(402) Wessel, J. R., ibid., p 172. (403) Westlake, A., Gunther, F. A,, Westlake, W. E., J . Agr. Food Chem., 17, 1167 (1969). (404) Westlake, A,, Hearth, F. E., Gun-
ther, F. A,, Westlake, W. E., ibid., p
1160. (403) Westlake, A., Westlake, W. E., Gunther, F. A,, ibid., 18, 159 (1970). (406) Zbid., p 686. (407) Westoo, G., Analust, 94, 406 (1969). (408) Wheeler, L., Strother, A., J. Chromatogr., 45, 362 (1969). (409) White E. It., Kilgore, W. W., Mallett, b., J . Agr. Food Chem., 17, 585 (1969).
(410) Williams, P. W., Teasley, J. I., J . Ass, Oflc. Anal. Chem., 52, 782 (1969). (411) Windham, E. S., J . Ass. Ofic.Anal. Chem., 52, 1237 (1969). (412) Winterlin, W., Mourer, C., Beckman, H., J . Agr. Food Chem., 18, 401 (i~70\. \ - - . - I .
(413) Wisman, E. L., Young, R. W., Poultry Sci., 49, 83 (1970). (414) Wohlenberg, D., Bonderman, D., J . Agr. Food Chem., 17, 1420 (1969). (415) Wood, N. F., Analyst, 94, 399 (1969). (416) Woolson, E. A,, Kearney, P. C., J . Ass. Oflc. Anal. Chem., 52, 1202 (1969).
E'. C., Riner, J. C., Gilbert, B. N., J . Agr. Food Chem., 17, 1171
(417) Wright,
(1969). (418) Wright, F. C., Riner, J. C., Palmer, J. S., Schlinke, J. C., ibid., 18, 845 (1970 1. (419) Yamamoto, I., Kimmel, E. C., Casida, J. E., J . Agr. Food Chem., 17, 1227 (1969). (420) Yeo, C. Y., Bevenue, A., J. Ass. Oflc. Anal. Chem., 52, 1206 (1969). (421) Yip, G., ibid. 53,358 (1970). (422) Young, R. J . Agr. Food Chem., 18, 164 (1970). (423) Young, S. Y., 111, Berger, R. S., J . Econ. Entomol., 62,929 (1969). (424) Yu, S.J., Morrison, F. O., ibid., p 1296.
u'.,
Petroleum R. W. King, Sun Oil Co., Marcus Hook, Pa.
T
HIS IS THE TENTH ill the Series Of reviews of analytical chemistry in the petroleum industry (1A-9A) sponsored by the Petroleum Division of the American Chemical Society. The current material covers essentially the years 1968 and 1969, or more specifically, the papers abstracted in Chemical Abstracts, in the American Petroleum Institute Refining Literature Abstracts and in Analytical Abstracts (London) for the period from July 1968 through June 1970. All reference citations conform to the Chemical Abstracts "Guide for Abbreviating Periodical Titles." 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. The abbreviations C.A., A.P.I.A. and B.A.A. are used to identify, in order, the abstract journals listed above. These abbreviations are followed by the volume number, the abstract number and the year. The abstract searching was done by C. A. Simpson, ilIobil Research and Development Corp., F. D. Tuemmler, Shell Development Co., and the Library staff of the Sun Oil Co. The initial collection was intensively screened and organized by various subjects that seemed to possess a community of interest. The subject classifications were in the main related to products, properties, or certain constituents. These smaller collections were further screened by the sixteen Reviewers of the twelve subsections which follow. The existence of this review is due entirely t o the generous assistance of these contributors.
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Crude Oils F. C. Trusell Marathon Oil Co.,littleton, Colo. Boulet et al. (6B) have reported a detailed analysis of crude oils, and have shown its application to geochemical problems. The CL-C8hydrocarbons are determined by gas chromatography. The liquid portion is distilled into six cuts. The c7-C~ cut is examined by gas chromatography. The remaining cuts, ranging up to Cz6, are separated into saturate and aromatic portions by liquid chromatography. The saturate portion is analyzed by mass spectrometry for its paraffin and cycloparaffin content, and the various classes of aromatic compounds are determined in that fraction by the same technique. The structural composition of the aromatic fraction is studied by NMR. B nomograph has been prepared by Erwin (16B)for determining pressure gradient, weight, specific gravity, and API gravity of oil and the salt content of water if any one of these properties is known. Markhasin et al. found a close relationship between the absorbance of the asphaltene fractions from several eastern European USSR crudes and the molecular weights of the fractions, and have presented a rapid means for estimating the molecular weight of asphaltene fractions (28B). The thermal stability of Baku crude oil, containing 4.575 sulfur, was studied by Mahmoud and Ahmed (26B) by carrying out a fractional distillation under atmospheric pressure, and a
ANALYTICAL CHEMISTRY, VOL. 43,
NO. 5, APRIL 1971
second distillation a t 5 mm Hg. A comparative study of the sulfur group analyses on the 50 "C cuts taken up to 350 OC was made, and the changes occurring during distillation were shown, Skripnyak (44B) investigated the thermal stability of Radaevskii crude which had been freed from gasoline and asphalt, and separated by adsorption chromatography into paraffin-naphthene, intermediate, and aromatic fractions. Each fraction was then heated a t 300 O C and 400 "C and the conversion of sulfur compounds to HZS was measured. Sergienko et al. studied the composition of the gasoline fractions of four crude oils from the eastern shore of the Caspian Sea (40B). After dearomatization the n-paraffins, amounting to 3.45.7% of the sample, were removed by urea adduction. I n the C7-CI3 fraction n-nonane was the predominant species. Among the branched paraffins, methyland dimethyl-substituted derivatives predominated, with the substituents near the ends of the chains. When benzene and cyclohexane were disubstituted, the 1,3 isomers predominated. The aromatic fraction of the gasolines ran from 4.1 to 10.2%. Shevchenko reported on the composition of the gasolines from 18 Ukranian oil wells (43B). After separation by silica gel chromatography, the aromatic fractions were analyzed by gas chromatography. The saturate fractions were examined t o determine the isoparaffinln-paraffin ratio and the naphthene content. On the basis of these parameters, the crudes could be categorized into three groups which also correlated with their geographic origin. The gasolines in the
first group have a relatively high nparaffin content (26.8-32.6%) and branching coefficients of 0.8-0.9: 1. Those in the second group have 18.519.3% n-paraffins and branching coefficients of 1.1-1.9:1, while those in the third group contain 12,3-16.3% nparaffins and exhibit branching coefficients of 2.5-3.2 :1. Sevast'yanova and Popova examined the aromatic hydrocarbons in the 180-200 "C fraction of Arlansk petroleum (4ZB). After oxidizing the sulfurcontaining compounds in the sample with H20sin acetic acid, it was separated into 2-5 "C cuts with a distillation column of 38 theoretical plates. The I R spectra (1000-650 cm-I) were recorded, and the UV spectra (290-330 nm) of the samples in isooctane solution were obtained. Sevast'yanova and Ivchenko (41B) fractionated the 177339 "C portion of this crude into naphthenic-paraffin, sulfide concentrate, resin, and aromatic fractions. This latter was further separated into monocyclic and bicyclic aromatic compounds. Yields and physical properties are given for each fraction. Beumann and Jobelius (SWB) examined oil field brines and detected the presence of phenols and alkali naphthenates capable of acting as emulsifying agents in the formation of oil-inwater emulsions. They discuss oil migration to, and deposition in, reservoirs in the light of their findings. Artem'ev determined the hydrocarbon content of bottom sediments from the Kuril-Kamchatku trench (3B). Values ranged from 375 to 1659 y/gram of dry sediment. The highest hydrocarbon contents were observed in silty-pelitic and pelitic diatomaceous muds. Decreasing amounts were observed during the transition to coarse-grained sediments on the continental shelf and to the pelitic mass of the ocean bottom. Neutron activation analysis was used by Gorski et al. (16B) to determine salt, water, and sulfur in crude oils. A flux of l o 9neutrone/sec was employed. For salt and water, the range covered is 0.01-6 and 0.01-1.6 gram/l., respectively. An automatic determination of salt in crude oil was developed by Rieckmann and Koepf (S5B). The sample is mixed in a 1 : 3 ratio in the solvent mixture of benzene, isopropyl alcohol, nitric acid, and a known amount of silver nitrate, and the potential measured with a silver-glass electrode pair. Chloride concentration is read from a calibration graph. A patent (29B)describes the apparatus and technique for a conductimetric determination of salt in crude oils. A mixture of xylenes and lower alcohols provides an adequate solvent which is electrically conductive. Sarkovic used flame spectrometry
to analyze for V, Ni, Mo, Zn, Cu, Ba, and T i in the residues of Vojvodina crudes (37B), and lists quantitative results. Zul'fugarly and Getseu (62%) separated resins, oils and asphaltenes from the heavy portions of Dagestan crudes. These fractions were calcined and the Cr, %In, Co, Cu, Ag, Zn, and Pb contents of the ash were determined by emission spectroscopy. Smekhova (46B) analyzed crude oils from the Saratov-Volga region for their trace element content. Results for V, Ni, Fe, B, Cu, Mn, Pb, Sr, Si, Al, Mg, and K are given. The V:Ni ratio is significant in classifying and correlating crude oils. Krayushkin and Kazakov (21B) made less extensive analyses of crude from the Dnieper-Donets depression and interpreted the nearly constant V:Ki ratios as supporting the theory that in this region petroleum in given strata arise from a single source. Abyzgil'din et al. (1B) determined the ash compositions of three crude oils (one each of low, medium, and high sulfur content) after one thermochemical desalting and after each of two electrical desalting steps. Vanadium present as a porphyrin complex was partially removed by desalting. More nickel (85$Z0) was removed from the low sulfur crude than high sulfur crude (44%). More than 80% of the aluminum, 90% of the calcium, and practically all of the iron and sodium were also removed. Rozenberg et al. report the isolation and identification of 7 isoprenoid alkanes from the fractions of Romashkino and Irkutsk crude oils boiling a t 180-350 "C under 10 mm Hg. Quantitative results from gas-liquid chromatography, infrared spectrometry, and mass spectrometry are reported (36B). The bicyclic aromatic and naphthenic hydrocarbons from the 150-300 "C fractions of three Baku crude oils were studied by Kulieva et al. by gas-liquid chromatography and mass spectrometry (Z4B). Of the 10 dimethylnaphthalenes, only the 1,8 isomer was not found. The samples contained 1- and 2-methyldecalin, 1- and Z-ethyldecalin, and nine dimethyldecalins. ,4shumov et al. (4B) isolated and examined the bicyclic aromatic compounds from fractions of three Baku crude oils boiling between 147-317 "C. Data on the yield and characteristics of the monoand bicyclic aromatic hydrocarbons are tabulated. In all three cases, the content of monocyclic aromatic hydrocarbons was 2.6-2.8 times that of the bicyclics. Korotkii et al. examined the high molecular weight aromatic hydrocarbons from Ciscaspian and Bukhara crude oils using infrared and ultraviolet spectrophotometry ($OB).The monocyclic aromatic compounds were hybrid structures, containing naphthenic rings
and paraffinic chains as well as a benzene ring. The benzene rings tended to be 1,2,4- and 1,3,5-trisubstituted, 1,3disubstituted, or monosubstituted. The di-and polyaromatic hydrocarbons are hybrid paraffinic-alicyclic-aromatic structures with branched aliphatic substituents and condensed aromatic rings. The aromatic compounds in six fractions boiling between 200-470 "C were isolated from Korobkov and Zhirnov crudes and were examined by Kuklinskii and Pushkina (ZZB). They note the ratio of aromatic ring carbon to naphthenic and paraffinic carbon decreased with an increase in boiling point,, as did the content of aromatics based on benzene and naphthalene. Other structural correlations with boiling point are also recorded. Kuklinskii et al. separated an isoparaffin-naphthene fraction from the 200470 "C boiling range of Korobkovskii and Zhirnovskii crude oils (WSB), removing the aromatics by silica gel chromatography and the n-paraffins by urea adduction. These fractions were examined by mass and infrared spectrometry. The percentage of compounds containing from zero to six rings per molecule were determined for each oil. Hoering reported the isolation of optically active steranes from Los ilngeles basin crude oil (18B). A combination of liquid chromatography, distillation, adduct formation, molecular sieves, and gel permeat,ion chromatography was employed for bhe separation. Some compounds were identified by gas chromatography and mass spectrometry. Slobodin and Kovyazin used gasliquid chromatography to determine the adamantane content of five different crude oils. They report an inverse relationship between the adamantane content and the age of the producing reservoir (46B). Using molecular sieves and urea adduct,ion, Hanna et al. determined the n-paraffin distribution in the 60-150°, 150-250°, and 250-350 "C fractions of Marine Belayim crude oil (17 B ) . They determined that 10-l5yG isoparaffin impurities were carried along in the urea adduction. The identities of 14 of the isoparaffins were established by XMR spectrometry. Vasil'eva identified and determined some 60 hydrocarbons boiling between isopentane and n-octane in the gasoline fractions from six Siberian crudes by (61B). gas-liquid chromatography The range of n-paraffin contents was 1.69-3.1 1%, of isoparaffins 1.75-3.07% , of cyclohexanes 0.91-1.69%, of cyclopentanes 1.42-2.45%, and of aromatics 0.02-0.0701,. Manjarrez et al. discuss the theoretical and practical considerations of evaluating crude oils by gas chromatography, pointing out the
ANALYTICAL CHEMISTRY, VOL. 43, NO. 5, APRIL 1971
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advantages and limitations of this method as a substitute for distillation. The results obtained by gas chromatography are compared with those obtained by traditional means (27B). Decastille et al. developed a rapid gas chromatographic analysis for the direct determination of light hydrocarbons in crudes (11B). They describe the apparatus used and give a statistical analysis of the results produced for propane, isobutane, n-butane, isopentane, and n-pentane. Litovchenko has reported a gas chromatographic analysis of the saturates in crude oil from methane through n-heptane (25B). h 6-meter packed column with a liquid phase of 10% petrolatum oil and 2% sodium carbonate is used to achieve the desired separations. An analysis requires 35-40 minutes. The n-paraffins in the 234-270' fraction, chiefly n-Clr, CI4,and Cis were determined by I3abakhanov et al. (5B) using gas chromatography. The separation was achieved isothermally a t 125 'C using a 1-meter column of 10% asphaltenes on diatomite brick. A preliminary separation of normal from iso-paraffins was accomplished by adsorption on 5A molecular sieves. Akopova and Semkin determined the C1-Cs hydrocarbons in emulsified crude oils (2B). Calcium carbide was added to react with the water. The resulting acetylene helped to sweep out the desired hydrocarbons, which were entrained with a carrier gas and passed through a chromatograph. The method can be used on crude oils containing up to 25y0 water. Diskina has reviewed the substitution of gas chromatographic methods for conventional methods such as distillation, type analyses, vapor pressure measurements, octane number determination, and heating value measurements (12B). Coleman et al. (1OB)used gel permeation chromatography to fractionate high boiling petroleum samples without exposing them to thermal degradation. The resulting fractions were studied, and analyt,ical data pertaining to structure and composition within each fraction are presented. Oelert et al. separated 5 crude oils, previously stripped of the material boiling below 180 'C, into fractions using Poragel A-3 and -4-1 resins, They found crudes with similar amounts of residue and similar average molecular weights can have widely differing compositions of their high molecular weight fractions. GPC elution volumes and molecular weight data can provide useful information on the ratio of ring to nonring compounds (SSB). Done and Reid obtained chromatograms of more than 40 crude oils using a simple gel permeation system and differential refractometer. Each chromatogram was unique, but could be 164R
grouped according to the light or heavy nature of the oil. A chromatogram can be obtained from a 10-mg sample in 40 minutes. The use of this method for predicting crude oil properties, studying crude oil fractions, and determining the source of pollutants is discussed ( I S B ) . Hustiu (19B) determined there is a linear relationship between the refractive index, measured with the sodium D line a t 70 'C, and the Dean-Davis viscosity index of paraffinic cuts. This permits rapid evaluation of the quality of the lubricating oils from a given crude. Sattar-Zade et al. obtained twelve distillation fractions between 60 and 500 'C from each of two Bulla Lake crudes. The physical properties and optical activity of each fraction are given, along with some composition data (S9B). The optical rotation ranged from -0.19 to 2-09', increasing with the boiling range of the fraction. Satter-Zade et al. measured the optical activity of dearomatized distillation fractions of crude oils from the Peschanyi Island deposit. They found the optical activity of fractions (0.36 to 1.28') to be lower than that of distillates from other sources (S8B). Efendieva et al. extended this study and determined that optical activity increases with increasing viscosity, molecular weight, and density. It also increases with decreasing refractive index ( I 4B). Triems classified 31 crude oils as paraffinic-naphthenic, naphthenicaromatic, or aromatic-naphthenic, according to their composition as determined by silica gel chromatography (49B). Each class is subdivided into three groups according to the sulfur content. Ulm (5OB) analyzed oils from twelve horizons in the Middle Jurassic sediments of the Zhetyba deposit. The samples were paraffinic and highly metamorphosed. Asphalt-tar and sulfur content decreased with increasing depth, while the yield of fractions boiling below 200' and below 300 "C increased. The gas compositions (CI thru Cs, Nz, HzS, and COZ) and type analyses of various fractions are reported. A similar study of oils from nine horizons in the Uzen deposit is also described, along with analytical data from five other oils. Thein determined the hydrocarbon-type composition of Prome crude oils from different depths (48B). He found the specific gravity decreased with depth a t a rate of 0.0095/1000 ft. Naphthene content of the middle and heavy distillates decreased with depth, while the paraffin content increased. The octane number of the gasoline decreased with depth, but the quality of the kerosine and diesel oils improved. Thein also investigated the
ANALYTICAL CHEMISTRY, VOL. 43, NO. 5, APRIL 1971
hydrocarbon-type composition of Indaw crude (47B). Prohaska and Budec investigated the composition of some Yugoslav crudes using the U.S. Bureau of Mines distillation and the Oldershaw distillation. The characteristics of the whole crudes and of their basic fractions are reported (34B). ru'ater mixed high sulfur, high asphalt, low pour point crudes from five diverse wells of the Souedie area, Syria. The amount of dissolved gases was measured and a T.B.P. curve was determined. Seven distillation fractions were analyzed to determine their physical and chemical properties (SOB). Nater also evaluated Pleven crude with regard to its white products and oils (SIB). This is a paraffin-base crude having a low sulfur and asphalt content. A detailed analysis of the separated fuel and oil fractions is presented. Cena et al. examined oils from Quezon Province and Mindoro Oriental using distillation and chromatography. Neither oil contained a gasoline fraction, and both had low n-paraffin contents (7B). Using the U.S.Bureau of Mines routine method of distillation, Charbonnier et al. analyzed more than 55 crude oils from Quebec and Ontario (8B, 9B). Analytical results are reported along with some reservoir characteristics.
Engine Fuels K. I. Shull and J. D. Beardsley The Sfandard Oil Co. (Ohio), Cleveland, Ohio
Nottes (51C) presents a discussion of newly developed and older published analytical methods for the detection and determination of additives such as anti-icing compounds, antioxidants, corrosion inhibitors, metal deactivators, dyes, etc., in gasolines and diesel fuels. This discussion contains 48 references. A gas chromatographic procedure for determination of freezing point depressants (methanol, ethanol, isopropyl alcohol, toluene, xylene, aliphatic hydrocarbons, and acetone) in various deicers has been developed by LePera (47C). He uses a copper column containing Porapak Q with helium as the carrier gas and a thermal conductivity detector. Amos (SC) estimates 2,4-dimethyl-6tert-butyl phenol in aviation turbine fuel by thin-layer chromatography. First, the polar compounds in the fuel are concentrated by adsorption onto alumina; then, after desorption with ethanol, the DTBP is separated from the other compounds by TLC. The amount of phenol on the chromatogram is then estimated by visual comparison or by densitometry in comparison with standards. A colorimetric determina-
