Anal. Chem. 1989, 6 1 , 84R-95R (P3) Rudzik, L., Dtsch. &folk.-Ztg., 1987, 108, 1090. CA107(25):234907f. (P4) Tatsubayashi, K., Shokuhin to Kalhatsu, 1986, 2 1 , 20. CA106(17):137068e. (P5) Iwamoto, M., Jpn. fudo Saiensu, 1986, 2 5 , 39. CA109(21):174729s. (P6) Robert, P.; Bertrand, D.; Devaux, M. F., Sci. Aliments, 1988, 8. 113. CA109(9):72149x. (P7) Kemeny, G. J.; Wetzel, D. L., Appl. Spectrosc., 1987, 4 1 , 161. CA 106(15):118251t. (Pa) Rubenthaler, G. L.; Pomeranz. Y . , Cereal Chem., 1987, 6 4 , 407. CA108(11):9318Ov. (P9) Bartholomew, D. T.; Osuala, C. I., J . Food Sci., 1988. 5 3 , 379. CA 108(25):220420a, (P10) Belton, P. S.;Saffa, A. M.; Wilson, R. H.; Ince, A., FoodChem., 1988, 2 8 , 53. CA109(1):5366c. (P11) Meuser, F.; Pfaller, W.; Specht, I., Getreide, 1987, Mehl Brot, 4 7 , 203. CA108(3):20638r. (P12) Newsome, W. H., J.-Assoc. ON. Anal. Chem.. 1988, 6 9 , 919. CA 106(5):31442g. (P13) Hitchcock, C. H. S.,Anal. Proc. (London), 1987, 2 4 , 146. CA107(9):76185n. (P14) Alien, J. C.; Smith, C. J., Trends Blotechnol.. 1987, 5 , 193. CA107(21):196562e. (P15) Page, S. W., Food Technol. (Chicago). 1988, 4 0 , 104. CA106(5):31437j. (P16) Ohta, M., Shimadzu Hyoron. 1988, 4 3 , 59. CA106(15):118217m. (P17) Guilbert, S.;Morin, P., Lebensm.-Wiss. Technol., 1986, 79, 395. CA 106(25):212592b. (P18) Iwamoto, M., Bunseki, 1987, 191. CA107(3):21991s. (P19) Vamos Vigyazo. L.; Szakacs Dobozi, M., E b l m z . I p . , 1987, 47, 121. CA107( 19):174458~. (P20) Klein, H.;Teichmann, R.. Ernaehrung (Vienna), 1988, 10, 689. CA 1061,1Ok72980z. , (p21) Klein, H., Tichmann, R , Ernaehrung (Vienna), 1988, 70, 608. CA106(7):48703r
(P22) Pribela, A.; Durcanska, J., S b . UVTIZ, 1987, Potravin. Vedy, 5 , 307. CA 108(23):203343k. (P23) Takahashi, S.; Ohnishi, S..ShlmadzuHyoron, 1986, 4 3 , 65. CA106(15):118218n. (P24) Self, R., Appl. Mass Spectrom. food Sci., 1987, 239. CA108(3):20585w. (P25) Startin, J. R.. Appl. Mass Spectrom. Food Sci., 1987, 289. CA108(3):20586x. (P26) Brumley, W. C.; Sphon, J. A., Appl. Mass Spectrom. Food Sci.. 1987, 141. CA 108(3):20583u. 0'27) Gilbert, J., Appl. Mass Spectrom. food Sci., 1987, 73. CA108(3):20582t. (P28) Games, D.E., Appl. Mass Spectrom. Food Sci., 1987, 193. CA108(3):20584v. (P29) Leppard, J. P., food Anal., 1987. 4 , 365. CAlO6(19):154847a. (P30) Jennings, W., fwd Anal., 1987, 4 , 409. CA106(19):154848b. (P31) Bakes, W., fesenius' 2. Anal. Chem.. 1987, 327, 220. CA107(1 1):95323x. (P32) Froehlich, 0.; Kahre, C.; Schreler, P.. GIT-Suppl., 1987, 54. CA108(2h1.5531~. (P33j Hayes, M. A., J . Chromatogr. Sci., 1988, 2 6 , 146. CA109(1):5327r. (P34) Saito, M.; Hondo. T., Jpn. fudo Saiensu, 1986, 2 5 , 45. CA107(1):5801z. (P35) Tanaka, A., J . flow Injection Anal., I986 3 , 112. CA107(21):192342k. (P36) Owens, G. D.; Burkes, L. J.; Pinkston, J. D.; Keough, T.; Simms, J., ACS Symp. Ser., 1988, Volume Date 1987, 366(Supercrit. Fluid Extr.) CA109( 10):85464w. (P37) Flscher, L., food Anal., 1987, 4 , 219. CA106(19):154845y. (P38) Strathmann. H., food Anal., 1987. 4 , 135. CA106(19):154844x. (P39) Sherma, J.. food Anal., 1987, 4 , 297. CA106(19):154846z. (P40) Whitaker, J. R.. food Anal.. 1987, 4 , 55. CA106(19):154843w. (P41) Oikawa, K., Jpn. Fudo Salensu, 1986, 2 5 , 31. CA106(21):174728r. (P42) Hurst, W. J., LC-GC,1988, 6 . 216, 218. CAl08(19):166149d.
Solid And Gaseous Fuels Hyman Schultz,* Arthur W. Wells, Elizabeth A. Frommell, and Marjorie R. Hough Coal Science Division, Pittsburgh Energy Technology Center, U.S. Department of Energy, Pittsburgh, Pennsylvania 15236
SOLID FUELS This section covers methods of sampling, analyzing, and testing coal, coke, and coal-derived solids reported in the literature between October 1,1986, and September 30,1988. Chemical Abstracts was used as the reference source. In most categories the volume of material available made it necessary to limit the number of publications in this review to those judged to be most relevant. SAMPLING AND PROXIMATE ANALYSIS
Sampling. Dutcher et al. ( A I ) developed a method to obtain and store premium coal samples that would eliminate the lack of uniformity of the coal samples in a coal bank. The Argonne National Laboratory's Premium Coal Sample Program discussed by Vorres and Janikowski (A2) includes lignites; subbituminous coal, high-volatile, medium-volatile, and low-volatile bituminous coals; resinite-rich coals; inertinite-rich coals; and coking coals. Kruse et al. (A3) developed a program called the Illinois Basin Coal Sample Program for basic and applied research and will provide samples of six coals to the users of the program. Sample Preparation. Kettlewell ( A 4 ) conducted two coal-testing round-robin programs and discusses sample preparation, analysis, and laboratory error. Tatro and Giampa ( A 5 ) developed a technique for rapid dissolution of samples for coal ash analysis by inductively coupled plasma emission (ICPE) spectrometry. Methods for safely preparing and storing pulverized coal are discussed by Wells ( A 6 ) . Moisture and Proximate Analysis. Klein (A7) and De (A81 compared various techniques for on-line moisture determination in coal. The best results for moisture were obtained by the microwave phase shift method. Beuerman (A9) used microwaves to dry low-rank coals to determine their moisture content; the accuracy and precision are consistent 84 R
This article not subject to
US.
with those indicated for ASTM methods. An apparatus for automatic determination of the moisture content of metallurgical coke using thermogravimetric analysis (TGA) was discussed by Heitz et al. (AIO). Zhang et al. ( A l l ) studied the maximum inherent moisture of coal and its relationship to carbon content, oxygen-to-carbon ratio, hydrogen-to-carbon ratio, volatile matter, and total acid groups. A fully automated apparatus for the proximate and total sulfur analyses of coal and coke using a computer-controlled robot was developed by Ishibashi et al. (A12). Conditions in the laboratory and the precision of analysis were both improved compared to the manual method. Mao et al. (A13) discuss a rapid TGA method for proximate analysis; they found the precision to be within the ASTM tolerance limits. A continuous proximate analysis procedure was developed by Kawaguchi et al. (A14). Ash. An on-line ash monitor using two-energy transmission and a forward scattering of quantum radiation was discussed by Thuemmel (A15). Dombrovskii et al. (A16) determined the ash content of blast furnace coke on-line using neutronactivation analysis (NAA). Pak ( A l 7 ) used y radiation to rapidly determine ash. X-ray fluorescence (XRF) was employed by Pan'kov et al. ( A H ) to determine ash. The analysis was completed in 15 min with a standard deviation of 0.006. Wawrzonek (A19) applied multivariate linear regression to determine the ash content of coal by XRF. The best results are obtained when a 55Fesource is used. To determine ash in solid samples, Rao and Anjaneyulu (A20) used X-ray backscatter (XRB) and reported a relative precision of 6-10%. Pandey (A21) used XRR and Compton scattering as a rapid means to determine ash in coal and coke. Wang and Wu (A22) measured the ash content of coal by X-ray diffraction. The ash content in brown coal was determined by Leonhardt and Thuemmel (A23), Votava and Kubant (A24), Pak and Vdovkin (A25),and Weber et al. (A26) using X-ray radiom-
Copyright. Published 1989 by the American Chemical Society
SOLID AND GASEOUS FUELS
U p a n Schvltr joined the staff of the P m s burgh Energy Technology Center (PETC) then a part of Me U.S. Bureau 01 Mines and now a pan 01 the U S Department of Energy in May 1971. He received his B.S. in chemistry at Brooklyn College in New Y a k in 1956 and his m.0. in 1962 at The Pennsybania Slate Universky. Or. Schukz is currently Chief 01 the Coal Analysis Branch at PETC. Prior to Ioinlng Me US. Bureau of Mines. [x. SChUn2 was engaged in industrial research In analytical chemistry.
marked the reproducibility, comparability, and accuracy. A fast method for determining the carbon content of raw coal by inelastic scattering of neutrons was developed by Heinrich et al. (82). Hase ( 8 3 )evaluated an instrumental method for analyzing sulfur and nitrogen in coal and oil. The sulfur was determined by IR spectroscopy combined with combustion, and the nitrogen was determined by using GC. He discussed both methods from the standpoint of their precision, accuracy, time required, and safety. Nitrogen. Saito (84)determined nitrogen in coal by mixing coal with soda ash, alumina, and water containing iron oxide. The mixture is first heat-reacted at 430 20 "C under steam containing inert gas and then a t 95C-loo0 OC. This generates ammonia (NH,) gas, which is passed through an alkali bath in a steam distillation apparatus, where the HzS is removed. The NH, is then absorbed in a solution containing H3B03and HzSO,, where the ammonia is determined by titration. The nitrogen results are equivalent to those determined by standard ASTM methods. Burchill (85) and Wallace e t al. (86)studied the variations in nitrogen content and functionality with coal rank. Oxygen. Zischka and Stremming (87)determined total oxygen in coal (using a commercially available instrument) by converting both organic and inorganic oxygen to carbon monoxide and determining it by infrared (IR) spectrometry. Ehmann et al. (B8)studied the organic oxygen in coal by fast neutron activation analysis (FNAA). They compared three methods for determining the organic oxygen in coal and found that FNAA was superior to the other methods. Sulfur. Ishihashi et al. (89)used an automated acid-base titrator for determining the total sulfur content in coal. The analysis time and accuracy are improved compared to the Japanese Industrial Standards (JIS) methods. Kalandadze (810) developed a rapid method for the determination of sulfur in coal. A sample is heated in a stream of air, first a t 380-400 "C for 13-15 min and then a t 1000-1100 "C for 4-5 min. The gases are absorbed in an HzO, solution. The absorbent solution is boiled to decompose H20zand then titrated with a 0.05 N sodium hydroxide solution to determine the H,SO, formed. The heating-oxidation method minimized hydrogen sulfide (H,S) formation. The standard deviation of the method was 0.6%. He discusses the precision, accuracy, time required, and safety of the method. Kimura (811) and Kocman (812) used an XRF method that required no sample preparation to determine sulfur and trace elements. Kocman (812) discusses the development of calibrating standards, detection limits, and peak-counting times for XRF. Duffey and Wiggins (B23) and Olivier e t al. (814) explored the application of y-ray spectrometry to determine the sulfur content of coals. Total sulfur in coal and fly ash was determined by Caroli e t al. (815)using ICPE spectrometry. The reproducibility of ICPE was between 3.8% and 1.4%. Forms of Sulfur. Markuszewski (816) reviewed 32 references on methods to determine sulfur forms in coal. He discussed the associated errors and the methods and research needed in the future. A rapid and simple method for the isolation of condensed thiophenes and other types of aromatic sulfur compounds (S-PAC) based on ligand-exchange chromatography was developed by Nishioka (817). He identified a variety of S-PAC in coal extracts. Huffman e t al. (818) investigated the atomic and physical structure of both inorganic and organic sulfur in coal. They used a combination of Miisshauer spectroscopy, computer-controlled SEM, and X-ray absorption fine structure to provide a relatively complete characterization of the atomic structure and microstructure of sulfur in coal. Pyrite decomposition in coal and the direct measurement of organic sulfur content in coal macerals were studied by Tseng (819). Pyrite (FeSz). A rapid method to determine pyrite in coal was developed by Finkelman (820). Ten grams of coal was ground to less than 325 mesh; 8 g was treated with dilute HCI. Five grams of the acid-treated coal was reacted with 100 mL of 15% H,O, by boiling the solution for 30 min. After the solution was cooled to room temperature and diluted to the original volume, an aliquant was taken and was diluted to between 251 and 1001. The diluted sample was analyzed by colorimetry. A soluble sulfate solution was made with 2 g of coal that was not acid treated. The pyrite value is equal to the total sulfate minus the soluble sulfate. The total time required for sample preparation and analysis is 1 h. Re-
*
Arthvr W. Walk 1s a chemist in Me Process Mannoring and Analysis Branch. Pinsburgh Energy Technomy Center. He rowlved his O . A and M.A. demws in chemlsbv from Me Universky of Nortiern Colorado in.1969 and 1973. respectively. Before joining the Pmsbur* Energy Techncmy Center. he was an analvticai chemist for the OCCuOalionaI BnalYtiCai Occupational Safev and Hesnh Administration. U.S. Da partment of Labor. HB is presently engam in research on c m i surface chemistry.
4
Ellnb.lh A. f-l 10 a chemist in Me Coal Scbnw Branch. Pinsburgh Energy Technology Center. She received her B.S. degrees in math and chemistry trom the Universky of Pinsburgh in 1970 and 1977, rerpectiveiy. Before blning the Pinsburgh Energy Techmlogy Center she was a senior technician at Calgon Subsidary of Merk. Inc., and e research technichn at Mellm Instnute. CarnegieMelbn universiiy. She is presently engaged in X-ray diffraction analysis of coal CatalySts and Sorbents for flue gas cleanup.
P W a r m R. Uwgh I?I a rewardl dwmlsl In the Process Sciences Branch. Pinsburgh Energy Technology Center. She received her B.S. degree in chemistry from Saint Louis Univermily &tore jdning Pinsburgh Energy Technology Center. she was e m ployed as an industrial analytical Chemist. She is presently engaged in research on methcds for the characterization of cml lib quetaction catalysts.
etric analysis. Ohkubo et al. (A27) reported a new method that utili~esa specific.-gravity meter to estimate the ash content of coals. Volatile Matter. To determine combustible volatile matter in solid fuels Eklund et al. (A2Rj developed a flash pyrdysis method that i i applicahle to materials with H C vnlues between 0.2 and 2.05 and has a precision similar to gas chromatography (GC!. Le., 6%-8%. Ohrbach et al. ( A B )describe the use of simultaneous thermal analysis-mass spertrometry r'l'A-.MSj in coal analysia to identity the wlatiles released during a temperature-cuntrolled progrnm. Baranovskii and Polyashov (A3Li showed that the effect of mesh size of coal on the voltaile yields varies with rod rank, while Wells rAfi) determined that autoignition increases as the Content of volatiles in coal increuies nnd as the average particle sire decreases. ULTIMATE ANALYSIS AND SULFUR FORMS
Schuchardt et al. ( B 1 ) investigated the efficiency of auto mated carbon, hydrogen, and nitrogen analvzers by using 13 labs and 5500 determinations on samples of petrolrum products, coals, rokes. coal oils, and methanol. Thev sum-
ANALYTICAL CHEMISTRY, VOL. 61. NO. 12. JUNE 15. 1989
* 85R
SOLID AND GASEOUS FUELS
peatability for the H202oxidation method is reported as fO.O1 wt % . Straszheim et al. (B21) used a scanning electron microscopy (SEM) based automated image analyzer (AIA) to measure the mineral matter and pyrite content of two highsulfur coals (Illinois No. 6 and Pittsburgh seam). The directly measured values of mineral matter and pyrite content agreed reasonably well with values obtained by using ASTM methods. Organic Sulfur. Agus and Garbarino (B22)studied the organic sulfur content in coal macerals by using an electron microprobe. Hippo et al. (B23)separated individual macerals in coal by a density gradient centrifuge, and the organic sulfur was determined by the ASTM procedure. Boudou et al. (B24) identified some sulfur species in an American coal with high organic sulfur content. They used optical microscopy, SEM, and electron microprobe to study relationships among sulfur, metals, and coal petrography. They studied both the oxidation and reduction of two U.S.A. coals and one French coal with high organic sulfur content. Tests revealed the presence of thermally stable sulfur compounds (aromatic and high molecular weight) and labile sulfur compounds (aliphatic thiols and sulfides). Unlike the sulfur compounds, the metal compounds in the coals are homogeneously distributed throughout the macerals. In comparing all the methods they used to determine organic sulfur, they concluded that ASTM methods should be chosen for quantification and the other methods for specificity. Majchrowicz et al. (B25)reduced finely ground coal samples by heating them in hydrogen-donor solvents and continuously determining H2Sthat evolved from the solution. Plotting the volume of H2Sevolved vs temperature allowed the assignment of H2S peaks to sulfur-containing functional groups in the coal. Model compounds were employed to assign peaks to functional groups. They found that most of the organic sulfur in coal is present as thiols, sulfides, and thiophenic groups. INORGANIC CONSTITUENTS
Two methods were developed by Hurley et al. ( C l ) to quantify the inorganic elements in coal. One method was by chemical fractionation, and the second used SEM point counting. Alvarado et al. (C2) studied both conventional and microwave wet-acid di estion procedures. The resulting solutions were analyzed Ey electrothermal atomization atomic absorption spectrometry (EAAAS) to determine iron, nickel, and vanadium in coal samples. Sample digestion time was 12 h per sample for conventional digestion and 8-10 min per sample for microwave digestion. A potentiometric titration procedure was used by Yu et al. (C3)to determine vanadium in its trivalent, tetravalent, and pentavalent forms in coal and coke. Two methods for the extraction of vanadium from coal were developed by Mitoseriu et al. (C4)and Inoue et al. (C5). Pak and Vdovkin ((26) studied particle size and its effect on the results of the y-Albedo method. They found that the optimum energy of the primary radiation at which the particle size effects are minimized increases with increasing y-ray absorbing properties of the samples and is 30 keV for coal and 75 keV for iron ore. Selenium was determined by Ebdon and Parry (C7) using EAAAS on whole powder coal without sample digestion. Selenium was determined in four certified reference coals, with a typical relative standard deviation of 5% a t the 1 pg of selenium per gram level. The limit of detection for the method is 0.05 pg/g. Coleman (C8) developed a rapid method for elemental analysis using a dc plasma emission spectrometer and whole powdered coal (ground to a fine powder in less than 10 min). An arsenic and selenium method for coal was develoDed bv Lindahl (C9) usine hvdride generation AAS. The met'hod 6as been accepted fzr &e by ASTM as D 4606-86. Hurley (ClO) used AAS to determine sodium by conventional acid digestion of low-rank coal rather than by analysis of ash. Sodium and aluminum in coal were studied by Howarth et al. ((211) using the magic angle spinning nuclear ma netic resonance (MAS-NMR) technique. The raw coals a n t dried coals were analyzed for sodium, and the results indicated that sodium is surface-bound and hydrated in raw coal, and sodium chloride is a minor component of dry coals. Nelson (C12) described an on-line analytical method for calcium in coal using FNAA. Ion chromatography (IC) was used by Cox and Saari (C13) to determine total chlorine in coal. They discovered that chlorine in coal was entirely in 86R
ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
the ionic form. Their method, which employs 0.1 M potassium nitrate in dimethyl sulfoxide as the leaching solution and uses IC to analyze the leachate, is much faster than oxygen bomb combustion. Doolan (C14) describes a pyrohydrolysis method for determining low fluorine concentrations in coals and minerals. Recovery and precision are favorable when compared with the alternative sodium peroxide fusion or oxygen bomb combustion methods. The relative standard deviation is less than 0.05 for most samples. Manganese and chromium in coal were determined by Kosasa and Nakajima (C15). The samples were excited in a shock tube. By use of simultaneous measurements of the background and line intensities with a multichannel spectrometer, errors were eliminated. The results agreed with the values given by the National Bureau of Standards (NBS) for their certified materials. Inoue et al. ((216)determined titanium in coal, fly ash, pond sediment, and asphalt by spectrophotometry using N-rn-tolyl-N-phenylhydroxylamine. An automated direct sample insertion system for the ICPE spectrometry was developed by Pettit and Horlick (C17). Steps like drying and ashing are performed in situ. Nissen and Greulich (C18) used the AIA with an electron microprobe to determine minerals and particle sizes in raw coals. SEMenergy dispersive spectroscopy (EDS) was used by Ocaranza (C19) for the determination of inorganic constituents of coal on a particle-by-particle basis. Trace Elements. Parry and Ebdon (C20) determined major and trace elements in aqueous coal slurries by inductively coupled plasma (ICP) mass spectroscopy (MS) and ICP atomic emission spectroscopy. The results were low for aluminum because of its incomplete atomization. Tamura et al. (C21) used AAS to determine trace elements, such as nickel, chromium, zinc, cadmium, and lead, in coal and fly ash. They discuss the digestion method used and how they employed a boat-shaped tungsten ribbon atomizer. Fifteen trace and minor elements were determined in coal by using a rhodium tube and XRF spectrometry by Dewison and Kanaris-Sotiriou ((222). They discuss the calibration and pellet-making methods utilized and present the results obtained with standard coals. Ryan et al. (C23) discuss the use of NAA in the determination of trace elements in a variety of materials including coal; NAA was also used by Tomza and Kaleta (C24) to determine trace elements in brown coal and its combustion products. Salama and West (C25) determined trace amounts of fluoride ion by a spectrophotometric method using ternary complex formation with zirconium and acid Alizarin-Black SN. The method has less than a 2% error in the range of 0.1-0.4 pg of fluoride ion. CALOR1FIC ANALYSIS
Sandulescu et al. (01)calculated the calorific value of lignite from its noncombustible and moisture content after drying it a t 140 "C for 50-150 min. Calorific values were calculated by Ferguson and Rowe ( 0 2 ) on 23 lignites from their proximate analysis, and the calculated values were compared to experimental values. The average deviation from bomb calorimetry measurements is f1.2%. Bao (03) computerized an equation for calculating calorific values and collected data from 40 coals for a data base. The software gives results with less than 5 % difference between experimental values. Corrales Zarauza ( 0 4 )studied the calorific values of high-ash coals and developed an equation for calculating them. Data from an elemental analyzer were used by Sole and Colombo (05) to calculate calorific values. On the basis of the inelastic scattering of neutrons by carbon-12, Cywicka-Jakiel (D6)developed a formula to calculate calorific values for coals. A new formula using a variable value for percentage of relative temperature rise (PRTR) in the bomb calorimetry of coal that is related to the cooling correction was developed by Sun (07). The formula was checked against 158 calorific test results on coals with calorific values ranging from 6900 to 33 500 J/g. Qian and Yang ( 0 8 ) developed a formula for evaluating the calorific values from models of real combustion processes and applied it to 44 coals. PETROGRAPHY
Milley ( E l ) presented the possibility of using redox potentials in ranking coals. The coals are first treated with a
SOLID AND GASEOUS FUELS
strong aqueous oxidant; then a plot is made of the characteristic curve of working electrode potential to reference electrode potential vs time. The method is rapid and the instrumentation is simple. The degree of both metamorphism and oxidation of anthracites was characterized by Kotkin et al. (E2)using the hydrogen-carbon and oxygen-carbon ratios. There was a high degree of correlation to other coal-rank and coal-quality parameters, such as density, electrical resistance, microhardness, ash, and volatile contents. Larsen and Wei (E3) evaluated the pyridine extracts from a series of lower Kittanning coals and found that both the amount and average molecular weight of the extracts increased with coal rank up to 86% carbon content. A computer-interfaced gel permeation chromatograph and mass-sensitive detector were constructed for this purpose. Aromatic distribution patterns and thermal maturation effects were studied by Radke et al. (E4) for five coals containing an amorphous type of kerogen and for five coals where vitrinite and inertinite were the predominant kerogen constituents. Concentrations of phenanthrene, dibenzothiophene, and certain isomers of alkylphenathrene, alkylnaphthalene, and alkyldibenzothiophene were determined for this purpose. Alkylnaphthalene isomer distributions were related to variations of maturity for carbon-normalized concentrations. Crelling (E5)and Jobling and Crelling (E6)isolated coal macerals from a high-volatile bituminous coal using a density gradient centrifugation technique. Micronized and HC1-HF demineralized coal was dispersed in water using ultrasound and layered to the top of the density gradient, and each layer was centrifuged. An Australian bituminous coal was reproducibly fractionated by Pandolfo et al. (E7) using density gradient centrifugation into high-purity (198.5%) liptinite, vitrinite, and inertinite maceral groups, which were subsequently analyzed with DRIFT spectroscopy, pyrolysis-GC, and pyrolysis-GC/MS. Chen and Bodily (E8)used density gradient centrifugation of Yanzhous coal, and pyrolysis-MS of the isolated macerals, to identify exinite, vitrinite, and inertinite. An Upper Kittanning high-volatile bituminous coal was separated by Dyrkacz et al. (E9)into seven fractions in a manganese chloride solution of 1.182 g/cm3 density containing Brij-35 surfactant and subjected to magnetohydrostatic separation. Vitrinite and inertinite were separated by the technique, but liptinite remained bound to other macerals and gave a broad distribution. Crelling et al. (ElO) used a simple coal combustion reactivity test on lithotype concentrates, individual macerals, and two rank series of single seam-coals and determined that 45% of the rank reactivity variation was accounted for by changes in maceral concentration. Vitrinite reflectance accurately determined the rank of coals in the Irui and Candiota deposits of Brazil, while discrepancies in the determination of the rank of Chico Lima and Lea0 I1 deposit coals were attributed by Correa da Silva et al. ( E l l ) to impregnation of the vitrinite with bituminous and oil substances generated during coalification. Riepe and Stellar (EI2) developed a total reflectance-frequency distribution method of predicting the degree of conversion in the hydrogeneration of 12 seam (hard) coals. Rank determinations made from the fluorescence of coal induced with an ultraviolet (W) nitrogen laser were found by Death et al. (El31 to correlate with a standard vitrinite reflectance procedure. Fourteen Australian coals, ranging in rank from low- to high-volatile bituminous were used in the study, and the fluorescence area was more than 4 orders of magnitude greater than the area of individual macerals. Salehi and Hamilton (EI4) stained the surface of coal and coke with an aqueous mixture of iron(II1) chloride and potassium iron(II1) cyanide and found that the colors observed with a light microscope depended on rank and maceral type. Color intensity for vitrinite increased with coal rank, while the color was more intense for coke, anthracite, and inertinite than for vitrinite. These observations suggest that the stains originate with aromatic compounds. PHYSICAL METHODS
A critique on the use of adsorption methods and theoretical adsorption equations for determining the microporosity of coals and carbons was given by Marsh (FI).Problems in the interpretation of adsorption data were discussed and included polar interactions, molecular sieve effects, activated diffusion,
cooperative adsorption, and the limitation of equations. The terms ultramicroporosity, microporosity, and supermicroporosity were defined. Larsen and Wernett (F2) evaluated adsorption data for carbon dioxide and a set of alkanes (ethane, cyclopropane, etc.) into the pore structure of Illinois No. 6 coal and concluded that coal pore structure is not an interconnected network of bottle-necked pores but that adsorbate must diffuse through coal to reach isolated pores. Although adsorbate size correlated strongly to the surface area obtained, the adsorbate diffusion rate in coal was identified as the crucial factor. A method for the analysis of coal pore structure using low-field NMR spin-lattice relaxation measurements was presented by Glaves et al. (F3). The procedure, in principle, avoids problems found in other methods, such as pore shape assumptions, network and percolation effects, and sample compression. Hewel-Bundermann and Juentgen (274) reviewed investigations of the pore structure and water-adsorbing capacity of bituminous coal in conjunction with moisture retention and transport properties in coal seams. The solvent-induced swelling of coals in chlorobenzene, THF, and pyridine was found by Cody et al. (F5)to be anisotropic. The time required to reach maximum swelling was different for swelling parallel to and perpendicular to the bedding plane of the coals and was a function of coal rank. Hall et al. (F6) evaluated the swelling properties of eight coals using solvents in two series arranged by electron donor number and pKb values correlated to coal-swelling behavior. The comminution characteristics of coal were determined by Narayanan et al. (F7) using a single-particle breakage technique that involves a computer-monitored pendulum impact system that is capable of measuring the energy of breakage for a single coal particle upon impact. Dybala et al. (F8) gave an equation that predicts the bulk densities of coal and coal-briquet mixture feedstocks for coking based upon the porosities of such feedstocks. Gumkowski et al. (F9)employed two thermochemical methods to study the interaction of 12 organic solvents with 6 Argonne premium coals. The heats evolved for coals when compared to various prototype materials gave better correlations than homogeneous analogues, such as the Taft-Kamlet parameters. Information on surface acidic and basic sites of coal was obtained by Fowkes et al. (FIO)using microcalorimetry and isooctane carrier solvent containing tert-butyl substituted pyridine and phenol probe compounds to limit subsurface penetration and to permit quantitative desorption. Golesteanu ( F I I ) determined parameters of drying, evolution of volatile matter, burning of the residual carbon, and coal chemical reactivity from DTA on coal dust. SPECTROSCOPY
Solomon and Carangelo ( G I ) investigated the possible application of Fourier transform infrared (FT-IR) spectroscopy to the determination of the aliphatic and aromatic hydrogen content of coals. Reasonable agreements with nuclear magnetic resonance (NMR) methods were obtained by using rank-dependent absorptivities, with the exception of aromatic hydrogen content for coals of less than 85% carbon. A computerized IR method for characterization of materials was presented by Verheyen et al. (G2) as showing potential as a rapid tool for monitoring the quality of coal. Smyrl and Fuller (G3) applied diffuse reflectance FT-IR spectroscopy to the determination of hydroxyl functional groups in coal. The procedure involves observing the disappearance of various hydroxyl functional group absorptions and the appearance of carbonyl absorptions resulting from the in situ reaction with acetic anhydride while the coal is heated. As described by Larsen (G4),FT-IR dichroism and photoacoustic detection indicated a lack of anisotropy with respect to the bedding plane of aromatic structures in coal. These results, however, are contraindicated by coal solvent-swelling studies. Diffuse reflectance FT-IR was used by Griffiths (G5) for the quantitation of functional groups in coals and in air-oxidized coals. Methods for improved quantitation of functional groups involved curve-fitting regions previously subject to Fourier self-deconvolution. Calemma et al. (G6) employed FT-IR to evaluate chemical changes resulting from the dry-phase air oxidation of a subbituminous coal at 200, 250, and 275 "C. Mechanisms for the low-temperature oxidation of an Illinois ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
87R
SOLID AND GASEOUS FUELS
No. 6 bituminous coal by oxygen were studied by Gethner (G7) using FT-IR difference spectroscopy with in situ oxidation. Olson et al. (G8) developed an isotope dilution-capillary GC/FT-IR method for determining carboxylic acids and applied the procedure to the qualitative analysis of aqueous mixtures of coal oxidation products. Seehra and Ghosh (G9) utilized in situ electron spin resonance (ESR) to investigate the pyrolysis of eight American coals and found that the free-radical density displayed four distinct stages corresponding to temperature ranges of 25-250 "C, 250-400 OC, 400-600 "C, and above 600 "C. Apparent activation energies (about 10 kcal/mol) increase with the coal hydrogen-to-carbon ratio while room temperature free-radical densities decrease. The ESR spectral line widths and spin concentrations were determined by Lin et al. (GIO) during the pyrolysis of two Chinese coals (bituminous and anthracite). The effects of pyrrhotite and pyrite additives on free-radical formation were evaluated, and only pyrite showed a catalytic effect. Thomann et al. ( C I 1 )measured spin-lattice relaxation rates and carbon radical phase coherence for vitrinite macerals isolated from coals ranging in rank from subbituminious (63.6% carbon) to low-volatile bituminous (88.3% carbon). Carbon radical relaxation rates proved to be a more sensitive probe of microscopic intermolecular structure than of the carbon radical molecular structure, with spin-lattice relaxation rates correlating strongly to rank for coals above 80% carbon. The sorption of nitroxide spin-probes in toluene on the surface of coal was studied by Jeunet et al. (G12) and indicated a medium of high polarity, close to ethanol or methanol, for low-rank coals. The polarity and immobilization ratio decreased with coal rank. Some assumptions were required by Wieckowski and Duber (G13)in analyzing the macromolecular and molecular phases of bituminous coals using ESR spectroscopy. Zilm and Webb (G14) evaluated and described the application of three new two-dimensional solid-state NMR spectroscopies and zero-field NMR spectroscopy to solid fuel analysis. The zero-field method was assessed as showing future potential as a powerful method in coal structure analysis. The potential for application of two-pulse NMR techniques where unpaired electrons constitute the second spin species was evaluated by Barton and Lynch ((315) for coal protons and experimentally assessed by using several coals and chars. Howarth and Ratcliffe ( G I 6 ) applied sodium-23 and aluminum-27 MAS-NMR to the study of coal and coal ash. The carbon and oxygen distributions in six coals covering a range of coal rank were evaluated by Yoshida and Maekawa (G17). Davis et al. (GIB) used carbon-13 NMR to evaluate the pyridine-insoluble residues of telocollinites and sporinites separated from British carboniferous coals. Pyridine extracts of seven coals and the insoluble residues left after the extraction were analyzed by using carbon-13 NMR by Erbatur et al. (G19). Tekely et al. (G20) used cross polarization (CP)-MAS-carbon-13 NMR to study changes in the mobile molecular components in coal after pyrolysis a t 590 "C. X-ray pulse scattering (XPS) was used by Burchill ((221) to study variations in nitrogen functionality with coal rank from peat through bituminous coal and between coal macerals. Pyrrolic nitrogen, five-membered rings, predominated over the bituminous range, while pyridinic nitrogen, six-membered rings, increased with coal rank. Solvent fractionation into basic and neutral components of coal, solvent-refined coal, coal tar pitch, and coal liquids, followed with analysis by XPS, was employed by Bartle et al. (G22) to show that hydroliquefaction, flash pyrolysis, and solvent extraction have no effect on the nitrogen compounds in coal, which remain predominantly pyrrolic and pyridinic. Oxygen-bcarbon ratios for oxidized coals obtained from XPS spectra were reported by Hollenhead et al. (G23) to parallel heat-of-immersion results in water. Huffman et al. (G24) employed K-shell extended X-ray absorption fiie-structure (EXAFS) spectroscopy to investigate organic sulfur in exinite, vitrinite, inertinite, and biologically desulfurized coals and found some similarities to dibenzothiophene spectra but attributed a broad peak in the EXAFS to sulfur bonded to oxygen. COKING PROCESS AND COKE TESTING
Coking indexes and volatile matter content were used by Chen ( H I ) to classify bituminous coals into 1 2 groups. Ni88R
ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
shioka et al. (H2) measured the coking properties (fluidity) of coal by packing coal particles of 250-840 l m to a density of 11.0 g/cm3 in glass or metal test tubes, heating the tubes to 470-550 "C a t 10-250 OC/min, and measuring the length of coal expansion. The method is rapid when compared to the standard Giesler method. A caking index for bituminous coals, and factors that affect the index, were discussed by Chen and by Du et al. (H4). Chaudhuri et al. ( H 5 ) and Yang (H3) determined the coking value of coal, tar,pitch, etc., in a muffle furnace maintained at 570 f 5 "C in less than ' I 2h. A set of X-ray structural methods for evaluating coke quality was given by Biktimirova et al. (H6), while Nozawa (H7) presented a quick method for predicting metallurgical coke quality by washing, drying, and combusting a coal sample and then determining the color, particle size, and stiffness of the redescribed an on-line sulting ash pile. Dobashi et al. (H8) apparatus for determining the size distribution of coal used in the manufacture of metallurgical coke. An apparatus to measure coal swelling during the coking A coal tablet process was described by Sheikhet et al. (H9). was placed in a vertical tube inside a furnace, and the swelling pressure was recorded by a rod in contact with both the tablet and a membrane whose movement was followed with a manometer. A rapid, GC-based evaporation analysis for determining the swelling and pore volume in porous polymers was used by DoNascimento et al. (HIO)to evaluate the structure of coke obtained from eucalyptus-based briquets. A carbon form classification system to relate quantifiable microscopic features of coke to coal rank and type was discussed by Gray and Devanney ( H I I ) . Skylar et al. (HI2) used polarized-light scanning microscopy to determine anisotropic structures in cokes, such as grains, mosaic streaks, and fibers that reduce the reactivity of coke. Transmission electron to microscopy was employed by Bensaid and Oberlin (H13) characterize the microtexture of cokes obtained from 16 coals of increasing rank and from 22 coal blends with additives. Medek and Weishauptova (HI4) discussed applications of SEM for the textural analysis of coal, coke, and carbonaceous materials. High-resolution electron microscopy was utilized by Shevlin et al. (H15)to analyze the microstructure of metallurgical cokes and to evaluate factors that contribute to coke degradation. The tensile strength of coke was determined from SEM textural data by Moreland et al. (HI61 with a standard error comparable to that of the diameter compression test. A rotary drum apparatus with a weighing scale, square-mesh sieves, and an automatic control circuit for the continuous determination of the high-temperature strength of metallurgical Yoshino et al. coke was described by Itagaki et al. (H17). ( H I 8 ) gave an equation for determining the mechanical strength, reaction yield, drum index, tensile strength, fracturing tendency, characteristic strength, and porosity development of coke. The drum test procedure for examining the size reduction behavior of coke was investigated by using a four-parameter exponential function Smirnow (HI9) to calculate median particle size, fine-grain parameter, coarse-grain parameter, standard scattering width, and the size reduction degrees. MISCELLANEOUS
Methods for the removal of pyrite (FeS2) from Illinois coals were developed by Gidaspow et al. (11)and Doctor et al. (12). Gidaspow's group used electrofluidized beds and electrostatic sieve conveyors to remove about 50% of the FeS2. Doctor's group used superconducting quadrupole magnets to remove FeS2 from pulverized dry coal with a size range of 120-325 mesh. A method for the removal of organic sulfur from coal was developed by Wapner et al. (13). Electrolysis in an alkaline media was used and removed more than 60% of total sulfur; 70% of the organic sulfur was removed by using 2.0 V, while 85% of the FeSz was removed at 1.2-1.4 V. Thorpe et al. (14) oxidized coal and used magnetic separation to reduce sulfur. He discusses the different oxidation states of sulfur that are formed through heating coal in an oxygen-deficient atmosphere. Chemical changes associated with coal oxidation were identified by using IR photothermal beam deflection spectroscopy by Cagigas et al. (15). Coke abrasion index was used for evaluating oxidized coals. The activity of coal toward oxygen explains spontaneous ignition in coal. Sykorova et al.
SOLID AND GASEOUS FUELS
(16)used an adiabatic method to evaluate oxygen activity sites in brown coal. Reaction conditions in this study corresponded partly to the conditions prevailing in situ. New exchangeable oxygen sites in coals were determined by Olson and Diehl(17). They used p-toluenesulfonic acid in 1,2-dimethoxyethaneas a catalyst and determined methyl benzoate by GC-FTIR-MS. Wyodak subbituminous coal was characterized by Knudson (18)using proximate and ultimate analyses, petrography, pyrolysis, mineral content, ion exchange, and carbon-13 NMR. Luminescence in coal was studied by Hessley (19). A coal containing 1.25% ash exhibits luminescence during dehydration, but an ash-free coal sample does not exhibit any photon emission. An extraction of organosulfur (e.g., thiophenes) from Bevier Seam Coal was studied by White et al. (110).They used low-voltage high-resolution-MS to identify mercaptans, sulfides, and disulfides. The aromaticity of 26 high-sulfur Pennsylvanian period coals was studied by Neil1 et al. (111)using carbon-13 CPMAS-NMR and showed a surprising degree of heterogeneity. No correlation between aromaticity and carbon content was found. The heterogeneity was partly attributed to the variation and distribution of the organic sulfur. Polycyclic aromatics in coal ash were studied by Mamantov and Wehry (112) using matrix isolation spectroscopy. Arai (113)discusses the precision obtained with an on-line continuous coal analyzer using a californium-252 neutron source and compares it to conventional methods of chemical analysis. A coal sample is pulverized and then irradiated with neutrons emitted by californium-252. The fast y-rays emitted are measured by using either a NaI (TI) crystal or a Ge (Li) semiconductor detector. Eleven elements can be determined in 1 h.
Coal by the Oxygen - - Bomb Combustion/Ion Selective Electrode Method. Gills and Mavrodineanu (J2)published a book summarizing the coal, ore, mineral, rock, and refractory standards issued by NBS. The book contains remarks in tabular form concerning each of the standard reference materials (SRM’s) issued by NBS, which are described. The appendix contains reproduction of the certificates issued with the SRM’s. A handbook of the NBS-SRM’s was prepared by Taylor (J3) and provides both guidance for the use of the SRM’s and an accuracy base for chemical measurements. Taylor discusses the general concepts of precision, accuracy, and quality assurance in the measurement process.
STANDARD METHODS
GAS CHROMATOGRAPHY
The development and standardization of test procedures for coal and coke are coordinated by ASTM (JI)through the D5 committee. Standards that were adopted, revised, or reapproved during the period covered by this review include the following: D 197-87, Sampling and Fineness Test of Pulverized Coal; D 388-88, Classification of Coals by Rank; D 1757-86, Sulfur in Ash From Coal and Coke; D 1857-87, Fusability of Coal and Coke Ash; D 2013-86, Preparing Coal Samples for Analysis; D 2795-86, Analysis of Coal and Coke Ash; D 2796-88, Definition of Terms Relating to Megascopic Description of Coal and Coal Seams and Microscopical Description and Analysis of Coal; D 2799-86, Microscopical Determination of Volume Percent of Physical Components of Coal; D 4182-87a, Evaluation of Laboratories Using ASTM Procedures in the Sampling and Analysis of Coal and Coke; D 4606-86, Determination of Arsenic and Selenium in Coal by Hydride Generation/Atomic Absorption Method; D 4621-86, Accountability and Quality Control in the Coal Analysis Laboratory; D 4810-88, Hydrogen Sulfide in Natural Gas Using Length-of-Stain Detector Tubes; E-11-87, WireCloth Sieves for Testing Purposes; and E 323-85, Perforated-Plate Sieves for Testing Purposes. Standards that were covered by this review with no revision are the following: D 720-83, Free-Swelling Index of Coal; D 1756-84, Carbon Dioxide in Coal; D 2014-85, Expansion or Contraction of Coal by the Sole-Heated Oven; D 2015-85, Gross Calorific Value of Coal and Coke by the Adiabatic Bomb Calorimeter; D 2361-85, Chlorine in Coal; D 2492-84, Forms of Sulfur in Coal, D 2639-85, Plastic Properties of Coal by the Constant-Torque Giesler Plastometer; D 2797-85, Preparing Coal Samples for Microscopical Analysis by Reflected Light; D 2798-85, Microscopical Determination of the Reflectance of the Organic Compounds in a Polished Specimen of Coal; D 3174-82, Volatile Matter in the Analysis Sample of Coal and Coke; D 3176-84, Ultimate Analysis of Coal and Coke; D 3177-84, Total Sulfur in the Analysis of Coal and Coke; D 3178-84, Carbon and Hydrogen in the Analysis Sample of Coal and Coke; D 3179-84, Nitrogen in the Analysis Sample of Coal and Coke; D 3180-84, Method for Calculating from As-Determined to Different Bases; D 3302-82, Total Moisture in Coal, D 3682-83, Major and Minor Elements of Coal and Coke Ash by Atomic Absorption; D 3683-83, Trace Elements of Coal and Coke Ash by Atomic Absorption; D 3761-84, Total Fluorine in Coal by the Oxygen Bomb Combustion Ion Selective Electrode Method; and D 4208-83, Total Ch orine in
Hesbach et al. ( L I )characterized the polycyclic aromatic hydrocarbons present in coal gas using capillary column GC and GC-MS. The rapid GC identification procedure and the accompanying software that were developed provided a convenient method of building a data base of analytical results from gasifier samples. A modified GC system with increased selectivity and sensitivity for hydrogen chloride gas was reported by Huston (L2). Hydrogen chloride gas present in coal gas can be detected at parts per billion (ppb) levels. Song and Jiang (L3)studied carbon molecular sieves as GC column packing material for coal gas analysis. The carbon columns have a longer life and better stability than the 5-A type molecular sieve columns that were previously used t~ analyze for CH,, C02, 02,Nz, and CO. Huston et al. (L4) used a GC equipped with an electron capture detector to detect low ppb concentrations of arsine in coal gas samples. The variablefrequency constant-current detector has a linear response range of 5-250 ppb of arsine with an average standard deviation of 7%. Bulanov et al. (L5)monitored the composition of coke oven gases by GC using columns packed with Polysorb 1 and NaX zeolite. The calorific values of the coke oven gases were calculated on the basis of the compounds detected by GC, and the values were found to be 420-620 kJ m3 greater than values determined by standard methods. ombustion gases from metallurgical furnaces were separated by Yin et al. (L6)using GDX-104 and molecular sieve columns before analysis by GC. The GC equipped with an electron capture detector analyzed the gases for H2, 02,N2, CO, COz, and CHI. Tong (L7) presented a new method for the analysis of petroleum-associated gases based on a condensation method that separated the low-boiling alkanes. A capillary column and a flame ionization detector were used to separate and identify the fractions. Zhuze et al. (L8)used a GC to study the effect of temperature and pressure on the phase behavior of gaspetroleum systems. The molecular weight of the gas phase increased as the temperature and applied pressure increased. Zou (L9)included 26 references in a review of recent advances in GC analytical methods for natural gas and refinery gas. Cox (L10)reviewed the fundamental principles of GC with respect to the natural gas industry. General characteristics of porous-layer open-tubular (PLOT) columns and their application in the analysis of natural gas by GC were examined by Gaspar (L11). Tijssen et al. (1512)discussed theoretical aspects of a new rapid capillary GC injection system using a wide-bore A1203/KC1PLOT column to sepa-
i
GASEOUS FUELS This section covers methods for the chemical, physical, and instrumental analyses of gaseous fuels and related materials reported in the literature between October 1,1986, and September 30,1988. Chemical Abstracts was used as the reference source. In some categories the volume of material available made it necessary to limit the number of publications in this review. GENERAL REVIEWS
Kettrup and Ohrback (K1)reviewed the literature regarding the standard thermal analysis methods for coal, coal-derived products, and coal gas. Static and dynamic measurements of liquefied petroleum gas were reviewed by Brunner (K2). Karl (K3)reviewed methods for testing calibration gas used in the GC determination of gross and net calorific values for test gases.
(4
ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
89R
SOLID AND GASEOUS FUELS
rate hydrocarbons in natural gas within seconds. A simple multidimensional GC with macrobore WCOT and PLOT columns was used by Naizhong and Green (LI3)to improve natural gas analysis. De Andrade Bruning (L14) described the components of a rapid GC analyzer for natural gas. The analyzer had two detectors and three columns. The first contained molecular sieve 5A, the second Chromosorb 102, and the third Parasil B as stationary phases. This method provided efficient and precise determinations of 02,N2, CHI, C2Hs,C02, and C1-C12 hydrocarbons. Suzuta (LI5)developed a method to analyze natural gas samples in less than half the time required by conventional GC methods of analysis. The new GC analytical method involved a device that included two six-way valves. Each valve was connected to the inlets and outlets of two separate columns. With the sample flow alternated through the selected columns, the gas components were separated according to their retention times. Reed’s (LI6)rapid fully automated method for the analysis of mixtures of hydrocarbon and inorganic gases used simultaneous dual-channel sampling. Sample separation and peak detection were performed by using a single chromatograph. The analysis took less than 4.5 min. SULFUR COMPOUNDS
Phillips et al. ( M I )used chemical analysis and GC to detect volatile sulfur compounds and low-molecular-weight hydrocarbons in a gas stream. A microprocessor controlled the addition of known components in a divided portion of the gas stream and correlated their concentrations to the actual concentrations present in the sample. Trace amounts of COS and H S were detected by Wang and Xie (M2) in coal gas using 6 C with a flame ionization detector and a Porapak-QS stationary phase. Vincent (M3)used a multicell coulometric titration technique and a microcompressor-based analyzer to detect mercaptans, H2S, and residual sulfur in natural gas. The most sensitive indicator electrodes for the potentiometric titration of mercaptans and H2S in natural gas condensates are 1- and CNS- electrodes, according to Kiyanskii and Burahkta (M4). Optimum reference electrodes were composed of Zr and Sb. Tomm and Mohr (M5) discussed a centrally monitored and controlled H2S detection system for acid gas fields. The sensors for H2S detection were based on electrochemical or semiconductor cells. All H2S limit values and data were transmitted to a data control center. Samples are taken during the recovery, transport, and storage of natural gas. The H2S is catalvticallv oxidized. and the exothermic effect is measured by usiig a method for H2S detection developed by Nadzhafov et al. ( M 6 ) . CONDENSATES AND MOISTURE
Negative-ion mass spectrometry was used by Shmakov et al. ( N I )to characterize the negative ions formed from dissociation of organic disulfides in natural gas condensates. Kul’dzhaev et al. ( N 2 )characterized high-molecular-weight hydrocarbons from gas condensates and related the concentration of the aromatics to their boiling points. Bagir-Zade et al. (N3)discussed the distribution of methane, naphthalene, aromatic hydrocarbons, and the molecular ratio of n-alkanes to isoalkanes in natural gas condensates. The labile n-Clo-Cm and iso-C11-C23hydrocarbons in geological condensate samples provided information on the origin and development of gas and oil reservoirs. Yue et al. ( N 4 ) described the phase behavior, methods of detection, and data processing for natural gas condensates. A method to calculate the production rate of water in gas condensates was reported by Reinhardt et al. ( N 5 ) . The technique’s potential error was due to water dissolved in the condensate. Gates and Scelzo (N6) reviewed problems found in the detection of moisture in natural gas and concluded that the thin-film aluminum oxide moisture sensor is the best analyzer. Various methods for the determination of the water vapor content and the dew point of natural gas were reviewed by Dodds ( N 7 ) . Techniques reported included the Bureau of Mines tester, electrolytic water vapor analyzer, capacitance hydrometer, water vapor titrator, and appurtenant devices. Mayeaux (N8) discussed the performance of the Ramarex SOR
ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
Model 721 analyzer and the Ramarex Model 741 H P calibrator for the detection of moisture in natural gas. Kahmann (N9) described the use of the Bureau of Mines-type dew-point testers for moisture detection in natural gas. The tester that was based on the principle of condensing moisture in a pressure chamber was accurate and has been in use for about 50 years. Folmer (NIO)measured the dew point of natural gas by an on-line monitoring technique employing a hygroscopic salt-glycerol solution. CALORIMETRY
Solov’ev et al. ( P I ) reported on a method in which combustible gas and an oxidizing agent were placed in an isothermic apparatus consisting of identical measuring and reference cells, a system to control the heat flow between the cells, and a device to measure the specific heat of fuel gas. Mondeil and Robert (P2)continuously measured the gross calorific value of fuel gas in a calorimeter operated at a temperature that maintained an equilibrium between the water that condensed and the water that formed during combustion. Measurement of the calorific value was alternated with measurements of a standard reference fuel gas. Cheney (P3) measured the calorific value of fuel gas with an apparatus that had a combustion chamber, a temperature sensor, and a heat supply monitor. The apparatus correlated the electrical energy change in the combustion chamber that was filled with thermally conductive particles to the calorific value of the fuel gas. Solov’ev et al. (P4) measured the gross and net calorific values of a fuel gas by feeding the fuel gas into a continuous measuring cell maintained at constant flow rate, pressure, temperature, and moisture content in order to assure complete combustion of the gas. Nozawa (P5)calculated the calorific values of fuel gases based on combustion time and electrical resistance of a known amount of fuel gas. Combustion time and electrical resistance were compared with calibration curves obtained from the electrical-resistance-calorific value and the electrical-resistance-combustion time correlations to calculate the calorific value of a fuel gas. Both a catalytic calorimeter and one that determines the heat of combustion of natural gas by using a series of temperature controllers and sensors attached to a combustion chamber and a heat sink were described by Rockwell International Corp. (P6). The controller was connected to an output device that recorded the amount of heat removed from the heat sink. Singh et al. (P7)proposed a new, highly accurate on-line method for determining the heat of combustion of natural gas. The method is based on controlling and monitoring the mole fraction of oxygen present in the combustion product gases and the carrier air. Singh et al. (P8) simplified the method they described in ref P7 and eliminated the need for oxygen enrichment while predicting natural gas heats of combustion to within 1%. The Btu content of a combustible fluid, such as natural gas, was determined by Brown et al. (P9)by measuring the absorbance of radiation directed into the sample components. The resulting spectral lines from each of the compounds were related to the heat energy proportionality factor, and these values were summed discussed the to determine the Btu content. Van Meter (PIO) use of the Cutler Hammer calorimeter, the precision measurement titrator, and the Honeywell valve transmitter combustion instrument for the determination of calorific values of natural gases. In another article, Van Meter ( P I I )reported further on the Cutler Hammer calorimeter and a stoichiometric method of natural gas analysis and described their use in determining calorific values by combustion. Bukacek (PI2) stated that during the determination of heating values of natural gas, calorimeter calibrations are not affected by C6+ trace compounds if the trace-compound-free gas does not reach its dew point. Wilde (P13) reviewed the advantages and disadvantages of manometric, volumetric, and gravimetric preparation of test gases prior to chromatographic determination of gross and net calorific values. Gross and net calorific values for West German natural gases that were determined by using process chromatography were discussed by Below and Herbst (PI4). Heating values measured by GC differed from values determined by using calorimetry by approximately 2 W h/m3. Mowery (P15) used a computerized on-line silicon micromachined process GC to determine the calorific value, specific
SOLID AND GASEOUS FUELS
avity, Wobbe index, and compressibility of natural gas. The E C consisted of three different micro GC units that operate together as a single unit and provide a rapid detailed analysis. Cox (PI6)described the use of a computerized on-line GC to measure the calorific value of natural gas. A practical method to calculate calorific values based on thermodynamic principles was proposed by Paunovic et al. (PI7).Values from this method and values from GOST and ASTM standard methods used to determine the calorific value of natural gas were compared. Raman spectrometry was used by Florisson and Joosten (P18)to qualitatively and quantitatively identify the physical properties of natural gas. The method provided rapid determination of gross calorific values and specific gravity determinations. Donahue et al. (P19)evaluated for near-infrared (NIR) multicomponent analysis methods in spectral and Fourier domains to assess the feasibility of determining the energy content of natural gas spectroscopically. The methods were applied to a set of NIR spectra, and superior energy values were obtained when the spectra were Fourier transformed before analysis of the data. Blanke and Weiss (P20)calculated the entropy, enthalphy, and calorific values of natural gas mixtures from thermodynamic principles. Values were presented in tabular form for temperatures of 5,15, and 25 "C. A BASIC computer program to calculate complete combustion values for heating oil and natural gas was developed by Grimm (P21). Examples of complete combustion calculations were included. METERING AND DENSITY
Mader (81)reviewed gas meters, quantity converters, and other devices that measure large quantities of natural gas. Natural gas chemistry and the kinetic theory of natural gas behavior and their relationship to gas measurement were discussed by Tefankjian (Q2). Smith (Q3) defined terms commonly used in natural gas measurement. Equations of state based on fundamental gas laws were developed by Ellington (Q4),and these equations, developed for gas measurement, were discussed. Edalat et al. (Q5)showed that gas distribution networks can be accurately designed by using a new mathematical model based on mass flow rates and pressure balances. The nonlinear equations accurately calculated the length and diameter of pipe needed for transport networks. Kruk and Lesovoi (86)determined natural gas flow rates by measuring the drop in pressure as the gas passed through an orifice. The measurement was corrected for moisture, pressure, temperature, density, compressibility, Reynold's number, and the amount of N2 and CO,; and the quantitative flow rate was determined. Clingman (87)evaluated two methods of determining energy flow in a natural gas pipeline and found that the direct calorific value determination method was superior to a GC method of determining the energy delivery rate. Falque (Q8) designed a metering device for measurin the amounts of natural gases from different origins in a distritution network. The gases can be distinguished from one another by measurement of their thermal characteristics. Hughes (Q9) used a critical flow prover to meter natural gas delivery and gas well performance. Lee (810) verified that a well-designed gas turbine flowmeter calibrated in air has the same accuracy when it is operated in natural gas. Kohda et al. (811)developed a computer program for the analysis of transient gas-liquid two-phase flow in natural gas pipelines. The analytical method is based on the two-velocity mixture model. Hassapis (Q12)developed methods to select the algorithm and to determine the number and type of sensors required for the measurement of the consumption of fuel gas using a computer-based instrument. The selection of the number and types of sensors necessary to ensure precise measurements of gas will define the microcomputer selection. Corresponding-state liquid densities (COSTALD) correlation in custody transfer of natural gas lipids was evaluated by Thomson and Hankinson (Q13). Russell (Q14)discussed the supervisory control and data acquisition remote terminal unit (SCADA-RTU) for the custody transfer of natural gas. Norman and Jepson (Q15) calculated the estimate of the errors when natural gas flows are measured by orifice meters and turbine meters. The gas that is unaccounted for is primarily due to flowmeter errors.
Starling et al. (816)reviewed new developments in determining the supercompressibility and thermodynamic properties of sweet and sour pipeline natural gas. The American Gas Association (AGA) Transmission Measurement Committee Report Number 8 that describes the supercompressibility and compressibility factors for rich pipeline quality natural gas was evaluated by Starling et al. (Q17). Starling (Q18)concluded that a method to compute the compressibility of natural gas in the AGA Transmission Measurement Committee Report Number 8 was an improvement over methods used in Report NX-19. Luebbe (Q19) found the supercompressibility factor program developed by the AGA gave values that were in agreement with measured supercompressibility values for natural gas. Sivaraman and Gammon (Q20)reported that the determination of compressibility, supercompressibility, and metering of natural gas could be improved by measuring the speed of sound in methane. A new equation developed by Schouten et al. (Q21)predicts the compressibility of natural gas when three out of four of the following values are known: gross calorific values, mole fraction of N,, mole fraction of CO, and specific gravity. Ellington et al. (Q22)derived compressibility factors from temperature, volume, and pressure data for natural gas. Jaeschke and Hinze (Q23)discussed vibrating-element densitometers to predict the densities of natural gases and applied these data to gas metering. Tunheim et al. (Q24) discussed the use of methane as a density-meter calibration gas in natural gas density determinations. The calibration experiments were carried out in custody transfer by the Solarton 7811 d meter. A simple equation of state developed by Kleinrahm et al. (Q25)to measure and correlate the gas density of methane yielded results that compared well with values calculated by using the AGA method of determining methane in natural gas. Eubank et al. (Q26)reported Virial coefficients and Burnett-isochoric densities for two well-defined sweet and sour natural gases. Densities at 50-210 "C and 0.1-16.9 MPa were considered accurate to &0.04%. The effects of N,, COz, and H2S on the viscosities of natural gas at temperatures of 293-513 K were calculated by Dadash-Zade (Q27). Individual components of natural gas contribute to its viscosity in proportion to their volumes or mole fractions in the gas. Pedersen and Fredenslund (Q28)extended and modified the viscosity model equation to predict the viscosities of gas and oil at temperatures below 0.4 "C. SAMPLING
The sampling systems and operation of electrical cell devices used to detect moisture in natural gas were reviewed by Barnes (RI). De Andrade (R2)discussed natural gas sampling and the application of the N-1979a standard methods for obtaining representative samples. To detect possible gas leaks, Sevcik et al. (R3)collected soil gas samples by inserting perforated tubes into the ground above natural gas storage facilities. Several portable CH, gas analyzers were also described. In addition to CH, content, He content, and the lZCto ratio, other gases present in natural gas can be determined. Jordan and Menzel (R4)used a helium-neon laser-based field device capable of operating from a moving vehicle while continuously sampling and measuring small changes in CHI concentration in the near-surface atmosphere. This sampling method allows large areas to be rapidly surveyed to detect CH,. MISCELLANEOUS
An automatic method to continuously detect ammonia in coke-oven gas was discussed by Nakamura and Iio ( S I ) . The coke-oven gas was contacted with a solution containing ammonium phosphate [ (NH4),P04]; the acid gas was removed by passing the coke-oven-gas solution through a heat exchanger. Portions of the final solution were sampled using an on-line refractometer both before and after the removal of the NH3. The deviation of NH3 concentrations determined by this method from those determined by the Phosam process was 0.1-1.4%. Markuszewski et al. (S2)described a method for on-line detection of alkalies in coal gas using a system based on flame atomic emission spectrometry. The surface tension of gas-saturated petroleum in contact with natural gas was calculated from the surface tension of ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
91 R
S O L I D AND GASEOUS FUELS
petroleum in air, the amount of gas dissolved, and the constant a in a method devised by Korshak and Burdygina (S3). The relative error was 0.1-6.5%, and the relative square deviation was 2.6%. The determination of heavy compounds in natural gas was reviewed by McCann (S4). Moore and Sigler (S5)surveyed natural gases from 20 states of the United States of America and analyzed the gases by using GC and mass spectrometry. Helium content, densities, and calorific values were also determined. Faber et al. (S6) reviewed a 56-page document on the uses of mass spectrometry to determine the deuteriumto-hydrogen ratios in natural gas. This isotope data provided information about the biogenesis of the natural gases that were characterized. Baillie and Skinner (S7) determined bubble point pressure, vapor pressure, and composition of natural gas and hydrocarbon liquids by using a system having one or more eductors at selected pressure differentials. Composition was determined by comparing vapor pressure characteristics of the liquid stream with the vapor pressure of known compounds. Methane, ethane, and propane were separated from natural gas by GC before Shen et al. (S8)combusted them to form COz and H20.Mass spectrometry was used to determine the I3C content of the COP. Water was reacted with zinc to form hydrogen gas that was adsorbed on activated C before determination of deuterium. Scarano et al. (S9) assembled an innovative ready-to-use electrochemical Severinghaus-type COPanalyzer to detect COz in natural gas. The COz analyzer was placed in the line of a carrier gas stream, and gaseous samples were introduced. This technique both improved the performance of the analyzer and increased its applications. An apparatus that filters, dries, automatically samples, and removes condensates before analyzing fuel gas and natural gas was devised by Kawachi and Kaneko (S10). After analyzing natural gas for C1-CI9 hydrocarbons, Demczak and Kegel (SI 1) determined the heavier hydrocarbons. The natural gas was cooled to -78 "C, and the resulting condensate was analyzed by using GC to determine Czoand heavier hydrocarbons. Mulyono (5'12) developed a method to determine the presence of mercury (Hg) in natural gas. Mercury vapor contained in a natural gas stream was extracted by a dilute acidic solution of potassium permanganate (KMnO,). The concentration of the resulting Hg salt was determined by AAS. An on-line instrument based on the Raman scattering of laser light was used by Florisson and Burrie (S13) to detect molecular and nitrogen concentrations with a mean error of f0.2% and a standard deviation of 0.1%. Concentrations of COP, CO, H2S, and other molecular components can be determined by choosing the appropriate optical filter. Troeger and Hausknecht (S14) reviewed the developmental status of the semiconductor natural gas sensors used in the detection of gas pipeline leaks and in air monitoring. In feasibility studies regarding the use of semiconductor lasers as IR sources for portable natural gas leak detectors, Elliott ( S I 5 ) concluded that the cleaved-coupled-cavity carbon-3 structures were the most promising. Stan (S16) calculated losses from leakage of natural gas owing to cracks and corrosion in transport systems. The effects of pipe defects, plugging by porous materials, and pressure at the exterior surface of pipes were considered as factors in the calculations.
D 2163-87, Method for Analysis of Liquefied Petroleum (LP) Gases and Propene Concentrates by Gas Chromatography; D 2725-87, Test Method for Hydrogen Sulfide in Natural Gas; D 3956-87, Methane Thermophysical Property Tables; D 3984-87, Ethane Thermophysical Propery Tables (Methylene Blue Method); D 4650-87, Normal Butane Thermophysical Property Tables; D 4651-87, Isobutane Thermophysical Property Tables; and D 4810-88, Test Method for Hydrogen Sulfide in Natural Gas Using Length-of-Stain Detector Tubes. LITERATURE CITED SOLID FUELS
Sampllng and Proxlmate Analyels (AI) Dutcher, R. R.; Gunter, M. E.; Crelling, J. C.; Brower, W. E. Report 1985, GRI-85/0008; Order No. PB86-103876/GAR, 151 pp; avail. NTIS. From Gov. Rep. Announce. I n d e x ( U . S . )1988. 86(1), 601 947. (A2) Vorres, K. S.; Janikowskl, S. K. Prepr. Pap.-Am. Chem. SOC., Div. Fuel Chem. 1987, 32(1). 492-9. (A3) Kruse, C. W.; Harvey, R. D.; Rapp, D. M. Process. Mil. High Sulfur Coals, Proc. Int. Conf. 2nd 1987, 49-57. (A4) Kettlewell, D. E. Proc. Conf.-Int. Coal Test. Conf. 1986, 5th, 57-61. (A5) Tatro, M. E.; Giampa, V. M. Spectroscopy(Eugene, Oreg.) 1988, 3(2), 22, 24-5. (A6) Wells, P. Ann. Mines Be@. 1988, 3-4, 593-615, (Fr); Chem. Abstr. 1986, 105. 175618. (A7) Klein, A. Aufbereit-Tech. 1987, 28(1), 10-16 (Eng/Ger). (A8) De, S. K. Fuel 1988, 67(7), 1020-3. (A9) Beuerman, D. R. Proc. Conf.-Int. Coal Test. Conf. 1986. 5th, 5-9. (A10) Heitz, G.; Boury, 8.; Phlllppe, J. Fr. Demande FR 2,573,530 (CI. GOlN9/36), 23 May 1986, Appl. 84/18,076, 21 Nov 1984. ( A l l ) Zhang, C.; Wu, J.; Song, Y. Ranliao Huaxue Xuebao 1987, 75(4), 378-84 (Ch); Chem. Abstr. 1988, 709, 9121. (A12) Ishibashi, Y.; Fukumoto, K.; Maeda, K.; Ogawa, A.; Goto, K.; Ishii, T. Tetsu to Hagane 1987, 73(2), 387-93 (Japan); Chem. Abstr. 1987, 706, 140848. (A13) Mao, J.; Yang, D.; Zhao, B. Ranliao Huaxue Xuebao 1987, 15(3), 268-70 (Ch); Chem. Abstr. 1988, 108, 78436. (A141 Kawaguchi, H.; Miyazaki, Y.; Fukuyama, S. Jpn Kokai Tokkyo JP 61,191.950 [86,191,950] (C1.GOIN 25/58), 26 Aug 1986, Appl. 85/31, 409, 21 Feb 1985. (A151 Thuemmel, H. W. Ger. (East) DD 252 441 (Cl. G01N23/201), 18 Dec 1987, Appl. 293,829, 27 Aug 1986. (A16) Dombrovskii, V. P.; Dyusembaev, D. E.; Ryashchikov, V. I . Metallurg (Moscow) 1988, (4), 28-9 (Russ); Chem. Abstr. 1988, 109, 85481. (A17) Pak, Yu. N. Koks Khim. 1987, 72, 39-41 (Russ); Chem. Ab&. 1988, 108, 40817. (Al8) Pan'kov, S. D.; Smagunova, A. N.; Pan'kova, L. M. Zavod. Lab. 1987, 53(11), 91-3 (Russ); Chem. Abstr. 1988, 108, 24360. (A19) Wawrzonek, L. Isotopenpraxis 1988, 24(2), 82-4. (A20) Rao, N. V.; Anjaneyulu, S. Geophys. Res. Bull. 1987, 25(4). 188-90. (A21) Pandey, H. D. Steel India 1988, 9(1), 1-13. (A22) Wang, Q.; Wu, D. Ranliao Huaxue Xuebao 1988, 14(2), 163-9 (Ch); Chem. Abstr. 1988, 105, 155895. (A23) Leonhardt, J.; Thuemmel, H. W. Wlss. Fortschr. 1988, 36(8), 203-6 (Ger); Chem. Abstr. 1987, 706, 7250. (A24) Votava, P.; Kubant, J. Czech CS 233,658 (CI. G01N23/02), 01 Jul 1986, Appl. 8219,756, 27 Dec 1982. (A25) Pak, Yu. N.; Vdovkin, A. V. Fiz.-Tekh. Probl. Razrab. Polezn. Iskop. 1986, (6), 96-100 (Russ); Chem. Abstr. 1987, 706, 69954. (A26) Weber, M.; Beckmann, M.; Haeusler. S.;Bordihn, J.; Zocher. B.; Schaefer, K. Ger. (East) DD 250,186 (Cl. GOIN33/22), 30 Sept 1987, Appl. 291, 430, 19 Jun 1986. (A27) Ohkubo, T.; Honma. T.; Kuriyarna, M. Yamagata Da/gaku Kiyo, Kogaku 1988. 20(1), 63-8 (Japan); Chem. Abstr. 1988, 108. 207427. (A28) Eklund, G.; Pedersen, J. R.; Stroemberg, B. Fuel 1987, 66(1), 13-16. (A29) Ohrbach, K. H.: Matuschek, G.; Kettrup, A. Thermochim. Acta 1987, 121 87-96. (A301 Baranovskii, V. I.; Polyashov, A. S. Ugol Ukr. 1987, 10, 24 (Russ); Chem. Abstr. 1988, 108, 8587. ~
Ultlmate Analysls and Sulfur Forms
STANDARDS
Niedung ( T I )reported the Federal Republic of Germany's calibration specifications for chromatographic determinations of gross and net calorific values of natural gas supplied by pipelines. Standard calculations for the gas behavior of both low CH, and hi h CH, natural gases were introduced by Jaeschke ("2). 8olka and Attari (2'3) discussed the preparation of certified calibration standard gases for GC analysis of natural gas and the precautions necessary to maintain the integrity of the calibration gases. The ASTM standards (T4)that have been newly adopted or revised during this period include the following: D 1265-87, Practice of Sampling Liquefied Petroleum (LP) Gas; D 1266-87, Test Method for Sulfur in Petroleum Products (Lamp Method); I> 1826-88,Test Method for Calorific Value of Gases in Natural Gas Range by Continuous Recording Calorimeter; D 1835-87,Specification for Liquefied Petroleum (LP) Gases; 92R
ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
(BI) Schuchardt, K.; Ewers, H.; Aitmann, B. R. &r.-Dtsch. Wiss. Ges. Erdoel, Erdgas Kohle 1987, 305, 249 pp (Ger); Chem. Abstr. 1988, 108, 115320. (82) Heinrich, B.; Irmer, K.; Poetschke, R. Radbkot. Appl. Redlat. Prcces. Ind., Work. Meet., Proc., 3rd 1985, 2, 841-7. (83) Hase, R. Nenryo Kydalshi 1985, 64(2), 141-50 (Japan); Chem. Absb. 1988, 105, 155712. (84) Saito, A. Jpn. Kokai Tokkyo Koho JP 61,71,356 [86,71,356] (CI. GOIN31/00), 12 Apr 1986, Appl. 84/192, 629, 17 Sep 1984. (85) Burchill, P. Coal Sci. Technol. 1987, 7 7 , 5-8. (B6) Wallace. S.; Bartle, K. D.; Perry, D. L.; Hodges, M. G.; Taylor, N. Coal Sci. Technol. 7987, 1 1 , 9-12. (87) Zischka, B.; Stremming, H. J. Coal Qual. 1986, 5(4), 138-42. (B8) Ehmann, W. D.; Hamrin, C. E., Jr.; Koppenaal, D. W. Report 1985. DOE/PC/60785-8: Order No. DE86005087, 1I 1 pp.; avail. NTIS. From ERA 1986, 71(19), 42483. (B9) Ishibashi, Y.; Fukumoto, K.; Sasaki, T.; Ogawa. A.; Maeda, K. Jpn. Kakai Tokkyo Koho JP 61,189,458 [86,187,458] (CI. GOlN35/00), 23 Aug 1986. Appi. 85129,413 19 Feb 1985. (BIO) Kalandadze, N. D. I z v . Akad. Nauk. Gruz. SSR, Ser. Khlm. 1988, 12(4), 252-5 (Russ); Chem. Abstr. 1987, 106, 69957.
SOLID AND GASEOUS FUELS ( B l l ) Kimura, T. Nenryo Kyokaishi 1987, 66(1), 28-34 (Japan); Chem. Abstr. 1987, 106, 159187. (812) Kocman, V. Adv. X-Ray Anal. 1987,30, 243-9. (813) Duffey, D.; Wiggins, P. F. Nucl. Technol. 1987, 77(1), 68-81. (814) Oiivier, C.; Pelsach, M.; Morland, H. J.; DeWet. B. S. J . Radioanal. Nucl. Chem. 1986, 106(2), 107-21. (815) Caroli, S.;Mazzeo, A. F.; Laurenzi, A,; Senofonter, 0.; Vloiante, N. J. Anal. At. Spectrom. 1988,3(1), 245-8. (816) Markuszewski, R. J . Coal Qual. 1988, 7(1), 1-3. (817) Nlshioka. M. Energy fuels 1988,2(2), 214-19. (Bl8) Huffman, G. P.; Huggins, F. E.; Shah, N.; Bhattacharyya, D.; Pugmire, R. J.; Davis, B.; Lytle, F. W.; Groegor, R. B. Process. Mll. Hlgh Sulfur Coals, Proc. I N . Conf., 2nd 1987,3-12. (B19) Tseng, B. H. Ph.D. Dissertation Univ. Illinois, Urbana, IL, USA, 1986, 107 pp. avail.; Univ. Microfilms Int., Order No. DA8623426 From Dlss. Abstr. I n t . 6 1987,47(7), 3082. (820) Finkeiman, R. B. J . Coal Qual. 1987,6(2), 50-2. (821) Straszheim, W. E.; Younkin, K. A,; Markuszewski, R. Process. Mil. H/gh Sulfur Coals, Proc. Int. Conf., 2nd 1987,41-8. (822) Agus. M.; Garbarlno, C. Rend. Soc. Ita/. Mineral. Petrol. 1988, 41(1), 69-74 (Ital); Chem. Abstr. 1988, 105, 175608. (823) Hippo, E. J.; Crelling, J. C.; Sarvela, 0. P.; Mukerjee, J. Process Mil. H/gh Sulfur Coals, Proc. Int. Conf., 2nd 1987, 13-22. (824) Boudou, J. P.; Bouiegue, J., Maiechaux, L.; Nip, M., DeLeeuw, J. W.; Boon, J. J. Fuel 1987,66(1 l), 1558-69. (825) Majchrowicz, B. 8.; Yperman, J.; Reggers, G.; Francois, J. P.; Geian, J.; Martens, H. J.: Muilens, J.; Van Poucke, L. C. Fuelprocess. Technol. 1987, 15, 363-76. Inorganic Constituents
( C l ) Hurley, J. P.; Steadman, E. N.; Kleesattel, D. R.; Report 1986, DOE/ FE/80181-2094; Order No. DE86014277, 63 pp; avail. NTIS. From ERA 1988, 11(20), 45618. (C2) Aivarado, J.; Leon. L. E.; Lopez, F.; Lima, C. J . Anal. At. Specfrom. 1988,3(1), 135-8. (C3) Yu, G.; Zha. Y.; Liu, G.; Li, D. Youkuangye 1987, 6(3), 67-70 (Ch); Chem. Abstr. 1988, 109, 9117. Popescu, M.; Banu, G. An. Univ. Galati, Fasc. 9 1987, (C4) Mltoseriu, 0.; 5 , 13-18 (Russ); Chem. Absb. 1988, 108, 115433, (C5) Inoue, S.; Hoshi, S.; Matsubara, M. Talanta 1986, 33(7), 611-13. (C6) Pak, Yu. N.; Vdovkln, A. V. flr.-Tekh. Probl. Razrab. Polezn. Iskop. 1987,6,98-102 (Russ); Chem. Abstr. 1988. 108, 123602. (C7) Ebdon. L.; Parry, H. G. M. J . Anal. At. Specfrom. 1988,3(1), 131-4. (C8) Coleman, G. N. Report 1965, NP-6900917; Order No. TI86900917, 27 pp.; avail. SOMED, Box 6282, Univ. Ala., Tuscoioosa, AL 35486; From ERA 1986, 11(9), 19025. (C9) Lindahl, P. C. Report 1985 ANLIACL-85-3; Order No. DE86006516, 31 pp.; avail. NTIS. From ERA 1988, 71(8), 16752. (C10) Hurley, J. P. Proc. Conf.-lnt. Coal Test. Conf. 1988, 5th, 24-8. (C11) Howarth, 0. W.; Ratciiffe, G. S.; Burchiii, P. Fuel 1987,66(1), 34-9. (C12) Nelson, J. B. Adv. Instrum. 1985,40(2), 1407-33. (C13) Cox, J. A.; Saari, R. Analyst (London) 1987, 112(3), 321-3. (C14) Doolan, K. J. Anal. Chim. Acta 1987,202, 61-73. ((215) Kosasa, K.; Nakajima, S.Spectrochim. Acta, Part 6 1987,426(3), 501-3. (C16) Inoue, S.; Hoshi, S.; Matsubara, M. Talanta 1987,34(10), 889-91. (C17) Pettit, W. E.; Horlick, G. Spectrochim. Acta, Part 6 1988, 416(7), 699-712. (C16) Nissen, D. A.; Greullch, F. A. Proc.-Electrochem. SOC. 1988,88-5. (C19) Ocaranra, C. P. G. Ph.D. Dissertation Pennsylvania State Univ. 1986, 223 DD; avail. Unlv. Microfilm Int., Order No. DA8815189. From Diss. Abstr.' Int. 6 1988,47(5), 2113. (C20) Parry, H. G. M.; Ebdon, L. Anal. Proc. (London) 1988,25(3), 69-71. (C21) Tamura, H.; Inui, T.; Fudagawa. N. Shlruoka-Ken Kogyo GVutsu Senta Kenkyu Hokoku 1988, 3 0 , 73-9, (Japan); Chem. Absfr. 1986, 105, 155862. (C22) Dewlson, M. G.; Kanaris-Sotirlou, R. Int. J . Coal Geol. 1988,6(4), 327-41. (C23) Ryan. D. E.; Chatt, A.; Holzbecher, J. Anal. Chim. Acta 1987,200(1), 89- 100. (C24) Tomza, U.: Kaleta, P. J . Radioanal. Nucl. Chem. 1988, 107(1), 1-10. ((225) Saiama, S. B.; West, T. S. Arab Gulf J . Sci. Res. 1988, 4(1), 105- 15. Caloriflc Analysls
( D l ) Sandulescu, E.; Maftei, M.; Krauss, S. Rom. RO 84,047 (CI. G01K17/ 501, 30 Jun 1984, Appl. 107,245, 06 Feb 1981. (02) Ferguson, J. A.: Rowe, M. W. Thermochim. Acta 1986, 107, 291-8. (D3) Bao, H. Jisuanl, Yu Yingyong Huaxue 1987, 4(3), 206-8, 188 (Ch); Chem. Abstr. 1988, 108, 78434. (D4) Corrales Zarauza. J. A. Energia (MadrM) 1988, 14(1), 111-15 (Span); Chem. Abstr. l988* 108, 189563. (D5) Sole Ribalta, J.; Colombo. B. Quim. Ind. (Madrid) 1988. 32(2). 119-21 (Span); Chem. Abstr. 1987, 106, 52880. (D6) CywickaJaklel, T. Rap.-lnst. f i z . Tech. Jad. AGH 1986.67-80 (Pol); Chem. Abstr. 1986. 105, 136704. (D7) Sun. X. Kexue Tongbao (Foreign Lang. Ed.) 1987,32(22), 1567-71. (DE) Qian, S.;Yang, D. Nuadong Huagong Xueyuan Xuebao 1988, 12(1), 95-105 (Ch); Chem. Abstr. 1987, 106, 122745. Petrography
(El) Millev. J. Fuel 1988, 67(1). 143-4. (E2) Kotkin, A. M.; Svyatets, I. E.; Nesterov, N. I.Ugol'ukr. 1988, 10,43-4 (Russ); Chem. Abstr. 1987, 106, 7255. (E3) Larsen, J. W.; Wei. Y. C. Energy fuels 1988, 2(3). 344-50.
(E4) Radke, M.; Weite, D. H.; Willsch, H. Org. Geochem. 1986, lO(1-3), 51-63. (E5) Creiling, J. C. Coal Sci. Technol. 1987, 11, 119-22. (E6) Jobling, J. L.; Creiling. J. C. Report 1987, DOE/PC/91272-T12; Order No. DE 87011026, 22 pp; avail. NTIS. From ERA 1987, 12(17), 34477. (E7) Pandolfo, A. G.; Jones, R. B.; Dyrkacz, G. R.: Buchanan, A. S. Energy Fuels 1988, 2(5), 657-62. (E8) Chen, P.; Bodily, D. M. Ranllao Huaxue Xuebao 1988, 14(2), 142-7 (Ch); Chem. Abstr. 1988, 105, 155861. (E9) Dyrkacz, G. R.; Aznavoorian. P.; Young, J.; Neiil, P.; Bioomquest, C. A. A.; Turner, L. R. Coal Sci. Technol. 1987, 11. 907-10. (E10) Creiiing, J. C.; Skorupska, N. M.; Marsh, H. fuel 1988, 67(6), 781-5. (El 1) Correa da Silva, 2. C.; Puettmann, W.; Wolf, M. Coal Sci. Technol. 1987, 11, 165-8. (E12) Riepe, W.; Stellar, M. fuel 1987,66(1), 83-5. (E13) Death, D. L.; Haub, J. G.; Eberhardt, J. E. fuel 1988, 67(6), 859-62. (E14) Salehi, M. R.; Hamilton, L. H. Fuel 1988, 67(2), 296-7. Physical Methods
(Fl) Marsh, H. Carbon 1987,25(1), 49-56. (F2) Larsen, J. W.; Wernett, P. Energy Fuels 1988, 2(5), 719-20. (F3) Glaves, C. L.; Davis, P. J.; Gallegos, D. P.; Smith, D. M. Energy Fuels 1988,2(5), 662-8. (F4) Hewei-Bundermann, H.; Juentgen, H. Erodoel. Erdgas, Kohle 1988, 104(3), 124-30 (Ger); Chem. Abstr. 1988, 109, 8973. (F5) Cody, G. D., Jr.; Larsen, J. W.; Siskin, M. Energy Fuels 1988, 2(3), 340-4. (F6) Hall, P. J.; Marsh, H.; Thomas, K. M. fuel 1988,67(6), 863-6. (F7) Narayanan, S. S.; Lira, B. B.: Rong, R. X. Coal Prep. (Gordon & Breach) 1988,5(3-4), 211-27. (F8) Dybala, P.; Wasiiewski, P.; Mianowski, A. Koks, Smola, Gar 1987, 32(10), 227-33 (Pol); Chem. Abstr. 1988, 108, 153334. (F9) Gumkowski, M.; Liu, Q.; Arnett, E. M. Energy fuels 1988, 2(3), 295-300. (FIO) Fowkes. F. M.; Jones, K. L.; Li, G.; Lloyd, T. B. Prepr. Pap.-Am. Chem. Soc., Div. f u e l c h e m . 1987,32(1), 218-25. (F11) Golesteanu, I.Energetica 1987,35(8), 364-70 (Rom); Chem. Abstr. 1988. 108, 170521. Spectroscopy
(GI) Solomon, P. R.; Carangeio, R. M. fuel 1988,67(7), 949-59. (G2) Verheyen, T. V.; Heng, S.; Perry, G. J.; Fredericks. P. M. Coal Sci. Technol. 1987, 11, 127-30. (G3) Smyrl, N. R.; Fuller. E. L., Jr. Prepr. Pap-Am. Chem. SOC.Div. fuel Chem. 1987,32(1), 337-47. (G4) Larsen, J. W. Prepr. Pap.-Am. Chem. SOC.,Div. f u e l c h e m . 1988, 33(1), 400-6. (G5) Griffiths, P. R. Report 1988. DOE/PC/50797-T12; Order No. DE86011951, 98 pp; avail. NTIS. From ERA 1986, 11(18), 39492. (G6) Caiemma, V.; Rausa, R.; Margarit, R.; Giradi, E. fuel 1988, 67(6), 764-70. (G7) Gethner, J. S. Appl. Spectrosc. 1987,41(1), 50-63. (G8) Olson, E. S.; Diehl, J. W.; Froeiich, M. L. Anal. Chem. 1988,60(18), 1920-4. (G9) Seehra, M. S.; Ghosh, B. J . Anel. Appl. Pyrolysis 1988, 13(3), 209-20. (G10) Lin, X.; Xiao. Q.; Huang, K.; Liao, X. Ran/& Huaxue Xuebao 1987, 15(4), 354-8 (Ch); Chem. Abstr. 1988, 108, 224077. (G11) Thomann, H.; Silbernagei, B. G.; Jin, H.; Gebhard, L. A,; Tindali, P.; Dyrkacz, G. R. Energy fuels 1988,2(3), 333-9. (G12) Juenet, A,; Nickel, B.; Rassat, A. J . Chim. Phys. Phys.-Chlm. 6iol. 1988,85(1), 97-102 (Fr); Chem. Abstr. 1988, 108, 207415. (G13) Wieckowski, A. B.; Duber, S.ferroelectrics 1987,8 0 , 95-8. (G14) Ziim, K. W.; Webb, 0. G. fuel 1988,67(5), 707-13. (G15) Barton, W. A.; Lynch, L. J. J . Magn. Reson. 1988, 77(3), 439-59. (GI61 Howarth, 0. W.; Ratcilffe, G. S. Coal Sci. Technol. 1987, 11, 143-6. (G17) Yoshida, T.; Maekawa, Y. Hokkaido Kogyo Kahatsu Shlkensho Hokoku 1985,36, 19-25 (Japan); Chem. Abstr. 1986, 105, 155865. (G18) Davis, M. R.: Abbott, J. M.; Cudby, M.; Gaines, A. fuel 1988,67(6), 960-6. (G19) Erbatur. G.; Erbatur. 0.: Davis, M. F.; Maciel. G. E. fuel 1988,65(91.
.---
.-.
1965-79
rG20) Tekeiy, P.; Nicole, D.; Deipuech, J. J.: Julien, L.; Bertho, C. Energy fuels 1987, 1(1), 121-2. (G21) Burchill, P. Coal Sci. Technol. 1987, 11, 5-8. (G22) Bartie, K. D.; Perry, D. L.; Wallace, S.fuel Process. Technol. 1987, 15. 351-61. (G23) 'Holienhead, J. B.; Glanville, J. 0.; Wightman, J. P. Energy Fuels 1988, 2(21. 121-4. (G24) Huffman, G. P.; Huggins, F. E.; Shah, N.; Bhattacharyya, D.; Pugmire, R. J.; Davis, B.; Lytie, F. W.; Greegor. R. B. Prepr. Pap.-Am. Chem. Soc., Div. FuelChem. 1988,33(1), 200-8. Coking Process and Coke Testing
(HI) Chen, P. Coal Sci. Techno/. 1987, 7 1 , 159-63. (H2) Nishloka, K.; Miura, K.; Yamamoto, T. Jpn. Kokai Tokkyo Koho JP 61,161,455 [86.161,454] (Cl. GO1 N 33/22), 22 Jul 1986, Appl. 8511,926, 09 Jan 1985. (H3) Chen, P.; Yang, J. Meifan Kexue Jishu 1965, 11, 9-12 (Ch); Chem. Absfr. l987, 106, 140853. (H4) Du, M.; Dai, H.; An. F. Ranliao Huaxue Xuebao 1988, 14(4), 331-7 (Ch); Chem. Absb. 1987, 106, 179498. (H5) Chaudhuri A.; Seth, A. K.; Ray, S. K.; Mukherjee, P. N. J . Indian Chem. Soc. 1986, 63(2), 260-2. (He) Biktimirova. T. G.; Vakhitov, R. R.; Novoseiov. V. F. S b . Nauch. Tr. 6ashk. N I I po Pererab. Nefti 1986, 25, 75-83 (Russ); Chem. Absfr. 1987, 106, 159237. ANALYTICAL CHEMISTRY, VOL. 61,
NO. 12,
JUNE 15, 1989
93R
SOLID AND GASEOUS FUELS (H7) Nozawa, T. Jpn. Kokai Tokkyo Koho JP 62.12,655 [67,12,855] (CI. GOlN 33/22), 21 Jan 1987, Appl. 85/151,804, 10 Jul 1985. (H6) Dobashi, K.; Imachl. KT; Nakamura, T.: Kataoda, S. Jpn. Kokal Tokkyo Koho JP 61,163,968 (86,163,9881 (Cl. ClOB57/04), 24 Jut 1986, Appl. 8515,564, 16 Jan 1985. (H9) Shelkhet, A. M.; Goncharov, V. F.; Starovoit, A. G.; Samoilov, V. I.; Rubchevskll, V. N.; Chernyshov, Yu. A,; Danllov, S. N. Koks Khlm. 1988. 4, 13-16 (Rus); Chem. Ab&. 1988, 709, 25059. (HlO) DoNascimento, E. A.; Schuchardt, U.; Haeusler, K. G.; Richter, R.; Fanghaenel, E. Chem. Tech. (Lelprig) 1988, 40(7), 301-3 (Ger); Chem. Abstr. 1988, 709, 95900. (H11) Gray, R . J.; Devanney, K. F. Int. J. Coal Geol. 1988. 6(3),277-97. (H12) Sklyar. M. G.; Slobodskol, S.A.; Dang, V. Kh.; Gamazlna, G. A. Koks Khim. 1988, 3 , 9-11 (Russ); Chem. Abstr. 1988. 708, 170549. (H13) BensaM, F.; Oberlln, A. J. Chlm. Phys. fhys.-Chlm. E b l . 1987, 84(11-12), 1457-67 (Japan); Chem. Abstr. 1988, 708, 153340. (H14) Medek, J.; Weishauptova, 2 . Acta Mont. 1988, 73, 159-70 (Russ); Chem. Abstr. 1987, 706, 69953. (H15) Shevlin, M. J. F.; Fryer, J. R.; Baird, T. Carbon 1988, 24(5),527-34. (H16) Moreland, A.; Patrick, J. W.; Walker, A. CoalScl. Technol. 1987, 7 7 , 729-32. (H17) Itagaki, S.;Konishi, N.; Furukawa, T.; Shimoyamada, M.; Kimura, T.; Nakano, K. Jpn. Kokai Tokkyo Koho JP 61,110,057 [66,110.057] (CI, GOlN33/22), 28 May 1986, Appl. 84/231,393, 05 Nov 1964. (H18) Yoshim, Y.; Dobsahl, K.; Komatsu, Y.; Torimaru, H. Jpn. Kokai Tokyyo Koho JP 61,145,289 [66,145,289] (Ci. ClOB57/04), 02 Jui 1986, Appl. 841267,893, 19 Dec 1984. (H19) Smirnow, S. Aufbere/t.-Tech. 1988. 29(2), 81-7 (Eng/Ger). Mlscelaneous (11) Gidespow, D.; Gupta, R.; Mukhsrjee, A.; Wasan, D. Process. Ull. High Sulfur Coals, Roc. Int Conf ., 2nd 1987, 27-8 1. (12) Doctor, R. D.; Livengood. C. D.; Genens, L. E.: Swletlik, C. E.; Foote, K. ROCess. Ut#.H@I Sulfur C o a l s , Roc. I n t . Conf., 2nd 1987, 749-60. (13) Wapner, P. G.; Lalvani, S. B.; Awad, 0. Fuel Rocess. Technol. 1988, 78(1), 25-36. (14) Thorpe, A. N.; Senftle, F. E.; Alexander, C.; Dulong, F. T.; Lacount, R. B.; Friedman, S . Fuel 1987, 66(2), 147-53. (15) CagigS, A.; Escudero, J. B.; Low, M. J. D.; Pis, J. J.; Tascon, J. M. D. Fuel Rocess. Technd. 1967, 75, 245-56. (16) Sykorova, I.; Kas, V.; Sebesta, P. Acta Mont. 1988, 76, 31-5 (Czech); Chem. Abstr. 1988, 709, 9140. (17) Olson, E. S.;Dlehl, J. W. Rmr. faD.-Am. Chem. Soc., Dlv. Fuel Chem. 1988, 33(2). 415-21. (18) Knudson, C. L. Report 1966, EPRI-AP-4536; Order No. TI86920266, 76 pp; avail. RRC, Box 50490, Palo Alto, CA 94303. From ERA 1988, 1 . 1114). . ,. .,, 31335 - . - - -. (19) Hessley, R. K. frepr. Pap.-Am. Chem. SOC.,Dh. Fuel Chem. 1988, 33121. 431-9. (110) ‘White, C. M.; Douglas, L. J.; Perry, M. B.; Schmidt, C. E. Energy Fuels 1987. 712). 222-6. ( I l l ) Neill; P. H.; Maciel, G.; Given, P. H.; WeMon, D. Fuel 1987, 68(1), 96-6. (112) Mamantov, 0.; Wehry, R. L. Report 1987, EPRI-EA-5148; Order No. TI67920456, 210 pp; avail. RRC, Box 50490, Palo Alto, CA. 94303. From ERA 1987, 72(17), 34476. (113) Arai, T. Nlppon Kogyo Kaishl 1985, 707(1172), 632-5 (Japan); Chem. Abstr. 1988, 705, 194156.
.
Standards ( J l ) ASTM Standards; ASTM: Phlladelphai, PA, 1988; Vol. 5.05. (J2) Gllls, T. E.; Mavrodlneanu, R. Report 1965, NBSSP-260197; Order No. PB86-110830/GAR, 137 pp; avall. NTIS. From Gov. Rep. Announce, Index ( U . S . ) 1988, 86(1), 660 633. (J3) Taylor, J. K. Report 1985, NBS/SP-260/100; Order No. PB86-110897/ GAR, 101 pp; avail. NTIS. From Gov. Rep. Announce. Index ( U . S . ) 1988, 86(l), 600 633. GASEOUS FUELS General Revlewe ( K l ) Kettrup, A.; Ohrback, K. H. Eer. Msch. Oes. MineraloelluLPs. Kohiechem. 1966. 289-07. 153 (Ger); Chem. Abstr. 1987, 706, 104812. (K2) Brunner, R. R o c . Int. Sch. l$&mrbon Maas. 1987, 62nd, 330-3. (K3) Karl, W. Gas-Wasserfech: QaslErdgas 1988, 729(1), 16-21 (Ger); Chem. Abstr. 1988, 708, 97370. Chromalography (Ll) Hesbach, P. A.; Lamey, S.C.; Green. W. C. Report 1966, DOE/METC86-4061; Order No. DE66006605, 24 pp; avail. NTIS. From ERA 1988, 77(15), 33561. (L2) Huston, G. C. Morgantown Energy Technd. Cent. [Rep.] DOE/METC (U.S. Dep. Energy) 1986, DOE/METC-65/6025, Roc. Annu. Contract. Meet. Contam. Control Coal-hrk. Gas Streams. 5th 1985, 474-60. (L3) Song, 0.; Jlang, 2. Sepu 1987, 5(1), 58-9 (Ch); Chem. Abstr. 1987. 707, 137260. (L4) Huston, 0. C.; Romanosky, R. R., Jr.; Wachter, J. K. J. Chromatogr. Scl. 1988, 24(10), 458-61. (L5) Bulanov, E. A,; Zlnov’eva, L. A. Koks Khim. 1987, 70, 36-9 (Russ); Chem. Abstr. 1968, 708, 8621. (L6) Yin, D.; Zhang, G.; Deng, Y. Gangtle 1987, 22(4), 71-4 (Ch); Chem. Abstr. 1987, 707, 249097. (L7) Tong, Q. Sepu 1988, 4 ( 6 ) , 361-4 (Ch); Chem. Abstr. 1987, 106, 69844.
94R
ANALYTICAL CHEMISTRY, VOL. 61, NO. 12, JUNE 15, 1989
(L8) Zhuze, T. P.; Ushakova, G. S.;Bobrova, N. A. W l . Nefti Gaze 1988, 7 7 , 46-9 (Russ); Chem. Abstr. 1987, 706, 35649. (L9) Zou, N. Shlyou Huegong 1987, 76(12), 869-75, and 860 (Ch); Chem. Abstr. 1988, 108, 189404. (LIO) Cox, L. N. froc. Int. Sch. Hydrocarbon Meas. 1987, 62nd, 268-70. (L11) Gaspar, G. Spectra. 2OOO[Deux Mille)] 1987, 722, 63-8 (Fr); Chem. Abstr. I98& 708, 31026. (L12) Tijssen, R.; Van den Hoed, N.; Van KreveM, M. E. Anal. Chem. 1987, 5917). 1007-15. (L13) ‘Naizhong, 2.;Green, L. E. J. High Resolut. Chromatogr. Chromatogr. Commun. 1988. 9(71. 400-4. (L14) De Andrade BruGng. I.M. R. Eo/. Tec. PETROERAS 1988, 29(2), 115-20 (Port); Chem. Abstr. 1988, 705, 117707. (LIS) Suruta, Y. Jpn. Kokal Tokkyo Koho JP 61,196,161 [86,196,161] (Cl. G01N30/38), 30 Aug 1986. Appl. 85/36.519. 27 Feb 1985. (L16) Reed, L. E. J. Chromatogr. Scl. 1987, 25(11), 485-8. Sulfur Compounds
(Ml) Phllllps. J. B.; Gordon, R. J.; Meredith, D. E. PCT Int. Appl. WO 87,01,204 (Cl. GOlN33/00), 26 Feb 1967, US Appi 766.022, 15 Aug 1985. (M2) Wang, Q.; Xle, J. Shiyou Huagong 1988, 75(10), 633-5 (Chi); Chem. Abstr. 1987, 706, 60559. (M3) Vincent, A. Oper. Sect. Roc.-Am. Gas Assoc. 1988, 636-9. (M4) Kiyanksil, V. V.; Burahkta, V. A. Khim. Tekhnol. T o p / . MeselI987, 9 , 10-12 (Russ); Chem. Abstr. 1987, 707, 179679. (M5) Tomm, H.; Mohr, T. Erodoel. Erdgas, Kohle 1987, 703(12), 515-19 (Ger); Chem. Abstr. 1988, 708, 137116. (M6) Nadzhafov, Yu. B.; Kutsyn, P. V.; Smelova, V. E. Neft. Khoz. 1988, 7, 67-7 (Russ); Chem. Abstr. 1988, 705, 117712.
Condensates and Moisture (Nl) Shmakov, V. S.; Furlei, I.I.; Lyapina, N. K.; Khvostenko, V. I.; Polyakova. A. A.; Parfenova, M. A.; Vol’tsov, A. A.; Tolstikov, 0. A. Neftekhimlya 1988, 26(5),693-701 (Russ); Chem. Abstr. 1987, 706, 20762. (N2) Kul’dzhaev, B. A.; Makarov, V. V.; Serglenkl, S. R.; Khramova, E. V. Neftekhlrniya 1987, 27(3), 319-22 (Russ); Chem. Abstr. 1987, 707, 60665. (N3) Bagir-Zade, F. M.; Kuliev, A. D.; Akhmedov, E. I.Izw. Vyssh. Uchebn. Zaved., Neft Gaz 1988, 29(7), 7-13 (Russ); Chem. Abstr. 1987, 706, 69772. (N4) Yue, 0.;Wang, F.; Zheng, X. Shlyou Kantan Yu Kalfa 1987, 14(2), 68-74 (Ch); Chem. Abstr. 1987, 107, 201597. (N5) Reinhardt, J. R.; Garber, J. D.; Bradburn, J. Oil Gas J. 1987, 85(4), 63-4, and 86. (N6) Gates, L. M.; Scelzo, M. J. R o c . Int. Sch. Hydrocarbon Meas. 1987, 62&, 166-9. (N7) Dodds, D. E. f r o c . Int. Sch. HydrocarbonMeas. 1987, 62&, 265-7. (N6) Mayeaux, D. P. froc. Int. Sch. Hydrocarbon Meas. 1987, 62nd, 153-7. (N9) Kahmann, A. R. R o c . Int. Sch. Hydrocarbon Meas. 1987, 62nd, 170-1. (N10) Foimer, G. R o c . Int. Sch. Hydrocarbon Meas. 1987, 62nd, 162-5. Calorimetry (Pl) Solov’ev, V. I.; Rykov, V. A.; Shurinov, S. G.; Upadyshev. V. V. U.S. S.R. SU 1,286,979 (CI. G01N25/32), 30 Jan 1967, Appl. 3,949,954, 18 Sep 1985. From Otkrytlya, Isobret. 1987, 4177. (P2) Mondell, L.; Robert, F. Fr. Demands FR 2,583,517 (Cl. G01N25/20), 19 Dec 1986, Appl. 8519, 238, 18 Jun 1985. (P3) Cheney, M. C. U.S. US 4,613,482 (CI. 422-51: GOlN25/22), 23 Sep 1986, Appi. 564,791, 23 Dec 1983. (P4) Solov’ev, V. I.; Shurinov, S. G.; Upadyshev, V. V.; Rykov, V. A. U.S. S.R. SU 1,286,978 (Cl. GOlN25/32), 30 Jan 1987, Appl. 3,949,953, 18 Sep 1985. From Oktry?iya, Izobret. 1987, 177. (P5) Norawa, Y. Jpn. Tokkyo Koho JP 61,18,964 [86,16,984] (CI. GOIN25/22), 15 May 1986, Appl. 79152,028, 28 Apr 1979. (P6) Rockwell International Corp. Jpn. Kokai Tokkyo Koho JP 61,140,848 [86,140,846] (CI. G01N25/42), 27 Jun 1986, US Appl. 680,193 10 Dec 1984. (P7) Singh, J. J.; Sprinkle, D. R.; Puster. R. L. Report 1985, NASA-TP-2531. L-16054, NAS1. 60: 2531; 13 pp; avail. NTIS. From Sci. Tech. Aerosp. Rep. 1988, 24(1l), N86-20753. (P6) Singh, J. J.; Cheglni, H.; Mall, G. H. Report 1987, NASA-TP 2662. L16261. NAS1. 60: 2682. 15 pp; avail. NTIS. From Sci. Tech. Aerosp. Rep. 1987, 257(13), N67-20514. (P9) Brown, C. W.; Maris. M. A.; Lavery, D. S.;Caputo, B.; Model, M. US. US 4,594,510 (CI. 250-339; 001N21/31), 10 Jun 1986, Appl. 707,265, 01 Mar 1985. (PIO) Van Meter, R. R o c . I n t . Sch. Hydrocarbon Meas. 1987, 62nd, 296-7. (P11) Van Meter, R. R o c . Int. Sch. Hydrocarbon Meas. 1987, 62nd, 294-5. (P12) Bukacek, R. F. Oper. Sect. Roc.-Am. Gas Assoc. 1988, 630-2. (P13) Wiide, K. Gas-Wasseffach: GaslErdgsa 1988, 729(1), 13-17 (Ger); Chem. Abstr. 1988, 708. 97369. (P14) Below, L.; Herbst, G. Gas-Wasserfach: GaslErdgas 1988, 129(1), 22-30 (Ger); Chem. Abstr. 1988, 108, 97439. (P15) Mowery, R. A.. Jr. ISA Trans. 1986, 25(4), 41-9. (P16) Cox, L. N. R o c . Int. Sch. HydfmrbonMeas. 1987, 62nd. 448-50. (P17) Paunovic, R.; Durlc, M.; Miscevlc, D. M f t a (Zagreb) 1088, 37(12), 627-34 (Serbo-Croatlan); Chem. Abstr. 1987, 706, 140825. (P18) Florisson, 0.; Joosten, G. E. H. Eur. Pat. Appl. EP 242,926 (Ci. GOlN33/22), 28 Oct 1967, NL Appl 661986, 19 Apr 1986.
Anal. Chem. 1989, 6 1 , 95R-109R
(P19)Donahue, S.M.; Brown, C. W.; Caputo, 6.; W e l l , M. D. Anal. Chem. 1988, 60(18),1873-8. (P20) Blanke, W.; Welss, R. Gas-Wasserfach: GaslErdgas 1987, 128(8), 350-7 (Ger); Chem. Abstr. 1987, 107,179676. (P21) Grlmm, W. Industriefeuerung 1987. 42. 13-18 (Ger); Chem. Abstr. 1988, 108,170451. Meterlng and D o n l y
(01)Mader, H. Energ. Atomtech. 1987, 40(9).405-7 (Hung); Chem. Abstr. 1987, 107,239370. (02) Tefankjlan, D. A. Proc. Int. Sch. Hydrocarbon M a s . 1987, &nd, 405-9. (03) Smith. J. P. P r m . Inst. Sch. Hydrocarbon Meas. 1987, 62nd. 307-9. (04) Ellington, R. T. Proc. Int. Sch. Hydrocarbon Meas. 1987, &nd, 401-4. (05) Edalat, M.; Zaman, A. A,; Tooba, H. Iran J . Chem. 1987. 9 (pt. A), 38-43. (06) Kruk, I.S.; Lesovoi, L. V. Vestn. L'vov. Politekh. Inst. 1987, 217, 40-1 (Russ); Chem. Abstr. 1988, 108,78325. (07) Clinaman. W. H. Proc. Annu. Svmo. . . Instrum. Process. Int. 1987. . 42nd. 43-7. (08) Falaue, J. Fr. Demande FR 2,574,181(CI. GOlN25118). 06 Jun 1986, Appl. 84118,331,30 Nov 1984. (09) Hughes. S. Proc. I n t . Sch. Hydrocarbon Meas. 1987, 62nd, 11-18. (010) Lee, W. F. 2 . Oil Gas J . 1988, 86(16),75-6, 80,and 82-4. (011) Kohda. K.; Suzukawa, Y.; Furukawa. H. Nippon Kokan Tech. Rep. Overseas 1987, 50, 43-50. (012) Hassapis, G. D. I€€€ Trans. Instrum. Meas. 1987, IM-36(3), 815-24. (013) Thomson, G. H.; Hankinson, R. W. Proc., Annu. Conv.-Process. Ass&. 1988,65th,215-17. (014) Russell, J. A&. Instrum. 1985, 40(2), 1531-41. (015) Norman, R.; Jepson, P. Oil Gas J. 1987, 85(14), 47-54, and 56. (016) Starling. K. E.; Savidge, J. L.; Ellington, R. T.; Reid, T.; Shankar, S. Oper. Sect. Roc.-Am. Gas Assoc. 1986. 753-63. (017) Starling. K. E.; Mannan, M.; SavMge, J. L. 011 Gas J . 1987, 85(46), 49-52. (018) Starling, K. E. Proc. Int. Sch. Hydrocarbon M a s . 1987, 62nd, 322-4. (019) Luebbe, D. Gas-Wasserfach: GaslErdgas 1987. 128(7), 301-8 (Ger); Chem. Abstr. 1987, 107,179672. (020) Sivaraman. A.; Gammon, B. E. Oper. Sect. Roc.-Am. Gas Assoc. 1987, 767-72. (021) Schouten, J. A.; Mlcheis, J. P. J.; Joosten, G. E. H. Oil Gas J. 1988, 86(8).37-42. (022) Ellington, R. T.: Starling, K. E.; Hill, M. J.; Savidge. J. L. Proc., Annu. Conv.-Gas Process. ASS&. 1988, 65th, 193-201. (023) Jaeschke, M.; Hlnze, H. M. Hydrocarbon Process., Int. Ed. 1987, 66(6),37-41. (024)Tunheim, H.; Danielsen, H. 6.; Rosenkllde, L.; Tambo, M.; Wiicox, P. L. ON Gas J . 1987, 85(8),61,and 64-6. (025) Kleinrahm, R.; Duschek, W.; Jaeschke, M.; Wagner, W. Gas-Wasserfach: GaslErdgas 1988, 129(2),77-82 (Ger); Chem. Abstr. 1988, 108, 1 15342. (026) Eubank, P. T.; Scheloske, J. J.; Hail, K. R.; Holste, J. C. J. Chem. Eng. Data 1987. 32(2),230-3. (027) Dadash-Zade, M. A. I z v . Akad. Nauk A I . S S R , Ser. Nauk Zemle 1988, 2,82-6 (Russ); Chem. Abstr. 1988, 105,136597.
(028) Pedersen, K. S.;Fredenslund, A. Chem. Eng. Sci. 1987, 42(1), 182-6. SampIIng
(Rl) Bames, W. R. R o c . Int. Sch. HydrocarbonMeas. 1987. 62nd, 172-4. (R2) De Andrade, I. R. G.501. Tec. PETROBRAS 1988, 31(1),15-17 (Port); Chem. Abstr. 1988, 108, 189470. (R3) Sevcik, A.; Odstrcilova, V.; Vecera, S.; Hlousek, E. Plyn 1988,66(6), 174-9 (Czech); Chem. Abstr. 1988. 105,229604. (R4) Jordan, K. T.; Menzel, E. R. Proc. SPIE I n t . Soc. Opt. Eng. 1987, 737,80-4. (Sll Nakamura, M.; Iio, T. Jpn. Kokai Tokkyo Koho JP 61,219,853 86,219,8531(Cl. G01N21/41),30 Sep 1986, Appl. 85/62.397.26 Mar 1985. (S2) Markuszewski, R.; Haas, W. J., Jr.; Eckeis, D. E.; Lee, S.H. D.; Myles, K. M. Morgantown Energy Techno/. Cent. 1988, DOEIMETC-8616042, 6th 1988, 343-53. (S3) Korshak, A. A.; Burdygina, N. G. I z v . Vyssh. Uchebn. Zaved., Neft. Gaz 1988, 29(9),61-3 (Russ); Chem. Abstr. 1987, 106, 69831. (S4) McCann, P. M. Proc. Int. Sch. Hydrocarbon Meas. 1987, 62nd,
339-41. (S5)Moore, B. J.: Slgler, S. I n f . Circ.-US., Bur. Mines 1987, IC 9167,103 PP. (S6) Faber, E.; Dumke. I.; Ott, A.; Poggenburg. J. Erodei, Erdgas, Kohle 1988, 102(10),456 (Ger); Chem. Abstr. 1987, 106, 104896. 67) Baillie, L. A.; Sklnner. J. L. U.S. US 4,733,557,(Ci. 73-64.2;G01N71 loo), 29 Mar 1988,Appl. 921,919,22 Oct 1986. (S8) Shen, 0.; Llao, Y.; Zhang, 2. Chenji Xuebao 1988, 4(4), 129-30 (Ch); Chem. Abstr. 1987, 107, 25696. (S9) Scarano, E.; Russo, M. V.; Belli, R. Rass. Chim. 1985, 37(6),321-5. (S10) Kawachi, K.; Kaneko, M. Jpn. Kokai Tokkyo Koho JP 61,129,093 [86,129,093](CI. C02F3/12),17 Jun 1986, Appl. 841252,322,29 Nov 1984. (S11) Demczak, M.; Kegel, M. NaRa (Katowice, Pol.) 1988, 42(4),117-19 (Pol); Chem. Abstr. 1987, 106,20768. (S12) Mulyono. S.Lembararan Publ. Lemigas 1988, 20(2),13-18 (Indonesia); Chem. Abstr. 1987, 106, 140728. Burrle, P. H. Tech. Mess. 1988, 55(5), 194-7 (Ger); (513) Fiorisson, 0.; Chem. Abstr. 1988. 109,40404. (S14) Troeger, H. J.; Hausknecht, M. Energietchnik (Leiprig) 1986, 36(10), 373-5 (Ger); Chem. Abstr. 1987, 106. 69745. (S15) Elllott, R. A. Report 1985, GR-8510140;Order No. PB856-1028111 GAR, 39 pp; avail. NTIS. From Gov. Rep. Announce, Index ( U . S . ) 1988, 88(1),601 303. (Sl6) Stan, A. D. Mlne, Pet. Gaze 1987, 38(2),99-102 (Rom); Chem. Abstr. 1987, 107,42713. Standards
(Tl)Niedung, W. Gas-Wassetfach: GaslErdgas 1988, 129(1),9-12 (Ger); Chem. Abstr. 1988, 108,97368. (T2)Jaeschke, M. Gas-Wasserfach: GasIErdgas 1988, 129(1),30-7 (Ger); Chem. Abstr. 1988, 108,97438. (T3) Solka, B. H.; Attari, A. Report 1987,GRI-8810298;Order No. PB87185161lGAR, 96 pp; avail. NTIS. From Gov. Rep. Announce. Index ( U S ) 1987, 87(15),732 154. (T4) ASTM Standards; ASTM: Philadelphia, PA, 1988;Vol. 5.05.
Forensic Science T. A. Brettell and R. Saferstein* N e w Jersey State Police, Forensic Science Bureau, Box 7068, West Trenton, New Jersey 08628
It is the aim of this article to present a concise survey of articles appearing in publications that primarily appeal to forensic practitioners. T o accomplish this objective, we have focused our attention on the following journals: Journal of Forensic Sciences, Journal of the Forensic Science Society, Forensic Science International, Journal of the Canadian Society of Forensic Science, Analytical Toxicology, and The Microscope, as well as Chemical Abstracts Selects: Forensic Chemistry. Our survey encompasses the period from January 1987 through December 1988. Because of the normal delays in the abstraction of journal articles by Chemical Abstracts, some work covering this period will inadvertently be omitted. Hopefully these references will be included in the next biennial review.
The format selected for this survey divides coverage into three distinct areas: Drugs and Poisons, Forensic Biochemistry, and Trace Evidence. Within the scope of each of the areas, articles have been selected to describe current forensic science practices in analytical chemistry and to outline relevant forensic science research interests. To keep our discussion concise and meaningful, we have limited our survey to drugs regulated under the United States Controlled Substances Act, ethanol, and common poisons. Furthermore, to eliminate unnecessary duplication of effort, citations of articles appearing in Clinical Chemistry, the Journal of Pharmaceutical Sciences, and other pharmaceutical journals have been avoided. We believe that ample coverage of these journals is provided within the pharmaceutical and clinical chemistry 0 1989 American Chemical Society
95 R
