements to determine cream-
ing in emulsions. Schmid (91D) re-
 ported that there was little correlation
between laboratory tests on cutting
oils and their performance in service.
Testing of oils for oxidation stability
and corrosion properties was carried
out by a wide variety of laboratory
techniques. A highly accelerated oxy-
gen absorption test reported by Denton
and Thompson (2SD) showed that zinc
dithiocarbamates were the most active
antioxidants evaluated. Oxygen con-
sumption was also used as a measure of
oxidation in an automatic device de-
scribed by Sanin et al. (88D), and Ru-
denko and Sobolev (86D) described a
semimicro oxygen absorption test.
Shroff and Wilson (93D) used the
CERL method and oxygen absorption
in laboratory tests to compare the labo-
ratory assessment with service per-
formance of inhibited insulating oils.
An evaluation of procedures for deter-
mining aging resistance of a variety of
oils was carried out by a number of
eastern European countries and re-
ported by Belcheva et al. (11D). Wil-
son (10SD) reported that service be-
havior and performance can be predicted
from ASTM D 1314 on the new oil with
no catalysts, and with metallic copper
and a soluble copper catalyst.
Dolby (25D) described apparatus and
handling practices used by Gulf Re-
search Center in testing steam turbine
oils. Krawetz and Tovrog (60D)
studied the application of differential
thermal analysis to determine thermal
decomposition of lubricating oils. In a
method reported by Kosyakin and Us-
penskaya (59D) heat resistance of
lubricating oils is characterized by time
required for their total “drying” or
polymerization at a given temperature.
Steinmann (96D) used ultraviolet ir-
radiation of small amounts of lubricants
spread on paper to test for stability of
oils containing animal or vegetable fats
or fatty acids. A method for estimation
of thermooxidative stability of aviation
lubricating oils at high temperatures was
developed by Starikova et al. (95D).
Corrosive properties of motor oils were
determined by measuring weight loss of
lead specimens in a method developed
by Maczel et al. (73D). Bartholomaei
et al. (8D) described an oil mist deposits
test for evaluating the deposit-forming
tendency of jet engine lubricants.
Doernenburg and Gerber (24D) de-
scribed the mechanism of gas formation
in oil-filled transformers and analyzed
the gas by mass spectrometer and gas
chromatograph. Kaegler (51D) auto-
mated the Woerner apparatus to sim-
plify determination of gas-absorbing
characteristics of electrical insulating
oils. Gasing stability of insulating oils
was tested by Brzuska and Widmann
(14D) using an oil/paper dielectric under
simulated operating conditions. Di-
electric loss tangent and specific con-
ductivity were among the tests applied
by Mason and Simmons (78D) to
monitor the quality of insulating oils.
Jones and Angerer (48D) showed by
electroluminescence measurements in
high direct current fields that the num-
ber of pulse discharges through an oil is
directly proportional to anode current
and their shape appeared to be a func-
tion of the test circuitry.
The problem of flammability or fire
resistance of hydraulic fluids was the
subject of a number of papers. Ker
(55D) reported a study in which aviation
hydraulic fluids were subjected to a hot
brake test. The test showed that only
snuffer fluid C withstood ignition at a
temperature of 700 °C. A combined
“high pressure spray manifold test”
correlated reasonably well with the hot
brake test.
A review by MacDonald (72D) of
methods for assessing fire resistance of
aircraft fluids indicated that present
closed vessel and hot manifold tests are
inadequate and may be misleading.
Other tests are too narrow in scope.
Adequate information could be obtained
by improved versions of the lower and
upper flash point tests and by carrying
out the minimum spontaneous ignition
temperature test in a larger isothermal
apparatus.
McCord (70D) reported the environ-
mental variables in supersonic aircraft
prevent sure extrapolation of a fluid’s
experimental hazard rating to actual
conditions of use. Hamilton and Hollo-
way (41D) described an apparatus for
evaluating fire hazards of hydraulic
fluids which approximates the environ-
ment and conditions in high speed air-
craft. A closed-compartment fire test
for evaluating fire resistance of hy-
draulic fluids in advanced supersonic
aircraft was developed by Kander (52D).
An apparatus for studying fire resistance
of hydraulic fluids at elevated pressures
was developed by Marzani (77 D).
Rowand and Sargent (84D) used simple,
inexpensive equipment in a low pressure
spray-flammability test for hydraulic
fluids.
Johnson and Furby (46D) described
four miniaturized tests for evaluating
fire resistance of aerospace fluids.
These small tests require 40 ml of fluid
compared to approximately 2500 ml for
the full-scale tests. Goodall and Ingle
(88D) reported the effects of mixture
strength, atomization, and wall mate-
rials on the spontaneous ignition of
kerosine tested in a static rig.
Activation analysis for 35 common
elements in amounts of 1 ppm or less in
lubricants was reported by Jester (45D).
Erhart et al. (28D) described chromato-
graphic techniques for determining in-
sulating oil additives, identifying aging
products, and evaluating the stability of
mixtures of inhibited oils. Jenkins
(44D) discussed the interdependence
and significance of inspection tests,
elemental analyses, and carbon type
analyses on the characterization of
lubricating oil basestocks. Fluores-
cence in ultraviolet light of oil spread on
filter paper was used by Alekseev and
Tobolova (ID) to monitor regeneration
of lubricants.
Lyashenko et al. (67D) used potentio-
metric titrations to determine alkali
numbers of additives and oils with addi-
tives, and Bakmutaskaya and Butkov
(7D) reported that a color indicator
titration gave results in agreement with
potentiometric titrations. Zulin and
Yartsev (105D) used physicochemical
values (color, density, viscosity, and
surface tension) to optimize a system
for asphalt removal from lubricating
oils. Dispersant additives in unused
oils were determined by Fabry (29D)
with a spot test after carbon black was
added to the sample.
A “Seal Compatability Index” for
classifying mineral oils was reported in
the Journal of the Institute of Petroleum
(49D). Bornong (13D) used infrared
spectrometry to examine preservative,
hydraulic, and specialty fluids. The
only additives easily detected were cor-
rosion inhibitors and tricresylphosphate.
It was concluded that infrared spectrom-
etry could not accurately detect changes
in composition in these products. A
technique for obtaining microgram
amounts of materials, separated by thin
layer chromatography, for infrared ex-
amination was described by McCoy
(7 ID). Przybylski and Lichowska
(83D) prepared a catalog of infrared
spectra of lubricant additives.
Two new methods and test jars for
rapid determination of pour points of
mineral oils were described and patents
applied for by Shell Internationale
Research Maatschappij NV (92D).
Costa (20D) published a nomograph for
calculating flash point of lubricating
oils from composition and the flash
points of the components. Rowe (85D)
described a simple apparatus for deter-
mining viscosity at temperatures up to
70 °C and pressures to 20 tons per sq
in. A method for plotting volatility
curves of lubricating oils at a given
temperature was described by Martynov
(74D), who also published, with Bon-
dareva and Kuchinskaya (79D), a
description of the PIM-Z device for the
laboratory determination of evaporation
rates of lubricating oils. A spring-type
microbalance was described by Marty-
nov (75D) for determining hygro-
scopicity of lubricants. Kruys et al.
(6ID) reported the results of swelling
tests with cable insulating materials in
four types of oil.
In the examination of used oils,
Gardner (37D) used infrared spectrom-
etry to measure quantitatively oxida-
tion, nitration, additive depletion, and
contamination. Lizogub and Klimenko
(66D) described an infrared procedure
VOL. 41, NO. 5, APRIL 1969 · 157 R
for determining acid and ester numbers.
A centrifuge method was described by
Hammerich and Gondermann (42 D) for
determining total contamination in used
additive motor oils. Komarmy (58D)
used the rate of diffusion of a drop of
used oil into a clean oil to determine the
solid contaminant content. Kishi et al.
(56D) described a new method for
insolubles in used oils in which coagulant
is added, sample is extracted in a Sohx-
let extractor, and weight gain of the
thimble is determined. Studeny (97D)
used loss caused by evaporation on
heating to determine gasoline content
of used oils. Feasley and Pellicciotti
(31D) used neutralization number to
decide when transmission fluids should
be replaced. A carbon black dispersion
spot test to evaluate oil condition was
described by Fabry (30D) and by Cucu-
lic (21D). Cross-contamination of lu-
bricants was detected with radioisotopes
in a procedure described by Anderson
and Black (3D).
Greases. The history and possible
areas of application of differential
thermal analysis to problems of grease
production were discussed by Trze-
bowski (99D). Vanos and Flora (100D)
studied thermal transitions of greases
and changes in body at various tem-
peratures to determine dropping points
and phase diagrams. McCarthy (69D)
reported results of cooperative testing
programs on the method for determining
dropping point of grease.
The Coordinating Research Council
(19D) developed equipment and a
technique to evaluate performance
characteristics of two greases in size 204
antifriction bearings up to 450 °F and
10,000 rpm and under thrust loads up to
320 lb. A method for determining the
amount of oil separating from greases
under dynamic conditions was developed
by Mitterhauser et al. (79D). Ellis
(27D) presented a review of design and
use of grease machines for antifriction
bearings. An ASTM study reported by
Stallings (94D) showed that the four-
ball wear test (ASTM D-2266) is a
practical method for determining wear
properties of grease.
Ficker (32D) and Guba and Vamos
(39D) described use of the electron
microscope for examination of the soap
fraction of greases. Anderson et al. (2D)
described a solvent-deoiling technique
for preparing greases for electron mi-
croscopy. The use of trichlorotrifluoro-
ethane as a safe solvent for determining
grease and oil in waste water and sludge
was proposed by Chanin et al. (1SD).
Torque tests on grease-lubricated size
204 bearings were carried out by Linde-
man (65 D). Blank and Lindeman
(12D) described a study made with a
novel torque tester. Patzau (82D) re-
ported use of an SKF grease-testing ap-
paratus to study oxidation stability of
greases. A new method for determining
158 R · ANALYTICAL CHEMISTRY
colloidal stability of greases was de-
scribed by Suchanek (98D). Haines
et al. (40D) described laboratory
methods used to determine rheological
and electrical properties of greases and
other fluid systems.
Wax
D. R. Cushman and R. T. Edwards
Mobil Research and Development Carp.,
Paulsboro, N. J.
Roemer and Hochreiter (18E) de-
scribed an apparatus for automatic de-
termination of flow and drop points of
waxes. The apparatus, based on the
photoelectric cell principle, indicates and
records results of 12 samples simultane-
ously.
Two papers dealt with oil content in
paraffins. Mal’nev et al. (12E) used an
infrared method, with the sample either
in CCU solution, or without solvent in a
high temperature cell, measuring inten-
sity of the CH3 band frequency at 1380
cm-1. Osipov and Popov (15E) used a
double beam uv spectrophotometer with
a phase detector providing a direct read-
ing of the difference of intensities of the
two beams.
Three papers covered the quantita-
tive determination of wax in oils
and oil products. Demyanchik and
Mikhalevich (7E) treated a 250° resid-
uum with solvent, acid, solvent, alkali,
water wash, and distillation to obtain a
paraffin residue. Demyanchik et al.
(6E) included a sulfonation step to re-
move resinous compounds from a resid-
uum dissolved in gasoline. After the
gasoline was distilled off, the sample was
treated with an alcohol-ether mixture
and cooled to —20° to precipitate the
paraffin. Triems and Heinze (21E)
used a 30:35:35 volume ratio acetone-
benzene-toluene mixture following ini-
tial separation of asphalt and resin using
an oil-hexane solution with active earth.
Hard paraffins were detected at —10 and
total paraffins at 30 °C, the difference
—
being soft paraffins.
Elbadrawy and Heinze (9E) sepa-
rated components of a microcrystalline
wax by deoiling and fractional crystal-
lization. Fractions were separated by
adsorption chromatography and further
separated by urea adduction. They
were then characterized by conventional
methods. Spengler and Roessner (20E),
by selective extraction and urea adduc-
tion, identified iso- and alkylcycloparaf-
fins and mono- and bicyclic alkyl aromat-
ics with 23 to 51 C atoms in crude oil
fractions. Triems and Heinze (22E) pre-
pared microcrystalline waxes from slack
waxes obtained by propane deasphalting
of vacuum distillation residues from
various crude oils by solvent deoiling
followed by sulfuric acid and/or bleach-
ing earth refining. Wax yields and
quality depended on the nature of the
crude. Leibnitz et al. (11E) separated
olefins, which are inadvertently pro-
duced during high temperature process-
ing of crude oils, from hard paraffins in
the form of their heavy metal complexes
and characterized them by ir spectrom-
etry.
Two papers dealt with differential
thermal analysis. Currell and Robinson
(5E) showed that an endothermic peak
at 475 to 480 °C is characteristic
of microcrystalline and polyethylene
waxes, whereas paraffinic waxes show
broad diffuse peaks which return to the
baseline below 460 °C. Kawasaki et al.
(10E) reported phase changes of eight
commercial paraffin waxes, generally
showing two peaks for each wax corre-
sponding to thermal absorption during
melting and during a solid-solid pre-
melting transition.
Reid (16E) used high resolution mass
spectrometry to study petroleum waxes,
microcrystalline waxes, and ozokerite.
Spectra of microcrystalline waxes were
obtained by a direct-probe sample-inlet
system.
Berthold (4E) used an ir spectrometric
method to determine the degree of
branching in hydrocarbon waxes by
determining the relative and absolute
methyl-group content of paraffins and
waxes, based on a theoretical relation
between the maximum extinction co-
efficient and the methyl-group mole
fraction. Tudorovskii et al. (23E)
described a phasometric method for
petroleum analysis, passing two identical
uv beams through cells containing a
standard and the specimen. The beams
were focused on the same photoreceiver.
A phase angle shift was formed by a re-
volving slotted disk which interrupted
the beams before they entered the cells.
Three papers covered determination
of polycyclic aromatic compounds in
refined paraffin waxes. Mazee et al.
(13) compared various methods and
showed preference for quantitative mea-
surement of uv absorption after extrac-
tion with Me2SO and H3P04. Woggon
and Jehle (24E) reported a thin layer
chromatographic method using silica
gel treated with dimethylformamide and
developed with cyclohexane. Spots
were located by examination under uv
light and compared with reference to
known polycyclic compounds. Shabad
and Khesina (19E) extracted benzo[a]-
pyrene from wax, cooled the extract to
—
196 °C, and excited it by 365-nm
radiation, measuring intensity of fluores-
cence at 403-nm.
Three papers dealt with crystallization
of paraffin. Abezgauz et al. (IE) de-
termined temperature for the onset of
crystallization of paraffin from petro-
leum from the change in slope of the
optical density vs. temperature curve.
To increase accuracy, the transition
point is registered in the ir region of the
spectrum.
Andriasov and Os’kin (3E) deter-
mined paraffin crystallization tempera-
ture by measurement of the volume ex-
pansion coefficient. They described an
apparatus with gas chamber connected
to a graduated capillary tube. The
same authors (2E) used a photometric
method to determine initial temperature
of paraffin crystallization in a moving
solution of different paraffin concentra-
tions. Turbidity temperatures of var-
ious wax-kerosine solutions were mea-
sured. The temperature difference be-
tween the beginning of turbidity and
the beginning of crystallization was
0.1 °c.
One paper reported on determination
of petroleum wax odor by gas chroma-
tography. Durrett (8E) established a
correlation between the odor rating
given by a panel of 10 and that obtained
by the gas chromatographic analysis of
wax samples. Compounds contributing
to odor were determined.
Rheological properties of petroleum
jellies were described,-by Mozes et al.
(.HE) as a substitution’for the empirical
methods of consistency qualification
hitherto used.
Robinson and Johnson (17E) re-
viewed recent developments in wax
analysis, covering 25 references.
Asphalt
J. A. Wronka
Cities Service Oil Co., Cranbury, N. J.
Levin et al. (39F) described a rapid
method for the determination of soften-
ing point of medium and high melting
point petroleum asphalts based on time
required for a threaded pin screwed into
an asphalt to sink to the bottom of a
beaker placed in a constant temperature
bath. Lopatinskii (40F) estimated
softening point for blends of two as-
phalts using a mathematical formula
and/or graphical method.
Glass-transition temperature of as-
phalts was determined by Schmidt and
coworkers (57F, 58F) using a dilato-
metric procedure and by Conor and Spiro
(12F) using a differential thermal anal-
ysis. DuBois (18F) reported that as-
phalt-filler mixtures have higher glass-
transition temperatures than asphalt
alone.
Silica gel chromatography was used by
Sato and Imazumi (56F) for determina-
tion of wax in asphalts. In this proce-
dure, isobutyl methyl ketone was used to
precipitate the wax from a cyclohexane-
eluted fraction. Bestougeff (3F) sepa-
rated cold n-heptane-precipitated as-
phaltenes from Libyan, Boscan, Lagh-
ouat, and Hassi Messaoud crude oils into
20 to 30 subfractions using selective
extraction with elution chromatography.
Analysis of asphalts using inverse gas-
liquid chromatography was described by
Davis et al. (15F) and used by Davis and
Petersen (14F, 16F) for a comparison
with the Kleinschmidt and Rostler-
Sternberg analyses and for study of
oxidation characteristics. Gradient-
elution chromatography using an ul-
traviolet monitor was described by Mid-
dleton (46F, 47F) to separate asphaltic
petrolenes into six fractions, and Kles-
ment et al. (29F) used thin layer chro-
matography for the analysis of a shale tar.
A combination of pyrolysis, hydrogena-
tion, and gas-liquid chromatography
was used by Knotnerus (30F, 31F) for
analysis of bitumens and bitumen con-
stituents.
A structural analysis of asphalt frac-
tions was made by Blyler and Daane
(4F) using X-ray diffraction, osmom-
etry, electron microscopy, and mass
spectrometry; by Corbett and Swar-
brick (13F) using mass and nuclear
magnetic resonance spectrometry; by
Wetmore et al. (68F) using ultraviolet,
infrared, and nuclear magnetic reso-
nance spectrometry; by Gallegos (21F)
and Baker (2F) using high resolution
mass spectrometry; by Schweyer and
Busot (59F) using infrared and nuclear
magnetic resonance spectrometry; by
Girdler (22F) using elemental analysis,
infrared and nuclear magnetic resonance
spectrometry, and molecular weight
and color intensity determinations; and
by Ferris et al. (20F) using elemental
analysis, light absorbance, nuclear mag-
netic and electron-spin resonance mea-
surements, and X-ray diffraction.
Ramsey et al. (54F) reported that
nuclear magnetic resonance gives reli-
able data with respect toaverage formula
and molecular weights and structural
details, requires no instrument calibra-
tion with known compounds, and
provides results rapidly. Nicksic and
Jeffries-Harris (5IF) concluded that
acid-precipitated asphaltenes constitute
a distinct chemical class on the basis of
molecular weight determinations; car-
bon, hydrogen, sulfur, nitrogen, nickel
and vanadium contents; and electron-
spin and nuclear magnetic resonance.
Yen and Boucher (69F) summarized
electron-spin resonance studies on six
asphalts.
Laguros et al. (37F) correlated asphalt
content of a bituminous pavement with
neutron scattering and Kuykendall et al.
(36F) applied neutron activation analy-
sis to asphalt and concluded that oxida-
tion does not account for all in-service
hardening of asphalt road surfacings.
Infrared spectrometry was used by
Martin (44F) to evaluate durability of
eight air-blown asphalts; by Campbell
and Wright (7F) to measure oxidative
changes in a Kuwait asphalt flux; by
Smith et al. (60F) to predict weather-
ability behavior of coating grade as-
phalts; by Petersen (S3F) to demon-
strate existence of hydrogen bonding in
asphalt; and by Campbell and Wright
(6F) to study asphalt hardening by
gaseous oxidants.
Krom (SSF) investigated methods of
improving repeatibility and reproduc-
ibility of the Fraass breaking point test
for high softening point bitumens and
concluded the preparation of test
plaques affected results obtained. Ewers
(19F) studied bending and impact tests
on paving asphalts and concluded that
conventional bending tests were too
slow and impact tests too fast to predict
behavior in service. Dobson (17F)
described an instrument for measuring
dynamic elastic properties of bitumens.
Krchma (S2F) developed a rapid, small-
sample test for evaluating ductility.
Baibazarov and Zizin (IF) described
a rapid optical density method for
determining asphaltenes in a deasphalted
oil. Other methods were described
by Strokina and Muzychenko (62F),
Swaminathan et al. (63F), Brejcha (5F),
and Neumann et al. (50F). Neumann
and Bellstedt (49F) showed that pri-
mary particle aggregation and mean rela-
tive mass of asphaltenes increased with
concentration and decreased with tem-
perature.
Kuchma (35F) described an apparatus
for determining emulsifiability of an
asphalt based upon flow of the asphalt
into an aqueous solution of electrolyte,
and Meda (45F) used a modified Soxhlet
extractor for determining the amount of
bitumen in an emulsion. Oliensis (52F)
described a new transudation test for
determining compatibility of tar and
asphalt.
Grading of asphalts by viscosity at
140 °F and other aspects of their use in
paving were discussed by Welborn (66F),
McLeod (41F, 4®F), Chaffin (8F),
Hawthorne (25F), Krom (34F), Izatt
and Buchanan (27F), Griffith et al.
(23F), Halstead et al. (24F), and Wel-
born et al. (67F).
Walter (65 F) compared various
methods of measuring viscosity of as-
phaltic binders and Cogill (10F) mea-
sured viscosities of two groups of as-
phalt cutbacks using the following vis-
cometers: Pochettino type falling co-
axial-cylinder, couette-type rotating co-
axial, capillary, vacuum, and Ostwald-
tube. Chari and Awasthy (9F) mea-
sured viscosities of pitch-tar binders
using a torsion blade and penetrometer;
Cogill et al. (11F) adapted the Kuehn-
Rigden viscometer for use with an inter-
ferometer for determining viscosity of
weathered asphalts. Majidzadeh and
Schweyer (43F) and Herrin et al. (26F)
explained rheologic behavior of 13 as-
phalts determined by a sliding-plate
viscometer by the Eyring rate processes
theory and reaction kinetics principles.
Santucci and Schmidt (SSF) com-
pared laboratory tests with full scale
pavement-laboratory tests and con-
VOL. 41, NO. 5, APRIL 1969 · 159 R
eluded that pavement toughness cor-
relates with viscosity at 100 °F of as-
phalts received from test pavements and
with viscosity at 140 °F of asphalts ex-
posed in rolling thin film oven. The
rolling thin film viscosity was proposed
for grading setting quality of a paving
asphalt. Lee and Csanyi (38F) showed
that the Bureau of Public Roads’ thin-
film oven test ages asphalt in the same
manner as the normal hot-mixing opera-
tion at asphalt plants.
Heat of reaction during asphalt blow-
ing was determined by Smith and
Schweyer (6 IF).
Effect of bacteria and other micro-
organisms on asphalt was studied by
Traxler (64F) and Jones (28F).
Catalysts
Ralph O. Clark
Gulf Research & Development Co.,
Pittsburgh, Pa.
Acidity. Only one report in the
two-year period covered by this re-
view described use of indicators for
measurement of catalyst acidity.
Drushel and Somers (6G) followed tran-
sition from a protonated species to a
neutral indicator using a spectrofluo-
rometer when the cracking catalyst was
titrated with a basic amine. Qualita-
tive agreement was found with data
reported by Hirschler, who used a visible
color change in an indicator rather than
a change in fluorescence.
Chemisorption of dioxane was em-
ployed by Charcossett et al. (2G) to
demonstrate the presence of a limited
number of nonprotonic acid sites of a
silica-alumina cracking catalyst; pure
silica exhibited none of these sites.
Resulting data were compared with
those obtained by titration using n-
butylamine.
Pohl and Rebentisch (16G) described
a dynamic method for determining sur-
face acidity of alumina catalysts us-
ing ammonia; Tanabe and Yamaguchi
(25G) utilized thermal measurements of
the reaction of silica-alumina with n-
butylamine. Acidities so measured
were higher than published values by
the indicator method; this was inter-
preted as indicating the presence of
weak acid sites not detected by the in-
dicator technique.
Bertolacini (1G) determined activity
of reforming catalysts containing one or
more noble metals on a refractory sup-
port as per cent of the total noble metal
in the catalyst that is soluble in acetyl-
acetone. An adaptation of the Atlan-
tic-Richfield microactivity test was
described by Ciapetta and Henderson
(4G); various advantages are claimed.
Also, Harriz (11G) reported on a new
160 R · ANALYTICAL CHEMISTRY
testing apparatus, built around the
Houdry test equipment, that is useful in
both control of catalyst manufacture
and in following aging in commercial
process units. One catalyst manu-
facturer is now using a microactivity
test (14G) instead of the D + L test for
equilibrium catalyst testing; distortions
due to unrealistic coke buildup and vary-
ing amounts of metal contaminants were
claimed to be minimized.
Polyakin (17G) described a semimicro
method for evaluating activity of syn-
thesis gas catalysts at ambient pressure.
A rapid microprocedure for testing
effiacy of catalysts for oxidation of
combustible gases was reported by
Ghosh et al. (8G). Dzhavadov et al.
(5G) employed the gas chromatographic
technique in an investigation of different
active sites on catalyst surfaces.
Physical Properties. A new method
for surface area of catalysts was de-
veloped by Schay and Nagy (22<?)
involving graphical extrapolation of
liquid adsorption data. Isotherms
for charcoal with benzene-ethanol
were the same as those obtained by
BET determination; other liquid pairs
were used for aluminas and silicas.
Groszek (9G) applied flow microcalorim-
etry to powders having surface areas of
1 m2 per g or less; Orr (15G) reported
excellent agreement with BET values
using low pressure permeametry for
surface areas up to 6 m2 per g.
Lester (12G) compared pore size dis-
tributions by nitrogen adsorption when
12 to 15 data points rather than 40 or
more were used. Results obtained by
the abbreviated method were only
slightly less accurate than the more de-
tailed analysis. Comparison of a trans-
formed Cranston-Inkley equation with
the Dollimore-Heal and Tambouze
equations for estimation of pore size
distributions from adsorption isotherms
was reported by Emig and Hofmann
(7G). Other equations were derived by
Viswanathan and Sastri (26G) by which
cumulative surface areas, and pore dis-
tributions in terms of surface areas, can
be computed with a desk calculator
directly from nitrogen-desorption iso-
therms. Roberts (20G) devised a simple
and rapid procedure for estimation of
pore volume and area distributions of
catalysts from sorption isotherms. Re-
sults obtained agreed with data calcu-
lated by the method of Barrett, Joyner,
and Halenda.
A new mercury porosimeter was re-
ported on by Reich (19G). The in-
strument will accommodate a relatively
large specimen and is applicable for
measurement of pore diameters over the
range 0.05 to 500 µ.
Calibration of a Coulter counter for
particles having diameters of about 1 µ
was covered by Mercer (13G). Chat-
field (SG) proposed a particle size com-
parator in which a 35-mm photograph
of the particulate material is projected
on a translucent screen. Particle sizes
are then compared with a superimposed
spot of light projected from the reverse
side of the screen.
Elemental Analysis. A pyrolytic
separation of fluorine from catalysts
was covered by Gulyaeva and Khy-
anina (10G), who followed this by
titrating the recovered fluoride with
thorium nitrate or colorimetrically
using the bleaching effect on sodium
zirconium alizarinsulfonate. Russow
(21G) patented a thermal neutron
activation method for boron in reform-
ing catalysts, and Stone and Rayburn
(24G) described an X-ray spectrographic
procedure for certain rare earths used in
silica-alumina base catalysts.
Potter et al. (18G) reported increased
conversion of charge to gasoline and a
slightly higher gasoline yield in FCC
operations by the use of an on-stream
analyzer for carbon content of catalysts.
A patent on this device was issued to
Senyk and Toohey (23G).
Physical Properties
W. A. Wright
SunOil Co., Marcus Hook, Pa.
The Coordinating Research Council
test technique to evaluate low tempera-
ture cranking characteristics of engines
at 0 °F was evaluated at —20 °F (14H)
and found suitable at the lower tem-
perature. Data on various engines and
motor oils reconfirmed that predictions
of performance should be based on ap-
propriate actual viscosity measurements.
Problems of predicting low temperature
cranking characteristics were discussed
by Vick et al. (66H). Development of
laboratory tests was reported by Selby
and Staffin (57H).
Correlations between engine tests and
bench tests on the cold-cranking simula-
tor reciprocating viscometer and cone-
plate viscometers at —20 °F were re-
ported by Meyer et al. (39H). A de-
tailed study of the cold-cranking simula-
tor by Cox et al. (15H) was made in
preparation of an ASTM standard
method. A similar report was made on
construction of the reciprocating visco-
meter by Stewart et al. (62H) and on its
correlation to engine tests by Stewart
and Meyer (40H).
Viscosity studies of lubricating oil at
low temperatures were made by Freund
et al. (21H). In the region of the wax
cloud point, the oil lost its Newtonian
characteristics and exhibited a time-
dependent yield value. Gadzhiev
(22H) studied viscosity-temperature
relations for several lubricating oil
fractions from +10 to —40 °C. Log-
log kinematic viscosity varied linearly
with t emperature over this short range.
Nogami and Kobayashi (42H) examined
stability of polymer-containing oils and
relation to the test method. Automatic
control of vibration and resonance was
desirable. Nogami (43H) related vis-
cosity loss to exposure time in a sonic
tester by a simple equation. He also
found (44H) that the vibrating surface
should be a hard metal to resist erosion.
Eroded surfaces produced more severe
viscosity loss.
Flow properties of pure organic com-
pounds under high shear rates were
studied by Paushkin et al. (48H). Vis-
cosity and compressibility of lubricants
at 500 to 2000 atmospheres and 20 to
100 °C were determined by Raetzsch
(51 , 52H). Falling sphere viscometer
and piezometer compressibility data are
reported for paraffin oil, glycerine, poly-
propylene glycol, and isoceresine. Ali
(2H, 3H) evaluated and compared
several methods of correlating oil vis-
cosity with temperature. Methods of
measurement of estimation of viscosity
at temperatures up to 700 °F were ap-
plied to problems of thermal recovery of
petroleum.
Kobashi (38H) used a coaxial cylinder
viscometer to measure viscosity of Ca
and Li greases at constant shear rate.
Apparent viscosity decreased linearly
with log time. Structural breakdown
also was related to type of base oil.
Patzau and Ligezowa (47H) compared
apparent viscosity-temperature mea-
surements for several types of greases
with torque measurements taken on a
roller bearing using the same greases.
Pavlov and Vinogradov (49H) made
extensive rheological measurements on
greases using techniques of both con-
stant shear rate and shear stress. Shear
rates range from 10-6 to 104 sec-1. At
very low shear rates, greases first work-
harden, followed by creep. As shear
rate increases, there is increasing struc-
tural breakdown with softening. At
high shear rates, grease flow becomes
essentially Newtonian.
Brungraber et al. (7H) glued plastic
vanes to the faces of a cone-plate viscom-
eter to combat slippage at the wall.
Turian (65H) continued studies on
viscous heating in cone-plate viscom-
eters by analyzing the case for non-
Newtonian fluids between infinite paral-
lel planes.
Chen et al. (9H) developed equa-
tions for terminal velocity of the
cylinder in a falling cylinder viscometer
when eccentricity existed. Schurz and
Tomiska (56H) studied the Hagenbach-
Couette correction factor experimentally
in a variety of straight and curved capil-
laries interupted by bulbs. Individual
instrument calibration with a known
fluid was advisable.
Cogill et al. (12H) described a viscom-
eter for the range of 10® to 10 11 P using
0.1 ml of sample. Viscosities within
20% of correct were obtained 5 min after
start of reading. Cussler and Fuoss
(16H) designed and tested a remote con-
trol viscometer for use in a pressure
bomb up to 5000 atm.
Klaus et al. (30H) described a capillary
kinematic viscometer usable from 0 to
10,000 psig. Klein and Fusser (31H)
studied effects of capillary length to di-
ameter ratios and their relationship to
temperature rise and elastic effects.
L/D ratios up to 4000 were studied.
Speaker (60H) devised a high pressure
viscometer of the Ostwald type. Elec-
troluminescent panels and photocells
were used as the sensing device.
Stromskii et al. (63H) developed a roll-
ing ball viscometer for measuring vis-
cosity in gas-condensate systems up to
1500 kg/cm2 and temperatures below
200 °C. Inductive timing of the falling
ball gave an accuracy within 0.2 sec.
Viscometer accuracy was better at high
pressures than at low. An automatic
parallel plate viscometer measuring
absolute viscosity was developed by
NASA (38H). It was said to be useful
for both normal and viscoelastic ma-
terials. Mitterhauszer (41H) used the
Spengler viscometer to determine high
shear viscosities of a series of Li, Ca, and
Na greases. Greases gave lower friction
resistance in ball bearings than lubricat-
ing oils of equal or lower viscosity.
Onoyama and Sato (45H) specially
calibrated a Brookfield viscometer.
Reproducibility was 1.7 to 3.5%.
Used engine oils gave evidence of
non-Newtonian characteristics. Wohl
(70H) compared use of capillary, rota-
tional, coaxial, and cone and plate vis-
cometers, as well as calculations involved,
when testing non-Newtonian fluids.
Gaeta described very low shear, high
sensitivity, electromagnetic viscom-
eters (23H). Liquid motion is induced
magnetically rather than mechanically,
and very low stresses can be obtained.
A review (34H) was published covering
type of fluids, viscometers, viscosity-
temperature relations of lubricating oils,
lubrication, fluid flow in pipes, hydrau-
lic systems, etc.
Ghigliazza (24H) discussed the incor-
rect evaluation of oils of greater than 100
vi using the Dean and Davis scale. A
proposal of a more logical extension
is given. Schnurmann (55H) also dis-
cussed this subject and described the
new standard, ASTM D 2270, adopted to
reduce discrepancies. Kelley and Cau-
dle (28H) presented a graphical method
of predicting gas-free oil viscosities up
to 500 °F. API gravity and one vis-
cosity are used to determine the slope on
the ASTM chart. The slope and a
single viscosity permit prediction at
other temperatures. Du Parquet (46H)
compared viscosity-temperature rela-
tions for mineral oils. The study cov-
ered formulas proposed by Walther,
Vogel, Andrade, Eyring, Umstatter, and
Van Ness/Van Western Rumpf (53H)
reevaluated the constant in Walther’s
equations and found it to be 0.8. With
this value, slope and boiling points were
correlated to viscosity at 50°. Kay
(27H) described a method of calculating
ternary blends on the ASTM viscosity-
temperature chart. Cost, gravity, and
other properties of blends were also
discussed.
Ambrose (4H) described new boilers
for ebulliometric determination of vapor
pressure. The boiler permitted smooth
boiling of water down to 15 mm Hg.
Davis (17H) presented a nomograph
which gives vapor pressure of a com-
pound from —50 to +500 °F, given its
normal boiling point. Davison et al.
(18H) described a static vapor pressure
apparatus for mixtures. Martynov and
Morozova (37H) developed an appara-
tus to determine saturated vapor pres-
sures of lubricating fluids. It was based
on the Bremer Frowein differential
tensimeter. Jentoft et al. (26H) pre-
sented an apparatus for rapid deter-
mination of vapor pressure of lubricating
oils, based on the design of Hickman.
Kerr and Landis (29H) demonstrated
that reliable boiling point data can be
obtained by differential thermal analysis
of 2- to 5-µ1 samples trapped at exit of
gas-liquid chromatographic columns.
Wadsoe (68H) described a calorimeter
to obtain heat of vaporization at 25 °C.
Amount of sample is about 100 mg and
the test requires less than 45 min.
Harney (25H) described the Sperry
Gravitymaster as a transducer of the
balanced-flow continuous-weighing type.
On-line use measures specific gravity
from butane to heavy fuel oil. Tisinger
(64H) described a microbalance for gas
densities. Current in an electromagnet
used to restore torque is proportional to
density. Baranov et al. (5H) described
a pycnometer suitable for use at 250-atm
pressure.
Wostl et al. (71H) described an appa-
ratus to determine both adiabatic and
isothermal bulk modulus. The range
was 0° to 50° and 0 to 300 kg/cm2.
Wright (72H) made a detailed analysis
of published pvt data on petroleum oils
and pure hydrocarbons. Charts were
prepared to predict these moduli from
0 to 500 °F and up to 100,000 psig.
Atmospheric density at the desired
temperature is the only required in-
formation.
Bruno and Garfinkel (8H) devised an
apparatus to measure dielectric con-
stant and tangent of the loss angle for
greases used with electrical cable. It is
suitable for other material with a high
loss angle or small capacitance. Sen
and Churova (58H) described a device
to determine quality of fuel oil by mea-
suring its dielectric constant. Skow-
ronski and Lutynski (59H) found that a
new spherical cup-sphere gap test cell
showed greater sensitivity for water than
spherical electrodes. Stepanov and
VOL 41, NO. 5, APRIL 1969 · 161 R
Maksimov (61H) correlated dielectric
constant and tangent of the loss angle of
gasolines and gas oil to density of the
fluid. Colin and Setton (13H) de-
scribed an improvement on equipment to
determine electrical resistivity by in-
duced currents. Klinkenberg (32H)
found polarization errors in measuring
electrical conductivity below 10-11 per
ohm per cm by direct current methods
could be reduced by reading promptly or
by extrapolating to zero time.
Popov et al. (50H) experimentally
determined heat capacities for diesel
fuel, kerosine, spindle oil, and motor oil.
Adiabatic data were determined at at-
mospheric pressure and isothermal data
at 3 atm. In all cases, the heat capac-
ity increased with temperature.
Madejski (36H) disclosed a method of
measuring thermal conductivity of liquid
and gaseous dielectrics using free con-
vection from a fine wire. It was ap-
plied to ethanol and petroleum fractions.
Yamamoto and Akiyama (73H) used
an improved hot wire technique to ob-
tain rapid thermal conductivities of
liquid samples of 1 to 1.5 ml. End and
other thermal effects were compensated
by double-bridge circuits.
Bozso (6H) used cryoscopic and ebul-
liometric methods to determine molec-
ular weights of hydrocarbon blends.
Automatic cooling and registration of
cooling curves improved cryoscopic data.
Comparative precision of both methods
was determined. Cir et al. (HH) re-
ported on semiautomatic equipment for
cryoscopic molecular weight determina-
tion. An electronic potentiometer re-
cords temperature curves of benzene
solutions at various concentrations.
Extrapolation to infinite dilution agreed
better with theory than the usual Beck-
mann thermometer method.
Lyashkevich (35H) studied errors in
cryoscopic analysis as related to crys-
tallization and heating rates in a ben-
zene-naphthalene system using 0.05-ml
samples. Very rapid crystallization
showed least bias. Ryasnyanskaya et al.
(54H) determined molecular weight of
heavy petroleum products cryoscopially
in naphthalene solution. Temperatures
were determined by thermistors.
Molecular weights were determined for
pure hydrocarbons and oil products up
through asphalt. Repeatability ranged
up through 3%.
Yamamoto and Oura (74H) described
an automatic recording apparatus to
obtain freezing points from time-tem-
perature freezing and melting curves.
Repeatability was +0.01 “from —190 to
+ 250 °C. Driscoll et al. (19H) made
purity determinations using a differ-
ential scanning calorimeter with 1.25°
per min scan rate. A computer program
correcting for heat of fusion was used.
Precision was ±0.02 mole %.
Alba et al. (1H) studied factors in-
volved in variation of water-petroleum
162 R · ANALYTICAL CHEMISTRY
interfacial tension with time. Effects
are related to interface aging, drop size,
surface, and relative volumes of fluids
present. Volovick and Himbert (67H)
reviewed the principal methods for
measuring surface tension and their use
at high pressures. About 10 methods
are considered. High pressure measure-
ments were made on liquid-liquid and
liquid-gas systems. Williams (6911)
studied the effect of surface tension and
meniscus shape on hydrometer readings
and a method devised to evaluate menis-
cus shape. Chulkov (1 OH) modified the
Bass formula for calculating heat of
combustion for petroleum products as a
function of density at 20 “C. A co-
efficient varying with density was intro-
duced. Calculations were within ±30
kcal per kg of experimental value. A
nomogram was prepared. Dymond and
Hildebrand (2011) described an appara-
tus for rapid determination of gas solu-
bility in liquids. Degassed solvent was
exposed to gas and undissolved gas
pressure used to calculate solubility.
Accuracy was better than 1%. Data
were given for 12 gases in cyclohexane
at 15 to 35 “C.
Hydrocarbons
R. W. King
Sun Oil Co., Marcus Hook, Pa.
Developments in analytical methods
for hydrocarbon analysis during the
past two years were evolutionary rather
than revolutionary. No new techniques
of broad import were introduced during
this period. The bulk of reports in the
literature deal primarily with applica-
tion of methods that are now fairly well
established. As might be expected,
instrumental techniques continued to
receive major emphasis.
Reports concerned with methods for
determination of carbon and hydrogen
in hydrocarbons have been confined
principally to the description of instru-
mentation that depends on attenuation
or absorption of either neutrons or ß-
rays emitted from radioactive sources.
Most of the instruments described are
intended for continuous determination
of the hydrogen content of hydrocarbon
streams. Pomierny et al. (1071) and
Silipetar (1311) both described 0-ray
equipment; Johannes and Jaeckel (621)
described a continuous method for
determination of per cent hydrogen that
depends upon measurement of attenua-
tion of neutrons generated by a pluton-
ium-beryllium source; accuracy of
0.15% hydrogen by weight is claimed.
Gardner and Roberts (451) reviewed
problems involved in calibration of ß-
ray methods and proposed a simple
model that has some advantages over
techniques commonly in use.
Liquid chromatographic methods were
accorded a fair share of attention. Dis-
placement techniques for analysis of
lower-boiling fractions were concerned
principally with descriptions of the
fluorescent indicator adsorption (FIA)
method. Kurchatkina et al. (761) de-
scribed preparation of fluorescent indica-
tors suitable for use in determining aro-
matic hydrocarbon content of light
petroleum products by liquid chromatog-
raphy; these can be considered Russian
counterparts of indicators originally
described by Criddle and LeTourneau
which are available commercially in the
United States. Kurchatkina (751) also
described an improved chromatographic
column for the FIA method that was
claimed to give results for total aro-
matics that agree within 0.7% with data
obtained by the sulfonation method.
Zhorov et al. (1571) used a fluorescent
indicator technique for gas oil fractions
in which diphenyl-1,3-butadiene was
used as the indicator. Hydrocarbon
eluents were used to distribute sample
down the adsorption column. The
indicator served to locate the position of
aromatic and olefinic components when
the system was illuminated by ultravio-
let radiation.
Several related but drastically modi-
fied methods were described for special
applications. Puerifoy et al. (1051)
developed a detector tube for rapid
determination of aromatic hydrocarbons
in gasoline. They used a silica gel pack-
ing impregnated with a 2,4,7-trinitro-
fluorenone solution containing methy-
lene blue. The blue color of the packing
changes to green in the presence of
aromatics owing to formation of molec-
ular complexes. The length of the
green zone can be related to the weight
per cent of aromatics by calibrating with
known samples. It was claimed that
results compared favorably with those
obtained by gas chromatography or the
conventional FIA method. Suatoni
(1431) described a method for determin-
ation of traces of aromatics in paraffins
by column chromatography over a mix-
ture of silica gel and Radelin phosphor
GS-115. When an adsorbed sample is
irradiated with short wavelength ul-
traviolet light, a dark band can be ob-
served at the top of the column. The
length of this dark zone can be related to
the volume per cent of aromatics by
calibration of the system with known
blends.
Applications of linear elution adsorp-
tion chromatography (LEAC) have
continued to grow. Data published
during the past several years demon-
strate that principles of linear elution
can be successfully extended to other
than hydrocarbon systems. Snyder
(1341,1351) described qualitative analy-
sis of petroleum and related materials
and reported some preliminary work
concerned with separation of aromatic
isomers. In three additional papers
(.1361-1381) he presented results of
studies of behavior of different adsor-
bents when used in the linear elution
mode. Snyder and Buell (1391) as-
sembled a comprehensive tabulation of
acid and base dissociation constants and
relative adsorptivities on alumina of the
various compound types which may be
present in petroleum and related mate-
rials. They suggested that these data
can form a basis for separation and
classification of petroleum nonhydro-
carbons by compound type using titra-
tion, ion exchange, or adsorption chro-
matography.
There were several reports that dealt
with application of conventional elution
techniques for analysis of high boiling
hydrocarbon mixtures. Pavlovschi
(1031) described chromatographic sepa-
ration of carbon black oils over activated
alumina. By using heptane, benzene,
and ethanol as successive eluents, oils
were fractionated into saturated hydro-
carbons, mononuclear aromatics and
thiophenes, dinuclear aromatics, tri-
nuclear aromatics, and polynuclear
aromatics plus heterocyclic oxygen and
nitrogen compounds. Separation was
followed using ultraviolet spectrometry
Results were claimed to be reproducible
to within ±5%.
Driatskaya and Zhmykhova (351)
used silica gel and activated alumina in
series for analysis of kerosine, gas oil,
and light lubricant fractions. They
claimed that the binary adsorbent sys-
tem is superior to silica gel alone. Car-
rying this idea several steps further,
Grinberg and Shved (491) used a column
composed of several sections, each
packed with an adsorbent of different
polarity. They reasoned that each
adsorbent selectively retains different
groups of hydrocarbons and estimated
the percentage of these different hydro-
carbon groups from the increase in
weight of the column sections.
Liebisch and Eckardt (801) found that
a column of activated alumina containing
adsorbed picric acid was effective for
separation of aromatic hydrocarbons.
Mononuclear aromatics were eluted
with heptane, dinuclear aromatics with
carbon tetrachloride, and trinuclear
aromatics with benzene.
Column electrophoresis was used by
Rothwell and Whitehead (1191) for
isolation of polycyclic aromatics from
complex hydrocarbon mixtures. The
method was based on migration of caf-
feine-aromatic hydrocarbon complexes
to the cathode in an electric field.
Sel’yanova (1381) reported use of porous
glass to separate mixtures of tetra-
chloroalkanes and hydrocarbons. He
suggested that separation is achieved by
a combination of molecular sieve action
and different rates of adsorption of the
components in a complex mixture.
Gel permeation chromatography was
applied to separation of hydrocarbons
by Edstrom and Petro (371) and by
Mair et al. (871). The former authors
determined elution behavior of more
than a hundred polycyclic aromatics.
Results suggest that gel permeation
separations are a complex function of
molecular size, shape, and polarity.
Mair et al. (871) found that gel permea-
tion can be used effectively to separate
paraffins from cycloparaffins and alkyl-
benzenes from cyclanobenzenes in the 19
to 21 carbon atom range.
Several applications of the Heinrich
and Grimes and Larson and Becker
molecular sieve methods for determina-
tion of n-paraffins in gasoline, kerosine,
and light gas oil have been reported.
Gurina et al. (531) described their ap-
plication of what is essentially the Hein-
rich and Grimes method, while Nes-
meyanova et al. (991) and Rennhak et al.
(1131) detailed their experience with
the Larson and Becker volumetric-
technique. Jaworski (611), on the other
hand, allowed n-paraffins to be selec-
tively adsorbed for solution by molec-
ular sieves, then cryoscopically deter-
mined amount of unadsorbed isoparaf-
fins. Cyclohexane was used both as a
diluent for adsorption and as a solvent
for cryoscopic determination.
Thin layer separation of hydrocarbons
was described by several authors.
Berthold (161) found that under suitable
conditions thin layer chromatography
will produce Rf values for aromatic
systems that are a direct measure of the
aromatic ring content of the molecule
and are independent of the type of ring
condensation. The method appears to
be applicable to both individual com-
pounds and complex mixtures. Kessler
and Mueller (671) described the use of
silica gel impregnated with picric acid
for thin layer separation of polynuclear
aromatics. They used a binary adsor-
bent plate, one half of which contained
impregnated gel, and one half of which
contained untreated silica gel. Initial
application of the sample was made to
the picric acid section, and the plate was
developed with petroleum ether. Rf
values of 21 polynuclear aromatics were
tabulated. Harvey and Halonen (541)
used silica gel impregnated with 2,4,7-
trinitrofluorenone to separate complex
cyclanoaromatics by thin layer methods.
Porous ethylvinylbenzene polymers
were used by Janak and Kubecova
(601) for tic separation of aromatic
hydrocarbons, heterocyclic compounds,
and phenols. Behavior of Porapak Q
was investigated most extensively.
Data obtained using five different de-
velopers and 46 model compounds are
given.
Physical property methods for hy-
drocarbon type analysis of viscous oils
and for rapid type analysis of lighter
fractions continue to be of some interest.
McAninch (841) studied the relation
between boiling point and density of
heavier hydrocarbons and their molec-
ular structure. He presented graphs
and equations which allow use of experi-
mentally determined boiling points and
densities for estimating carbon numbers
of Cu+ hydrocarbons and ring numbers
of aromatic or saturated hydrocarbon
concentrates in the same range of
molecular size.
Kurtz and Doolittle (771) reevaluated
parameters of the Kurtz-Lipkin molec-
ular volume equation for hydrocarbons.
The improved equation may be used to
calculate temperature coefficients of
density and the bulk modulus of pure
hydrocarbons and of petroleum oils
whose carbon-type composition and
molecular weight can be estimated. A
procedure for determining aromatic
hydrocarbon content of pyrolysis prod-
ucts from their refractive dispersion
and iodine number was proposed by
Aliev and Kushelevskaya (41). The
method incorporated a correction factor
to eliminate interference from conju-
gated diolefins. The authors claimed
that results compare favorably with
those obtained by conventional tech-
niques.
Gas chromatography continues to be
one of the most useful and versatile tools
available to the petroleum analyst. It
is now used extensively for detailed
analysis of petroleum fractions boiling
up to about 450 °F. Combinations of
gas chromatography with other separa-
tion methods such as distillation or
adsorption chromatography were cited
extensively. Primavesi et al. (1081) out-
lined features that should be specified in
describing every gas chromatographic
method, those that should be specified
under certain conditions, and those that
need not be specified under any condi-
tions. They also suggested a simple
method for testing linearity of a flame
ionization detector and a method for
measurement of incompletely separated
peaks.
Parameters that influence reproduci-
bility of response of flame ionization
detectors were studied in some detail by
Batt and Cruickshank (71). There are
a number of reports that described use of
relatively novel partitioning liquids or
solid adsorbents for separation of hy-
drocarbons. Alumina is becoming in-
creasingly popular for separation of both
hydrocarbon gases and higher boiling
materials. Hoffmann and Evans (571)
studied separation of hydrocarbons up
to C12 over alumina using a wide variety
of carrier gases. They reported that
molecular weight and structural types of
hydrocarbons amenable to gas chroma-
tography on alumina are strongly in-
fluenced by the carrier gas selected.
List el al. (831) successfully used
alumina to separate cis- and trans-iso-
VOL. 41, NO. 5, APRIL 1969 · 163 R
meric olefins. They found the cis form
is retarded relative to the trans con-
figuration. Hoffman (561) also used a
short column of silver nitrate-impreg-
nated alumina in a subtractive fashion
to remove olefins from a paraffin-olefin
mixture quantitatively. Paraffins were
then further separated using a conven-
tional alumina column. Hu and P'eng
(591) described the preparation and use
of firebrick coated with a thin layer of
alumina for separation of gaseous hydro-
carbon mixtures. The Firebrick was
impregnated with aluminum isoprop-
oxide in benzene, the alcoholate hydro-
lyzed in situ, and the adsorbent acti-
vated at 600 °C. Very rapid analyses
are possible.
Bellar and Sigsby (121) evaluated a
number of silica gels for use in analysis
of light hydrocarbons. Their work
indicated that Davison type 58 silica gel
is suitable for separation of hydrocar-
bons containing up to five carbon atoms.
They also studied modification of silica
gel with various polar and nonpolar
liquid phases.
Porous glass was used by Gnauck
(471) to separate low molecular weight
hydrocarbons at room temperature.
Modification of its properties by in-
corporation of low loadings of liquid
phases was also studied. Gas chromato-
graphic separation of C4 hydrocarbons
on graphitized carbon black was studied
by Kiselev and coworkers (691). Graph-
itized carbon black also was used by
Boikova and Shcherbakova (191) to
separate various isoparaffins and cyclo-
paraffins in the gasoline boiling range.
Lithium and sodium salts have also
been used for separation of mixtures of
high boiling hydrocarbons. Wolf et al.
(1551) loaded potassium nitrate or
sodium chloride crystals lightly with
a high boiling liquid and used this to
separate mixtures of Cn-Cis w-paraffins.
In this application the salt served mainly
as a support for the separating liquid.
Chortyk et al. (291) successfully sepa-
rated a number of polynuclear aromatic
hydrocarbons on a column of Chromo-
sorb P containing 20% of lithium chlo-
ride. They reported that in many cases
the separation was better than that
achieved with capillary columns. Lith-
ium chloride dissolved in Carbowax 400
was used by Bighi et al. (171) for separa-
tion of a number of gasoline boiling-
range hydrocarbons. The authors sug-
gested that addition of electrolytes to
polar phases provided an additional
parameter for adjusting elution order of
solutes.
Bendel et al. (141) used a solution of
silver borofluoride in ß, /3'-hydroxidi-
propionitrile on Chromosorb R to
separate all isomers of normal octenes,
normal hexynes, and hexadienes. The
use of “Fluhyzon” as a stationary
liquid phase for separation of high
boiling aromatics was described by
164 R · ANALYTICAL CHEMISTRY
Hildebrand and Leschner (551);
“Fluhyzon” is a commercial material
developed originally for separation of
«-paraffins. Stationary phases that are
extremely selective for aromatic hydro-
carbons have been described by several
investigators. Rogozinski and Kauf-
man (1181) reported that with a column
of 40% AT,Ar-bis(2-cyanoethyl)forma-
mide on Chromosorb P, n-hexadecane is
eluted before benzene at 160 °C. 2,4,6-
Trinitrophenetole was recommended by
Maczek and Phillips (851) for selective
separation of gasoline-range aromatics.
With this stationary phase, benzene
emerges between n-undecane and n-
dodecane, and m-xylene precedes p-
xylene. The authors suggested that
the mechanism is one which rejects
aliphatics rather than retains aromatics.
Medvedovskaya and Osadchaya (911)
used a stationary phase of dairy butter
to separate C*e-C8 aromatic hydrocarbons
from other hydrocarbons found in gaso-
lines. The butter was heat-treated at
200 °C for 2 hr, filtered, and depo sited
on the solid support from benzene solu-
tion.
Considerable attention was devoted to
studies of organoclays as stationary
phases for separation of aromatics.
Mortimer and Gent (961) described use
of modified Bentone 34 coated on celite
for the analysis of xylene, dichloroben-
zene, and cresol isomers. They re-
ported fairly comprehensive studies of
the effect of temperature and the amount
of modifying agent used. Vergnaud
et al. (1501) used Benton 34 modified
with silicone oil to separate isomers of
xylenes, triphenyls, and naphthalenes.
The modified Bentone was coated on
celite for xylene and naphthalene analy-
sis and on glass beads for triphenyl
separation. Columns were operated at
71 °C for xylenes, 180 °C for naphtha-
lene, and 200 °C for triphenyls.
Chabrova (261) reported complete
separation of a mixture of C8 aromatics
using a 60-40 mixture of Bentone 34 and
dinonyl phthalate coated on firebrick.
Winfrey and Ahlberg (1531) discussed
in detail the use of modified Bentone 34
for analysis of mixed 5° xylene streams
and for high purity xylene isomers.
Gupta and Kumar (511) reported
some applications of series arrangements
of modified Bentone columns and other
polar stationary phases for separation of
xylene isomers in straight-run naphtha
fractions. Best results were obtained
using a mixture of 5% Bentone 34 and
5% dinonyl phthalate on Chromosorb W
followed by 10% tricresyl phosphate on
Chromosorb P. Results for C8 aromatic
isomers obtained using this arrangement
agreed within ±3% with those obtained
by ultraviolet spectrometry. A com-
plete separation of cymene isomers was
reported by Rihani and Froment (1161).
They combined two b-meter 60-80 mesh
Chromosorb W columns in series. The
first was coated with 5% SE-30 silicone
plus 15% Bentone 34, and separated
meta and para isomers. The second
column was coated with 10% didecyl
phthalate plus 20% Bentone 34 and
separated ortho and meta isomers.
Karger and Hartkopf (651) successfully
separated mixtures of C10-C14 n-paraffins
at temperatures more than 200° below
their boiling points by using water as a
liquid phase. Helium presaturated with
water was used as the carrier gas and
detection was by flame ionization.
Considerable attention was devoted to
analysis of mixtures of hydrogen, non-
condensable gases, and light hydrocar-
bons by gas chromatography. Jones
(64I) reported analysis of hydrogen-rich
refinery streams using two Porapak Q
columns in series. The first was pro-
grammed from ambient temperature to
125 °C and the second was operated at
dry ice temperature. A mixture of
91.5% helium and 8.5% hydrogen was
used as carrier gas. Hydrogen, oxygen,
nitrogen, carbon monoxide, carbon
dioxide, hydrogen sulfide, ammonia,
water, and C1-C5 saturated hydrocar-
bons were successfully determined in
single samples containing as little as
0.1% of the minor components. Anal-
ysis was completed in slightly over 1 hr.
A Porapak Q column and a 5A Molec-
ular Sieve column connected in series
were used by Bennett (151) to analyze
mixtures containing oxygen, nitrogen,
methane, carbon dioxide, and nitrous
oxide. A length of copper tubing be-
tween columns permitted gases sepa-
rated on the first column to be eluted
and measured in a thermal conductivity
cell before they emerged from the second
and entered the same detector.
Cross (311) successfully used 80-100
mesh beads of an ethylvinyl polymer to
separate mixtures containing hydrogen,
air, carbon monoxide, carbon dioxide,
and Ci-C2 hydrocarbons. A parallel
column arrangement was reported by
Doran and Cross (341) for analysis of
mixtures containing oxygen, nitrogen,
carbon monoxide, carbon dioxide, and
light hydrocarbons. A stream splitter
was used to divert part of the sample
through a 5A Molecular Sieve column
and the remainder through dimethyl-
sulfolane and hexadecane columns ar-
ranged in series. Flow of carrier gas
was adjusted so that oxygen, nitrogen,
methane, and carbon monoxide from
the molecular sieve column passed
through the detector just before gases
from the other column emerged. Split
ratio was determined from the ethane
area ratio from the two columns.
Three columns connected in series
were successfully used by Afanas’ev (21)
for analysis of mixtures of hydrogen and
C1-C5 hydrocarbons. The first column
contained dibutyl phthalate on fire-
brick, the second silica gel, and the third
activated carbon. The columns were
maintained at 55, 22, and 150 °C, re-
spectively. Hydrogen was eluted from
the series arrangement with air, and the
columns were then disconnected and
eluted separately to determine indi-
vidual hydrocarbons.
Gas chromatographic determination
of «-paraffins in petroleum products
was reported by a number of authors.
Mortimer and Luke (971) described a
method suitable for distillates with boil-
ing points less than 900 °F. The «-
paraffins are adsorbed from sample in
the vapor phase by type 5A Molecular
Sieves. Materials to be separated are
deposited on the sieves which are con-
tained in a microsorption unit. The
adsorber is heated from 25 to 300 °C in
20 min and maintained there until non-
linear hydrocarbons are eluted. Sieves
containing adsorbed «-paraffins are then
removed and decomposed with hydrogen
fluoride; «-paraffins are extracted from
the neutralized aqueous HF solution
with isooctane. An aliquot of the
isooctane solution is analyzed by tem-
perature-programmed gas chromatog-
raphy using a lightly loaded silicone
gum rubber column. The percentage
of individual «-paraffins is related to the
sample originally taken by an internal
standard.
Brunnock (221) described a combina-
tion of extractive crystallization and
molecular sieve adsorption, followed by
sieve decomposition and gas chromatog-
raphy of recovered «-paraffins. The
method is applicable to extremely heavy
distillates.
Sojak and Hybl (1401) published a
useful review of application of molecular
sieves in gas chromatography. Of
particular interest is a section which
described properties of various types of
synthetic zeolites and suitable applica-
tions for each, including Linde molecular
sieves, calcium-12 zeolites, East German
Zeosorbs, and Czechoslovakian Calsit-5.
Blytas and Peterson (181) modified
the method of Eggertsen and Groen-
nings to allow determination of «-
paraffins in kerosine fractions. The
original method utilized a partition
column and molecular sieve column
in series. Modifications involved ad-
sorption of «-paraffins on molecular
sieves at 350 °C rather than at 200 °C
and injection of sample downstream
rather than upstream from the partition
column.
Knight (711) described a procedure
for determination of «-paraffins in
kerosine that involved addition of an
internal standard, adsorption of «-paraf-
fins in liquid phase on 5A Molecular
Sieves, decomposition of sieves, and
recovery of «-paraffins, followed by gas
chromatography on a 5% SE-30 Chro-
mosorb W column.
Reports of applications of gas chro-
matography to relatively high boiling
hydrocarbon mixtures are limited. The
basic problem in using gas chromatog-
raphy for analysis of such materials
lies in their complexity, combined with
the difficulty of assigning peak identities
even when reasonable separation is
accomplished. Dembovskaya (321)
described the use of gas chromatog-
raphy to separate narrow-boiling frac-
tions of kerosines and gas oils into paraf-
fins and mono- and dinuclear aromatics.
Perkins et al. (1041) suggested that it
should be possible to calculate the con-
tribution of each fraction to the com-
position of a blend of petroleum prod-
ucts with a gas chromatographic elution
curve even if the separation were poor.
They demonstrated that binary mix-
tures of complex fractions can be ana-
lyzed with an error of less than 10%.
Maher (861) used gas chromatography
in combination with reagents that
successively removed olefins, aromatics,
and «-paraffins to analyze a high boiling
neutral oil sample in some detail.
Reports of applications of gas chro-
matography to special problems ap-
peared with some frequency. Deter-
mination of small amounts of low boil-
ing hydrocarbons in solvents was re-
ported by Alekseeva and coworkers
(31) and by Chirikova et al. (281).
The former described methods for de-
termination of C4 and C5 hydrocarbons
in dimethylformamide, acrylonitrile,
and gasoline. The method involves
absorption of sample on firebrick in a
special absorber. Desired hydrocarbons
are then desorbed by emitting carrier
gas and separated by passage over a
partition column. Either an internal
standard or absolute calibration is used
to quantify the results.
Chirikova et al. (281) reported use of
gas chromatography for determination
of C4 hydrocarbons in methylamine
using two columns in series. The first
column, containing firebrick impreg-
nated with a 10% solution of sodium
iodide in diethanolamine, retains meth-
ylamine, while the second column
of 15% diethylene glycol butyrate on
firebrick separates the hydrocarbons.
Chovin et al. (SOI) used two columns
in series with a hot-wire detector be-
tween to determine aromatic hydrocar-
bons in turpentine oil, hydrocarbon
solvents, and complex solvent mixtures.
The first column contained 7.5%
Apiezon L on Chromosorb W and sepa-
rated the sample into fractions con-
taining components of similar boiling
point. A control valve located after
the detector allowed selected fractions
to be diverted to a second column
packed with 35% of tetrakis-(0-2-
cyanoethyljpentaerythritol on Chro-
mosorb W, which separated the frac-
tions into individual compounds that
were measured by a second detector.
The determination of benzene in varnish
thinners was described by Scrima
(1261). The sample of thinner was
mixed with water and steam-distilled,
and the hydrocarbon layer was washed
with sodium chloride solution. An
aliquot was then gas chromatographed
at 90 °C on a 2-m column of Chromosorb
containing 20% of polyester succi-
nate. Ethanol, benzene, toluene, and
xylenes were separated.
Packed-column gas chromatography
is still used extensively for trace analyses,
largely because such columns will ac-
cept high sample loadings. Klett and
Korous (701) described determination
of traces of hydrocarbon impurities in
high purity chemicals derived from
petroleum. Down to 0.5 ppm of im-
purities can be estimated in cyclohexane,
styrene, or propylene. Successful use of
gas chromatography in these applica-
tions is dependent upon selection of a
stationary phase that retards the major
constituents without significantly affect-
ing elution time of the impurities.
Determination of impurities in pro-
pane-propylene streams was reported
by Tsifrinovich and Lulova (1471) who
used a 12-m X 6-m id column of 20%
2,4-dimethylsulfolane on firebrick and
ionization detection. Zocchi (1591) used
a cold trap concentration technique
followed by chromatography over
Carbowax 20M on 40-60 mesh alumina
to determine hydrocarbon impurities
in methane in the part per billion range.
Concentrating traps were filled with
the same material as the chromato-
graphic column and immersed in liquid
oxygen.
Rennhak et al. (1111) determined
small amounts of acetylenes and 1,2-
dienes present in the C2-C4 olefins
formed by the cracking of petroleum.
They used a 12-m column of 20%
dimethylsulfoxide on firebrick. Al-
though a thermal conductivity detector
would ordinarily suffice, an argon ioniza-
tion detector was used for very low
concentrations. In this case, a cooling
trap was placed between the column
and detector to prevent contamination
of the latter by dimethylsulfoxide
vapor. Porous polymers were success-
fully used by Zlatkis and Kaufman
(1581) to determine trace impurities in
ethylene. Gel Q and Amberlite XAD-2
were equally effective in resolving
nitrogen, methane, carbon dioxide, and
ethane from ethylene.
Capillary chromatography is still
being utilized extensively for detailed
analysis of gasolines and naphthas.
Most methods reported are limited to
hydrocarbons containing eight or fewer
carbon atoms. However, a few labora-
tories have achieved a measure of suc-
cess in extending capillary methods to
full range gasolines. There are several
reports that deal with analysis of
gaseous hydrocarbons and special mix-
tures of aromatics using capillary meth-
ods.
Leveque (791) described determina-
VOL. 41, NO. 5, APRIL 1969 · 165 R
tion of Cy-Ce hydrocarbons in naphthas
and reformates using a stainless steel
capillary coated with a binary stationary
phase containing 4.35 parts of w-hexade-
cane and 1 part of Fluorolube oil LG-
160. An electronic integrator and
computer were incorporated into the
analytical system to provide data in
the shortest time possible. Sample
composition, research octane number,
and specific gravity were computed
from chromatographic output. These
results permitted predictions regarding
ease of reforming a given naphtha to
obtain a reformate with improved
octane number. Bryanskaya et al.
(231) reported use of squalene-coated
capillaries to determine 37 of the possi-
ble 38 hydrocarbons in straight-run
gasoline fractions boiling up to 230 °F.
They provided data on gasolines dis-
tilled from five Soviet crudes.
Willis and Engelbrecht (1521) de-
scribed a capillary method for separa-
tion of Ci-Cio paraffins and aromatics
through naphthalene using a di-w-
decyl phthalate capillary. The column
was programmed at 4° per min up to
140 °C. d’Aubigne and Guiochon (51)
studied composition of distillates from
13 crudes using a squalane-coated
capillary column programmed from 25
to 110 °C at 12 to 30 °C per hr. The
system incorporated a flame ionization
director and electronic integrator. Con-
centrations of 85 hydrocarbons were
reported, including most of those that
elute before n-octane.
Sanders and Maynard (1211) de-
scribed analysis of full range motor
gasolines for individual Cs-Ci2 hydro-
carbons. They used a 200-ft squalane
capillary and flame ionization detector.
Both column temperature and column
inlet pressure were programmed to
provide optimum resolution. Approxi-
mately 240 chromatographic peaks
were observed, of which 180 (accounting
for 233 hydrocarbons) were specifically
identified.
Capillary-column analysis of the 175
to 350 °F aromatic portion of petroleum
was discussed by Schwartz et al. (1251).
Selectivity of a number of liquid phases
coated on 100- or 200-ft X 0.01-in. i.d.
stainless steel capillaries was investi-
gated. A column coated with 1.5%
squalane plus 4% dipropyl tetrachloro-
phthalate produced a separation of 21
components in 45 min.
Vitt et al. (1511) found it was
not possible to separate all C8-Ci2
dialkylbenzenes in a single run on
capillaries coated with Apiezon L,
polyoxypropylene glycol, or squalane.
However, such mixtures could be satis-
factorily analyzed either by successive
runs on two columns with different
stationary phases or on one column at
two different temperatures.
Copper capillaries coated with a 1:1
mixture of lanolin-Bentone 34 were
166 R · ANALYTICAL CHEMISTRY
used by Dimov and Shopov (SSI) to
separate mixtures of C6-C9 aromatics.
Use of capillary columns coated with
a hydrophobic silica adsorbent for
separation of hydrocarbons was sug-
gested by Schwartz et al. (1241).
The capillary chromatography of low
boiling hydrocarbons was studied by
Miyake and Mitooka (941). They
found that low temperature operation
was necessary for satisfactory separa-
tion of C1-C4 paraffins, monoolefins,
diolefins, acetylenes, and cycloparaffins.
They reported that mixtures of dibutyl
maleate and /3,/3'-oxydipropionitrile are
useful stationary phases when columns
are operated at -30 °C.
Bryanskaya et al. (241) described
synthetic methods for preparation of
calibration mixtures of Ce-Cs iso- and
w-alkanes. These mixtures should be
useful as secondary reference standards
for calibration of capillary columns
intended for use in analysis of gasolines
and naphthas.
Although the problem of peak identi-
fication is still an important one, few
papers that deal with trapping of gas
chromatographic effluents have ap-
peared in the past several years. One
interesting contribution by Witte and
Dissinger (1541) gave details of con-
struction and use of a device consisting
of a glass U-tube 2.5-mm i.d. X 180 mm
long which contained about 20 µ . of a
solvent suitable for subsequent spectro-
metric examination. They claimed that
rapid cooling of the tube in liquid argon
converted the solvent to a microcrystal-
line form which did not hinder passage
of carrier gas but served as a filter to
trap even the most volatile hydrocar-
bons.
A method for identifying individual
components in unknown mixtures by
continuously determining carbon-hy-
drogen ratios of fractions leaving a gas
chromatograph was described by Franc
and Pour (411). They used a special
combustion chamber to burn effluents
to carbon dioxide and water and con-
vert water to hydrogen. Reactor
effluent then passed through a thermal
conductivity detector to record com-
bined amounts of carbon dioxide and
hydrogen, through an absorbent to
remove carbon dioxide, then through a
second detector to record hydrogen.
Papers describing new developments
or novel applications in temperature-
programmed gas chromatography are
few. Geiss et al. (461) reported use of a
temperature-programmed packed col-
umn of alumina to achieve complete
separation of all possible hydrocarbons
up to and including C4 in off-gases from
cracking operations. They found only
Fluka-Camag 507-C neutral or Camag
5016-A basic alumina would produce
the desired separation. Other aluminas
or graphized carbon black were not
suitable.
Behling et al. (101) described a two-
stage temperature-programmed capil-
lary system which they used for analysis
of gasoline. Sample passes first through
a DC 550 silicone oil capillary. A
portion of effluent is then diverted to a
flame ionization detector and the rest
passed to a column coated with poly-
oxypropylene glycol R, then to a second
detector. The two columns are tem-
perature-programmed independently,
the first from 30 to 175 °C, and the
second from 20 to 150 °C. The authors
claimed that it was possible to identify
and determine nearly all the hydrocar-
bons in a full boiling range gasoline.
Temperature-programmed gas-solid
chromatography on inorganic salts such
as lithium chloride or calcium chloride
was used by Sauerland and Zander
(1281) for separation and characteriza-
tion of aromatic hydrocarbons in coal
tar.
Combinations of gas chromatography
and mass spectrometry are increasingly
common for analysis of complex hy-
drocarbon mixtures. Studier and
Hayatsu (1421) described instrumenta-
tion that utilizes a capillary chromato-
graph followed by a time-of-flight mass
spectrometer. Utility of the system
was demonstrated by following the
iron-catalyzed reaction of a gaseous
mixture of carbon monoxide and deu-
terium. A chromatogram was presented
for the reaction product, and perdeutero
hydrocarbon assignments were tabu-
lated for 102 peaks.
Teeter et al. (1441) reported analysis
of 1-olefins using a gas chromatograph-
mass spectrometer combination. A
mixture of Cu-Cu 1-olefins was sepa-
rated by chromatography over a 50-ft
X l/i-in. packed column containing
15% of Ucon LB-550X, 0.2% of
Alkaterge T and 0.2% sorbitan mono-
oleate on 60-80 mesh firebrick. The
column was temperature-programmed
from 100 to 185 °C at 1° per min, then
from 185 to 225 °C at 0.5° per min.
Effluent was passed either directly, or
through a catalytic hydrogenator, to
the mass spectrometer. Methods were
described for interpreting results and
determining individual components.
Aczel and Johnson (II) used gas
chromatographic distillation to produce
fractions which are then examined by
high resolution mass spectrometry.
The method is based on parent peak
analysis at low ionizing voltages. Pre-
cise masses are determined from a chart
by using carbon-12 to carbon-14 dis-
tances as internal mass-measuring stan-
dards. This technique yields component
types and carbon number distributions
as a function of boiling range for as
many as 50 homologous series containing
carbon, hydrogen, nitrogen, oxygen, and
sulfur atoms.
Combinations of gas chromatography
with other chemical or physical sepa-
ration methods, or with in-line hydro-
genation or dehydrogenation proved
useful for analysis of especially difficult
types of samples and for characteriza-
tion of relatively pure hydrocarbons and
nonhydrocarbons. Analysis of Cg-Cio
alkylbenzenes and aromatic olefins in
gasolines produced by naphtha pyrolysis
was described by Nakamura et al. (981).
One portion of sample was partially
hydrogenated with Raney nickel and
aromatics were separated and analyzed
by gas chromatography. Olefins in a
second aliquot were polymerized by
reaction with aluminum chloride and
removed by steam distillation, and
aromatics were determined as above.
Content of aromatic compounds and
olefins in the original sample was then
estimated from differences between the
two gas chromatograms. In all, 43
homologs and isomers of Ce-Cio aro-
matics and seven aromatic olefins were
determined.
Thompson et al. (1451) successfully
characterized many nonhydrocarbon
constituents of petroleum by microhy-
drogenation. They used a microreactor
to hydrogenate extremely small frac-
tions condensed from effluent of a gas
chromatographic column. When such
trapped fractions are hydrogenated,
heteroatoms are quantitatively removed
from molecules, leaving paraffins and/or
cycloparaffins with unaltered structures
which can be identified by rechroma-
tography. Their identification leads to
identification of their precursors. The
method was successfully applied to
oxygen-, nitrogen-, halogen-, and metal-
containing compounds.
Fluorescence indicator adsorption
combined with gas chromatography was
used by Leont’eva et al. (781) to deter-
mine concentrations of individual Cs-Cs
hydrocarbons in catalytic gasoline.
Retention volumes and relative amounts
of 70 components of gasolines examined
were reported. Gupta et al. (501) used
adsorption chromatography followed
by gas chromatography to estimate
concentration of naphthalenes and meth-
ylnaphthalenes in a kerosine fraction.
Gas chromatography combined with
fluorescence and phosphorescence spec-'
trometry was used by Drushel and
Sommers (361) to analyze petroleum
fractions rich in nonhydrocarbons. Yew
and Mair (1561) used a combination
of azeotropic distillation, nuclear mag-
netic resonance and ultraviolet spec-
trometry, gas chromatography, and
mass spectrometry to identify 29 com-
pounds in a 500 to 520 °F dinuclear
aromatic fraction of petroleum. Com-
pounds reported included eight C13 and
seven C14 alkylnaphthalenes, five Ci4
and four Ci5 alkylbiphenyls, four di-
benzofurans, and fluorene.
A number of reports concerned prin-
cipally with descriptions of specialized
or novel apparatus for the analysis of
petroleum products appeared in the
literature. The majority of these
employ some form of gas chromatog-
raphy and most are directed toward
applications involving continuous or
semicontinuous stream analysis. Green
et al. (481) described a semiautomatic
gas chromatographic unit which can be
used for the hydrocarbon-type analysis
of gasolines and naphthas. Krylov
(7/7) gave details of a high vacuum
ionization detector for gas chromatog-
raphy which is based on ionization of
sample gas by slow electrons. Sensi-
tivity data were given for several com-
mon gases including methane, ethane,
ethylene, propylene, and butane.
A process chromatograph designed to
provide optimum separation of mix-
tures containing predominantly C4 hy-
drocarbons but containing a condensable
fraction of Cs-Ce hydrocarbons was
described by Bossart and Zinn (201).
Fenske (391) gave details of an appara-
tus capable of producing certain hy-
drocarbon-type analyses on a semi-
continuous basis. The apparatus can
be used as a stream analyzer in a great
many manufacturing and refinery opera-
tions.
A novel chemical process stream
composition transducer that utilizes
gas chromatographic principles was
described by Carter (251). A process
chromatograph designed especially for
use with liquids containing nonvolatile
components was reported by Sanford
and Calhoun (1221).
Putscher et al. (1101) gave details of
a rapid response gas chromatograph
designed specifically for determination
of traces of hydrocarbons in compressed
gas supplies. The chromatogram was
displayed on a long-persistence cathode
ray tube. The unit samples, analyzes,
and displays in less than 30 sec and is
capable of detecting 0.05 ppm of high
molecular weight condensable hydro-
carbons in air and 0.5 ppm in helium.
A novel stream analyzer based on
cool-flame oxidation was detailed in
recent patent literature (7/97). In-
strumentation is arranged to immobi-
lize the flame front relative to the inlet
end of a combustion chamber regardless
of changes in sample composition. As a
consequence, changes in combustion
pressure, sample flow rate, or induction
zone temperature required to achieve
immobilization are related to changes
in sample composition. The apparatus
should be particularly suitable for con-
tinuous stream analysis in a petroleum
refinery or chemical plant.
Spectrometric methods are still im-
portant for analysis of petroleum hy-
drocarbons. A critical survey of the
more important infrared techniques for
qualitative and quantitative structural-
type analysis of hydrocarbon mixtures
was reported by Serfas and Geppert
(1291).
An infrared method for determination
of degree of branching in alkanes was
described by Rericha and Horak (1131),
who developed a simple procedure to
correct overlap empirically in the in-
frared absorption bands of antisym-
metrical stretching vibrations of carbon-
hydrogen bonds in methyl and meth-
ylene groups. The ratio of corrected
absorbances was correlated with the
ratio of the number of methyl and
methylene groups in the alkane mole-
cule. A similar method based on mea-
surements of infrared spectra of n-
paraffins was suggested by Ch’ien and
Tung (271).
Korcek et al. (731) used infrared
spectrometry to determine aromatic
carbon content of heavy oils. Results
obtained spectrometrically agreed well
with similar data obtained using physi-
cal property correlations.
Infrared was used by Moniwa and
Honma (951) to examine a number of
turbine oils containing from 8 to 29%
aromatic hydrocarbons. They found
that absorbance at 1600 or 810 cm-1
was suitable for determination of con-
centration of aromatic hydrocarbons in
oils. They further discovered a correla-
tion between aromatic content and
oxidation stability of oils examined.
Lindval and Velikanov (811) used
infrared spectrometry for determination
of small concentrations of acetylene in
ethylene by measuring the absorbance
band due to acetylene at 730 cm-1.
They were also able to determine as
little as 0.004 vol % of acetylene.
Rochkind (1171) described a system
for infrared analysis that uses a con-
densed-phase sampling technique em-
ploying cryogenic equipment. Use of
the method in air pollution analyses,
airborne atmospheric research, geo-
chemistry, and general laboratory anal-
yses is discussed.
A high pressure absorption cell that
permits recording of well resolved in-
frared spectra was described by Sher-
man (1301). The cell provides a resolu-
tion of 1 cm-1 in the near infrared and
slightly poorer resolution in the 400 to
50,000 cm-1 region. Construction and
use of a special cell for rapid infrared
analysis of multicomponent mixtures
were described by Beckering et al. (91).
Ultraviolet spectrometry w*as used by
Balint (61) to determine concentrations
of mono-, di-, and trinuclear aromatic
hydrocarbons in petroleum distillates
boiling above 350 °F. After determina-
tion of average molecular weight of the
sample, extinction coefficients at 2000,
2300, and 2600 A were measured.
Prior calibration using aromatics iso-
lated by chromatography vras necessary.
An accuracy of ±2% was claimed.
Estep et al. (381) determined alkyl-
naphthalenes in neutral oils derived
from low temperature coal tars by elu-
tion chromatography and subsequent
VOL. 41, NO. 5, APRIL 1969 · 167 R
 analysis of the fractions by ultraviolet
spectrometry. They claimed that in-
dividual classes of Cio-Ci8 naphthalenes
could be determined by the method,
although none higher than C15 was
found in the neutral oils examined.
An ultraviolet method for deter-
mination of naphthalene, phenanthrene,
and anthracene rings in petroleum
products was suggested by Siryuk and
Zimina (1321). Absorption bands at
225 to 230, 255, and 375 µ are used
for naphthalenes, phenanthrenenes, and
anthracenes, respectively. Mononu-
clear aromatics do not interfere with
the determination and their concentra-
tion can be calculated as the difference
between total aromatics determined by
infrared and amounts of condensed
ring aromatics determined by the ul-
traviolet method.
A detailed study of use of ultraviolet
spectrometry for determination of small
quantities of aromatics in white oils
was reported by Belova et al. (131).
Przybylski (1091) described a method
for structural-group analysis of petro-
leum fractions using a combination of
ultraviolet and infrared spectrometry.
Concentrations of mono- and dinuclear
aromatics are determined by ultraviolet,
and proportions of methyl and meth-
ylene groups and of tertiary and
quaternary carbon atoms in the paraf-
fin-naphthene portion of the oil are
determined by infrared spectrometry.
Luminescence and phosphorescence
spectrometry show' promise for analysis
of aromatic types and certain nonhydro-
carbons in petroleum fractions. Smith
(1331) demonstrated that most aromatic
types of interest can be analyzed by
fluorescence and phosphorescence meth-
ods and that the incremental excitation
technique allows one to obtain spectra
of each aromatic type which are com-
pletely independent of the other types
present. Usefulness of fluorescence and
phosphorescence techniques was em-
phasized by Parker (1011) and illus-
trated by references to published mea-
surements. Although microwave spec-
trometry is not yet a tool of general
utility, its potential for hydrocarbon
analysis was emphasized in a compre-
hensive review7 by Millen (931).
High resolution nuclear magnetic
resonance spectrometry was used by
Stehling and Bartz (H1I) for deter-
mination of the molecular structure of
olefins. They presented tables cor-
relating structure with chemical shift,
spin-coupling constant, and the char-
acteristic spectral pattern at 60 Me.
Data presented were used to interpret
structures of some oligomers of mono-
olefins and high polymers of diolefins.
Nuclear magnetic resonance was
successfully applied by Flanagan and
Smith (401) to determination of olefinic
impurities, particularly 1,1- and 1,2-
disub stituted ethylenes, in 1-olefins.
168 R · ANALYTICAL CHEMISTRY
Samples containing compounds having
a wide range of molecular weights can
be analyzed without preliminary sepa-
ration.
Louis (831) used nuclear magnetic
resonance for both qualitative and
quantitative analysis of gasolines. He
concluded from evaluation of nuclear
magnetic resonance spectra for 38
gasolines that hydrogen concentration
as measured by nuclear magnetic
resonance is characteristic for a par-
ticular gasoline; that regular gasolines
have lower aromatic and higher paraf-
fin content than high octane gasolines,
and that gasoline quality depends upon
relative concentrations of individual
components as determined from char-
acteristic nuclear magnetic resonance
spectral patterns.
Absorption mode carbon-13 nmr
spectrometry used by Knight (721)
to characterize aromatic fractions from
petroleum. The method permits direct
determination of relative amounts of
carbon in aromatic rings, in unsub-
stituted sites in aromatic rings, and in
saturated groups using carbon-13 nu-
clear magnetic resonance spectra and
total carbon content obtained by com-
bustion. The fraction can be further
characterized if analytical data for the
weight per cent of carbon, hydrogen,
and sulfur and the molecular weight
are obtained. Used in conjunction with
hydrogen nuclear magnetic resonance
spectral data, the method was purported
to give excellent characterization in
terms of molecular structure.
Oelert (1001) used a combination of
nuclear magnetic resonance, infrared
spectrometry, and elemental analysis
for compound-type and structural-
group analysis of mineral oils. Van-
Meurs (921) recorded nuclear magnetic
resonance spectra of a number of 1,3-
and 1,4-di- and 1,3,5-trisubstituted
benzenes and calculated nmr substituent
constants.
Khmel’nitskii el al. (681) described a
group-type mass spectrometer method
for application to gasolines produced by
hydrocracking of heavy distillates. The
method is applicable to gasolines in the
following range of composition: n-
paraffins, 0.7 to 8.8 mol %; isoparaffins,
23.5 to 24.5; monocycloparaffins, 31.1
to 39.2; dicycloparaffins, 3.3 to 8.8;
alkylbenzenes, 15.4 to 27.4; and tetra-
lins plus indans, 4.9 to 12.4.
Martin (881) evaluated mass spec-
trometer methods for hydrocarbon-type
analysis of gasolines by running pure
samples of 15 typical C8-Ci2 alkanes
with cyclopentane and with four alkyl-
cyclohexanes.
High resolution mass spectrometry
was used by Gallegos et al. (441) for
analysis of high boiling petroleum frac-
tions without preliminary separation of
aromatic and saturated hydrocarbon
portions. The procedure described
determines 19 components, including
seven saturated hydrocarbon paraffins
and cycloparaffins, nine aromatic hy-
drocarbons containing from one to four
rings, and three aromatic sulfur com-
pound types.
Johnson and Aczel (631) employed
high resolution mass spectrometry at
low ionizing voltages to analyze complex
mixtures of aromatic hydrocarbons in
the gas oil boiling range. A molecular
ion method was applied by Polyakova
et al. (1061) for analysis of aromatic
hydrocarbons present in petroleum
fractions of 400 to 850 °F boiling range.
Gallegos (431) reported mass spectral
data, including metastable transitions
and appearance potentials, for a sub-
stantial number of polyphenyls.
Howard (581) developed a computerized
procedure for editing data from a
mass spectrometer digitizer capable of
greater certainty of mass number identi-
fication than previous methods. A
computer procedure for deriving meta-
stable ion transitions in the mass spectra
of hydrocarbons was reported by Rhodes
et al. (1151).
Tunnicliff et al. (1481) published
ordered exact mass and abundance
tables for mass spectrometry. One
mass-ordered table covers the 1 to 600
mass range and contains selected com-
binations of carbon, hydrogen, oxygen,
and nitrogen. A second table, which
covers the 1 to 400 mass range, con-
tains selected combinations of the same
four elements plus halogens, sulfur, phos-
phorus, silicon, boron, gallium, iron, tin,
and aluminum.
A limited number of chemical meth-
ods for analysis of hydrocarbons ap-
peared in recent literature. As is
usually the case, most of these are
directed to analysis of olefins or certain
aromatic species. Marxmeier et al.
(891) determined conjugated dienes and
monoenes in mixtures of hydrocarbons
by measurement of intensity of color
obtained by coupling them with ti-
trazotized p-phenylenediamine in the
form of its boron fluoride salt.
Reaction with maleic anhydride in
toluene at 100° was used by Ryasnyan-
skaya et al. (1201) to determine con-
centration of conjugated diene hydro-
carbons in olefin fractions from paraffin
cracking, and in propylene dimer and
trimer fractions. Best results were
obtained when the reaction continued
for 15 hr in the presence of a small
quantity of iodine.
Belcher and Fleet (111) found that
hindered olefins which do not undergo
normal addition reactions with elec-
trophilic reagents will react with the
nucleophilic reagent morpholine to form
a tertiary amine. They proposed a
method based on this reaction for deter-
mination of such hindered olefins.
Reuter (1141) described an improved
apparatus for quantitative hydrogena-
tion of 0.5- to 5.0-mg samples of organic
compounds containing olefinic double
bonds. Sedlak (1271) also developed a
simplified catalytic hydrogenation ap-
paratus for application to petroleum
products. It was claimed that the
method is often superior to bromination
in accuracy and can be used to deter-
mine as little as 0.05 meq of unsatura-
tion per g of sample.
Brown (211) described another novel
microhydrogenation method in which
hydrogen was generated from sodium
borohydride. The catalyst was pre-
pared directly in the reactor flask by the
action of sodium borohydride upon
chloroplatinic acid in isopropanol in
the presence of a high surface area
carbon. Analyses in triplicate generally
required only 30 to 60 min, including
catalyst preparation.
Fritz and Wood (421) determined
olefinic unsaturation in simple olefins
by addition of sample to acetic
acid containing 10% water, followed
by spectrophotometric titration of this
solution with bromine. They also
proposed a method suitable for most
unsaturated organic compounds which
involves adding a sample to a solution of
bromine and hydrobromic acid in acetic
acid, recording absorbance as a function
of time, then using Beer’s law to cal-
culate bromine consumed.
Patek (1021) determined styrene by
reaction with bromine in glacial acetic
acid. Karpov and Bystrova (661) de-
termined styrene or indene by reaction
with excess iodine trichloride in ethanol
and backtitration of excess iodine with
sodium thiosulfate. ASTM Method
D 1492 (coulometric determination of
unsaturation using electrolytically gene-
rated bromine) was modified by Baud-
isch and coworkers (81) to allow its
application to compounds that consume
more than 150 g of bromine per 100 g
of sample. Details of construction and
operation of the apparatus were given.
Maslennikova and Muzychenko (901)
described construction and operation of
instrumentation for coulometric de-
termination of low bromine numbers.
Hanna and Siggia (531) studied the
relationship between rate of addition
of bromine to unsaturated compounds
and dielectric constant of the solvent.
They demonstrated that, by considering
the substituent constants of the Ham-
mett relationship, it is possible to select
a solvent that will provide the most
efficient bromination of variously sub-
stituted compounds.
A procedure for determination of
xylene in air in the presence of benzene
and toluene was proposed by Trzesz-
czynski and Luczak (1461). The
method is based on colorimetric deter-
mination of nitration products of xylene
in acetone-benzene mixtures. Five
micrograms of xylene in 200 ml of air
can be detected in the presence of a
10-fold excess of benzene or a fivefold
excess of toluene.
Metals in Oils
. A. Braier
Gulf Research and Development Co.,
Pittsburgh, Pa.
Nuclear Methods. Fanning and
Bruce (11J) determined per cent
amounts of aluminum in a flowing
hydrocarbon stream. The method
is based on attenuation by aluminum
of soft X-rays from an iron-55 source.
Neutron activation analysis was used
by Jester and Klaus (22J) to determine
traces of aluminum, bromine, chlorine,
cobalt, copper, manganese, mercury,
sodium, and sulfur in high purity lubri-
cants.
A rapid but nonspecific procedure to
determine barium in additives and
lubricants was developed (14J), based
on intensity of scattering of beta par-
ticles from a KHiCi strontium-90 and
yttrium-90 source. Fast neutron activa-
tion associated with gamma-ray spec-
trometry was used (8J) to determine
silicon in mineral oils with a detection
limit of 6 ppm if nuclear reactor neu-
trons are used and vanadium is absent.
Atomic Absorption Spectrometry.
High results in determination of lead
in gasolines using a total consumption
burner were brought to normal by
diluting the sample with a 1:1
acetone-isooctane mixture rather than
with isooctane alone (64J). Zinc in
lubricant oils was determined by atomic
absorption spectrometry (20J) using a
propane-air flame and diluting the
sample with isobutylmethylketone.
Accuracies are comparable to those
obtained by ashing with a titrimetric or
polarographic finish.
Kerber (26J) established a technique
for direct analysis of nickel in catalytic
cracking feedstocks with a sensitivity
of 30 ppm and a precision of ±0.05
ppm. Vanadium was determined in gas
oils with a nitrous oxide-acetylene
flame and a high intensity hollow
cathode lamp (5J) with a detection
limit of 0.05 ppm. Bowman and Willis
(2J) studied the application of nitrous
oxide-acetylene flame to chemical anal-
ysis, including determination of vana-
dium in fuel oils with a limit of detection
of 1 ppm. Light elements (lithium,
sodium, potassium, aluminum, and
silicon) were extracted from greases and
fuel oils by different organic solvent-
hydrochloric acid mixtures and deter-
mined by atomic absorption using
appropriate flames (25J). Determina-
tion of wear metals in lubricating oils
by atomic absorption was reported by
Means and Ratcliff (87J). Separation
of volatile metal compounds by gas
chromatography and their specific de-
termination by atomic absorption spec-
trometry with special application to lead
alkyls in gasolines were reported (27J).
Finally, a procedure was described by
Slavin and Slavin (54J) for fully auto-
matic analysis of nine wear metals in
used aircraft lubricating oils. About
100 samples can be analyzed in 8 hr
with a precision of ± 10% and limits of
detection ranging from 0.01 to 1 ppm.
X-Ray Analysis. A rapid X-ray
emission spectrometric determina-
tion of elements present in trace
amounts in diesel engine lubricating
oils was established (15J). With this
technique, lead, tin, iron, copper, and
chromium have been determined at
concentrations under 100 ppm. Vajta
and Moser (63J) investigated lead in
gasolines and mineral oils by X-ray
fluorescence spectrography, reporting
that hydrocarbon makeup of sample
affects results.
An X-ray fluorescence technique was
used by Johnson (23J) to determine
zinc, phosphorus, and sulfur in oil
additive decomposition films on bear-
ings. Louis (S2J) used X-ray fluores-
cence to determine several metallic and
nonmetallic impurities in used motor
oils. Samples are made homogeneous
by ashing and dissolving the ash in a
borax melt. An X-ray fluorescence
technique was described (18J) to de-
termine from 0.007 to 0.24% of zinc in
greases. Sample is dissolved in a 1%
solution of dithizone in chloroform from
which an aliquot is deposited on a
filter paper, dried, and examined. A
simultaneous X-ray fluorescence de-
termination of calcium (0.02 to 0.12%)
and barium (0.04 to 0.32%) in lubri-
cating oils was described (16J) in which
the presence of sulfur significantly
affected results. From 0.1 to 0.8% of
particulate iron in machine oil was de-
termined by diluting the sample with
appropriate hydrocarbons, filtering, and
examining the paper by X-ray fluores-
cence(9J).
Emission Spectrometry. Nickel
and vanadium were determined in
coke and tar by emission spectrom-
etry from the parts per million to
the low per cent range (35J) using gold
as internal standard and a graphite-
silica gel buffer mixture. Petho (43J)
analyzed oils for nickel and vanadium
by ashing samples with sulfuric acid
and mixing the ash with a buffer
of graphite and silica gel containing
cobalt as internal standard. From
0.005 to 30% of either element can be
determined by exciting samples in an
ac arc.
Effect of organic solvents in enhance-
ment of emission lines was used by
Heemstra and Foster (17J) to deter-
mine vanadium in petroleum fractions
by atomizing a chloroform solution of
sample into the plasma arc. Lead was
VOL. 41, NO. 5, APRIL 1969 · 169 R
 determined in gasolines from 0.005 to
1% by diluting samples with amyl
alcohol and using a special double-disk
rotating electrode (Si/). Determination
of as little as 0.0001% of sodium in gas
turbine distillates was achieved by im-
mersing red-hot graphite electrodes in
the sample and exciting them in an ac
arc (36J).
A fast, precise method for analysis of
barium in lubricating oils was developed
by using a special porous-cup carbon
electrode (62J). A routine procedure
for analysis of additive concentrates and
lubricants using physical methods of
separation (dialysis and gl-c) and spec-
trometry (emission and ir) was devel-
oped by Jenkins and Humphreys (21 J).
Copper, barium, aluminum, silicon,
iron, chromium, and lead were directly
determined in used automobile crank-
case oil by a rotating disk electrode,
with a maximum mean relative error of
30% (38J).
A spectrographic determination of
nine metallic elements in ashed tractor
oils was described (83J). Ashes are
mixed with a lithium fluoride-graphite
buffer and excited in an ac arc. Traces
of vanadium, nickel, and manganese
were determined in crude oils without
ashing (66J). Determination of 23
elements in ashed petroleum products
with a mean quadratic error of 10%
was achieved (65J) using lithium
fluoride buffer and an ac arc. Nine
metallic elements were determined in
used lubricating oils without ashing
with a mean relative error of 6 to 16%
(SOJ). Traces of several elements in
petroleum products were determined
by emission spectrography with sensi-
tivities ranging from 10 ~s to 10“®%
(61 J). Distribution of trace elements
in crude oil was studied by Korosteleva
and Koprova by coking the oils and
using an ac arc (28J) achieving mean
relative errors of 8 to 15%. A general
review on uses and applications of
emission spectrometry to the study of
engine oil lubricants was published
(48J).
Miscellaneous. Trace metals in
mineral oils were rapidly determined
by burning the oil with an oxygen-
hydrogen flame, dissolving the residue
in water, and measuring the metals by
flame photometry or polarography
(1J). LePera (31 J) studied determina-
tion of traces of zinc in engine fuels by a
dithizone spectrophotometric procedure
with an error of —0.2 to +0.3 ppm in
the 1 to 15 ppm range; interference of
lead is discussed.
Traces of copper were determined
spectrophotometrically in residual fuels
with additives by reaction between
cuprous ion and diethyldithiophosphate
(60J). Electrochemical, titrimetric, and
spectrophotometric techniques were
used by Studeny (58J) to determine
copper, lead, iron, aluminum, calcium,
170 R · ANALYTICAL CHEMISTRY
and zinc in used lubricating oils. The
same author (57J) studied photometric
determination of iron and copper and
complexometric titrations of zinc and
calcium in lubricating oils. Chromium
and calcium were investigated in anti-
static additives by extracting metal
oxides from the ashed sample with
hydrochloric acid and using a polaro-
graphic finish (6J).
Curti and Riganti (7J) determined
vanadium in petroleum products by
a fast, accurate oscillopolarographic
technique. Gasolines were analyzed for
lead with a maximum error of 0.5%
by potentiometric titration with EDTA
(44J)· Sodium in viscous petroleum
products was estimated by flame pho-
tometry prior to dilution of the sample
with sodium-free solvents (45J).
A titrimetric method using Trilon B
for milligram amounts of zinc and
barium in oil additives was reported
(51J). A procedure was studied to de-
termine lead alkyls in liquid hydrocar-
bons by a specifically developed gas
chromatograph (SOJ). A review cover-
ing determination of additives in engine
lubricating oils giving specific proce-
dures was written by Nagypataki (41 J).
Sergeeva (49J) developed a flame photo-
metric method to determine sodium and
potassium in ashed solid fuels. A rapid
gravimetric method was reported for
determination of barium in lubricating
oil additive concentrates containing no
other metals that form insoluble sul-
fates (19J).
A detailed procedure was reported by
Campbell and Moss (4J) to estimate
traces of lead in petroleum products by
extraction followed by a dithizone
colorimetric finish. The same authors
(39J) described another procedure to
analyze for lead in gasoline, this time
by EDTA titration. Another EDTA
titration technique for lead in gasoline
was also described by Fernandez et al.
(1SJ). Determination of lead alkyls
in gasoline by gas chromatography
using an electron capture detector was
reported by Kramer (29J); 0.002 g of
lead alkyl per liter can be determined
in 45 min with an average error of
±1%, in agreement with ASTM
Method D 1949 64 or IP 118. Traces of
lead in industrial hydrocarbons were
determined by inverse polarography
with a relative standard deviation of
±7% (46J).
A rapid spectrophotometric method
for cobalt in products of the Oxo process
with a range of 0.05 to 0.5% was re-
ported (52J). A redox titrimetric
procedure for lead in lubricating oils
was studied by Samanta et al. (47J).
Differential oscillopolarography was
applied to a variety of products, in-
cluding gasolines, to determine lead
with a sensitivity of 0.01 Mg/ml (42J).
Oscillometric or conductimetric end
point redox titration was used by
Jovanovic et al. (24J) to estimate
tetraethyl lead in gasolines. Vanadium
in the range from 1 to 10 ppm in heavy
petroleum fractions was analyzed by
intensity of color developed with hema-
toxylin after the sample was ashed with
benzenesulfonic acid (84J)· Manganese
was determined in crude oils by polarog-
raphy previous treatment with 30%
bromine solution in place of the ASTM
hydrochloric acid extraction (40J).
An EDTA titrimetric procedure was
developed to determine zinc in lubri-
cating oils within the 0.01 to 0.1%
range with a standard deviation of 8%
(12J). Diethyl zinc, as well as its
hydrolysis or oxidation products, was
rapidly and precisely determined in
toluene solutions by titration with 8-
quinolinol (10J).
Flame spectrophotometric determina-
tion of sodium, potassium, and calcium
in fuels by the method of standard
additions was established by Thomas
(59J) with a sensitivity in milligrams
per liter of 0.05 for potassium and 0.1
for calcium. Soulages (56J) established
a gas chromatographic technique using
a flame ionization detector to deter-
mine lead alkyls and halide scavengers
in gasolines. The same author (55J)
extended the previous method for
simultaneous analysis of halide scaven-
gers and five different lead alkyl com-
pounds. High temperature jet fuels
were analyzed for iron in parts per
million by a spectrophotometric tech-
nique using bathophenantroline (53J).
The iron-bathophenantroline complex
follows Beer’s law over the 1- to 20-Mg
range.
Nonmetal Elements
and Compounds
J. C. Morris, D. R. Latham, and W. E.
Haines
Bureau of Mines, U. S. Department of
the Interior, Laramie, Wyo.
Sulfur. Increasing interest was
shown in determining nature and
amounts of sulfur compounds pres-
ent in petroelum fractions. Osborn
and Douslin (11 IK) compiled vapor
pressure data on “key” members of the
alkane-thiols, alkane sulfides, alkane
disulfides, and cyclic sulfides with equa-
tions provided as an aid in interpolating
and extrapolating experimental results.
Thompson et al. (148K) identified
1-thiaindan and a number of its methyl
and ethyl derivatives by a technique
which involved preparing a sulfur con-
centrate, and removing thiols, phenols,
sulfides, and benzothiophenes by ex-
traction and chromatography, leaving
thiaindans in the final solution. Identi-
fications were made by infrared studies
of this material, plus infrared identifica-
tion of hydrocarbons formed by Raney
nickel desulfurization. Sulfur types,
including benzo-, dibenzo-, naphthano-,
and naphtheno-thiophenes, were de-
tected by Thompson et al. (149K) in a
225 to 400 °C fraction, using concentra-
tion techniques followed by low voltage
mass spectrometry; the procedures are
recommended generally for high boiling
petroleum fractions.
Drushel and Sommers (JfiK) isolated
and characterized sulfur compounds by
oxidation of the sample with hydrogen
peroxide in a benzene-acetic acid solu-
tion, chromatographic fractionation of
sulfoxides or sulfones formed, and re-
duction to original sulfur compounds
followed by analyses using mass, ultra-
violet, and nmr spectrometry and thin
layer chromatography. A stepwise
oxidation-separation technique was a
rapid and reliable procedure for sulfur-
type analysis of high boiling petroleum
fractions. A formula for calculating
ring composition and mean molecular
weight of organic sulfur compounds
using sulfur content, molecular masses,
and group composition of aromatic
sulfur concentrates was proposed by
Krein et al. (78K).
Sulfur content of gases was deter-
mined by Jaworski and Chromniak
(65K) who passed the sample over
heated Raney nickel, treating the nickel
with hydrochloric acid to release hy-
drogen sulfide which is absorbed in a
sodium hydroxide-acetone mixture, and
titrated with mercuric acetate using
dithizone as the indicator. Successful
use of an apparatus for determining
sulfur oxides in fuel-oil flue gas was
described by Wang (157K). Low con-
centrations of sulfur dioxide in flue
gases were determined by Dresia (38K),
who used soft gamma-ray absorption
with iron-55 as the radiation source.
Sulfur in liquefied gases was deter-
mined by burning in a stream of air,
absorbing the oxidized products in hy-
drogen peroxide, and titrating with
barium perchlorate using thoron as the
indicator, as reported by Widmaier and
Dudek (159K). Nitrogen and chloride
interferences in the iodometric and
microcoulometric determination of sul-
fur dioxide were studied by Bremanis
et al. (23K). Terabe et al. (147K) com-
pared sulfur dioxide concentration mea-
surements made by an electroconduc-
tivity technique with measurements
made using West-Gaeke bubblers, and
found the electroconductivity method
gave consistently higher results.
Kuz’mina et al. (81K) used discolor-
ation of silica gel impregnated with lead
acetate to determine sulfur in gases and
other petroleum products; sample was
passed over the impregnated gel con-
tained in a glass tube and amount of
sulfur present was calculated from the
length of the colored section of the col-
umn.
Ryashentseva and Afanas’eva (126K)
recommended two silica gel columns,
one impregnated with lead acetate and
the other with copper acetate, to de-
termine hydrogen sulfide and sulfur
dioxide concentrations in gas samples.
The samples were passed through the
columns, then heights of the colored
layers formed were compared with
calibration curves.
Risk and Murray (126K) devised an
instrument for continuous monitoring
of hydrogen sulfide content of stack
gases that also contain sulfur dioxide;
ultraviolet absorptions of an oxidized
stream and an unoxidized stream of a
gas-air mixture are measured contin-
uously at 2850 1, the difference corre-
sponding to hydrogen sulfide content.
A spectrophotometric method for
determining micro amounts of sulfur
dioxide, useful for air pollution studies,
was reported by Okutani and Utsumi
(108K). The method depends on ab-
sorption at 562 µ of the benzene-
soluble complex formed by reaction of
excess mercuric reagent and diphenyl-
carbazone. Carbonyl sulfide in gases
from coal or oil was determined by
Geyer et al. (5IK) by measuring the
infrared absorption at 2054 or 2972
cm-1 in a double beam instrument.
Absorption owing to carbon monoxide
is corrected by introducing carbon
monoxide into the comparison cell
until transmission at 2170 cm-1 is equal
in the sample and comparison cell.
An infrared spectrometric analysis was
developed by Zentgraf (163K) to mea-
sure effectiveness of desulfurization of
combustion gases.
Gas-chromatography has been used
in several applications to analyze sulfur
compounds in gases. Reinhardt et al.
(122K) used an argon detector to mea-
sure relative retention times of typical
thiols, sulfides, disulfides, thiophene,
hydrogen sulfide, and hydrogen cyanide
on columns of various stationary phases
supported on Sterchamol, and showed
glc to be adapted to the analysis of
these gases. Popl and Weisser (117K)
analyzed sulfur in gases using flame
ionization detection; best results were
obtained with polypropylene glycol
sebacate on Chromosorb, Rysorb, or
Sterchamol. Berezkina et al. (12K)
resolved completely a mixture of hy-
drogen sulfide, sulfur dioxide, carbonyl
sulfide, and carbon disulfide on a silica
gel column; they also described a col-
umn consisting of successive sections
of polyethylene glycol and of dinonyl
phthalate supported on Teflon for
separating hydrogen sulfide and sulfur
dioxide. Weisser et al. (158K) sepa-
rated mixtures of thiols and sulfides on a
column of polypropylene glycol sebacate
on Chromosorb at 55 °C, with nitrogen
as the carrier gas and a hydrogen flame
ionization detector.
Improvements in irradiation and
X-ray techniques have been reported
by several investigators. Tamura and
Yamaki (146K) described the use of a
14-MeV neutron generator with a flux
of 1010 neutrons per sec to bring about
the 160(«, )1ß reaction to determine
oxygen and the 34S(ra,p)84P to determine
sulfur in petroleum products.
Jester and Klaus (66K) reported the
determination of sulfur in petroleum
lubricants by conversion of sulfur-32
to beta-emitting phosphorus-32 by fast
neutron irradiation. Chlorine and phos-
phorus, which can both produce phos-
phorus-32, are first removed, and the
irradiated sample can either be ashed
and counted, or converted to magnesium
ammonium phosphate and weighed.
Shibuya et al. (135K) developed a
vacuum X-ray technique for deter-
mining sulfur in heavy oils. A vacuum
X-ray spectrometer, an ethylenedi-
amine d-tartrate crystal, and a gas-flow
proportional counter were used, and
results agreed well with conventional
chemical methods.
Noguchi and Nomura (103K) dis-
cussed the accuracy and reliability of
X-ray absorption of tritium brems-
strahlung to determine sulfur in fuel
oils; the method is recommended for
routine analyses and certain precautions
to be taken are described. An apparatus
for the continuous determination of
sulfur in oil products on the basis of
absorption of tritium bremsstrahlung
was reported by Solt et al.
(141K); the
minimum measurable sulfur content
claimed was 0.1% with an absolute
error of ±0.03%.
Visapaa (154K) developed a method
for determining sulfur in fuel oils using
X-ray fluorescence. With calibration
samples made up by adding different
amounts of teri-butyl disulfide to a fuel
oil, lowest detectable sulfur concentra-
tration was about 0.002% and standard
deviation at a sulfur concentration
of 2.0% was +0.0097%. Sulfur in
heavy oils was determined by Shibuya
et al. (IS4K) who used an X-ray tube
with a tungsten target at an excitation
potential of 40 kV and a tube current
of 25 mA; with a properly chosen
scattered line in the background as an
internal standard, the authors indicated
that the effect of variations in equip-
ment, sample loading, C/H ratio, ash,
and water in heavy oils can be satis-
factorily eliminated.
Several publications reported new
applications and innovations in polar-
ography. Holzapfel and Schoene (60K)
described a method for determining
total sulfur in gasoline which they rec-
ommended for fractions boiling up to
250 °C; after reduction to hydrogen
sulfide, total sulfur as low as 0.0001%
was determined by direct voltammetry.
A process polarograph for continuous
monitoring of parts per million concen-
trations of hydrogen sulfide in gas
VOL. 41, NO. 5, APRIL 1969 · 171 R
 streams was described by Connelly and
Wagner (31K). Sampling, reagent flow,
mercury flow and recovery, and sample
degassing were performed automatically.
Wolf and Langen (162K) developed a
method to determine trace amounts of
hydrogen sulfide and carbonyl sulfide
in waste gases containing sulfur dioxide;
when large amounts of sulfur dioxide
were present, they were first removed by
absorption.
Impulse polarography was used by
Bel and Maurice (9K) to determine free
sulfur and thiols in gasoline; hydrogen
sulfide does not interfere in the thiol
determination. Jaworski et al. (64K)
used polarography to determine benzo-
[5]thiophene in naphthalene fractions.
The method depends on reduction of
benzo[i>]thiophene-l, 1-dioxide formed
by adding hydrogen peroxide to the
sample in warmed acetic acid. Kashiki
and Oshima (73K) developed a method
for the square-wave polarographic de-
termination of free sulfur in liquefied
petroleum gases. Samples were col-
lected in specially fitted glass pressure
bottles and the gases allowed to volatil-
ize; the free sulfur was taken up in a
methanol-methyl iodide-acetic acid-
sodium acetate solvent and determined
polarographieally. Kashihi and Ishida
C72K) determined thiols, disulfides, and
free sulfur in petroleum naphtha using
square-wave polarography; wave heights
were proportional to the concentrations
predicted by the theory of square-wave
polarography.
Several improvements in total sulfur
determinations using combustion meth-
ods were reported. Dokladalova (36K)
reported a rapid method of sulfur de-
termination in higher boiling petroleum
products; sample was oxidized in air at
800 °C and sulfur dioxide determined
spectrophotometrically using pararos-
aniline methanesulfonate. Bernardini
et al. (1SK) compared several combus-
tion methods of sulfur determination, in
which products were measured by titrim-
etry, gravimetry, and nephelometry.
Low concentrations, 0.01% to
0.0005% of sulfur in organic products,
were determined by Bota et al. (19K)
who burned the sample in excess oxygen,
oxidized the sulfur dioxide with hydro-
gen peroxide, and determined the sul
fate turbidimetrically with barium
chloride at a pH of 2.5 to 3.5. Engel
(42K) used a modified thread wick
capillary lamp for rapid determination
of sulfur in petroleum distillates; halo-
gens, nitrogen, and phosphorus inter-
fered.
An improved Wickbold apparatus for
determination of low concentrations of
sulfur in liquid hydrocarbons was de-
scribed by Liederman and Glass (84K),
who used a pressurized burner feed and
an extended high temperature combus-
tion chamber that minimized formation
of sulfur trioxide until the gases were
172 R · ANALYTICAL CHEMISTRY
quenched in hydrogen peroxide absorber
solution. Barium sulfate was deter-
mined by nephelometry.
Schoeffmann and Roth (129K) rec-
ommended a coulometric titration as
the finish for combustion-flask deter-
mination of sulfur in fuel oils; combus-
tions gases were fed directly into the
absorption cell of a coulometer with
sulfuric acid being determined in the
usual manner. Dubois (41K) described
the French standard method for deter-
mination of sulfur in heavy oils (AFNOR
M 07-025) and recommended increasing
the length of high temperature zone in
the combustion chamber and the adap-
tion of an automatic titration set for the
use of intensity-potential curves.
Houzim and Zeman (62K) discussed
alternate finishes for the determination
of sulfur in fuel using the Eschka igni-
tion technique: In the first method,
the aqueous acidified residue is passed
through Amberlite IR-120 resin, barium
chloride added to the percolate, and the
excess barium titrated with EDTA using
Eriochrome black T as indicator. In
the second, the aqueous solution is
acidified with nitric acid, and sulfates
are precipitated with benzidine and
titrated with sodium hydroxide.
In a rapid method for determination of
sulfur in petroleum products, Popiel
(116K) injected the sample in an oxygen
stream into a hot quartz tube; nephelom-
etry was used for sulfur concentrations
of less than 30 ppm, titration for higher
concentrations. According to a Shell
Internationale Research patent (131K),
sulfur content of hydrocarbons was
determined automatically by burning
the sample stream continuously in ex-
cess oxygen in an oxyhydrogen flame,
cooling the gases to about 20 °C to con-
dense the water, and recording the con-
ductivity of the water to calculate the
sulfur content. Chlorine compounds in
the flue gas were removed before cooling.
Methods for microdetermination of
total sulfur in petroleum products re-
ceived the attention of several workers.
Attari (6K) recommended combustion
of sample and oxidation of sulfur to sul-
fur trioxide, reduction to hydrogen sul-
fide with hydriodic acid, and conversion
to methylene blue for colorimetric
measurement. A perceptible color was
developed at sulfur concentrations as
low as 2 gamma per 100 cc and sulfur
levels up to 500 ppm were determinable.
Gulyaeva and Khyanina (S7K) ex-
tended the Raney nickel reduction
technique for sulfur determination to
include higher oxidation states, includ-
ing sulfones and alkyl sulfates. Grie-
pink et al. (56K) recommended a method
for determining as little as 20 µg of sulfur
in organic samples; sample is oxidized in
a hot phosphoric acid-potassium dichro-
mate solution, sulfur reduced to hy-
drogen sulfide by treatment with metal-
lic tin and phosphoric acid, and hydro-
gen sulfide absorbed in cadmium sulfate
solution and titrated with sodium hy-
droxide to form cadmium sulfide.
The Schoeniger method was adapted
by Pietrogrande and Fini (11SK) to
accommodate 1.5- to 2.0-mg samples by
using a modified combustion flask.
Debal and Levy (32K) reported quanti-
tative microdeterminations of sulfur in
organic materials by burning the sample
(2.0 to 4.5 mg) in a stream of oxygen,
absorbing the sulfur dioxide in aqueous
sodium sulfate-hydrogen peroxide solu-
tion, and determining the sulfuric acid
by microcoulometric titration. Details
were given for eliminating interferences,
including halogens and various metals.
Specialized techniques were developed
to determine specific types of sulfur com-
pounds in petroleum products. Sul-
foxides were concentrated by cation ex-
change chromatography from petroleum
fractions boiling from 250 to 500 °C by
Okuno et al. (107K); the amount of sul-
foxides, titrated potentiometrically as
weak bases in acetic anhydride with
perchloric acid, was quantitatively re-
lated to intensity of the infrared ab-
sorption band at 1040 cm-1 and to in-
crease in sulfide content after reduction
with lithium aluminum hydride. Bol’
shakov et al. (18K) recommended deter-
mining thiols in petroleum fuels either
by volumetric titration with ammoniacal
copper sulfate or by potentiometric ar-
gentometric titration.
A method to determine thiols in gaso-
line was reported by Oelsner and Hueb-
ner (105K), who treated the aqueous
sodium plumbite extract of the gasoline
sample with excess complexon III, and
titrated the excess with a zinc solution
using Eriochrome black T as indicator.
The end point in the titration of thiols
in nonaqueous samples was determined
by Berges and Perez (13K) using high
frequency conductivity; preferred sol-
vents were ethanol and methanol-ben-
zene, with alcoholic or aqueous solutions
of mercury salts as titrants. Witzel and
Hoerding (16IK) used an indirect colori-
metric method, a direct amperometric
method, and a dead-stop process in
determining sulfur types, including
hydrogen sulfide, thiols, sulfides, and
disulfides, in petroleum products.
Lipinski and Debowski (87K) de-
scribed an indicator mixture consisting of
lead acetate in acetic acid and aqueous
barium chloride supported on silica gel
which develops a visible and stable
color suitable for measuring low con-
centrations (7 to 70 ppm) of hydrogen
sulfide.
Alkyl sulfides with carbon numbers up
to 18 could be separated from most other
classes of organic compounds in petro-
leum, and from each other, by Orr
(110K), who used liquid-liquid chroma-
tography with normal hexane as the
mobile phase and a stationary phase
consisting of different concentrations of
mercuric acetate in aqueous acetic acid.
Equivalent retention volumes for the
sulfides decreased with increasing carbon
number, and with decreasing acetic acid
concentration in the stationary phase.
Nonthiophenic sulfur, including thiols,
and sulfides, was determined by La-
mathe (82K) using perchloric acid titra-
tion of the basic complexes formed
when these compounds react with mercu-
ric acetate; a correction for basic nitro-
gen present is obtained by a separate
titration omitting the mercuric acetate
treatment. A photocolorimetric pro-
cedure for measuring carbon disulfide
content of an aromatic stream was re-
ported by Orlov et al. (109K); the rea-
gent is a solution of copper acetate and
diethylamine in toluene.
Kashiki and Ishida (7IK) determined
thiophene spectrophotometrically by
the color formed with alpha-nitroso-
beta-naphthol in the presence of sulfuric
acid. Kremer et al. (79K) determined
sulfides by dispersing the sample in
aqueous sodium hydroxide and titrating
potentiometrically with lead nitrate
solution; a rotating silver wire serves as
indicating electrode, with see as a ref-
erence.
Sulfonates and inorganic salts in
treated oils were determined by Vdmos
and Simon (152K) by adsorption chroma-
tography on silica gel; oily components
were eluted with benzene and acetone,
and the sulfonate fraction with ethanol.
Separation and determination of naph-
thalenesulfonic acids in products of sul-
fonation were reported by Funasaka
et al. (47K). The acids were converted
to methyl esters by treatment with di-
azomethane and analyzed by a gas-
liquid chromatographic technique.
Bennewitz (11K) critically reviewed
methods for determination of degree of
sulfation of alkyl sulfates.
Nitrogen. The petroleum industry
has been especially active the past
two years in developing reliable meth-
ods to determine trace quantities
of nitrogen. Because of the adverse
effects of nitrogen compounds on
many catalytic processes and on
product stability, total nitrogen must
be determined to 1 ppm in a variety
of feeds and products.
One approach to determining nitrogen
in the parts per million range, developed
by Martin (91K), involves quantita-
tively converting the nitrogen to am-
monia over a nickel-on-magnesium
oxide catalyst; the ammonia is auto-
matically titrated with coulometrically
generated hydrogen ions. The method
can be used on samples boiling up to
500 °C containing as little as 0.2 ppm of
nitrogen. Rhodes et al. (124K) ex-
tended the range of the Dohrmann nitro-
gen analyzer to the 0.1 ppm level and to
petroleum fractions with end boiling
points up to 600 °C. The changes made
included an all-quartz inlet system,
palladium pH-sensing electrodes, and
electrical shielding.
Modifications of the Coleman nitrogen
analyzer to determine nitrogen in parts
per million quantities were made by
two researchers. Oita (106K) combined
the small nitrometer of Model 29 with
the large combustion tube and high
temperature furnace of Model 29A to
determine nitrogen in the range of 30 to
1000 ppm. Winkler and Farley (160K)
determined nitrogen in the 100 to 200
ppm range by using a sample pretreat-
ment system, a movable furnace, and an
enlarged postheater section.
Several research workers extended the
acid extraction technique to determine
nitrogen in parts per million quantities.
Svajgl (144K) extracted gasoline sam-
ples with 92% sulfuric acid, then deter-
mined the nitrogen removed by the
Kjeldahl method. Total nitrogen was
determined in the range of 0 to 50 ppm.
Trace quantities of nitrogen in gasolines
containing a high content of unsaturated
hydrocarbons were determined by a
method developed by Shestakova and
Bychenkova (133K). The method com-
bined sulfuric acid extraction with the
Kjeldahl procedure; a colorimetric tech-
nique was used for samples containing
less than 10 ppm of nitrogen.
The method of extractive percolation
using 98% sulfuric acid supported on
pumice was modified by Smith et al.
(.137K). A 1:1 mixture of iron chloride
and zinc chloride was added to the sul-
furic acid-pumice mixture to increase
efficiency of extraction of nitrogen.
After concentration, nitrogen is deter-
mined by the Kjeldahl method with the
exception of converting the ammonia to
indolphenol blue and making a spectro-
photometric analysis. Nitrogen values
of 5.7 to 87.0 ppm were determined in
gas oil, kerosine, and gasoline samples.
Chumachenko and Pakhomova (28K)
determined carbon, hydrogen, and nitro-
gen in organic materials by the oxidation
of approximately 1 mg of sample over
nickel oxide at 900 °C in an atmosphere
of helium. Reaction products (nitro-
gen, carbon dioxide, and ethylene) were
analyzed by gas chromatography on an
activated charcoal column with an ac-
curacy of ± 0.2%. The same authors
(29K) studied the effect of metal oxide
oxidant in various methods for simul-
taneous determination of carbon, hydro-
gen, and nitrogen in organic substances.
Methods considered included classical
oxidation, pyrolysis, and oxidation in an
inert atmosphere. In the inert gas at-
mosphere, nickel oxide was the most
active oxidant.
Hofstader and Swarbrick (58K) used
combustion, absorption, and gas chroma-
tography to determine nitrogen in the
100 ppm range. A gas chromatographic
method to analyze fluid streams for ni-
trogen in the 0 to 30 ppm range was
developed by Steinle et al. (142K).
The method eliminates problems created
by non instantaneous sample introduc-
tion into the chromatographic column.
A patent issued to Shell Internationale
Research Maatschappij NV (1S0K)
describes an automated procedure for
determination of nitrogen in a petroleum
stream with a sensitivity of 0.5 ppm.
The procedure involves combustion of
sample over copper oxide, reduction of
gaseous products with copper, and de-
tection of nitrogen with a katharometer.
A simple micromethod to determine
nitrogen in heterocyclic compounds
without N—N linkage was developed
by Morita and Kogure (95K). The pro-
cedure is a modification of the Kjel-
dahl method and determines nitrogen in
the 100 to 500 ppm range.
Faulhaber and Liebetrau (44K) com-
pared the Kjeldahl and Dumas methods
for determination of total nitrogen; the
Kjeldahl method was more reliable.
A modification of the Dumas method
was introduced by Nepryakhina et al.
(101K). The authors used a prelimi-
nary pyrolytic combustion before de-
composition of the sample in the pres-
ence of copper oxide; the resulting
nitrogen, water, and carbon dioxide
were analyzed gas chromatographically.
Galik and Landa (48K) modified the
copper oxide catalyst and reduced the
extra space in the burning tube of the
Dumas apparatus.
Two methods were proposed that
start with conversion of nitrogen to
oxides by burning the sample in an
oxyhydrogen flame. Gouverneur et al.
(55K) adsorbed oxides on sodium chlo-
rite supported on alumina, reduced them
to ammonia with Devarda’s alloy, and
titrated the ammonia with hydrochloric
acid. A patent issued to Shell Inter-
nationale Research Maatschappij NV
(132K) describes an automatic method
for determining nitrogen utilizing oxy-
hydrogen combustion. Nitrogen oxides
produced are dissolved in a water-iso-
propanol-hydrogen peroxide solution
and electrical conductance is measured
in an analyzer.
A scheme for classifying basic and
very weak basic nitrogen compounds in
petroleum was developed by Buell
(24K). The procedure utilizes poten-
tiometric titrations with perchloric acid
in acetic anhydride and in acetonitrile
solutions to give four classes of nitrogen
compounds based primarily on pKa.
Results are presented for titration of
crude oils, straight-run fractions and
cracked fractions.
Abbott and Bowman (2K) found per-
chloric acid titration in glacial acetic
acid a more satisfactory method for
determining basicity of lubricants than
the ASTM D 664 method. Snyder
(139K) used adsorption chromatography
on alumina to determine total nitrogen
plus oxygen compounds in heavy petro-
leum distillates; the procedure is simple
VOL. 41, NO. 5, APRIL 1969 · 173 R
and requires only one-half man hour per
sample. Gas chromatography was com-
bined with a catalytic hydrogenation-
coulometric titration detection system
by Albert (SK) to determine nitrogen
compound types and their distribution
in light catalytic cycle oils.
A separation technique for isolation of
nitrogen compounds from petroleum
which provides fractions of specific
chemical classes was devised by Drushel
and Sommers (39K). Separations were
made by adsorption chromatography,
chemical extraction, and gas chroma-
tography ; resulting fractions were char-
acterized by mass, infrared, ultraviolet,
fluorescence, and phosphorescence spec-
tral techniques.
A gas chromatographic method was
developed by Veening and Dupre (153K)
for separation of basic nitrogen com-
pounds and hydrocarbons. Molar re-
sponse data were obtained for numerous
basic compounds. Jewell et al. (67K)
reviewed the literature on isolation,
separation, and characterization tech-
niques used to separate and identify the
types of basic nitrogen compounds found
in petroleum.
Several methods -were developed to
analyze for nitrogen or nitrogen com-
pounds found in petroleum products as
additives or solvents. Lynes (89K) sep-
arated and identified alkanolamine ad-
ditives in cutting oils and brake fluids
by thin layer chromatography. Delves
(33K) also used thin layer chromatog-
raphy to detect and identify aromatic
amines and thiazines used in aviation
lubricants as antioxidants. Traces of
dimethylformamide, used to extract
aromatic hydrocarbons from straight-
run petroleum distillates, were deter-
mined in a method developed by Bai-
bazarov and Popova (7K), using in-
frared spectrometry. Analysis time is
short (15 to 20 min), and sensitivity of
the method is 0.005%. Dol’berg (37K)
used a modified Kjeldahl procedure to
determine nitrogen in petroleum prod-
ucts that had been nitrated to improve
their anticorrosive properties.
Gilbert (52K) discussed advantages
and disadvantages of a prototype in-
frared analyzer for determination of
nitrogen oxides in automobile engine
exhaust gas.
Oxygen. Determination of total
oxygen, dissolved oxygen, and oxygen
compounds received the attention of
several workers. For determination of
low oxygen contents in hydrocarbons,
Pippel and Roemer (114K) modified the
combustion arrangement in the Unter-
zaucher apparatus so that decomposition
took place rapidly at 750 °C. Hydro-
gen was used as the carrier gas, and the
products were passed over carbon at
1120 °C to produce carbon monoxide
which was determined chromatographi-
cally by passage through successive col-
174 R · ANALYTICAL CHEMISTRY
umns of silica gel and Molecular Sieve
5A.
Meade et al. (9SK) determined total
oxygen by pyrolyzing the sample at
1050 °C over carbon in a quartz tube,
separating and measuring the carbon
monoxide gas chromatographically on a
molecular sieve column. Alishoev ef al.
(5K) separated oxygen dissolved in liq-
uids in a gas chromatographic system
which included a special inlet system, a
precolumn of silica gel, and a column of
molecular sieves, and measured it with
a katharometer.
A method for determination of total
oxygen plus nitrogen compounds in
heavy distillates proposed by Snyder
(.139K) involves separation of these com-
pounds by chromatography on alumina
treated with 4% water. Rentrop et al.
(123K) compared analyses of oxygen in
aged mineral oils by the Unterzaucher
method with analyses by infrared spec-
trometry. A semimicro test for de-
tection of oxygen in organic compounds
proposed by Buscarons and Pareira
(26K) is based on the blue color resulting
from treatment with solid potassium
thiocyanatocobaltate reagent.
Determination of water in gases was
the subject of several papers. Bara-
nenko and Krivorotov (8K) studied the
AVE-1 apparatus used for determining
water in natural gas and suggested
modifications necessary to make it
accurate at low ambient temperatures.
Traces of water in gases were determined
by Turkel’taub et al. (151K) using a
scheme in which the water was frozen
out of the gas, then rapidly evaporated
into a layer of calcium hydride. The
hydrogen produced was determined
chromatographically.
Polyak et al. (115K) measured traces
of moisture in inert gases and hydro-
carbons by variations in readings of a
coulometric phosphorous pentoxide unit
when the sample was introduced into the
stream of dry nitrogen which flowed
continuously through the unit. A phos-
phorous pentoxide coulometer sys-
tem for measuring moisture content of
propylene and butylene was patented by
Abaev ef al. (IK). Khodako and L’vov
(76K) determined water in hydrocarbon
gases with Fischer reagent; extraction
with methanol and electrometric titra-
tion were carried out at room tempera-
ture in a special apparatus. An attach-
ment to the Orsat apparatus that allows
measuring the gas volume before and
after removal of water with sulfuric acid
was described by Martynyuk (92K).
Gas chromatography was the basis of
several methods for determining water.
Castello and Munari (27K) used micro-
porous polymer beads coated with 5%
SE-30 methyl silicone and 3% Carbo-
wax 20M to separate water which was
measured with an electron capture de-
tector. Conventional thermal conduc-
tivity gas chromatographic apparatus
with columns of synthetic porous poly-
mer beads such as Porapak, polyethyl-
enimine, tetraethylenepentamine, and
diphenylamine was used by Hollis and
Hayes (59K). Swensen and Key worth
(146K) suggested an ethylvinylbenzene
column and detection by thermal con-
ductivity. For samples that may poly-
merize, Sanford and Ayers (128K) used
polyethylene glycol or polypropylene
glycol as the liquid phase; the portion of
the chromatographic zone which con-
tained water was passed to an electro-
lytic water analyzer.
Water in liquid petroleum products
was determined in a variety of ways.
Prietsch (119K) reported results of a
program in which seven samples of
aerojet fuels were analyzed for water
content in several laboratories using
Fischer reagent, calcium hydride, or
mangesium nitride. An instrument de-
veloped by Liderman and Ul’yanova
(83K) is based on reaction of water with
calcium hydride to produce hydrogen
which is measured by a thermal con-
ductivity detector.
For microdetermination of water in
cooling oils, Zhukoborskii et al. (I64K)
suggested a direct electrometric titration
with Fischer reagent in a sealed titrim-
eter. Muroi et al. (98K) determined
water in grease by immersing the grease
in dry insulating oil at 120 to 140 °C and
sweeping with nitrogen; moisture in the
nitrogen is absorbed in a mixture of
methanol and ethylene glycol and ti-
trated with Fischer reagent. A pre-
viously published procedure for deter-
mining water using a calcium carbide-
gas chromatographic method was eval-
uated by Goldup and Westaway (33K),
particularly with regard to its applica-
tion to streams containing methanol.
Moule and Thurston (97K) deter-
mined water in nonpolar organic liquids
by an isotope dilution technique in-
volving the exchange of water with DaO;
the change in isotopic composition is
determined by infrared spectrometry.
A method for determining free water in
fuel developed by Bitten (16K) is based
on adsorption of water by precondi-
tioned cellulose pads. Water in the pad
is measured electronically with a cali-
brated vacuum ohmeter.
Pearson (112K) determined water in
lubricating oils using the near-infrared
absorbance at 5450 to 5150 cm-1. The
sample was distilled with ethyl acetate
and absorbance of the distillate com-
pared to a calibration graph. Bel-
lonbono (10K) described a method for
determining water in hydrocarbon sol-
vents which depends on measurement of
ultraviolet absorbance of the reaction
product of water and W-benzylideneani-
line.
Norel (104K) determined water in
crude oil by adding a water-soluble
salt, such as barium nitrate, the cation
of which is radiopaque toward X-rays,
and measuring the X-ray absorption.
Water adsorbed on silica surfaces was
determined by Kellum and Smith {7 4K)
by titration with a modified Fischer re-
agent.
Automatic monitoring of water in
liquid hydrocarbon streams was the
subject of a review by Berliner {UK),
who included methods based on changes
in properties of the liquid, on hydro-
thermal equilibrium, and on devices
using an auxiliary gas medium. Bizot
{17K) found that automatic coulometric
determinations were facilitated by gen-
erating iodine, the unstable component
of the Fischer reagent, from a stable
intermediate in response to feedback
from the sample. Johnson {68K) passed
the fluid stream across a semiperme-
able membrane; the water that dialyzed
through the membrane was picked up in
a stream of anhydrous gas and carried
to an electrolytic moisture analyzer.
Apparatus for the automatic measure-
ment of water in emulsions was de-
scribed by Fukushima and Itoh {46K);
the apparatus consists of a transformer
bridge which has a circuit part with a
fixed capacitor immersed in the sample,
a phase detector, and a Schmitt trigger
circuit.
The analysis of phenolic compounds
indigenous to products, in fuel gases, or
in aqueous effluents was the subject of
several investigations. Lille and Kun-
del suggested two different approaches
to analysis of shale oil phenols. In the
first method {85K), phenols were con-
verted to hydrocarbons over a platinum
or palladium catalyst and analyzed
by gas chromatography. The second
method {86K) involves esterification of
phenols, gas chromatographic fraction-
ation of esters obtained, and identifica-
tion by ultraviolet and infrared spec-
trometry and catalytic hydrogenation.
Kudryavtseva et al. {80K) analyzed
cresols and xylenols by two-stage gas-
liquid chromatography, using dodecyl-
phthalate and 2,4-xylenylphosphate as
liquid phases. In a study of the absorp-
tion spectra of alkylphenols, Kotova and
Zimina {77K) found certain regularities
in the range 1670 to 2000 cm-1 which
may be used to determine the structure
of individual alkylphenols. A colori-
metric determination of the phenol in
fuel gas by Vlckova and Base {155K) de-
pends on absorbing the phenol in potas-
sium carbonate solution and treating the
solution with aminoantipyrine in the
presence of potassium ferricyanide.
A news note in Hydrocarbon Processing
{63K) reports a continuous analyzer for
phenols in aqueous media; the analyzer
measures ultraviolet absorbance dif-
ferential between two samples of the
stream, one of which has been made
slightly acidic and the other highly basic.
A review of methods for determination of
carbonyl compounds, acids, and phenols
was published by Nambu {100K).
Determination of phenol-type inhibi-
tors was the subject of several papers.
Suatoni {14SK) determined 2,6-di-ferf-
butyl-p-cresol in transformer oils which
contained inherent phenols. The sam-
ple was freed of interfering compounds
by chromatography on wet alumina;
the cresol was then concentrated on dry
alumina, eluted from the gel with po-
larographic solvent, and measured
by anodic polarography. Voelker and
Fischer {156K) suggested a direct
polarographic method for this inhibitor
as well as a thin layer chromatographic
procedure for rapid checking of inhibitor
level.
Thin layer chromatography was the
basis for two methods for determin-
ing phenol-type antioxidants. Diamond
{34K) separated and identified MC1-C12
p-alkylphenols in chloroform solutions
of lubricating oils using polyamide
plates, an aqueous sodium hydroxide-
methanol solvent system, and fast Blue
Salt B as the locating agent. Dichter et
al. {3BK) analyzed transformer oils con-
taining Topanol 0 and Antioxidant 733
on a Kieselgel-gypsum plate using n-
heptane as the eluent. Of several de-
veloping agents used, the best was a 2%
solution of tetranitromethane in chloro-
form.
Two groups of workers considered
analysis of the phenolic-type additives
by infrared spectrometry. Kadushin
and Korcek {69K) reported the wave-
length of bands corresponding to the
hydroxyl groups for three of the
bisphenolic additives. Qualitative and
quantitative analysis methods for eight
hindered phenols were developed by
Shimazu and Ogawa {136K), who mea-
sured infrared spectra by the compensa-
tion method using an oil from which
phenols had been removed. Phenols
were classified as, 2,6-di-teri-butyl- and
2-methyl-6-ierf-butylphenol types by
position of the OH band at 3650 cm-1
and 3614 cm-1, respectively. Knight
and Siegel {76K) analyzed for the in-
hibitor l,3,5-trimethyl-2,4,6-tris(3,5-di-
ier<-butyl-4-hydroxybenzyl)benzene by
a combination of phase solubility analy-
sis and gas chromatography.
Two groups of Russian workers de-
pended on steam distillation with
added sulfuric acid to remove the phe-
nols and cresols. Gatilova and Belova
{49K) measured phenol content of the
steam distillate using the ultraviolet
absorbance at 270 µ; Geller et al.
{50K) used a colorimetric finish. Field
and Godly {45K) studied a previously
published method for determination of
quinizarin and suggested improvements
to the method.
Study of potentiometric titration of
acids in petroleum continued. Kahs-
nitz and Moehlmann {70K) determined
simultaneously the strong and weak
acid numbers and the total amount of
very weak acids used as lubricant addi-
tives. The sample in a 1:2 mixture of
chlorobenzene and dimethylsulfoxide
was titrated with tetramethylammo-
nium hydroxide in isopropanol contain-
ing 0.9% water. Buell {25K) titrated
acids and very weak acids with tetrabu-
tylammonium hydroxide in a pyridine-
benzene solvent to determine acidic sub-
stances in heavy gas oils and shale oil
fractions.
Sulfolanes as solvents provide a wide
potential range for analysis of mixtures
containing a variety of acids or bases,
according to Morman and Harlow
{96K).
Using triisoamylbutylammonium tet-
raphenylboride as the reference elec-
trolyte and methanol and ASTM
solvent, Popovych {118K) studied me-
dium effects of single ions and their role
in interpretation of nonaqueous pH.
Luneva and Burdenyuk {88K) found a
bismuth electrode to be superior to a
glass electrode in potentiometric ti-
trations of alcohol-benzene solutions
of lubricant additives. According to
Quilty {12IK), thermometric titrimetry
overcomes some disadvantages of po-
tentiometric titration in determination
of acids in petroleum products.
A method by Alekperov and Efend-
ieva {4K) for determining small
amounts of naphthenic acids involves
extraction of the sample in w-heptane
with 1% solutions of pyridine and cupric
sulfate; using the organic phase, the
intensity of the 650- µ band of the
pyridine-cupric naphthenate complex is
measured. Goryaev et al. {54K) deter-
mined naphthenic acids by passing a
solution containing sodium salts of
naphthenic acids through a column of
cation-exchange resin; the resin was
washed with methanol or ethanol and
the eluate titrated potentiometrically
with ethanolic potassium hydroxide.
A review of analyses procedures for
determining organic peroxides in petro-
leum was published by Nambu {99K).
Tsiguro et al. {150K) determined active
oxygen of peroxide compounds in de-
pleted oils by dissolving the oil in pro-
panol, adding an excess of arsenite ions
in sodium bicarbonate, and titrating
with iodine. A direct-current polaro-
graphic method by Niederstebruch and
Hinsch {102K) is specific for hydroper-
oxides and will detect 10 ~6 mol per. 1.
The iodometric determination of buta-
diene polyperoxide reported by Braith-
waite and Penketh {22K) involves treat-
ment with hydrogen iodide generated in
situ from lithium iodide and phosphoric
acid and backtitration of excess iodine
with sodium thiosulfate.
For determination of carbon dioxide
in nonaqueous systems, Snoek and
Gouverneur {1S8K) developed a photo-
electric titrator; titrations were made
with sodium methoxide in 1: 4 metha-
nol-pyridine solvent. Solomon and
VOL 41, NO. 5, APRIL 1969 · 175 R
Lazeanu ( ) evaluated methods for
the analysis of carbon dioxide, carbon
monoxide, and oxygen in gases from
various sources.
An
Phosphorus and Halogens.
apparatus for routine analysis of
chlorine, phosphorus, and sulfur in
gear oils, which was described by
Hooks and McDonnell (61K), provides
for combustion in an Erlenmeyer flask
with a constant flow of oxygen and
absorption of combustion products in
hydrogen peroxide; elements are then
determined by procedures approximat-
ing standard ASTM methods.
A method for determination of phos-
phorus in gasolines reported by Conde
and Bonnin (80K) combines previously
published sample preparation and colori-
metric procedures. Salvage and Dixon
(127K) adapted a previously published
method for use on a microgram scale;
the sample is wet oxidized, the molyb-
dovanadophosphate complex developed
in situ, and its concentration measured
at 430 µ in a microcell.
A volumetric determination of phos-
phorus in heavy petroleum products
developed by Makarov et al. (90K) is
based on conversion to orthophosphoric
acid by dry ashing in the presence of
magnesium nitrate at 500 to 600 °C.
After treatment with concentrated sul-
furic and nitric acids, ammonium nitrate
and ammonium molybdate are added
and the resulting deposit is dissolved in
excess 0.1 A sodium hydroxide which is
backtitrated to determine phosphorus
content. Pukhonto et al. (120K) pub-
lished a method for simultaneous deter-
mination of butyl hydrogen phosphates,
tributyl phosphate, and kerosine in
aqueous solution.
Chloride content of greases is deter-
mined by potentiometrie titration with
silver nitrate according to a method
published by Fachausschuss Mineraloel-
und Brennstoffnormung (48K) as a
replacement for the color-indicator
method DIN 51,800. Braier and Mott
(21K) described an equipment assembly
that produces a greater and more uni-
form thermal neutron flux and permits
activation analysis of chlorine to 0.05
ppm. Organic fluorides in hydrocar-
bons were determined down to 0.2 ppm
by Miller and Keyworth (94K); the
procedure involves treating with bi-
phenylsodium to cleave the carbon-
fluorine bond, separating resulting inor-
ganic fluoride by ion exchange chroma-
tography, and titrating fluoride conduc-
tometrically with lanthanum acetate.
A continuous, automatic analytical
method for boron trihalides in liquid
hydrocarbons was the subject of a
patent by Boyd and Rockey (20K).
Water was added to a sample of the
process stream to hydrolyze to boron
trifluoride. The aqueous phase was
then passed through a conductivity cell.
176 R · ANALYTICAL CHEMISTRY
Analytical
and Process
Instrumentation
W. V. Cropper
Precision Scientific Co., Chicago, III.
Emphasis on instrumentation in the
petroleum industry shifted significantly
during the two years covered by this
review toward refinery applications of
automatic process analyzers. Little de-
velopment in new laboratory instru-
ments took place compared to prior
years; a major share of published re-
search was concerned with adaptation of
such techniques as atomic absorption
spectrometry, neutron activation analy-
sis, temperature-programmed gas liquid
chromatography, and linear as well as
gel-permeation chromatography.
Indicative of the current status of
process analyzer use is the report by
Carl and Kerley (11L) that a 1967 API
census showed 1903 analyzers in use at
119 U. S. refineries. The most common
ones are gas chromatographs, followed
by oxygen analyzers, monitors for
ASTM distillation, gas and liquid
gravity, pH, viscosity, and vapor pres-
sure. Although 92% of all on-stream
analyzers are used for process control,
6% monitor final product quality; this
latter proportion is increasing.
Recognizing the importance of the
trend toward continuous product qual-
ity control, the American Society for
Testing and Materials presented a six-
paper Symposium on Automated Ana-
lyzers and Quality Control for the Petro-
leum Indsutry (SL). More than half
the 166 ASTM tests on products have
instrumental counterparts, and such
instruments are generally more precise,
faster, and more economical, but more
limited in scope than conventional tests.
Advanced designs for process chromato-
graphs have led to their expanded use,
rapidly changing the functions and in-
strumentation requirements of the plant
control laboratory. On-stream contin-
uous measurement of viscosity per-
mits control of a lubricating oil blending
plant, but other inspection tests have
not yet been automated because eco-
nomic justification and need for continu-
ous monitoring are lacking.
On the other hand, the full economic
potential of automatic in-line blending
of gasolines cannot be realized until con-
tinuous test methods are employed for
verification of product quality involving
custody transfer. The present use of
automatic analyzers by a pipeline trans-
porting large volumes of segregated
products indicates that such instruments
are ideally suited for testing products
before transfer from the pipeline system
to the final delivery point. It is possi-
ble to apply automated test procedures
to certain critical characteristics of jet
fuels during transfer from refinery to
terminal facilities, but cost of doing so
must be weighed against degree of im-
proved control that could be achieved.
Elemental Analysis. An instru-
ment for continuous measurement of
hydrogen in liquid hydrocarbons uti-
lizes neutron activation by a pluto-
nium-beryllium source with boron
trifluoride counter tubes, and has a
reported accuracy of ±0.15 wt %.
A new paramagnetic susceptibility
oxygen analyzer was reported by Luft
and Mohrmann (SSL), and may be ap-
plied to laboratory samples or process
gas streams.
Stream analyzers for sulfur content
have been developed by the American
Oil Co. (62L) and Shell Internationale
Research (81L). One of the American
Oil instruments and the Shell instrument
utilize combustion of the hydrocarbon
sample followed by measurement of
change in conductivity of an aqueous
phase owing to absorption of sulfur
dioxide.
A Russian instrument (28L) for
laboratory use depends on matching
absorption of weak -radiation from
Fe55 by positioning a polyethylene
compensating wedge; position of the
wedge is recorded as a measure of sulfur
content of the sample. In Hungary,
the -radiation absorption principle
was applied to a continuous analyzer for
hydrogen, sulfur, and cobalt using
Sr90—'Y90, Fe55, and Cd109, respectively,
as radiation sources (SL).
Shell Internationale Research also uti-
lized a combustion technique to mea-
sure fixed nitrogen in petroleum fractions
automatically; oxidation products of
sulfur and chlorine are absorbed in hy-
drogen peroxide and the nitrogen oxides
(reduced to ammonia or further oxidized
to nitrogen dioxide) are determined by
increased conductivity of an aqueous
phase.
A fully automated atomic absorption
analyzer (89L) may be operated by non-
professional workers and is sensitive to
most metals in the parts per billion con-
centration range.
An automatic in-stream analyzer for
estimating carbon content of regenerated
cracking catalyst from changes in re-
flectance of a leveled surface of sample
was employed to improve FCU per-
formance, according to Potter el al.
(69L).
Specific Compound Determination.
Reliable, continuous determination of
water is an international goal, and
remains elusive. A Russian instru-
ment (71L) for automatic control of
moisture in crude oil is based on a dual
frequency method which allows tuning-
out the effect of sample density.
Concentric electrodes were used by
Tocanne (92L) for capacitative estimate
of water in crude oil or well fluids; his
device can be lowered into boreholes.
Kochinashvili et al. (48L) devised a con-
tinuous indicator for water in crude oil,
employing a variable capacitor incor-
porated in a frequency-balance discrim-
inator nulled at 1 MHz; a change in
water content of sample flowing through
the variable capacitor causes reposition-
ing of the latter, while changes in gravity
are compensated by displacing the coil
in a separate induction-sensing circuit.
The capacitance-change effect is also
employed by Japanese researchers (82L)
in an automatic instrument for measur-
ing water in water-in-oil emulsions with
accuracy better than ±0.1% at contents
up to 5%. A Russian process analyzer
(48L) apparently uses a similar principle
and is reported to have a range of 0 to
40% water.
A laboratory instrument to replace
the Dean-Stark apparatus was described
by Taukin and Bryakin (90L) and uti-
lizes an inductively coupled bridge cir-
cuit; the instrument range can be elec-
trically adjusted in five steps from 0 to 3
to 0 to 40% water. Another Russian
laboratory instrument (52L) is based on
the reaction between water and calcium
hydride; the resulting hydrogen is mea-
sured by thermal conductivity change of
the nitrogen carrier gas, with a sensitiv-
ity of 0.01% per recorder scale division.
Anisimova et al. (4L) described an on-
stream automatic coulometer to deter-
mine water in ethylene, propylene,
butene, and butadiene. Unfortunately,
their solution to fouling of the coulo-
metric cell by polymerized olefins is not
made clear. The instrument is reported
to be capable of determining hydrogen
content of organic gases.
Freeland (SOL) passed metered quan-
tities of a fuel gas through a thermo-
stated, isobaric water bath and measured
the amount of water evaporated in
saturating the sample stream.
A novel approach was used by Heeps
and Kopai (84L), who passed hydrocar-
bon fuel through two resistivity cells of
different widths but both smaller than
0.008 in.; a voltage is applied between
detector electrodes when direction of
liquid flow is abruptly altered and
change in resistivity due to build-up of
water droplets is a measure of the trace
amount of (free) water in the fuel.
Mild steel corrosion probes (14L) can
respond to changes in trace water con-
tent within 10 to 20 min and the corre-
sponding change in electrical resistance
of the probe may provide an on-stream
means of detecting moisture. Chroma-
tographic separation of water from a
vaporized hydrocarbon stream sample is
followed by detection with a sensitive
hygrometer in Davidson’s process ana-
lyzer (22 L).
Continuous determination of carbon
dioxide in air or other gases containing
oxygen rests on a modified Hersch cell
(86L) having a platinum or palladium
cathode, pure mercury anode, and po-
tassium hydroxide electrolyte. Current
output at constant gas flow is propor-
tional to carbon dioxide concentration
and oxygen does not interfere. Small
amounts of carbon dioxide in a gas
stream are determined by a photoelec-
tric titrator (85L) that employs sodium
metholate titrant in pyridine-mono-
ethanolamine electrolyte.
Dworak and Davis (25L) patented a
continuous mercaptan analyzer in which
silver ion is coulometrically generated
while the gas sample is continuously
bubbled through aqueous ammonium
nitrate-ammonium hydroxide solution;
the silver ion concentration is measured
by potentiometric electrodes and is kept
constant by controlling the Ag-generat-
ing current, which then is proportional
to the mercaptan concentration in the
sample gas. Accuracy is ±2 ppm and
the range is up to 60 ppm.
A microwave spectrometer (1L) al-
lows methanol, ethanol, and isopropanol
to be measured quantitatively in gaso-
line. The analysis lines are 26,847,
26,830, and 26,510 MCi respectively,
and the error is reported to be 1%.
Prince et al. (70L) evaluated a photo-
ionization detector for gas chromatog-
raphy; its response is 1000 times greater
than flame ionization detectors and has
a minimum detectable concentration of
1 X 10 ~12. The photoionization de-
tector is especially useful for air pollu-
tion analyses. A small mass spectrom-
eter was coupled by Henneburg et al.
(85L) to a capillary-type gas chromato-
graph for determining lead alkyls and
silicate esters dissolved in gasolines or
oils.
Compounds Estimation by Types.
For automatic plant control of aro-
matic in catalytic reformate, Pavlova
et al. (65L) used a uv
spectrophotometer
at 246 nm; after local calibration to
allow for unknown impurities in each
plant stream, mean relative error is
±1.3%. Kosov’s portable laboratory
instrument (44L) measures the aromatic
content of process samples by capaci-
tance change of a cell in which a 50-ml
sample serves as the dielectric. Abso-
lute error is less than ±2% over
range 10 to 40% aromatic content.
An automatic multicolumn glc ana-
lyzer handles a stream typically contain-
ing 90% H2 plus Ci-Cu paraffins and Ca-
Cn aromatics (24L); hydrogen and meht-
ane are resolved, as are all paraffins
through hexane, but the aromatics are
analyzed as one group and the Ci-Cn
paraffins as another group.
Storey (89L) measured the tempera-
ture of a gas sample upon expansion
through a fixed orifice for detecting the
interface between two gases successively
passing through a pipe, as in the molec-
ular sieve process for separating n-par-
affins. Kuchta (47L) analyzed binary
mixtures by comparing the vapor pres-
sure in a rectifying column with that of a
standard' solution maintained at the
same temperature; automatic control of
rectification was achieved.
Titration Instruments. Everson’s
thermometric titrator (27L) may be
expected to find general application in
petroleum laboratories, especially for
measuring trace acidity or alkalinity of
used oils and for determining naphthenic
acids in distillates. An automatic coulo-
metric titrator (101L) for continuously
flowing streams senses titration potential
and automatically controls current flow
so that time off is equal to time on.
An alkalinity meter having a four-
electrode conductivity sensor (4SL) was
developed in Russia as an adjunct to an
automatic control system; it has a linear
scale and a relative error less than 5%.
Another Russian development (9BL) is
an automatic two-stage titrimeter for
in-stream applications which can be
adapted for analyzing multicomponent
mixtures where sharp changes in pH
occur during titration.
The salt content of crude oil was
monitored automatically on a periodic
basis potentiometrically (75L), employ-
ing silver and glass electrodes and dis-
solving the crude oil sample in a ben-
zene-isopropanol solvent slightly acidi-
fied with nitric acid solution.
Physical Property Measurement.
API Gravity or Density. An elec-
tronic hydrometer was developed
by Cropper and Kapff (20L) to read
out in API gravity at 60 °F. In the
instrument, a strain gauge detects
differential pressure between two
levels in the test sample, while a
thermocouple measures sample tem-
perature and an operational amplifier
transforms pressure and temperature
functions into API units. A Czech
density meter (12L) uses a float im-
mersed in the sample liquid having
magnetic and damping elements which
interact with an inductive-capacitance
measuring circuit. The pattern of
damped oscillations is sensitive to very
small changes in the equilibrium position
of the float, hence fluid density.
Octane Number. A modification of
the the CFR engine to give continuous oc-
tane ratings was described by Crespin
(18L) for control of in-line blending.
Maximum knock intensity for sample
and reference fuel is obtained by the
micro, falling-level principle and is
stored and compared electronically.
The difference signal actuates a control-
ler that governs addition of antiknock
compound. An octane analyzer system
was introduced by Ethyl Corp. (15L)
which has quick-connect facilities for
power and water and is skid-mounted
for movement to any point in a refinery.
Universal Oil Products Co. (9SL) pa-
tented a stabilized-flame apparatus in
which the pressure in a combustion
chamber is varied to keep the flame in a
chosen position; the instrument is used
VOL. 41. NO. 5, APRIL 1969 · 177 R
for analysis of hydrocarbon mixtures
C1-C22 and results can be correlated with
octane number.
Distillation. A distillation ana-
lyzer patented in Russia (2L) counts the
drops of distillate and, through suitable
electronics, controls the rate of heat
input and relates vapor temperature to
the total volume distilled. Butler and
Pasternak (10L) rapidly distilled high
boiling materials in a horizontal column
that can be operated in vacuum and with
a controlled temperature gradient.
Pour Point. Automatic measure-
ment of pour point was accomplished by
Fischer {Z9L) by measuring the pressure
drop of a slow ascendant gas stream
through a column of oil sample that is
progressively cooled. When a predeter-
mined inlet gas pressure is reached,
the Peltier element is switched to warm
the sample and solenoid valves are
opened to empty the vertical test cell;
the minimum reading from a thermo-
couple in the sample denotes pour point.
Shell Internationale Research pat-
ented two ways to determine pour point
automatically (80L). In the first, a
slowly rotating jar of sample is cooled
and a hanging rod is immersed near the
edge of the jar; displacement of the rod
by a predetermined amount indicates
the pour point, the temperature being
sensed by a thermocouple in the lower
end of the rod. The second method is
similar, except that the test jar is period-
ically tilted while being cooled until the
hanging rod is displaced.
Conklin et al. {17L) described an
electronic device for automatically de-
termining pour point in which congeala-
tion of an oscillating sample deflects a
light beam onto a detecting photocell
while a thermocouple semicontinuously
indicates the pour point temperature.
Cloud Point. Automatic determina-
tion and control of cloud point were
achieved by Crespin and Axon {19L)
using two thermistors vertically spaced
in a small column of sample within
a Peltier cooler. Convection currents
during cooling keep the lower thermistor
cooler than the upper, but wax precipita-
tion blocks these currents and the upper
thermistor becomes the cooler. A suit-
able bridge circuit detects change in
differential temperature to signal the
cloud point, while a separate thermo-
couple measures the cloud point temper-
ature.
Keitel (42L) employed differential
thermal analysis for cloud point deter-
mination. In his apparatus, the sample
and a paraffin-free reference liquid are
simultaneously cooled in nearly identical
cells; differential temperature increases
markedly when cloud point is reached,
owing to heat of fusion of the wax.
Shell Internationale Research received
a patent {83L) on an optical sensor for
cloud point using polarized red light and
a photocell for detecting the appearance
178 R · ANALYTICAL CHEMISTRY
of the wax cloud when the sample
is cooled in a transparent container.
Isotropic crystals such as water do not
interfere and accuracy is ±0,3 °C.
Flash Point. A semiautomatic ap-
paratus for determining Pensky-Martens
flash point was described by Krivoshein
{46L) in which a sample is fed into a test
chamber where it is heated until the
flash is induced by a spark discharge.
A similar apparatus (68L) has been in
use in the U.S.A. for several years.
The Abel-Pensky flash point procedure
was automated by Lange {SOL).
Viscosity. A remote-sensing Ost-
wald-type viscometer developed by
Speaker {86L) uses electroluminescent
panels, is explosionproof, and is able to
operate at pressures up to 2000 psig.
Gleim and Khentov {S3L) worked out
an Ostwald-type viscometer for weakly
conducting liquids, employing electrical
recording of flow time as well as detec-
tion of position of the liquid meniscus.
For measurement of viscosity as high as
15,000 P, Hodgetts and Norman {37L)
employed a disposable 4-ml sample con-
tainer and an electronic transducer;
gelation-time and viscosity-time rela-
tions can also be obtained. Highly vis-
cous samples can be measured by a ro-
tational viscometer patented by Specht
et al. {87L).
A linear electronic analog computer
invented by Martin {57L) produces vis-
cosity index values from continuous vis-
cometers operating at 100 and 210 °F;
the L and D values for the viscosity
index equation are derived from the elec-
tric signal outputs from the viscometers
and the computer output signal can be
used for process control purposes.
Other Physical Properties. The
on-line measurement of particle size be-
tween 100 and 500 µ was accomplished
by Nakajima et al. {61L). Their in-
strument is fast, allowing a cumulative
size distribution curve to be obtained in
less than a minute. Welch’s nephelom-
eter {98L) displays and records the num-
ber of particles in various sizes from
10 to 1000 µ in a flowing liquid. In an
instrument {67L) for monitoring clean-
liness of jet fuels, the sample stream is
passed through two fine filters in series,
both of which are visible; any contami-
nation is immediately evident in the first
filter in contrast to the second, which
remains clean.
The ASTM D 1660 test for heat
stability of fuels was modified by Fabuss
and Borsanyi {28L) to provide a coiled
or flat channel that may be opened for
inspection or to provide a permanent dis-
play of the path length to first appear-
ance of coking. A recording unit for
the four-ball extreme-pressure and wear
test apparatus was devised by Frenkel
and Grivtsov {S1L) as part of the auto-
mation of laboratory tests and analyses
of lubricants.
Sampling. An automatically oper-
ated sampling device invented by Vana
et al. {94L) has a removable sample
container with quick-disconnect fit-
tings and a moving plate to admit
or discharge the sample; a program
timer operates the moving plate to
discharge the sample; a program
timer operates the moving plate to
isolate the sample. The programmed
sampling device of Tetlow et al. {91L)
provides automatic selection of a sample
stream or either of two standard solu-
tions.
An electrical or gravitational force
field supported by a nonturbulent in-
ert liquid is the basis for a device pa-
tented by Whitlock and Bell {100L) for
automatically controlling the sampling
of solutions or suspensions. Cole et al.
{16L) described a tape-controlled se-
quencing device to carry out routine
laboratory operations in almost any ex-
periment or procedure that can be re-
duced to a set of sequential operations.
Light Hydrocarbon Analysis. In a
gasoline stabilization plant producing
LPG as depropanizer overhead, the
temperature set-point of the de-
ethanizer reboiler is adjusted accord-
ing to glc measurement of ethane in
the downstream debutanizer overhead,
according to Case et al. (13L). Ethane
content of the LPG is maximized with-
out exceeding vapor pressure specifica-
tions.
In a Russian refinery {8L) diesel fuel
quality is controlled by the 96%-
evaporated temperature and measured
on-stream by a commercial analyzer,
coupled to an automatic controller;
deviations in product end point were
+2°, and yield was increased 0.3%.
Morrison {60L) described how Shell
uses three gas chromatographs for pro-
cess and quality control of a n-butane
product stream at the Pernis refinery.
The computer-controlled gas chroma-
tograph described by Mears {59L) is
nearly devoid of programming and gat-
ing timers but reliably produces analyti-
cal data needed for sophisticated auto-
matic control of distillation columns.
Wherry and Miller {99L) reported on
versatile and reliable chromatographs
with high sampling rate that were de-
signed for automatic process control.
The control systems incorporate predic-
tive and feedback characteristics to en-
sure meeting quality specifications pre-
cisely and to maximize profitability of
distillation units.
Transportation Testing. In trans-
porting LPG, process analyzers proved
valuable. Specific gravity, vapor pres-
sure, butane content, and non-
volatile residue were determined by
a process gas chromatograph eval-
uated by Mid-America Pipeline Co.
{66L), and similar applications were dis-
cussed by Ball {6L). A potentiometric
titrator monitors and controls sulfur-
 containing odorant in a gas-distributing
system, according to Vlasek (96L).
Detection of interfaces between prod-
ucts flowing in pipelines is aided by
Bond’s apparatus (9L) which utilizes
static electricity by passing a sample
stream through a strong electrostatic
field. The downstream charge will re-
main constant if composition does not
change, but a new product will carry
a different charge. Ratway and Wood
(7SL) used a flash point apparatus oper-
ating at constant temperature to moni-
tor the interface between two products.
Provision was made to blend a fuel of
different, known, flash point into the
interface sample in such a ratio that the
mixture’s flash point varied from one
side of the fixed temperature to the other,
thus producing at least one flash for
positive location of the cut-point. A
further refinement (74L) produced at
least two signals for increased reli-
ability.
Process Analyzer Application. Sev-
eral publications are valuable be-
cause they reveal the extent to which
on-stream analysis instrumentation
is being used. Wall (97L) reviewed use
and discussed efficiency of gas chroma-
tographs, radiation-type instruments .for
analysis or density measurement, and
some chemical analyzers. Mawson
(58L) pointed out that critically im-
portant product quality cannot be as-
sured by automatic control of tempera-
ture, pressure, and flow in conjunction
only with laboratory analyses. There-
fore, there is an increasing demand for
on-line analysis and automatic control;
this type of equipment is reviewed.
Optimization of large processing sys-
tems and company-wide refining opera-
tions is first made possible by applica-
tion of automatic quality analyzers and
further aided by advanced mathematical
techniques and automatic data reduc-
tion (41L).
The status of automatic control of
petroleum and chemical process systems
was discussed by Rijnsdorp (76L), who
cited specific examples. A comprehen-
sive review of process instrumentation
and control in Great Britain was given
by Young (102L). Lorinc (5j-L) de-
scribed process analyzers made in Hun-
gary, including gas chromatographs,
titrimeters, and mass spectrometers.
Quality control of petroleum products
by automatic analyzers was reported by
Bassalert (7L), with examples of how in-
line analyzers are incorporated in auto-
matic control loops.
Sellers and Spencer (79L) not only
gave a schematic refinery flow diagram
indicating locations for 38 process
analyzers, but briefly discussed avail-
ability and operation of many com-
monly used quality-measuring instru-
ments. They stressed that process con-
trol based on product quality will gain
in importance and be further aided by
mathematical correlation of conven-
tional properties, plus finding new,
more-significant quality parameters and
methods of measuring them continu-
ously.
Shpunt ef al. (84L) investigated the
possibility of making few different tests
for controlling operation of a reformer;
they found that product octane number
and the 10% evaporated point could be
inferred from vapor pressure, but initial
and final boiling points were needed to
characterize fractional composition.
It is possible, according to Makkaveev
and Shpakov (56L), to select a minimum
number of control variables in a refining
operation by establishing mathematical
correlations between variables; as a
simple example, in desalting crude oil,
an increase of water content by 0.01%
increases salt content about 0.5 ppb.
The derivation and use of predictive
data on distillation characteristics of
distillation products for automatic con-
trol of the process were described by
Lapa and Fainerman (51L). Success
of in-line blending of gasolines results in
large measure from application of con-
tinuous quality-measuring instrumenta-
tion, according to Page (63L). A full
description of an automatically con-
trolled blender was given by Laird ef al.
(49L), together with information on
savings realized.
Benefits of octane control were delin-
eated by Ruegnitz (77L), and Hurst and
Sewell (38L) described application of
continuous Reid vapor pressure and
octane analyzers to controlling quality
of gasoline from automated blend-
ing systems. Dyess (26L) outlined how
continuous analyzers can profitably be
used even in a 24,000 bbl per day re-
finery.
To capture the advantages of apply-
ing process analyzers to operating units
requires surmounting problems, not all
of which are purely technical. Page and
Caldwell (64L) affirmed from experience
that continuous monitors can be trusted
because, when properly calibrated and
maintained, they are as effective as
(sometimes superior to) conventional
ASTM tests for quality control and can
effect significant savings in maintaining
close control of product quality.
Liffland and Mosher (SSL) outlined a
profit-oriented approach to analyzer
application comprising a new type of
engineering function responsible for all
stages of instrument application and a
follow-up to see that the expected profit
is accruing.
The “common-sense” approach to use
of stream analyzers was stressed by
Stallings (88L). Processing profitabil-
ity at some refineries is improved by use
of van-mounted or trailer-mounted
analyzers with computers, according to
Puzniak (72L), who fully described this
new method of gathering on-site data
with a minimum investment. Ryan
(78L) told how a large number of ana-
lyzers were installed in a single refinery by
a subcontractor who was responsible for
pretesting, calibration, and commission-
ing of 84 instruments of 15 different
types.
The growing use of process analyzers,
especially for controlling product quality,
deserves the attention of present labora-
tory managers, as pointed out by Crop-
per (21L) in a discussion of how quality-
measuring instruments affect refinery
laboratory operations and responsibil-
ities.
Contamination
Control
F. D. Tuemmler
Shell Development Co., Emeryville, Calif.
Refinery Air. With the broader
subject of atmospheric pollution left
to other reviews, it is intended here to
discuss those possible contaminants
arising from operation of petroleum
refineries. Thus, those materials aris-
ing from automotive exhaust gases
and fuel tanks are not considered as
part of this review, even though methods
for their analysis may be usable in that
context.
The Air Pollution Control Associa-
tion’s Petroleum Committee (18M)
published a general review covering
possible airborne contaminants from
refining operations describing control
methods in use at that time. Listed are
particulate matter, sulfur oxides, hy-
drocarbons, nitrogen oxides, mercaptans,
hydrogen sulfide, organic sulfides, phe-
nolic compounds and naphthenic acids,
nitrogen bases, aldehydes, and carbon
monoxide. The U. S. Public Health
Service (38M) described tests used to
measure the atmospheric concentration
of some of these.
Hydrogen Sulfide. Sanderson
(SOM) described limitations of the lead
acetate paper tape method for estimat-
ing hydrogen sulfide at the odorthresh-
old concentration; Pare (27 M) de-
scribed an improved tape reagent which
used mercuric chloride as the sensing
material. Austin (SM) reported on a
coulometric titrator for determination
of both hydrogen sulfide and sulfur
dioxide. Nicols (25M) described a com-
mercial sulfur dioxide meter based
on photochemical measurement of de-
colorization of starch-iodine solution by
absorption of sulfur dioxide; by change
of reagent and filter, he was able to use
the instrument for measurement of hy-
drogen sulfide.
Sulfur Dioxide. Absorbed in aque-
ous sodium chloromercurate, sulfur
dioxide forms a complex which de-
colorizes pararosaniline dye; the extent
of decolorization is measured spectro-
VOL. 41, NO. 5, APRIL 1969 · 179 R
photometrically (West-Gaeke method).
Dokladalova ef al. (11M) described ex-
tensive studies on selectivity of the
method, Scaringelli et al. (32M) and
Saltzman and Wartburg (29M) devel-
oped refinements, and Huhn et al. (17M)
showed how the method could be used
at temperatures below 0 °F.
Lyshkow (21M) described a contin-
uous analyzer based on use of a unique
rotary scrubber containing only the
rosanaline dye in water. Bracewell
and Hodgson (5M) demonstrated that
hydrogen peroxide solution in the British
standard method removed 99% of sulfur
dioxide from low concentration gas
streams. Hochheiser et al. (16M) com-
pared the West-Gaeke and the hydrogen
peroxide methods with and without
prefilters and indicated the different
interferences responsible for variation of
results by the seven versions examined.
Caeusescu (9M) based a microvolu-
metric method for sulfur dioxide on re-
action with an alcoholic potassium chlo-
rate solution and titration of the sulfate
formed using sodium alizerin-sulfonate
as adsorption (on barium sulfate) in-
dicator. Berezkin et al. (4M) reported
on a gas chromatographic method in
which hydrogen sulfide and carbonyl
sulfide did not interfere. Adams et al.
(1M, 2M) detailed a microcoulometric
cell which, when combined with selec-
tive chemically impregnated membrane
prefilters, could determine any of
several sulfur-containing gases occurring
in refinery atmospheres.
Hydrocarbons. The usefulness and
limitations of gas-liquid and thin layer
chromatography in characterizing alkyl-
ated hydrocarbon air pollutants were
shown by Sawicki et al. (31 ). Stephens
and Burleson (36M) were able to analyze
in concentrations below 1 ppb some 25
hydrocarbons having volatilities below
m-hexane; Jueng and Helwig (20M) de-
scribed a rapid method for air contain-
ing only C1-C4 hydrocarbons. Clemons
and Altshuller (10M) showed the useful-
ness of fluorinated polymeric films for
storage of air samples containing hydro-
carbons.
Lead Compounds. For areas where
lead compounds are handled, Linch,
et al. (22M) described a useful selfpow-
ered constant rate sampler contain-
ing solid iodine absorbing better than
98% lead alkyls; Browelt and Moss
(6M) described and automatic analyzer
using iodine monochloride as absorbent.
Skalicka and Cejka (35M) compared
three different methods and commented
on their relative usefulness. Cantuti
and Cartoni (8M) described a gas chro-
matographic method applicable at con-
centrations up to 100 ppb; Thilliez
(37M) reported on an infrared procedure
applicable down to 1 ppb.
Gas Lines. In the production of
liquid air or oxygen, it is important that
the air source to be compressed is
180 R · ANALYTICAL CHEMISTRY
hydrocarbon-free. Visani et al. (39M)
described a batch, and Roissart (28M)
a continuous gas chromatographic pro-
cedure. Grishin et al. (14M) were able
to measure quantities of 0.002 g of oil
per 1 of nitrogen using an infrared spec-
trophotometric method. Evans (12M)
sampled and analyzed gas stream clean-
up devices at pressures of 4500 psi for
0.1 to 1 ppm oil concentrations; glass
fiber filters were used and the oil was
determined gravimetrically.
Effluent Water. Forbes and Witt
(13M) and Hickey (15M) published
reviews of pollution control by eval-
uating quality of refinery effluent;
in both papers, emphasis was placed
on selection of suitable and effective
analytical methods, including new
methods suitable for research and
monitoring.
Burmeister (7M) described results of
interlaboratory cooperative tests using
a petroleum ether extraction method;
only heavier oils were determined be-
cause a nonvolatile residue was mea-
sured after evaporation of the petroleum
ether. A gas chromatographic method
applicable to gasoline contamination
was developed by Jeltes and Veldink
(19M); as little as 0.1 mg of gasoline
per 1 of water was measured.
Osipov and Belova (26M) employed
a broad band ultraviolet method cover-
ing the spectral region containing strong
absorption bands of aromatics and
phenols, the sample being extracted
first with isooctane; it is assumed that
the hydrocarbon-type composition of
the waste oil is fairly constant at any
given refinery. Martin et al. (23M)
reported on a differential uv differential
absorption method which is nonselec-
tive and rapid for measurement of
phenols alone.
Foods. Methods have been pro-
mulgated for control of tetra- and
higher aromatics (carcinogens) in
mineral oils and waxes used in food
and drug industries. Mazee et al.
(24M) compared three methods and
found the dimethyl sulfoxide method
(ASTM D 2269) most reliable when
applied with described amendments;
an ultraviolet method was most con-
venient but required correlation with
the DMSO method.
Silverberg et al. (84M) described a
satisfactory cooperative test program
using a chromatographic method which
was recommended for adoption as an
AOAC test for mineral oil in bakery
products. Seitz (S3M) also described a
thinlayer chromatographic procedure
for detection of mineral oils in fats.
Miscellaneous
Flue Gases. Knowledge of com-
position of flue or stack gas is neces-
sary for efficient operation of furnaces
or for control of pollutants. An
interesting steam-operated ejector
coupled to a carbon dioxide analyzer
was shown in Hydrocarbon Processes
(4N). Schneider (UN) described an
experimental comparison of three simple
methods for determination of sulfur
dioxide and sulfur trioxide in furnace
stacks. Renzanigo discussed methods
for determination of solids content in
industrial stacks (9N) and domestic
flues (10N); Wickert (12N) discussed
effects of the solid content of stack gases
on determination of sulfur trioxide.
Low (5N) described an interesting
infrared interference spectrometer
mounted on a truck capable of measur-
ing the sulfur dioxide emissions from
distances of one-half mile and at night.
Products. Murphy (6N) described
procedures for testing petroleum coke,
a subject not frequently reported.
Norbury (7N) described methods for
measuring lubricating oil content of
fluorinated refrigerating agents. Herr-
mann and Cleverley (3N) described a
method for determining paraffin oil
content of fungistatic preparations.
Use of odor panels for detection of un-
wanted components in various petro-
leum products was reported in the Oil
and Gas Journal (8N).
Processes. Apel and Witzel (IN)
described methods for determination
of corrosion in petroleum processing
plants. Frazier and Huddle (2N) de-
scribed use of the Erdco CFR fuel-
coker for measuring a fouling index
or an antifouling effectiveness factor
of a chemical antifoulant to prevent
clogging of preheater tubes.
ACKNOWLEDGMENTS
The author thanks P. Swanson and
E. T. Scafe of Mobil Research and
Development Co., Paulsboro, N. J., J. F.
Hickerson, Humble Oil and Refinery Co.
Baytown, Tex., who assisted in search-
ing abstract journals for a collection of
abstracts of appropriate papers. These
abstracts were then divided into logical
groupings and further screened by the
15 reviewers of the 13 subject classifica-
tions of this review. The success of this
review is due to the generous assistance
of these dedicated people.
LITERATURE CITED
Introduction
(1A) Barras, RC, Smith, HC, 7th World
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(2A) Bassalert, JL, Mes, Regul, Automat,
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(3A) Boreham, GR, Armstrong, WE,
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(4A) Chem Eng News, 44, 43 (l5-Mar-66).
(5A) Caigneau, M, Chimlnd (Paris),'93,
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(6A) Fritz, W, 16th Deut Mineraloel
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(7A) Gambrill, CM, Anal Chem, 35,
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(8A) Ibid., 37,143R (1965).
(9A) Gray, PR, 7th World Petrol Cong,
Mexico City 1967, (4), PD-15.
(10A) Gunn, EL, Amer Soc Test Mater,
Spec Tech Publ, 349 (1963).
(11A) Harding, JH, Morgan, WA, Proc
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(12A) Inst Petrol Rev, 21,302 (1967).
(13A) Jenkins, GJ, Behling, RD, Heil-
mann, G, Erdoel Kohle, 19, 890 (1966).
(14A) Kajikawa, M, Okamoto, N, Sekiyu
Gakkai Shi, 10, 358 (1967).
(15A) Karau, WAA, Patterson, TB,
Balint, FJ, Anal Chem, 37, 27A (1965).
(16A) Keil, G, Hung Chem Ass Conf,
Budapest 1965, API 13, 5641 (1966).
(17A) Kerenyi, E, Magy Tud Akad, Kem
Tud Oszt Koslem, 23 393 (1965).
(18A) Kienitz, H, Kaiser, R, Erdoel
Kohle, 20, 209 (1967).
(19A) Killer, FCA, Amos, R, J Inst
Petrol, 52,315 (1966).
(20A) Lawrey, DMG, Amer Soc Test
Mater, Spec Tech Publ, 389 (1965).
(21A) LeFeuvre, T, Meyers, PS, Shi-
pinski, JH, el al., SAE (Soc Auto Eng)
Cong, Detroit 1968, Pap 680133.
(22A) Not cited.
(23A) LeTourneau, RL, Anal Chem, 29,
684 (1957).
(24A) Ibid, 31 730 (1959).
(25A) Ibid 33 (5)92R (1961).
(26A) Levin, HL, Anal Chem, 25, 47
(1953).
(27A) Ibid, 27, 599 (1955).
(28A) Lumpkin, HE, 7th World Petrol
Cong, Mexico City 1967, (3) PD-15.
(29A) Magin, CT, Oil Gas J, 64, 128
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(2N) Frazier, AW, Huddle, J, Power,
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(10N) Ibid, 21, 506 (1967).
(11N) Schneider, W, Brennstofftech Ges
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VOL. 41, NO. 5, APRIL 1969 · 189 R