petroleum research laboratory has been reviexved by Bird (BA); he deals with analysis of surface layers of lubricants on metals and specimen sections of bearing metals. Several papers from abroad indicate the growing use of modern methods there; such reviews as those of Ternoysksya (41A),Keil (19A),and Luther and Louis et al. (29A) are indicative. The role of statistics in analysis was paid attention by Calder (4A). The ranking of laboratories and evaluating of analytical test methods used in cooperative test programs, as is very commonly done in petroleum analytical laboratories, n a s discussed b y Lashof (2IA). Most interesting is a neFv slant on the construction of specifications for petroleum products as described by Cranston and Gammon (6-4).
Crude Oil J. L. Ellingboe, Marafhon Oil Co., Findlay, Ohio
A
for the analytical batch distillation of petroleum crudes on a packed column was reported by Schwartz (1SB). This proposed dist,illation t'echnique was shown to be faster than the T7igreux column method, Jvith good agreement between the tvvo. The time advantage is obtained because a smaller sample is fractionated a t a lower reflux ratio. Gaylor, Jones, Landerl, and Hughes (5B) have developed a gas chromatography method for the simultaneous determination of crude oil boiling range distribution and hydrocarbon-type distribution. The exact location of a peak is achieved by assigning a major group number and a partial relative retention time. A qualitative characterization of major peaks and shoulders was done by using a time-of-flight mass spectrometer attached to the detector vent of the gas chromatography unit. The boiling range distribution obtained for paraffinic crudes was close to the dist,illation curves from an efficient fractionating column. Typical analyses of heavy naphtha and crude oil are given. Infrared spectroscopy was used by Leutner (9B) to make approximate estimations of certain structural groups in crude oils from the Vienna Basin. By this method, a view of the hydrocarbon composition of an oil is obtained quickly. Karbasian (7B) reviewed the procedure for the evaluation of crude oils a t Abadan, Iran. A. detailed analysis of a crude oil from the .Ihwaz Field is shonn. Kerenyi (8B) has continued his studies of Hurigarian domestic and imported petroleum. In this paper he describes a process for the laboratory investigation of crude oil by which the RAPID hfETHOD
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ANALYTICAL CHEMISTRY
chemical composition and economic value can be accurately estimated. This involves distillation; fraction investigation with graphical evaluation of the results. Schenck and Eisma (12%) developed a gas chromatography method to determine n-alkanes in crude oils and rock extracts. A gas chromatography column was placed in series with a column filled with molecular sieves. Two chromatograms &*ere obtained, with and lvithout n-alkanes, thus permitting their determination and distribution. X unique sampling analysis method for crude oil directly from the well was developed by Giraud (6B). The analysis is done by gas chromatography: specific peak areas for n-paraffins were established. Nestler, Triems, and Heinze (10B) have also reported a method for the determination of the paraffin content of crude oils. The crude is dissolved in hexane and filtered over fuller's earth. After removing the hexane, the waxes are crystallized and separated by precipitation from an acetone-toluene solution. Reproducibility is about 0.5 weight per cent for paraffin contents of 10 to 20 weight per cent. Seutral resins in crude oil or wax were determined by a procedure developed b y Tronov and Khamzina (16B). Asphaltenes are first separated and the sample is then split into two portions. One is treated with silica gel and then extracted with petroleum ether. The ether extract is combined with the unextracted portion, the optical density measured, and the resin content calculated by a formula derived by the authors. Tumasyan and Babalyan (16B) measured the adsorption of asphaltenes from crude oil and synthetic mixtures of asphaltenes in kerosine-benzene solutions on sand and quartz. They observed the largest asphaltene adsorption from the synthetic mixture using sand as the filtration media. X small angle x-ray scattering study of the colloidal nature of petroleum by Dwiggins (ZB), showed that colloids derived from seven crude oils had different average Guinier radii of gyration, and some polydispersity. Comparison of these results with those of other studies suggests the colloids seen by x-ray scattering are the same as the asphaltic-rich colloids seen in ultracentrifuging. The small angle x-ray method shows promise for further study of colloids in petroleum. Forney, Gulbrandsen, and Borup (4B) determined the salt content of crude oil by measuring the conductance of a solution of the crude 011 in a mixture of xylene, methanol, and butanol. The apparatus was calibrated using a mixture of NaC1, CaC12, and MgC12; 7 to 2 to 1, respectively. Re-
sults were in good agreement with those obtained using a conventional extraction method. Apparatus was also developed to analyze a plant stream at 3to 60-minute intervals, with a single analysis requiring about two minutes, Farley and Leonard (SB) developed a procedure for the determination of the salt content of heavy crude oils and asphalts. The crude or asphalt is dissolved in phenol-chloroform and extracted with a 0.1% solution of sodium or ammonium nitrate in water. The aqueous evtract is centrifuged, and an aliquot titrated for chloride with silver ion. The method is fast and accurate. Crude oil as light as 27' *\PI and asphalt as hard as 10 penetration have been analyzed successfully. Trace amounts of vanadium in hydrocarbons mere determined by Roberts (11B) using electron spin resonance. The samples were solidified to avoid inherent errors when samples are run in the liquid state. Ultrasonic atomization of oil samples diluted 1: 1 m-ith alcohol gave improved flame photometric sensitivity when compared with other methods in the detection of alkali and alkaline earth metals. -4ugsten (1B) also reported a significant reduction in analysis time. The results suggest this technique can be adapted to the quantitative determination of sodium crude oils. Sugihara and Garvey (I@) obtained higher recoveries of etioporphyrin I and mesoporphyrin IX when they substituted formic acid for acetic acid using the hydrogen bromide demetalation method for vanadyl porphyrins. This modified method has been used in the analysis of asphaltenes and crude oil.
Fuels K . I. Shull and I. D. Beardsley, The Standard Oil Co. (Ohio), Cleveland, Ohio
V
ERNET AND KNIAZEFF (Iloc) describe methods of determining viscosity, thermal conductivity, and latent heat of liquefied natural gas a t 2 - 175' C and 5 1067 psi, but no experimental results are given. An apparatus constructed with practically inert niaterials is being used for measuring viscosity of a corrosive natural gas b y Lazarre, Martin, et al. (sac). Sens and Sallaberry (97'2) discuss the theory of density measurement of natural gas. They have studied both a static and a dynamic densimeter. Gebert, Lugt, and Herbst (34C) have worked up a simple gravimetric technique for density measurement. They have compared results with those obtained on six different instruments of four types. Prahacs
and Gravel (85C) arranged a positivedisplacement gas metwing device in series with an orifice flowmeter to serve as a rapid, simple molecular weight monitor and on-stream gas analyzer for a process stream. The compressibility indexes of natural gases of various compositions are reported b y Herning and Wolowski (46C) and compared with U. S. published data. Makogon (65C) discusses the moisture capacity of natural gas. A table of water contents from -40’ to 80’ C and 1 to 500 atmospheres is given for natural gas with a density of 0.6 gram/cibic meter. A correction curve is provided for gases of other densities. Olund (78C) describes the application of the Rayleigh equation for calculating variability in composition of both residual and va2orized odorant added to natural gw. Andreen, Kniebes, and Tarman ( I C ) have developed a two-stage gas chromatograph for determining odorant sulfur compounds in natural gas. Twelve CZto Ca mercaptans and sulfides were separated from interfering hydrocarbons and from each other. Mitrofanov and Makarov (7OC) modified the MI-] 305 mass spectrometer to allow the determination of helium and argon in natural gases with an accuracy of 5 0 . 7 5 and *0.05’%, respectively. A gas chromatographic method is used for the simultaneous component analysis and BTU value of natural gas by Thompson and Cavenah (106C). Woelk (11SC) has derived a formula for the calculation of calorific value of town gases, natural gases, etc. Experimental studies by Koecker (58C) indicate that errors in the, determination of combustion heats of hydrocarbons and liquid and solid fuels, are caused by incomplete combustion. These errors can be significantly reduced by an increase in the free combuc,tion surface of the compound and by an increase in oxygen pressure from 30 to 45 atmospheres. Gas chromatography is ufied for comprehensive analysis of fuel gas by Blakemore and Hillman (9C‘). Razumovskaya and Kurenkov (87C) determine the composition of gas from butylenes dehydrogenation by means of gas chromatography. Gas chromatography continues to be a popular method for the analysis of combustible gases. Aranda and Flaquer (2C) discuss the Janak method and compare it with the Orsat method. Roberts and Ward (9OC) present a new gas chromatographic me ,hod with the density balance as the detector for permanent gases. The density balance detector has become comniercially available only recently. For hydrocarbons, the argon ionization detxtor is used. Hofmann (@C) describes rapid test methods for checking the quality of LPG shipments when laboratory facilities are not available. A sturdy densitometer has been developed for use a t an
unloading station or LPG plant reports the same author (48C). The determination of density and pressure of liquefied (C, to C,) hydrocarbon mixtures from chromatographic analytical data is reported by Thomas and Zander (105C). Gas chromatographic data are also used to calculate vapor pressure of LPG a t elevated temperatures by Hammerich and Schmitz (4SC). Baxter (SC) discusses knock rating of gaseous fuels. The standardized apparatus and technique used in the proposed ASTM Motor Method for LPG are described. A rapid color test for mercaptan odorant in LPG has been designed by Peurifoy, O’Neal, and Dvoretzky (82%’). This technique can be used without laboratory facilities. Solbrig, Saffert, and Schuberth (101C) make a quantitative analysis of flue gases by programmed gas chromatography, Rueb (9SC) describes instruments which automatically determine carbon dioxide and carbon monoxide plus hydrogen in stack gases, thus permitting direct control of the combustion process. Rate of conductivity buildup and peak rate temperature are better indicators of the corrosiveness of flue gas than is the actual dew point report Clark and Childs (2%’). Engineer (26C) describes a portable apparatus far measuring carbon in flue gas. Weber ( l I 4 C ) describes a new device for the continuous measurement of the solids content of flue gases. Freund and Zalai (S2C) present a summary of the testing and properties of motor fuels. Aviation turbine fuels can differ in their ability to cause sulfide corrosion of silver. Thompson, Hills, Brown, and Lewis (107C)have devised a simple laboratory test for determining silver corrosion and correlated it with full-scale laboratory pump rig tests under similated operating conditions and with practical aircraft operating experiences. The Coordinating Research Council (23C) has made a study of the test for assessing the water separation characteristics of fuels containing surfactants. The Journal of the Institute of Petroleum (54C) describes a method of fuel sampling for the determination of particulate matter. This method has been proposed by I P to ensure a common basis for discussion of contaminant levels. Ismailov (52C) evaluates the filterability of airplane gasoline by means of a special apparatus. Plogsties and Eckardt (84C) have established an empirical equation for predicting the luniinometer number from a single measurement. They also have correlated luminometer number with chemical structure and with carbon deposition. Laboratory expressions for motor fuel volatility and their significance in terms of performance are the subjects of a paper prepared by Morrison, Ebersole, and Elder (74C). Xorrison, Ebersole,
and Tooke (76C) have modified the Reid vapor pressure test so that it predicts precisely the vapor lock tendencies of gasolines and other hot fuel handling difficulties. The change in pressure of a mixture of vapor(s) and air is determined by Neumann (77C) over the surface of the tested liquid fuel in a closed vessel immersed in a heated bath. Shikhov and Sitnikov (98C) describe an apparatus which may be used for measuring the density of electrostatic charges on the surface of flammable liquids, on the carbon-coated walls of vessels, pipes, or tanks, and on the portions of electrical conduits insulated from the ground. A portable instrument for measuring electrical conductivity of aviation fuel a t airfields is described by Foster and Marsh ( S I C ) . Using this electrostatic monitor, Marsh and Hawks (67C) have collected measurements of the generation of static electricity during the routine fueling of aircraft. These data show that, although significant amounts of static electricity are frequently generated during fueling, it seems to be a negligible hazard. Finnigan and Pfeifer (SOC) have made a review of current methods for the evaluation of fuel and lubricant properties. A computer is used by Walker (1 I ZC) to calculate the effect of varying the compression ratio, combustion period, and spark angle on CFR en,’nines. The development of methods for displaying knock signals from a car gasoline engine accelerated under Modified Uniontown conditions is described by Brockhaus ( I S C ) . The Journal of the Institute of Petroleum ( 5 3 3 reports the results of an experimental study on the effect of engine operating condition tolerances on the accuracy of Xotor, extended Motor, and Research Knock ratings. Robinson and JT7agner ( $ I C ) have modified the Coordinating Research Council, Inc.’s vapor-lock procedure Fhich employs full-throttle acceleration. They found that partthrottle acceleration provides a more realistic comparison with actual driving conditions. Road octane equations can be established by the regression analysis of the results of CFR bench engine experiments, report Brockhaus and Fischer ( I 4 C ) . Bauer and Callat (5C) describe the progress in the development of the distribution octane number (DON). The petroleum industry can realize savings through improvements in the precision of laboratory knock test methods and improvements in the ability of the methods t o predict road octane number. Morris and Hoffman (7SC) list some of the means for improving the precision and significance of these methods. Mechanical Engineering (69C) reports the development of an engine test rig for conducting comprehensive performance trials and analyses on diesel fuel or VOL. 39, NO. 5 , APRIL 1967
159 R
gasoline. The ignition tendency (cetane number) of diesel fuels has been studied at low air intake temperatures by Wolf ( f f 7 C ) . Futterer (3%') has conducted experiments on the scattering of cetane number measurements on commercial diesel fuels. Bird and Small (8C) have examined the carbonaceous residues and ash in the gas stream from the combustion of residual fuel. A technique has been devised by Monaghan (72'2) to assess the effect of the initial size of liquid fuel drops on their rate of combustion. Kuchta, Bartkowiak, and Zabetakis (60C) give data on autoignition temperatures of JP-6 in oxygen-nitrogen atmospheres under constant volume and pressure. A number of references on storage stability appear in the literature. Drabkina, Zyryanov, and Orechkin ( 2 K ) propose color change as a quality characteristic of kerosine which would permit an estimation of its stability during storage. Schwartz and Ward (94C) have studied the effects of fuel insoluble gums on the storage stability of distillate-type fuels and of soluble gums on gasoline stability. From these data, a general equation has been obtained which can be used to express fuel deterioration as per cent reaction of a fuel component or as the amount of gum formed. Roels (92C) has tried the accelerated aging of motor fuel in the presence of copper as a modification of the IP 40 and ASTM D 525 methods. An extensive experimental study including radioactive tracer measurements and accelerated aging by ultraviolet irradiation has been carried out by Schwartz, Whisman, et al. (95C). This study shows that gum formation results from chemical reactions in the presence of oxygen and not from extensive polymerization; the presence of sulfur compounds is essential to the formation of gum. X simple, rapid test for existent gum has been developed by Hills (47'2). The results obtained with this test correlate well with the fouling of fuel inlet systems in the field. Haltner (41C) has used a tritium tracer technique to study the effect of 70 compounds on gasoline storage stability. This study reveals that sulfur and nitrogen compounds are the most reactive components in the gum-forming process. The thermal stability of supersonic jet engine fuel is measured by means of a miniature, single-tube heat exchanger. This exchanger has been developed by Burggraf and Shayeson ( I S C ) . Xlardanov, Markhaseva, and Bizyaeva (66'2) determine the thermal stability of fuel fractions by irradiation with ultraviolet light. J . R. Ritchie (89C) reports on a sixyear laboratory and field study on the storage stability of six distillate diesel fuels. The tests for soluble and insoluble gum, water retention, Thornton injector needle lacquering, and the U. S. 160 R
ANALYTICAL CHEMISTRY
Navy filter clogging were of little or no use in evaluating the stability characteristics of these fuels; but the 16-hour a t 210' F (ESSO)and the four-week a t 120' F (BP) stability tests predicted reasonably well the storage behavior of these fuels. A method for the investigation of the oxidation kinetics and thermoxidative stability of diesel fuels is described by Losikov, Rubinshtein, and Sobolev (633. Brink and Scholtz (1SC) have made a general survey of the FIX procedure with emphasis on the effect of water in the silica gel. The Journal of the Institute of Petroleum (55C) reports a study of the precision of the FIA method on products distilling below 315' C. F I d combined tvith aniline point determination is a rapid analytical method for light petroleum distillates or products of catalytic reforming, report Kurchatkina, Orekhova, and Skripnik (61C), Liquid chromatography with luminescent indicators is used by Panchenkov, Zhorov, Venkatachalam, and Gurevich (8OC) to determine the groups in hydrocarbon mixtures. Zhorov, Panchenkov, et al. (121C) introduce a new indicator-l,3diphenylbutadiene-for the determination of aromatic hydrocarbons in the gasoline-kerosine range. The indicator spreads uniformly throughout the zone of aroniatic hydrocarbons in silica gel chromatography, giving a bright bluishpurple color upon irradiation with ultraviolet light. The indicator is used together with Sudan I11 dye in benzene solution. Chromatographic analysis, using this new indicator (1,3-diphenylbutadiene), combined with the bromine number method is employed by Zhorov and Panchenkov (12OC) to determine hydrocarbon types in petroleum products containing alkenylaromatic hydrocarbons. Washall, hiameniskis, and Xelpolder (11SC) determine saturates in heavy petroleum oils by treating the sample with a mixture of fuming sulfuric acid and nitric acid, absorbing the treated olefins, aromatics, and nonhydrocarbons on a bauxite-silica gel column, and recovering the saturates by solvent elution. Integrated analysis by FIX, bromine number, gas chromatography, and infrared spectroscopy is illustrated for a CS to CI8 olefin fraction by Hachenberg and Gutberlet (39C). Ioffe and Batalin (60C) describe refractometric methods for the group analysis of gasolines. The molar absorptivity of the compound formed by the reaction of cyclohexene with sulfuric acid is measured by Makarov (64C) in the determination of small amounts on cyclohexane. Karzhev et al. (57C) report the separation of p-xylene from a mixture of CS hydrocarbons by the formation of a complex with antimony trichloride. Complex formation with Ni(SCS')p4-methylpyridine is used by Casu and Casellato (18C) to separate terphenyl isomers.
Tetramethyluric acid has been found by Mold, Walker, and Veasey (YlC),to be a satisfactory and selective complexing agent for the separation of several polycyclic aromatic hydrocarbons of similar structure. Vasilescu and Focsa (1O9C) suggest urea adduction for estimating the n-paraffin content of gas oils t o be used in microbiological processes. This same technique has been used by Orszag and Bathory (79C) for the determination of n-paraffins in commercial oils and petroleums. Tago, Nambu, and Noguchi (104C) compare a photometric procedure with a gas chromatographic procedure for the determination of dicyclopentadiene in petroleum products, Baranova, Xoskvin, and Kurochkina (3C) describe applications of colorimetric methods for the determination of cyclopentadiene in isoprene. An ultraviolet spectrophotometric analysis of hydrocarbon oil streams has been patented by Gulf Research and Development Co. (37C)* The ozone titration for the determination of unsaturation in olefins has been modified by Guenther, Sosnovsky, and Brunier (S6C). This modification eliminates the problems of ozone control and end point detection without sacrificing accuracy. Belcher and Fleet (7C) have determined olefinic double bonds on 40 to 80 pg of organic material by their reaction with the nucleophilic reagent morpholine to form a tertiary amine. Phenols, C : C unsaturated compounds, and ethers are determined by photometric titrimetry with pyridinium bromide perbromide by Williams, Krudener, and McFarland (115C). U.K. Atomic Energyduthority (108C) reports an acid equilibrium procedure for the determination of tributyl phosphate in active and nonactive mixtures with kerosine. Two procedures for the determination of Santolene C in jet fuel are described by Blok, Dahmen, and Verjaal (IOC). The additive is extracted and then determined by either a potentiometric microtitration or spectrophotometic measurement of a methylene blue complex. Spitler (102C) reports on a carburetor icing field test, held a t Vancouver, involving 129 cars and about 15,000 runs. An accurate laboratory method for determining the tendency of gasolines toward carburetor icing has been developed by Hammerich and Schildwaechter (4215'). The advantages of a laboratory method over the use of a multicylinder engine are discussed. The analysis of anti-icing additives in jet fuel by infrared spectrophotometry is described by Hasegawa, Kajikawa, Kawaguchi, and Kishijima (44C). In a method developed by Yates, Rai, and Klass ( f f S C ) , fuel detergency in carburetors is evaluated by electrical charge measurement during engine operation. Feldman (29C) combines solvent elution and infrared spectrophotometry to de-
termine the amount of ester polymer additives in distillate fue:.oils. A large number of ahtracts pertain to the determination of lead in gasolines. Five of the references 5ted make use of the chelatometric tit:-ation. Cipriano (2fC) extracts t’he lee,d as directed in ASTM D 526, then titrates with ethylenediaminetetraacetic acid (EDTA) using Eriochrome black T indicator. Escolar and Castro (27C) treat the sample with a soluticn of chlorine in carbon tetrachloride, cxt,ract lead with water, then tit,rate (:helatometrically. Koyama, Taguchi, ar.d Eguchi (69C) have devised a procedure in which T E L is decomposed with a sclution of bromine in carbon tetrachloride, the lead extracted with nitric acid, and titrated with EDTA. Riquelnie (88C) extracts the lead frcm the gasoline by refluxing with concentrated h;rdrochloric acid, adds nitrilotriacetic acid t,o chelate the lead, and titrates the excess acid with sodium hydroxide. Zlall (119C) employs electrolysis in twcl stages to remove the lead from the gasoline, then determines the lead content by one of three procedures: by weighing the anode; by stripping the anode rind titrating with EDTA; or by strippirg the anode and determining lead photometrically wit.h diphenylcarbazone. A cooperative testc ing program was carried out by laboratories in six member countries of IS0 on ASThl D 526-61, the Gost 63-52 modified by the Russians, and Gost 63-52 further modified by the Americans. The results are discussed by Siniramed and Renzanigo (fOOC‘). Farkas and Fodor (28C) determine TEL in gasoline by means of absorption of tritium bremsst’rahlung. Dagnall and West (24C) have examined the effects of extraneous ions, solvents, and flame height on the determination of lead by atomic absorption spectroscopy. Three sources have used x-ray fluorescence spectroscopy for t’he determination of lead. Szeiman (1OSC) determines small amounts of lead in 3 to 4 minutes. Guiin (38C) uses an iron rod as an internai intensity reference to compensate fcsr the effects of differences in absorpticln between samples. Ilasegawa, Kaji:
