Anal. Chem. 1983, 55, 245R-313R
US”.Atmos. Environ., 15(10-ll), 2017-30 (1981). (4MM) Hering, S. V., Bowen, J. L., Wengert, J. G., Richards, L. W., ”Characterization of the regional haze in the southwestern United States”, Atmos. Environ., M ( l 0 - l l ) , 1999-2009 (1981). (5MM) Macias, Edward S., Zwicker, Judith O., Oulmette, James R., Hering, Susanne, V., Friedlander, Sheldon K., Cahill, Thomas A,, Reglonal haze case studies in the, southwestern US. I . Aerosol chemical composltion”, Atmos. Envlron., 15(10-ll), 1971-86 (1981). (6MM) Ruby, M. G., Waggoner, A. P., Intercomparison of integrating nephelometer measurements”, Envlron. Scl. Techno/., 15(1), 109-13 (1981). (7MM) Weiss, R. E., Larson, T. V.,Waggoner, A. P., “In situ rapid-response measurement of sulfuric acidlammonium sulfate aerosols in rural Vlrginla”, Envlron. Sci. Technol., 16(8), 525-32 (1982). (8MM) Kapustin, V. N., Rozenberg, G. V., Ahlquist, N. C., Covert, D. S., Waggoner, A. P., Charlson, R. J., “Characterization of nonspherlcal atmospheric aerosol particles with electrooptical nephelometry”, Appl. Opt., l9(8), 1 3 4 5 4 (1980). (9MM) Gerber, Hermirnn E., “Optlcal techniques for the measurement of llght absorption by particulates”, 145-58 pp., Part. Carbon: Atmos. Llfe Cycle froc ., Woiff, GI. T: Klimisch, R. L., Eds., Plenum, New York, NY, 1982. (10MM) Clarke, A. [I., Integrating sandwlch: a new method of measurement of the light aidsorption coefficient for atmospheric partlcles”, Appl. Opt., 21(16), 301 1-20 (1982). (1 1MM) Mita, A., Isono, K., “Effective complex refractive index of atmospherlc aerosols containing absorblng substances”, J. Meterol. SOC Jpn ., 58(1), 89-80 (1980). (12MM) Allegrinl, I., “Optical absorption constant of suspended particulate matter. An air pollution Index”, Envlron. Scl. Technol., 14(10), 1221-7 (1980). (13MM) Clarke, A. G., Morris, I10 mg of MeOH/m3, determination by gas chromatography after absorption in water for b > a. In a study reported by Nagai et al. (96F), proton NMR spectra of 13 crude oils and 12 asphalts were obtained. Structural parameters were calculated based on Brown's procedures (33F). Carbon to hydrogen ratios had better relation to aromaticity than to density of crude oil and softening point of asphalt, thus it was presumed to be a better indicator of structural behavior for petroleum products. Bagautdinova and co-workers ( 1 4 0 through NMR reported that proton mobility in petroleum coke depends on the starting material and on the final temperature of coking. The gradual increase in structural density during carbonization produces a reduction in proton mobility, especially in cokes prepared at greater than 1400O.
Weinberg et al. (163F)characterized pyrolyzed asphaltenes obtained from coal liquids. Aromaticities increased with high temperature treatment for asphaltenes. For both first and second moment I3C NMR, the solvent refined coal sample was relatively insensitive to high temperature treatment, the COED residue contained mainly carbonyl and some ether while the solvent refined coal contained carbonyl and partically no ether. Bandurski (17F)through NMR and other techniques reported on structural similarities between oilgenerating kerogen and petroleum asphaltenes. He found that asphaltenes may be fragments of the original kerogen from which the crude oil was derived and may be expelled as part of the crude oil, so that asphaltenes set a lower limit of the size of openings in source rocks through which the oil can be expelled. Murphy and co-workers (97F) determined the chemical functionality asphaltenes by 13CNMR. Studies of the first and second moments suggested that the average number of polynuclear condensed rings in asphaltenes is much smaller than what is thought to exist in a high-rank anthracite coal. Also, the aliphatic side chains attached to the polynuclear backbone may have large variations in both lengths and branchings. Miknis et al. (9OF)characterized residual carbon from retorted oil shale using 13C NMR. They found that measurements of the organic carbon distribution of oil shales heated to various temperatures have practical relevance and that this information can be valuable in discriminating between unconverted kerogen and residual carbon in heated oil shales. Seshadri and co-workers ( 1 3 5 0 characterized an ethylene pyrolysis tar using both proton and 13C NMR. The results were compared with those from petroleum decant oil. Structural differences obtained were related to pyrolysis behavior. A four-part characterization study of hea oils was re orted by the Japan Petroleum Institute (2-5F).yroton NM%, IR, gel permeation chromatography, and other methods were used to study low temperature cracking steam refoming and hydrodesulfurization of heavy crude oils. Infrared Spectroscopy (IR). Robin et al. (112F) characterized kerogens by using infrared spectroscopy. They found that with the decrease of the hydrogen-to-carbon ratio, there was a diminution of alphatic bonds, a relative enrichment of methyl groups and, in a first stage, formation of aromatic CH. They also reported that the removal of the latter during a structural reorganization in determined by the degree of catagenesis or thermal treatment and not by the parent material. In another paper, Rouxhet and Robin (115F)used IR to study the kerogens from different origins during catagenesis and pyrolysis. They found that catagenesis leads to residual kerogens with a chemical composition independent of the parent material. Pyrolysis of more oxygenated kerogens leads to products with higher oxygen concentration in the form of COR functions. Posadov and Pokonova (11OF)made an IR study of the structure of petroleum asphaltenes. The spectra revealed that significant amounts of alycyclic structures are present. The degree of asphaltene aromaticity of 0.32 corresponded to 53 aromatic carbon atoms per asphaltene molecule. Ivanov and co-workers (663')studied the chemical stability of kerosine fractions by IR. They determined the composition of tarry substances in a kerosine produced by distillation, hydrofining, and hydrogenation. A Japanese report (1F) presented a method for analysis of heavy aromatic residues in the presence of solids using IR among other methods. 260 R
ANALYTICAL CHEMISTRY, VOL. 55,
NO. 5, APRIL 1983
Sawatzky et al. (1230 determined by IR spectroscopy and titration, the properties of nitrogenous products in four Athabasca bitumen samples which had been thermally cracked. The analyses of the eluates and heavy fractions are discussed. John and Matuszewska (708') applied to IR to discriminate products of low-temperature carbonization of cod and sapropelic and humic schist. They found that IR spectra were suitable for rapid evaluation of chemical properties and the possible technological uses of the products of carbonization. Petersen and Plancher (103F) used selective chemical reactions followed by IR to determine the concentration of carboxylic acid and anhydrides in asphalts and asphalt fractions. The method is based on the selective interaction of triphenyltin hydroxide with free carboxylic acids, the hydrolysis of acids and anhydrides with sodium hydroxide, and the silylation of the free acids and their salts. Lyakhevich and Stupakov @IF) reported the IR spectra of high-molecular-weight petroleum compounds. Absorption Spectrometry. Kozlova et al. (7987 reported an absorption spectrometric method for the rapid quantitative determination of petroleum bitumen group compounds in solution. The method is based on the individual luminescence characteristics of light, middle, and heavy aromatic hydrocarbons, resins, and asphaltenes. Paukku and co-workers (101F)complexes polar components of asphaltene-resinous substances of petroleum with metals of variable valence. The best results determined from absorption spectra of the complexes are obtained by treating chlorides of Fe, Ti, or V in benzene with extracts from heavy petroleum residues. A rapid absorption spectrophotometric method for determining asphaltene contents in residual oils was reported by Kaibara et al. (71F). Excellent correlation between this method and that of Method 143 by the Institute of Petroleum (London) was noted. Bunger and Cogswell (35F) studied the chemical characteristics of tar-sand-bitumen asphaltene by means of absorption spectroscopy and hydropyrolysis. They found no chemical features (e.g., carbon type, hetroatom type, molecular weight, etc.) to distinguish species found in the asphaltene fraction from those in the maltene fraction. Asphaltenes, therefore, tend to be chemically nondistinct from maltenes, and correlations between asphaltene content and processability, while useful to the engineer, are chemically fortuitous. Ruiz et al. (116F) determined the sulfur content in asphalts using selective oxidation and spectroscopy for chemical analysis. Mass Spectroscopy (MS). Mass spectroscopy followed by IR was employed by Scheppele and co-workers (124F, 1250 to obtain detailed analysis of fractionated coal-derived liquids and asphaltenes. They noted that the lack of unique oil and asphaltene compositions necessitates detailed molecular analysis as a prerequisite for understanding, assessing, and controlling the chemical-physical phenomena of the production and processing of coal liquids. Mitera (93F) reported a quantitative mass spectrometric determination of petroleum asphaltenes and lactam oligomers. Equations for calculating the average molecular weight of the compounds studied are presented. Sebor et al. (131F) characterized by mass spectroscopy metalloporphyrins in asphalt and asphaltene fractions of a Russian crude oil. Mass spectrometry was used to perform group analysis of a neutral position of generator for boiling at 1200O. The fraction contained mainly aromatic compounds. Barvise and Whitehead (200 developed a novel scheme using alkylsulfonic acid functionalized silica for the separation of vandyl parphyrine. The porphyrins were analyzed by mass spectroscopy. Squalene in petroleum asphaltenes was detected by mass spectroscopy in asphaltene pyrolyzates from various tar sands and crude oil (122F). The results indicated that squalene was a significant constituent of the biomass from which the asphaltenes were formed and that it was chemically bound to the asphaltene. Miller and co-workers (92F) characterized tars from the gasification of low-rank coals using mass spectroscopy. About 20 constituents varied markedly in the tars produced from different coals gasified under identical conditions. Aczel and co-workers (7F) found that more than 1000 aromatic and hetrocyclic compounds by using mass spectroscopy on asphaltenes derived from coal liquids. Coal asphaltenes consist predominantly of units of 3 to 10 ring heteroaromatic components with 1 to 3 of these units per
PETROLEUM
molecule. Schronk et al. (126F) demonstated the efficacy of probe microdistillation combined with mass spectroscopy in the analysis of high-boiling petroleum distillates. They found that volatility decreases with increasing molecular weights of a given hydrocarbon type but is independent of --Z(H) for compounds having the same carbon number. X-ray Methods. The determination of molybdenum, nickel, vanadium and titanium in asphaltite and its ash was reported by Saltoglu and co-workers (119F) using X-ray fluorescence spectroscopy. Ho (65F) used small angle X-ray scattering to obtain particle size configuration of cod-derived asphaltenes ancl preasphaltenes in solution. Asphaltenes from six crude oils were characterized by Bosch et al. (31F) using X-ray scattering. Electron Spin Resonance Methods (ESR). ESR spectra of heavy hydrocarbon oils containing vanadium compounds at high temperatures were studied to determine the rotational activation energies of vanadium compounds (102F). The spectra provided a means for predicting the coking properties of an unknown ]pitch. Yamada and Sanada (165F)investigated the carbonization mechanism of petroleum- and coal-based heavy oils as well as certain pitches. The coal-based heavy oil was carbonized through polycondensation of aromatic molecules whereas petroleum-based oils were carbonized through splitting of alkyl chains from aromatic molecules followed by aromitization and polymerization. Durand and co-workers (46J')made ESR measurements on natural kerogens and on those subjected to programmed thermal treatment. Electron paramagnetic susceptibility was studied as a function of the catagenetic evolutionary stage and pyrolysis temperature. Agreement between results from natural and thermally treated samples were observed. Other Instrumental Methods. Akcetin (10) identified 37 elements and their quantities by using neutron activation analysis on asphaltites. Voropaev (158F) studied 23 hard bitumens by using microphotometry. The results compared favorably with literature data. Photocolorimetric determination of the deposition threshold of asphaltenes in petroleum fractions was reported by Rogacheva et al. (114F). Evstafeva and co-workers (51F) made polarographic determinations of peroxide microimpurities in isoprene, higher paraffins, and reforming raffinates. Pitches were characterized by Barr and Lewis (18) using differential scanning calorimetry and thermomechanical #analysis.They found that the glass transition temperature bears a fixed relationship to the softening point.
CHEMICAL AND MISCELLANEOUS METHODS Rezapova and Taskina (1118') used a method for determining pyrite siulfur by way of iron and adapated if for the analysis of kerogen. Pyrite iron released after decomposition of the sample was titrated with EDTA. Bluemer and Zauder (22F) reviewed the use of chemical reactions for the analysis of coal tar pitch and coal extracts. Jha et al. (69F) oxidized Athabasca oil sand and its fractions which resulted in a substantial increase in the asphaltene content at the expense of the maltenes. The oxidation could be a factor affecting bitumen quality during storage of mined oil sands and liquid bitumen. Katayama and co-workers (72F, 73F) modified a method for the analysis of petroleum heavy residues, asphaltenes, coal tar pitch, etc. for applicability to residues rich in naphthenes and poor in aromatic hydrocarbons. Five different solvent separation methods currently used for determing asphaltenes in coal-derived liquids 'were evaluated by Schultz and Mima (127F). The data presented included the weight percent asphaltenes, insolubles, and oils. The precision for each of the procedures was reported. These same authors (128F), 129F) took the results from the previous research and voted that they were statistically different. Their findings suggest the need for a standardized procedure. Darlage et al. (43F) titrated 34 nitrogen-containing compounds with a wide range of basicities in acetophenone and nitrobenzene. Asphaltenes isolated from an H-coal process were also tested. Each asphaltene Contained a titratable class of nitrogen-containing cornpounds of the pyridine or aniline type. Nosal and co-workers (97F) reported a method for determining the dispersion stability of asphaltene-containing petroleum residues. Organic structural studies of lignite coal tars were presented by Miller et al. (91F). They found that
the relation between compound types in the tar and those obtained by solvent extraction suggests that the molecular structures in the tar are determined not only by thermal processes but also by the structural relation in the parent lignite. Boduszynski (26F) compared fractions of petroleum asphalts obtained by precipitation methods with those obtained by chemical separation means. The results imply that the formation of asphaltenes is determined by two mechanisms: asphaltenes are formed due to the association through hydrogen bonding, resulting in the formation of aggregates of limited solubility, and asphaltenes are formed due to chemical reactions occurring in the asphalt upon oxidation. In a later study, Boduszynski (28F) showed that asphaltene compositions varied because the precipitation method is based solely on solubility parameters and is chemically nonspecific. Ciais and Lambelin (39F) reported a method involving the contacting of petroleum products with hot heptane to precipitate asphaltenes which are separated by filtration. Aczel and co-workers (6F) studied asphaltenes from coal liquids. They concluded that the asphaltenes are extremely complex mixtures of hydrocarbons and heterocompounds vvith an average molecular weight between 500 and 800. Smith et al. (139F)explored the interaction of salt-forming agents with asphaltenes and preasphaltenes from H-coal vacuum bottoms. Their objective was to achieve improved separations which would allow good material balances and equivalent weight determinations. Aigistova and co-workers (8F) presented a method for determining water in various crudes containing asphaltenes by adding demulsifiers. These agents break the asphaltene-water emulsions and permit accurate Dean-Stark determinations. Rogers (113F) adapted a method of solubility class firactionation originally developed for petroleum asphalts to coal liquids. The stability of coal-derived particles was classified as moderate while asphaltenes appeared to be highly stable. Veski et al. (156F) studied the products of a stepwise nitric acid oxidation of kerogen. The results showed that the degradation products were nonaromatic, mostly linear compounds containing CH2 groups adjacent to CO and COOH groups. SaintiJust (118F)reported using the adsorption of asphaltenes on catalysts to characterize the catalysts. Podobaeva et al. (108F) extracted asphaltenes from a Russian crude by using n-heptane followed by mass spectroscopy to identify metal porphyrins in the asphalteines. Oxygen groups of asphaltenes from a Siberian crude were studied by Svintitshikh and co-workers (146F). These asphaltenes contained 3.27% oxygen present in phenolic OH and COOH groups. Klesment et al. (78F) characterized a coal bitumen and semicokin tar by extraction with CHC13. The results are described in fetail. An American Chemical Society Symposium on the characterization of heavy petroleum ends was presented by Hall (15F). A characterization study of oil shale tars by Saluste 200 ppm of nitrogen. Dolle et al. (54K) reported on a new technique for chemiluminescence analyses by using a platinum crucible, mixing the vapors with helium and oxygen, and passing it through a silica combustion tube before measurement is made. The Kjeldahl method was modified by Avgushevich et al. (21K) for coal hydrogenates by oxidizing in two steps, adding glucose in one step and potassium permanganate or hydrogen peroxide in the other. Tabata and Furukawa (226K) used CuS04 and Se instead of Hg in the Kjeldahl method as a catalyst to reduce pollution problems. No catalyst was used in the Kjedahl digestion by Ozawa (177W, using hydrogen peroxide instead. A large interest was apparent in separation and characterization of nitrogen containing compounds in petroleum, petroleum products, shale oils and tar sands. Holmes and Thompson (97K) determined nitrogen distribution in shale oils derived from different processes and report concentrations of nitrogen base compounds can be estimated from total nitrogen in the feedstocks. Statistical correlations between basic 280R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
nitrogen content and the concentration of total sulfur, tars, and asphaltenes were obtained by Ivchenko et al. (106K). Ford et al. (71K) reported a separation scheme by absorption chromatography on basic and neutral alumina as applied to shale oil products produced under different retorting processes. A modified API-USBM separation by Sawatzky et al. (202K) on bitumen and heavy oils indicated only limited elutions were necessary for satisfactory results rather than exhaustive extractions. A combination of hydrochloric acid extraction, separation on Amberlyst A15, and colloid precipitation was used to separate nitrogen compounds by Neumann et al. (169K) and the compounds were analyzed by IR, NMR, elemental analysis, and gel permeation chromatography. Kisielow et al. (177K) and Kaernbach et al. (108K) separated polar nitrogen compounds by liquid chromatography on macroporous ion exchangers. Mass spectral characterization was reported by Buchanan (35K) to differentiate aminosubstituted polycyclic aromatic hydrocarbons, azaarenes, and compounds containing two nitrogen atoms from a coal-derived liquid. Albert (1OK) described a thermionic nitrogen detector used in combination with a flame-ionization detector for gas chromatographic determination of nitrogen distribution in a light catalytic cycle oil and a light vacuum gas oil. Straight-run petroleum fractions were found to contain mainly derivatives of quinoline while the nitrogen containing compounds of fractions from residues by hydrocracking were mostly analine and pyridine derivatives by Baikova et al. (22K). Tominaga and Tatsumi (235K) characterized the organic nitrogen compounds in hydrotreated residual oils. Nitrogen compounds were found to be concentrated in the tars of three Soviet petroleums by Artemeva and Mikhailov (19K),with neutral nitrogens being predominant. The nitrogen containing compounds complexed with TiC14from a high boiling fraction were further fractionated by multiple silica gel chromatography by Bembel et al. (27K);characterization by potentiometric titration and mass spectrometry showed nearly half to be strong bases. Allain et al. (14K) determined two types of nitrogen compounds by coupling thermogravimetric analysis with oxidation of volatile nitrogen compounds to NO and subsequent analyses by chemiluminescence. Analysis of specific nitrogen-containing compounds was a popular subject of articles. Three nickel catalysts were evaluated by Bulusek et al. (36K) for converting the nitrogen in nitro, nitroso, and azo compounds to ammonia for determining the nitrogen in those compounds. Sahu and Tandon (198K) described a qualitative test for nitro compounds based on reduction in a neutral solution to hydroxylamines that are reacted with ammonium metavanadate which forms a colorful layer in chloroform. Another test for aromatic nitro compounds was discussed by Verma and Dubey (244K) by means of thin-layer chromatography detection of a-complexes with N,N-diethylaniline. Medium resolution mass spectrometry coupled with a gas chromatograph was used for a nitrogen compound specific detector by Gallegos (78K) in analyzing gasoline where he found one main component: 4-methylbenzenamine. Novotney et al. (175K)reported high precision retention measurements of pyridine and quinoline derivatives by capillary gas chromatography with deactivated glass columns. The location of the nitrogen atom in petroleum triaromatic azaarenes was determined by Schmitter et al. (204K) by recording the UV spectra on-line during a reversed-phase liquid chromatography separation. Primary and secondary amines were determined by Tomkins and Feldman (236K) after a five-step separation scheme by GLC using a glowdischarge detector. Takagi et al. (228K) analyzed 16 nitrate and nitrite esters using gas chromatography/photoionization mass spectrometry. Three classes of nitrogen-containing aromatic compounds (neutral azaarenes with a pyrol-type nitrogen, basic azaarenes with a pyridine-type nitrogen, and the basic aromatic amine with an aniline-type nitrogen) were analyzed by Garrison (80K) using matrix-isolated Fourier transform IR spectroscopy. A system employing a molecular sieve trap between a pyrolyzer and a chemiluminescent NO detector was discussed by Rounbehler and Reisch (193K) for analyzing nitrosamines. Simonov et al. (213K) discussed the effects of substituted dichloromaleic acid imides on the gas chromatographic analysis of elemental nitrogen. The effects of chlorinated organic compounds on oxidative pyrolysis and gas chromatography were eliminated by Safarova (197K) by use of
PETROLElJM
AgMn04 and KMn04 as catalysts. The thermal stability of nitrogenous compounds separated from petroleum on a cation exchanger was studied by Zamulinskii and Sevastyanova (26810. Grigsby et al. (85A7 evaluated fast atom bombardment mass spectrometry for identifying nitrogen-containing compounds in fossil fuels against field ionization spectra.
WATER The Karl Fischer method is still the method of choice for the determination of low ’levelsof water in petroleum products, so modification to this nnethod was a popular subject. Mitsubishi Chemical Industries Co., Ltd. (159K), developed a solvent system for the Karl Fischer determination which consisted of CHCl,-alk ylene carbonate to which pyridine sulfodioxide and a small amount of an alcohol have been added. Sherman (207K) discussed the mechanism of the reaction with water of a IDMF-modified Karl Fischer reagent and determined that a water equivalent should be determined under the same conditions as the water determination. Fischer and Krenn (70K) reported on pyridine-free Karl Fischer reagents using mono-, dii-, or triethanolamine; titration end points could be detected visually, photometrically, or coulometrically. Marik-KordaL (147K) developed a direct injection enthalpimetric method for the determination of water in several organic solvents and solid samples using a solution calorimeter and measurements of the temperature change from the heat of reaction of water with Karl Fischer reagents. Water was also determined by gas chromatography by several researchers. Konopczynski and Siedlecki (120K) used a special sample injection apparatus on a Chrom-4 GC to determine water in gasoline-type fuels; water in the sample is reacted with calcium carbide and the resultant acetylene is determind on a stainless steel column packed with Chromosorb 101. Liu and Chen (135K) determined the moisture content of electric insulating oils by gas chromatography by using the saturation values of water in benzene or n-heptane at various temperatures ils the reference values. The Peking Institute of Chemistry (18OK) analyzed the reaction products of lithium aluminum hydride and water by gas chromatography. A’Campo et al. ( 1 K ) discussed the problem of a systematic error introduced by interactions of polar compounds on porous polymer gas chromatographic columns used in the determination of water. Wu and Lu (258K) used high- and low-temperature columns connected in series to monitor ex traction of butadiene by acetonitrile and for the rapid analysis of water-acetonitrile-gaseous hydrocarbon systems. Ksiazczak and Buchowski (125K) used the differences between the vapor pressure of a solvent containing traces of water and that of the dry solvent to determine trace levels of water in nonpolar solvents. Water in petroleum-water mixtures from oil production wells was determined sonically by Conoco (46K) using an apparatus containing a chamber for the separation of petroleum from water and a way of sending sonic waves through the separated water. Kuehl et al. (126K) described an apparatus for the determination of water in oils which consisted of a Dewar-type flask in which the temperature rise is measured from the water absorbed by Zeolite 4A in isooctane. Radushnov and Ginatullina (189K) received a patent for a radiospectroscopic technique, the accuracy of which was increased by measuring the ESR signal from the paramagnetic probe of copper acetate or its nearest homologues added to the sample. In an investigation of‘ the electrochemical reduction of halosilanes, Corriu et al. (47K) developed a method for the polarographic determination of water in organic solvents based on the high sensitivity of chlorosilanes to hydrolysis which is a possible source of misleading reduction waves. A “Signal”-type coulometric device was described by Emelyanov et al. (63K) in which water is stripped from the liquid sample in a desorption column by a carrier gas and the water concentration in the gas is monitored with a coulometric detector. Zhou et al. (271K) measured the water content and density of the H-rich material in an oil well using a system consisting of a single probe and a radioactive source emitting two kinds of low-energy photons of different energies and intensities. OXYGEN The detection of oxygen in exhaust gases was the subject of a t least three patents. An oxygen detector using a solid
electrolyte cell housing was described by Mase et al. (14910. Maurer et al. (156K) developed an electrochemical sensor for determining the partial pressure of oxygen in gases, which c,m be used for potentiometric and for polarographic measurements, depending on the cover coatings on the electrodes. Fujishiro (75K) has a1 patent for a device useful in monitorirag automotive exhausts which uses three electrodes, only two of which are in direct contact with the combustion gases; the third electrode is in contact with one of the other two electrodes through a gas-permeable layer of an oxygen ion conductive solid electrolyte. For the conversion to CO of COz, HzO, and oxygen-containing organic complounds, Campbell and Chang (37K) found that thermal decomposition products of Ni, Co, and Fe were effective catalysts a t about 900’ for the determination of oxygen in organic compounds using a modified Unterzaucher-type apparatus. Kopycki et al. (121K) described an apparatus for the automatic microdetermination of oxygen in organic compounds using the Schuetze-Unterzaucher method with coulometric titration; analysis time for 23 samples was 4 h. Microdetermination of oxygen in small samples (3-5 mg) of organic and organometallic samples was accomplished by Wan et al. (252K)in about 15 min by a coulometric titration method with photometric end point detection in an electrolyte solution containing ethanolamine, KI, DMF, and thymolphthalein. Nakajima et al. (167K) developed an apparatus for the microdetermination of oxygen by coulometric titration; a 0.5-2 mg sample in pyrolyzed in a carrier gas and reacted with Pt-C to evolve CO which is then oxidized to COz by 1206; the COz is absorbed in 5% Ba(C104)zsolution of pH 9.7 arid titrated coulometrically. Gas chromatography was used by four authors to determine oxygen by first pyrolyzing the sample and converting the oxygen to CO. Duan et al. (55K) decomposed the sample in a quartz pyrolysis tukie containing a highly active carbon black packing with a nickel and platinum coating; the carrier g,as was helium and the column packing was TDX-01 and 5A molecular sieves. Kuznetsova et al. (129K) pyrolyzed their samples in silver foil with carbon in a quartz reactor at 1140’ using helium as the carrier gas and a 1-m column packed with SKT carbon. Uhdeova and Razl (239K) analyzed pyrolysis gases by frontal gas chromatography on a Porapak Q column using a thermal conductivity detector; pyrolysis was accornplished in helium with conversion of oxygen to CO on a nickel coated carbon packing a t 1050O and oxidation of hydrogen produced and CO to llZ0and C02 on CuO at 650’; interfering halogens and sulfur are retained on silver. Thuerauf (23210 detected and determined oxygen by conversion to CO and IR measurement in a nondispersive spectrometer having a range of 0 to 0.1% (v/v) of CO; this detection system was used in conjunction with a thermal conductivity detector for identtification of oxygen-containing substances in oil produced froim coal. Snape et al. (218K) used NMR to estimate the concentr,stion of hydroxyl and inonhydroxyl groups in coal extracts and compared results to those obtained by enthalpimetry. Khalil et al. (112K) determined the oxygen content in liquid samples from coal conversion processes by 14-MeV neutron activation analysis, sequentially irradiating samples and standards.
HALOGEN A variety of methods was used to determine halogens in petroleum and petroleum products. Preis and Esenwein (185K) described a rapid X-ray spectrophotometric method for the determination of chlorine in mineral oils which gave results comparable to those obtained by wet chemical analysis. Kim (114K)determiined the chlorine content in refined petroleum or crude oil by measuring the differences in viscosity and specific gravity. Campiglio and Traverso (38K) described an accurate argentornetric microdetermination method for chlorine in organic compounds in which the sample was burned in an oxygen flask, the products absorbed in an alkaline solution of hydrazine, and the chloride titrated potentiometrically. In a study of a chloroorganic compounds in petroleum, Karaulova et al. (11OK)determined the chloride content by the combustion of desalted petroleum, sorption of the combustion products in a sodium carbonate solution, and determination of the chloride concentration mercurimetrically in the presence of diphenylcarbazide. Coulometric titrations of ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
281 IR
PETROLEUM
small amounts of chloride ions with electrogenerated silver ion in mixed aqueous solvents were compared by Hulanicki et al. (101K);the solvents investigated contained 50 and 90% of ethanol, acetone, or acetic acid; end point detection was by zero-current potentiometry, potentiometry with indicator electrode polarized to the end point potential, potentiometry with two polarized electrodes, and amperometry with two polarized electrodes. Heunisch (93K) described a method for the determination of chlorine in coal-derived synthetic fuels that is also applicable to the analysis of petroleum products; the sample was decomposed with sodium biphenyl to produce NaCl in a cloudy, aqueous mixture; the addition of acetone produced a clear solution that could be titrated potentiometrically with silver nitrate. Bedareva et al. (25K) also used a decomposition with sodium biphenyl to decrease the analysis time for determining chloride in ethylbenzene; chloride was determined by a turbidimetric method with silver nitrate. Mitrofanov (158K) determined chlorides in samples containing petroleum and stratal water by diluting with gasoline if necessary to decrease the viscosity, dissolving in a mixture of acetic acid and carbon tetrachloride with sulfuric acid to break the emulsion and provide the necessary electrical conductivity, and titrating conductometrically with silver nitrate or mercuric nitrate. Kawara et al. (111K)used hydrogen peroxide to eliminate the interference by nitrogen and sulfur in the measurement of trace chlorine in light gas oil by the Wickhold combustion-absorption method. The interference by nitrogen, sulfur, and phosphorus compounds on the determination of chlorine in petroleum products by a combustion and microcoulometric titration procedure described by Coulson and Cavanaugh was eleminated by placing a scrubber tube packed with cupric oxide wire between the combustion furnace and the coulometric cell by Matsuzaki and Koyano (155K). Bem and Ryan (26K) described a neutron activation analysis procedure with thermal neutrons for the determination of fluorine in organic compounds, even in the presence of large amounts of chlorine and oxygen. Csikai et al. (50K) received a patent for the quantitative determination of the chlorine content of chlorinated hydrocarbons by the neutron activation analysis with thermal neutrons. In the determination of ultramicro amounts of fluoride in high-octane alkylate, a sample of alkylate obtained by alkylation of isobutane in the presence of H F as a catalyst was to absorb the HF; treated by Valueva et al. (241K) with A1203 the absorbent was then pyrolyzed in the presence of W03 and free fluoride was absorbed in water; the fluoride content was then determined by using the trisodium salt of 3-(4-sulfopheny1azo)chromotropic acid. Wilson and Marczewski (256K) determined fluoride in crude oils by a procedure which includes decomposition with sodium biphenyl followed by aqueous extraction of sodium fluoride and determination with the fluoride electrode. Antonova et al. (17K) determined trace HF and BF3 in hydrocarbon alkylation products by extracting the sample three times with water and measuring the absorbance of the zirconium complex with SPADNS reagent. In the simultaneous microdetermination of nitrogen and halogens, Khanzadyan and Abramyan (113K) mixed the sample with 40-60 mg of KMn04 deposited on 1.5 g of granulated corundum in a copper tube, combusted the mixture using an adaptation of the Dumas-Pregl method for the volumetric microdetermination of nitrogen, potentiometrically titrated the fluoride with thorium nitrate, and titrated the other halogens with silver nitrate. Farag et al. (67K) used polyurethane foam as an internal and an external absorbent for iodine in the analysis of iodoorganic compounds. In a method for the simultaneous determination of carbon, hydrogen, and halogen, reported by Kozlowski and Sienkowska-Zyskowska (123K), samples in aluminum capsules with Vz05were flash combusted in a stream of air in the presence of Co304and the final determination of halogen was by gravimetric or iodogravimetric means. Sienkowska-Zyskowska and Kozlowski (211K)also developed a method to determine chlorine, bromine, and iodine in organo-halo compounds also containing sulfur; the sample was combusted in a stream of air in the presence of Co304and Vz05;the combustion gases containing chlorine and bromine were absorbed on quartz wool wetted with hydrogen peroxide and the chloride and bromide titrated with mercuric perchlorate, with diphenylcarbazone as an indicator; iodine was 282R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
determined by Leipert's method after the combustion gases were absorbed in a solution of sodium hydroxide. Wang and Su (253K) used the oxygen flask method in combination with potentiometric titration with a standard silver solution for the determintion of chlorine and bromine in organic compounds; a chloride ion selective electrode was used for detecting the end point in 90% acetone solutions. Von der Ohe et al. (249K) determined dichloroethane and methylene chloride in dewaxed lubricating oils by stripping off the volatile materials a t 100' and measuring them with a flame ionization detector and a halogen detector developed by Battelle Institute.
CARBON AND HYDROGEN Carbonate and sulfate were determined in organic and inorganic samples by Edwards (57K)with a microprocessor controlled Leco CS-244 analyzer. Moriarty and Barclay (162K) described modifications to a Perkin-Elmer Model 240 elemental analyzer enabling them to determine organic carbon and carbonates in the same sample. A procedure for the routine analysis of organic and inorganic carbon in oil shale was developed by Puxbaum and Leyden (188K);the oil shale samples were decomposed in oxygen at 450', 550', and 900°, and the resulting COz was determined conductometrically after absorption in 0.02 M NaOH; the decomposition temperatures of the organic material (450') and the inorganic fractions (500' and 900') were established by temperature differentiated carbon analysis. In determining the true acidity of corrosive media in oil and gas wells where COz corrosion occurs, Bonis and Crolet (33K) built a pH meter that can be used a t high temperature and pressure and found that the acidity of production waters under well conditions is weaker than usually claimed. Espitalie et al. (65K) described an apparatus for the determination of total carbon in such a way that the organic and mineral carbon fractions can be distinguished; the apparatus has two furnaces for pyrolysis of the sample a t different temperatures in inert and oxidizing atmospheres. Total carbon in a water solution was determined by Kofanov et al. (119K) by conversion on a heated catalyst with separation of the conversion products by column chromatography, reduction of COz to CHI with hydrogen, and detection with a flame ionization detector. Total organic carbon was also determined by Creason and Kehoe (48K) using Beckman's latest TOC analyzer. The carbon content of microsamples of rocks and minerals was determined by Hansen (86K)by fusion of the sample with an oxidizing flux (PbC12,PbCr04, and glass) at 700', transportation of the combustion product through an oven with an oxidation catalyst packing, absorption of the COz formed in 0.01 N NaOH, and detection by the change in electrical conductivity of the absorbing solution. Sumitomo Chemical Co., Ltd. (225K), developed an apparatus and a method for the determination of total carbon and total nitrogen in solid and viscous samples; the sample is oxidized at 800-1100' in an oxygen atmosphere in the presence of a catalyst (CuO); the oxidation products are swept into a second reaction chamber packed with a reducing agent (Cu) and heated to 400-700°, and then passed through a gas sorption tube packed with MgC10, to remove moisture and (or) a sorbent for CO,; the mixture is then separated by GC on a column packed with activated carbon and the nitrogen and (or) C02is determined with a thermal conductivity detector. The measurement of carbon and oxygen isotopic ratios was done by Matsubaya and Etsu (153K) with a Varian MAT 250 mass spectrometer. The isotopic composition of carbon in petroleum and gas deposits was used as an indicator in petroleum and natural gas prospecting by Galimov (77K). Sowerby (219K) developed a method and apparatus for elemental analysis based on the combined measurement of y-rays from neutron inelastic scattering over a selected volume of the sample measurement of y-ray scatter over the same selected volume; the carbon content of coal samples was determined using this technique. The simultaneous determination of carbon, hydrogen, and traces of tellurium in organic substances which also contain oxygen was done by Anisimova and Klimova (16K) by titrating FeOz coulometrically, determining hydrogen by electrolysis of the water formed, and titrating excess alkali formed when COz is absorbed in a solution of barium perchlorate. Allain
PETROLEIJM
and Le Francios (13K) developed a rapid method for the simultaneous determination of carbon and hydrogen in petroleum products using a carbon-hydrogen analyzer with two IR-specific detectors in series to detect C and H after flash combustion in oxygen in a vertical furnace. Yu e t al. (264K) used porous cobalt oxide and a silver tungstate--magnesium oxide mixture as catalytic packings for the quartz combustion tube in the determination of carbon and hydrogen in organic compounds; the packing effectively reduces the interference jfrom combustion products containing sulfur, halogens, and metals. The distribution of carbon and hydrogen in the various structures of tars (from pyrolysis of delayed-coker gas oils and kerosenes, and mixtures of the tars with coker aromatic fractions) is reported by Shmirs et al. (209K) in a study of molecular structure by a combined IRNMR method. Musha and Nanata (165K) studied the detection and determination of soke functional groups containing active hydrogen in organic compounds and an 19FNMR technique. Krishnamurthy and DelViro (124K) found that sulfur interference in the determination of hydrogen concentration and stable isotopic composition (by combustion in sealed evacuated Vycor or quartz tubes folllowed by determination of hydrogen by mass spectrography) could be significantly reduced by heating the combustion tube a t 200" for 2 h under vacuum prior to reduction of the water to hydrogen gas. Gardner and Lee (79K) proposed a model for three-particle transmission and backscatter gauges; measurements of the transmission and backscatter responses for ten compounds containing hydrogen, carbon, and oxygen were reported. '
MULTIELEMENT
Chromatographic techniques accounted for the largest number of papers for researchers working with the determination of a combination of parameters. Conditions for the gas chromatographic analysis of mixtures containing hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide, ethylene, and acetylene were reported by Levchenko and Deeva (133K);these mixtures are products obtained from the carbonylation of ethylene. Carbon, hydrogen, and nitrogen were determined by Tuan et al. (238K) in small samples (>lo0 bg) of organic compounds by burning the sample in a stream of helium containing oxygen in the presence of a Cr20,-Ag,W04 oxidation catalyst; the nitrogen oxides formed were then reduced to elemental nitrogen an metallic copper and the gaseous products analyzed on a GDX-105 column. A method for the chromatographic analysis of complex mixtures containing hydrogen, oxygen, nitrogen, carbon dioxide, acetylene, chlorine, and hydrogen chloride was patented by Airapetyan (4K). Arefev et al. (18K) used a two-column chromatograph for the analysis of pyrolysis and methane conversion gases; oxygen, nitrogen, methane, hydrogen, and carbon monoxide were determined on a column containing 13X molecular sieves with argon as the carrier gas; ethane, acetylene, and carbon dioxide were determined on the second column which contained Chezasorb treated with triethylene glycol isobutyrate or Silochrome, with nitrogen as the carrier gas. Conditions for the chromatographic analysis of a reaction mixture in the oxidative chlorination of methane, ethane, ethylene, and propylene were reported by Aglulin and Dmitrieva (3K). Glass capillary gas chromatography with simultaneous flame ionization and Hall element specific detection were shown to be a valuable complement to conventional computerized GC-MS for the analysis of complex environmental samples by McCarthy et al. (140K). In a study of amino polycyclic aromatic compounds in solvent refined coal, Later et al. (131K) reported on the derivatization of an amine-rich SRC liquid fraction for selective detection and semiquantiflcation by capillary column GC using an electron capture detector and identification by mass spectrometry. Phenolics in coal gasifier condensate were determined by Sparacino and Minick (220K) by HPLC with low wavelength UV detection. Zabairova et aX. (2651(, 266K) discussed the GC determination of tetraethyllead and tetramethyllead, and De Jonghe et al. (52K) reported conditions for sampling of tetraalkyllead compounds in air for determination by GC-AA. Trialkyllead chlorides were analyzed by Estes et al. (66K) by high-resolution GC with an inert-solvent-venting interface for microwave excited helium plasma detection. Hughes and Fry (IOOK)
reported on the near-IR atomic emissions of sulfur and carbon in the argon inductively coupled plasma; they found the ICP-excited spectrum for sulfur to be markedly different from that reported for atmospheric pressure microwave-induced helium plasmas. The simultaneous analysis of polar and nonpolar compounds by gas chromatography was accomplished by Gates et al. (81K)using an arrangement of parallel columns and only one detector. Mathew (152K) used a GC method for the determination of trace amounts of some chloro- and nitrophenols by direct acetylation in aqueous solution; attractive features of this methlod include increased extraction efficiency, short extraction time, and small volume of organic solvent used. Researchers at the Talien Institute of Chemical Physics (229K) developed a GC detector for organic compounds containing nitrogen and/or phosphorus which used a rubidium silicate glass bead to increase the stability and service life of the detector. A new ;ugon ionization detector for the detection of carbon monoxide, methane, and ethane was discussed by Gawlowski and Niedzielski (82K). The carbon/nitrogen ration was determined by Franc (73K) by separating components of organic compounds in a gas chromatograph, decomposing them to carbon dioxide, watler, and nitrogen, and then absorbing the water; the amounts of carbon dioxide and nitrogen were detected with two detectors. The atomic ratio between carbon, hydrogen, oxygen, nitrogen, chlorine, bromine, and iodine in an organic halogen compound was obtained by Hara et al. (88K) by pyrolytic sulfurization gas chromatography estimation of the amount of halogen in the reaction residue and calculation of the weight percent using a correction factor and peak areas in gas and ion chromatograms. Steudel and Rosenbauer (223K)reported on a rapid separation of several structurally related cyclic sulfur-nitrogen compounds by HPLC using solvents of low toxicity and dletection by UV spectrometry. Skelly (215K) presented a method of separating inorganic and organic anions on reversed-phase liquid chromatography columns; he used conventional LC apparatus, UV detection, and an eluent which contained the octylamine salt of a mineral acid for the separation of several inorganic anions and the anions of several weak organic acids. Yonemori and Noshiro (262K) studiied a method for the determination of chlorine, bromine, phosphorus, and sulfur in organic compounds by oxygen-flask combustion and ion chromatography; bromate and condensled phosphate in the combustion products were decomposed lby alkali fusion, and this residue was dissolved in water and injected into the ion chromatograph. The microdetermination of sulfur and nitrogen was reported by Franc (72K) who pyrolyzed samples in an oven, transported the products in a stream of hydrogen through a quartz tu be packed with a platinum gauze heated to 950-1000", and detected the H2S formed in a glass tube filled with silica gel soaked with a 0.5% Pb(OA& solution; nitrogen was detected by the presence of a blue color on a cotton thread impregnated with an alcoholic solution of phenol and 2,6-dibromoquinome chlorimide. Alben (7K) used GC-MS to analyze the effects of chlorination on commercial coal tar leachate; samples were first leached and then extracted, and finally analyzed on either a capillary column coated with OV-17 and temperature programmed from 100 to 225", or a 30-m Supelco SE-54 capillary column programmed from 100' to 260"; MS data were obtained in the electron-impact and chemical ionization modes. Brodskii et al. (34K) used high-resolution mass spectrometry for the analysis of neutral nitrogen and sulfur compounds in a 35Oo-45O0 fraction of Volga-Urals petroleum. High-rosolution mass spectroinetry and low-voltage electron-impact ionization with interpretation by computer of the data collected was used by Albers (8K)in the characteriztion of nitrogen and oxygen heterocyclic compounds in high boiling mineral oil fractions. Albers (9K)also discussed the applications of electron-attachment MS and high-resolution M[S to the structural analysis of petroleum fractions in a study of soluble nitrogen-, oxygen-, and sulfur-containing substances. In a study of further developments, affirmation and use of methods for the separation of concentrates of soluble nitrogenand oxygen-containing compounds and polycyclic aromatic hydrocarbons from high- and nonboiling petroleum fractions ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
283 R
PETROLEUM
and coal byproducts, Neuman et al. (170K) separated basic nitrogen compounds from the vacuum residue of Kirkuk crude oil by cation exchange, cation exchange following enrichment in petroleum resins, and enrichment at interfaces with aqueous weak acids. Russel et al. (196K) outlined a procedure useful for the analysis of fossil fuels which employed MS-MS reversed geometry (mass-analyzed ion-kinetic-energy spectrometry). Bohatka et al. (32K) analyzed gaseous and liquid samples by mass spectrometry with a quadrupole spectrometer. Bodzek et al. (31K) used a variety of methods including TLC, IR field ionization, and high-resolution MS in the characterization of coal liquids. In an examination of the liquefaction products of coal, Schmal (203K) used thermogravimetry, NMR, and other spectroscopic methods for the identification of compounds extracted by the Mobil SESC successive extraction method. In a study of vacuum sublimination and solvent extraction of polycyclic aromatic compounds adsorbed on carbonaceous materials, Stenberg and Alsberg (221K) found that the yield was affected by extraction time, sample size, and the type of solvent. A solvent extraction scheme with total carbon determinations on the fractions obtained was used by Tobben et al. (234K) in the characterization of water-borne organic byproducts of in situ coal gasification. Nitrogen- and oxygen-containing compounds in shale oil malthmes were concentrated by FeCl,-clay complexation chrorirJ,ography by Shue and Yen (210K) and identified by GC-Mc Csikai and Al-Jobori (51K) developed an XRF method for the determination of sulfur and chlorine in crude oil for the case of overlapping peaks; the method is reported to be independent of the matrix composition. Koyano (122K) determined nitrogen, sulfur, and chlorine in naphtha, gasoline, kerosene, lubricating oils, and heavy petroleum oils by coulometric microtitration. Hoberg and Klein (94K) presented a method for the determination of polar components in nonpolar materials (water in coal, for instance) by electromagnetic waves. In an investigation of the oxygen and nitrogen groups in supercritical gas extracts of coal, Martin et al. (148K) demonstrated that NMR techniques provide viable alternatives to existing titration techniques for determining phenolic hydroxyl and basic nitrogen groups. Raith and Lanik (19OK) determined the distribution of sulfur and nitrogen compounds in fractions of nine Middle East crude oils and reported an increase in sulfur content with an increase in the fraction boiling point. Nadkarni (166K) used an oxygen bomb combustion technique for sample preparation before determining a number of volatile elements in coal, shale oil, and other organic materials. Mamchur (146K) used the isotopic composition of carbon and sulfur as indicators for petroleum and natural gas prospecting; he found that the presence of hydrocarbons was also indicated by the presence of native sulfur deposits. Maklakova and Osadchi (145K) determined halogens, phosphorus, and sulfur in organic samples by mineralization in heptane vapors in the presence of powdered aluminum, disand complexsolving the products formed in 0.15 N "Os, ometric G Iration of aluminum with PAN; mineralization temperat :xi's were reported for each element determined. Verciei i t3K) described a new tool for studying heavy end of petroleum and bitumens which included programmed pyrolysis, programmed combustion, and specific nitrogen and sulfur detection. In the simultaneous determination of sulfur and chlorine in petroleum products, Sliepcevic and Sprajc (215K) combusted the sample over pieces of quartz heated to 950' to 1000° and trapped the products in aqueous hydrogen peroxide; chloride was determined by titration with silver perchlorate and sulfur by titration with barium perchlorate in aqueous 80% isopropyl alcohol. Nitrogen and sulfur in kerogen ozonization products were determined by Etorkov (58K);oil shale kerogens were ozonized a t 20' in acetic acid and the water soluble products were esterified to give a fraction insoluble in diethyl ether which contained practically all sulfur and nitrogen originally present in the sample.
MISCELLANEOUS A portable apparatus for the colorimetric determination of dissolved gases in oils was patented by Furukawa Electric Co., 284R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
Ltd. (76K). Hue (99K) determined the permeability of protective oils to sulfur dioxide and water vapor by electrical conductivity, titration, and colorimetry, and found that the conductivity method gave the most accurate results. High molecular weight compounds containing heteroatoms were found to be major constituents of two groups of bituminoids isolated from the Chaganskof shale oil deposit of the Orenburg region in a study by Klesment et al. (118K). Tameesh et al. (230K) used GC to determine trace levels of N-formylmorpholine in water and hydrocarbons. Tomkins et al. (237K) described two methods for the determination of benzo[a]pyrene in petroleum substitutes: a conventional method and an abbreviated method for the isolation of the compound, with detection by GC, HPLC, or spectrofluorimetry. Coleman and Boyd (45K)reported on the determination of hydroxyl-containing compounds in synthetic fueb by ?Si NMR. Balya and Farrah (23K) used a column chromatographic procedure for the determination of polychlorinated biphenyls in certain industrial oils, while Ogata et al. (176K) used a GC method. Albro and Parker (11K) used GC-MS combined with prefractionation in a general approach to the fractionation and class determination of complex mixture of chlorinated aromatic compounds. Fialko et al. (69K) determined zinc dialkylphosphorodithioates by ion exchange chromatography and potentiometric titration of the eluate. Plaza (181K) used high voltage paper electrophoresis for the determination of zinc dialkyl- and diarylphosphorodithioate lubricating oil additives. Coe et al. (44K) used GC-AA for the determination of tricarbonylmethylcyclopentadienyhanganese at nanograms per cubic meter levels in air samples.
REVIEWS In addition to the parallel review to this one (Latham and Thomas (132K))there were a t least 13 other review articles published, either as journal articles or chapters in books. Kan et al. (109K) published a review with 58 references covering 1975-1980 on organic elementary microanalysis including halogens, sulfur, and phosphorus. Honma (98K) wrote a review with 34 references covering 1974-1979 on organic elemental analysis including carbon, hydrogen, and nitrogen. Isotopic composition of carbon, oxygen, and sulfur in terrigenous and carbonate rocks, petroleums, and stratal waters of Siberia were covered in a review with 153 references by Golyshev et al. (84K). Feuerhelm (68K) discussed the determination of carbon distribution in mineral oil and coal products including comparison of methods similar to practical ones in a review with four references. The composition of hydrocarbons, sulfur, nitrogen, and oxygen compounds, and nickel and vanadium porphyrins in petroleum crudes is reviewed by Elliott and Melchior (62K) with 34 references. The elemental analysis of kerogens (carbon, hydrogen, oxygen, nitrogen, sulfur, and iron) is the subject of a review by Durand and Monin (56K) with 48 references. Attar (20K) discussed novel methods of coal sulfur analysis and sulfur groups in coal and their determinations. A review with 26 references by Thompson (231K) was on the identification of sulfur compounds in petroleum and alternative fossil fuels. In a review with 72 references on the determination of moisture content in various materials, Kim and Ro (115K) discussed the applicability of various methods, including dehydration by heating, drying at ambient temperature, use 01 absorbents, distillation, extraction, and gas chromatography. The determination of carbon oxides in air and other gases is discussed in a review with 71 references by Volberg and Pochina (247K). Volborth (248K)reviewed the use of neutron activation analysis in accurately monitoring elements in liquefaction, gasification, solvent refining and in situ combustion of coal. Nitrogen compounds in petroleum and methods for their separation and analysis were covered in a review with 28 references by Boduszynski et al. (30K). In a review with 77 references on element-selective detection for chromatography by plasma emission spectrometry, Carnahan et al. (39K) discussed the application of this method to a wide variety of samples and especially to metal ions and elements not traditionally determined by atomic spectrometry. The chemical properties and methods for analysis of halogenated biphenyls, terphenyls, naphthaleins, dibenzodioxins, and related products are discussed in a review by Rappe and Bauser (191K).
PETROLEUM
In a review of analysis of complex industrial samples by gas chromatography, Lu and Li (137K) discussed past activities concerning selected industrial analytical problems, including preparation of pure gal3 mixtures for calibration, catalytic conversion of ester and pyridine samples to COz, and identification of hydrocarbons in shale oil and petroleum fractions and analysis of wine, eight references. Engelmann (64K) reviewed nuclear methods for the isotopic analysis of carbon, nitrogen, and oxygen, including activation by thermal or fast neutrons, charged particles, and y photons, and direct observation of nuclear reactions produced by low-energy charged particles, eight references.
ANALYTICAL AND PROCESS INSTRUMENTATION J. W. Loveland and C . N. Whlte Sun Tech, Inc ., Newtown Square, Pennsylvania 19037
In this year’s review, we have used the section headings previously used in the ‘1981 review (131L). Because of the frequent reference to familiar techniques and terminology, we are again using abbreviations to aid the readter in his perusal of the text. Abbreviations recommended by Chemical Abstracts Service will be used and are not itemized here. Other abbreviations are as follows: AA, atomic absorption; AF, atomic fluorescence; IR, infrared; UV, idtraviolet; MS, mass spectrometry; GC, LC, GPC, PC, TLC, gas, liquid, gel permeation, paper and thin-layer chromatography, respectively; GCD, GC distillation; XRA, XRD, XRF, X-ray absorption, diffraction, and fluorescence, respectively; NMR, nuclear magnetic resonance; TCD, FID, FPD, PID, ECD, HECD, thermal conductivity, flame ionization, flame photometric, photoionization, electron capture, and Hall electrolytic conductivity detector, respectively; P, microprocessor; RSD, relative standard deviation; vis., viscosity; psig, pounds per square inch gauge; o.d., i.d., outer and inner diameter; in., inch; HC, hydrocarbon(s); st. st., stainless steel; PCB, polychlorinated biiphenyl; PAH, polynuclear aromatic hydrocarbons; FIA, fluorescent indicator analysis; QC, quality control; RI, refractive index. In preparing this review, we noted increased activity in some areas and less activity in others. In the area of laboratory analysis, GC is still the most widely reported analytical technique, followed by LC. No other analytical technique accounted for very many papers. There was a notable lack of papers on elemental analysis. In both the Process and Laboratory Instrumentation area, there is an increasing use of microprocessors and minicomputers for automatic control of GCs, MS, and other analyzers. Process Instrumentation aimed at energy savings is very apparent as are various aspects of pollution. The following are recommended for a general reading and cover a broad spectrum of techniques and/or applications.
IREVIEWS Laboratory. The biannual review of analytical chemistry in the petroleum industry included the following: crude oil, Trusell (214L); fuels, gaseous and liquid, Beardsley (15L); physical properties, Sudbury (207L);metals in oils, Fabec (62L);nonmetal elements and compounds, Latham (125L); analytical and process instrumentation, Loveland and White (131L);solid and gaseous fuels, Schultz et al. (189L). Ball (11L) gave a brief review of the characterization of heavy ends of petroleum, including asphaltenes, asphalt characterization, crude oiils studied under API Project 60 and new crude oil sources. Tissot (211L)surveyed recent studies of the heavy components of crude oils and coal liquids, including the solubility, molecular weight, polarity, composition, mol. structure, viscosity and Ni, V, and S content of asphaltenes. Constantinides and Lomi (44L)surveyed different methods for separating rind characterizing asphalts, as well as correlating asphalt characteristics with road building performance. Kabulov and Zalyalieva (114L) published a literature survey on the analysis of crude oils and petroleum products by gel chromatography, with particular attention to fractions boiling above 400 “C. Applications of GPC to analyze high mol. wt. petroleum compounds were surveyed by Popov et al. (17410. GPC provides a rapid method to determine mol. wt. distribution (which can be used to monitor compositional variations of such materials as road asphalt), as well as to study
the chemical structure of asphaltenes and maltenes and the distribution of heteroatoms and metals (V and Ni). Abbott (1L)surveyed published LC data on the sepn. of liquid fuels into saturates, aromatics, resins and asphaltenes for char,acterizing crude oils or monitoring refinery processes. An aminopropyl bonded phase gives a single saturate peak and aromatic peaks in sequence of condensed ring number, while resins are backflushed. A cyanopropyl phase was used to separate asphaltenes, aromatics, and resins in bitumen and crude oils. LC can be used to separate PAH for characterizing fuels and fuel traces i~nair and water. Diamino columns appear promising for characterizing PAH mixtures. Lamb et al. (122L) reviewed literature on organic compounds in urban atmospheres published between 1959 and 1979. The data include pollutants, occurrence, reactivity, toxicity, collection systems, and analytical techniques. Lipkea et al. (129L) reviewed the physical and chemical character of diesel particulate emissions. Topics covered are phys. and chem. prop. and phys. and chem. characterization. Also included is work on PAH fram diesels at Michigan Technical University. Articles (183L)presented at the 4th European Conference on Anal.Chem. “Euroanalysis IV” at the University of Helsinki in 1981 covered the simultaneous detn. of trace metals Pb, Zn, Cu, Ni, Cd, and Co in water by capillary GC of metals chelates, the use of IC for environmental control, the use of GC/MS methods, the analysis of phenol in air using a thinlayer adsorbent, and the identification of marine oil by a new vapor-phase UV method. Another article (37L)discusses the availability of a new standart reference material for priority PAH pollutants from the U.S. NBS. The certificate of analysis for the reference material SRM 1647 lists concentration in pg per mL in acetonitrile of 16 PAH’s. UV absorption data between 205 and 600 nm are supplied. Majors (137L)reviews the multidimensional aspects of HPLC and emphasizes on-line techniques in which the primary separation is by HPLC and the secondary is by HPLC or GC and notes applications to the detn. of PAH in smoke, phenols in water, antioxidants in oils, etc. Some 49 references are given. De Walle et al. (51L)reviewed 1980 literature on the cletermination of total organic compds. in water, including cletergents, surfactants, HCs, pesticides, chlorinated HCs, and naturally occurring contaminants. Fishman et al. (68L) published the 19th review of water analysis literature from October 1978 through September 1980. This review covers methods for organics (light, aromatic, and polycyclic aromatic hydrocarbons, phenols, halohydrocarbons, pesticides, detergents, acids) and various elements and ions n(Pb, SO2-, S2-, NO3-, NOz-, NH3, Organic N, CN-CNS-). Horlick (97L) reviewed 1980-1981 literature on AA, AF, and flame spectroscopy. Topics covered include instrumentation and measurement, sampling, magnetooptical phenomena, laser-enhanced ionization spectroscopy, electrothermal atomization, hydride generation, combined GC/AA systems, and applications (metals in lube oils, P b in gasoline/water mixtures, fluorescence in kerosene-and gasoline-air). Ma et al. (132L)reviewed October 1979 to September 1981 literature on organic elemental analysis. Areas covered included petroleum, and trace analysis of As in petroleum by colorimetry. Smith amd Patterson (197L)reviewed Decembler 1979 to November 1981 literature on the detn. of elements and groups in org. compds., including new methods for detg. aromatic HCs. Cosniacini and Berti (45L) discussed the objectives, tasks, responsibilities, and organizational structures of six major international and six Italian national standardization organization institutions, including their work on quality, compn., analysis, and testing methods for petroleum and its products. Risby et al. (182L)reviewed the 1980-81 literature on GC, including column technology, detector types, qual. and quant. anal. sampling methods and applications. The latter include sepn. of PAH, retention time for n-alkanes on a series of stationary phases, and detn. of Pb(Et)( in gasoline. Jaworski (108L) reviewed the use of LC for analysis of HCs in petroleum, with special reference to column prepn. and the use of reversed-phase systems. Hagnauer (87L) reviewed the Dec 1977-Nov 1981 lit. on size exclusion (gel permeation) chromatography, including the anal. of cyclic HCs, petroleum, and lubricants. Sherma and Fried (195L)reviewed literature from December 2, 1979 to December 7, 1981 on TLC and paper chromatography. Applications covered include hydrocarbons. ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
285 R
PETROLEUM
McDonald (134L)reviewed IR spectroscopy, including trends, books, reviews, instrumentation, methods, and applications. The latter include quantifying soot in piston deposits, crankcase oil insolubles, neutralization of corrosive acids in engine oils, ethanol content of gasoline, analysis of automotive exhaust, and petroleum-contg. wastewaters. Wasson (229L) reviewed NMR literature from July 1979 to July 1981. Applications covered include the analysis of crude oil and petroleum products. Wehry (231L) reviewed literature on mol. fluorescence, phosphorescence, and chemiluminescence for 1979 to 1981. Topics include fluorometric detection of PAH in LC sepns., low-temp. luminescence, and synchronous luminescence (or phorphorescence)/excitation-emission matrix methods in oil identification, and detn. of N in petroleum. Wendlandt (233L) reviewed thermal analysis literature for January 1980 to November 1981. Applications of various thermal techniques include evolved gas analysis to determine the thermal stability of oil in Nz or 0 and a .TG method to determine the country of origin of crude oil (Alaska Prudhoe Bay oil and others). Process. A variety of reviews relating to the use of process analyzers in refineries and petrochemical plants were issued over the past few years. Black (2OL)reported on studies performed on a refinery computer model showing increased earnings for a number of refinery units that installed various analyzers. For a 670000 bbl/day refinery, one distillation analyzer on the crude unit would annually net $220 000 and 4 units would net $535 000/year. Examples were also given for use of a pour pointer on No. 2 fuel oil, a Reid vapor press. unit on gasoline, and a viscometer on a vacuum crude unit. Graphs are available for extrapolating the effects on earnings for refineries I 200000 bbl/day. Guelfi (84L)discusses Shell’s generalized procedures for installing analyzers, method of sample prep, and analyzer protection. Sampling and sample conditioning are given equal importance to the analyzer itself. Dubois (55L)reviews the use and value of 54 product quality analyzers in a refinery which treats 8000 to 12 000 tons/day of crude and has a production capacity of 3.4million tons/year of refined products. The review covers the special design and performance requirements of the analyzers, the procedures used to check the results vs. the laboratory, the maintenance service, and coordination of responsibilities of all involved. An average on-stream availability of 95% was achieved over the past 5 years which is probably above average when compared to most refineries. Bailey (8L) in a survey of some on-line analyzers indicates that these instruments now tend to make on-off decisions and permit adjustments in chemical and refining processes. Examples were given such as the 973 Miran IR analyzer (Foxboro Analytical Co.) which provides a continuous digital readout of some specific component in a gas or liq. such as CO, C02,or CH4 in methanol mfgr. and Westinghouse Electric Corp.’s MP-based TC910 system for analyzing CO and 02,which can control fuel/air ratio based on changes in CO or O2 stack content. Frant and Oliver (71L) discusses design considerations for in-plant analyzers including that for extreme and harsh conditions in refineries including S cpds., HC’s, and smoke. Installations in sulfuric and nitric acid plants and gasoline storage terminals are covered. Safety considerations including the NEC (National Elect. Code) hazard designations for combustible material are given. Alexander (5L)gave an overview of on-line instrumentation. He covers the tremendous increase in instrument capabilities due primarily to modern microcomputer technology, sampling and measmt. techniques, factors affecting instrument selection including costs and maint. requirements, adv. of direct, noninvasive methods which do not require sampling, over indirect methods, sensor, data transmission and sampler types for instruments from U.K. companies for measmt. of H2S, HzO, oil in water, density, temp., Oz, C 0 2 , NO4, and SOz. Verdin (219L)surveyed the nature and application of on-line monitors for safety, quality and pollution control, the use of ~ P ’ with s anal zers, various type sensor methods including contact metho& (filaments, etc.), radiation methods (IR, etc.), and separation methods (GC, etc.), sample systems, and calibration and analyzer safety requirements. Shaw (193L) discusses the current state of process instrumentation. Based on an IC1 study about 50% of total instrument support was devoted to proc. measmts. and analytical equipment incurred 20% of instrument maintenance. A breakdown of total maintenance for each type sensor and priority problems are 286 R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
provided. New trends in data extraction from sensors and in self-diagnostics are noted. Medlock (147L) covers the past trends in instrumentation and control systems; the present usage of systems for the measurement of variables such as press., temp., flow, level, and analytical quantities and the probable future trends in instrumentation. Bajek (9L) described the improved efficiency of a reformer by using new on-line monitors that provide tighter control and minimize dependency on lab. anal. The refiner conserves both feedstock and energy and increases savings on gasoling blending since octane quality is known and controlled. A discussion (104L) is given which covers a Frost and Sullivan study which forecasts a rise in demand for on-stream process analyzers by 15 and 10%/year in U.S. and Europe, respectively, with the petroleum and petrochemical industries among the major markets. Tsuge (215L) provides a review with 65 references for various types of interfaces and applications of on-line LC and MS systems. Wilholm (237L) reviewed several different analyzers as to their construction, method, and use for continuous analysis for process control. The operating principles of various sensors and transducers were discussed by Hall (88L) and included liquid density, moisture in a gas, pH, conductivity such as the electrodeless type, 02, and CO detectors. Sampling systems for process analyzers and the consequences of improper design of accuracies was the subject covered by Nichols (154L). Subjects discussed were sampling system hardware such as tubing, piping, valves, pressure regulators, flow and temp. controllers, filters, sample driers, strippers, and pumps. Also covered were acceptable materials of construction for widely differing chemicals, multistream sampling design, sample point selection, sample returns for hazardous substances, and compliance with the National Electrical Code. Examples were given for flue gas process analyzers for combustion control and a monitor for oil and grease in effluent wastewater. Jutila (113L) discussed the limitations often associated with sampling of process streams for automated, in situ, and manual systems, work on sampling technology to offset problems associated with sample withdrawal, transport and conditioning, such as the development of J. Autotrol of a sampler for crude oil transfer pipelines that draw samples continuously at 1500 psi and L. Roofs work on a high-temp. sampling system for LC in which fluids are cooled by dilution. The paper provides 37 references for the reader.
ELEMENTS, COMPOUNDS, AND COMPOUND TYPES Laboratory. Several papers were published on elemental analysis. An Institute of Petroleum (IP) sponsored correlation program to evaluate IP’s draft AA method on ten different samples of premium and regular gasolines contg. Pb(Et), or Pb(Me), (0.1-0.5g/L) showed that AA is comparable to Iodine Monochloride Method for detg. total P b in gasolines (169L). AA repeatability was 0.026 g/L, reproducibility was 0.008-0.038 g/L with concns. of 0.1-0.5g/L. The method is not affected by variations in gasoline composition and is instudied dependent of P b alkyl type. Boorn and Browner (22~5) the effects of 30 common org. solvents used in ICP emission spectroscopy (detn. of wear metals in used lube oils and trace elements in various other petroleum products) as a function of radio frequency power, various nebulizer parameters, and the relative volatility of the solvent. Wolters (241L)described a computer controlled simultaneous (ICP) spectrometer which can determine up to 48 elements in oil within 1 min. All elements, except halogens, in organic fluids can be detd. Sample prepn., including diln. for uniform viscosity, is automated, and up to 40 samples can be analyzed without operator intervention. Christensen and Agerbo (42L) used energy dispersive XRF to determine S and heavy metals in crude oil and petroleum products. No sample prepn. was required. Analysis of two residual fuel oil reference stds. showed good agreement with the certified values. Comparison of results by this method with wavelength-dispersive XRF and neutron activation analysis showed that the three methods agreed within 1-3 std. deviations for a crude oil and various fractions of a desulfurized feed for S, V and Ni. Orav et al (158L)used GC (0.25mm X 100 m stainless steel column coated with 1,2,3-tris(2-cyanoethoxy)propane)to separate the cis/trans isomers of Clo to CISn-alkenes at 60
PETROLEUM
"C and 80 "C. Results were compared with those obtained for columns with less polar stationary phases. Sojak et al. (198L) studied conditions for the sepn. of mixts. of all 60 isomers of ClS-Cl8 linear alkenes in the presence of the corresponding n-alkanes. Specially prepared soda-lime glass capillary columns were used. Problems associated with sepn. and identification are discussed and chromatograms and retention-index data are presented. Ghaderi et al. (77L)used chemical ionization in FTIR MS to distinguish between 1-pentene and cis-2-pentene with methyl vinyl ether as a reagent ion. D20was used as a reagent ion for isotopic exchange to count active H in benzene and tetralin. Langhorst (124L)found that the PID sensitivity of org. compds. sepd. on several GC columns depended mainly on C-number, functional groups and bonding type. PID sensitivities (normalized against benzene) increased in the order: alkanes, alkenes, aromatics, noncyclic compds., cyclic compds., nonbranched compds., branched compds. Musaev et al. (152L) identified tricyclic satd. HCs in (U.S.S.R.) Naphthalan crude by GC and GC-MS analysis of the narrow fractions obtained by thermal diffusion, followed by thiocarbamide complexing hom a 180-250 "C straight-run Naphthalan distillate which contd. 33.6,45.5, and 18.6% mono-, bi-, and tricyclic HCs. A total of 15 compds. were identified. Relative GC retention tiimes and characteristic MS peak parameters of each compd. are given. Matsunaga and Kusnyanagi (144L) compared seven LC column packing for the sepn. of aromatic and polar compds. in fossil fuel liquids. Retention times were detd. for 13 aromatic compds. (including toluene and pyrene), 16 polar N compds. and 9 phenolic compds. in columns packed with silica, alumina, styrene-divinylbenzene copolymer, and Nucleosil NOz, NH:!, CN, and SA. The same authors (145L) described a rapid method for detg. S compds. in lube base oils by palladium chloride impregnated TLC on vertical silica gel plates. A clear sepn. of sulfides from thiophenes and from HCs. A model mixt. of n-dodecyl, diphenyl, benzylphenyl, and pentamethylene sulfides with 2,3 dehydrobenzothiophene, benzothiophene, dibenzothiophene, HCs, and N compds. was used. Prep scale TLC of the base oils and an MS study showed the presence of mono- to tetracyclic sulfides as major components. About 50% of the S compds. in the base oils were sulfides. Paukku et al. (165L) studied the chemical compos. of the polar components in resin-asphaltene petroleum compds. (RAPC). A resin-asphaltene conc. from a residual asphalt fraction of Arlan crude was sepd. into asphaltenes and maltenes by Soxhlet extn. with n-hexane, and both were extd. with either dimethylformamide or a 4:l EtOH-CHC13 mixt. to isolate polar compds. The four fractions of polar RAPCs were then studied by a combination of physicochemical and spectral techniques to determine mol. wt., elemental compos., and structural-group characteristics. Rawat and Prasad (177L)determined the trace solvent content of waxes and lube oils obtained from solvent dewaxing with methyl ethyl ketone (MEK)/toluene mixts. by refluxing for 1 h and analyzing the distillate (63-90 "C) by GC. Samples contg. 30-200 ppm by wl,. of MEK and toluene showed errors from 5.6 to 11.2%. A significant increase in the number of papers on HC type detn. was noted. Ury (216L)analyzed 40 test gasolines and 10 com. gasolines with B wide range of API gravities, Reid vapor pressures and octane nos. to determine HC types by means of GC. The aromatics were sepd. from saturates and olefins on one packed column (35% N,N-bis(2-cyanoethyl)formamide on Chromosorb P), and olefins were sepd. from saturates on a second packed column (CuS04on purified silica gel). The FID detector output was fed to three parallel channels, each dedicated to a HC type, for which each was calibrated. Some loss of ciaturates occurred above n-undecane; recovery of olefins was not quantitative even for low boiling compds. Results compared well with those from FIA analysis, but were obtained faster and were more reproducible. Beshai used LC to determine HC types in synthetic and George (19L) fuel naphtha and samples from hydrocracking Lloydminster and Boscan heavy oils. Saturates, olefins and aromatics can be detn. in a 2.5-pL sample of 200 "C initial b. pt. naphtha fraction in 20 min. Detectors used were RI (all compds.) and UV (aromatics). Some sepn. of mono- and diolefins was obtained. The method, which can be fully automated, requires less operator involvement and results are not dependent on
analyst interpretation as with the standard FIA analysis. The latter method gave erroneously low olefin contents when iapplied to the hydrocracked products. Durand and Persin (5;7L) developed a rapid method for det . PONA in catalytic reformate feedstocks. This is the uatoni et al. procedure modified to include the detn. of naphthenes. Aromatics are first sepd. by atmospheric LC on silica (ASTM D-936) and the aromatic content calcd. by comparing the LC peak areas of the initial and dearomatized sample. A variation of ASTM D-2159 is then used to det. the naphthene content in the aliphatic fraction tal within +2% (LC on silica with ARI detector and a low RI eluant). The technique is based on the different RI/density correlations for the two HC classes. The method is as accurate as the conventional MS technique, but is more cost effective. George et al. (75L)used GC and quadrupole MS for identifying HCs present in a fraction from synthetic fuel naphtlha. The following were obtained: complete distribution information, S content, saturates, olefins, and aromatics, and identification of individual HCs. The fraction studied covered C&13 and was isolated by prepscale GC. Sample size is 30 pL and analysis time is 90 min. Data are given for five samples from thermally hydrocracked Athabasca bitumen. Semrau (19OL)described a simplitled and improved procedure for detg. total paraffins, naphithenes, and aromatics or carbon number fractions of petroleum distillates boiling up to 200 OC and having a maximum olefin content of 1%.The method is based on a network of GC columns and FIDs. Ozubko et al(1611L) compared MS, NMIR, and FIA for the determination of HC type in three petroleum fractions boiling below 200 "C. RLS is preferred for light fractions free of dienes, olefins, and heteroatoms. NMR is less affected by interferences when used for aromatics, olefins, saturates, and H content. FIA appeared to give incomplete separation. Feuerhelm (6715) compared aromatic C detns. in 17 lube oils by IR/n-d-M analysis and 13C NMR spectroscopy. A nonlinear correlation was obtainled with increasing percent (%) aromatic C, the IR method gave increasingly high values. For the analysis of gasolines (50-180 OC) by NMR, MS, and FIA, a good correlation was obtained between NMR and FIA on mononuclear aromatics content, but deviations were observed for the paraffin content obtained by all three methods. Schronk (187L)used probe microdistn. and 70-eV MS to analyze seven fractions of a 535-675 "C Wilmington, CA crude oil distillate. Results were as follows for various hydrocarbon fractions: saturates, 508-610 (C37C&), Z no. peaks -4 to -16; monoaromatics 550-626 (C41-CtL8), -18 to -24; 3 GPC subfractions, monoaromatics 456-870 (C2,-C6 ); -18 to -22; diaromatics 488-596 (C37-C44),-20 to -30; pofar polyaromatics 450-800, including S and N cornpounds. Schronk et al. (188L)studied a monoaromatic GPC fraction from the same Wilmington crude fraction discussed in (187L)(535-675 "C), obtained by an API project method. MS spectra generated by 70 eV and 10 eV electron impact were very similar to iepectra generated by field ionization MS. A quant. distribution of the 400-776 molecular weight components in the monoaromatic GC fraction was calculated. Srivastava (202L) measured the % aromatic C's in crude petroleum quantitatively using 13CNMR spectroscopy. The sample studied contained about 10% (vol.) of Nahorkaitia (Indian) and 30% (vol.) of Basrah (Middle Eastern) crude oils in CDC13. Gillet et a]. (7%) used previously derived structural parameters involving quant. 13C and proton NMR spectroscopy to estimate the aromatic, aliphatic, and naphthene content of five heavy ends derived from the same Arabian Li ht crude. The fractions were as follows: gas oil (150-388 O R , vacuum distillate (327-535 "C), vacuum residuum (>535 "C); pentane-ppd. asphalt from vac. resid., deasphalted soh. from vac. resid. Aromaticity increased regularly from light to heavy fractions, constituting 18% of the gas oil and 53% of the asphalt. The ratio of aliphatic to naphthenic C olecreased from 7.2 1 to 2.5/1 going from the gas oil to the vacuum residue. opiov et al. (173L)studied the mol. structure compos. of residual fractions obtained from the high-resincontent Romashkino (U.S.S.R.) crude. Sepn. was obtained by multistage Soxhlet extn. of a straight-run asphalt fractbon (660 mol. wt.), followed by chromatographic sepn. of silica gel. Each fraction was characterized by IR and ESR spectra and GPC. All structures are pericondensed naphthenno-aromatic systems contg. 4-6 rings and alkyl substituents with a max. of 2-3 C atoms. Poirier and George (171L)sepd. and identified
s
d
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
287R
PETROLEUM
olefins in a virgin Lloydminster naphtha (30-200 "C) (I) and in naphthas from thermally (11) and catalytically (111) hydrocracked Lloydminster heavy crude. The olefins were hydroborated, the resulting alkanols were separated by elution on alumina, and identified by GC-MS. Olefin contents were: I, 0.5%;11, 26.8% (mostly C7-Cl0); and 111, 19.5% (mostly C5-Cd. Several papers appeared on PAH. Tomkins et al. (213L) used LC to separate and identify benzo[a]pyrenes in two crude petroleums, two coal oils, and two crude shale oils. A two-step process was used: semi-prep scale sepn. (Partisil M9 10/25 PAC column, 1:l methylene ch1oride:hexane) followed by analytical sepn. (Zorbax ODs-BP column, 25:75 water: acetonitrile). Recoveries exceeded 95%, precision was f6%, and detection limit was 2.5 pg/g of crude sample. Ishii and Takeuchi (107L) sepd. aromatic and PAH by using an open tubular capillary LC column (30-60 m X 3-20 m coated with chemically bonded octadecylsilane) and a packed column (8.8% styrene-divinylbenzene copolymer) with a UV detector. The HC mixture contained 0.0028 to 3.3% of benzene, naphthalene, biphenyl, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene. Solvent used was acetonitrile/ water:capillary 4060, packed column 5050,45:55,4060. The use of MS with capillary LC is also discussed. Gore (82L)used matrix isolation site selection fluorometric analysis to determine benzo[a]pyrene and 1,5-dihydroxynaphthalenewith detection limits of 1and 50 ng, respectively. Maple and Wehry (140L) used the matrix isolation technique with polarized laser-excited fluorescence photoselection to resolve mixtures of pyrene/chrysene (270 nm excitation) and benzo[a]anthracene/pyrene. Samples were deposited with a Knudsen effusion vacuum sublimation apparatus on a gold-plated surface at 15 K. Hershberger et al. (93L)were able to separate spectrally and identify benzo[a]pyrene (BaP) and benzo[e]pyrene using LC equipped with a video fluorometer detector. Perylene calibration curves were linear at 1.16 to 116 ng with a detection limit of 1ng. Quant. analysis of a shale oil showed a BaP content of 38 f 2 ppm va. 29 ppm from GC/MS analysis. Stenberg and Alsberg (205L) used vacuum sublimation and solvent extn. of PAH adsorbed on carbonaceous materials prior to GC analysis in order to separate the PAH from highly sorptive matrices. Vacuum sublimation (300 OC, 0.1 mmHg) gave yields dependent on the vapor pressure of the component at a given temp. and pressure. Solvent extn. was tested with acetone (I), dichloromethane (II), methanol, and cyclohexane. I and I1 gave best extn. yields, with I1 being as efficient as vacuum sublimation. However, the latter showed evaporative losses for 3- and 4-ring PAHs. Battiste et al. (14L) detd. EtOH in gasoline with IR spectrometry by spectral subtraction and measurement of the absorbance of the resulting EtOH spectrum at 880 cm-l. Calibration curves were linear. Analysis of three samples of com. gasohol showed good agreement with GC analysis of aq. exts. of the gasohols. The method is applicable to any type of gasoline and is specific for EtOH. Several papers were published concerning compounds containing other elements in addition to C and H. Reim and H a m (179L) used reductive pyrolysis with differential pulse polarographic detection to det. total S in HC samples containing >5 pg/mL of s. Differential pulse cathodic stripping voltammetry (DPCSV) was used for samples containing 0.10 g/gal. may be diluted, or a higher level calibration curve may be used in lieu of dilution if the curve is linear and accurate based on controls. Process: GC, LC, IC. Lim et al. (128L)reported on the use of a process GC with a FID. The optimum column configuration and GC program was used on C1 to C4 HC and the min. detection concn. was 0.2 ppmv and the reproducibility was 2%. Springer et al. (2OOL)report on the use of a new automated BTU meas'g. system using GC methods. Its use for custody transfer of natural gas is discussed. Mukerji (151L) reviews specifications used for various aspects of on-line GC systems for plant process control. Items covered were system design, piping and elec. requirements, sampling systems, analyzer shelters, documentation, drawings, and inspection and testing. Glajch and Schunn (79L) discuss the use of glass capillary GC for rapid on-line analysis of low mol. wt. HC's.
PETROLEUM
The gaseous or vaporized samples were injected via heated gas sampling valves of
