Petroleum F. D. Tuemmler, Shell Developmenf Co., Emeryville, Calif.
T
HIS IS THE NIXTH in the series of reviews of analytical chemistry as used in the petroleum industry (YA, 8 A , ISA-2YA), sponsored by the Petroleum Division of the American Chemical Society. It covers essentially the years 1966 and 1967, or rather the papers abstracted in Chemical Abstracts (Analytical and Petroleum Sections), in the American Petroleum Institute Rejining Literature Abstracts, in the Journal of the Institute of Petroleum, and in Analytical Abstracts (London) for the period from July 1966 through June 1968. Generally, those papers published in 1968 and abstracted have been set aside for the next in this series of reviews. Organization of the Review. I n 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 component or by property measured to simplify location of the more closely related material. 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 journals, journal abbreviations differed. Further, during this time period, Chemical Abstracts “Guide for -4bbreviating 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 abstract references, the abbreviations CA, A P I , J I P , and A A 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 discussions of specific analytical processes or the application of a variety of analytical techniques to the examination of a variety of petroleum products or process streams. For the first time in a considerable number of years, Kerenyi (17A) re-
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viewed recent advances in analytical distillation (101 references). Caigneau (6A) looked a t the progress in mass spectrometry over the past 10 years, while St. George et al. (41A) and Lumpkin (28A) listed the variations of mass spectrometric applications in the petroleum and petrochemical industries Reed (SQA,37 references) covers theory, design, abbreviations, and resolutions. The use of X-ray spectrographic analysis of liquids and solutions has been described by Gunn (IOA, 36 references), Kajikawa et al. (14A, 46 references), and Magin (2QA). Infrared spectrometry bas been reviewed by Shimazu ( @ A , 59 references) and Whetsel (46A, 10 references). The use of nuclear magnetic resonance in fuel science has been described by Rao et al. (SYA, 10 references) and Yamamoto ( @ A , 26 references). Gas chromatography as a tool for the analysis of petroleum, petroleum gases, and petrochemical processes has been reviewed by Tagiev (&A) and Moghadam (SOA). Killer et al. ( I Q A )described the application of thin-layer chromatography to a variety of products (54 references). Barras et al. ( I A , 20 references) reviewed the basic principles of atomic absorption; Mostyn (S2A, 28 references) reviewed the use of this technique as applied to fuels and lubricants. Gray ( Q A ) and Perdijon (S4A) reviewed the principle of analysis based on thermal, fast-neutron activation. Boreham et al. (SA, 42 references) summarized the use of all the above analytical processes and, in addition, included electrophoresis, flame photometry, and polarography as used in research and control in the gas and petroleum industries. Keil (16 A ) concentrated on physical chemical methods such as electrochemistry, thermodynamics, and absorption and emission spectrometric techniques. Methods Coordination. Of particular interest during this review period is the appearance of several papers concerned with the integration and coordination of new techniques. 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 (2OA) made this comparison for gasoline and blended fuels. Powell (S6A,26 references) did not deal with any particular product class. Texaco ( S I A , 33 references) provided a searching look a t the analysis of lubricants. Jenkins,
et al. (1IA) looked a t the redundancy of specification tests. Although this paper concerns itself with gasoline specifications, the principles of mathematical correlations and choice of the most sensitive are applicable to other products. Data Handling. The use of computers 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 preparing control reports for optimizing use of work space and analytical personnel; Harding et al. ( 1 I A ) described a comparable system. Ogle (SSA) described problems relating analytical and computer - 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 (4A1. Tunnicliff (4SA) detailed a sophisticated general Fortran program for interpreting and reporting results of emission spectrographic analyses. LeFeuvre et al. ( H A ) , Wellington et al. (&A), and Williams et al. (4YA) described means of operation and logging and computing data from an engine test laboratory; a comparable system installed in England has also been described (1S A ) . Automated Control. The automatization of analytical test methods used for plant control continues and as it applies to specific procedures is described in detail later in this review. Kienitz et al. (18A) discussed the problem in a general way; Bassalert (2A) directed his review to petroleum product quality control. Wherry (46A) described the roll of chromatographs in meeting some demanding refinery control needs. Standardization. Rather (38A), 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 ( M A ) . A necessary feature of a standardized method is a statement of its precision when applied in several laboratories; Fritz ( 6 A ) evaluated the problem of developing necessary data from which such precision can be estimated.
Crude Oils G. W. Ruth Marathon Oil Co., littleton,
Colo.
McAuliffe (21B) described an improved method and apparatus for separating hydrocarbon constituents from samples so the hydrocarbons may be quantitatively analyzed. The method consists of establishing a vacuum of a t 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 (15B). Synthetic sodium-A zeolite was used as the dehydrating agent. Oil samples containing 2% moisture were completely dehydrated a t up to 200 ml/hr. Regeneration time for the zeolite was reasonably short. A rapid method for crude oil evaluation without distillation was developed by Gaylor and Jones (14B). The method consists of six tests on the whole crude oil-ie., 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 procedure. The six tests, along with multiple regression equations that were derived, give the yields and qualities of all fractions 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 subsequently eluted by isooctane, benzene, and acetone. By comparing the group analysis thus obtained with the sulfur, asphaltene, paraffin, and naphtha content and density, a crude oil can be characterized effectivel).. Crudes from 10 regions were examnietl. Attempts were made by Bene and Louis (4B) to characterize crude oils by nuclear magnetic resonance. The proton 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 reported by Boulet et al. (8B). The procedure consists of gas chromatographic analysis of c1-C~ compounds, mass
spectrometry and gas chromatographic analysis of the c7-C~ compounds, and division of the remainder of the crude into several fractions by distillation followed by separation of each fraction by liquid chromatography. Aromatic compounds are further analyzed by nmr. Both Bene and Boulet made comparisons among several crudes of different origins. Smith and Hale (S2B) summarized several methods of crude oil characterization. Routine analyses data were used as a basis in all cases. A similar survey covering the standard tests performed in French refineries and used in the analysis of crude oils was reported by Henrion and Picard (16B). Specifications required, along with numerous examples 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 (25B) proposed standard methods for rapidly determining the main characteristics of crude oils. Methods were proposed for measuring the c1-C~ hydrocarbons by gas chromatography, for identifying crude oils by uv spectrophotometry, for evaluating surfaceactive agents as crude oil demulsifiers, and for measuring the hydrocarbons ,present in water by ir spectrophotometry. A review of the uses of modern physicochemical and analytical methods for determining the geochemical features of petroleum oils was compiled by Podkletnov (26B). The review concentrated on methods associated with the carbohydrate composition of oils. The methods surveyed were : gas-liquid chromatography, 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 fractionation, and chromatographic separations on alumina gel were used to concentrate the cyclic sulfides. The resulting sulfide-containing fractions were then analyzed by gas-liquid chromatography. Eighteen species were identified by their retention times, by microdesulfurization, and by ir spectra. Gas chromatography was also used by Guichard-Loudet and Follain (16B) to determine light hydrocarbons in crude oil. Results were compared with those of distillation tests, and satisfactory agreement was obtained except for ethane. Brunnock (5B) reported separation and distribution of normal paraffins from petroleum heavy distillates by a combination of molecular sieve adsorption and gas chromatography. I n this procedure, 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 nparaffins are determined by gas-liquid chromatography. The method was applied to contrasting waxy crude oil from Libya and Nigeria. A rapid method for determining the asphaltene content in crude oil was developed by Biktasheva (7B). Solutions of crudes, I%, in petroleum ether and in o-oxylenol were prepared and electrical conductivity of the solutions was measured. 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 determined. Analysis time was 10 minutes and accuracy was 0.3'%. Another procedure for the determination of asphaltene in crudes was reported by Neumann et al. (%@). Asphaltenes were first determined by precipitation from crude oil followed by sixstage ultrafiltration. The most satisfactory 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 determine 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 (SOB) 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 determina ,i 11 of the phenol content. Jordan and Care1 (18B) reported a rapid semiqualitative method for determining the halogenated hydrocarbons content of crude oils. The equipment is completely portable and can be used for field testing, as well as in the laboratory. The procedure consists of a distillation 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 (1B). -4comparison of the results obtained by this procedure and the results obtained by a refractometric method is given. Mikhal'kov (22B) concluded that the starting temperature for parafVOL. 41, NO. 5, APRIL 1969
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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 (28B) 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. hfoore et al. (23B) applied atomic absorption spectrometry to trace analyses of petroleum. Cu, Xi, Zn, and P b were determined at concentrations 5 1 ppm. A liquefied petroleum gas %as 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 reported 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 determined simultaneously. Augsten (2B) described an apparatus and procedure for flame photometric determination of alkali and alkali earth metals in nonprocessed petroleum. while Popescu et al. (27B) reported a technique for the direct determination of traces of sodium in crude oil cuts by flame photometry. Sodium content is determined by direct atomization of the liquid into the flame of a Zeiss-Jena type I11 photometer. For cuts covering light and medium distillate, 1 to 3 ppm sodium can be determined with a relative error of about loyo. Calcium and magnesium were determined in the filtrate of drilling mud by a complexometric method proposed by R y d r a (38B). The sample is titrated with EDTA a t pH 12 using one indicator to determine calcium. The titration is then carried out at p H 10 using a different indicator to determine total calcium and magnesium. hlagnesium is calculated by difference. Gates and Caraway (13%) also described a method for determining calcium and magnesium, along with barium, strontium, and iron in oil well scale. Carbon disulfide was used l o remove the oil and water and the scale was then dissolved in concentrated hydrochloric acid. Ba, Ca, Sr, Alg, and Fe were then determined by flame photometry, the method of additions being used. Sulfate and phosphate were determined colorimetri154 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 MacMillan and Samuel (20B). The method makes use of the fact that hematoxylin gives a pink color with vanadium in 6N to 7 N orthophosphoric acid with an absorbance peak a t about 520 to 523 mp. Results obtained from the analysis of six crude oil samples are given. Steinke (53B) described a photometric method for the determination of 1 to 5 ppm of vanadium in oil fractions with 4-(2-pyridylazo)resorcinol. An accuracy of hO.4 was reported. 4 - Methooxybenzothiohydroxamic acid was used by Skorko-Trybula ( S I B ) to determine to of vanadium in crude oil and petroleum products. I n 6N hydrochloric acid medium, V4+ with this reagent forms a green complex which is easily extracted with CHCl, 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 benzoylphenylhydroxylamine, 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 determining vanadium and nickel in oil ash was reported by Petho (25B). The crude oils were purified and dehydrated by centrifuging, then dissolved in the presence of concentrated sulfuric acid. Ash was mixed with silicon dioxide containing 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 ( 5 B ) . The metals are concentrated on a disk of cation exchange paper and then determined by X-ray fluorescence. Analysis time was 4 hr, and the relative error is 5 to lOyo a t 0.1 to 1.0 ppm nickel or vanadium. KO interelement effect between nickel, vanadium, and iron was noticed. Alternating-current polarography was used by Ishii and hlusha (I7B) to determine vanadium in petroleum. The method was rapid and simple and no interferences were noted. Veal (S7B)described a method of preparing internal standards for determination 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. (36B). Determinations were made on several Hungarian crudes and on a few Russian crudes. The amount of vanadium carried over in distilling 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 vanadium were dissolved in acid, V4+ was and the vanadium was oxidized to V+, then extracted as vanadium tungstophosphate. The complex is measured colorimetrically. Interference of Mo, Cr, Fe, and W was a t a minimum. A mass spectrometric characterization of petroporphyrins was carried out by Baker (5%). Xsphaltenes were prepared in the standard way by precipitation 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 obtained showed that up to 12 homologs of the deoxophyllo and etio series may be present in a Gaussian-type distribution with a band width of three to five methylene groups. High resolution mass spectrometry indicated the presence of only alkyl porphyrins with no oxygen functional groups, but chromatographic separation of the petroporphyrins 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 relationship to the porphyrins and asphaltenes was discussed b\ Colombo (11B). Their determination by neutron activation and their use in investigating the origin, migration, and evaluation of petroleum was also discussed.
Engine Fuels K. I. Shull and 1. 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 : l to 25:l and the test temperature was raised from 100 to 130 O F . These test conditiolis correlated best with direct vapor-liquid ratio measurements at 120, 140, and 160 O F . This modification was also suitable for characterizing motor fuels with regard
to hot-weather acceleration performance in automobiles. Perry (S8C) described the gas chromatographic determination of dibromoethane 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 programs on evaporation losses from motor vehicles were reported by the Coordinating Research Council (I7C, 4 9 c ) . Six methods of determining total fuel lost from the carburetor (cold trapping, air cup, bag enclosure, fuel-line reservoir, syringe, and API gravity) and three methods of determining losses from the fuel tank (cold trapping, charcoal 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 ( 2 l C ) determined the components of exhaust gas by using nondispersive infrared and polarographic analyzers to measure fuel-air ratios. Bentur et al. (5C) established that kerosine contamination of 83-octane gasoline from 0.5% upward can be determined by semimicro paper chromatography. This application was extended to catalytically reformed and 91-octane gasoline by Babitz and Rocker (4C). A simple bench apparatus was developed by Johnstone and Dimitroff (29C) to test gasolines for depositforming characteristics; this apparatus closely simulates the engine intake system. 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 without 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; autoignition 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 f r o n t a d octane is essential for optimum prediction. I n addition, they obtained
a single equation which predicted road octane numbers of both grades of gasolines from their research and delta research octane numbers, lead contents, and API gravities ( I S C ) . Chassis dynamometer and field tests carried out by Ingamells et al. (2%") demonstrated that effects of temperature 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 requirements for car populations in specific localities. The Journal of the Institute of Petroleum (SOC) 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 individua1:LPG components were used by ASTM Committee D-2 to develop an octane calculation method for LPG fuels of known composition; Boldt (7C) described the work of this committee. Churshukov et al. (11C) evaluated the corrosive action of fuels and the effectiveness of anticorrosive additives. A steel or bronze plate was weighed, then immersed in the fuel sample for 4 hr a t constant temperature and maximum moisture content; the plate was cleaned to remove corrosion products, and weighed again. An apparatus for measurement of changes in potential in a flowing hydrocarbon fuel was described by Lamouche (34C). Tararyshkin and Chechkina (46C) determined the pressure 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 a t low pressures was given by Tararyshkin (44C). Kuster and Comery (SSC) used refractive index to determine water-soluble additives in liquid hydrocarbon fuels. An apparatus for determination of low boiling material in diesel fuel, motor oil, etc. was patented by Lohrmann et at. (S6C). Hazes produced in petroleum fractions (boiling range, 300 to 482 OF) were studied by Hermanie and van der Waarden (24C). Rybakov et al. ( 4 W ) visually determined the particle size distribution of impurities in such petroleum products as motor and jet fuels. Dyatlov (I9C) described an apparatus for fractional distillation of fuels a t 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, coefficient 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 simulating those of fuel tanks in a flying airplane was described in detail by Alekseeva and Ivanov ( I C ) . The Coordinating Research Council (16C) evaluated a modification of the standard ASTMCRC 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 ASTRS-CRC fuel coker and results obtained with a Minex heat exchanger in determination of thermal stability of hydrocarbon fuels. Whisman and Ward (50'2) reported a 5ml bomb and method which shows promise of permitting precise measurement of labeled fuel components that contribute to deposits during thermal stressing. Three test methods were developed and evaluated for separation and measurement of radioactivity contributed to deposits and gums by selected fuel components. A method and apparatus for maintaining a minimum concentration of ethane and lighter components in transferring liquefied petroleum gas were described by Smith (4SC). Hooper et al. (26C) determined oily residues (in the lubricating oil range) in liquefied petroleum gas by a methyl ethyl ketone-sodium bisulfate method. Reinhardt et al. (doc) described a gas chromatographic procedure for trace substances in fuel gases which utilizes an argon ionization detector and two columns. A photometric comparator was used by Dasgupta and Dey (182) 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 NantesChevire power plant of Electricite de France in an attempt to alleviate air pollution. Yuhara and Kat0 (51C) studied the influence of suspended particles on rheological properties of residual fuel oil using a rotational viscometer. Kouzel (SIC) presented a chart which permits rapid estimation of the true boilingpoint (JBP) cut pointfor anASTM D 86 end point when the 30% TBP temperature and the 30 to 90% TBP slope are known. Fluorescent indicators for chromatographic determination of aromatic andolefinic components in light petroleum products were prepared by Kurchatkina et al. (SIC). The amount of gasoline in lube oil was determined by Alvey (2C) VOL. 41, NO. 5, APRIL 1969
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with an apparatus consisting of a heated funnel attached to a calibrated capillary. Borisov et al. (E)described an apparatus for determination of the amount of gas dissolved in liquid fuels or in water. The principal part of the apparatus 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 measurement of equilibrium constants. Panels of sniffers were used by Humble to determine 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. (102) 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) investigated the mechanism of microbiological contamination of jet fuel and developed techniques for detection of this contamination. Hazzard (232) described two sampling procedures, the nutrient media, and the procedure for culturing microorganisms on filter membranes 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. ( l 4 C ) ; the new method involves measurement of the flow limiting temperature 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 laboratory 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 propensity 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 a t the color transition from yellow to blue instead of from yellow to green. 156 R
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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 ( 5 5 0 ) . Vichard and Godet ( 1 0 1 0 ) 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 properties. Sayles (900) presented a review on the development of the four-ball E P tester. An automated four-ball testing machine was described by Frenkel and Grivstov (540). Bartz and Goettner (100) made a systematic study of the variables in evaluating automotive gear oils with the four-ball machine, and Bartz ( 9 0 ) used this machine to investigate 33 oils to generalize corrosion and load results for different classes of oils. Appeldoorn and Royle ( 4 0 ) substituted 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 (650). A cooperative program was carried out by the Institute of Petroleum Gear Lubricant Rig Tests Subpanel and the Deutsche Gesellschaft fuer Mineraloelwissenschaft und Kohlechemie to investigate correlation between IAE and FZF test machines. Correlation was good when tooth-tip sliding velocities were similar ( 5 0 0 ) . Niemann and Assmann (800) reported that 10 years experience with the FZG gear test rig shows the test classifies lubricants clearly with respect to loadcarrying and wear. An analytical investigation by McCain and Alsandor (680) showed that important factors in gear lubrication are oil jet orientation, oil velocity, and use of disengaging lubrication. Harris (450) reported an analytical method to predict skidding in high speed roller bearings and to evaluate corrective measures. Darling and Isherwood ( 2 2 0 ) described apparatus for determining antiscuffing properties of marine turbine oils and for testing machine-type failures of turbine thrust blocks. Jonach and Baker (470) discussed laboratory and shipboard testing of selected diesel cylinder lubricants. Weaver (1020) used a radiotracer technique to measure the antiwear performance of hydraulic fluids. A method for determining critical temperature for the appearance of a boundary oil
film was developed by Klimov and Kichkin (670). Gansheimer (560) described a press-fit test which, on the basis of 16 year’s experience, provides a rapid, exact, and simple evaluation of lubricants operating a t low speeds and high pressures. Kellermann and Turlach ( 5 4 0 ) developed a simple apparatus to measure the relative coefficient of friction a t high contact pressures, as in wire drawing, and to provide for control of surface quality of wire. A variety of engine tests for determining oil quality have been described and Sandulescu ( 8 7 0 ) 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. (810) to correlate well with standard engine tests, and to be faster and less expensive. The test didn’t show much differentiation between high detergent premium oils. The Coordinating Research Council reported results of a study of a new crankcase ventilation system to improve L-38 oxidation test results ( 1 6 0 ) and recommended new reference oils for studying oil oxidation characteristics in the CLR oil test engine ( 1 7 0 ) . I n cooperation with the Army Engine, Fuels, and Lubricants Group, a useful engine test technique for predicting fuel and lubricant cornpatability was developed ( 1 8 0 ) . Zarubin et al. (1040) reported evaluation of new PZV-60 units for evaluating detergent properties of oils according to Gost 5726. Levrague et al. ( 6 4 0 ) discussed use of a supercharged Petter AV diesel engine to cover the ever-increasing bmep and thermal loads of modern diesel engines. Saxe et al. (890) used a water-cooled onecylinder diesel engine for testing motor oils. Baist ( 6 0 ) modified the MWM test A by changing the cylinder liner, coolant, and fuel to permit testing oils of S-1and higher classes. Dysart ( 2 6 0 ) reported use of a modified CooperBessemer/Lufkin GSC engine for predicting deposit formation in two-cycle, spark-ignited gas engines. Laboratory bench tests for determining oil quality include a device described by Kyuregyan ( 6 2 0 ) for evaluating detergent properties of motor oils. Varnish deposits formed on a heated aluminum bushing in contact with a rotating steel shaft were the basis for evaluation. Forbes and Wood (550) 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 ( 5 0 ) developed an apparatus for determining oxidation stability of oils for selfsaturating lubricated bearings. Kaye and Seager (630) used dielectric constant measurements to determine creaming in emulsions. Schmid (910) 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 oxygen absorption test reported by Denton and Thompson (230) showed that zinc dithiocarbamates were the most active antioxidants evaluated. Oxygen consumption was also used as a measure of oxidation in an automatic device described by Sanin et al. (880), and Rudenko and Sobolev (860) described a semimicro oxygen absorption test. Shroff and Wilson (930) used the CERL method and oxygen absorption in laboratory tests to compare the laboratory assessment with service performance of inhibited insulating oils. An evaluation of procedures for determining aging resistance of a variety of oils was carried out by a number of eastern European countries and reported by Belcheva et al. (110). Wilson (1030) reported that service behavior 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 (250) described apparatus and handling practices used by Gulf Research Center in testing steam turbine oils. Krawetz and Tovrog (600) studied the application of differential thermal analysis to determine thermal decomposition of lubricating oils. I n a method reported by Kosyakin and Uspenskaya (590) heat resistance of lubricating oils is characterized by time required for their total “drying” or polymerization a t a given temperature. Steinmann (960) used ultraviolet irradiation 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 a t high temperatures was developed by Starikova et al. (950). Corrosive properties of motor oils were determined by measuring weight loss of lead specimens in a method developed by Maczel et al. (730). Bartholomaei et al. ( 8 0 ) described an oil mist deposits test for evaluating the deposit-forming tendency of jet engine lubricants. Doernenburg and Gerber (240) described the mechanism of gas formation in oil-filled transformers and analyzed the gas by mass spectrometer and gas chromatograph. Kaegler (510) automated the Woerner apparatus to simplify determination of gas-absorbing characteristics of electrical insulating oils. Gasing stability of insulating oils was tested by Brzuska and Widmann (140) using an oil/paper dielectric under simulated operating conditions. Dielectric loss tangent and specific conductivity were among the tests applied
by Mason and Simmons (780) to monitor the quality of insulating oils. Jones and Angerer (48D)showed by electroluminescence measurements in high direct current fields that the number of pulse discharges through an oil is directly proportional to anode current and their shape appeared to be a function of the test circuitry. The problem of flammability or fire resistance of hydraulic fluids was the subject of a number of papers. Ker (550) 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 a t a temperature of 700 “C. A combined “high pressure spray manifold test” correlated reasonably well with the hot brake test. A review by MacDonald ( 7 2 0 ) 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 (700) reported the environmental variables in supersonic aircraft prevent sure extrapolation of a fluid’s experimental hazard rating to actual conditions of use. Hamilton and Holloway (410) described an apparatus for evaluating fire hazards of hydraulic fluids which approximates the environment and conditions in high speed aircraft. A closed-compartment fire test for evaluating fire resistance of hydraulic fluids in advanced supersonic aircraft was developed by Kander ( 6 2 0 ) . An apparatus for studying fire resistance of hydraulic fluids a t elevated pressures was developed by Marzani ( 7 7 0 ) . Rowand and Sargent (840) used simple, inexpensive equipment in a low pressure spray-flammability test for hydraulic fluids. Johnson and Furby ( 4 6 0 ) 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 (380) reported the effects of mixture strength, atomization, and wall materials 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 (450). Erhart et al. (280) described chromatographic techniques for determining insulating oil additives, identifying aging products, and evaluating the stability of mixtures of inhibited oils. Jenkins (440) discussed the interdependence and significance of inspection tests,
elemental analyses, and carbon type analyses on the characterization of lubricating oil basestocks. Fluorescence in ultraviolet light of oil spread on filter paper was used by Alekseev and Tobolova ( I D ) to monitor regeneration of lubricants. Lyashenko et al. (670) used potentiometric titrations to determine alkali numbers of additives and oils with additives, and Bakmutaskaya and Butkov ( 7 0 ) reported that a color indicator titration gave results in agreement with potentiometric titrations. Zulin and Yartsev (1050) 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 (290) 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 (490). Bornong (130) used infrared spectrometry to examine preservative, hydraulic, and specialty fluids. The only additives easily detected were corrosion inhibitors and tricresylphosphate. It was concluded that infrared spectrometry 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 examination was described by McCoy ( 7 1 0 ) . Przybylski and Lichowska (830) 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 (920). Costa (200) published a nomograph for calculating flash point of lubricating oils from composition and the flash points of the components. Rowe (850) described a simple apparatus for determining viscosity a t temperatures up to 70 “ C and pressures to 20 tons per sq in. A method for plotting volatility curves of lubricating oils a t a given temperature was described by llartynov ( 7 4 0 ) , who also published, with Bondareva and Kuchinskaya (790), a description of the PIM-Z device for the laboratory determination of evaporation rates of lubricating oils. A spring-type microbalance was described by Martynov (750) for determining hygroscopicity of lubricants. Kruys et al. (610) reported the results of swelling tests with cable insulating materials in four types of oil. In the examination of used oils, Gardner ( $ 7 0 ) used infrared spectrometry to measure quantitatively oxidation, nitration, additive depletion, and contamination. Lizogub and Klimenko ( 6 6 0 ) described an infrared procedure VOL. 41, NO, 5, APRIL 1969
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for determining acid and ester numbers. A centrifuge method was described by Hammerich and Gondermann (420) for determining total contamination in used additive motor oils. Komarmy (580) used the rate of diffusion of a drop of used oil into a clean oil to determine the solid contaminant content. Kishi et al. (560) described a new method for insolubles in used oils in which coagulant is added, sample is extracted in a Sohxlet extractor, and weight gain of the thimble is determined. Studeny ( 9 7 0 ) used loss caused by evaporation on heating to determine gasoline content of used oils. Feasley and Pellicciotti (S1D) 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 (SOD) and by Cuculic (210). Cross-contamination of lubricants was detected with radioisotopes in a procedure described by Anderson and Black ( 3 0 ) . Greases. The history and possible areas of application of differential thermal analysis to problems of grease production were discussed by Trzebowski (99D). Vanos and Flora (1000) studied thermal transitions of greases and changes in body a t various temperatures to determine dropping points and phase diagrams. McCarthy ( 6 9 0 ) 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. -4method 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 ( 9 4 0 ) showed that the fourball wear test (ASTM D-2266) is a practical method for determining wear properties of grease. Ficker (320) and Guba and Vamos (S9D) described use of the electron microscope for examination of the soap fraction of greases. Anderson et al. (20) described a solvent-deoiling technique for preparing greases for electron microscopy. The use of trichlorotrifluoroethane as a safe solvent for determining grease and oil in waste water and sludge was proposed by Chanin et al. (150). Torque tests on grease-lubricated size 204 bearings were carried out by Lindeman (65D). Blank and Lindeman (120) described a study made with a novel torque tester. Patzau (820) reported use of an SKF grease-testing apparatus to study oxidation stability of greases. A new method for determining 158 R
ANALYTICAL CHEMISTRY
colloidal stability of greases was described by Suchanek (980). Haines et al. (400) described laboratory methods used to determine rheological and electrical properties of greases and other ffuid systems.
Wax D. R. Cushman and R. T. Edwards Mobil Research and Development Corp., Paolsboro, N. 1.
Roemer and Hochreiter (I8E) described an apparatus for automatic determination of flow and drop points of waxes. The apparatus, based on the photoelectric cell principle, indicates and records results of 12 samples simultaneously. Two papers dealt with oil content in paraffins. Mal'nev et al. (12E) used an infrared method, with the sample either in CClk solution, or without solvent in a high temperature cell, measuring intensity of the CH3 band frequency a t 1380 crn-l. Osipov and Popov (15E) used a double beam uv spectrophotometer with a phase detector providing a direct reading of the difference of intensities of the two beams. Three papers covered the quantitative determination of wax in oils and oil products. Demyanchik and Mikhalevich (YE) treated a 250' residuum with solvent, acid, solvent, alkali, water wash, and distillation to obtain a paraffin residue. Demyanchik et al. (6E) included a sulfonation step to remove resinous compounds from a residuum 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 acetonebenzene-toluene mixture following initial separation of asphalt and resin using an oil-hexane solution with active earth. Hard paraffins were detected a t - 10 and total paraffins a t -30 "C, the difference being soft paraffins. Elbadrawy and Heinze (9E) separated components of a microcrystalline wax by deoiling and fractional crystallization. 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 adduction, identified iso- and alkylcycloparaffins and mono- and bicyclic alkyl aromatics with 23 to 51 C atoms in crude oil fractions. Triems and Heinze (22E)prepared 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 produced during high temperature processing of crude oils, from hard paraffins in the form of their heavy metal complexes and characterized them by ir spectrometry. Two papers dealt with differential thermal analysis. Currell and Robinson (5E) showed that an endothermic peak a t 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 corresponding to thermal absorption during melting and during a solid-solid premelting 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 coefficient and the methyl-group mole fraction. Tudorovskii et al. ( W E ) 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 revolving 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. ( I S ) compared various methods and showed preference for quantitative measurement of uv absorption after extraction with MenSO and &Pod. 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 fluorescence a t 403-nm. Three papers dealt with crystallization of paraffin. Abezgauz et al. (1E) determined temperature for the onset of crystallization of paraffin from petroleum from the change in slope of the optical density us. temperature curve. To increase accuracy, the transition
point is registered in the ir region of the spectrum. Andriasov and Os’kin (SE) determined paraffin crystallization temperature by measurement of the volume expansion coefficient. They described an apparatus with gas chamber connected to a graduated capillary tube. The same authors (BE) used a photometric method to determine initial temperature of paraffin crystallization in a moving solution of different paraffin concentrationi,. Turbidity temperatures of various wax-kerosine solutions were measured. The temperature difference between the beginning of turbidity and the beginning of crystallization was 0.1 “C. One paper reported on determination of petroleum wax odor by gas chromatography. 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 described5by hlozes et al. (14E) as a substitution’ftir the empirical methods of consistency qualification hitherto used. Robinson and Johnson (17E) reviewed recent developments in wax analysis, covering 25 references.
J. A. Wronka Cities Service Oil
Co., Cranbury, N. 1.
Levin et al. ( S Q F ) described a rapid method for the determination of softening 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 (4OF) estimated softening point for blends of two asphalts using a mathematical formula and/or graphical method. Glass-transition temperature of asphalts was determined by Schmidt and coworkers (57F, 58F) using a dilatometric procedure and by Conor and Spiro (12F) using a differential thermal analysis. DuBois ( 1 8 F ) reported that asphalt-filler mixtures have higher glasstransition temperatures than asphalt alone. Silica gel chromatography was used by Sato and Imazumi (66F) for determination of wax in asphalts. In this procedure, isobutyl methyl ketone was used to precipitate the wax from a cyclohexaneeluted fraction. Bestougeff ( S F ) separated cold n-heptane-precipitated asphaltenes from Libyan, Boscan, Laghouat, and Hassi Illessaoud crude oils into 20 to 30 subfractions using selective extraction with elution chromatography.
Analysis of asphalts using inverse gasliquid chromatography was described by Davis et al. (16F) and used by Davis and Petersen (14F, 16F) for a comparison with the Kleinschmidt and RostlerSternberg analyses and for study of oxidation characteristics. Gradientelution chromatography using an ultraviolet monitor was described by Middleton (46F, 47F) to separate asphaltic petrolenes into six fractions, and Klesment et al. (29F) used thin layer chromatography for the analysisof ashaletar. A combination of pyrolysis, hydrogenation, and gas-liquid chromatography was used by Knotnerus (SOF, 3 1 F ) for analysis of bitumens and bitumen constituents. A structural analysis of asphalt fractions was made by Blyler and Daane (48’) using X-ray diffraction, omometry, electron microscopy, and mass Spectrometry; by Corbett and Swarbrick ( 1 S F ) using mass and nuclear magnetic resonance spectrometry; by Wetmore et al. (68F) using ultraviolet, infrared, and nuclear magnetic resonance 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 magnetic and electron-spin resonance measurements, and X-ray diffraction. Ramsey et al. (54F) reported that nuclear magnetic resonance gives reliable data with respect toaverage formula and molecular weights and structural details, requires no instrument calibration with known compounds, and provides results rapidly. Kicksic and Jeffries-Harris (b’1F) concluded that acid-precipitated asphaltenes constitute a distinct chemical class on the basis of molecular weight determinations; carbon, hydrogen, sulfur, nitrogen, nickel and vanadium contents; and electronspin and nuclear magnetic resonance. Yen and Boucher (69F) summarized electron-spin resonance studies on six asphalts. Laguros et al. (S7F) correlated asphalt content of a bituminous pavement Kith neutron scattering and Kuykendall et al. (S6F) applied neutron activation analysis to asphalt and concluded that oxidation 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 ( Y F ) to measure oxidative changes in a Kuwait asphalt flux; by Smith et al. (60F) to predict weatherability behavior of coating grade asphalts; by Petersen ( 6 S F ) 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 reproducibility 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 (3”) developed a rapid, smallsample test for evaluating ductility. Baibazarov and Ziain ( I F ) 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. ( 6 S F ) , Urejcha ( 5 F ) , and Neumann et al. (50F). ”u’eumann and Bellstedt (49F) showed that primary particle aggregation and mean relative mass of asphaltenes increased with roncentration and decreased with temperature. Kuchma ( S 5 F ) 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 (62F) described a new transudation test for determining compatibility of tar and asphalt. Grading of asphalts by viscosity a t 140 O F and other aspects of their use in paving were discussed by Welborn (66F), McLeod (41F, @F), Chaffin ( 8 F ) , Hawthorne (B5F), Krom (34F), Izatt and Buchanan (27F), Griffith et al. (BSF), Halstead et al. ( I 4 F ) , and Welborn et al. (67F). Walter (65F) compared various methods of measuring viscosity of asphaltic binders and Cogill (10F)measured viscosities of two groups of asphalt cutbacks using the following viscometers: Pochettino type falling coaxial-cylinder, couette-type rotating coaxial, capillary, vacuum, and Ostwaldtube. Chari and Awasthy (YF) measured viscosities of pitch-tar binders using a torsion blade and penetrometer; Cogill et al. (118‘) adapted the KuehnRigden viscometer for use with an interferometer for determining viscosity of weathered asphalts. Majidzadeh and Schweyer (4SF) and Herrin et al. ( d 6 F ) explained rheologic behavior of 13 asphalts determined by a sliding-plate viscometer by the Eyring rate processes theory and reaction kinetics principles. Santucci and Schmidt (56F) compared laboratory tests with full scale pavement-laboratory tests and conVOL. 41, NO. 5, APRIL 1969
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cluded that pavement toughness correlates with viscosity a t 100 O F of asphalts received from test pavements and with viscosity a t 140 O F of asphalts exposed in rolling thin film oven. The rolling thin film viscosity was proposed for grading setting quality of a paving asphalt. Lee and Csanyi (S8F) showed that the Bureau of Public Roads' thinfilm oven test ages asphalt in the same manner as the normal hot-mixing operation a t asphalt plants. Heat of reaction during asphalt blowing was determined by Smith and Schweyer (61F). Effect of bacteria and other microorganisms on asphalt was studied by Traxler (64F) and Jones (28F).
Catalysts Ralph 0 . Clark Gulf Research Pittsburgh, Pa.
& Development Co.,
Acidity. Only one report in the two-year period covered by this review described use of indicators for measurement of catalyst acidity. Drushel and Somers (6G) followed transition from a protonated species to a neutral indicator using a spectrofluorometer when the cracking catalyst was titrated with a basic amine. Qualitative 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 employed by Charcossett et al. ( I C ) 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 nbutylamine. Pohl and Rebentisch (16G) described a dynamic method for determining surface acidity of alumina catalysts using ammonia; Tanabe and Yamaguchi (65G) utilized thermal measurements of the reaction of silica-alumina with nbutylamine. Acidities so measured were higher than published values by the indicator method; this was interpreted as indicating the presence of weak acid sites not detected by the indicator technique. Bertolacini (1G) determined activity of reforming catalysts containing one or more noble metals on a refractory support as per cent of the total noble metal in the catalyst that is soluble in acetylacetone. An adaptation of the Atlantic-Richfield microactivity test was described by Ciapetta and Henderson (4G); various advantages are claimed. Also, Harriz ( I I G ) 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 manufacturer is now using a microactivity test (14G) instead of the D L test for equilibrium catalyst testing; distortions due to unrealistic coke buildup and varying amounts of metal contaminants were claimed to be minimized. Polyakin (I7G) described a semimicro method for evaluating activity of synthesis gas catalysts a t 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. (6G) 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 developed by Schay and Nagy (22G) 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 microcalorimetry to powders having surface areas of 1 m2 per g or less; Orr (16G) reported excellent agreement with BET values using low pressure permeametry for surface areas up to 6 m2per g. Lester (12G) compared pore size distributions 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 detailed analysis. Comparison of a transformed 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 distributions in terms of surface areas, can be computed with a desk calculator directly from nitrogen-desorption isotherms. Roberts (2OG)devised a simple and rapid procedure for estimation of pore volume and area distributions of catalysts from sorption isotherms. Results obtained agreed with data calculated by the method of Barrett, Joyner, and Halenda. A new mercury porosimeter was reported on by Reich (19G). The instrument will accommodate a relatively large specimen and is applicable for measurement of pore diameters over the range 0.05 to 500 b. Calibration of a Coulter counter for particles having diameters of about 1 I.( was covered by Mercer (1SG). Chatfield (SG) proposed a particle size comparator 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 Khyanina (IOG), who followed this by titrating the recovered fluoride with thorium nitrate or colorimetrically using the bleaching effect on sodium zirconium alizarinsulfonate. Russow (WIG) patented a thermal neutron activation method for boron in reforming catalysts, and Stone and Rayburn (W4G)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 (W3G).
Physical Properties W. A. Wright Sun Oil Co., Marcus Hook, Pa. The Coordinating Research Council test technique to evaluate low temperature cranking characteristics of engines a t 0 O F was evaluated a t -20 O F (14H) and found suitable a t the lower temperature. Data on various engines and motor oils reconfirmed that predictions of performance should be based on appropriate 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 (67H). Correlations between engine tests and bench tests on the cold-cranking simulator reciprocating viscometer and coneplate viscometers a t -20 O F were reported by Meyer et al. (39H). A detailed study of the cold-cranking simulator by Cox et al. (16H) was made in preparation of an ASTM standard method. A similar report was made on construction of the reciprocating viscometer by Stewart et al. (6WH) and on its correlation to engine tests by Stewart and Meyer (40H). Viscosity studies of lubricating oil a t 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 timedependent yield value. Gadzhiev (26H) studied viscosity-temperature relations for several lubricating oil fractions from +10 to -40 "C. Loglog kinematic viscosity varied linearly with temperature over this short range.
Noganii and Kobayashi ( 4 I H )examined stability of polymer-containing oils and relation to the test method. Automatic control of vibration and resonance was desirable. Nogami (4SH) related viscosity loss to exposure time in a sonic tester by ti 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 compounds under high shear rates were studied by Paushkin et al. (48H). Viscosity and compressibility of lubricants at 500 to 2000 atmospheres and 20 to 100 "C were determined by Raetzsch (51H, 52H). Falling sphere viscometer and piezometer compressibility data are reported for paraffin oil, glycerine, polypropylene glycol, and isoceresine. Ali ( Z H , S H ) evaluated and compared several methods of correlating oil viscosity with temperature. Methods of measurement of estimation of viscosity at temperatures up to 700 O F were applied to problems of thermal recovery of petroleum. Kobashi (33H) used a coaxial cylinder viscometer to measure viscosity of Ca and Li greases a t constant shear rate. Apparent viscosity decreased linearly with log time. Structural breakdown also was related t o type of base oil. Patzau and Ligezowa (47H) compared apparent viscosity-temperature measurements for several types of greases with torque measurements taken on a roller bearing using the same greases. Pavlov and Vinogradov ( 4 9 H ) made extensive rheological measurements on greases using techniques of both constant shear rate and shear stress. Shear rates range from 10-6 to lo4 sec-I. At very low shear rates, greases first workharden, followed by creep. As shear rate iiicreases, there is increasing structural breakdown with softening. At high shear rates, grease flow becomes essentially Newtonian. Brungraber et al. ( 7 H ) glued plastic vanes to the faces of a cone-plate viscometer t o combat slippage at the wall. Turian (65H) continued studies on viscous heating in cone-plate viscometers by analyzing the case for nonKewtonian fluids betlveen infinite parallel planes. Chen et al. ( 9 H ) developed equations for terminal velocity of the cylinder in a falling cylinder viscometer when eccentricity existed. Schurz and Tomiska (56H) studied the HagenbachCouette correction factor experimentally in a variety of straight and curved capillaries interupted by bulbs. Individual instrument calibration with a known fluid was advisable. Cogill et al. ( 1 2 H ) described a viscometer for the range of 108 to 10 l 1 P using 0.1 ml of sample. Viscosities within 20% of correct were obtained 5 min after
start of reading. Cussler and Fuoss ( 1 6 H ) designed and tested a remote control viscometer for use in a pressure bomb up to 5000 atm. Klaus et al. (SOH) described a capillary kinematic viscometer usable from 0 t o 10,000 p i g . Klein and Fusser ( S I H ) studied effects of capillary length to diameter ratios and their relationship to temperature rise and elastic effects. LID ratios up to 4000 were studied. Speaker (6OH) devised a high pressure viscometer of the Ostwald type. Electroluminescent panels and photocells were used as the sensing device. Stromskii et al. (63H)developeda rolling ball viscometer for measuring viscosity in gas-condensate systems up to 1500 kg/cm* and temperatures below 200 "C. Inductive timing of the falling ball gave an accuracy within 0.2 sec. Viscometer accuracy was better a t 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 materials. Nitterhauszer ( 4 1 H ) used the Spengler viscometer t o determine high shear viscosities of a series of Li, Ca, and Na greases. Greases gave lower friction resistance in ball bearings than lubricating oils of equal or lower viscosity. Onoyama and Sat0 (46H)specially calibrated a Brookfield viscometer. Reproducibility was 1.7 to 3.5%. Used engine oils gave evidence of non-Newtonian characteristics. Wohl (7OH) compared use of capillary, rotational, coaxial, and cone and plate viscometers, as well as calculations involved, when testing non-Newtonian fluids. Gaeta described very low shear, high sensitivity, electromagnetic viscometers ( W H ) . 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, viscositytemperature relations of lubricating oils, lubrication, fluid flow in pipes, hydraulic systems, etc. Ghigliazza ( I 4 H ) discussed the incorrect 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 discussed this subject and described the new standard, -4STM D 2270, adopted to reduce discrepancies. Kelley and Caudle (28H) presented a graphical method of predicting gas-free oil viscosities up t o 500 O F . .4PI gravity and one viscosity are used to determine the slope on the ASTM chart. The slope and a single viscosity permit prediction a t other temperatures. Du Parquet (46H) compared viscosity-temperature relations for mineral oils. The study covered formulas proposed by Walther, Vogel, Andrade, Eyring, Umstatter, and Van Ness/Van Westen. Rumpf ( 5 S H )
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 a t 50". Kay ( 2 7 H ) described a method of calculating ternary blends on the ASTM viscositytemperature chart. Cost, gravity, and other properties of blends mere 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 ( 1 7 H ) presented a nomograph which gives vapor pressure of a compound from -50 to +500 O F , given its normal boiling point. Davison et al. ( 1 8 H ) described a static vapor pressure apparatus for mixtures. llartynov and blorozova ( S 7 H ) developed an apparatus to determine saturated vapor pressures of lubricating fluids. It was based on the Bremer Frowein differential tensimeter. Jentoft et al. (26") presented an apparatus for rapid determination 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- t o 5-pl samples trapped a t exit of gas-liquid chromatographic columns. Wadsoe (68H) described a calorimeter t o obtain heat of vaporization a t 25 "C. Amount of sample is about 100 mg and the test requires less than 45 min. Hamey (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. ( 5 H ) described a pycnometer suitable for use a t 250-atm pressure. Wostl et al. ( 7 I H ) described an apparatus to determine both adiabatic and isothermal bulk modulus. The range was 0" to 50" and 0 t o 300 kg/cm*. 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 t o 500 O F and up to 100,000 psig. Atmospheric density a t the desired temperature is the only required information. Bruno and Garfinkel (8H)devised an apparatus to measure dielectric constant and tangent of the loss angle for greases used with electrical cable. I t 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 measuring its dielectric constant. Skowronski and Lutynski (59N) 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
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Maksimov (61H) correlated dielectric constant and tangent of the loss angle of gasolines and gas oil to density of the fluid. Colin and Setton (1SH) described an improvement on equipment to determine electrical resistivity by induced currents. Klinkenberg (32H) found polarization errors in measuring electrical conductivity below lo-" 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 a t atmospheric pressure and isothermal data a t 3 atm. In all cases, the heat capacity increased with temperature. Madejski (36H) disclosed a method of measuring thermal conductivity of liquid and gaseous dielectrics using free convection from a fine wire. It was applied to ethanol and petroleum fractions. Yamamoto and Akiyama ( 7 3 H ) used an improved hot wire technique to obtain rapid thermal conductivities of liquid samples of 1 t o 1.5 ml. End and other thermal effects were compensated by double-bridge circuits. Bozso ( 6 H ) used cryoscopic and ebulliometric methods to determine molecular weights of hydrocarbon blends. Automatic cooling and registration of cooling curves improved cryoscopic data. Comparative precision of both methods was determined. Cir et al. ( 1 1 H ) reported on semiautomatic equipment for cryoscopic molecular weight determination. An electronic potentiometer records temperature curves of benzene solutions a t various concentrations. Extrapolation to infinite dilution agreed better with theory than the usual Beckmann thermometer method. Lyashkevich (35H) studied errors in cryoscopic analysis as related to crystallization and heating rates in a benzene-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 ( 7 4 H ) described an automatic recording apparatus to obtain freezing points from time-temperature freezing and melting curves. Repeatability was f0.01" from -190 to +250 "C. Driscoll et al. (19H) made purity determinations using a differential scanning calorimeter with 1.25' per mill scan rate. A computer program correcting for heat of fusion was used. Precision was A0.02 mole yo. Alba et al. ( 1 H ) studied factors involved 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 a t high pressures. About 10 methods are considered. High pressure measurements were made on liquid-liquid and liquid-gas systems. Williams (69N) studied the effect of surface tension and meniscus shape on hydrometer readings and a method devised to evaluate meniscus shape. Chulkov (10H) modified the Bass formula for calculating heat of combustion for petroleum products as a function of density a t 20 "C. A coefficient varying with density was introduced. Calculations were within *30 kcal per kg of experimental value. A nomogram was prepared. Dymond and Hildebrand (2OH) described an apparatus for rapid determination of gas solubility 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 a t 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. KOnew techniques of broad import were introduced during this period. The bulk of reports in the literature deal primarily with application of methods that are now fairly well established. -4s 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 instrumentation that depends on attenuation or absorption of either neutrons or prays 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 @-ray equipment; Johannes and Jaeckel(62Z) described a continuous method for determination of per cent hydrogen that depends upon measurement of attenuation of neutrons generated by a plutonium-beryllium source; accuracy of 0.15% hydrogen by weight is claimed. Gardner and Roberts (451) reviewed problems involved in calibratioii of 0ray 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. Displacement techniques for analysis of lower-boiling fractions were concerned principally with descriptions of the fluorescent indicator adsorption (FIA) method. Kurchatkina et al. (761) described preparation of fluorescent indicators suitable for use in determining aromatic hydrocarbon content of light petroleum products by liquid chromatography; 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 aromatics that agree within o,7y0 with data obtained by the sulfonation method. Zhorov et al. (1571) used a fluorescent indicator technique for gas oil fractions in which diphenyl-l,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 ultraviolet radiation. Several related but drastically modified 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 packing impregnated with a 2,4,7-trinitrofluorenone solution containing methylene blue. The blue color of the packing changes to green in the presence of aromatics owing to formation of molecular complexes. The length of the green zone can be related to the weight per cent of aromatics by calibrating with known samples. I t was claimed that results compared favorably with those obtained by gas chromatography or the conventional FIA method. Suatoni (143Z) described a method for determination of traces of aromatics in paraffins by column chromatography over a mixture of silica gel and Radelin phosphor GS-115. When an adsorbed sample is irradiated with short wavelength ultraviolet light, a dark band can be observed a t 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 adsorption chromatography (LE.4C) have continued to grow. Data published during the past several years demonstrate that principles of linear elution can be successfully extended to other than hydrocarbon systems. Snyder (1341, 1351) described qualitative analysis 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 adsorbents when used in the linear elution mode. Snyder and Buell (1391) assembled 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 materials. They suggested that these data can form a basis for separation and classification of petroleum nonhydrocarbons by compound type using titration, ion exchange, or adsorption chromatography. There were several reports that dealt with application of conventional elution techniques for analysis of high boiling hydrocarbon mixtures. Pavlovschi (1031) described chromatographic separation of carbon black oils over activated alumina. By using heptane, benzene, and ethanol as successive eluents, oils were fractionated into saturated hydrocarbons, mononuclear aromatics and thiophenes, dinuclear aromatics, trinuclear aromatics, and polynuclear aromatics plus heterocyclic oxygen and nitrogen compounds. Separation was followed using ultraviolet spectrometry Results were claimed to be reproducible to within =t5y0. 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 system is superior to silica gel alone. Carrying this idea several steps further, Grinberg and Shved (49Z) 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 hydrocarboils and estimated the percentage of these different hydrocarbon 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 caffeine-aromatic hydrocarbon complexes to the cathode in an electric field. Sel’yanova (1281) reported use of porous glass to separate mixtures of tetrachloroalkanes 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 permeation can be used effectively to separate paraffins from cycloparaffins and alkylbenzenes 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 determination of n-paraffins in gasoline, kerosine, and light gas oil have been reported. Gurina et al. (521) described their application of what is essentially the Heinrich and Grimes method, while Nesmeyanova et al. (991) and Rennhak et al. (1121) detailed their experience with the Larson and Becker volumetrictechnique. Jaworski (611),on the other hand, allowed n-paraffins to be selectively adsorbed for solution by molecular sieves, then cryoscopically determined amount of unadsorbed isoparaffins. 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 (261) found that under suitable conditions thin layer chromatography will produce R, 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 compounds 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 adsorbent 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. R, values of 21 polynuclear aromatics were tabulated. Harvey and Halonen (541) used silica gel impregnated with 2,4,7trinitrofluorenone to separate complex cyclanoaromatics by thin layer methods. Porous ethylvinylbenzene polymers were used by Janak and Kubecova (601) for tlc separation of aromatic hydrocarbons, heterocyclic compounds, and phenols. Behavior of Porapak Q was investigated most extensively. Data obtained using five different developers and 46 model compounds are given. Physical property methods for hydrocarbon 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 molecular structure. He presented graphs and equations which allow use of experimentally determined boiling points and densities for estimating carbon numbers of CM+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 molecular 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 products from their refractive dispersion and iodine number was proposed by Aliev and Kushelevskaya (41). The method incorporated a correction factor to eliminate interference from conjugated diolefins. The authors claimed that results compare favorably with those obtained by conventional techniques. 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 O F . Combinations of gas chromatography with other separation methods such as distillation or adsorption chromatography were cited extensively. Primavesi et al. (1081) outlined 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 conditions. 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 reproducibility of response of flame ionization detectors were studied in some detail by Batt and Cruickshank (?Z). There are a number of reports that described use of relatively novel partitioning liquids or solid adsorbents for separation of hydrocarbons. Alumina is becoming increasingly popular for separation of both hydrocarbon gases and higher boiling materials. Hoffmann and Evans (671) 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 chromatography on alumina are strongly influenced by the carrier gas selected. List el al. (821) successfully used alumina to separate cis- and trans-isoVOL. 41, NO. 5, APRIL 1969
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meric olefins. They found the cis form is retarded relative to the trans configuration. Hoffman (561) also used a short column of silver nitrate-impregnated alumina in a subtractive fashion to remove olefins from a Garaffin-olefin mixture quantitatively. Paraffins were then further separated using a conventional 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 hydrccarbon mixtures. The Firebrick was impregnated with aluminum isopropoxide in benzene, the alcoholate hydrolyzed in situ, and the adsorbent activated a t 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 hydrocarbons 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 (47'1) to separate low molecular weight hydrocarbons a t room temperature. hlodification of its properties by incorporation of low loadings of liquid phases was also studied. Gas chromatographic separation of Cq hydrocarbons on graphitized carbon black was studied by Kiselev and coworkers (691). Graphitized carbon black also was used by Boikova and Shcherbakova (191) to separate various isoparaffins and cycloparaffins in the gasoline boiling range. Lithium and sodium salts have also been used for separation of mixtures of high boiling hydrocarbons. Wolf et al. ( 1 5 2 ) loaded potassium nitrate or sodium chloride crystals lightly with a high boiling liquid and used this to separate mixtures of C11-C18 n-paraffins. In this application the salt served mainly as a support for the separating liquid. Chortyk et al. (291) successfully separated a number of polynuclear aromatic hydrocarbons on a column of Chromosorb P containing 20% of lithium chloride. They reported that in many cases the separation was better than that achieved with capillary columns. Lithium chloride dissolved in Carbowax 400 was used by Bighi et al. (171) for separation of a number of gasoline boilingrange hydrocarbons. The authors suggested 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 p, p'-hydroxidipropionitrile 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
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Hildebrand and Leschner (651); "Fluhyzon" is a commercial material developed originally for separation of n-paraffins. Stationary phases that are extremely selective for aromatic hydrocarbons have been described by several investigators. Rogozinski and Kaufman (I181) reported that with a column of 40% N,N-bis(2-cyanoethyl)formamide on Chromosorb P, n-hexadecane is eluted before benzene at 160 "C. 2,4,6Trinitrophenetole was recommended by Maczek and Phillips (851) for selective separation of gasoline-range aromatics. With this stationary phase, benzene emerges between n-undecane and ndodecane, and m-xylene precedes pxylene. 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 C6-C8 aromatic hydrocarbons from other hydrocarbons found in gasolines. The butter was heat-treated a t 200 "C for 2 hr, filtered, and deposited on the solid support from benzene solution. 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, dichlorobenzene, and cresol isomers. They reported 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 analysis and on glass beads for triphenyl separation. Columns were operated a t 71 "C for xylenes, 180 "C for naphthalene, and 200 "C for triphenyls. Chabrova (261) reported complete separation of a mixture of Cs 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 591, dinonyl phthalate on Chromosorb W followed by 10% tricresyl phosphate on Chromosorb P. Results for CSaromatic isomers obtained using this arrangement agreed within rt3% with those obtained by ultraviolet spectrometry. A complete 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% $E-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 Cl0-C14 n-paraffins a t 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 vas devoted to analysis of mixtures of hydrogen, noncondensable gases, and light hydrocarbons by gas chromatography. Jones (641) reported analysis of hydrogen-rich refinery streams using two Porapak Q columns in series. The first was programmed from ambient temperature to 125 "C and the second was operated a t 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 CI-CS saturated hydrocarbons were successfully determined in single samples containing as little as 0.1% of the minor components. Analysis was completed in slightly over 1 hr. A Porapak Q column and a 5.A Molecular 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 between columns permitted gases separated 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 (31I ) successfully used 80-100 mesh beads of an ethylvinyl polymer to separate mixtures containing hydrogen, air, carbon monoxide, carbon dioxide, and Cl-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 5.4 Molecular Sieve column and the remainder through dimethylsulfolane and hexadecane columns arranged 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-Cs hydrocarbons. The first column contained dibutyl phthalate on firebrick, the second silica gel, and the third activated carbon. The columns were
maintained at 55, 22, and 150 "C, respectively. Hydrogen was eluted from the series arrangement with air, and the columns were then disconnected and eluted separately to determine individual hydrocarbons. Gas chromatographic determination of n-paraffins in petroleum products was reported by a number of authors. iMortimer and Luke (97Z) described a method suitable for distillates with boiling points less than 900 "F. The nparaffins are adsorbed from sample in the vapor phase by type 5A Molecular Sieves. Materials to be separated are deposited on the sieves which are contained in a microsorption unit. The adsorber is heated from 25 to 300 "C in 20 min and maintained there until nonlinear hydrocarbons are eluted. Sieves containing adsorbed n-paraffins are then removed and decomposed with hydrogen fluoride; n-paraffins are extracted from the neutralized aqueous HF solution with isooctane. An aliquot of the isooctane solution is analyzed by temperature-programmed gas chromatography using a lightly loaded silicone gum rubber column. The percentage of individual n-paraffins is related to the sample originally taken by an internal standard. Brunnock (22Z) described a combination of extractive crystallization and molecular sieve adsorption, followed by sieve decomposition and gas chromatography of recovered n-paraffins. The method is applicable to extremely heavy distillates. Sojak and Hybl (fQOZ) 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 applications 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 Groennings to allow determination of nparaffins in kerosine fractions. The original method utilized a partition column and molecular sieve column in series. Modifications involved adsorption of n-paraffins on molecular sieves a t 350 "C rather than a t 200 "C and injection of sample downstream rather than upstream from the partition column. Knight (7lZ) described a procedure for determination of n-paraffins in kerosine that involved addition of an internal standard, adsorption of n-paraffins in liquid phase on 5A Molecular Sieves, decomposition of sieves, and recovery of n-paraffins, followed by gas chromatography on a 5y0 SE-30 Chromosorb W column. Reports of applications of gas chromatography to relatively high boiling hydrocarbon mixtures are limited. The
basic problem in using gas chromatography for analysis of such materials lies in their complexity, combined with the difficulty of assigning peak identities even when reasonable separation is accomplished. Dembovskaya (3.21) described the use of gas chromatography to separate narrow-boiling fractions of kerosines and gas oils into paraffins and mono- and dinuclear aromatics. Perkins et al. ( l O 4 Z ) suggested that it should be possible to calculate the contribution of each fraction to the composition of a blend of petroleum products with a gas chromatographic elution curve even if the separation were poor. They demonstrated that binary mixtures of complex fractions can be analyzed with an error of less than 10%. Maher (861) used gas chromatography in combination with reagents that successively removed olefins, aromatics, and n-paraffins to analyze a high boiling neutral oil sample in some detail. Reports of applications of gas chromatography to special problems appeared with some frequency. Determination of small amounts of low boiling hydrocarbons in solvents was reported by Alekseeva and coworkers (SI) and by Chirikova et al. (281). The former described methods for determination of C4 and Cs 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 impregnated with a 10% solution of sodium iodide in diethanolamine, retains methylamine, while the second column of 15% diethylene glycol butyrate on firebrick separates the hydrocarbons. Chovin et al. (SOZ) used two columns in series with a hot-wire detector between to determine aromatic hydrocarbons in turpentine oil, hydrocarbon solvents, and complex solvent mixtures. The first column contained 7.5'35 Apiezon L on Chromosorb W and separated the sample into fractions containing components of similar boiling point. A control valve located after the detector allowed selected fractions to be diverted to a second column packed with 35oJ, of tetrakis-(0-2cyanoet h yl) pentaeryt hritol on Chromosorb W, which separated the fractions into individual compounds that were measured by a second detector. The determination of benzene in varnish thinners was described by Scrima (126Z). 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 chromatographcd at 90 "C on a 2-m column of Chromosorb containing 20% of polyester succinate. Ethanol, benzene, toluene, and xylenes were separated. Packed-column gas chromatography is still used extensively for trace analyses, largely because such columns will accept high sample loadings. Klett and Korous (70Z) described determination of traces of hydrocarbon impurities in high purity chemicals derived from petroleum. Down to 0.5 ppm of impurities can be estimated in cyclohexane, styrene, or propylene. Successful use of gas chromatography in these applications is dependent upon selection of a stationary phase that retards the major constituents without significantly affecting elution time of the impurities. Determination of impurities in propane-propylene streams was reported by Tsifrinovich and Lulova (147Z) 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 chromatographic column and immersed in liquid oxygen. Rennhak et al. (1111) determined small amounts of acetylenes and 1,2dienes present in the C2-Ca olefins formed by the cracking of petroleum. They used a 12-n1 column of 20% dimethylsulfoxide on firebrick. Although a thermal conductivity detector would ordinarily suffice, an argon ionization 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 successfully used by Zlatkis and Iiaufman (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 laboratories have achieved a measure of success in extending capillary methods to full range gasolines. There are several reports that deal with analysis of gaseous hydrocarbons and special mixtures of aromatics using capillary methods. Leveque (791) described determinaVOL. 41, NO. 5, APRIL 1969
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tion of CTCS hydrocarbons in naphthas and reformates using a stainless steel capillary coated with a binary stationary phase containing 4.35 parts of n-hexadecane and 1 part of Fluorolube oil LG160. 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. (%?I) reported use of squalene-coated capillaries to determine 37 of the possible 38 hydrocarbons in straight-run gasoline fractions boiling up to 230 "F. They provided data on gasolines distilled from five Soviet crudes. Willis and Engelbrecht (1521) described a capillary method for separation of Cl-ClO paraffins and aromatics through naphthalene using a di-ndecyl 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 a t 12 to 30 "C per hr. The system incorporated a flame ionization director and electronic integrator. Concentrations of 85 hydrocarbons were reported, including most of those that elute before n-octane. Sanders and Naynard (1211) described analysis of full range motor gasolines for individual C d & hydrocarbons. They used a 200-ft squalane capillary and flame ionization detector. Both column temperature and column inlet pressure were programmed to provide optimum resolution. Approximately 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 investigated. A column coated with 1.5% squalane plus 4% dipropyl tetrachlorophthalate produced a separation of 21 components in 45 min. Vitt et al. (1511) found it was not possible to separate all CS-Clz dialkylbenzenes in a single run on capillaries coated with Apiezon L, polyoxypropylene glycol, or squalane. However, such mixtures could be satisfactorily analyzed either by successive runs on two columns with different stationary phases or on one column a t two different temperatures. Copper capillaries coated with a 1:l mixture of lanolin-Bentone 34 were 166 R
ANALYTICAL CHEMISTRY
used by Dimov and Shopov (381) to separate mixtures of Cs-Ce aromatics. Use of capillary columns coated with a hydrophobic silica adsorbent for separation of hydrocarbons was suggested by Schwartz e.! 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 segaration of Cl-C4 paraffins, monoolefins, diolefins, acetylenes, and cycloparaffins. They reported that mixtures of dibutyl maleate and p,p'-oxydipropionitrile are useful stationary phases when columns are operated a t -30 "C. Bryanskaya et al. (241) described synthetic methods for preparation of calibration mixtures of CrCs iso- and n-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 identification is still an important one, few papers that deal with trapping of gas chromatographic effluents have appeared in the past several years. One interesting contribution by Witte and Dissinger (1541) gave details of construction and use of a device consisting of a glass U-tube 2.5-mm i.d. X 180 mm long which contained about 20 pl. of a solvent suitable for subsequent spectrometric examination. They claimed that rapid cooling of the tube in liquid argon converted the solvent to a microcrystalline form which did not hinder passage of carrier gas but served as a filter to trap even the most volatile hydrocarbons. A method for identifying individual components in unknown mixtures by continuously determining carbon-hydrogen 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 convert water to hydrogen. Reactor effluent then passed through a thermal conductivity detector to record combined 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 temperatureprogrammed gas chromatography are few. Geiss et al. (461) reported use of a temperature-programmed packed column 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 5 0 1 6 4 basic alumina would produce the desired separation. Other aluminas or graphized carbon black were not suitable.
Behling et al. (101) described a twostage temperature-programmed capillary 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 polyoxypropylene glycol R, then to a second detector. The two columns are temperature-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 hydrocarbons 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 (1231) for separation and characterization of aromatic hydrocarbons in coal tar. Combinations of gas chromatography and mass spectrometry are increasingly common for analysis of complex hydrocarbon mixtures. Studier and Hayatsu (1421) described instrumentation that utilizes a capillary chromatograph 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 deuterium. A chromatogram was presented for the reaction product, and perdeutero hydrocarbon assignments were tabulated for 102 peaks. Teeter et al. (1441) reported analysis of 1-olefins using a gas chromatographmass spectrometer combination. A mixture of Cll-C14 1-olefins was separated by chromatography over a 50-ft X l/d-in. packed column containing 15% of Ucon LB-55OX, 0.2% of Alkaterge T and 0.2% sorbitan monooleate on 60-80 mesh firebrick. The column was temperature-programmed from 100 to 185 OC a t 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 (11) used gas chcomatographic distillation to produce fractions which are then examined by high resolution mass spectrometry. The method is based on parent peak analysis a t low ionizing voltages. Precise masses are determined from a chart by using carbon-12 to carbon-14 distances as internal mass-measuring standards. 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 hydrogenation or dehydrogenation proved useful for analysis of especially difficult types of samples and for characterization of relatively pure hydrocarbons and nonhydrocarbons. Analysis of CrClo 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 Cf,-C10 aromatics and seven aromatic olefins were determined. Thompson et al. (1461) successfully characterized many nonhydrocarbon constituents of petroleum by microhydrogenation. They used a microreactor to hydrogenate extremely small fractions 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 rechromatography. Their identification leads to identification of their precursors. The method mas successfully applied to oxygen-, nitrogen-, halogen-, and metalcontaining compounds. Fluorescence indicator adsorption combined with gas chromatography was used by Leont'eva et al. (781) to determine concentrations of individual c6-C~ hydrocarbons in catalytic gasoline. Retention volumes and relative amounts of 70 components of gasolines examined were reported. Gupta et al. (601) used adsorption chromatography followed by gas chromatography to estimate concentration of naphthalenes and methylnaphthalenes in a kerosine fraction. Gas chromatography combined with fluorescence and phosphorescence spectrometry was used by Drushel and Sommers ($61)to analyze petroleum fractions rich in nonhydrocarbons. Yew and Mair (1561) used a combination of azeotropic distillation, nuclear magnetic resonance and ultraviolet spectrometry, gas chromatography, and mass spectrometry to identify 29 compounds in a 500 to 520 "F dinuclear aromatic fraction of petroleum. Compounds reported included eight C13 and seven (214 alkylnaphthalenes, five C14 and four Cis alkylbiphenyls, four dibenzofurans, and fluorene. A number of reports concerned principally 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 chromatography 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 (741) gave details of a high vacuum ionization detector for gas chromatography which is based on ionization of sample gas by slow electrons. Sensitivity data were given for several common gases including methane, ethane, ethylene, propylene, and butane. A process Chromatograph designed to provide optimum separation of mixtures containing predominantly Cq hydrocarbons but containing a condensable fraction of c&f, hydrocarbons was described by Bossart and Zinn (201). Fenske (351) gave details of an apparatus capable of producing certain hydrocarbon-type analyses on a semicontinuous basis. The apparatus can be used as a stream analyzer in a great many manufacturing and refinery operations. 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 (1121). 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 hydrocarbons in air and 0.5 ppm in helium. A novel stream analyzer based on cool-flame oxidation was detailed in recent patent literature (1491). Instrumentation is arranged to immobilize 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 continuous stream analysis in a petroleum refinery or chemical plant. Spectrometric methods are still important for analysis of petroleum hydrocarbons. A critical survey of the more important infrared techniques for qualitative and quantitative structuraltype 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 ( I l S I ) , who developed a simple procedure to correct overlap empirically in the infrared absorption bands of antisymmetrical stretching vibrations of carbonhydrogen bonds in methyl and methylene groups. The ratio of corrected absorbances was correlated with the ratio of the number of methyl and methylene groups in the alkane molecule. A similar method based on measurements of infrared spectra of nparaffins 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 physical 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 a t 1600 or 810 cm-l was suitable for determination of concentration of aromatic hydrocarbons in oils. They further discovered a correlation 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 a t 730 cm-1. They were also able to determine as little as 0.004 vol 70 of acetylene. Rochkind (1171) described a system for infrared analysis that uses a condensed-phase sampling technique employing cryogenic equipment. Use of the method in air pollution analyses, airborne atmospheric research, geochemistry, and general laboratory analyses is discussed. A high pressure absorption cell that permits recording of well resolved infrared spectra was described by Sherman (1301). The cell provides a resolution of 1 cm-l 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 was used by Balint (61) to determine concentrations of mono-, di-, and trinuclear aromatic hydrocarbons in petroleum distillates boiling above 350 O F . After determination of average molecular weight of the sample, extinction toefficients a t 2000, 2300, and 2600 A were measured. Prior calibration using aromatics isolated by chromatography was necessary. An accuracy of *2Y0was claimed. Estep et al. (581) determined alkylnaphthalenes in neutral oils derived from low temperature coal tars by elution chromatography and subsequent VOL. 41, NO. 5, APRIL 1969
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analysis of the fractions by ultraviolet spectrometry. They claimed that individual classes of C~O-CM naphthalenes could be determined by the method, although none higher than CIS was found in the neutral oils examined. An ultraviolet method for determination of naphthalene, phenanthrene, and anthracene rings in petroleum products was suggested by Siryuk and Zimina (1821). Absorption bands a t 225 to 230, 255, and 375 mp are used for naphthalenes, phenanthrenenes, and anthracenes, respectively. Mononuclear aromatics do not interfere with the determination and their concentration can be calculated as the difference between total aromatics determined by infrared and amounts of condensed ring aromatics determined by the ultraviolet 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 petroleum fractions using a combination of ultraviolet and infrared spectrometry. Concentrations of mono- and dinuclear aromatics are determined by ultraviolet, and proportions of methyl and methylene groups and of tertiary and quaternary carbon atoms in the paraffin-naphthene portion of the oil are determined by infrared spectrometry. Luminescence and phosphorescence spectrometry show promise for analysis of aromatic types and certain nonhydrocarbons in petroleum fractions. Smith (13.31) demonstrated that most aromatic types of interest can be analyzed by fluorescence and phosphorescence methods and that the incremental excitation technique allows one to obtain spectra of each aromatic type which are completely independent of the other types present. Usefulness of fluorescence and phosphorescence techniques was emphasized by Parker (1011) and illustrated by references to published measurements. -4lthough microwave spectrometry is not yet a tool of general utility, its potential for hydrocarbon analysis was emphasized in a comprehensive review by Millen (931). High resolution nuclear magnetic resonance spectrometry was used by Stehling and Bartz (1411) for determination of the molecular structure of olefins. They presented tables correlating structure with chemical shift, spin-coupling constant, and the characteristic spectral pattern a t 60 Mc. Data presented were used to interpret structures of some oligomers of monoolefins and high polymers of diolefins. Xuclear magnetic resonance was successfully applied by Flanagan and Smith (401)to determination of olefinic impurities, particularly 1,l- and 1,Zdisubstituted ethylenes, in 1-olefins. 168 R
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Samples containing compounds having a wide range of molecular weights can be analyzed without preliminary separation. 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 particular gasoline; that regular gasolines have lower aromatic and higher paraffin content than high octane gasolines, and that gasoline quality depends upon relative concentrations of individual components as determined from characteristic 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 unsubstituted sites in aromatic rings, and in saturated groups using carbon-13 nuclear magnetic resonance spectra and total carbon content obtained by combustion. 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 structuralgroup analysis of mineral oils. VanMeurs (921) recorded nuclear magnetic resonance spectra of a number of 1,3and 1,4-di- and lJ3,5-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: nparaffins, 0.7 to 8.8 mol yo; 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 tetralins plus indans, 4.9 to 12.4. Martin (881) evaluated mass spectrometer methods for hydrocarbon-type analysis of gasolines by running pure samples of 15 typical C8--Cl2 alkanes with cyclopentane and with four alkylcyclohexanes. High resolution mass spectrometry was used by Gallegos et aZ. (441) for analysis of high boiling petroleum fractions without preliminary separation of aromatic and saturated hydrocarbon portions. The procedure described
determines 19 components, including seven saturated hydrocarbon paraffins and cycloparaffins, nine aromatic hydrocarbons containing from one to four rings, and three aromatic sulfur compound types. Johnson and Aczel (631) employed high resolution mass spectrometry a t 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 aZ. (1061) for analysis of aromatic hydrocarbons present in petroleum fractions of 400 to 850 O F boiling range. Gallegos (431) reported mass spectral data, including metastable transitions and appearance potentials, for a substantial number of polyphenyls. Howard (581)developed a computerized procedure for editing data from a mass spectrometer digitizer capable of greater certainty of mass number identification than previous methods. A computer procedure for deriving metastable ion transitions in the mass spectra of hydrocarbons was reported by Rhodes et al. (1151). Tunnicliff et aZ. (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 combinations of carbon, hydrogen, oxygen, and nitrogen. A second table, which covers the 1 to 400 mass range, contains selected combinations of the same four elements plus halogens, sulfur, phosphorus, silicon, boron, gallium, iron, tin, and aluminum. -4limited number of chemical methods for analysis of hydrocarbons appeared 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 titrazotized p-phenylenediamine in the form of its boron fluoride salt. Reaction with maleic anhydride in toluene at 100° was used by Ryasnyanskaya et al. (1201) to determine concentration of conjugated diene hydrocarbons 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 electrophilic reagents will react with the nucleophilic reagent morpholine to form a tertiary amine. They proposed a method based on this reaction for determination 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 apparatus for application to petroleum products. It was claimed that the method is often superior to bromination in accuracy and can be used to determine as little as 0.05 meq of unsaturation per g of sample. Brown (211) described another novel microhydrogenation method in which hydrogen was generated from sodium borohydride. The catalyst was prepared 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 calculate bromine consumed. Patek (1021) determined styrene by reaction with bromine in glacial acetic acid. Karpov and Bystrova (661) determined 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 generated bromine) was modified by Baudisch 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 Rluzychenko (901) described construction and operation of instrumentation for coulometric determination 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 Hammett relationship, it is possible to select a solvent that will provide the most efficient bromination of variously substituted compounds. A procedure for determination of xylene in air in the presence of benzene and toluene was proposed by Treeszczynski and Luczak (1461). The method is based on colorimetric determination 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 H. 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 a n 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 lubricants. A rapid but nonspecific procedure to determine barium in additives and lubricants was developed ( 1 4 4 , based on intensity of scattering of beta particles from a 10-MCi strontium-90 and yttrium-90 source. Fast neutron activation associated with gamma-ray spectrometry was used (8J) to determine silicon in mineral oils with a detection limit of 6 ppm if nuclear reactor neutrons 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 ( 2 6 4 established a technique for direct analysis of nickel in catalytic cracking feedstocks with a sensitivity of 30 ppm and a precision of ~t0.05 ppm. Vanadium was determined in gas oils with a nitrous oxide-acetylene flame and a high intensity hollow cathode lamp (65) with a detection limit of 0.05 ppm. Bowman and Willis ( 2 J ) studied the application of nitrous oxide-acetylene flame to chemical analysis, including determination of vanadium 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 solventhydrochloric acid mixtures and determined by atomic absorption using appropriate flames (25J). Determination of wear metals in lubricating oils by atomic absorption was reported by Means and Ratcliff ( 3 7 4 . Separation of volatile metal compounds by gas
chromatography and their specific determination by atomic absorption spectrometry with special application to lead alkyls in gasolines were reported (27J). Finally, a procedure was described by Slavin and Slavin (544 for fully automatic 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 determination of elements present in trace amounts in diesel engine lubricating oils was established (16J). 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) t o determine zinc, phosphorus, and sulfur in oil additive decomposition films on bearings. Louis (32J) used X-ray fluorescence 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 determine from 0.007 to 0.24% of zinc in greases. Sample is dissolved in a 1% solution of dithisone in chloroform from which an aliquot is deposited on a filter paper, dried, and examined. A simultaneous X-ray fluorescence determination of calcium (0.02 to 0.12%) and barium (0.04 to 0.32%) in lubricating 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 determined by diluting the sample with appropriate hydrocarbons, filtering, and examining the paper by X-ray fluorescence (9J). Emission Spectrometry. Nickel and vanadium were determined in coke and tar by emission spectrometry from the parts per million t o the low per cent range (36J)using gold as internal standard and a graphitesilica gel buffer mixture. Petho ( 4 3 4 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 enhancement of emission lines was used by Heemstra and Foster (17J) to determine vanadium in petroleum fractions by atomizing a chloroform solution of sample into the plasma arc. Lead was
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determined in gasolines from 0.005 to 1% by diluting samples with amyl alcohol and using a special double-disk rotating electrode ( S J ) . Determination of as little as 0.0001% of sodium in gas turbine distillates was achieved by immersing red-hot graphite electrodes in the sample and exciting them in an ac arc (S6J). 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 spectrometry (emission and ir) was developed by Jenkins and Humphreys (21J). Copper, barium, aluminum, silicon, iron, chromium, and lead were directly determined in used automobile crankcase oil by a rotating disk electrode, with a maximum mean relative error of 30% ( 3 8 4 . A spectrographic determination of nine metallic elements in ashed tractor oils was described (SSJ). 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 (667). 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 sensitivities ranging from 10-8 to lo”% (61J). 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 oxygenhydrogen flame, dissolving the residue in water, and measuring the metals by flame photometry or polarography (1J). LePera (S1J) studied determination 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 (6OJ). 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 ( 5 7 4 studied photometric determination of iron and copper and complexometric titrations of zinc and calcium in lubricating oils. Chromium and calcium were investigated in antistatic additives by extracting metal oxides from the ashed sample with hydrochloric acid and using a polarographic finish (6J). Curti and Riganti ( 7 4 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 photometry prior to dilution of the sample with sodium-free solvents ( 4 5 4 . A titrimetric method using Trilon B for milligram amounts of zinc and barium in oil additives was reported ( 6 1 4 . A procedure was studied to determine lead alkyls in liquid hydrocarbons by a specifically developed gas chromatograph (505). A review covering determination of additives in engine lubricating oils giving specific procedures was written by Nagypataki (41J). Sergeeva (49J)developed a flame photometric 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 sulfates ( I N ) . -4detailed procedure was reported by to estimate Campbell and Moss traces of lead in petroleum products by extraction followed by a dithizone colorimetric finish. The same authors (S9J) 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 +l%, 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% ( 4 W . A rapid spectrophotometric method for cobalt in products of the Oxo process with a range of 0.05 to 0.5% was reported (62J). A redox titrimetric procedure for lead in lubricating oils was studied by Samanta et al. (4YJ). Differential oscillopolarography was applied to a variety of products, including gasolines, to determine lead with a sensitivity of 0.01 pg/ml ( 4 2 4 . Oscillometric or conductimetric end point redox titration was used by
(u)
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 hematoxylin after the sample was ashed with benzenesulfonic acid ( 3 4 4 , Manganese was determined in crude oils by polarography previous treatment with 30% bromine solution in place of the ASTM hydrochloric acid extraction (4OJ). An EDTA titrimetric procedure was developed to determine zinc in lubricating 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 8quinolinol (1OJ). Flame spectrophotometric determination 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 ( 5 6 4 established a gas chromatographic technique using a flame ionization detector to determine lead alkyls and halide scavengers in gasolines. The same author (56J) extended the previous method for simultaneous analysis of halide scavengers and five different lead alkyl compounds. High temperature jet fuels were analyzed for iron in parts per million by a spectrophotometric technique using bathophenantroline ( 5 3 4 . The iron-bathophenantroline complex follows Beer’s law over the 1- to 2Oug 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 present in petroelum fractions. Osborn and Douslin (111K) compiled vapor pressure data on “key” members of the alkane-thiols, alkane sulfides, alkane disulfides, and cyclic sulfides with equations 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 concentrate, and removing thiols, phenols, sulfides, and benzothiophenes by extraction and chromatography, leaving thiaindans in the final solution. Identifications 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 detected by Thompson et al. (149K) in a 225 to 400 "C fraction, using concentration techniques followed by low voltage mass spectrometry; the procedures are recommended generally for high boiling petroleum fractions. Drushel and Sommers (40K) isolated and characterized sulfur compounds by oxidation of the sample with hydrogen peroxide in a benzene-acetic acid solution, chromatographic fractionation of sulfoxides or sulfones formed, and reduction to original sulfur compounds followed by analyses using mass, ultraviolet, and nmr spectrometry and thin layer chromatography. A stepwise oxidation-separation technique was a rapid and reliable procedure for sulfurtype analysis of high boiling petroleum fractions. -4 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 e t al. (78K). Sulfur content of gases was determined by Jaworski and Chromniak (65K) who passed the sample over heated Raney nickel, treating the nickel with hydrochloric acid to release hydrogen 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 R a n g (157K). Low concentrations 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 determined by burning in a stream of air, absorbing the oxidized products in hydrogen peroxide, and titrating with barium perchlorate using thoron as the indicator, as reported by Ridmaier and Dudek (159K). Y'itrogen and chloride interferences in the iodometric and niicrocoulometric determination of sulfur dioxide were studied by Bremanis et al. (ZSK). Terabe et al. (147K) compared sulfur dioxide concentration measurements made by an electroconductivity technique with measurements made using West-Gaeke bubblers, and found the electroconductivity method gave consistently higher results. Kuz'mina ef al. (81K) used discoloration of silica gel impregnated with lead acetate to determine sulfur in gases and other petroleum products; sample was passed over the impregnated gel contained i n a glass tube and amount of sulfur present was calculated from the length of the colored section of the column.
Ryashentseva and Afanas'eva (1266K) recommended two silica gel columns, one impregnated with lead acetate and the other with copper acetate, to determine 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 (125K) 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 continuously a t 2850 A, the difference corresponding 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 absorption a t 562 mh of the benzenesoluble complex formed by reaction of excess mercuric reagent and diphenylcarbazone. Carbonyl sulfide in gases from coal or oil was determined by Geyer et al. (51K) by measuring the infrared absorption a t 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 a t 2170 cm-l is equal in the sample and comparison cell. An infrared spectrometric analysis was developed by Zentgraf (163K) to measure 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 measure 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. Pop1 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 hydrogen sulfide, sulfur dioxide, carbonyl sulfide, and carbon disulfide on a silica gel column; they also described a column coiisisting of successive sections of polyethylene glycol and of dinonyl phthalate supported on Teflon for separating hydrogen sulfide and sulfur dioxide. Weisser et al. (158K) separated mixtures of thiols and sulfides on a column of polypropylene glycol sebacate on Chromosorb a t 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. Tarnura and Yamaki (146K) described the use of a 14MeV neutron generator with a flux of 1O1O neutrons per sec to bring about the 'Q(1~,p)l~Nreaction to determine oxygen and the a4S(n,p)a4P 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 phosphorus, which can both produce phosphorus-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. (136K) developed a vacuum X-ray technique for determining sulfur in heavy oils. A vacuum X-ray spectrometer, an ethylenediamine d-tartrate crystal, and a gas-flow proportional counter were used, and results agreed well with conventional chemical methods. Noguchi and Nomura (103K) discussed the accuracy and reliability of X-ray absorption of tritium bremsstrahlung 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 =50.03%. Visapaa (164K) developed a method for determining sulfur in fuel oils using X-ray fluorescence. With calibration samples made up by adding different amounts of tert-butyl disulfide to a fuel oil, lowest detectable sulfur concentratration was about 0.002% and standard deviation a t a sulfur concentration of 2.0% was +0.0097%. Sulfur in heavy oils was determined by Shibuya et al. ( l S 4 K ) who used an X-ray tube with a tungsten target a t 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 equipment, sample loading, C/H ratio, ash, and water in heavy oils can be satisfactorily eliminated. Several publications reported new applications and innovations in polarography. Holzapfel and Schoene (60K) described a method for determining total sulfur in gasoline which they recommended for fractions boiling up to 250 OC; 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 concentrations of hydrogen sulfide in gas VOL. 41,
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streams was described by Connelly and Wagner (S1K). 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 ( 9 K ) 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[blthiophene in naphthalene fractions. The method depends on reduction of benao/b]thiophene-1,l-dioxide formed by adding hydrogen peroxide to the sample in warmed acetic acid. Kashiki and Oshima (7SK) developed a method for the square-wave polarographic determination of free sulfur in liquefied petroleum gases. Samples were collected in specially fitted glass pressure bottles and the gases allowed to volatilize; the free sulfur was taken up in a methanol-methyl iodide-acetic acidsodium acetate solvent and determined polarographically. Kashihi and Ishida (72K) 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 methods were reported. Dokladalova (S6K) reported a rapid method of sulfur determination in higher boiling petroleum products; sample was oxidized in air a t 800 "C and sulfur dioxide determined spectrophotometrically using pararosaniline methanesulfonate. Bernardini et al. (15K) compared several combustion methods of sulfur determination, in which products were measured by titrimetry, 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 hydrogen peroxide, and determined the sul fate turbidimetrically with barium chloride a t a p H of 2.5 to 3.5. Engel (42K) used a modified thread wick capillary lamp for rapid determination of sulfur in petroleum distillates; halogens, nitrogen, and phosphorus interfered. -411improved Wickbold apparatus for determination of low concentrations of sulfur in liquid hydrocarbons was described by Liederman and Glass (84K), who used a pressurized burner feed and an extended high temperature combustion chamber that minimized formation of sulfur trioxide until the gases were 172 R
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quenched in hydrogen peroxide absorber solution. Barium sulfate was determined by nephelometry. Schoeffmann and Roth (119K) recommended a coulometric titration as the finish for combustion-flask determination of sulfur in fuel oils; combustions 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 determination of sulfur in heavy oils (AFNOR M 07-025) and recommended increasing the length of high temperature zone in the combustion chamber and the adaption 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 ignition 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. I n the second, the aqueous solution is acidified with nitric acid, and sulfates are precipitated with benzidine and titrated with sodium hydroxide. I n a rapid method for determination of sulfur in petroleum products, Popiel (116K) injected the sample in an oxygen stream into a hot quartz tube; nephelometry was used for sulfur concentrations of less than 30 ppm, titration for higher concentrations. According to a Shell Internationale Research patent ( I S I K ) , sulfur content of hydrocarbons was determined automatically by burning the sample stream continuously in excess oxygen in an oxyhydrogen flame, cooling the gases to about 20 "C to condense the water, and recording the conductivity 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 received the attention of several workers. Attari ( 6 K ) recommended combustion of sample and oxidation of sulfur to sulfur trioxide, reduction to hydrogen sulfide 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 (57K) extended the Raney nickel reduction technique for sulfur determination to include higher oxidation states, including sulfones and alkyl sulfates. Griepink et al. (66K)recommended a method for determining as little as 20 fig of sulfur in organic samples; sample is oxidized in a hot phosphoric acid-potassium dichromate solution, sulfur reduced to hydrogen sulfide by treatment with metallic tin and phosphoric acid, and hydro-
gen sulfide absorbed in cadmium sulfate solution and titrated with sodium hydroxide 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 quantitative 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 solution, 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 compounds in petroleum products. Sulfoxides were concentrated by cation exchange chromatography from petroleum fractions boiling from 250 t o 500 "C by Okuno et al. (107K);the amount of sulfoxides, titrated potentiometrically as weak bases in acetic anhydride with perchloric acid, was quantitatively related to intensity of the infrared absorption band a t 1040 cm-1 and to increase in sulfide content after reduction with lithium aluminum hydride. Bol' shakov et al. (18K) recommended determining thiols in petroleum fuels either by volumetric titration with ammoniacal copper sulfate or by potentiometric argentometric titration. A method to determine thiols in gasoline was reported by Oelsner and Huebner (105K), who treated the aqueous sodium plumbite extract of the gasoline sample with excess complexon 111, 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 solvents were ethanol and methanol-benzene, with alcoholic or aqueous solutions of mercury salts as titrants. Witzel and Hoerding (261K) used an indirect colorimetric 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) described 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 concentrations (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 petroleum, and from each other, by Orr ( I IOK), who used liquid-liquid chromatography 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 Lamathe (82K) using perchloric acid titration of the basic complexes formed when these compounds react with mercuric acetate; a correction for basic nitrogen present is obtained by a separate titration omitting the mercuric acetate treatment. A photocolorimetric procedure for measuring carbon disulfide content of an aromatic stream was reported b y Orlov et al. (109K); the reagent is a solution of copper acetate and diethylamine in toluene. Kashiki and Ishida (YlK) determined thiophene spectrophotometrically by the color formed with alpha-nitrosobeta-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 sce as a reference. Sulfonates and inorganic salts in treated oils were determined by VLmos and Simon (152K)by adsorption chromatography on silica gel; oily components were eluted with benzene and acetone, and the sulfonate fraction with ethanol. Separation and determination of naphthalenesulfonic acids in products of sulfonation were reported by Funasaka et al. (4°K). The acids were converted to methyl esters by treatment with diazomethane and analyzed by a gasliquid 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 methods t o 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 t o 1 ppm in a variety of feeds and products. One approach to determining nitrogen in the parts per million range, developed by Martin (01K ) , involves quantitatively converting the nitrogen to ammonia over a nickel-on-magnesium oxide catalyst; the ammonia is automatically titrated with coulometrically generated hydrogen ions. The method can be used on samples boiling up to 500 O C containing as little as 0.2 ppm of nitrogen. Rhodes et al. (124K) extended the range of the Dohrmann nitrogen 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 (16OK) determined nitrogen in the 100 to 200 ppm range by using a sample pretreatment 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 (14433 extracted gasoline samples with 92% sulfuric acid, then determined 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 (1SSK). The method combined sulfuric acid extraction with the Kjeldahl procedure; a colorimetric technique was used for samples containing less than 10 ppm of nitrogen. The method of extractive percolation using 980/, 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 sulfuric acid-pumice mixture to increase efficiency of extraction of nitrogen. After concentration, nitrogen is determined by the Kjeldahl method with the exception of converting the ammonia to indolphenol blue and making a spectrophotometric 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 nitrogen in organic materials by the oxidation of approximately 1 mg of sample over nickel oxide a t 900 O C in an atmosphere of helium. Reaction products (nitrogen, carbon dioxide, and ethylene) were analyzed by gas chromatography on an activated charcoal column with an accuracy of h 0.2%. The same authors (29K) studied the effect of metal oxide oxidant in various methods for simultaneous determination of carbon, hydrogen, and nitrogen in organic substances. Methods considered included classical oxidation, pyrolysis, and oxidation in an inert atmosphere. In the inert gas atmosphere, nickel oxide was the most active oxidant. Hofstader and Swarbrick (58K) used combustion, absorption, and gas chromatography to determine nitrogen in the 100 pprn range. A gas chromatographic method to analyze fluid streams for nitrogen in the 0 to 30 ppm range was developed by Steinle et al. (142K).
The method eliminates problems created by noninstantaneous sample introduction into the chromatographic column. A patent issued to Shell Internationale Research Maatschappij NV (ISOK) 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 detection of nitrogen with a katharometer. A simple micromethod to determine nitrogen in heterocyclic compounds without K-N linkage was developed by Morita and Kogure (95K). The procedure is a modification of the Kjeldah1 method and determines nitrogen in the 100 to 500 ppm range. Faulhaber and Liebetrau (44K) compared 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. (IOIK). The authors used a preliminary pyrolytic combustion before decomposition of the sample in the presence 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. (65K) adsorbed oxides on sodium chlorite supported on alumina, reduced them to ammonia with Devarda's alloy, and titrated the ammonia with hydrochloric acid. A patent issued to Shell Internationale Research Maatschappij NV (132K) describes an automatic method for determining nitrogen utilizing oxyhydrogen combustion. Kitrogen oxides produced are dissolved in a water-isopropanol-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 potentiometric titrations with perchloric acid in acetic anhydride and in acetonitrile solutions to give four classes of nitrogen compounds based primarily on pK,. Results are presented for titration of crude oils, straight-run fractions and cracked fractions. Abbott and Bowman ( 2 K ) found perchloric acid titration in glacial acetic acid a more satisfactory method for determining basicity of lubricants than the ASTM D 664 method. Snyder (IS9K)used adsorption chromatography on alumina to determine total nitrogen plus oxygen compounds in heavy petroleum distillates; the procedure is simple VOL. 41, NO. 5, APRIL 1969
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and requires only one-half man hour per sample. Gas chromatography was combined with a catalytic hydrogenationcoulometric titration detection system by Albert ( S K ) 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 (S9K). Separations were made by adsorption chromatography, chemical extraction, and gas chromatography; resulting fractions were characterized by mass, infrared, ultraviolet, fluorescence, and phosphorescence spectral techniques. A gas chromatographic method was developed by Veening and Dupre (15SK) for separation of basic nitrogen compounds and hydrocarbons. Molar response data were obtained for numerous basic compounds. Jewel1 et al. (67K) reviewed the literature on isolation, separation, and characterization techniques used to separate and identify the types of basic nitrogen compounds found in petroleum. Several methods were developed to analyze for nitrogen or nitrogen compounds found in petroleum products as additives or solvents. Lynes (89K) separated and identified alkanolamine additives in cutting oils and brake fluids by thin layer chromatography. Delves (SSK) also used thin layer chromatography to detect and identify aromatic amines and thiazines used in aviation lubricants as antioxidants. Traces of dimethylformamide, used to extract aromatic hydrocarbons from straightrun petroleum distillates, were determined in a method developed by Baibazarov and Popova ( 7 K ) , using infrared spectrometry. Analysis time is short (15 to 20 min), and sensitivity of the method is 0.005%. Dol'berg (S7K) used a modified Kjeldahl procedure to determine nitrogen in petroleum products that had been nitrated to improve their anticorrosive properties. Gilbert (52K) discussed advantages and disadvantages of a prototype infrared 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 Unterzaucher apparatus so that decomposition took place rapidly a t 750 "C. Hydrogen was used as the carrier gas, and the products were passed over carbon a t 1120 "C to produce carbon monoxide which was determined chromatographically by passage through successive col174 R
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umns of silica gel and Molecular Sieve 5-4. illeade 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 et al. ( 5 K ) separated oxygen dissolved in liquids 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 (1S9K) involves separation of these compounds by chromatography on alumina treated with 4y0 water. Rentrop et al. (12SK) compared analyses of oxygen in aged mineral oils by the Unterzaucher method with analyses by infrared spectrometry. A semimicro test for detection 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. Baranenko and Krivorotov ( 8 K ) studied the AVE-1 apparatus used for determining water in natural gas and suggested modifications necessary to make it accurate a t 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 hydrocarbons 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 phosphorous pentoxide coulometer system for measuring moisture content of propylene and butylene was patented by Abaev et al. ( 1 K ) . Khodako and L'vov (75K) determined water in hydrocarbon gases with Fischer reagent; extraction with methanol and electrometric titration were carried out a t room temperature in a special apparatus. An attachment 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 Xunari (27K) used microporous polymer beads coated with 5% SE-30 methyl silicone and 3% Carbowax 20M to separate water which was measured with an electron capture detector. Conventional thermal conductivity gas chromatographic apparatus
with columns of synthetic porous polymer beads such as Porapak, polyethylenimine, tetraethylenepentamine, and diphenylamine was used by Hollis and Hayes (59K). Swensen and Keyworth (145K) suggested an ethylvinylbenzene column and detection by thermal conductivity. For samples that may polymerize, Sanford and Ayers (128K) used polyethylene glycol or polypropylene glycol as the liquid phase; the portion of the chromatographic zone which contained water was passed to an electrolytic 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 d e veloped by Liderman and Ul'yanova (8SK) is based on reaction of water with calcium hydride to produce hydrogen which is measured by a thermal conductivity detector. For microdetermination of water in cooling oils, Zhukoborskii et al. (164K) suggested a direct electrometric titration with Fischer reagent in a sealed titrimeter. Muroi et al. (98K) determined water in grease by immersing the grease in dry insulating oil a t 120 to 140 OC and sweeping with nitrogen; moisture in the nitrogen is absorbed in a mixture of methanol and ethylene glycol and titrated with Fischer reagent. A previously published procedure for determining water using a calcium carbidegas chromatographic method was evaluated by Goldup and Westaway (53K), particularly with regard to its application to streams containing methanol. Moule and Thurston (97K) determined water in nonpolar organic liquids by an isotope dilution technique involving the exchange of water with D 2 0 ; 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 preconditioned cellulose pads. Water in the pad is measured electronically with a calibrated vacuum ohmeter. Pearson (112K) determined water in lubricating oils using the near-infrared absorbance a t 5450 to 5150 cm-'. The sample was distilled with ethyl acetate and absorbance of the distillate compared to a calibration graph. Bellonbono (1OK) described a method for determining water in hydrocarbon solvents which depends on measurement of ultraviolet absorbance of the reaction product of water and N-benzylideneaniline. Norel (IO4K) 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 (74K) by titration with a modified Fischer reagent. Automatic monitoring of water in liquid hydrocarbon streams was the subject of a review by Berliner (14K), who included methods based on changes in properties of the liquid, on hydrothermal equilibrium, and on devices using an auxiliary gas medium. Bizot (17K) found that automatic coulometric determinations were facilitated by generating 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 semipermeable 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 measurement of water in emulsions was described 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 Kundel suggested two different approaches to analysis of shale oil phenols. In the first method (85K), phenols were converted to hydrocarbons over a platinum or palladium catalyst and analyzed by gas chromatography. The second method (86K) involves esterification of phenols, gas chromatographic fractionation of esters obtained, and identification by ultraviolet and infrared spectrometry and catalytic hydrogenation. Kudryavtseva et al. (80K) analyzed cresols and xylenols by two-stage gasliquid chromatography, using dodecylphthalate and 2,4xylenylphosphate as liquid phases. In a study of the absorption 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 colorimetric determination of the phenol in fuel gas by Vlckova and Base (155K) depends on absorbing the phenol in potassium 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 differential 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 (2 OOK).
Determination of phenol-type inhibitors was the subject of several papers. Suatoni (143K) determined 2,6-di-tertbutyl-p-cresol in transformer oils which contained inherent phenols. The sample was freed of interfering compounds by chromatography on wet alumina; the cresol was then concentrated on dry alumina, eluted from the gel with polarographic solvent, and measured by anodic polarography. Voelker and Fischer (166K) 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 determining phenol-type antioxidants. Diamond (34K) separated and identified nC+& p-alkylphenols in chloroform solutions of lubricating oils using polyamide plates, an aqueous sodium hydroxidemethanol solvent system, and fast Blue Salt B as the locating agent. Dichter et al. (35K)analyzed transformer oils containing Topanol 0 and Antioxidant 733 on a Kieselgel-gypsum plate using nheptane as the eluent. Of several developing agents used, the best was a 2’% solution of tetranitromethane in chloroform. Two groups of workers considered analysis of the phenolic-type additives by infrared spectrometry. Kadushin and Korcek (69K) reported the wavelength 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 ( I M K ) , who measured infrared spectra by the compensation method using an oil from which phenols had been removed. Phenols were classified as, 2,fkdi-fert-butyl- and 2-methyl-6-tert-butylphenol types b y position of the OH band a t 3650 cm-’ and 3614 cm-’, respectively. Knight and Siege1 (76K) analyzed for the inhibitor 1,3,5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzy1)benzene by a combination of phase solubility analysis and gas chromatography. Two groups of Russian workers depended on steam distillation with added sulfuric acid to remove the phenols and cresols. Gatilova and Belova (49K) measured phenol content of the steam distillate using the ultraviolet absorbance a t 270 mp; Geller et ul. (60K) 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. Kahsnitz and hloehlmann (7OK) 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 tetramethylammonium hydroxide in isopropanol containing 0.9% water. Buell (25K) titrated acids and very weak acids with tetrabutylammonium hydroxide in a pyridinebenzene solvent to determine acidic substances 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 tetraphenylboride as the reference electrolyte and methanol and ASTM solvent, Popovych (118K) studied medium 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 titrations of alcohol-benzene solutions of lubricant additives. According t o Quilty ( I a l K ) , thermometric titrimetry overcomes some disadvantages of POtentiometric titration in determination of acids in petroleum products. A method by Alekperov and Efendieva (CK) for determining small amounts of naphthenic acids involves extraction of the sample in n-heptane with 1% solutions of pyridine and cupric sulfate; using the organic phase, the intensity of the 6.50-mp band of the pyridine-cupric naphthenate complex is measured. Goryaev et al. (54K) determined 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 petroleum was published by Nambu (99K). Tsiguro et al. (150K) determined active oxygen of peroxide compounds in depleted oils by dissolving the oil in propanol, adding an excess of arsenite ions in sodium bicarbonate, and titrating with iodine. A direct-current polarographic method by Niederstebruch and Hinsch (102K) is specific for hydroperoxides and will detect mol per. 1. The iodometric determination of butadiene polyperoxide reported by Braithwaite and Penketh (22K) involves treatment with hydrogen iodide generated in situ from lithium iodide and phosphoric acid and backtitratioii of excess iodine with sodium thiosulfate. For determination of carbon dioxide in nonaqueous systems, Snoek and Gouverneur (138K) developed a photoelectric titrator; titrations were made with sodium methoxide in 1: 4 methanol-pyridine solvent. Solomon and VOL. 41, NO. 5, APRIL 1969
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Lazeanu (14OK) evaluated methods for the analysis of carbon dioxide, carbon monoxide, and oxygen in gases from various sources. Phosphorus and Halogens. An 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 approximating standard ASTM methods. A method for determination of phosphorus in gasolines reported by Conde and Bonnin (SOK) combines previously published sample preparation and colorimetric procedures. Salvage and Dixon (1 27K) adapted a previously published method for use on a microgram scale; the sample is wet oxidized, the molybdovanadophosphate complex developed i n situ, and its concentration measured a t 430 mg in a microcell. A volumetric determination of phosphorus 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 a t 500 to 600 OC. After treatment with concentrated SUIfuric and nitric acids, ammonium nitrate and ammonium molybdate are added and the resulting deposit is dissolved in excess 0.1N sodium hydroxide which is backtitrated to determine phosphorus content. Pukhonto et al. (120K) published a method for simultaneous determination of butyl hydrogen phosphates, tributyl phosphate, and kerosine in aqueous solution. Chloride content of greases is determined by potentiometric titration with silver nitrate according to a method published by Fachausschuss Mineraloelund Brennstoffnormung (4SK) as a replacement for the color-indicator method DIN 51,800. Braier and Mott (BIK) described an equipment assembly that produces a greater and more uniform thermal neutron flux and permits activation analysis of chlorine to 0.05 ppm. Organic fluorides in hydrocarbons were determined down to 0.2 ppm by Miller and Keyworth ( 9 4 K ) ; the procedure involves treating with biphenylsodium to cleave the carbonfluorine bond, separating resulting inorganic fluoride by ion exchange chromatography, and titrating fluoride conductometrically 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
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Analytical and Process Instrumentation W. V. Cropper Precision Scientific Co., Chicago, 111. Emphasis on instrumentation in the petroleum industry shifted significantly during the two years covered by this review toward refinery application9 of automatic process analyzers. Little development in new laboratory instruments took place compared to prior years; a major share of published research was concerned with adaptation of such techniques as atomic absorption spectrometry, neutron activation analysis, 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 (1IL) that a 1967 API census showed 1903 analyzers in use a t 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 pressure. Although 92y0 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 quality control, the American Society for Testing and Materials presented a sixpaper Symposium on Automated Analyzers and Quality Control for the Petroleum 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 chromatographs have led to their expanded use, rapidly changing the functions and instrumentation requirements of the plant control laboratory. On-stream continuous measurement of viscosity permits control of a lubricating oil blending plant, but other inspection tests have not yet been automated because economic justification and need for continuous monitoring are lacking. On the other hand, the full economic potential of automatic in-line blending of gasoiines cannot be realized until continuous test methods are employed for verification of product quality involving custody transfer. The present use of automatic analyzers by a pipeline transporting 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. I t is possible 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 improved control that could be achieved. Elemental Analysis. An instrument for continuous measurement of hydrogen in liquid hydrocarbons utilizes neutron activation by a plutonium-beryllium source with boron trifluoride counter tubes, and has a reported accuracy of *0.15 wt yo. A new paramagnetic susceptibility oxygen analyzer was reported by Luft and Mohrmann (66L),and may be applied 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 (WSL) for laboratory use depends on matching absorption of weak y-radiation from FeS5 by positioning a polyethylene compensating wedge; position of the wedge is recorded as a measure of sulfur content of the sample. I n Hungary, the yradiation absorption principle was applied to a continuous analyzer for hydrogen, sulfur, and cobalt using Srso-Yso, Fe551and CdlOg, respectively, as radiation sources (6L). Shell Internationale Research also utilized a combustion technique to measure fixed nitrogen in petroleum fractions automatically; oxidation products of sulfur and chlorine are absorbed in hydrogen 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 (S9L) may be operated by nonprofessional workers and is sensitive to most metals in the parts per billion concentration range. An automatic in-stream analyzer for estimating carbon content of regenerated cracking catalyst from changes in r e flectance of a leveled surface of sample was employed to improve FCU performance, according to Potter el al. (69L). Specific Compound Determination. Reliable, continuous determination of water is an international goal, and remains elusive. A Russian instrument (71L) for automatic control of moisture in crude oil is based on a dual frequency method which allows tuningout the effect of sample density. Concentric electrodes were used by Tocanne (QZL)for capacitative estimate of water in crude oil or well fluids; his device can be lowered into boreholes.
Kochinashvili et al. (49L) devised a continuous indicator for water in crude oil, employing a variable capacitor incorporated in a frequency-balance discriminator nulled a t 1 MHz; a change in water content of sample flowing through the variable capacitor causes repositioning 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 (98L) in an automatic instrument for measuring water in water-in-oil emulsions with accuracy better than *O.l% a t 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 (9OL) and utilizes an inductively coupled bridge circuit; the instrument range can be electrically 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 measured by thermal conductivity change of the nitrogen carrier gas, with a sensitivity of 0.01% per recorder scale division. Anisimova et al. ( 4 L ) described an onstream automatic coulometer to determine water in ethylene, propylene, butene, and butadiene. Unfortunately, their solution to fouling of the coulometric cell by polymerized olefins is not made clear. The instrument is reported to be capable of determining hydrogen content of organic gases. Freeland (9OL) passed metered quantities of a fuel gas through a thermostated, isobaric water bath and measured the amount of water evaporated in saturating the sample stream. A novel approach was used by Heeps and Kopai (94L), who passed hydrocarbon 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 content within 10 to 20 min and the corresponding change in electrical resistance of the probe may provide an on-stream means of detecting moisture. Chromatographic separation of water from a vaporized hydrocarbon stream sample is followed by detection with a sensitive hygrometer in Davidson’s process analyzer (18L). Continuous determination of carbon dioxide in air or other gases containing oxygen rests on a modified Hersch cell (96L) having a platinum or palladium cathode, pure mercury anode, and po-
tassium hydroxide electrolyte. Current output a t constant gas flow is proportional to carbon dioxide concentration and oxygen does not interfere. Small amounts of carbon dioxide in a gas stream are determined by a photoelectric titrator (85L) that employs sodium metholate titrant in pyridine-monoethanolamine electrolyte. Dworak and Davis (15L) 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-generating 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) allows methanol, ethanol, and isopropanol to be measured quantitatively in gasoline. The analysis lines are 26,847, 26,830, and 26,510 MCi respectively, and the error is reported to be 1%. Prince et aZ. (70L) evaluated a photoionization detector for gas chromatography; its response is 1000 times greater than flame ionization detectors and has a minimum detectable concentration of 1 X lo-’*. The photoionization detector is especially useful for air pollution analyses. A small mass spectrometer was coupled by Henneburg et al. (95L) to a capillary-type gas chromatograph for determining lead alkyls and silicate esters dissolved in gasolines or oils. Compounds Estimation by Types. For automatic plant control of aromatic in catalytic reformate, Pavlova et aZ. (65L) used a uv spectrophotometer at 246 nm; after local calibration to allow for unknown impurities in each plant stream, mean relative error is f1.3%. KOSOV’S portable laboratory instrument (44L) measures the aromatic content of process samples by capacitance change of a cell in which a 50-ml sample serves as the dielectric. Absolute error is less than *2y0 over the range 10 to 40% aromatic content. An automatic multicolumn glc analyzer handles a stream typically containing 90% Hz plus C1-C11 paraffins and CaCIIaromatics (84L); hydrogen and mehtane are resolved, as are all paraffins through hexane, but the aromatics are analyzed as one group and the CI-CI, paraffins as another group. Storey (89L) measured the temperature 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 molecular sieve process for separating n-paraffins. Kuchta (47L) analyzed binary mixtures by comparing the vapor pressure 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 (17L) 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 coulometric 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 fourelectrode conductivity sensor (46L) 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 (95L) is an automatic two-stage titrimeter for in-stream applications which can be adapted for analyzing multicomponent mixtures where sharp changes in p H occur during titration. The salt content of crude oil was monitored automatically on a periodic basis potentiometrically (75L), employing silver and glass electrodes and dissolving the crude oil sample in a benzene-isopropanol solvent slightly acidified with nitric acid solution. Physical Property Measurement. API GRAVITYOR DENSITY. An electronic hydrometer was developed by Cropper and Kapff (1OL) to read out in API gravity a t 60 OF. I n the instrument, a strain gauge detects differential pressure between two levels in the test sample, while a thermocouple measures sample temperature and an operational amplifier transforms pressure and temperature functions into API units. A Czech density meter (I.%) uses a float immersed 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 CFR engine to give continuous octane 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 controller 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) patented a stabilized-flame apparatus in which the pressure in a :ombustion chamber is varied to keep the flame in a chosen position; the instrument is used VOL. 41, NO. 5, APRIL 1969
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for analysis of hydrocarbon mixtures CI-C22and results can be correlated with octane number. DISTILLATION.A distillation analyzer patented in Russia (RL) 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 (IOL) rapidly distilled high boiling materials in a horizontal column that can be operated in vacuum and with a controlled temperature gradient. POURPOINT. Automatic measurement of pour point was accomplished by Fischer (R9L) by measuring the pressure drop of a slow ascendant gas stream through a column of oil sample that is progressively cooled. When a predetermined 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 thermocouple in the sample denotes pour point. Shell Internationale Research patented two ways to determine pour point automatically (8UL). 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 periodically tilted while being cooled until the hanging rod is displaced. Conklin et al. (17L) described an electronic device for automatically determining pour point in which congealation of an oscillating sample deflects a light beam onto a detecting photocell while a thermocouple semicontinuously indicates the pour point temperature. CLOUD POINT.Automatic determination 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 precipitation blocks these currents and the upper thermistor becomes the cooler. A suitable bridge circuit detects change in differential temperature to signal the cloud point, while a separate thermocouple measures the cloud point temperature. Keitel (4RL) employed differential thermal analysis for cloud point determination. 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
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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 zk0.3 "C. FLASH POINT. A semiautomatic apparatus 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 (5UL). VISCOSITY.A remote-sensing Ostwald-type viscometer developed by Speaker (86L) uses electroluminescent panels, is explosionproof, and is able to operate a t pressures up to 2000 psig. Gleim and Khentov (SSL) worked out an Ostwald-type viscometer for weakly conducting liquids, employing electrical recording of flow time as well as detection 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 container and an electronic transducer; gelation-time and viscosity-time relations can also be obtained. Highly viscous samples can be measured by a rotational viscometer patented by Specht et al. (87L). A linear electronic analog computer invented by Martin (57L) produces viscosity index values from continuous viscometers operating a t 100 and 210 O F ; the L and D values for the viscosity index equation are derived from the electric signal outputs from the viscometers and the computer output signal can be used for process control purposes. OTHERPHYSICAL PROPERTIES. The on-line measurement of particle size between 100 and 500 p was accomplished by Nakajima et al. (61L). Their instrument is fast, allowing a cumulative size distribution curve to be obtained in less than a minute. Welch's nephelometer (98L) displays and records the number of particles in various sizes from 10 to 1000 p in a flowing liquid. In an instrument (67L) for monitoring cleanliness of jet fuels, the sample stream is passed through two fine filters in series, both of which are visible; any contamination 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 display of the path length to first appearance of coking. A recording unit for the four-ball extreme-pressure and wear test apparatus was devised by Frenkel and Grivtsov (31L ) as part of the automation of laboratory tests and analyses of lubricants.
Sampling. An automatically operated sampling device invented by Vana et al. (94L) has a removable sample container with quick-disconnect fittings 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 t o isolate the sample. The programmed sampling device of Tetlow et a1. (91L) provides automatic selection of a sample stream or either of two standard solutions. An electrical or gravitational force field supported by a nonturbulent inert liquid is the basis for a device patented by Whitlock and Bell (1UUL) for automatically controlling the sampling of solutions or suspensions. Cole et al. (16L) described a tape-controlled sequencing device to carry out routine laboratory operations in almost any experiment or procedure that can be reduced to a set of sequential operations. Light Hydrocarbon Analysis. I n a gasoline stabilization plant producing LPG as depropanizer overhead, the temperature set-point of the deethanizer reboiler is adjusted according. to glc measurement of ethane in the downstream debutanizer overhead, according to Case et al. (1SL). Ethane content of the LPG is maximized without exceeding vapor pressure specifications. 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 (6UL) described how Shell uses three gas chromatographs for process and quality control of a n-butane product stream a t the Pernis refinery. The computer-controlled gas chromatograph described by Mears (59L) is nearly devoid of programming and gating timers but reliably produces analytical data needed for sophisticated automatic control of distillation columns. Wherry and Miller (99L) reported on versatile and reliable chromatographs with high sampling rate that were designed for automatic process control. The control systems incorporate predictive and feedback characteristics to ensure meeting quality specifications precisely and to maximize profitability of distillation units. Transportation Testing. I n transporting LPG, process analyzers proved valuable. Specific gravity, vapor pressure, butane content, and nonvolatile residue were determined by a process gas chromatograph evaluated by Mid-America Pipeline Co. (66L),and similar applications were discussed 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 products flowing in pipelines is aided by Bond’s apparatus (QL)which utilizes static electricity by passing a sample stream through a strong electrostatic field. The downstream charge will remain constant if composition does not change, but a new product will carry a different charge. Ratway and Wood (7SL) used a flash point apparatus operating a t constant temperature to monitor 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 a t least one flash for positive location of the cut-point. A further refinement (74L) produced a t least two signals for increased reliability. Process Analyzer Application. Several publications are valuable because they reveal the extent to which on-stream analysis instrumentation is being used. Wall (97L) reviewed use and discussed efficiency of gas chromatographs, radiation-type instruments for analysis or density measurement, and some chemical analyzers. Mawson (58L) pointed out that critically important product quality cannot be assured by automatic control of temperature, pressure, and flow in conjunction only with laboratory analyses. Therefore, there is an increasing demand for on-line analysis and automatic control; this type of equipment is reviewed. Optimization of large processing systems and company-wide refining operations is first made possible by application of automatic quality analyzers and further aided by advanced mathematical techniques and automatic data reduction (41L). The status of automatic control of petroleum and chemical process systems was discussed by Rijnsdorp (76L),who cited specific examples. A comprehensive review of process instrumentation and control in Great Britain was given by Young (102L). Lorinc (54L) described process analyzers made in Hungary, including gas chromatographs, titrimeters, and mass spectrometers. Quality control of petroleum products by automatic analyzers was reported by Bassalert (7L),with examples of how inline analyzers are incorporated in automatic control loops. Sellers and Spencer (79L) not only gave a schematic refinery flow diagram indicating locations for 38 process analyzers, but briefly discussed availability and operation of many commonly used quality-measuring instruments. They stressed that process control based on product quality will gain in importance and be further aided by
mathematical correlation of conventional properties, plus finding new, more-significant quality parameters and methods of measuring them continuously. Shpunt et 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 Rlakkaveev 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 O . O l ~ o increases salt content about 0.5 ppb. The derivation and use of predictive data on distillation characteristics of distillation products for automatic control of the process were described by Lapa and Fainerman ( 6 f L ) . Success of in-line blending of gasolines results in large measure from application of continuous quality-measuring instrumentation, according to Page (63L). A full description of an automatically controlled blender was given by Laird et al. (@L), together with information on savings realized. Benefits of octane control were delineated 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 blending systems. Dyess (26L) outlined how continuous analyzers can profitably be used even in a 24,000 bbl per day refinery. T o capture the advantages of applying process analyzers to operating units requires surmounting problems, not all of which are purely technical. Page and Caldwell (S4L) 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 blosher (5%) 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 profitability a t 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 iiuinber of analyzers were installed in asinglerefinery by a subcontractor who wm responsible for pretesting, calibration, and commissioning of 84 instruments of 15 different types. The growing use of process analyzers, especially for controlling product quality, deserves the attention of present laboratory managers, as pointed out by Cropper ( d l L ) in a discussion of how qualitymeasuring instruments affect refinery laboratory operations and responsibilities.
Contamination Control F. D . Tuemmler Shell Development Co., Emeryville, Calif. Refinery Air. R7ith the broader subject of atmospheric pollution left to other reviews, it is intended here t o discuss those possible contaminants arising from operation of petroleum refineries. Thus, those materials arising 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 Association’s Petroleum Committee (18J1) published a general review covering possible airborne contaminants from refining operations describing control methods in use a t that time. Listed are particulate matter, sulfur oxides, hydrocarbons, nitrogen oxides, mercaptans, hydrogen sulfide, organic sulfides, phenolic compounds and naphthenic acids, nitrogen bases, aldehydes, and carbon monoxide. The U. S. Public Health Service (58-11) described tests used to measure the atmospheric concentration of some of these. HYDROGEN SULFIDE. Sanderson ( S O X ) described limitations of the lead acetate paper tape method for estimating hydrogen sulfide a t the odorthreshold concentration; Pare (27;ll) described an improved tape reagent which used mercuric chloride as the sensing material. Austin (3.11) reported 011 a coulometric titrator for determination of both hydrogen sulfide and sulfur dioxide. Nicols (25M) described a commercial sulfur dioxide meter based on photochemical measurement of decolorization 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 hydrogen sulfide. SULFUR DIOXIDE. Absorbed in aqueous sodium chloromercurate, sulfur dioxide forms a complex which decolorizes pararosaniline dye; the extent of decolorization is measured spectroVOL. 41, NO. 5, APRIL 1969
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179R
photometrically (West-Gaeke method). Dokladalova et al. (11M) described extensive studies on selectivity of the method, Scaringelli et al. (S2M) and Saltzman and Wartburg (29M) developed refinements, and Huhn et al. (17M) showed how the method could be used a t temperatures below 0 O F . Lyshkow (21M) described a continuous analyzer based on use of a unique rotary scrubber containing only the rosanaline dye in water. Bracewell and Hodgson ( 6 M ) demonstrated that hydrogen peroxide solution in the British standard method removed 99% of sulfur dioxide from low concentration gas streams. Hochheiser et al. ( 1 6 M ) compared 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 microvolumetric method for sulfur dioxide on reaction with an alcoholic potassium chlorate solution and titration of the sulfate formed using sodium alizerin-sulfonate as adsorption (on barium sulfate) indicator. Berezkin et al. (4-11) reported on a gas chromatographic method in which hydrogen sulfide and carbonyl sulfide did not interfere. Adams et al. ( I M , 2 M ) detailed a microcoulometric cell which, when combined with selective 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 alkylated hydrocarbon air pollutants were shown by Sawicki et al. ( S 1 M ) . Stephens and Burleson (S6M) were able to analyze in concentrations below 1 ppb some 25 hydrocarbons having volatilities below n-hexane; Jueng and Helwig ( 2 O X ) described a rapid method for air containing only C1-C4 hydrocarbons. Clemons and Altshuller ( 1 O N ) showed the usefulness of fluorinated polymeric films for storage of air samples containing hydrocarbons. LEADCOMPOUNDS. For areas where lead compounds are handled, Linch, et al. (22111) described a useful selfpowered constant rate sampler containing solid iodine absorbing better than 98y0 lead alkyls; Browelt and Moss ( 6 X ) described and automatic analyzer using iodine monochloride as absorbent. Skalicka and Cej ka ( S 5 X ) compared three different methods and commented on their relative usefulness. Cantuti and Cartoni (8M) described a gas chromatographic method applicable a t concentrations up to 100 ppb; Thilliez ( S 7 N ) reported on an infrared procedure applicable down to 1ppb. 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 (38M) a continuous gas chromatographic procedure. Grishin et al. (14M) were able to measure quantities of 0.002 g of oil per 1 of nitrogen using an infrared spectrophotometric method. Evans (18M) sampled and analyzed gas stream cleanup devices a t 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 ( I S M ) and Hickey ( 1 6 M ) published reviews of pollution control by evaluating quality of refinery effiuent; in both papers, emphasis was placed on selection of suitable and effective analytical methods, including new methods suitable for research and monitoring. Burmeister ( 7 M ) described results of interlaboratory cooperative tests using a petroleum ether extraction method; only heavier oils were determined because a nonvolatile residue was measured after evaporation of the petroleum ether. A gas chromatographic method applicable to gasoline contamination was developed by Jeltes and Veldink ( 1 9 X ) ; as little as 0.1 mg of gasoline per 1 of water was measured. Osipov and Belova (26M) employed a broad band ultraviolet method covering 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. (2JM) reported on a differential uv differential absorption method which is nonselective and rapid for measurement of phenols alone. Foods. Methods have been promulgated 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 convenient but required correlation with the DMSO method. Silverberg et al. ( S 4 M ) 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 ( S S M ) also described a thinlayer chromatographic procedure for detection of mineral oils in fats.
Miscellaneous Flue Gases. Knowledge of composition of flue or stack gas is neoessary 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 (11N) 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 (ON) and domestic flues ( I O N ) ; Wickert (15") discussed effects of the solid content of stack gases on determination of sulfur trioxide. Low (6N) described an interesting infrared interference spectrometer mounted on a truck capable of measuring the sulfur dioxide emissions from distances of one-half mile and a t night. Products. Murphy ( 6 N ) described procedures for testing petroleum coke, a subject not frequently reported. Norbury (7") described methods for measuring lubricating oil content of fluorinated refrigerating agents. Herrmann and Cleverley ( J N ) described a method for determining paraffin oil content of fungistatic preparations. Use of odor panels for detection of unwanted components in various petroleum products was reported in the Oil and Gas Journal (8N). Processes. Ape1 and Witzel ( 1 N ) described methods for determination of corrosion in petroleum processing plants. Frazier and Huddle ( 2 N ) described use of the Erdco C F R fuelcoker for measuring a fouling index or an antifouling effectiveness factor of a chemical antifoulant t o 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 searching 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 classifications 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 WorZd Petrol Cong Proc, Mexico City 1967, (8) PD-15. (2A) Bassalert, JL, Mes, Regul, Automat, 31 (ll), 79 (1966). (3A) Boreham, GR, Armstrong, WE, JInst GasEng, 5,228 (1965). (4A) Chem Eng News, 44,43 (15-Mar-66). (5A) Caigneau, M, Chim Ind (Paris),'93, 223 (1965). (6A) Fritz, W, 16th Deut Mineraloel Wiss Kohlchem Annu Meet, Cologne 1964.
(7A) Gambrill, CM, ANAL CHEM, 35, l l l R (1963). (8A) Zbid., 37,143R (1965). (9A) Gray, PR, 7th World Petrol Cong, Mexico City 1967, (4), PD-15. (10A) Gunn, EL, Amer SOCTest Mater, Spec Tech Publ, 349 (1963). (11A) Harding, JH, Morgan, WA, Proc Amer Petro Znst, Sect ZZZ, 3, 616 (1962). (12A) Znst Petrol Rev, 21,302 (1967). (13A) Jenkins, GJ, Behling, RD, Heilmann, G, Erdoel Kohle, 19,890 (1966). (14A) Kajikawa, M, Okamoto, N, Sekiyu Gakkai Shi, 10,358 (1967). (15A) Karau, WAA, Patterson, TB, Balint, FJ, ANALCHEM,37,27A (1965). (16A) Keil, G, Hung Chem Ass Conf, Budapest 1965, APZ 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) Killir, FCA, ‘Amos, R, J Znst I
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(1B) Abramov, VN, Kovalev, AG, Nefteprom Delok Naueh-Tech Sb, 5,20 (1967); CA, 67,118782t (1967).
(2B) Augsten, K, Frez%erg Forsch A , 380, 9 (1966). (aBj-Baker, EW, ACS, Diu Petrol Chem, Preprint, 1966 (Mar) B145. (4B) Bene, GJ, Louis, M, Assoc Rech Tech Forage Prod, Comp Rend 2nd Colloq, Rueil-Malmaison, 91, 1965. (5B) Bergmann, JG, Ehrhardt, CH, Granatelli, and Janik, JL, ANAL CHEM, 39,1258 (1967). (6B) Biechler, G, Jordan, DE, US Pat 3,345,126 3-Oct-67. (7B) Biktasheva, AD, Nefteprom Deb, Nauch-Tech Sb, 5, 29 (1967); CA, 67, 118781s (1967). (8B) Boulet. R. Guichard-Loudet. N. Henrion, P, ei al., Rev Inst Fr Petrol Ann Combust L i uides, 23,315 (1968). (9B) Brunnock, SV, ANAL CHEM, 38, 1648 (1966). (10B) Coleman, HJ, Thompson, CJ, Hopkins, RL, and Rall, HT, J Chromalo r, 25,34 (1966). (11B) olombo, U, Riv Combust, 18, 462 (1964). (12B) Friedel, RA, Retcofsky, HL, Chem Znd (London), 11,455 (12-Mar-66). (13B) Gates, GL, Caraway, WH, U S Bur Mines, R e p Znves, 6602, 10 pp (1965). (14B) Gaylor, VF, Jones, CN, ACS, Diu Petrol Chem, Preprint, August 9, 1967. (15B) Guichard-Loudet, N, Follain, G, Rev Znst Fr Petrol Ann Combust Liquides, 21,1271 (1966). (16B) Henrion, P, Picard, P, Zbid, 21, 586 (1966). (17B) Ishii, T, Musha, S. Bunseki Kagaku, 14,886 (1965); A A , 14,4799 (1967). (18B) Jordan, DE, Carel, AB, Oil Gas J , 65,104 (29-Aug-67). (19B) Linderman, IS, Tsesarskaya, MA, Khim Tekhol Topl Masel, 12, (5), 59 (1967). (20B) MacMillan, E, Samuel, BW, ANAL CHEM,38,250 (1966). (21B) McAuliffe, CD, US Pat 3,303,002, 7-Feb-67. (22B) Mikhal’kov, PV, Bor’ba Otlozh Para$na, Vses Konf, Oktyabrsk, USSR, 1964,73; CA, 65,6962h (1966). (23B) Moore, EJ, Milner, 01, Glass, JR, Mimochm J , 10,148 (1966). (24B) Neumann, HJ, Rahimian, I, and Taghizadeh, D, Brennst-Chem, 48, 66~
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( 2 7 ~Pouescu, i (28B.) Prikhod’ko, NK, In, Vyssh Ucheb (28B-j Zaved, Neft Gas, 9, 81 (1966); CA, 65, 5271 r ( 1966). l RAA’l 5271e( (29B) Rev Znst F T Petrol Ann Combust (29B. Liquides, 22,411 (1967). (30B) Seevers, D( DO, US Pat 3,287,088, 22-Nov-66. (31B) Skorko-Trybula, Z, Nafta (Katowice), 22, 141 (1966). (32B) Smith, HM, Hale, JH, U S Bur Mines, Rep Znves, 6846,22 pp (1966). (33B) Steinke, I, Z Anal Chem 233, 265 (1968). (34B) Triems, K, Heinee, G, Chem Tech (Berlin).20.40 (1968). (35B) Vajta., L, Palma;, GY, Szebenyi, I, Toth, G, Period Polytech, 10, 269 (1966); CA, 67,237410 (1967). ( 3 6 ~Vial, j ~ j ANAL ; CHEM, 38, io80 (1966). (37B) Veal, DJ, US Pat 3,334,233, 1AUE-67. (38Br Wydra, J, Nafta (Katowice), 22, 325 (1966).
Fuels (IC) Alekseeva, MP, Ivanov, KI, Metody Otsenki Expluat Svoistva Reaktiv Topl Mater, Sb Statei, 46 (1966); CA, 65, 16743b (1966). (2C) Alvey, FS, British Patent 1,030,506, 25-May-66. (3C) Arnov, DM, Robert, YA, et al., Kham Tekhnol Topl Masel, 12, (7), 47 (1967). (4C) Babitz, M, Rocker, A, Israel J Technol, 4, 271 (1966); A A , 15, 287 (1968). (5C) Bentur, S, Babitz, M, Rocker, A, Zbid, 3, 220 (1965); CA, 66, 478922 (1967). ~ .. - ,. . (6C) Blanchard, GC, Goucher, CR, CFSTZ AD 458,430,131 pp (1965). (7C) Boldt, K, S A E (SOCAuto Eng) Spec Publ. SP-285.29 (1966). (8C) Borisov, VD,‘ Gogitidze, LD, Logvinyuk, VD, et al., Metody Otsenki Expluat Sovistva Reaktiv Topl Mater, Sb Statei, 96 (1966); CA, 65, 16041c (1966). (9C) Boyer, M., Znd Petrol Petrochim, 34,41 (1966); APZ, 13,6563 (1966). (IOC) Burgoyne, JH, Roberts, AF, Alexander, JL, JZnst Petrol, 53,338 (1967). (11’2) Churshukov, ES, Gureev, AA, et al., Khim Tekhnol Topl Masel, 11, (12), 54 (1966). (12C) Clark, G, Forster, EJ, Hornbeck, DD, Erdoel Kohle, 20,791 (1967). (13C) Zbid, 20,857 (1967). (14C) Coley, T, Rutishauser, LF, Ashton, HM, JZnst Petrol, 52,173 (1966). (15C) Coord Res Coun Rep, 392, 81 pp (1966\. (16C) Zbid, 394,104 pp (1966). (17C) Zbid, 400,135 pp (1967). (18C) Dasgupta, S, Dey, DK, CMERZ Rep, AS, 19 pp (1966); A A , 15, 298 (1968). (19C) Dyatlov, IN, Tr Kaznsk Auhts Inst, 76, 106 (1963); CA, 62, 8903f (1965). (20C) Engel, D, Ticac, G, Nafta (Zagreb), 18,588 (1967). (21C) Fagley, WS Jr, Nunez, RR, S A E (SOCAuto Eng) Meeting Pap, 670483 (1967). (22C) Gutman, IR, Nil’man, VRI, Vladimirskaya, AY, Neftepererab R’eftekhim Nauch-Tekh Sb 9, 43 (1967); CA, 68,61300~(1968). (23C) Haezard, GF, J Znst Petrol, 53, 267 (1967). (24C) Hermanie, PHJ, van der Waarden, M, J Colloid Interface Sci, 21, 513 (1966). (25C) Hill, EC, Davies, I, Pritchard, JAV, Byron, D, J Inst Petrol, 53, 275 (1967). (26C) Hooper, JHD, et al., Zbid, 53, 169 (1967). (27C) Hydrocarbon Process Petrol Refiner, 46 (4)29 (1967). (28C) Ingamells, JC, Gerber, NH, et at?., S A E (SOCAuto Eng) Meeting Pap, 660544,9 pp (1966). (29C) Johnston, AA, Dimitroff, E, Ibid, 660783,7 pp (1967). (30C) JZnst Petrol, 53,294 (1967). (31C) Kouzel, B, Hydrocarbon Process Petrol Refiner, 46 (2) 161 (1967). (3%) Kurchatkina, TV, Skripnik, EI, Lyndina, VN, Zzv Vyssh Ucheb Zaved, Neft Gaz, 10, 65 (1967); CA, 67 75067~ (1967). (33C) Kuster, EC, Comery, D, Aust Commonwealth, Dep Supply, Def Stand Lab, Tech Note, 103,s pp (1967). (34C) Lamouche, R, Rev Petrol (1083), 51 (1966); JZP, 52, 1018 (1966). (35C) Lohrmann, F, Andresen, U, KoepJ. Ruediger, K, German (E) atent 51,722, 5-Dec-66; C A , 66, 97277~[1967). I - - - - , -
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(505) Shell Internationale Research Maatschappij NV, Neth Appl 6,511,077 27-Feb 27-67; CA, 68, 31816d (1968). (51J) Shestakova, NM, To orova, ZP, Neftepererabotka i Neftekftm, 5, 16 (1966); CA, 65,6967~(1966). (525) Singliar, M, Reckova, G, Chem Prum, 16, 535 (1966); A A , 14, 7513 (1967). \ - - _ ,. .
(535) Short, FR, Eyster, CH, Scribner, WG, ANALCHEM,39, 251 (1967). (545) Slavin, S, Slavin, W, At Absorp NewsLet, 5,106 (1966). (555) Soulages, NL, ANAL CHEM 39, 1340 (1967). (565) Zbid., 38,28 (1966). (575) Studeny, 5, Ropa Uhlie, 8, 244 (1966); CA, 66,20774~(1967). (585) Ibid., 9, 205 (1967); CA, 67, 1188099 (1967). (595) Thomas, RD, ANAL CHEM, 38, 785 (1966). (60J) Tlyustangelova, MV, Tr Vses Nauch-Issled Inst Pererabot Nefti, NO. 10, 137 (1967); CA, 68, 612509 (1968). (61J) Trawinski, 5, Wiod Noft, 11, 56 (1965); CA, 67,34603s (1967). (6251 Trawinski., J. ,Nafta . 22,. " (Katowice), . ' 328 (1966). (635) Vajta, L, hloser, M, Period Polytech, 9,275 (1965); CA, 66,20771t (1967). (645) Wilson, HW, ANALCHEM,38, 920 (1966). (655) Zimina, KI, Vorob'ev, GG, Orlova, MI, Spektral Anal Geol Geokhim, Mater Sib Sovesch Spektvosk, 2nd (Irkutsk) USSR 1963; CA, 68,51548~(1968). (665) Zul'fugaryl, DI, Karabekova, RK, Ermakova, TI, Uch Zep, Azerb Gos Univ, Ser Khim Nauk, 4, 41 (1966); CA, 68,41869n (1968). Nonmetal Elements and Compounds (1K) Abaev, GN, Taniyants, KD, Kotel, Nhl, et at., USSR Patent 186,739, 3Oct-66; CA, 67,29134r (1967). (2K) Abbott, AD, Bowman, LO, Sekiyu Gakki Shi, 9, 184 (1966). (3K) Albert, DK, ANALCHEM, . 39.. 1113 ' (1967). (4K) Alekperov, RA, Efendieva, NI, Dokl Akad h'auk Azerb SSR 22, 60 (1966); APZ, 13,7328 (1966). (5K) Alishoev, VR, Berezkin, VG, Pakhomov, VP, Zavod Lab, 32, 1204 (1966); CA, 66-61523g (1967). (6K) Attari, A, ACS Diu Fuel Chem, Preprint, 1966 (Sept) 34. (7K) Baibazarov, AA, Popova, LN, Khim Techbol Tip1 Masel, 13, 54 (1968). (8K) Baranenko, SE, Krivorotov, AA, Gaz Delo, Nauch-Tekh, Sb, 1967, 27; CA, 68,51633~ (1968). (9K) Bel, R, Maurice, 5, Chim Ind (Milan),49, 768 (1967); API 14, 14101 ( 1967). (10K) Bellobono, IR, ANALCHEM, 39, 1298 (1967). (11K) Bennewitz, R, Fette, Seifen, Anstrichm, 68,760 (1966). (12K) Berezkina, LG, Mel'nikova, SI', Elefterova, NA, Khim Prom, 42, 619 (1966). (13K) Berges, LS, Perez, TF, A n Real SOCEspan Fiz Quim (Madrid), Ser B, 62,807 (1966). (14K) Berliner, MA, Khim Tekhnol Topl Masel, 13, (11, 9! (1968). (l5K) Bernardini, R, Spaggiari, MA, Turtura, L, Riv Combust, 21, 63 (1967). (16K) Bitten, 5, ANAL CHEM,40, 960 (1968). (17K) Bizot, 5, Bull Soc Chim Fr, 1, 151, 1967. (18K) Bol'shakov, GF, Stekhun, AI, Chalykh, ND, Pokhitun, LE, il'eftepererab Seftekhim Nauch-Tekh Sb, 1967, ( 5 ) ,2; CA, 67,101623~ (1967). I
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(58K) Hofstader, RA, Swarbrick, RE, ACS, Diu Petrol Chem,. Preprint, . . 1965. (Apr) C31. (59K) Hollis, OL, Hayes, WV, J Gas Chromatogr,4,235 (1966). (60K) Holzapfel, H, Schoene, K, Talanta, 15,391 (1968). (61K) Hooks, RM, McDonnell, VG, NLGZ Spokesman, 31,245 (1967). (62K) Houzim, V, Zeman, P, Chem Prum, 16,167 (1966); A A , 14,4084 (1967). (63K) Hydrocarbon Process Petrol ReJiner, 46(5) 39 (1967). (64K) Jaworski, & Bogaczek, I, J, Dziekan, M, Chem Anal (Warsaw), 10, 1291 (1965). (65K) Jaworski, M, Chromniak, E, Ibid., 1303 (1965). (66K) Jester, WA, Klaus EE, ACS, Diu Petrol Chem, Preprint, 1967 (Apr) B129.
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(1
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