contents, and they determined that the ratio of saturates to aromatics in each fraction differed little from that of the ori inal residue (63B). !fatter-Zade et al. carried out spectropolarometric studies on Bibieibat (83B)and Ramany (84B)crude oils, and noted that optical activity, after passing through a minimum in the kerosene fractions, increased with increasing boiling point, and was higher for the saturate fractions than for the aromatics. Jackson et al. compared simulated T B P curves from GC using a 10-m capillary column with conventional T B P curves, and found the agreement to be excellent. Differences were easily explicable (49B).Levy et al. describe the modification of the injection port of a GC which facilitates the examination of tars and other viscous and/or high boiling samples (65B). API Research Project 60 has continued to be a source of new methods for analyzing the heavy ends (370-535 OC) of crude oil, and of data concerning the composition of this fraction in a world-wide series of representative crudes (22B, 23B, 41B, 42B,93B, 94B). Routine Characterizations.As in previous review periods, there has been a great number of reports dealing with the routine characterization of crude oils by conventional methods. One in particular stands out for its general interest, compiling data from 94 representative crudes from around the world (35B).
Fuels, Gaseous and Liquid J. D. Beardsley The Standard Oil Co. (Ohio) Cleveland, Ohio
Natural, Refinery, and Manufactured Gases. Cardwell (19C) lists the compositions of natural gases of the United States, Canada, Indonesia, and the United Kingdom for 1972 with emphasis on helium. Routine analysis and related source data for 278 United States natural gas samples from wells and pipelines are tabulated for 1973 by Moore (76C). Analyses were made by mass spectrometer and a special helium analyzer. He (77C)also tabulates for 1974 the analyses and related source data for 352 natural gas samples from gas and oil wells and pipelines in 18 states and five foreign countries. A procedure and apparatus for the preparation of natural gas samples for C isotope determination by mass spectrometry are described by Nesmelova and Sokolov (86C).Stufkens and Bogaard (I22C) analyze natural gas by means of gas chromatography, using one, sin le, temperature-programmed column and two detectors (T8D and FID) in series. From the composition, the calorific value can be calculated without any systematic error. A comparison of calculated and measured calorific values of natural gases was made for six Algerian and North Sea natural gas samples by White, Cross, et al. (129C). The calculated values were at least as precise as those obtained by calorimetry and the average difference between the two methods was 2.87 BTU/ft3. A discussion by Lambert and Juren (63C)covers the compositions of typical U.K. natural gases, properties, and impurities; and natural gas processing including removal of hydrocarbon liquids, water, hydrogen sulfide, carbon dioxide, and nitrogen and the recovery of ethane and heavier hydrocarbons. Jones (50‘2) defines gas quality in terms of acceptable standards for internal corrosion control; i.e., H2S, CO2,Oz; and water vapor contents, temperature, and free liquid content. Methods of analysis for the corrosive agents are described. Turowska and Pruszynska (124C) determine down to approximately 1 ppm of C02 by gas chromatography. The separated constituents are passed through a column acked with firebrick covered with a nickel catalyst. At 350 O 8 the CO2 is reduced to methane. The content of COZ is calculated by comparison of peak areas for the sample and for standard mixtures of methane with COS. The theory and technique of colorimetric analysis of fuel gases for impurities such as sulfur compounds, nitrogen oxides, acetylene, phenols, hydrogen cyanide, and others, in total 20 different determinations, is reviewed by Vlckova and Kavan (127C). Afanas’ev, Denisova,
Lomovtseva, et al. ( I C ) have determined microimpurities of hydrogen sulfide in a natural gas flow by gas chromatography. The chromatographic determination of water contents of approximately 1 ppm in natural gas has been achieved by Yusfin, Okhotnikov, Rotin, et al. (134C). Water contents of 40 to 200 ppm in natural gas are determined by Davies (26C) using a modified Karl Fischer titration apparatus. The method was tested on standard water mixtures and agreed well with gravimetric, P205, and dew point procedures. The method is free from interference by light hydrocarbons and methanol. Gokhberg and Ovchinnikova (39C)make a direct chromatographic determination of moisture in natural gas mixtures. Trace amounts of tetrahydrothiophen odorant in natural gas are determined by gas chromatography by Demczak, Gawlik, and Kegel (27C). Gas chromatography is used by Kavan (55C) to determine the odorants dimethyl sulfide and tetrahydrothiophene in natural gas. The impurities of these odorants plus 14 other compounds have been studied. Knight and Verma (56C) have developed a simple low cost field test for mercaptan odorants in natural gas. A metered amount of gas is bubbled through a disposable reagent tube containing N-ethylmaleimide and the red-pink color intensity of the product is compared with a standard color chart calibrated in parts per million of mercaptan. A procedure has been developed by Skorik, Zalkin, and Konyukhov (116C) for a gas chromatographic analysis of a mixture of flue gases from high sulfur natural gas using a single apparatus. Koroleva, Moroz, Khazanov, and Baranovskii (60C) use two gas chromatographs simultaneously to analyze the combustion products from natural gas. Pro erties of liquefied natural gas are calculated by Nanjo, H a r a g , Ono, and Saito (83C).Lyle, Burghard, and Lawler (69C) have developed an instrument to measure the corrosivity of liquefied petroleum gas b means of the increase in electrical resistance of thin (500-& copper film deposited on a glass slide as tarnish products forms. The results are quantitative in contrast to the ASTM D 1838 test which gives only qualitative results. The composition of gas from the catalytic cracking of vacuum gas oil has been studied, using capillary as chromatography, by Alymova, Lulova, and Kuz’mina ( 4 6 ) .The method is suitable for all refinery gases. Optyczne (89C)has patented an a paratus for the automatic monitoring of the presence of metfane in air. Aviation Fuels. Shelton (112C)tabulates analytical data for 104 samples of JP-4 and JP-5 military fuels and Jet A, A-1, and B commercial fuels from 15 companies. Correlation equations for calculating hydrogen content and heat of combustion on jet fuels have been evaluated by Angello (9C). Petrovic, Bogojevic, and Vitorovic (94C) contend that determining the temperature a t which 90% of the jet fuels are distilled is a better method for evaluating as compared to quality control based on determining the temperature a t the end of the distillation. The resins present in jet fuel from different USSR crudes were separated by adsorption on alumina and desorbed with methanol and acetic acid by Englin, Alekseeva, Sashevskii, et al. (28C). The varying content and composition of these resins have an important influence on the anti-wear properties and thermal stability of the fuels. Imhof and Worm (47C)have patented a device and method for determining the alcohol content of jet fuel. The alcohol is determined by a color reaction with an 8-hydroxyquinoline ester of vanadic acid (H3PO4). Gel permeation chromatography has been used by Hillman, Paul, and Cobbold (45C)to determine dilinoleic acid and acid phosphate ester in aviation fuels. Taylor (123C) has investigated the effect of trace impurity sulfur compounds on the rate of deposit formation in deoxygenated jet fuel. The results confirm that the ability of rigorous deoxygenation per se to suppress the deposit formation process depends on the type and level of the trace impurity sulfur compounds which are present in the fuel. The Coordinating Research Council (24C) reports that the use of the Alcor Inc. Mark 8A light reflectance instrument for measuring the deposits on JFTOT tubes shows promise that the Jet Fuel Thermal Oxidation Test will replace the ASTM-CRC Fuel Coker as the standard test for determining the oxidative stability of jet fuel. ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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Vdovin (125C) uses an acoustical method for determining microscopic particles in jet fuels. The acoustical method is based on the reduction of cavitation intensity by the presence of the particles. A bibliography on contamination of aircraft fuel tanks by microorganisms has been prepared by the Coordinating Research Council (23C). Motor Fuels. The octane numbers and lead contents of motor fuels used in major European countries are tabulated by Erdoel Kohle, Erdgas, Petrochem. Brennst.-Chem. (29C) for 1973 and 1974. Shelton reports the results of a cooperative study by the U.S.Bureau of Mines and the American Petroleum Institute on motor gasolines for Winter 1973-1974 (109C) and Summer 1974 (111C). Data are tabulated by geographical districts on Research and Motor octane numbers, antiknock index (Road Octane), vapor pressure, distillation gum, lead, phosphorus, and sulfur contents, API gravity, and ASTM corrosion number. Mayer, Camin, and Raymond (73C) have made a review of the development of instrumental methods for the analysis of gasoline components for 1947-1972. A study conducted in 1971-1972 by the Gasoline Division of the J a an Petroleum Institute on gasoline analyses is reported by 8ekiyu Gakkai Shi (103C). The tests used were for the depentanization of gasoline and na hthas (ASTM D 2001), c2-C~hydrocarbon distillation ( J I J K 2557), and CZ-C~hydrocarbons by gas chromatography (ASTM D 2427) and by fluorescent indicator adsorption (JIS K 2536). Jennings, Yabumoto, and Wohleb (49C) have developed a procedure for the routine manufacture and coatin of flint glass, open-tubular gas chromatogra hy columns. 7fhese columns are used to analyze gasoline. 8,s chromatography is used by Ozeris (91C) to identify 150 hydrocarbons in gasoline. Honarkhah (46C) has identified 106 components in super grade gasoline and 90 in regular grade by means of gas chromatography. The rapid quantitative determination of methyl tertiary butyl ether in asoline by gas chromatography has been accomplished by Gaftieri (34C). The method is also suitable for a complete compositional analysis. Schulz and Sedighi (101C) have examined the following methods for analysis of gasolines containing olefins: (1)separation of groups by liquid displacement chromatography as a preliminary step for gas chromatographic analysis; (2) reversible adsorption of olefins on columns combined with capillary gas chromatography; and (3) combining hydrogenation and absorption columns in conjunction with analysis by capillary gas chromato raphy. A gas chromatographic technique using an olefin aisorber column for the determination of the saturate, olefin, and aromatic composition of gasoline was evaluated by Stavinoha (121C). Myers, Stollsteimer, and Wims (8OC) have developed a nuclear magnetic resonance spectroscopy procedure for the determination of hydrocarbon-type distribution and hydrogenlcarbon ratio of gasolines. The results are compared with the FIA method and combustion method. A satistical evaluation of the mass spectrometric determination of paraffins, monocycloparaffins, and benzenes in non-olefinic ghsolines has been made by Kuras, Kubelka, and Mostecky (62C). Yamada, Yamamoto, and Hamamoto (132C) have determined aromatic hydrocarbons quantitatively by using a powder containing one or more styrene-divinyl benzene copolymers or their derivatives in the presence or absence of one or more surfactants. Ethyl proprionate and methyl propyl ketone have been found by Stavinoha (12OC) to be suitable standards for the analysis of gasolines of boiling point up to 252 “C, thus eliminating the need for precise sample introduction and external calibration. Nagasaka has patented a procedure for the rapid determination of aromatics in gasoline by using a thermoplastic resin. An experiment conducted by Runion (99C) showed that vapor-phase aromatics level was low for all gasolines analyzed and revealed a much lower level of benzene in air than is commonly believed to occur. The study su gests that 5% is a realistic target for the benzene content in E?uropean gasolines and that present U.S. gasolines should meet American Conference of Government Industrial Hygienists Threshold Limit Values under “normal” usage conditions. Can. Chem. Process ( 17 C ) reports that Shell Research Limited has developed a rapid method for the determination of motor gasoline volatility from gas-liquid chromatographic data. Thermal conductivities and isobaric heat capacities have been measured for a 39 to 193 OC gasoline fraction by Naziev, Aliev, and Efendiev (85C). Kodur and Lada (58C) have de236R
* ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
veloped a method for investigating the corrosive action of gasoline on copper. A spectrophotometric method for the evaluation of the color of automotive gasolines has been developed by Shcherbachenko, Bederov, Ivanov, and Satin (107C). Heilmann (42C) has developed a cheap, efficient procedure for testing motor fuel “clean up” and “keep clean” additives in the inlet system of internal combustion engines. A rapid laboratory test for evaluation of asoline antioxidants is described by Gelius and Rentz (378). The test used is a modification of the “rapid bomb test” of Schwartz et al. (API Abstract No. 15-5552 and 15-14765). Jungers, Lee, and Von Lehmden (52C) have found detectable amounts of 22 elements in 200 gasoline samples. Speculations on their environmental implications are made. The Federal Register (31C) has published lead and phosphorus procedures for use on lead-free gasoline. Guidelines are presented by Gilbert, Wagoner, and Smith for developing a qualit assurance program for the manual determination of phospgorus in gasoline by the molybdenum blue method (38C) and for the determination of the trace total lead content of asoline by atomic absorption spectrometry (128C). h a n y procedures for the determination of lead in gasoline appear in the literature during this review period. Most of them involve the technique of atomic absorption spectroscopy. A method has been developed by McCorriston and Ritchie (70C) which employs a total consumption burner, an isooctane-acetone solvent, and calibration with lead alkyls. Lukasiewicz, Berens, and Buell(68C) have found that use of the nitrous oxide-hydrogen flame permits direct aspiration of asoline. The method is based on an in situ reaction of alkyl t a d with iodine; complexation with a liquid ion exchanger levels response for all alkyl types. The use of a carbon rod atomizer for the analysis of small amounts of lead in gasoline is described by Kashiki, Yamazoe, Ikeda, and Oshima (54C). The samples are diluted with isobutyl methyl ketone, containing 1mg of iodine er mL of solvent. Oshima and Kashiki .(9OC) discuss the app ication of the atomic absorption spectroscopic method with halogen additives to traces of lead in unleaded gasolines. Nishishita, Yamazoe, Mallett, Kashiki, and Oshima (87C) have investigated the possible interference of olefins in the analysis of lead by atomic absorption spectroscopy (ASTM D 3237). Their work shows that the method is efficient even when the concentration of olefins is up to 254 times that of the iodine. Miyagawa (75C) has developed an atomic absorption method for the determination of lead in gasoline using various solvents. The procedure developed by Bowen and Foote (13C) involves the extraction of lead from the sample with nitric acid-hydrochloric acid and water before aspirating. Heistand and Shaner (43C) have developed an automated atomic absorption procedure for the determination of low levels of lead in gasoline. Analytical Chemistry (6C) describes the monitoring system for lead contamination of gasoline used by Ashland Oil Co., Inc. Testing is done with an atomic absorption spectrometer. A detector system for a gas-liquid chromatograph is described by Segar (102C) that consists of a flameless atom reservoir and an atomic absorption spectrometer. Robinson, Vidaurretta, Wolcott, Goodbread, and Kiesel (98C) describe a simple gas chromatographic atomic absorption device utilizing the electronically heated carbon atomizer as the detector. A sim le, plug-in gas chromatographic attachment was developed i y Coker (22C) to use with an atomic absorption spectrometer for analyzing lead alkyls in gasolines. Patents for the determination of trace lead in gasoline have been obtained by Fabbro and Wentzel (30C), Snyder (119C), and Zelaskowski (135C). Sekiyu Gakkai Shi (104C) reports the results of cooperative studies on lead determination in leaded and unleaded gasolines. Tests included were iodine monochloride, gravimetric, polaroraphic, and atomic absorption. Chemical and Engineering !hews (21C) reports that the U.S. National Bureau of Standards has produced standard reference materials for lead in automobile fuels. Shmulyakovskii, Baibazarov, Khapaeva, Biktimirova, and Zamilova (114C) determine copper, lead, and arsenic in gasoline by means of a spectrograph. Electron spectroscopy has been used by Wyatt, Carver, and Hercules (131C) to determine lead in gasoline. Chemical and Engineering News (20C) reports that Exxon Research and Engineering Co. and Princeton Gamma-Tech Inc. have developed a system for continuously monitoring 0.01 to 0.1 g/gal levels
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of lead in gasoline by x-ray fluorescence. Detailed information is given by An elo, Siegel, and Musser (8C). Larson, Short, and Bonfiglio f65C) have determined lead in gasoline in the range of 0.002 to 5 g/gal by an x-ray fluorescence method based on the use of Compton scattering as an internal standard and on a comparison of the unknown with a blank and with a standard solution. Price and Field (95C)have determined lead and sulfur by nondispersive x-ray fluorescence without any pretreatment. Gas chromatography is used by Wilkowa (130C) for the determination of lead alkyls in gasolines. A low resolution mass spectrometer is used by Knof, Ewers, and Albers (57C) for the determination of tetramethyllead and tetraethyllead in gasolines. Fessler (32C) has devised a special sepration chamber so that the Front octane number of motor fuels can be determined directly in the test engine without need for a large test sample. The chamber quenches the fuel-air mixture coming from the carburetor and removes the high-boiling fraction, so that only the components boilin below 100 "C actually reach the combustion chamber. d y e r s , Stollsteimer, and Wims (81C)calculate research and motor octanes of gasoline by a linear regression equation using the isoparaffin, aromatic, lead, and sulfur contents as independent variables. Empirical formulas have been derived by Yoon (133C) for calculating motor octane and distribution octane numbers from the research octane number and from the aromatics, olefins, and lead content of the sample. Paluszkiewicz, Magiera and Brudzynska (92C) give parameters for standard gas chromatographic analysis of crudes used in formulating gasoline and propose equations for calculating the octane number of the gasoline. A linear re ression equation is ro osed by Bryanskaya, Dracheva, ZEurba, and Sabirova 8 4 8 ) for the calculation of the octane numbers of straight-run gasoline from data on their chemical composition as determined by gas-liquid chromatography. McCoy (71C) has calculated the research octane of leaded reformates with f3 accuracy from a gas chromatographic analysis of total aromatics. Simultaneous blend analysis has been used by Robinson and Rakow (97C) to compute a single blending octane number for each component in a motor fuel blend instead of a blending equation. The method gives blend sets which provide unique compositional systems, minimize the number of octane ratings needed, and assure minimum imbalance in component interacting effects. Linear relationships between octane numbers and cetane numbers of gasolines have been developed by Bowden, Johnston, and Russell (12C). The statistical variability of the 1975 U S . Federal test procedure for automotive fuel economy and exhaust emissions, which is based on Constant Volume Sampling, is discussed by Milks and Matula (74C) and Paulsell and Kruse (93C). Mathematical equations have been obtained by Sirtori, Garibaldi, and Vincenzetto (115C) to relate the primary combustion properties of gasoline with properties such as density and hydrocarbon composition. Gas chromatography has been used by Spengler and Woerle (117 C ) to separate and identify the individual components of hydrocarbon emissions from Otto engines. Hydrocarbons in three gasolines and in the exhaust products from a laboratory engine have been analyzed by Calvin, Steel, and Howells (16C) using a gas chromatography-mass spectroscopy technique. Oelert, Siegert, and Zajontz (88C) have determined the emissions of individual hydrocarbons in internal combustion engine exhausts by application of gas chromatographic analysis to various operating states of passenger cars. A portable polarograph for the determination of aldehydes in automotive exhaust and production plant samples has been developed by McLean and Holland (72C). Candeli and Zoccolillo (18C) have determined the polycyclic aromatics hydrocarbons in engine exhaust products by means of thin layer and gas-liquid chromatography. The elemental composition and crystalline phases present in lead particulates from the exhaust of gasoline engines have been analyzed by Vitali and Perego (126C) using nondispersive x-ray fluorescence and x-ray diffraction. KOrotenko, Korotenko, and Leshchina (61C) have patented an apparatus for the determination of the composition of liquid fuel-gas mixtures. An adsorption technique for the determination of or anic lead in street air is described b Harrison, Perry, and !later (41C). Joselow and Singh (516) have developed a method for the micro analysis of lead in blood. Distillate Fuels. Shelton (111C) tabulates analytical data
for 241 samples of diesel fuel from 33 companies. Kerosines have been compared by Cain (15C) using gas-liquid chromatography. Herlan (44C) has carried out hydrocarbon type analysis of diesel fuel using high resolution mass spectrometry, gas chromatography, and separations on silica gel and molecular sieves. The composition and characteristics of 14 gas oil components have been determined by Garibaldi and Casalini (36C). Reinhard, Drevenkar, and Giger (96C) have investigated the effect of aqueous chlorination on the aromatic fraction of diesel fuel. A relationship between flammability index and the temperature and flash point of liquid hydrocarbon fuels has been developed by Affens, Carhart, and McLaren (2C). Andrzejewski, Bochenski, and Saragih (7C) have studied experimentally the relation between cetane number and the ignition quality of diesel fuels. The wear and friction characteristics for eleven aviation turbine and diesel fuels have been evaluated by Garabrant ( 3 C ) with the aid of the Exxon Ball-on-Cylinder machine and Vicker Vane Pump. Muetze (79C) has patented a procedure for determining the water content of heavy heating oils. A new method for determining additives and contaminants in petroleum fuels has been developed by Kolobielski (59C). The flash distillation method provides in a concentrated form the nonvolatile components present. Butyl phthalates as denaturants are added in Italy for fiscal purposes to gas oil intended for heating. Navarra and Pesapane (84C) describe a procedure for the detection of the denatured product using gas chromatography. An adsorption method for the determination of the resinous substances in diesel fuel is described by Gureev, Lebedev, Livshits, and Aleksandrova (40C). Details on standard fuel oil samples for nitrogen determination are given by Sekiyu Gakkai Shi (105C, 106C). The API Publication ( 5 C ) contains a listing covering existing and roposed sulfur limitations for fuel oil and coal. Bakhtiarov, bolodin, and Chelyabina (1OC) tabulate precision and reliability of certain characteristics for standard samples of commercial diesel fuels. These characteristics are total sulfur content, aromatic content, height of a nonsmoking flame, and ash and coking values. Sodium in gas turbine fuel oil is determined by Sherburn and Poole (113C) using a flame spectrophotometer. Moore, Machlan, et al. (78C) have developed a technique to determine nickel in fuel oil by thermal ionization mass spectrometry. Vanadium is determined spectrophotometrically by Banerjee, Sinha, and Dutta (11C). Tannic and mercaptoacetic acids are reacted with the vanadium to form an indigo blue complex. An analog computer model of a complete diesel engine/eddy current dynamometer test bed for air pollution control studies is described by Al-Bermani and Gravestock (3C). Spindt (118C) has developed a sampling system for collection of polynuclear aromatics. This sampler was used to study exhaust ases from 20 diesel fuels. Gas chromatography was used by kanden and Perez (64C) to derive diesel exhaust reactivity information. Levins and Kendall (66C) describe the design, construction, and evaluation of an automatic liquid chromatographic system which provides an output directly proportional to odor studies of diesel exhaust. Ryabinina and Oshman (1OOC) have analyzed a mixture of Son, HSOB-,S032-, and S Z O ~ using ~ - three titrations. This method can be used to analyze gaseous products from fuel combustion. After a brief discussion of the limitations of existing methods, Shen and Ayer (108C) propose an indirect procedure for the determination of SO2 in emissions from oil-fired boilers. They have derived an equation for calculating SO2 content from the measured (Orsat) value for CO? and the sulfur and carbon contents of the oil. Miscellaneous. Czembor (25C) has outlined a fluorescent measurine techniaue for detecting small auantities of oil in lyes and Gaste waters using the SPBKOL spectrocolorimeter. Instrument Technology (48C) reports that Foster Wheeler is investigating the exact composition of fuels for use in designing combustion equipment and in developing materials for petroleum pilot plant work. The accuracy of particle size distributions of supported metal catalysts determined by transmission electron microscope is examined by Flynn, Wanke, and Turner (33C). Karakchiev, Kotsarenko, et al. (53C) have studied the relative strength of acid sites in crystalline and amorphous alumina silicates. Liebman, Corry, and Richmond (67C) have atented a process for producing low ash solid fuel and distiiate liquid fuel from raw coal. ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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