H z S 0 4and ashing. Nowak (545) included analyses for antimony and lead with cadmium using flame and heated-vaporization AAS. Several Atomic Absorption Reviews were written by Lush (455) who compiled 78 references to trace element analysis. Lang et al. (405)developed a critical evaluation of 220 references. They stressed the need to check the correctness and accuracy of methods. Vigler and Gaylor (835) grouped abstracts of papers presented at the 166th National Meeting, American Chemical Society, according t o Society Divisions. The importance of nickel and vanadium porphyrins continued to hold attention as Vavrecka et al. (815) used these compounds for calibration standards for direct determination of the metals. They reported closer conformation to the Lambert-Beer law than oxide standards; however, the accuracy of vanadium is affected by the vanadium bonding and matrix so a standard addition technique was recommended. The standard addition technique was also used by Everett et al. (145) to reduce matrix effects at 1 ppm levels. For oils containin 0.01-0.1 ppm, the vanadium was extracted with 2 M HC1. h a y and Presley (495)claimed a saving of time by charring and atomizing as a C C 4 solution in a graphite tube. Grey (235)also reported on the determination of trace nickel and vanadium in petroleum. Viscosity differences affect the determination of trace iron in crude oil so Ibrahim and Sabbah (305) recommended matching standards and unknowns. Everett, West, and Williams (145)used a carbon-filament reservoir for the detection of tin at 0.1 ng and less. Hz and Ne were used as sheathing gases and results were given for both aqueous and organic media. Walker (845) reported on selenium and Grey (225, 235) on nickel, vanadium, cobalt, and molybdenum. Moving away from the usual reporting of one or two elements by atomic absorption, Vigler and Gaylor (825) determined 23 elements in the range 1ppb to 5 ppm by ashing after absorption on magnesium or potassium sulfonate and solution in dilute acid. A graphite capsule-flame atomizer was used by Katskov et al. (355) to determine 27 elements. Lower limits of detection are 0.001 to 0.1 ppm. The analysis of ten samples for ten elements took 4.5 h. Fletcher and Collins (215)determined 12 elements in oil field brines using the method of additions to overcome large matrix differences. For brines where concentrations of elements are low, they recommended a graphite furnace. Detection limits for 17 elements were listed by Kaegler (315) outlining some problems with the direct analysis of organic matrices. Araktingi, Chakrabarti, and Maines ( 2 5 ) used a carbon-rod atomizer and metal cyclohexanebutyrate salt standards to determine cobalt, magnesium, sodium, tin, cadmium, zinc, and aluminum in crude oil. Serbanescu et al. (725)listed conditions and detection limits for ten elements in fuel oils and petroleum cokes using airacetylene flame. NBS standards in xylene served Rozo (685) for the determination of copper, iron, nickel, lead, and vanadium in various petroleum products. A radiofrequency spectrometric source adapted to both atomic absorption and atomic emission was used by Talmi (785)for the determination of zinc and cadmium in environmental samples. A turbulent burner modified with a perforated cap permitted Mashireva et al. (485)and Korovin et al. (395)to report low concentrations of 16 elements in petroleum and its fractions. Nuclear Methods. Larson (415) applied neutron activation (NAA) and emission spectroscopy to the analysis of trace metals in petroleum. He and Tandeski (425)also studied the loss of mercury from sample vials, recommending sealed silica vials instead of polyethylene containers. Al-Shahristani et al. (35)used neutron activation to relate the origin and migration of Iraqi oils by the determination of trace elements present. Berkutova et al. ( 6 4 used the technique to follow the distribution of seven elements in petroleum fractions. Vanadium was determined in both petroleum and cracking catalysts by Passaglia et al. (595). Serebrennikova et al. (735) isolated vanadylporphyrin complexes in western Siberian petroleums and estimated the concentration by NAA. The technique was also used by Umarov and Khasanov (795),and Zaghloul et al. (905) to determine vanadium, sodium, sulfur, and bromine in crude oils. More than 40 elements were analyzed by Kobayashi (385) who studied metal impurities in petroleum products and environmental pollutants. Aluminum and silicon were determined by Kavtanyuk and Umarov (365);oxygen, 256R
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phosphorous, and barium by Vandlik et al. (805);cadmium (205)and 25 trace elements by Filby and Shah (175,195). A californium-252 source was used to determine vanadium by Mancini (465)and Braun (95).It was also used by Orange and Larson (565)to describe a vanadium on-stream analyzer. Emission Techniques. Trace elements in petroleum of marine deposits were determined by spectroscopic analysis of ash samples by Babaev ( 4 4 , while Mashireva and Biktimirova (475) attempted to increase sensitivities for trace analysis by activating carbon electrodes to improve their adsorption capacity. Hearn and Quigley (265)determined the nickel concentration in engine lubricating oils by calibrating with naphthenic acid standards. Woods (885) modified the sample holder for rotating disc electrodes to permit use of a 0.5-mL sample. Modified upper electrodes and evaporation of the sample in a lower electrode enabled Shmulyakovskii et al. (745)to determine trace amounts of copper, lead, and arsenic. Fez03 was used by Nasser (535)as an internal standard in the determination of chromium, manganese, and cobalt in ashes from crude oils. Piepen (605)used argon to stabilize the spark discharge in the analysis of oils by the rotating-disc technique. Ten impurities in crude oils were determined by Farhan and Pazandeh (165) by mixing the sample with graphite and sulfur. The residue after coking was excited by dc arc-and photographed in triplicate. X-ray Fluorescence. Smith et al. (775)employed sulfate ashing, concentration with ion exchange, and internal standard techniques to determine trace iron, nickel, copper, and vanadium by x-ray fluorescence. Detection limits as related to different transmission target tubes were discussed by Zulliger and Stewart (915).Price and Field (625) analyzed for sulfur and lead directly by nondispersive x-ray fluorescence, while Williams (865) discussed various methods employed in the petroleum industry. Miscellaneous. Banerjee et al. ( 5 4 , Gumus (245), and Wilson (875) used spectrophotometric techniques to determine vanadium in petroleum products. Vanadium was also determined by Ratovskaya et al. (645)using an amperometric method; and by Rappeport and Yutkevich (635)using a pyrocatechol technique. Ultraviolet analysis for nickel, vanadium, and chromium were reported by Pasculescu et al. (585). Amalgam polarography was used by Karbainov et al. (335) to detect trace elements in petroleum. Gas chromatography detected iron carbonyl complexes studied by Nametkin et al. (525), and gel chromatography separated porphyrin and nonporphyrin nickel and vanadium compounds as discussed by Sebor et al. (705).Shostakovskii et al. (755) studied different solvents for the extraction of metal porphyrin complexes, while Nuzzi and Casalini (555) used liquid-solid chromatography and pyridine-water extraction to analyze vanadium porphyrins in Venezuelean crude. Vanadyl porphyrins were also separated by Eletskii et al. (155)using anhydrous metallic halogenides. Dickson and Petrakis (125)and Yen (895) used electron spin resonance to characterize the vanadium species in petroleum. Campbell (105)developed a paper test strip for field testing low levels of lead in gasoline. The fluorescence of chloro complexes of lead enabled Weber et al. (855)to determine 0.1 ng lead in lubricating oils. Trace elements in fuels were determined by Carter et al. (115)using spark source and thermal emissions mass spectrometry. Filby (185)discussed the nature of metals in petroleum: porphyrin, nonporphyrin, arsine, and stibine forms. Reviews. Lehmden et al. (435)compared analytical techniques for trace elements in coal, fly ash, fuel oil, and gasoline; Braier and Eppolito ( 8 5 )reviewed instrumental methods for the determination of trace metals in petroleum.
Nonmetal Elements and Compounds W. E. Haines and D. R. Latham Laramie Energy Research Center, Energy Research and Development Administration, Laramie, Wyo. 8207 1
Sulfur. Methods for the determination of total sulfur in oils was the subject of many papers. Combustion methods were
the most popular. The sixth report on evaluation of results for sulfur determinations in fuel oil by the Japan Petroleum Institute (68K)contains extensive test data an data evaluations for the sulfur analyses of three standard fuel oils containing 0.3 to 0.1% sulfur obtained by four different methods a t 33 petroleum industry laboratories. Rousseau and Lerouge (135K) modified the Wickbold combustion method to de: termine sulfur in petroleum products; the final determination of sulfur as sulfate was made by titration with barium chloride using three methods for increasing microgram concentration ranges as follows: conductometric (12.5 to 200), automatic colorimetric (100 to 2500), and visual colorimetric (2000 to 10 000). A combustion train for sulfur determinations of substances that cannot be burned directly in oxygen was developed by Thuerauf and Assenmacher (148K);the sample is vaporized in a quartz tube and carried in an inert gas stream to a quartz burner and then to a secondary combustion chamber where the carrier gas is replaced by oxygen; after controlled burning, the sulfur oxides are absorbed and converted to sulfuric acid on a quartz-wool plug impregnated with hydrogen peroxide; the acid is then titrated. Kitamura (76K) determined sulfur in liquid fuels by burning the sample in a pressure vessel in the presence of liquid and gaseous oxidizing agents (hydrogen peroxide and oxygen) and titrated the sulfuric acid formed. An automated determination described by Garcia (54K) involves combustion in a stream of oxygen, followed by automatic iodometric titration. Svajgl et al. (145K)evaluated methods based on oxidation or on reduction for the determination of trace amounts of sulfur in petroleum distillates and found that both approaches were suitable for 1 to 100 ppm of sulfur in fractions boiling below 200’ but that only the oxidation method was suitable for higher boiling fractions. Sugawara et al. (144K) devised a method for determining the sulfur that had reacted with cop er in the copper strip corrosion test; the strip was refluxexin hydrochloric acid/stannous chloride to produce hydrogen sulfide that is adsorbed in a sodium hydroxide solution and titrated with mercuric acetate. Sulfur and chloride in petroleum samples were determined by Hetman (62K) by burning the sample in oxygen and absorbing the products in hydrogen peroxide; aliquots of the absorbate were titrated coulometrically with hydroxide for total acid and with silver for chlorine. Avgushevich et al. (IOK) used a similar combustion and absorption but titrated the chlorine with mercuric nitrate and the sulfur with barium nitrate. Several workers suggested changes or improvements in the determination of the sulfur oxides produced in the combustion procedures. The finish for the lamp sulfur procedure was modified by Krueger (88K) who suggested collecting the sulfur dioxide in a neutral solution containing tetrachloromercurate-EDTA and a buffer and measuring the sulfur dioxide with a potentiometric sulfur dioxide electrode. Killer (75K) suggested the conditions necessary for accurate subppm analysis of sulfur by microcoulometry and detailed the instrumental manipulations required. A spectrophotometric determination of traces (0.5 pg/mL) of sulfate reported b Lukin et al. (96K)involved treating the sulfate solution wit{ barium chlorphosphonazo I11 complex and measuring the extinction at 645 nm. A polarographic finish for the oxygenflask combustion procedure, suggested by Gawargious et al. (55K)involves reaction of the sulfuric acid in the flask with excess barium bromate and subsequent measurement of the cathodic reduction wave of the remaining bromate. The development of nondispersive x-ray (fluorescence) analyzers for the rapid determination of sulfur in petroleum and petroleum products was reported by Titarelli (149K)and by Nakai and Oshima (116K).A study by Frechette et al. (48K)compared nondispersive x-ray analysis with five ASTM methods and concluded that the x-ray method was superior in terms of speed, accuracy, economy, and ease of operation and maintenance. Gamage and Topham (53K)developed a prototype monitor for use on an on-line blending s stem for gas oils and fuel oils by adapting a laboratory non%spersive x-ray fluorescence instrument; a long-time precision of 0.033% sulfur a t the 95% confidence level was reported after a month on-line. Plesch (129K)suggests a nonlinear approximation for the relationship between intensity and concentration in x-ray spectrometry that gives good results for materials with unknown background intensity and would be useful in the
determination of sulfur and phosphorus in petroleum. Miscellaneous methods for the determination of total sulfur included the use of neutron capture y-ray spectrometry. Pouraghabagher and Profio (130K) used a zazCf neutron source and a thallium-doped sodium iodide detector to analyze 0.5 to 3.5% sulfur in fuel oil. Koenig et al. (81K)described commercial analyzers that can be used to determine sulfur at the 0.5 to 2% level in fuel oil by isotope fluorescence analysis using 55Fe as the isotope source. Proton activation analysis using the capture reaction 32S(pzy)33C1 was proposed by Eswaran et al. (44K);the method involves short irradiation of a few seconds by a mechanically chopped beam from a lowenergy Van de Graaff accelerator, coupled with the measurement of the residual positron activity of T1/2 = 2.52 s, resulting in the decay of 33Cl.Mayer et al. (110K)determined the amounts of sulfur deposited from the air-fuel mixture and the en ine oil using an isotope dilution method; diben~y1[3~Sfdisulfide was added to the oil, the test engine was run, and samples of oil and catalyst were withdrawn intermittently for analysis with respect to the specific activity and total sulfur. The determination of gaseous sulfur compounds such as hydrogen sulfide, sulfur dioxide, carbonyl sulfide, and the low-boiling organosulfur compounds was the concern of several workers. Chaigneau and Santarromana (31K)prepared a bibliographic review of methods of measuring hydrogen sulfide, sulfur dioxide, and their mixtures. Kneebone and Freiser (78K)developed two methods for determining carbon disulfide in industrial atmospheres; both are based on the reaction of carbon disulfide with pyrrolidine to form the dithiocarbamate which is reacted with copper to form a chelate; one method monitors the disappearance of the cupric ion potentiometrically with a solid-state copper electrode and the other extracts the chelate and determines it by atomic absorption. T o determine micro quantities of organosulfur impurities in refinery gases, Tsifrinovich and Lulova (150K) concentrated the impurities by low-temperature adsorption on squalene or dimethylsulfolane and desorbed these impurities at higher temperature into an analytical gas chromatographic column. Raulin and Toupance (132K) determined volatile organosulfur compounds and C1 to Cq hydrocarbons simultaneously by temperature-programmed gas chromatography on a column of 3,3’-oxydiproprionitrile chemically bonded to Porasil C. The analysis of sulfur dioxide and hydrogen sulfide in the presence of water vapor, suggested by Ben’kovskii and Sapunov (19K)involves diluting the gas mixture with inert gas to prevent condensation of water vapor, passing the mixture through U-tubes containing adsorbents, and measuring the increase in weight of the absorbents; Rousseau and Chelveder (134K)developed an indirect coulometric method for the determination of sulfur in thiols, hydrogen sulfide, or sulfur dioxide in liquid or gaseous samples; the sample was introduced into an electrolytic solution and thiol and hydrogen sulfide was determined by argentometric titration-the silver ions being produced from the coulometric oxidation of a silver anode; sulfur dioxide was determined by iodometric titration with iodine produced by the coulometric oxidation of an iodide solution. Wronsky (159K) developed a system for the analysis of mixtures of hydrogen sulfide, thiols, carbon disulfide, and carbonyl sulfide in the presence of each other which involves four titrations with 2-hydroxymercuribenzoic acid after selective removal of the other gases; carbon disulfide and carbonyl sulfide were determined by their reaction with 1,3-diaminopropane and titration with 2-hydroxymercuribenzoic acid before and after selective decomposition of the carbonyl sulfide derivative at pH 4.0. A simple method for the measurement of carbonyl sulfide in the presence of hydrogen sulfide suggested by Confer and Brief (37K) involves thermal decomposition of both components to sulfur dioxide in a selective combustor and determination of the carbonyl sulfide by difference when hydrogen sulfide is selectively removed from the sample by a lead acetate tape placed upstream from the combustor. A selective determination of the thiols and hydrogen sulfide in gas suggested by Mishina and Bryantseva (113K) involves passing the gas successively through tubes containing indicator powders and measuring the length of discoloration of the powders; the first powder for hydrogen sulfide is silica gel impregnated with lead acetate, and the second for thiols is silica gel impregnated with copper acetate. Rousseau (133K) ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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determined the hydrogen sulfide in petroleum cuts by titrating with cadmium chloride and monitoring the resulting cadmium sulfide with a cadmium-selective mixed-membrane electrode. An apparatus for the rapid field and laboratory determination of hydrogen sulfide dissolved in oils suggested by Whithair (157K)consists of a 4-arm glass stopcock fitted with interchangeable calibrated bore Teflon keys which allow known volumes of oil to be transferred from a pressurized container into a dispersion tube packed with kieselguhr; hydrogen sulfide stripped from the absorbed oil is passed into a commercial detector tube which produces a stain proportional in length to the hydrogen sulfide concentration. Afanas’ev et al. ( 3 K )determined micro amounts of hydrogen sulfide in natural gas by concentrating the hydrogen sulfide on one GLC column, then desorbing and chromatographing on a second column. Thiols were determined in a variety of ways. Damokos and Steingaszner (38K, 39K) suggested modifications of ASTM D 1232-62 (controlled current coulometry) so that it could be used on the micro scale. The colorimetric determination of butanethiol suggested by Namikoshi and Yamakawa (117K) depends upon the reaction of butanethiol with cobalt naphthenate to form a blood-red color which is measured a t 500 nm; secondary and tertiary butanethiols do not react. Verma et al. (154K)titrated thiols in dilute sulfuric acid solution with sodium cobalticarbonate in the presence of potassium iodide and starch. Paul et al. (124K) titrated thiols with chloramine-T in the presence of iodide. Kojima et al. (82K)selectively detected thiols emerging from a gas chromatograph; components eluted from the column are introduced into a gas absorption tube in which a silver nitrate solution flows constantly, and the solution is passed into a micro-cell equipped with a Ag+/S2 ion-electrode which measures the decrease in silver concentration caused by the formation of insoluble mercaptide. In a scheme by Wronski and Kudzin (160K),the thiols are extracted with sodium 2-hydroxymercuri-3-nitrobenzoate in a solution of potassium hydroxide, triethanolamine, P-ethoxyethanol, and ethylene glycol; the mercaptides are then decomposed with sodium sulfide in potassium carbonate and EDTA a t a p H of 10; the resulting thiols are extracted with xylene and determined by titration with 2-hydroxymercuribenzoic acid. Knof et al. (79K)investigated the use of electron-capture mass spectrometry for the quantitative determination of n-alkanethiol mixtures without preliminary separation. In a search for thiol derivatives that could be separated by gas chromatography, Korolczuk et al. (83K) found the alkyl thiobenzoate derivatives to be the most suitable. To improve the determination of trace amounts of lowboiling thiols and sulfides in natural gas by the gas chromatographylflame photometric-detector technique, Pearson (125K) modified the system to reduce sulfur compound losses. Organic sulfides were the subject of five articles. Vogh and Dooley (155K)separated alkyl and aryl sulfides from aromatic concentrates by ligand exchange chromatography on a copper-loaded carboxylic cation-exchange resin; the sulfides which were strongly adsorbed on the resin were recovered by backwashing with a mixture of pentane and ethyl ether. Microhydrogenolysis of monocyclic sulfides at 200 to 400’ over several catalysts was used by Beiko (15K)to desulfurize the compounds; the resulting hydrocarbons were analyzed by gas chromatography. Demczak et al. (41K)used gas chromatography with flame chemiluminescence detection for the determination of trace amounts of thiacyclopentane as an odorant in natural gas. Numanov et al. (119K) analyzed products of the multistep oxidation of sulfides with hydrogen peroxide by mass spectrometry; polycyclic sulfides, thiophenes, and thiaindanes were oxidized in later stages. Reference compounds for gas chromatography were prepared by Gal’pern et al. (52K)using methyl insertion reactions on ethyl and propyl sulfides to produce 47 thia-alkanes. Thiophene in benzene was determined by Maruyama and Kakemoto (109K)who used gas chromatography with flame ionization detection and reported a limit of detection of 0.01 ppm for untreated and 0.00005 ppm for preconcentrated samples. Gondermann (59K) suggested that method RLB 26/27 for the determination of very small amounts of thiophene in benzene could be used provided that three standardization and purification precautions were taken. The sulfur compounds in crude benzene were studied by Karabon 258R
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et al. (73K)by distillation in a column of 40 theoretical plates; disulfides, carbon disulfide, and thiophene accounted for 96% of the total sulfur with thiophene accounting for 50% of that sulfur. Methods for the group analysis of sulfur compounds in various petroleum products was the subject of several papers. Jewel1 et al. (71K)used a combination of oxydesulfurization with hydrogen peroxidelacetic acid, adsorption chromatography on basic alumina, charge-transfer complexation with 2,4,7-trinitrofluorenone,and reduction with Raney nickel followed by analysis by low- and high-resolution mass spectrometry and NMR. A method of Hypta and Lohinska (66K) for the group analysis of sulfur compounds in gasoline hydroraffinates containing sulfur only as sulfides and thiophenes, involves determining total sulfur by the Wickbold method, the sulfides by potentiometric titration with potassium iodate, and the thiophenes by catalytic decomposition on alumina followed by spectrometric analysis. Parfenova et al. (122K) separated diesel oil into sulfide and thiophene concentrates by distillation, complexation with silver nitrate, thermal diffusion, and adduct formation with thiourea; the resulting subfractions were examined by mass spectrometry and molecular spectroscopy to define number of rings, degree of substitution, and length of side chains. A simple potentiometric titrograph for analyzing sulfur compounds, except disulfides, suggested by Makhlitt and Sardanashvili (104K), includes an electrolytic cell with titration and comparison mercurous chloride electrodes. Bruening and De Andrade Bruening (29K) report that thiols, sulfides, and thiophenes can be separated from petroleum and shale oil by passing the oils through chromatographic columns containing transition metals that form reversible complexes with these compounds; five columns were prepared by adding small amounts of the following to the SF-96 silicon oil liquid phase: zinc n-hexylmercaptide, zinc cyclohexylbutyrate saturated to varying degrees with 2-propenethiol, and nickel cyclohexylbutyrate. Gallegos (51K)describes a technique for isolating and identifying low levels of sulfur compounds in a complex FCC naphtha by gas chromatography and mass spectrometry; a high-resolution peak-monitoring technique was develo ed for determining the CHS+ fragment ion which is produce! by all known organosulfur compounds on electron impact. Several studies reported data that may be useful in the analysis of sulfur compounds. Hoshika et al. (65K)studied the gas chromatography of sulfur compounds with and without a precolumn trap. Microwave spectra of some sulfur and nitrogen compounds reported by White (156K)were obtained by a computer-controlled Stark modulated spectrometer in the 26 500 to 40 000 Mcps frequency range. Pais et al. (123K) determined the activity coefficients of four thiols, eight sulfides, and three thiophenes in ten different solvents by gasliquid chromatography. K-values and activity coefficients of five thiols, three sulfides, and a disulfide in hydrocarbon solutions were reported by Turek et al. (151K);solution behavior of sulfur compounds with paraffin hydrocarbons was nearly ideal. Studies on miscellaneous petroleum-related sulfur compounds included sulfonated petroleum, sulfonic acids, sulfolane, and polysulfides. T o determine critical micelle concentrations, Barden et al. (14K) chromatographed sulfonated fractions of partially refined petroleum on Sephadex beads in water-ethanol solutions to obtain a polymeric colloid fraction and an association colloid fraction. Zakupra et al. (164K)analyzed oil-soluble sulfonates and sulfonic acids by liquid chromatography on a silica gel column wetted with chloroform; sulfonates and sulfonic acids were successively eluted by chloroform and a mixture of ethanol and aqueous ammonia. Sulfolane, an impurity in hydrocarbon mixtures, was determined by Turgel et al. (152K) by absorption on a column of alumina, elution of other sulfur compounds with benzene, and desorption of sulfolane with ethanol after washing the column with hexane to remove benzene; sulfur in the ethanol desorbate was then determined. Hiley and Cameron (63K)separated polysulfides used as lubricating oil additives on the basis of sulfur chain length, using thin-layer chromatography on silica gel GF254; the spots were developed with palladium chloride in dilute hydrochloric acid-acetone solution. Reports of type-sulfur analysis of petroleums, petroleum condensates, and tar sands came from Russian, Canadian, and
American workers. Lobanova and Kotova (95K) studied fractions of three western Kazakhstan petroleums and found that the thiol and disulfide content decreased with increasing boiling point, while the sulfide and residual sulfur content increased; in straight-run and thermally cracked gasolines, sulfides predominated; in catalytically cracked gasolines, residual sulfur predominated. Numanov and Golobokova (118K)found that Ravat petroleum does not contain hydrogen sulfide, thiols, disulfides, or elementary sulfur but that sulfur occurs as cyclic sulfides and thiophenes. The separation of sulfur compounds and aromatic hydrocarbons from hi h boiling fractions of Kuwait petroleum was reported by 8 u : cheryavaya et al. (98K).Kvasova et al. (90K)showed that the concentration of sulfides, disulfides, and residual sulfur in Tadzhikistan gas condensates was about 100 times higher than the concentrations of thiols and elemental sulfur. Anisonyan et al. ( 8 K )studied the thiols in Orenburg condensate; chromatographic analysis of an alkaline extract showed that all of the thiols from ethane- to isopentanethiol were present, with 2-propanethiol and 2-butanethiol being present in the largest amounts. Another study of the Orenburg condensate by Mazgarov et al. (111K)showed that this condensate has a high thiol sulfur content in all of its fractions; sulfides, disulfides, and thiophenes are concentrated mainly in the C5+ fractions. Clugston et al. (34K)studied the sulfur compounds in the gas oils produced from the Athabasca, Cold Lake, and Lloydminster heavy oils and compared them with similar distillates from the thermally mature Medicine River crude; gas chromatographic separations were made, and cuts with well resolved sulfur peaks were examined by mass spectrometry; the sulfur compounds are mostly alkylbenzothiophenes, with most of the alkyl groups being methyl. Jewel1 et al. (70K) studied the distribution and structural aspects of sulfur compounds in atmospheric and vacuum residua from Kuwait petroleum by isolating the major compound classes-saturates, aromatics, resins, and asphaltenes-and measuring properties of each class such as molecular size (GPC), molecular weight, content of sulfur and nitrogen, and reactivity to chemical desulfurization. Oxygen. The composition of acidic compounds in petroleum and petroleum products was investigated by several workers. McKay et al. (99K)developed an analytical method for the analysis of acid compounds in petroleum distillates boiling above 370 "C that involves the use of quantitative infrared spectrometry; the acids are removed from the distillate with an anion-exchange resin, separated into compound types using gel ermeation and adsorption chromatography, and analyzed f y infrared spectrometry to determine the amount of acidic compound types. In a second study by McKay et al. (loOK),the major compound types in the acid fraction of high-boiling petroleum distillates were studied by mass, infrared, fluorescence, and nuclear magnetic resonance spectrometry; carboxylic acids, phenols, carbazoles, and amides were identified as the major acidic compound types present in the oils examined. Pestrikov et al. (126K)investigated the composition of naphthenic acids separated from diesel and kerosine distillates; the acids consisted mostly of mono-, bi-, and tricyclic naphthenic acids according to qualitative infrared and quantitative mass spectrometric analysis of the acids and their derivatives. The composition of carboxylic acids present in the 146 to 250' fraction from a Polish petroleum was determined by Krasodomski (85K)using physicochemical, gas chromatography, infrared, and mass spectrometry techniques. Gadzhieva et al. (49K)determined the structure of the C7- to Cg-naphthenic acids from Baku petroleums by degradation followed by gas chromatography. An efficient chromatographic method for the quantitative determination of the composition of water-insoluble naphthenic acids using silica gel or alumina was suggested by Sabirova and Koval'chuk (137K);the new method has significant advantages over the time-consuming and involved extraction method. Zakupra et al. (163K) developed an adsorption chromatography procedure to analyze mixtures of sodium salts of alkylsalicylic acids; the three peaks of a typical chromatogram correspond to sodium alkylphenolates, alkylphenols and their ethers, and alkylsalicylic acids. Weak and very weak acids in mineral insulating oils were determined by catalytic thermometric titrations in a method described by Castle and Greenhow (30K);the end point in this method is indicated by the temperature rise caused by the
anionic polymerization of acrylonitriles initiated by the basic titrant tetra-n-butyl ammonium hydroxide in toluenemethanol-isopropanol solvent. Kravchenko et al. (86K)developed a spectrophotometric method for determinating phenols in alkylate samples by water extraction and measurement of the absorbance of the extract a t 270 nm. A gas chromatography-mass spectrometry method for qualitative analysis of phenolic mixtures was reported by Malikowska et al. (105K);three mass spectra are prepared for each gas-liquid chromatographic peak, and the results are compared with those reported in the literature and with spectra obtained from standards. The identification of phenols in complex mixtures by gas-liquid chromatography was described by Sidorov and Borovskaya (142K);relative retention volumes of 25 alkyl-substituted phenols were correlated with the number and nature of alkyl groups in the molecule. Zakupra and Chernetskaya (162K)used a gas-liquid chromatography technique to analyze the products obtained by alkylating phenol with 1-octene;using the nonpolar stationary phase SE-30 on silica gel, the presence of di- and trialkylphenols as well as octylphenol ethers was established. ~ Shoffner (140K)reported the use of shift reagent Eu f o d ] in a nuclear magnetic resonance spectroscopy metho for the structure determination and quantitative analysis of phenols; this reagent induces chemical shifts of aromatic ring and methyl protons of phenols and cresols. A spectrophotometric method for determining the carbonyl number of fatty alcohols in commercial olefin fractions described by Shtivel et al. (141K) utilizes the 1720 cm-l absorption band in the infrared spectrum; the results correspond to those obtainable by the oximation method, provided the concentration of carbonyl groups is above 1%. A gas-chromatography procedure for the determination of small amounts of methanol in natural gas was described by Karpov and Mizernitskaya (74K);the impurities in the gas sample, including methanol, are concentrated on a column packed with M 10/60 Polysorb; the concentrated impurities are desorbed a t 140' and separated on a GC column of polyethylene glycol supported on diatomite; methanol is eluted as a single peak. Taleb-Bendiab and Vergnaud (146K)studied the separation of C1 to Cq primary alcohols and C5 to Clz normal alkanes by gas chromatography using a number of ethylene glycol polymers as the stationary phase; the retention times of the alcohols decreased with increasing molecular weight of the polymers, while those for alkanes increased with increasing molecular weight of the polymers. A study of amino acids as stationary phases in the gas chromatographic separation of alcohols, ketones, and methyl esters of dibasic fatty acids was made by Iwase (67K);a column packed with 2.5% of poly-y-methyl-D-glutamate supported on Diasolid M or of 10% of the same phase on Diatoport S was found to successfully separate these compound types. Ghosh et al. (57K)reported that a modified silica gel used as a solid support in gas chromatographic separation of complex mixtures of alcohols, ketones, ethers, esters, and hydrocarbons gave excellent separations of these compound types with use of a neutral stationary phase such as squalane; the silica gel was modified by washing with hydrofluoric acid-sulfuric acid, water washing, drying at 140°, treating with a dilute aqueous ammonium solution, again drying at 140°, and igniting at 900' for 7 h. A method for the automatic analysis of trace amounts of 2-furaldehyde in gas oil described by Lidzey and Stockwell (94K) combines a gas chromatographic separation on a column of Carbowax 20M on Chromosorb G with a colorimetric determination using anilinium acetate reagent. Analysis of oxygen compounds produced from the oxidation of petroleum materials was the subject of numerous articles. Mironenko et al. (112K)analyzed the oxidation products from isopentane by gas chromatography using a column of polyethylene lycol sebacate supported on spherochrome; 26 individual aetones, alcohols, or carboxylic acids were identified. Bozesanu (27K)studied mixtures of formaldehyde, methanol, water, and hydrogen peroxide-compounds which may be encountered in studies on the oxidation of methane; a gas chromatographic column packed with 20% Carbowax 20M on Chromosorb P separated these compounds completely. Gaschromatographic determination of water, aldehydes, alcohols, and carboxylic acids in products from the radiation-chemical carboxylation of methane with carbon dioxide was reported
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by Klapishevskaya et al. (77K);a column of Poropak S is used for determining water, alcohols, acetone, and aldehydes, while a column of PTFE supporting 10%of polyoxyethylene glycol plus 1.5%of azelaic acid is used for determining water, formaldehyde, and acetic and propionic acids. Gas-chromatographic procedures using three columns for the determination of the reaction products from the catalytic oxidation of butane was reported by Laguerie and Aubry (91K);the sample is injected onto the appropriate column, or combination of columns, and the separations made to detect aldehydes, ketones, acids, water, and various other gaseous and liquid products. Boss (24K)used a combination of pyrolysis, gas chromatography, and mass spectrometry to determine the alcohol and ketone isomers formed during the oxidation of normal paraffins. The methyl esters of the water-soluble acids obtained by oxidation in aqueous base of asphalts, tars, and oil residues were analyzed gas chromatographically by Antonishin et al. ( 9 K ) ;the compound types identified included benzenecarboxylic acids and aliphatic dicarboxylic acids. A polarographic method for the determination of alcohols in products from the oxidation of hydrocarbons was reported by Sudnik and Romantsev (143K);the alcohols were converted to their nitrite esters and analyzed polarographically with a solution of 0.3 M lithium chloride in benzene-methanol as the supporting electrolyte. Dermanova et al. (42K)determined acetone in the products of oxidation of isopentane by a polarographic technique; the acetone is converted to the hydrazone and extracted with 0.2 M hydrazine in aqueous phosphate buffer with pH 7.4, and analyzed using the buffer as the supporting electrolyte. An automated system for the microanalytical measurement of carbon, hydrogen, and oxygen in petroleum products was developed by Rousseau et al. (136K).The oxygen content was obtained by sample pyrolysis in a nitrogen atmosphere and conversion of the products to carbon dioxide that is measured coulometrically. Trace concentrations of carbon dioxide in natural gas were determined by Turowska and Pruszynska (153K) by separation on a column of Porapak Q and subsequent reduction to methane at 350" on a column packed with a catalyst prepared by depositing nickel, thorium, and aluminum oxide on powdered thermolite brick; the resulting methane w s de mol termined by gas chromatography using a column of lecular sieves. Traces of peroxide in hydrocarbon rocess streams were determined by Thomson and Bell (147z)using an iodometric method based on the in situ generation of hydrogen iodide from lithium iodide and phosphoric acid in refluxing isooctanol; interferences from cyclic and acyclic unsaturated compounds were eliminated. A high-resolution, high-voltage mass spectrometry method for the analysis of oxygen compounds in petroleum was developed by Peters and Bendoraitis (127K).The method permits mass and intensity measurements on up to 2000 peaks per spectrum and provides intensity percentages for arbitrary compound classes. Gusinskaya et al. (61K) separated the neutral oxygen compounds together with nitrogen bases on a column of cation-exchange resin and separated this material into fractions by adsorption chromatography using alumina. The oxygen compounds were determined to be furan derivatives or were bound in two aromatic rings. A review of the characteristics of the principal groups of oxygen compounds and methods of their separation from petroleum fractions was presented by Krasodomski (84K). Bogorodskaya (21K)reviewed the determination of alcohol, acid, ester, ether, and carbonyl groups in debituminized organic substances scattered in bituminous shales, humus, and other rocks. The determination of water by a variety of methods was the subject of numerous studies. Ambartsumov et al. (6K) determined water in a butane-butylene fraction by gas chromatography on a column of Chromosorb W impregnated with 20 wt % of polyester 6. The water content of solvents such as acetone and methyl ethyl ketone was determined chromatographically by Mamaeva et al. (107K)using a column of 0.5% PEG 300 impregnated on sodium chloride. Lyle and Smith (97K)reported the chromatographic determination of water in nonaqueous phases of solvent-extraction systems using a column of Porapak Q; the method is superior to the Karl
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Fischer titration method in determining water content in benzene solutions of long-chain alkyl amines. The direct gas chromatographic determination of the moisture content of gas mixtures reported by Gokhberg and Ovchinnikova (58K) used a column packed with Poropak Q and a katharometer as a detector. Two publications suggested the determination of water by reactin a sample with calcium hydride and measuring the evolvecf hydrogen by gas chromatography. Krishnan and Nagvenkar (87K)measured the moisture content in gases by this procedure, while Baravalle and Saracino (13K)developed a macro method for petroleum products containing more than 100 ppm water and a micro method for contents of less than 100 ppm water. Fehrmann and Schnabel (45K) determined water in hydrocarbon materials by gel chromatography using a column of styragel with toluene elution and a differential refractometer as a detector. The lower limits for qualitative detection of water was 10-5 mol L-1. A colorimetric test for water in liquid fuels was developed by Pintilie and Petre (128K);tablets consisting of sodium carbonate, phenolphthalein, talc, and magnesium stearate turn red when introduced into a liquid fuel sample containing water. Another qualitative method for detecting water suggested by Goto and Nagashima (60K)involves introducing a pigment containing Brilliant Carmine 6B and Orotan 731DS into the liquid; a red color indicates the presence of water. Abadie et al. ( 1 K )reported that the use of dioxane as solvent in the dielectric determination of small amounts of water in gas-oil emulsions increases the sensitivity threefold; with the equipment used, the absolute precision obtained is approximately 20 ppm. An apparatus was developed by Kodrat'ev and Bondarenko (80K)for the automatic monitoring of water content in a petroleum stream by dielectric permeability measurements. In a method developed by Malyushitskaya and Osadchaya (106K), calcium carbide was reacted with the petroleum sample and the resulting acetylene gas was measured by gas chromatography; the method is applicable to the determination of dissolved and emulsified water in alcohols or liquid petroleum products and to the determination of water in refinery gases. A field method for the quick qualitative determination of water in petroleum emulsions by Mahn and Cosentino (103K)involves the addition of a known quantity of concentrated sulfuric acid and the measurement of the temperature before and after the addition of the acid; the magnitude of the temperature increase is proportional to the quantity of water in the emulsion. The Karl Fischer reagent was the basis for several methods of determining water. Davies (40K)described a method for the determination of water in natural gas that uses ethanediol and pyridine in a ratio of 4:l as a solvent; sufficient Karl Fischer reagent is added to the cell to bring the ammeter to its neutral position and then an additional amount of reagent is added corresponding to 1.5 mg of water; the quantity of gas necessary to return the ammeter to its neutral point is measured. Below (16K)determined the water content of gases by absorbing the water in methanol, which is then titrated with Karl Fischer reagent by the dead-stop method. Chemische Werke Huels A.-G. (32K)patented a process for the continuous determination of water in ethylene involving the coulometric titration of the sample with Karl Fischer reagent by the dead-stop method; the titration vessel is a glass loop in which the titration liquid is circulated by a continuous stream of anhydrous oxygen-containing gas. Galeeva et al. (50K) determined the moisture content of hydrocarbon gases in high pressure systems using a special stainless steel sampler; the gas was bubbled into an absorbing liquid in the titration vessel and titrated with Karl Fischer reagent. Gedemer and Frey (56K) reported on a cooperative testing study of the Karl Fischer method for water determination in electric insulating oil; the precision was good at concentrations of 15 to 30 ppm water. Bond (23K)described two hygrometers designed to measure dew points of hydrocarbon liquids and gases; one uses the change in impedance of an aluminum-alumina-gold sensor to measure the dew points from -110 to +60 OC; the second hygrometer is designed for monitoring high levels of relative humidity at high temperatures and measures dew points from -10 to +170 "C.
Ahmad'ian et al. ( 5 K ) successfully removed water from weathere petroleum samples by an initial centrifuging at 35 to 40" for 2 h, followed by a second centrifuging after thoroughly mixing a few grams of anhydrous magnesium sulfate with the oil. An infrared spectral study of petroleum products by Wilson (158K) established that five spectral absorption bands between 3480 and 3710 cm-' are due to the presence of small amounts of dispersed water; quantitative relationships were not found. Nitrogen. The composition of the basic nitrogen compounds in petroleum and petroleum products was the sub'ect of several papers. McKay and Latham (101K)developed an analytical method for the characterization of nitrogen bases in petroleum distillates boiling above 370 "C that removes the bases from the distillate with Amberlyst-15 cation-exchange resin, and separates these bases into six subfractions, using acidic and basic alumina; quantitative infrared spectral analyses of these subfractions showed that the basic compound types in the distillates are pyridine benzologues, amides, carbazoles and diaza compounds. In a second study by McKay et al. (102K),the basic nitrogen compounds in highboiling petroleum distillates from four crude oils were characterized using the chromatography and infrared spectrometry methods reported in Ref. 101K; structures of the compound types were examined in detail using fluorescence, mass, and infrared spectrometry. Baikova et al. ( I I K )separated and identified basic nitrogen compounds in an acid extract of a coker gas-oil fraction by a combination of gas-liquid chromatography, infrared, ultraviolet, and mass spectroscopy; compound types identified included cycloalkylpyridines, cycloalkylquinolines, alkylquinolines, alkylpyridines, dicycloalkylpyridines, and benzoquinoline. A similar study made by Ben'kovskii et al. (18K)on the diesel fuel obtained by hydrocracking an asphaltic residuum resulted in the identification of numerous individual methyl-, dimethyl-, and ethylanilines. Gusinskaya et al. (61K)studied the composition of the basic nitrogen compounds of several petroleums; bases were removed from the oil by ion-exchange chromatography and separated into fractions by adsorption chromatography on alumina; mass spectrometric analysis of these fractions identified quinoline compounds having the formulas of C , H Z , - ~ ~ Nto C , H Z , - ~ ~ N A . mass spectrometric study of basic nitrogen compounds in several distillates was made by Baranova et al. (12K);basic compounds in gas oil and diesel distillates were mainly pyridines and quinolines condensed with one or two naphthene rings; those in a heavy residue coker distillate were mainly pyridines and naphthenopyridines, with lesser amounts of dinaphthenopyridines and quinolines. Brodskii et al. (28K)used paramagnetic resonance and mass spectrometry to study the structure of basic nitrogen compounds separated from several Russian petroleums; the authors identified pyridine, quinoline, acridine, and benzoquinoline compound types, each condensed with three to four saturated rings. Yusupova et a1 (161K)studied the composition of basic nitrogen compounds from a Russian petroleum using mass spectrometry and identified quinolines and benzoquinolines as the main components, with smaller amounts of the hydrogenated homologues. A high-resolution, high-voltage mass spectrographic method for the analysis of nitrogen- and oxygen-containing fractions of petroleum and shale oil developed by Peters and Bendoraitis (127K)permits mass and intensity measurements on up to 2000 peaks per spectrum and provides intensity percentages for arbitrary nitrogen and oxygen compound classes. The mass spectra of several synthesized model quinolone compounds were studied by Lesko et al. (92K)to obtain information on the fragmentation patterns of these compounds that can be used to identify quinolone-type compounds in petroleum fractions. White (156K)obtained microwave spectra of several pyridine and other nitrogen compounds; tables of absorption frequencies, peak absorption coefficients, and integrated intensities were calculated that can be used in the analysis of these compounds in complex mixtures. Ben'kovskii et al. (17 K ) characterized the neutral nitrogen compounds extracted from a hydrocracked distillate with perchloric acid after removal of the acids and bases; the compound types identified by mass and infrared spectrometry
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were alkylindoles, cycloalkylindoles, carbazoles, and cycloand dicycloalkylpyrroles. Oelert and Giehr (121K)studied the interference of model aromatic compounds in the separation of neutral nitrogen compounds by coordination complex chromatography and concluded that aromatic hydrocarbons may contaminate the neutral nitrogen fraction and interfere with the quantitative gravimetric analysis of neutral nitrogen compounds. Vanadyl porphyrin concentrates from several western Siberian crudes were characterized mass spectrometrically by Serebrennikova et al. (139K);alkylporphyrins, cycloalkylporphyrins, and bicycloalkylporphyrins were identified, with the number of methylene groups in the side chains ranging from 6 to 26. Bol'shakov (22K)studied concentrates of organic nitrogen compounds separated from jet fuels by adsorption chromatography and acid extraction; infrared and ultraviolet spectrometry were used to identify aliphatic and aromatic amines, alkyl-substituted pyridines, pyrroles, aminopyrroles, quinolines, and neutral nitrogen compounds. The total and basic nitrogen content of 66 Russian petroleum samples was studied by Numanov et al. (120K);the total nitrogen content of these samples ranged from 0.04 to 0.25%, while the basic nitrogen comprised 21 to 58% of the total nitrogen and represented only tertiary nitrogen. A discussion covering nitrogen test methods, instrumentation, and current efforts in Japan to standardize nitrogen analyses for fuel oils is reported by Kajikawa (72K);results of comparative analyses of oil samples by 51 laboratories using Kjeldahl, microcoulometric titration, and automatic Dumas combustion methods are reported. A subcommittee of the Product Division of the Japan Petroleum Institute (69K) standardized test procedures for nitrogen analysis in fuel oil by macro-Kjeldahl, micro-Kjeldahl, automatic Dumas, and microcoulometric titration methods; the accuracy and precision of test data obtained for four standard samples containing known amounts of nitrogen were evaluated. Chumachenko et al. (33K) described a method for determination of total nitrogen in hard-to-burn organic materials by combustion at 950 to 1000° in the presence of a NiO-NizOB catalyst; the nitrogen thus formed was forced by helium through a column filled with activated carbon into a katharometer where the nitrogen was recorded as a chromatographic peak. A Coulson conductimetric detector incorporating a gas chromatographic column was reported by Adlard and Mathews ( 2 K ) for the determination of nitrogen compounds; selectivity of 106:1 for nitrogen compounds relative to hydrocarbons and esters was reported by the authors with no significant interference from compounds containing sulfur, chlorine, or phosphorus. A rapid coulometric method for the determination of nitrogen is described by Bostrom et al. (25K) in which the sample is digested by means of the Tecator AB digestion system; the digestion products are diluted and an aliquot is coulometrically titrated. The determination of total nitrogen in hydrocarbon feedstocks and petroleums by irradiation with fast neutrons was discussed by Botvina et al. (26K);the nitrogen content of 12 Russian oils was determined and reported. Miyahara (114K) described an improved nitrometer for the ultramicrodetermination of nitrogen in organic materials; a water jacket prevents errors caused by temperature variations within the nitrometer. McDonald (98K)reviewed recent developments in the microanalyses of nitrogen. Sulfur, Nitrogen, and Oxygen. An analytical scheme developed by Berthold et al. (20K)for the nonhydrocarbons in petroleum products, which is based on a combination of chromatographic, extractive, and spectroscopic methods, permits the separation of the following structural types: sulfur compounds, basic nitrogen compounds, nonbasic nitrogen compounds, and oxygen compounds. Mardanov et al. (108K) investigated concentrates of sulfur and nitrogen compounds and naphthenic acids from kerosine and gas oil fractions of selected crude oils by infrared and ultraviolet spectroscopy; sulfur concentrates were found to contain sulfides with aromatic rings and aliphatic chains; the nitrogen compounds were predominantly pyridines and quinolines, and the naphthenic acids contained one carboxylic acid functional group. A atent issued to Cohen et al. (35K)describes the separation ofpolar nitrogen, sulfur, and oxygen compounds from hydrocarbon mixtures with ion-exchange resins containing 5 to 30% HZO; the resin used may be chosen from a group of macroporous ANALYTICAL CHEMISTRY, VOL. 49, NO. 5, APRIL 1977
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cationic or anionic polystyrene, polyacrylic, polymethacrylic, or phenolic matrix-forming exchange materials, with acidic or basic groups such as sulfonic, phosphoric, phosphonic, or carboxylic acids and amino-, trimethyl ammonium, dimethyl ethanolamine, or quaternary ammonium groups. Drobot et al. (43K) investigated the sulfur, nitrogen, and oxygen compounds in a polar fraction isolated by silica gel chromatography from petroleum distillates boiling above 300 “C; the polar fractions were separated into benzene-soluble and benzenealcohol-soluble portions; the benzene-soluble portion contained large amounts of high-molecular-weight alcohols and carbonyl compounds, while the benzene-alcohol portion was rich in carboxylic acids, sulfoxides, quinones, and womatic hydrocarbons; carbazoles, indoles, and pyrroles were present in both fractions. Mukhopadhyay and Mukhopdhyay (115K) reviewed the literature for the nature, occurrence, and adverse effects on refinery processes of nonhydrocarbon constituents in petroleum, including sulfur, oxygen, nitrogen, and organometallic compounds; the processes for their effective removal are surveyed, and representative constituents are listed with their general formulas and occurrences in crude oil, straight-run products, and cracked products. Chlorine. The determination of chlorine in petroleum or petrochemicals was the subject of ten papers. Fernandez et al. (4610 determined traces of chlorine in naphthas by vaporizing a sample in a stream of carbon dioxide and burning it in an air-oxygen-carbon dioxide atmosphere; the combustion products were absorbed in hydrogen peroxide, and the chloride was determined by the addition of aqueous ferric nitrate/mercuric thiocyanate reagent and measurement of the extinction a t 460 nm; bromine and iodine interfere. Franks and Pullen (47K) describe a technique for the determination of trace amounts of chlorine by liquid chromatograph with a potentiometric sensor; a micro metering pump circu ates a mobile phase through a narrow-bore tube containing ionexchange resin in the metal ion form; the sample is injected into the system and the separated chloride is detected with a pair of silver-silver chloride electrodes, one in the flowing stream and one as reference. A three-column gas chromatographic method for analysis of chlorine-rich gaseous effluents was developed by Amouroux and Foll(7K); the columns involved were Chromosorb T for hydrogen chloride, chlorine, and acetylene; silica gel for hydrogen, methane, ethylene, and acetylene; and Chromosorb T with 7% Apiezon L for chlorinated hydrocarbons. Two papers (10K,62K) concernin the determination of chlorine and sulfur are discussed briehy in the “Sulfur” section of this review. Ramakrishnan and Subramanian (131K)analyzed mixtures of toluene and its side-chain-chlorinated derivatives by chromatography on Celite 545 coated with 15%DC 200. Vinyl chloride in industrial atmospheres can be monitored by absorption on activated charcoal followed by thermal desorption of the monomer directly onto an analytical chromatographic column according to Ahlstrom et al. (4K).Levine et al. (93K) developed a method to measure worker exposure to vinyl chloride monomer which overcomes the difficulties of the method proposed by OSHA; gases are sampled and stored in aluminized three-layer sample bags, and the contents of the bags are analyzed directly by gas chromatography on a column of Carbowax 400 on Porasil. Hofstader et al. (64K) showed that naturally occurring sulfur compounds of moderate electron affinity interfered with the electron capture gas chromatographic analysis for polychlorinated biphenyls in petroleum products. Sapiro et al. (138K) reported the nitro en and chloride content and the amount of hydrogen chlori8e evolved during distillation at 200 to 300° for five desalted Russian petroleums.
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Analytical and Process lnstrumentatior J. W. Loveland and C . N. White Suntech, Inc., Newtown Square, Pa.
In this year’s review we have retained the same section 262R
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headings as were used in 1975. Because of the frequent reference to familiar techniques and terminology we are again using abbreviations to aid the reader in his perusal of the text. Abbreviations recommended by Chemical Abstracts will be used and are not itemized here. Other abbreviations are as follows: AA, atomic absorption; IR, infrared; UV, ultraviolet; MS, mass spectrometry; GC, LC, TLC, as, liquid, and thinlayer chromatography, respectively; X R i , XRD, XRF, X-ray absorption, diffraction, and fluorescence, respectively; NMR, nuclear magnetic resonance; TC, thermal conductivity (detector); FID, flame ionization detector; FPD, flame photometric detector; std dev, standard deviation; vis., viscosity; psig, pounds per square inch gauge; o.d., i.d., outer and inner diameter; in., inch; and HC, hydrocarbon(s). In preparing this review, it was evident that there was considerable activity in several areas. In the laboratory, GC continued to be the most widely used technique, and LC showed increased usage over the 1975 review. The most active areas of work were Specific Compounds and Type Compounds, and Improved Instrumentation, as in the previous review, while Elemental Analysis and Pollution Analysis and Instrumentation showed considerably less activity. In the process instrumentation area there was little activity in Elemental Anal zers, except sulfur, a greater interest in Pollution systems andiPhysica1 Property systems when level, temperature, and pressure instruments are included with the analyzers, and a large increase in activity in Improved Instrumentation, particularly with computer and control devices. Whereas previous reviews covered review papers in the introduction, this year we will include only those of broad scope. Other review articles of a specific nature will be included in the appropriate sections. The following are recommended for a general reading and cover a broad spectrum of techniques and/or applications. Broad Reviews. Kroll (130L) gave a short overview of measurement analysis problems related to petroleum products and environmental air and water sampling and testing. He discussed the nature of the total measurement process, the role of the chemist, statistician, computer, and the ASTM in reaching decisions on quality assurance. Shved and Kuzevanova (205L)discussed the use of chromatography, spectroscopy, and potentiometry in quality control laboratories in the manufacture of by-product coke. Machida (152L) reviewed the laboratory use of GC, UV, and visible spectroscopy and AA in petrochemical plants. Kerenyi et al. (119L)reviewed methods for determining the composition of gasoline, lubricating oils, refined petroleum products, vacuum residues, bitumens, and petrochemical products. In the process instrumentation area, Clevett (45L) has written a book with 470 pages on process stream analysis. Several articles have reviewed the state of the art in the broad areas of analyzer measurement and automation in the processing industry. Becker (18L) covers the scope of control technology for environmental protection to space probes; the purpose and structure of control systems; new measuring systems, such as fluid temperature sensors, and new developments in process computers. Simeone (207L) reviewed the function performed by some 60 process analyzers at an oil refinery. The chemical laboratory has the prime responsibility for purchase, installation, operation, and maintenance of the equipment and regularly checks analyzer results vs. lab tests. Statistical analysis to establish reliability of one analyzer is given. Kikuchi (121L) presents a survey dealing with the maintenance of on-line analyzers for high accuracy. The report includes equipment, personnel, inspection methods, and record keeping methods. Foster (73L) discusses the advantages, limitations, and applications of typical instruments and analyzers and provides guidelines for selecting on-line process analyzers. The list of instruments and analyzers discussed is too lengthy to give here but includes all of those commonly used in the petroleum industry. Foster also covers sampling and prepackaged analyzer systems. Schiele (196L)reviews the measurement of: liquid level in distillation columns, flow of fuel oil and gas, viscosity, temperature in chemical reactions and flames, composition of waste ases, water and atmosphere by GC and spectrometric methofs, and electrical parameters by analo and digital techniques (82 refs.). At an NPRA meeting 807.L) eighteen questions and answers on analyzers
