(213) ivales, AI., Reference 133, p 343. (214) Westall, B., Polymer, 9, 243 (1968). (215) Williamson, G. R., J. Polym. Sci., Part A-2, 5 , 394 (1967). (216) Yasuda, S. K., J. Chromatog., 27, 72 (1967).
(217) Yau, W. W., Fleming, S. W., J. Pobm. Sei., 12, 2111 (1968). (218) Yau, W. w., Malone, C. P., J. Polym. Sci., Part B , 5, 663 (1967). (219) Yau, W.W.,Suchan, H. L., Malone, C. P., Ibid., Part A-2, 6 , 1349 (1968).
(220) Yuschkevichyute, S. S., Shlyapnikov, Y. A., Sou. Plastics (English trans.), 1967 (la), p 61.
Contribution No. 423 from the Research Division, The Goodyear Tire and Rubber Co., Akron, Ohio 44316.
Solid and Gaseous Fuels R . F. Abernethy and 1. G. Walters, Bureau of Mines, U.S. Department of the Interior, Pittsburgh, Pa.
T
in this series on methods of sampling, analyzing, and testing solid mineral and gaseous hydrocarbon fuels have been issued. This one covers the period from October 1966 through September 1968 inclusive, and, except for minor changes, follows the general format of the previous reports. EA- REVIEKS
SOLID FUELS
This section covers ivork done on methods of sampling and chemical and physical testing of coal, coke, and related materials. There are really few innovations and most of the reports consist of refinements in existing procedures to give greater accuracy and saving of testing time. Selected items have been included under the pertinent headings or in the miscellaneous section to supplement standard test methods and to indicate new testing trends. Sampling. Committee D-5 on coal and coke of the American Society for Testing a n d Materials (ASTAI) has revised t h e s t a n d a r d coal sampling methods, D 271 and D 492, and replaced them with A S T l I Designation D 2234, Sampling of Coal, and MThI Designation D 2013, Preparing Coal Samples for Analysis ( 1A ) The standard sampling procedure covers general purpose or commercial. sampling and special or referee sampling. The sample preparation standard covers the entire procedure from the gross sample to the analysis sample. Proximate Analysis. The proximate analysis of coal measures the moisture, volatile matter, fixed carbon, and ash content. Moisture, volatile matter, and ash are determined by specified procedures. Fixed carbon is calculated by subtracting the sum of the three determined values from 100. Humphreys and Lan rence (1223) used the proximate analysis from a large number of coals to develop control charts for coal preparation plants. Computer results of these analyses were used to determine the ultimate analyses and calorific value from the proximate analyses for plant control ( I S B ) . Hinz (10B) dereloped a procedure of proximate analysis for semimicro sample quantities. I
308 R
ANALYTICAL CHEMISTRY
MOISTURE.Rees (27B) used the twostep ASTM method for total moisture on the petrographic components of coal to show how moisture could be lost in grinding coals for the preparation of the analysis sample. Vapor pressure measurements made by Stewart and Evans (35B) indicated t h a t 40% of the ivater in bron-n coal was bonded to the coal. Viktorin (4OB) used gravimetric methods to establish equivalent moisture contents of four different lignites a t different temperature levels to indicate the binding of the moisture t o the lignite. The N l I R spectra of coals were used by Ladner and Wheatley (BOB)to measure the moisture in all coals regardless of rank, mineral matter content, or size less than 6 mm. It is possible t o adopt the principle to a moving stream of coal. Seutrons were employed in slightly different ways for determination of moisture in moving streams of coal and coke. Stewart and Hall (36B) were able to check moisture values within 0.275 in coal moving a t 20 tons/hour. Gee and Laslo (9B) used a neutron gage to measure moisture in coke and automatically make corrections in the weight of material charged to the blast furnace. Egami, Kano, and Semoto ( 7 B ) reported the neutron moisture gage very effective for coke with high moisture content. The total error for coke moisture w s 5 1.6%. Luckers (21B) reported tn-0 years of stable and reliable performance of a neutron probe used in measuring moisture in a coke bin. The standard deviation was 0.550.60%. Chernyshov a n d Gruzintsev ( 4 B ) described apparatus to measure continuously the moisture in a coal stream on a belt, using a meter to register the dielectric properties of coal. Industrial tests over a tno-year period showed t h a t 977, of all determinations fell within & 0.5% of values by the national standard. Kersting (14B) discussed the factors involved in measuring the moisture in the briquetting stock by the dielectric constant and also by -/-rays from 137Cs. -1summary of ten methods of measuring moisture contents of solids was
prepared by Roth (SIB). I t covers intermittent, continuous, and partially automatic t o completely automatic devices. VOLATILEMATTER. hST?*I Designation D 121 defines volatile matter as follows: “Those products, exclusive of moisture, given off by a material as gas or vapor, determined by definite prescribed methods m-hich may vary according to the nature of the material.” The portion of the statement, “definite prescribed methods,” is intended to show t h a t the method is empirical and t h a t adherence t o specifications is mandatory. Shipley (SdB) reported, in the revision of BS 1016 parts 3 and 4, volatile matter in coal and coke, respectively, that experimental evidence of suitable nature made it possible to reduce the testing temperature from 925 to 900 “C. This change brought the British Standard in line with the recomniendations of Technical Committee 27 on Solid Mineral Fuels of t h e International Organization for Standardization (ISO). The empiric nature of t h e volatile matter determination has motivated numerous workers to delve into the several factors t h a t influence the pyrolysis of the coal or coke. Zielinski (41B) explored the rate of heating as one of the major factors. Selson, Korrall, and Kalker (26B) conducted experiments under isothermal and nonisothermal conditions on the release of volatile matter from anthracite. Special attention nas given to rate of heating and to particle size. Volatile release was constant IT ith respect to temperature and particles ranging in size from 53 4 to 12 mm. Isothermal tests on rates of H evolution obeyed a logarithmic time law and exhibited a complex dependency upon particle size. A correlation between the volatile matter a n d ash contents was shown b y Kononenko ( I Q B ) from a statibtical evaluation of experimental data. The volatile matter from a specific deposit could be calculated from the ash content. .1study on the discharge of volatile matter on the degasification of a number of coals led Salcewics and Kijeiwka
Table I.
ASTM Standards and Specifications
Definitions of terms relating to coal and coke Drop shatter test for coke Test for volume of cell space of lump coke (reapproved 1967) Samuling and fineness test of Dulverized coal ireD 197-30 apprbvea 1961) Laboratory preparation of coke and analysis of coal D 271-68 and coke D 291-60 Test for cubic foot weight of crushed bituminous coal Test for cubic foot weight of coke (reapproved 1967) D 292-29 D 293-651' Test for sieve analysis of coke (tentative) Tumbler test for coke D 294-64 Test for size of anthracite (reapproved 1961) D 310-34 Test for sieve analysis of crushed bituminous coal D 311-30 (reapproved 1961) Sampling coke for analysis (reapproved 1961) D 346-35 Specifications for classification of coals by rank D 388-66 Definitions of the terms gross calorific value and net D 407-44 calorific value of solid and liquid fuels (reapproved 1958) Test for grindability of coal by the HardgroveD 409-51 machine method (reapproved 1961) Test for screen analysis of coal (reapproved 1961) D 410-38 D 441-45 Tumbler test for coal (reapproved 1961) D 492-48 Sampling coals classified according to ash content (reapproved 1958) (Superseded by D 2234-68) Definitions for commercial varieties of bituminous D 493-39 and sub-bituminous coals (reapproved 1958) Test for index of dustiness of coal and coke (reD 547-41 approved 1961) Test for free-swelling index of coal D 720-67 D 1412-61 Test for equilibrium moisture of coal at 96 to 97% relative humidity and 30C (reapproved 1968) D 1756-62 Test for carbon dioxide in coal D 1757-62 Test for sulfur in coal ash D 1812-66 Test for plastic properties of coal by the Gieseler plastometer D 1857-68 Test for fusibility of coal ash D 2013-68 Preparing coal samples for analysis D 2014-64 Test for expansion or contraction of coal by the sole-heated oven D 2015-66 Test for grosb calorific value of solid fuel by the Adiabatic bomb calorimeter D 2234-68 Sampling of coal D 2361-66 Test for chlorine in coal D 2490-66T Tumbler test for small coke (tentative) D 2492-68 Test for forms of sulfur in coal D 2639-67T Plastic properties of coal by the automatic Gieseler plastometer (tentative) D 2640-67 Drop shatter test for large coke D 2677-671' Lightability of barbecue briquets (tentative)
D 121-62 D 141-66 D 167-24
Table
II.
Status of Work of I S 0 Technical Committee 2 7
I. IS0 Recommendations
Rl57-60 R158-60 R159-60 R331-63 R332-63 R333-63 R334-63 R335-63
Determination of forms of sulfur in coal Determination of ash in hard coala Determination of sulfur in coal by the Strambi method Determination of moisture in analysis sample by the direct gravimetric method Determination of nitrogen in coal by the Kjeldahl method Determination of nitrogen in coal by the semimicroKjeldahl method Determination of total sulfur by the Eschka method Determination of caking power of coal by the Roga method
Table
II. (Continued)
R348-63 Determination of moisture in the analysis sample of coal by the direct volumetric method R349-63 Audibert-Arnu test for coal R350-63 Determination of chlorine in coal bv the bomb-combustion method R351-63 Determination of total sulfur in coal bv the hiehtemperature combustion method R352-63 Determination of chlorine in coal by the high-temperature combustion method R501-66 Determination of the crucible swelling number of coal R502-66 Determination of the Gray-King coke type of coal R540-66 Determination of fusibility of fuel ash R556-67 Determination of micum indices of coke R561-67 Graphical symbols for coal cleaning plants R562-67 Determination of the volatile matter of hard coal and coke R567-67 Determination of bulk density of coke in a small container R579-67 Determination of total moisture in coke R586-67 Determination of ash of coke R587-67 Determination of chlorine in coal and coke using Eschka mixture R589-67 Determination of total moisture in hard coal R601-67 Determination of arsenic in coal and coke R602-67 Determination of mineral matter in coal R609-67 Determination of carbon and hydrogen in coal and coke by the high-temperature combustion method R616-67 Determination of the shatter indices of coke R622-67 Determination of phosphorus in ash from coal R625-67 Determination of carbon and hydrogen in coal and coke by the Liebig method R647-68 Determination of the yields of tar, water, gas, and (coke residue by low-temperature distillation of brown roals and lignite R687-68 Determination of moisture in the analysis sample of coke R728-68 Sieve analysis of small coke 0
11. Draft IS0 Recommendations Determination of gross calorific value of coal and coke by the calorimetric-bomb method DR1057 Vocabulary for coal preparation DR1058 Expression and presentation of results of coal cleaning tests DR1059 Principles and conventions for flowsheets for coal preparation DR1125 Determination of carbon dioxide in coal by the gravimetric method DR1126 Determination of the yield of benzene-soluble extract in brown coals and lignites DR1127 llodification of coal analysis methods for coke DR1146 Determination of the bulk densitv of coke in a large container DR1147 Determination of apparent relative density of coke DR1148 Determination of the true relative density and porosity of coke DR1282 Determination of moisture in brown coals and lignites by the direct volumetric method DR1283 Determination of ash of brown coals and lignites DR1284 Determination of yields of acetone-soluble extract ("resinous substance") in the benzene extract from brown coals and lignites DR1285 Determination of the moisture-holding capacity of hard coals DR1611 Calculation of coal and coke analyses to different bases DR1612 Determination of ash of solid fuels OThe term "hard coal" used in the titles refers to coals having a gross calorific value over 5,700 kcaljkg on the moist, ash-free basis.
DR569
~
( S S B ) t o propose four stages in the degasification. The stages were defined b y temperature ranges and the composition of t h e products evolved. Resnik, Lyannay, a n d Yarovaya (68) experimentally determined unique curves for the therniophysical characteristics of coals and their mixtures in the devolatilization process. The differences between these curves explain the nonadditivity of volatile matter release from a mixture of coals.
Different methods used t o determine the volatile matter in coke mere examined by Barbu, Falk, and Ursu (1B). Some of the sources of error were claimed to be due to absorption of gases, oxidation, and surface reaction. It was suggested t h a t a few drops of CsH6added to the sample in the test crucible would displace t h e air in the apparatus and prevent oxidation. Nadziakiewicz and Heilpern (22B) examined a number of industrial cokes
~~
and found t h a t moisture and some COS were evolved at temperatures u p t o 350 "C, very little gas was given off in the range 300-700 "C and, H, CO, C 0 2 , CH4were released above 700 "C.D T A coke analyses show a n endothermic reaction u p t o about 700 "C. At this temperature t h e reaction becomes exothermic with formation of gases. Volatile matter of coke, determined under controlled conditions and plotted against temperature, showed a break VOL. 41, NO. 5, APRIL 1969
309 R
at the carbonization temperature according t o Queins and Schaefer ( I 6 B ) . It was also shown t h a t t h e test for volatile matter must be made at a temperature higher than t h a t of carbonization. The smaller particles of coke yielded larger amounts of gases. Knauf (18B) used a thermobalance t o determine the volatile matter in cokes a t 100-200 “C intervals. The gases for each interval were analyzed chromatographically. H e stated that the process of quenching produced a n irreversible reaction through t h e influence of water. Mineral matter had a n effect on the nature of the gases evolved. I n earlier Ivork Knauf (17B) determined the composition of coal and coke a t different decomposition temperatures. Kessler and Dockalova (15B) made thermogravimetric analyses of coke for volatile matter. The resulting curves indicated sorption bonding of part of the volatile matter to the coke and the other part to pyrolysis of the coke. The same authors (16B) used the crucible method for coke volatile matter, observing the necessary conditions of time, temperature, and rate of heating. It was concluded that the crucible method for coal could not be used for coke. They suggested a thermogravimetric method in an X atmosphere a t a temperature of 1000 “C for 30 minutes. ASH. Ruschev and Yankova (SIB) reduced the time required for determining the ash content of coal t o 15 minutes by adding ( 10Q/o)NH4XO3. (The original report should be consulted for details of the test procedure concerning the heating of a mixture of S H 4 K 0 3 and coal.) Dimitrov, Khristov, and Petkov ( 5 B ) used the relationship of ash content and weight of unit volume to prepare charts for estimating ash content. The term lignite-type ash was referred to by Duzy and Walker ( 6 B ) . Lignitetype ash, in which the sum of CaO plus MgO is more than the F e 2 0 3 ,is import a n t because most LT.S.coal reserves are of this type, and because these coals could cause boiler tube fouling. .A density scale was used with a n infrared moisture meter to establish a relationship between density, ash, and calorific value by Xehm and Olschewski (24B). A table prepared from these data was used to prepare various mixtures of coals. Burek (SB) used p-rays t o estimate the mineral matter of coals. X-rays (Cendrex) were used by Hudy and Deurbrouck (11B) t o evaluate the ash contents of coal to a n accuracy of 0.5% at a 95% limit of confidence. Rhodes, Daglish, and Clayton ( I Q B ) and Tanemura and Suita (S8B) used X-rays, modified to eliminate the effect of iron, in the determination of ash in coals, 310 R
ANALYTICAL CHEMISTRY
Gamma rays were used by Beizer, Goroshko, and Lokshin ( I B ) , Fushimi ( 8 B ) , and Nagy and Varga ( I S B ) in measuring the ash content of coals. There were slight variations in application. Richter and Polaschek (SOB) used ?-transmission and ?-backscattering in measuring the ash content of coal in the open face. The backscattering method was more accurate, giving a standard deviation of i-1.2 wt %. The ?-ray method to measure the ash content of coal, thickness of steel plate, glass, rubber, and plastics was modified by Trost (S9B). The energy source was originally l;oTm, but it was found t h a t 241Am, n-ith a n automatic drift compensator arrangement, gave a much longer time stability. Szymborski (37B) determined the ash content of brown coal in situ using drilling radiometry. Gamma-gamma profiling was based on selectivity and density with 6oCo and %e. The accuracy depended on the following factors: 1. The clay must consist mainly of A1203. 2. The composition of ash must remain constant. Ultimate Analysis. CARBONA N D HPDROGES. Gruson, Fritzsche, and Knauf ( 7 C ) evaluated a number of methods for elemental analyses of solid fuels and concluded that theRadmacher and Hoverath method was very rapid, simple, and suitable for most purposes. +A -,-activation method was used by Azimov, et al. ( 2 C ) to measure the carbon content of coal. Martin, Prud’homme, and Morgan (11C) described a method using fastneutron inelastic scattering and neutron activation analysis to monitor coal for C, 0, Si, and Al. TOTAL SULFUR. Mohrhauer (lac) tested the Eschka method, the Li reduction method, and two oxygen combustion methods for total sulfur in solid fuels. He found the accuracy of the four methods t o be about equal. H e pointed out sources of error in the several methods. The absorption equipment for the oxides of sulfur of the oxygen combustion method was modified by Thuerauf and .Issenmacher (IOC) and Khan, Subramanian, and Sharma (1OC). Olds, Patrick, and Shaw ( I 5 C ) also modified the oxygen combustion method by passing the products of combustion through a PzOs moisture trap and a PTFE column of a gas chromatograph for S O z determination. The weight of the test sample raried from 1 to 10 mg depending on the sulfur content. A rapid titrimetric method for the sulfates resulting from the combustion of solid or liquid fuels is described by aliDragusin and Gavriliuc ( 6 C ) . quot of the sulfate solution is diluted with acetone and titrated with BaCl, using Carboxyazo (I) indicator. At the
equivalence point the pink-violet solution abruptly turns to green-blue. Asthana (1C) reported a new method for sulfur in coal. The new feature consists of oxidizing the coal with HX03 and KClOa. After complete oxidation the sulfate is precipitated as BaS04 and determined gravimetrically. Care must be exercised in using mixtures of chlorate, nitrate, and organic matter. Prasad (1°C) used H N 0 3 and HC10, to oxidize the organic matter of coal. A portion of the resulting solution mas used to determine phosphorus by the molybdate method. Another protion was used t o determine sulfur by the gravimetric method. Ratcliffe a n d Cunningham (18C) burned 20- to 55-mg samples of coal in the 0-flask method for total sulfur. They stated that accuracy was not good enough for national standardization. X rapid q u a n t i t a t i v e method for sulfur and nitrogen was proposed by Rlukherjee, P. Dutta, and P. B. D u t t a ( 1 4 C ) . The sample of coal or coke is heated with RIg polvder, in the absence of air, to 600-660 “C. The resulting residue is treated with H3P04to liberate the sulfur as HzS which, after conversion to ZnS, is determined iodometrically. The original solution is treated n i t h excess alkali to liberate the KH3. Berman and Ergun (SC) determined S in coal by X-ray fluorescence. The coal must be ground to less than 2 in size for accurate work. This method can be used for the determination of hlg, Al, Si, Ca, and Fe, if certain interfering elements are considered. F o R h r s OF SULFUR. Although not a part of the ultimate analysis, the determination of the forms of sulfur is similar to t h a t of total sulfur. I n the review of analytical methods for “forms of sulfur,” James and Severn (8C) reported the particle size to be of considerable importance. Tests made on samples passing 210-, 124-, 76-, and 5 3 - p sieves showed higher values for pyritic sulfur with increasing fineness. -4 part of the organic sulfur of coal is removed in preparation. Kaminskii ( 9 C ) and Savchuk (19C) reported t h a t larger pyrite crystals are covered with fine grains of organic sulfur and are removed along with the pyrite on preparation. Pyritic sulfur can be estimated rapidly and n ith reasonable accuracy from the total iron content of the regular ash. Young and Zawadzki (21C) reported only slight differences between sulfur determined by standard methods and values calculated from iron in ash. XITROGEX. The distillation portion of the Kjeldahl method for nitrogen in solid fuels 11-aseliminated by Mukherjee and D u t t a (1SC). After the digestion of the coal or coke n-ith HzSOaand a catalyst, the digestion product is treated n i t h an excess of S a B r 0 3 . The excess
is determined by iodometric titration. After t h e chemical a n d physical treatment of coal, Birkofer and Orywal (4C) reported the possible nitrogen bonding, based on the assumed nitrogen distribution as the following: a n H 2 0phase containing purine bases, urea units, amino acids, and peptides (35%) ; carbazole structures giving N H 3 (lo%), low molecular weight cyclic bases and phenylamines (3%); CHCl, phase containing non-basic N compounds, fatty amines, and hydropholic bases (23y0) ; residual coal containing high molecular weight N compounds (3%) ; and off gas containing N compounds t h a t yield free Nz (26%). OXYGEN.The British Coke Research Association (5C) conducted a series of tests to determine the oxygen content of cokes. A modified Schutze-Unterzaucher method was used. The use of platinum with carbon permitted operating a t 900 "C rather than a t 1100 "C. The carbon dioxide was determined by change in conductance of the Ba(OH)z test cell. d precision of 0.04-0.1070 was claimed. P a n c h e n k o , Pogrebinskaya, a n d Leonidova ( I C ) used the Unterzaucher method for oxygen in coals. Activated carbon was used in pyrolysis and the mineral matter of the coal was reduced by heavy media a t 1.4 sp gr. Calorific Value. Koch, et al. ( I D ) described the principles, apparatus, and results of determining the calorific value of coals by the p-backscattering method. The reported error is less than 1%. Ziegenhardt (SD) did a statistical study of a large number of analyses of brown coals and developed several formulas to calculate the calorific values from the ash and tar contents. Different formulas were necessary because of the wide variations in ash and tar contents. Variations in mineral matter content of coalspresented aproblemto Kovatsits and Szava ( 2 D ) in determining the composition and heats of combustion. Petrography. The wide sphere of recent activity in coal petrography warrants its separate review. Denton, Bayer, and Hassel ( 5 E ) reported on the growth, development, and application of petrography to the study of coal. The Automatic Microscope Electronic Data Accumulator (AMEDA) has been of considerable help in the progress. Roselt (10E) discussed the sampling, macro- and micro-petrography, appearance, and physical properties of brown coals. The preparation of samples for examination by transmitted and reflected light are given. Three reports by de Vries, Habets, a n d Bokhoven (I.@) describe t h e apparatus, preparation of samples, explanation of reflectance, and effect of t e m p e r a t u r e on t h e reflectivity of bituminous coal.
The diff erentation between exinite, vitrinite, and micrinite was shown by Tschamler and D e Ruiter ( I S E ) from their studies using infrared and protonspin resonance measurements, H contents, and the aliphatic and aromatic groupings. Bennet ( 2 E ) showed that semifusinite was infusible in a polished block of medium-volatile coal after carbonizing. A study by Harrison and Thomas (YE)outlined experimental techniques for measuring differences in reflectance between wet and dry samples. Electron spin resonance studies of pure macerals of North American and British bituminous coals by Austen and Ingram ( I E ) clearly shows the differences between vitrinite, exinite, and fusinite. Taylor ( I 2 E ) examined ultrathin sections of coal with the electron microscope and observed two types of vitrinite. One type consisted of homogeneous vitrinite, while the other was a mixture of two components having properties similar to vitrinite and exinite. The mixture of components is the cause of loiv reflectance and higher volatile matter in the heterogeneous vitrinite. Although exinite, micrinite, and semifusinite n-ere identified in the thin section, vitrinite was identified only after impregnation with a P b salt. Electron micrographs of ultrathin sections of petrologic components of coals of different rank were made by McCartney, O'Donnell, and Ergun ( 9 E ) . Ultrafine structures were revealed t h a t heretofore had not been optically identified. Two general sizes of structures mere observed; one was several hundreds of 8, and the other less than 100 8,. Particles observed were spheroid, curved cylinder, and round and polygonal platelet forms. Koppe ( S E ) used the petrological components to correlate beds of lowand medium-volatile bituminous coals of Pennsylvania. An accumulation of test data from a number of bench-scale coal testing procedures i s required to predict the quality of coke that will result on carbonization of a coal. De Sieghardt, Riva, and Harris ( I I E )rated coal petrography one of the most informative of these procedures. Cameron and Botham (4E) used the distribution of fusinitic constituents of a coal to explain the abnormal coke produced. Ettinger, et al., ( 6 E ) have suggested t h a t blowouts might be anticipated in coal beds having layers or lenses of fusinite. Their studies show t h a t all ranks of fusinite are capable of much more rapid sorption of COz and CHI than vitrinites. Benedict and Berry ( S E ) studied a wide range of bituminous coals. Reflectance measurements can be used (1) to
determine carbonization products accurately, (2) to obtain the heating value and sp gr of the resulting gases, (3) to determine the free-swelling index and the calorific value of coals, (4) to classify coals for certain combustion uses, ( 5 ) to monitor oxidation tendencies of coals, and (6) to subdivide coals in certain areas of the present classification of coals according to rank. Coking Processes and Coke Testing. COKING. The dwindling sources of prime coking coals and the increased efficiency in blast furnace operation have incited researchers to develop coke v i t h definite specifications from less desirable coking coals. Three new developments have been made in the U.S.S.R. in the coking processes. Taits, Speranskaya, and Tyutyunnikov (S4F) reported on (1) semicoking and briquetting the product, with or without a binder, followed by thermal treatment a t loiv temperature, (2) continuous coking by separating the process into stages and determining the coke specifications by the proper treatment in the plastic stage, and (3) producing coke from briquetted coal. Ortuglio and Walters (22F) made a statistical study of the results of laboratory coking tests made in 13- and 18-inch (34- and 46-cm) retorts. Formulas were developed to convert the results from the 13-inch retort to the same basis as results from the 18-inch retort. A scheme of analysis of the liquid and gaseous products from various gasification and carbonization processes was presented by Pichler, Hennenberger, and Schwarz (24F). Approximately 1000 compounds were detected and 470 were identified. Hocman ( I O F ) developed an equation to calculate the yield of dry coke, total gas, carbonization tar, CsHa, "8, water, and overall loss from the ash, volatile matter, moisture of the coal charge, and the coking chamber temperature. -1ccording to Kunc ( 1 4 F ) the cokability of a coal can be determined rapidly from the elasticity index. The index is defined as a measure of the ability of the plastic coal mass t o form a thin film surface. A relationship between elasticity index and dilatation was calculated. Stankevich (SBF) used the distribution of the micro-components of coals charged into the coke oven to improve a method to predict the quality of the resulting coke. Nikolaev, et al., (20F) reported the necessity for laboratory testing of all coals used in making up a coal charge to produce coke of uniform quality. X fluidized-bed laboratory furnace and a test procedure were developed by Chowdhury and Banerjee (68') to measure the effect of preheating coal on the resulting coke. A reduction in VOL. 41,NO. 5, APRIL 1969
311 R
coking time resulted. PLASTICITY. Chernyshov, Elenskii, and Donkov (5F) have used t h e three zones of the plastic layer t o determine additivity of the plastic properties of coal mixtures having different plastic properties. Shapiro, et al., (SOF) determined the effect of the moisture in the coal test sample during the plasticity determination. The microscope was used by de Vries and Bokhoven (3727) t o observe the pore formation, rate of degasification, and dilatation of coal on coking S p e c i a l a p p a r a t u s was u s e d b y Biryukov (SF) and Nesterenko and Biryukov ( I 9 F ) to separate the fluid or plastic mass resulting from heating coal in the absence of air. Geguchadze (88')designed apparatus and developed a method t o determine fluidity, rate of destruction, and degree of slyelling. A 30-gram sample is heated rapidly (80-85 "C/min); the rate of heating and change in volume are registered. The method was proposed for monitoring the plastic state during continuous coking. Lightman, Street, and Weight ( 1 5 F ) studied the behavior of a coal particle on heating in the British Standard swelling test and in pulverized-fuel flame. The British swelling index procedure was not suitable for determining the behavior of a particle during combustion. Loboda, et al., ( I 6 F ) showed t h a t the dynamics of swelling are very sensitive t o changes in the properties of individual coals. This swelling sensitivity was measured with a specially designed dilatometer. These results and other coal properties mere used to predict the physical a n d mechanical properties produced in coking. F u ( 7 F ) found the thickness of the plastic layer inadequate for properly evaluating the cokability of a coal. It was shown t h a t t h e Audibert-Xrnu dilatometer and the Gieseler plastometer test results mere better indicators. COKE TESTING.The trend to use smaller coke in blast furnaces has made i t necessary to modify t h e present standard method or to develop a new one for testing t h e fraction of coke passing a %inch (50.8-mm) and retained on I-inch (25.4-mm) squaremesh sieve. The sizes of the coke pieces for the present standard are 3 inches (76.1 mm) by 2 inches (50.8 mm). Price and Kuchta ( 2 5 F ) developed a tumbler test for small coke. It was proposed t h a t the number of revolutions of the drum for small coke be reduced to to W of that used in the standard tumbler test. Ghatak (9F) conducted tests t o correlate the results of the Micum and Breslau indices. The following two equations were proposed : Micum index = 0.819 X Breslau index $- 9.97 (correlation coeff. 0.894) for 312
R
ANALYTICAL CHEMISTRY
Breslau index 75-80; and Micum index = 1.2 X Breslau index 21.0 (correlation coeff. 0.819) for Breslau index
+
>80.
T h e high t e m p e r a t u r e testing of metallurgical coke was carried out a t the British Coke Research Association (BCRA) station ( 2 F ) . The drum test was made a t 20, 700, 900, 1100, 1300, and 1500 "C. It was indicated t h a t the strength increased and abradability decreased a t 700 "C. At about 1300 "C all samples showed a decrease in strength and abradability. It was concluded t h a t t h e high-temperature strength could not be predicted from tests made a t room temperature. Rammler, Flachsbart, and Jakob (26F) conducted tumbler tests of lignite coke a t 600, 800, and 1000 "C in a drum of 500 mm diameter and length. The resistance to abrasion is given in percentage for 20-, 30-, and 40-mm sizes. REACTIVITY.The general procedure for determining the reactivity of coke is to pass CO, a t a specified rate through a tube filled with coke of a specified size consist and temperature. Reactivity is the rate of reaction between the C O z and the carbon of the coke. The many variables mere researched by the following: Kessler and Dockalova ( I d F ) , Oekstad ( 2 I F ) , Bruk, et al. ( 4 F ) , Speranskaya and Nevodnik ( S I F ) , and Agroskin and Svyatets ( I F ) . SURFACE AREA. The surface area of the test sample for reactivity is one of the many variables that influences the final results. Tada ( S S F ) and T'olkov and Komskaya ( S 8 F ) measured the surface areas by several different methods. SPECIFICRESISTANCE. The measurement of specific resistance or electrical conductance of coke is affected by such variables as particle size, compaction or porosity, pressure, moisture content, temperature of coking, and voltage input. Researchers Hoy and hIaehre (113')) Mosoczi ( f 8 F ) , Ouchi ( 2 S F ) , Schmeiser (28F), Thiele, Gruson, and Scheidig ( % F ) , and Tonkonogov and T'eksler ( S 6 F ) have worked on these factors. DEKSITY. Porosity, which is estimated by making true and apparent density measurements, is of considerable importance in the use of the coke. The true density is usually determined in a pycnometer with water or MeOH, using a very finely pulverized sample of the coke. Determining the apparent density is more difficult. Dry, weighed coke pieces can be covered with a thin coat of paraffin to keep water from entering the pores and then are weighed in water. The other method is to allow the dry pores of weighed sample to fill with water before removing from the water, allowing excess run off, and reweighing to deduct the weight of water retained in the coke. Some of the more important work on this subject has
been done by Rammler et al. (d?'F), Kijewska ( I S F ) , and Medek ( I 7 P ) . Shabo (29F) microscopically determined the specific gravity of coal, coke, and related materials. Liquids of different densities were used with only a very few particles of sample. Inorganic Matter in Coal and Coal Ash. Some confusion has resulted from the improper use of the terms "mineral matter" and "ash content" of coals. The mineral matter content of coal can be more than, less than, or equal to the ash content, because it depends on the minerals in the coal and on t h e extent of alteration of the minerals owing t o the heat required to burn out the carbonaceous matter. A number of formulas have been proposed t o estimate the mineral matter from the ash content. The variation in composition of the mineral matter is too great to obtain one formula t h a t would be satisfactory for all coals. Many testing techniques have been developed for the determination of mineral matter. M I N E R A LMATTER. F r i e d e l a n d Queiser (ICG) used a combination of coal petrography and absorption bands of minerals of the infrared spectra for the positive identification of a number of minerals and certain organic structures. The I R spectra was used by Estep, Kovach, and Karr (l2G) to determine quartz, calcite, gypsum, pyrite, and kaolite in coals. The ash obtained at 400 "C was used by Patko (28G) to identify minerals in coal by wet chemical, derivatographic, X-ray diffraction, and microscopic methods. X-ray analyses of coal were made by Chursina a n d Vdovenko (9G) a n d Maruyama and Kobayashi (2SG) to determine essentially the same minerals in coal. Kanjilal, et al., (18G) examined a range of different rank coals for mineral matter. Although a variety of analytical methods were used to derive formulas to estimate the mineral matter, i t was not possible to get one formula t h a t would be applicable to all ranks of coals. Berman and Ergun ('7G) used X-ray fluorescence to determine all elements n.ith atomic numbers of 12 (Mg) and higher in coal. The coal must be ground to less than 2 microns to obtain satisfactory results. ASH ANALYSIS.Zink, Tashington, and Peterson (48G) developed a spectrochemical scheme of coal ash analysis for six of the major elements. A spectrophotometric method for the determination of TiO,, SiOz, Al2O3,and F e z 0 8contents of coal ash was used by Novitskii, Kuleshova, a n d Ivanova (24G). Methods are given to prevent interference by other elements. Boar and Sullivan (6G) used atomic absorption to determine the Ca in a n HC1 extract of brown coal. ,1 complexometric titration method was used by Fedorovskaya, Kazakova,
and Surina (1SG) to determine the ferric iron content of solid fuel ash. Odnopozova (26G) described a titrimetric method for determining SiO, in coal ash. The Si is taken into solution in the presence of fluorides in strong acid solution and forms with I 200 grams Be/kni*/ month and a concentration in the atmosphere of 10-4 gram/m3. K o r k by Razdorozhynyi (34G) s h o w that Be and V are associated with the organic portion of coal. BOROX,Timofeev, et al., (44G) postulated t h a t the considerably higher concentration of boron in coal than in
the lithosphere indicates t h a t coal has concentrated the element. It was also shown t h a t the boron is associated with the organic matter, and evidence was presented t h a t sea water had enriched some deposits. CHLORINE. Chlorine determination using the 0-flask method was very rapid for Ratcliffe and Young (SSG). After combustion, the chloride was titrated with AgXOs potentiometrically. Daybell (10G) presented data to disprove the idea t h a t the ratio of Na to C1 was constant, and t h a t C1 content was not a good measure of the boiler-fouling property of coal. FLUORINE.A spectrophotometric method for the determination of fluorine in coal was reported by Abernethy and Gibson ( 1G ) . The fluorine content coals ranged from of a series of 83 U.S. 0.001 t o 0.019%. GERMAKIUM A N D GALLIUM.Colorimetric analyses of six coal seams for Ge and Ga were made by Inagaki (15 G ) . The Ga was uniform in the bed but the Ge was in a higher concentration a t the top and bottom of the seam. Smolina, et al., (@G) found as much as 5.8 grams/ton Ga, and 39 grams/ton Ge in brown coal. It mas indicated that by density separations of the coal, 40% of the Ge and 65% of the Ga was in the fractions heavier than 1.55 density. GERJISNIU~~. Chemical methods for the determination of Ge in coal were reported by Wang (45G) and Sendu1’skaya, Shpirt, and Yurovskii (S9G). Spectrographic methods were used by Turulina and Zakhariya (43G), Puzanova and Perkova ( S I G ) ,Arnautov (SG),Banerjee, e t a l . , (5G), andLebedeva and Lyakh (22G) to determine the Ge in coal or coal ash. Variations of applications are given. A gas chromatograph was used by Sazonov, et al., (37G) t o determine Ge in coal. The Ge was chlorinated and the GeC14was absorbed on active carbon AR-3 and released by heating the C in a stream of dry nitrogen. Prasad, et al., (29G) were able to extract most of the Ge from fly ash by hydrochlorination. Chlorination gave a better recovery of the Ge but it mas contaminated with too many undesirable volatile products. The minimum Ge concentration in the ash of a lo^ ash coal is indicative t h a t the Ge is associated with the coal material according to Yurovskii, et al. (47G). This work shows that the distribution of Ge on combustion is related to the type of combustion equipment and is not related to coal type. Laminar and cyclone type combustion removes more Ge from ash than by pulverized fuel combustion. Khrisanfoya, Losev, and Soboleva (2OG) found that oxidized coal contained more Ge than fresh coal. Work by Admakin and Vnukov (2G) indicated that some Ge was in all the macerals but t h a t “gelified” mass had
higher contents. Ryabchenko and Lisin (S2G) determined the chemical and physical properties of density fractions of coal as related to Ge compounds, confirming the idea by other workers that the Ge is associated with carbon. Vitrain contains more Ge than the other niacerals. Bonding was indicated to be OGeC. Several forms in which Ge occurs in coal are presented by Saprykin (S6G), Shpirt, Yurovskii, and Sendu1’skaya (4OG) followed the various forms of Ge compounds and their behavior during high-temperature coal oxidation. MERCURY.A description of Hg occurrence in the ranks of coals and structures of the beds was given by Dvornikov (11G). Pakter, et al., (27G) reported on a method of reclaiming Hg from the coal. The distribution of Hg and the form of occurrence was given by Karasik, et al. ( I 9 G ) . MOLYBDENUM. A photometric method for the determination of 110 in solid fuels \vas described by Bekyarova, Khristova, and Ruschev (8G). Ash obtained a t 500 “ C i s fused with KaOH, dissolved in HC1, and filtered. The filtrate is treated n i t h K rhodanide and thiocarbamide, the colored complex is extracted with BuO;lc, and the hIo determined. The h90 content of coal must be considered in the catalytic gasification or hydrogenation of coal. PHOSPHORUS. Asthana ( 4 G ) described a new method for the determination of P in coal. The coal is wet-ashed n i t h H S 0 3 and solid KC104. When oxidation is complete the coloration from molybdenum blue is measured spectrophotometrically. CRANIUM. Jedlvab (17G) reported that the mineragraphic and autoradiographic study of coals indicates that U mineralization was superimposed. Coals free of inclusions and fractures are lorn in radioactivity. ZINC. Weaver (46G) described a method of determining Zn in coal ash with dithizone and Zincon, plus a solvent extraction and spectrophotometric finish. Standard Methods. Standard methods of testing probably appear t o the layman and the tyro as a terse accumulation of strange words, copiously adulterated with abbreviations. However, these methods for which definitions and abbreviation codes are usually provided, are special forms of communication. The terseness is the result of refinement and special wording for legal acceptance. Standard methods are used by large corporations, professions, and political entities in order that discussions and transactions can be carried on in a common language. I n the early stages of development of a standard the “what” and “how” of a series of operations is specified. I n the refinement that comes with after extended use, the standard is refined VOL. 41, NO. 5, APRIL 1969
e
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such t h a t only the “what” must usually be given. Because a standard method is a tool t o accomplish an act, i t should remain only as long as i t serves the purpose for which i t was developed. It should be periodically reapproved, revised, amended, and abolished as the need dictates. The U.S. Bureau of Mines was very active in the development and standardization of test methods for coal evaluation, and has retained a considerable amount of information that is helpful i n t r a i n i n g technicians. Oppelt’s ( S H ) compilation of Bureau of Mines methods is one of the most comprehensive standards on analyzing and testing coal and coke. Rees (4H)has drawn on his many years of experience with development, standardization, and application of test procedures in the evaluation of coals and coke to describe the chemical and physical uses and the limitations of coal analysis procedures. The review of standard methods is emphasized by Shipley ( 5 H ) in his report on the continuing review and amendments of the 16 parts of the British Standard 1016 on coal and coke. NA~IONA STANDARDS. L The American Society for T e s t i n g a n d M a t e r i a l s (ASTRI) ( 2 H ) is the chief coordinator of the development and standardization of the test procedures for coal and coke in Xorth America. The ASTM Committee D-5 on Coal and Coke, composed of almost equal membership of producers, consumers, and those with general interest in coal, approves the need for new standards and the revisions of existing standards, and recommends the withdrawal of obsolete standards. It also recommends t h a t some of the standards should be approved b y t h e U n i t e d S t a t e s of =Imerica Standards Institute (USASI) as national standards in international participation. Table I lists present ASTM standards and specifications. INTERNATIONAL STASDARDS. The International Organization for Standardization (ISO) ( 2 H ) through its Technical Committee 27 on Solid Mineral Fuels has advanced 33 standard test procedures and specifications to the IS0 recommendation stage, and 16 to I S 0 Draft Recommendation status. Table I1 gives the title, number, and status of each standard. Miscellaneous. Kreulen (131) explored the possibility of a single classification system of coals ranging from hard coal t o and including peat. H e started the system with a rank concept and ended i t with information on aromaticity, ring condensation index, and molecular size of the mean structural unit. The same interest was shown by Zabavin, et al., (341) in developing a system of classification including hard 314 R
ANALYTICAL CHEMISTRY
and brown coals. Parameters used in the system are (1) the yield of mater and C o n from coal at 350 “C, and (2) the yield of products of hydrolytic cleavage by means of 5% KOH in alcohol-pyridine mixture. Vdovenko and Gulak (301) determined the fusibility of ash using the high-temperature heating microscope. Results were in close agreement with those by the standard cone method. Ziegenhardt (351) reported on the factors affecting the ash-melting behavior of salt coals. The study is based on the acidic and basic constituents of the ash. According to work by Szulakowski (261), finely divided SiO, reduced the melting point of coal ash. Yao (321) correlated the chemical composition of coal ash with the fusibility of ash. Shibaoka (241) used the microscope to determine the behavior of the individual particles of ash on heating and to predict the melting point and viscosity of the ash. The viscosity characteristics of molten coal ash mere measured by Vdovenko and Ershina (291) using a n EVS-4 self-exciting electrovibrational viscosimeter. The behavior mas correlated Fvith A1203,SiO,, CaO, and F e 2 0 3contents. Kirsch (111) reported the effects of acidic and basic constituents on the viscosity of coal ashes. H e found t h a t sulfates, P, Ti, and alkalies have only a small effect. The effects of the several petrographic components of a coal on the Hardgrove grindability index (HI) were determined by Marayama (191). The HI of vitrite is equal to or slightly higher than clarite, and t h a t of durite is lower than ritrite and clarite. He (201) also reported on the effect of the various minerals and size of particles of minerals on the HI. Dockter, Belter, and Ellman (21) determined the pulverizing characteristics of lignite a t various stages of drying. There was no correlation between the Hardgrove grindability index and the pulverizing capacity of a conical ball mill. Kagan, Belosel’skii, and Sorokin (91) determined the grindability index of petroleum coke. Although they found t h a t the index mas half t h a t of anthracite, the power consumption was 1.5 times t h a t required for the anthracite. The moisture-holding-capacity determination was developed to evaluate the lower rank bituminous, sub-bituminous, and lignitic coals. The principle classifications systems specify this testing method in order t o arrive a t a moist, mineral-matter-free Btu. This Btu is used a s a classification p a r a m e t e r . Edwards (31) examined a number of variations of the basic method and reaffirmed the suitability of K2SOato provide the necessary relative humidity of 96% at 30 “C. H e preferred the rapid methods to the I S 0 standard method. ( I t should be noted that the rapid method is limited to “hard” coals
and can be used t o classify only a small group of bituminous coals from highvolatile A bituminous coals through the sub-bituminous A groups.) Kozko, et al., (121) described a modification of the all-purpose method to accelerate the testing. The test sample, after the saturation with water, is pressed between filter papers t o remove the major portion of the excess moisture. Kubant and Flum (141) modified the pycnometer method for the specific gravity of solid fuels. They made a correction for the contraction in volume of the methyl alcohol when mixed with the moisture in the coal. Juentgen and Schwuger (81) determined the density and porosity of coal, coke, and miscellaneous substances using mercury porosimetry. The sizes of the pores are given on graphs. Fujii and Tsuboi (51) determined helium densities of a number of coals. It was shown that the hydrogen contents of Japanese and foreign coals were distinctly different. Parish (221) measured the abrasiveness of lom-ash coals. The wear due t o coal was parabolically related t o the volatile matter of the coal, and was less than t h a t of the more abrasive mineral constituents. The wear rate increased rapidly as the Hardgrove grindability index decreased below 70. Goddard and Duzy (61) determined the abrasiveness of solid fuels using a radiochemical method. The balls of a ball-race mill were i r r a d i a t e d a n d t h e wear was measured in the pulverized product of the mill. A comparison of the laboratory tests and actual field wear is given. The experimental wear data was used in mill design and to predict wear rates of milling equipment. Bayakhunov and Vdovenko (11) studied the abrasiveness of coal ash. A laboratory method was developed to predict the wear rates of heated surfaces by ashes. Ashes of similar chemical compositions gave different wear indices owing to the diff erent mineral properties. English and Hiorns (41)measured specific fracture energy. Breakage of a solid is accompanied by the formation of a new surface and characterized by a certain energy per unit area. The measurement of this energy may be used in the design of a pulverizer. Thiele (2’71) described in detail a laboratory procedure for the measurement of the specific heat of brown coal. Kirov (101) determined the specific heats of moisture, coke, hydrocarbons, liquids, gases, and volatile components of coal for temperatures between 0 and 1000 “C. From these data, a formula was derived to calculate the specific heat of coal. Moisture and rate loss during volatilization most affected the calculated results. Surface area or specific surface measurements of coals m-ere made by Thomas,
Benson and Hieftje ( H I ) ,Spencer and Bond (251),and Lavrik and Loskutova (171). Similar methods were used with some modifications of application and interpretation of results. Differential thermal analyses (DTA) of bituminous coals were made b y Yoshimura and Mitsui (331) and H. Luther, et al., (181). Yoshimura noted an endothermic change a t 150 "C which was thought to be due to the evaporation of water. Another change a t 400500 "C was concluded to be the result of evaporation of volatile matter and the degradation of the coal. Luther examined the experimental factors and concluded t h a t differences in the curves on carbonization for different ranks of coal were due to physical rather than chemical changes. The flotation process in coal preparation appeared to benefit from the salt content of mine water according to Laskowski a n d Mielecki (161) and Hoffmann and Pfeiffer (71). The salt adversely affected the sieving processes as described by Hoffmann. Vlasova (311) described the effects t h a t oxygen groups in coal, polar and nonpolar reagents, and free radicals have on the flotation of coal. Kun and SzaboPelsoczi (151) evaluated activators and depressants of pyrite in flotation processes. Depressants CaO and S a C N , collectors E t and Bu xanthates, and a c t i v a t o r s C u S 0 4 a n d N a l S were described. The plastic deformation of coal under compression was studied by Parish (211). An analysis of the compression of a cube of coal between platens suggests t h a t the type of failure is dependent on cube size and on several physical properties of coal that are rank dependent. Shnaper and Zinchuk (231) described in detail the apparatus and procedure for obtaining optimum technological parameters during the extraction of wax from brown coal. GASEOUS FUELS
This review is concerned with techniques, methods, and procedures t h a t have been or can be applied, with or without modification, to carbureted water gas, liquified petroleum gas, sludge gas, manufactured gas, natural gas, water gas, or other gases t h a t can be used as fuels. Reviews. M a n y analytical techniques are being applied to gaseous fuels. Fundamental developments have been reviewed in the following areas: Electroanalysis and coulometric analysis by Bard ( S J ); polarographic theory, instrumentation, and methodology by Hume ( 7 4 ; potentiometric titrations by Toren ( 1 6 J ) ; amperometric titrations b y Stock ( l Q J ) ;gas chromatography by Juvet and Dal Nogare (84;
mass spectrometry by Kiser and Sullivan (1OJ) ; ultraviolet spectrometry b y Crummett and Hummel ( 6 4 ; infrared spectrometry by Crisler ( 6 J ) ; and organic polarography by Pietrzyk ( 1 S J ) . Pertinent application reviews include air pollution, by Altshuller ( l J ) , and petroleum, by Tuemmler ( l 7 J ) , and Shull and Beardsley ( 1 5 J ) . TVilson and Duff ( 1 8 J ) have prepared a survey of industrial gas analysis, in which inorganic gases, fuel gases, flue gases, motor exhaust gases, atmospheric pollutants, and analytical methods are reviewed. Ball ( 2 J ) discusses the use and limitations of infrared spectroscopy and gas chromatography in gas analysis. The impact of space age technology on gas measurement and analysis through the use of computers, electronics, lasers, ultrasonics, fluidics, and nuclear techniques are described by Kemp ( 9 4 . Theory and equipment for multicomponent gas absorption are reviewed by Kosugi ( 1 1 J ) .Two books are pertinent: One by Brame and King ( 4 4 on solid, liquid, and gaseous fuels, and the other b y Lodding ( 1 2 J ) on gas effluent analysis. Gas Chromatography. Gas chromatography is still the fastest growing method of analyzing gaseous fuels. The articles included in this review are only those t h a t are unique in some aspect of application, procedure, column packing, or apparatus. Basic theory, applications, and techniques of gas chromatography are discussed by Purnell ( 6 5 K ) and Ettre and Zlatkis ( 2 6 K ) . Current advances in techniques, methods, and apparatus are discussed by Giddings and Keller (SOK-CCK) and Zlatkis ( 8 0 K ) . The 8th volume in the Gas Chromatography abstracts h a s been compiled b y Knapman ( 4 4 K ) , the second edition of ASTRS compilation of gas chromatographic data has been prepared by Schupp and Lewis ( 6 8 K ) ,and Volumes 8 and 9 of Chromatographic Reviews by Lederer have been published (48K,
4 9 K )' Boer ( 1 l K ) reviews the problems inherent in automated quantitative gas chromatographic analysis. Subjects considered are sample injection, type of column, stationary and mobile phases, detectors, temperature programming, signal evaluation, and quantitation methods. Gaumann (29K) considered column types, supports, liquid phases, detectors, injection, collection devices, and temperature in discussing the principals and practicability of gas chromatography. Halasz and Heine ( S 9 K ) reviewed the preparation of packed capillary columns, a comparison of packed columns and packed capillary columns, and analytical applications. Grasselli and Snavely ( S 5 K ) reviewed the equipment and techniques available for recovering gas chromatographic
fractions for infrared spectoscopy. Palm ( 5 9 K ) discussed the evaluation of gas chromatograms by Kovat's retention index. Retention energy values are presented for a number of the lighter hydrocarbons. Leathard and Shurlock ( 4 7 K ) discussed compound identification and review the many techniques and methods that have been used for this purpose. Air pollution studies have utilized the capabilities of gas chromatography to determine ppm and ppb with a high degree of success. The concurrent review on Air Pollution in this volume and the review by Ohta (57K) include articles on sampling procedures, injection, columns, detectors, and quantitation methods t h a t could be utilized in trace component analysis of gaseous fuels and their combustion products. Gas chromatography has been utilized to determine the following: C H I and COz in anaerobic digester gases (2SK, 7 5 K ) ; C4,Cs, and C6 hydrocarbons ( 1 2 K ); hydrogen in blast furnace gas ( 1 S K ) ; naphthalene in fuel gases ( 5 4 K ); hydrogen and hydrocarbons in bons ( 1 2 K ) ;hydrogen in blast furnace gas ( 1 S K ) ; naphthalene in fuel gases ( 5 4 K ); hydrogen and hydrocarbons in heptane (62K); impurities in propylene ( 2 K ); the heating value of blast furnace gas ( S 8 K ) ;traces of hydrocarbon gases i n oxygen ( 6 7 K ); hydrocarbons in methane ( 8 2 K ) ;C6 and heavier hydrocarbons in natural gas (61K ) ; isobutylene in the presence of 1-butene (5UK); p r o d u c t s of p y r o l y t i c c r a c k i n g of heptane ( 2 4 K ) ; pyrolytic products of natural gas (74K); pyrolysis products from pulverized fuel combustion (25K); impurities in gas streams ( S 6 K ) ; impurities in ethylene (16K, 8 i K ) ; C1 to C l zhydrocarbons in automotive exhaust (60K); methane in He, H, or Ne ( 8 S K ); pyrolysis p r o d u c t s from polymers ( 1 9 K ) ; Ar, CH4, and N in ammonia production gas ( 5 2 K ) ;unsaturated hydrocarbons in pyrolysis gas (?'OK); C3 to C,hydrocarbons in ammonia product gas ( 1 0 K ) ; COS, MeSH, and H z S in gases ( S 7 K ) ; impurities in CZH4 and other petroleum gases ( 4 5 K ); petroleum gases ( 5 S K ) ;pyrolytic products of biphenyl (78K); oxygen in gases ( 6 i K ); Ar, CH4, and H in ammonia synthesis gas (4OK); trace hydrocarbon contamination of gases ( 1 4 K ) ;permanent gases by a flame emission detector ( 5 8 K ) ; trace impurities in fuel gases (S4K, 6 6 K ) ; impurities in propane ( 6 9 K ); and the pyrolysis products of nitroalkanes ( 17 K ) . Methods, procedures, and apparatus for the GC determination of the compounds t h a t are normally found in gaseous fuels have been described in various publications ( l K , 6 K , 7 K , 9 K , 2OK, 21K, d l K , 42K, 46K, 5 6 K , 6 S K , 64K, 7 l K , 7 2 K , 7 7 K , 7 9 K ) . Aranda and Flaquer ( 4 K , 5 K ) described the VOL. 41, NO. 5, APRIL 1969
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construction and operation of a n apparatus t h a t utilizes t h e Janak method to analyze combustible gases. Farzane and Ilyasov ( 2 7 K ) presented a method of calibrating a chromatograph for the determination of impurities in gases. Araki and Kawamura ( S K ) discussed temperature programming in the analysis of inorganic gases and gaseous hydrocarbons. Quantitative interpretation of chromatograms of gaseous hydrocarbon mixtures was discussed by Nikolov, Kaishev, and Koleva (55K). T o eliminate the double peak t h a t occurs when the sample contains more than 10% H, Curren ( 1 8 K ) advocated a mixture of H (39-41%) and H e (51-59%) for use as the carrier gas. The effects of various concentrations of S r cation on X-type zeolites on the retention characteristics of mixtures of CI-C, hydrocarbons and CO mere presented by Tsitsishvili, et al. ( Y S K ) . Bellar and Sigsby ( 8 K ) discussed the evaluation of various silica gels for the analysis of C I A s paraffins, C2-C, olefins, and C2H2.Kalker (Y6K) described a n automatic sample injector, with which 36 different liquid or solid gaseous samples can be automatically introduced into the chromatograph at 5- to BO-minute intervals. Subtractive techniques in the analysis of the components of gaseous fuels were described by Chang (15K) and Klosterman and Sigsby ( 4 S K ) . S u l f u r Compounds. Bernardini, Spaggiari, and Turtura ( S L ) described and compared gravimetric, volumetric, and nephelometric methods of determining traces of organic sulfur in natural gas. Pop1 and Weisser ( 9 L ) described t h e gas chromatographic analysis of sulfur-containing compounds and sulfur-containing odorants. They found that the best quantitative results were obtained with a polypropylene glycol sebacate column. Smith, Hultz, and Orning (1SL) described the sampling and analysis of flue gas for oxides of sulfur and nitrogen, wherein a n adaption of the phenoldisulfonic acid procedure was used to determine the oxides of nitrogen and a modified Berk and Burdick procedure was d e v e l o p e d f o r t h e s u l f u r oxides. Nacovsky (8L) evaluated methods and procedures that have been used for the determination of sulfur oxides in flue gas, with respect to sampling devices, methods of separation, and the determination of SOs, SO2,and 02. Kacovsky ( ? L ) also presents a method for onstream determination of sulfur trioxide in stack gases. Color intensity changes occur when barium chloranilate is added t o stack condensate t h a t has been treated with 5% iso-PrOH-11-ater solution. Schneider (11L) evaluated the Corhett and Flint, the Goksoeyr and Ross, and the Christov techniques for determining SO2 and SO, in gases. H e 316 R
ANALYTICAL CHEMISTRY
selected these methods because of the simple testing and analytical procedures. Determination limits of hydrogen sulfide in natural gas by the French, German, and British lead acetate tests were found to give divergent results. Williams and Lom (14L) suggest t h a t the maximum acceptable concentration be expressed by a numerical limit rather t h a n for a q u a l i t a t i v e p r o c e d u r e . Leidnitz ( 6 L ) determined hydrogen sulfide in coke oven gas by the test tube method using a lead acetate reagent, and compared results with those made with the cadmium acetate method. Katoh ( 5 L ) has proposed a gas chromatographic method of determining low concentrations of H2S in a gas. The gas is reacted with PbS, the PbS is reacted with HC1, and the resultant gas is analyzed on a p,pJ-oxydipropionitrate column a t room temperature. Several methods of determining H 2 S have been patented. I n the method proposed by Fails (4L),H2Sreacts with a metal in a n aqueous solution, forming a n insoluble precipitate; the H+ concentration is then determined. Risk and 3lurray (1OL)catalytically oxidized gaseous H 2 S to SO2 with F e filings a t 200-250 "C, and compared the Ulabsorption a t ~ 2 8 5 A 0 with t h a t of an unoxidized sample. Because SO? in a gas will affect the color of Pb-impregnated paper, Schumann, Lobenstein, and Blaschke (1ZL)proposed the use of AgCS-impregnated paper and the determination of the color change with photoelectric cells. .lustin ( I L , ZL)described procedures for continuous monitoring of S odorants in natural gas, naturally occurring S compounds in raw or processed natural gas or LPG, S or H in ammonia plant feed gas. H 2 S and (or) SO2in stack gas, and H,S in the atmosphere. The method utilizes a Br- or I-generating titrator operating with a coulometric sensing circuit coupled to a solid-statereagent generating circuit. Dew Point, Water Vapor, and Suspended Matter. Gonzalez and Lee ( 1 2 M ) presented experimental dew and bubble points and densities of the saturated phase envelopes for 10 simulated natural gas samples. Smith and Free (22M) discussed the bases of many different types of dew point instruments and presented comparative data on their working range, response time, accuracy, and reliability. Dew point meters based on thermoelectric cooling were described by Thiele ( 2 4 M ) a n d Griffin a n d Stringfield (13-V). Dartsch ( 7 M ) presented a n apparatus with which the dew point is determined by the lowering of radiation from a ? O d T I , 22iAIc, 230Th) or ??9Th source. Bisherg (4M) described a miniature solid-state dew point sensor that will give dew point depressions of 40-60 O F . The proceedings of the 1963humidity,
moisture symposium have been published. Topics of specific interest include the following: The direct measurement of dew point temperature with semiconducting thermoelements ( I M ) , a manually operated dew point hygrometer using thermoelectric cooling ( g O M ) , improvements in dew point measurements of gases by the increased use of Peltier devices ( 1 8 M ) , a thermal conductivity gas analysis in hygrametric applications ( 6 M ) , the design and applications of a high performance dew point hygrometer ( 2 1 M ) , the dew or frost point hygrometer ( 5 M ) , the basic process of the dew point hygrometer ( 2 5 M ) ,a n automatic dew point hygrometer with thermoelectric cooling ( 9 M ) , and a dew point apparatus of high accuracy ( 1 4 M ) . Lueck (19.V)presented a review of the fundamentals and operating procedures involved in the moisture measurement in air and gases. Moisture in gases m a y be determined with a cobaltous chloride indicator ( 2 M ) , a transducer (SM),a gas chromatograph ( 2 S M ) , or a thermal conductivity bridge (17-V).as well as by determining the H20 saturation point ( I O M ) , or the adsorption and desorption from a fixed bed (8M).Hasko ( 1 5 M ) presents tables and graphs from which the saturation water vapor content of natural gases that are rich in COP and S can be determined a t various pressures and temperatures. Gast ( 1 1 M ) describes the development of a n automatic recording gravimetric apparatus for determining solid m a t e r i a l i n flue a n d w a s t e gases. Herrmann ( 1 6 M ) presented a procedure t h a t utilizes standard papers or membranes for the filter media and micropore metal foils for flow control to obtain constant flow rates for the investigation of nonvolatile impurities in gases. Calorific Value and Physical Properties. Brmstrong ( 1 P )presented detailed calculations of the heat of combustion of pure CH, in Kj,'mole, Btu/mole, Btu/ft3 (dry basis), and Btu:ft3 (saturated basis). Glushchenko (@) used the formula Q = a(CHa) b (CO) C H 2 t o construct a simple nomograph to predict heating values with i 1 kcal. Safety factors for fuel gases were reviewed by Brinke (ZP) with respect to Wobbe numbers, density, ignition rate, theoretical osygen demand/l,OOO kcal, explosion limits, and tendency t o autoignition. Masalov (?P) reviewed the empirical and semiempirical equations for calculating the Boyle temperature Tb, and concluded t h a t the best fit is obtained r r i t h t h e e q u a t i o n , T b = A'/'. Edmister (3P) tabulated values of heat capacity, enthalpy, and entropy under ideal gas state conditions at 10 O F intervals over the range 300 to 390 O F
+
+
for H, N, 0, CO, CO,, HzO, HzS, SO,, SO3, CH,, and C,H,. Moore and Shrewsbury ( 8 P ) presented routine analysis and source data for 3 i 4 natural gas samples from 24 U.S. states and 5 other nations. Physicaldataonnatural andfuelgasesappears in books by Hepple ( 5 P ) and Laurien (6P). Sampling. Romer (1ZQ) discussed time lag problems of gas sampling in continuous process monitoring, with respect to apparent volume, differential pressures, filter and dust factors, and conduit size. Bagwell and Pringle ( Z Q ) p r e s e n t e d a m e t h o d for s a m p l i n g ethane-rich liquid and gaseous streams. Many methods and devices were developed for sampling gases. The most interesting of these follow: A sampling device for stream generator flue gas ( S Q ) , sampling without air contamination ( l d Q ) , a device for sampling metallurgical furnace waste gases (CQ), a motor driven multipleport gas sampling valve ( l S Q ) , an automatic, high-pressure gas-sampling system ( 7 Q ) , a static gas sampling device ( I Q ) , stack emission sampling ( S Q ) , a rugged gas sampling tube (5Q), automatic sampling for CO, determination of blast furnace gas ( I O Q ) , a proportional gas sampling device (SQ), and continuous gas samplers (9Q and I f & ) . Orsat. Hobbs (1R) discussed the Orsat method with respect to reagents and operating procedure, as well as methods t h a t are used to determine CO, C1, H,S, mercaptans, 0, S, H 2 0 , C,H,, butadiene, and isobutylene. Tsisin ( 2 R ) described a n Orsat-type a p p a r a t u s which has been modified to allow pneumatic transfer of the absorbents to and from the measuring burets. T'eiga, D'-llessandria, and Barberis (JR) described a new Orsat-Lunge-type semimicro gas analyzer that utilizes plastic valves and a rubber membrane. Automatic Analyzers. Kharitonov (14s)graphically calculated the dynamic error introduced in the time log of gas analyzers because of the large volume of t h e measuring cuvettes. Piotroivski ( 1 8 s ) investigated basic e r r o r s of t h e r m o c o n d u c t o m e t r i c , thermomagnetic, thermochemical, and thermoancmometric analyzers particularly those errors attributed to instability. Dierkes (7s) discussed the applications and limitations of infrared absorption, thermal conductivity, magnetic susceptibility, and electrical conductivity as sensing methods in gas analyzers. Romer (ZOS) and Kankowicz (30s) discussed problems encountered in optimizing the measurements from gas analyzers, including design, theory, and measuring characteristics of photometric gas analyzers. Solomonand Lazeanu ( 2 3 s )presented data and methods for preparing refer-
ence standards for 0, C 0 2 , CH,, and CO gas analyzers, and evaluated which method of preparation was best for a given concentration. A discussion of all types of analyzers is presented by Vana ( 2 9 s ) . Acoustical detectors are discussed with respect to the following: Hydrogen specificity ( l S S ) , design (8S),dependence on the voltage developed by an optical-acoustical receiver having a capacitance microphone on the gas pressure chamber (5S), variation in sensitivity as a function of gas pressure in the analysis chamber (SS), and the use of an ultrasonic transducer as a detector ( 2 2 s ) . -4 hydrocarbon analyzer t h a t utilizes the temperature difference between the base and the top of the flame to determine composition has been developed (28s) and can be used for C1-CZ2 hydrocarbon mixtures. Boucher discussed the theory and applications of thermistors in temperature control, calorimetry, pressure measurement, gas analyzers, and flow meters. Tarasevich ( 2 5 s ) presented a study of the operation of a single-cell, thermocatalytic CH4 transducer under forced gas exchange conditions and concludes that the forced gas increases the level of the signal, decreases the influence of the cell angle of gradient, and improves the dynamic parameters of the CH, analyzer. Although oxygen is not a fuel gas per se, the metering and measuring of oxygen flow and concentrations is pertinent to most end uses of fuel gases. There have been a great number of analyzers developed to determine oxygen concentrations ( 1S,ZS,9S, 1 OS, 15S, 21 8,SdS, 26S, Z7S, and 51S ) . Piwowonska ( 1 9 s ) described and compared a number of analyzers t h a t use UT' absorption as the detector. Basic theory, schematic diagrams, and component functions are discussed in detail. Benz, Doughty, and Tibbetts (3s)developed a UV instrument that operates in a narrow wavelength region where there is high absorption by olefinic and aromatic hydrocarbons b u t none by 0, H 2 0 , and other common gases. Katoen, Lueckers, and Reints (138) described a procedure for the continuous analysis of blast furnace top gas; CO and CO, are detected by two I R analyzers and H by a thermal conductivity analyzer. Hummel (11s) described an 1R analyzer that uses the change in the capacitance of a condenser, caused by the absorption of chopped I R radiation, as a measure of the absorbing gas concentration. Janac (12s) described a single-bean1 I R analyzer in which the beam passes through layers of both the reference and the sample gas, and the deviation from zero is a measure of the concentration in the
(4s)
sample. A nondispersive I R analyzer for the analysis of combustion and synthesis gases is described by Luft, Kesseler, and Zorner (178). Calormetric. Maatschappij (27") described a method of determining the concentration of the odorant, tetrahydrothiophene, in fuel gas by observing the length of color change in a tube packed with SiOs gel, impregnated with acid KIO3, and separated with layers of sand. Takata and Muto (62') determined the H and 0 contents of fuel gases by controlled potential colormetric methods a t a water-repellent electrode plated with Pd or Pt black. Pilarczyk, Miller and Paterok (ST) determined 0 (10-100 ppm) in gases, particularly S' and C2H2,by measuring the absorbance of the product of CuCl oxidation. Shimomura, Itami, and Kosasayama (42') discussed the deterin C,H, by measuring mination of 3" the absorbance of the thymol and chloramine-T reagent solution a t 665 mp. Hobart, Bjork, and Katz ( I T ) advocated a modified Ilsovay reagent that stabilizes the suspensoid with gelatin and KCl in spectrophotometrically determined C z H z in gases a t 552 or 575 mp. Sweetser (52') claimed sensitivity of less than 1 ppm with his colorimetric method of determining 0 in gases by using a photochemically generated methyl viologen radical-cation. Potentiometric. Capuano (1C) described a method of determining low H,S concentrations in gases (air) by reacting the sample with ",OH to produce (NH4),S and measuring the "4() 2 polarographically. Janda and H r u d k a (ZC) d e s c r i b e a m u l t i chambered polarographic vessel for the determination of HzS or H C N in gases. Ammonia and pyridine in coke oven gas was determined by Kagasov and Zharkova ( S C ) by absorption in an H 2 S 0 4solution; the concentration was determined with a glass-calomel electrode system and colorimetric indicators. Moebius ( 5 C ) developed a n apparatus that is applicable to the determination of 0 in gases and special analysis of CO,, H 2 0 , inert gases, and fuel gases. Accuracy of the Clark microdetermination of 0 in gases and liquids \vas improved by the addition of a mechanical arrangement for tightening the membrane ( 4 C ) . Standards. ASTM standards t h a t are pertinent to the analysis of gaseous fuels are in parts 18 and 19 of the 1968 ASTM standards ( I V ) . Changes in method, procedure, or status have been made under the following headings: Analysis of Commercial B u t a n e Butylene Mixtures by Gas Chromatography (D1717-65), Analysis of Liquified Petroleum (LP) Gases by Gas Chromatograph (D2163-66), Analysis of Reformed Gas by Gas Chromatograph (D1946-67), Test for Specific Gravity VOL. 41, NO. 5, APRIL 1969
317 R
of Gaseous Fuels (D1070-67), Analysis of Katural Gas-Liquid Mixtures by Gas Chromatography (D2597-67T) , Chemical Composition of Gases by Mass Spectrometry (D2650-6iT) , Ethylene, Other Hydrocarbons, and Carbon Dioxidc i n H i g h P u r i t y E t h y l e n e (D2505-67) , Hydrogen Sulfide a n d Mercaptan Sulfur in S a t u r a l Gas (D2385-66), Hydrogen Sulfide in Liquified Petroleum (LP) Gases-Lead Acetate Method (D2420-66), Pressura n t Gas Sampling for Gaseous Analysis (D2544-66T), Soncondensable Gases in C3and Lighter Hydrocarbons by Gas Chromatography (D2504-67), Physical Characteristics of Liquified Petroleum (LP) Gases From Compositional Analysis (D2598-67T), Vapor Pressure of Liquified Petroleum ( L P ) Gases (D1267-67), and Interconversion of the .Inalpis of C s and Lighter Hydrocarbons t o Gas Volume, Liquid Volume, or Keight Basis (D2421-66). Miscellaneous. Rochkind ( I W ) utilized cryogenic condensed-phase sampling and analysis techniques in which the condensed sample was diluted 1OO:l with d r y ?; and deposited onto a CsI, CsBr, KBr, or XaC1 window t h a t was cooled to 200 “K for IR analysis. Spectra are presented for 13 C,-C4 hydrocarbons, and i t is suggested t h a t the method allows the determination of contaminants in air samples at levels of 100 ppm. A mass spectrometer, in conjunction with agas chromatography, mas used by Sokolov, et al., (SW) to determine alkene, alkadiene, a n d alkenyne hydrocarbons u p to C s in the ethylene fraction of a coke gas. The relative amounts of hydrocarbons were found by reference to molar peaks a t 12 Y ionization voltage. Zhurov ( 4 W ) used a n isotopic dilution technique to determine H, N, 0, Xr, Ne, CH,,CO,, and CO impurities (> 6.0001%) in natural and inert gases. Nozhnova ( I W ) analyzed gases by excitation of the sample and determined the concentration of the components from the spectral lines and their maximum. The procedure was simplified by exciting the mixture of gases by a single impulse folloived by registration of the phosphorescence. LITERATURE CITED
SOLIDFUELS Sampling
(I&) Amer. Soc. T e s t i n g M a t e r i a l s , ASTM Standardq, Gaseous Fuels Coal and Coke,” Vol 19, p 484, 1969. (ReleaGed >larch 1968.) Proximate Analysis
(1B) Barbu, I., Falk, E., Ursu, Gh., Metallurgia (Bucharest), 19 (lo), 541-4 (1967). (2B) Beizer, V. N., Goroshko, V. D., Lokshin, A. G., K h i m . Tverd. Topl. 1967 (31, 121-5. (3B) Burek, R., Prace Glownego I n s t . Gornictwa, Komun. No. 420, (1967). 318 R
ANALYTICAL CHEMISTRY
(4B) Chernyshov, Yu. A., Gruzintsev, V. G., Koks i K h i m . 1967 (4), 10-13. (5B) Dimitrov, M., Khristov, K., Petkov, N., Vuglishta (Sofia), 23 (2), 19-21 (1968). (6B) Duzy, A. F., Walker, J. B., Jr., U.S. Bur. Mines Inform. Circ. No. 8304. 2739 (1966). (7B) Egami, E., Kano, T., Nemoto, A, Sumitomo Kinzoku, 19 ( I ) , 23-7 (1967). (8B) Fushimi, H., Genshiryoku Kogyo, 13 (6), 47-51 (1967). (9B) Gee, K. H., Laslo, J. A., Ironmaking Proc., A I M E , 23, 359-68 (1964). (10B) Hinz, H., Brenstoff-Chem., 47 ( l l ) , 336-40 (1966). (11B) Hudy, J., Jr., Deurbrouck, A. IT.) U.S. Bur. Mines Rept. Invest. No. 7101, ( 1968). (12B) Humphreys, I(. K., Lawrence, IT.F., Coal Prep. 3 (l),12-18 (1967). (13B) Ibid., (2), 69-71 (1967). (14B) Kerstine. H. J.. Braunkohle 19 19). 321-3 (1967r.’ (15B) Iiessler, F. 11.,Dockalova, L., Vysledky Banskeho T’yskumzi (4), 24157, (1965). (16B) Kessler, 11. F., Dockalova, L., Frezberger Forschungsh., A No. 388, 75-92 (1967). (17B) Knauf, G., Brenstoff-Chem. 47, 69-76 (1966). - -, (18B) Knauf, G., Freiberger Forschungsh., A So. 388, 93-119 (1967). (19B) Kononenko, N. I., Nauchn. Tr., Permsk. Nauchn.-Issled. UQOl’n.Inst. 8, 5-14 (1965). 120B) Ladner. IT. R.. Kheatlev. R.. J. Inst. Fuel, 39, 280-4, (1966). (21B) Luckers, J., CNRM (Centre Natl. Rech. M e t . ) (Brussels) 1967 (ll),9-15. (22B) Nadziakiewicz, J., Heilpern, S., Koks, Smola, Gaz, 12 ( 8 ) , 202-8 (1967). (23B) Nagy, X, Varga, K., Radioisotope Instrum. Ind. Geophys., Proc. Symp., Warsaw, 1965, 1, 425-34 (1966). (24B) Nehm, G., Olschewski, G., Glzieckauj 103 (S), 383-6 (1967). (25B) Nelson, E. T., Worrall, J., Walker, P. L., Jr., Advan. Chem. Ser. No. 55, 602-18. discussion 618-20 (1066). (26B) Qbeins. H . . Schaefer. 8 . G.. Aach:ner B l . Ahfbereiten-Verkoken: Brikettieren, 16 (3-4)) 107-72 (1966). (27B’i Rees, 0. W., Talanta, 13, 1027-32 (1966). (28B) Reznik, 11. G., Lyannay, Z. G., Yarovaya, V. I., Met. Koksokhim. Mezhvedom, Respub. Nauch.-Telh. Sb., 1966 (2), 30-7. (29B) Rhodes, J. R., Daglish, J. C., Clayton, C. G., Radioisotope Instrum. Ind. Geophys., Proc. Symp., Warsaw, 1965, Vol. 1, pp 447-62, discussion, pp 462-3 (1966). (30B) Richter, S., Polaschek, H., Bergbautechnik, 17 (3), 126-8 (1967). (31B) Roth, >I., Chenz. En., 73 (16), 83-8 (1966). (32B) Ruschev, D., Yankova, K., Vuglishta (Sofia), 21 ( l o ) , 21-2 (1966). (33B) Salcewicz, J., Kijewska, A , , Koks, Smola. Gaz. 12 16). 141-5 (1967). (34B) Shiplei., D. E., Fuel (London), 45 (4), 283-94 (1966). (35B) Stewart, R., Evans, D. G., ibid., 46 (4-5), 263-74 (1967). (36B) Stewart, R. F.,Hall, A. W.,Trans. SOC.Mining Eng. A I M E (Amer. Inst. Mining, M e t . , Petrol. Eng.), 238 (3), 269-72 (196’7). (37B) Szymborski, A., Krajowe S y m p . Zastosow. Izotop. Tech. Srd, Stettin, Pol., 1966 (Sect. 121), 7 pp. (38B) Tanemura, T., Snita, H., Oyo Butsurz, 36 (6), 444-51 (1967). (30B) Trost, A., Radioisotope Instrum. Ind. Geophys., Proc. Symp., Warsaw, 1965, 1, 435-44, discussion 445 (1966). \ - - - - /
\ - -
“ l
>
(40B) Viktorin, Z., Zdrav. Tech. Vzduchotech., 10 (2), 65-9 (1967). (41B) Zielinski, E., Fuel (London), 46 (4-5), 329-40 (1967). Ultimate Analysis
(IC) Asthana, S.S.,Fuel (London), 46 (6), 425-9 (1967). (PC) Azimov, S. A., Alasagutov, V. S., Kasymov, A . IC, Khakimov, AI., Dokl. Akad. K a u k U z . SSR, 23 (2),24-7 (1966). (3C) Berman, AI., Ergun, S., Fuel (London), 47 (4), 285-301 (1968). (4C) Birkofer, L., Orywal, F., BrenstoffChem., 48 (8), 225-35 (1967). (5C) British Coke Research Association, Coke Res. Rept. 42, Chesterfield, England, Sept. 1966. (6C) Dragusin, I., Gavriliuc, A , , Rev. Roumaine Chim. 12, 1239-43 (1967). (7C) Gruson. G.. Fritzsche. L.. Knauf. G.. Freiberger ’ Forschungsh. A No. 388; 141-54 (1967). (8C) James, R. G., Severn, 11. I., Fuel (London), 46 (6), 476-8 (1967). (9C) Kaminskii, V. A , , Ugol’, 41 ( l o ) , 52-7 (1966). (lOC) Khan, A , , Subramanian, T. A., Sharma, I(. R., J . Mines, Metals, Fuels, 14 (lo), 315-16 (1966). (11C) llartin, T. C., Prud’homme, J. T., Morgan, I. L., AEC Accession No. 33249, Rept. KO.AED-CONF-65-155-10, Avail. Gmelin, 16 pp. (1966). (12C) llohrhauer, P., Gas-Wasserjach, 109 (21), 561-5, 1968. (13C) bIukherjee, S. X., Dutta, P. B., Indian J . Technol., 5 (9), 300-1 (1967). (14C) hlukherjee, S.N., Dutta, P., Dutta, P. B. ibid., 6 ( l ) ,31-2 (1968). (15C) Olds. F. 11. W..Patrick. J. K., Shaw, F. H., Analyst (London), 92, 54-56 (1967). (16C) Panchenko, S. I., Pogrebinskaya, AI. L., Leonidova, V. N., Podgotovka i Koksovanie Uglei J’ost. NauchJssled. Uglekhim. Inst., Sb. Statei, 1965 (6)
350-3, (Pub. 1966). (17C) Prasad, N. K., Chem. Ind. (London), 1968. 114) \ - - , ,444-5. (1iC) Ratcliffe, D. B., Cunningham, A. T. S., Fuel (London), 47 (2), 89-92 (1968). (19C) Savchuk, S. V., Mater. Soveshch. Rub. Lab. Geol. Organ., Qfh, Kiev 1965, 30-46. (20C) Thuerauf, W.,.4ssenmacher, H., Brennstoff-Chem., 48 (7), 206-7 (1967). (21C) Young, R. K., Zawadzki, E. 44.J Fuel (London), 46 (2), 1.51-2 (1967). ~
Calorific Value
(1D) Koch, S., Jugelt, P., Richter, S., Energietechnik, 17, 516-19, (1967). (2D) Iiovatsits, C., Szava, J., Pub. Hung. Res. I n s f . Min., (8/9), 283-87, (19651966)
(3D) Ziegenhardt, IT., Z. Angetc. Geol.,
12 (4), 175-9 (1966).
Petrography
(1966). (4E) Cameron, A . R., BoLham, J. C., ibid., 55,564-75, discussion575-6 (1966). 15E) Denton. G. H.. Baver, J. L., Hassel, ~R. E., J. h e t a l s , ’19, ( 5 ) , 88-92 (1967). (6E) Ettinger, I., Erimin, I., Zimakov, B., Yanovskaya, hl., Fuel (London), 45 (4), 267-75 (1966). (7E) Harrison, J. A., Thomas, J., Jr., ibid., 45 (6), 501-3 (1966).
(8E) Koppe, E. F., Advan. Chem. Ser., 55, 69-78, discussion 79 (1966). (9E) XcCartney, J. T., O’Donnell, H..J., Ereun, S..ibid.. 55. 261-71. discussion 27r-3 ’11966). (10E) Roselt, ’G., Freiberger Forschungsh. C, 189, 9-27 (1965). (11E) Sieghardt, W. C., de, Riva, L. A., Harris, H. E., J . Metals, 18, 1337-40 (1966). (12E) Taylor, G. H., Advan. Chem. Ser., 5 5 , 274-82, discussion 282-3 (1966). (13E) Tschamler, H., DeRuiter, E., ibid., 55, 332-41, discussion 342-3 (1966). (14E) Vries, H. A. W.,de, Habets, P. J., Bokhoven, C., Brennstoff-Chem., 49 (1j, 15-21; (2), 47-52; (4), 105-10 (1968). I
,
Coking Processes and Coke Testing
(1F) Agroskin, A. A., Svyatets, I. E., K o k s i K h i m . 1967 (a), 13-19. (2F) British Coke Research Association, Coke Res. Rept. No. 38, Chesterfield, England, MarEh 1966. f3F) Biryukov, Yu. V., Met Koksokhim. illezhvedom. Resvub. Nauch.-Tekh.., Sb.., 1968. 8. 29-36. (4F) Bruk, A. S., Leibovich, R. E. Osipovskii, Yu. Ya., Pinchuk, S. I., Rabukhina, G. G., Chuchminov, V. M.,Koks i K h i m . 1967 (5), 22-3. (5F) Chernyshov, Yu. A., Elenskii, F. Z., Donkov, V. I., ibid., 1967 (6), 8-12. (6F) Chowdhury, S. B., Banerjee, S., Brennstoff-Chem., 49 (6), !69-70 (1968). (7F) FLI,Yung-Xing, Acta Foculio Sinica, 6 (2), 170-4 (1965). (8F) Geguchadze, R. A,, K h i m . Tuerd. Topl., 1967 (2), 102-7. (9F) Ghatak, S . P., Tisco, 15 ( l ) , 23-8 (1968). (10F) Hocman, L., Paliva, 46 (lo), 373-6 (1966). (11F) Hoy, A., Naehre, K., BrennstoffChem., 47, 50-60 (1966). (12F) Kessler, AI. F., Dockalova, L., Freiberaer Forschunash. A No. 388. 2939 (1967). (13F) Kijewska, A., Koks, Smolva, Gaz, 12 i l l ) . 297-301 11967). ~ - - - . , (14F) Kunc, J.,-Brennstoff-Chem., 49 ( 7 ) , 211-17 (1968). (l5F) Lightman, P., Street, P. J., Weight, R. P., J . Inst. Fuel, 40, 433 (1967). (16F) Loboda, N. S., Smul’son, A. S., Obukhovskii, Ya. &I., Sheikht, A. M., K o k s K h i m . 1966 ( 7 ) , 3-7. (17F) Medek, J., Freiberger Forschiingsh. A NO. 388, 55-61 (1967). (18F) Mosoczi, F., Femip. K u t . Int. Kozlemen, 1966 ( 8 ) , 103-27. (19F) Nesterenko, L. L., Biryukov, Yu. V., K h i m . Tuerd. Topl., 1967 (l),27-36. (20F) Nikolaev, I. N., Davydova, I(. I., Egorova, L. S., Donde, 11. L‘., Akulov, P. V., Loba, 11.Ya., Koks i Khim,., 1967 (12), 14-19. (21F) Oekstnd, S., Conf. Ind. Carbon Graphite, Pap., 2nd, London 1965, 100-6 (Pub. 1966). (22F) Ortuglio, C., Walters, J. G., U.S. Bur. Mines Rept. Invest. No. 6871 (1966). (23F) Ouchi, K., Fuel (London), 46 (2), 71-85 (1967). (24F) Pichler, H., Hennenberger, P., Schwarz, G., Brennstoff-Chem., 49 (6), 175-86 11968). (25F) Pric‘e, J. G., Kuchta, B. R., J . Metals, 19 (4), 47-9 (1967). (26F) Rammler, E , Flachsbart, H. B., Jakob, K., Freiberger Forschungsh. A NO. 422, 35-48 (1966) (Pub. 1967). (27F) Rammler, E., Mueller, K. F., Stoeffgen, F., Fleitcher, K., ibid., No. 422, 49-58 (1966) (Pub. 1967). (28F) Schmeiser, K., Z . Erzbergbau MetalIhuettenw., 9 ( 7 ) , 328-30 (1966). \ - - - - ,
\--,,
~
(29F) Shabo, Z. V., Geol. Geokhim. Goryuch. Iskop, SO.11, 57-64 (1967). (30F) Shapiro, M. D., Al’terman, L. S., Keitel’eisser. S. R.. Kononenko.’ A. F.. K o k s ixhim..1967 (1). 3-6. (31F) Speranskaya, G. V., Nevodnik, V. I- f-~ . , K h i m . Tverd. Topl., 1967 (3), 97IUI.
(32F) Stankevich, A. S., Koks i Khim., 1967 (4), 1-7. (33F) Tada, Y., Nenryo Kyokaishi, 45 (4761. 906-12 (19661. (34F) Taits, E. hl., Speranskaya, G. V., Tyutyunnikov, Yu. B., K h i m . Tverd. Topl., 1967 ( l ) ,76-85. (35F) Thiele, H. Gruson, G., Scheidig, K., Freiberger Forschungsh. A 422, 59-70 (1966) (Pub. 1967). (36F) Tonkonogov, XI. P., Veksler, 5’. A., Izv. Vysshikh. Uchebn. Zavedenii., Fiz.,
1967 (11), 143-5. (37F) Vries, H. A. W.,de, Bokhoven, C., Brennstoff-Chern., 49 ( 7 ) ,206-11 (1968). (38F) Volkov, V. Z., La Komskaya, G. V., Term. Okislitel’nvi Piroliz Towl. Vusokopolim. Mater.,“ Akad. h r a i k SSYSR, Inst. Goryuch. Iskop., 1966, 64-7. Inorganic Matter in Coal and Coal Ash
(1G) Abernethy, R. F., Gibson, F. H., U.S. Bur. Mines Rept. Invest. No. 7054, (1967). (2G) Admakin, L. A., Vnukov, A. V., Geol. Polez. Iskop. Zabaikal., 1967, 61. (3G) Arnautov, N. V., Spektral. Anal.
Geol. Geokhim., Mater. Sib. Soveshch. Spektrosk., 2nd (Irkutsk), U S S R (1963),
229-30 (Pub. 1967). (4G) Bsthana, S. S., Chem. Ind., 1967, 190. (5G) Banerjee, N. N., Rao, K. D., Rao, H. S., Lahiri, A., Chem. Age India, 2 (2), 63-5 (1967). (6G) Boar, P. L., Sullivan, J. V., Fuel (London), 46 ( l ) ,47-52 (1967). (7G) Berman, hI., Ergun, S., U.S. Bur. Mines, Rept. Invest. No. 7124, (1968). (8G) Bekyarova, E., Iihristova, E., Ruschev, D., Godishnik Khim.-Tekhnol. Inst., 11 (l), 105-10 (1964) (Pub. 1965). (9G) Chursina, N. Ya., Vdovenko, hl. I., Probl. Teploenerg. Prikl. Teplo$z., 1967 (4), 126-34. (10G) Daybell, G. K.,J . Inst. Fuel, 40 (312), 3-6 (1967). (11G) Dvornikov, A. G., Dokl. A k a d . N a u k SSSR, 172 ( l ) , 199-202 (1967). (12G) Estep, P. .4.,Iiovach, J. J., Karr, C., Jr., ANAL.CHEW,40,358-63 (1968). (13G) Fedorovskaya, N. P., Kazakova, I. ll.,Surina, N. L., T r . Inst. Goryuch. Iskop. M i n . Ugol. Prom. SSSR, 23 (2), 14-9 (1967). (14G) Friedel, R. A., Queiser, J. A., Amer. Chem. Soc., Div. Fuel Chem., Preprints, 10 (3), 1-6 (1966). (15G) Inagaki, hl., Nenryo Kyokaishi, 46 (485), 684-8 (1967). (16G) Jirele, V., Nechyba, L., Pachner, P., Cesk. Hyg., 11 (6), 329-39 (1966). (17G) Jedwab, J., Geol. Runschau, 55 (2), 445-53 (1966). (18G) Kanjilal, K. K., Mukherjee, 11.L., Mukherjee, A. K., Moitra, A. K., Indian J . Technol.. 6 (4). 117-23 11968). (19G) Karasik, hl. A., Dvornikov; A. G., Talalaev, G. K., Zemblevskii, K. K., Koks i Khim., 1967 (9), 14-16. (20G) Khrisanfoya, A. I., Losev, B. I., Soboleva, G. N., T r . Inst. Goryush. Iskop. M i n . Ugol. Prom., SSSR, 23 (l), 73-7 11966~. j-___,.
(21G) Kirsch, H., Pollmann, S., Ottemann, J., Mitt. Vern. Grosskesselbesitzer, 48 ( l ) , 10-20 (1968).
(22G) Lebedeva, N. V., Lyakh, R. A,, Zavod. Lab., 32, 1334-5 (1966). (23G) Maruyama, T., Kobayashi, K., Nenryo Kyokaishi, 44 (461), 633-40 (19651. (24G) Novitskii, N. V., Kuleshova, I. A,, Ivanova, N. I., K h i m . Tverd. Topl., 1968 (l),62-7. (25G) Odnopozova, P. S., Novitskii, N. V., ibid., 1967 (2), 114-15. (26G) Odnopozova, P. S., ibid., 1967 (6), 152-4. (27G) Pakter, 11.K., Dubrovskaya, D. P., Pershin, A. V., Talalaev, G. K., ibid., 1967 (6), 145-50. (28G) Patko, G., Energia. Atomtech., 20 (lo), 474-8 (1967). (29G) Prasad, N. S. K., Abubacker, K. hl., Keshavadas, T., Mehta, C. T., India At. Energy Comm., At. Energy Estab. Trombay AEETjCD /25, (1964). (30G) Perez, A. hl., Ensayos Invest., 1 (l), 18-28 (1966). (31G) Puzanova, K. P., Perkova, R. I., Izv. Vyssh. Ucheb. Zaved., Gorn. Zh., 9
(11), 5-10 (1966). (32G) Ryabchenko, S. K., Lisin, D. M.,
Mater. Soveshch. Rab. Lab. Geol. Organ., Qth, Kiev., 1965, 110-15. (33G) Ratcliffe, D. B., Young, T. L., Fuel
(London), 1968, 47 (3), 185-92. (34G) Razdorozhnyi, V. F., Geokhimiya, 1967 (4), 472-5. (35G) Ratynskii, V. bl., Glushnev, S. V., Dokl. Akad. N a u k SSSR, 177, 1193-6 (1967). (36G) Saprykin, F. Ya., Mater. Soveshch. Rab. Lab. Geol. Organ., gth, Kiev, 1965,
103-9. (37G) Sazonov, hl. L., Alymova, T. E., Selenkina, M. S., Zhukhovitskii, A. A., K h i m . Tverd. Topl., 1968 (3), 64-70. (38G) Schafer, H. N. S., AKAL.CHEM.,39, 1719-26 (1967). (39G) Sendul’skaya, T. I., Shpirt, hl. Ya., Yurovskii, A. Z., Zh. Anal. Khim., 22, 445-8 (1967). (40G) Shpirt, hl. Ya., Yurovskii, A. Z., Sendul’skaya, T. I., T r . Inst. Goryuch. Iskop. Akad. N a u k SSSR. 24 13). 15-22
\ - -
--
,-
(42G)-Smolina, L. P., Bazarova, Zh. G., Ulanov, N. N., Dariev, A. D., Tr. Buryatsk. Kompleks. Nauch.-Issled. Inst., Akad. Nauk SSSR, Sib. Otd., 20, 266-32
119661. (43G) Turulina, 0. P., Zakhariya, N. F., Ukr. K h i m . Zh., 32, 1334-7 (1966). (44G) Timofeev, P. P., Bogolyubova, L. I., Miesserova, L. V., Fedorovskaya, N. P., K h i m . Tverd. Topl., 1967 (5), 96-102. (45G) Wang, ,Jy-Shih., Bull. Inst. Chem. Acad. Sinica No. 12, 34-9 (1966). (46G) Weaver, C., Fuel (London), 46 (6), 407-14 (1967). (47G) Yurovskii, A. Z., Shpirt, M. Ya., Tarnavskii, I. L., Grekhov, I. T., Zaitsev, 31. M.,K h i m . Tverd. Topl., 1967 (6), 135-44. (48G) Zink, J. B., Washington, W. D., Peterson, & J., I.U.S. Bur. Mines Rept. Invest. No. 6985, (1967). (49G) Zubovic, P., Advan. Chem. Ser., 55, 232-46, discussion 247 (1966). (50G) Zubovic, P., Sheffey, N. B., and Stadnichenko, Taisia, U.S. Geol. Surv. Bull. No. 1117-D, Dl-D33 (1967). Standard Methods
(1H) Am. Soc. Testing and Materials, “ASThI Standards, Gaseous Fuels, Coal, and Coke,” v. 19, 1968 p 482. (2H) International Organization for Standardization, information and documents available through United States of VOL. 41, NO. 5, APRIL 1969
319 R
America Standards Institute, 10 East 40th Street, New York, N.Y. 10016. (3H) Oppelt, W. H., U.S. Bur. Mines. Bull. No. 638. 11967). (4H) Rees, 0.\q., IllinbisState Geol. Suru., Rept. Invest. No. 220, (1966). (5H) Shipley, D. E., J . Inst. Fuel, 37, 510-14 (1967). Miscellaneous
(11) Bayakhunov, A. Ya., Vdovenko, hl. I., Probl. Teploenerg. Prikl. Teplofiz., 1967 (4), 135-45. (21) Dockter, L. Belter, J. W.,Ellman, R. C., U.S. Bur. Mines Rept. Invest. No. 7010, (1967). (31) Edwards, A. H., Fuel (London), 47 ( l ) ,29-49 (1968). (41) English, P., Hiorns, F. J., Inst. M i n ing Met., Trans. Secl. C, 75 (712), C87-C94 (1966). (51) Fujii, S., Tsuboi, H., Fuel (London), 46 (4-5), 361-6 (1967). (61) Goddard, C. W., Duzy, A. F., J . Eng. Power, 90 (2), 186-92 (1968). (71) Hoffmann, E., Pfeiffer, A., Glueckauf, 102 (21), 1104-10 (1966). (81) Juentgen, H., Schwuger, hf., Chem. Ing. Tech., 38 (12)) 1271-8 (1966). (91) Kagan, Ya. A., Belosel’skii, B. S., Sorokin, A. F., Thermal Eng. (English Transl.), 13, 56-60 (1966). (101) Iiirov, N. Y., Riv. Combust., 20 (4), 207-17 (1966). (111) Kirsch. H.. Mitt. Ver. Grosskesselbesitzer No: 107, 132-7 (1967). (121) Kozko, A. I., Konovalova, L. N., Kazakova, ll. D., Chesnokova, L. I., Khim. Klasszjikatsiya Iskop. Uglea, Akad. N a u k SSSR. Inst. Goruuch. Iskow.. ‘ , 1966. 156-63. (131) Kreulen, D. J. V., Geol. JIijnbouw, 45 ( 7 ) ,201-9 (1966). (141) Kubant, J., Flum, Zd., Ropa Chlie, 9 (2), 42-6 (1967). (151) I i u n , E., Szabo-Pelsocxi, M., Banvasz. Kut. Int. Kozlemen. 9 12). 31829 179641. (161) Laskowski, J., IIielecki, J., Przeglad Gorniczy, 20 151), 113-22 (1964). 1171) Lavrik, S. N., Loskutova, E. K., Mater. Soveshch. Rub. Lab. Geol. Organ., 9th, Kiev, 1965, 180-6. (181) Luther, H., Luther, V. H., Eisenhut, IT., Abel, O., Brennstoff-Chem., 47, 25864 (1966). (191) AIaruyRma, T., Senryo Kyokaishi, 44 (4641, 783-91 (1065). (201) llaruyama, T., ibid., 45 1476), 84350 (1966). 1211) Parish, B. M.,Brit. J . Appl. Phys., 18 (2), 233-40 (1967). 1221) Parish. B. >I., J . Inst. Fuel, 40 (313), 76-81 (1967). (231) Shnaper, B. I., Zinchuk, I. F., Khim. Tverd. Toal.. 1968 (3). 55-63. 1241) Shib‘aoka, AI., .Venryo Kyokaishi, 44 (464), 822-9 (1965). (261) Spencer, D. H. T., Bond, R. L., Advan. Chem. Ser., 5 5 , 724-8, discussion 728-30 (1966). (261) Szulakowski, IT., J . Inst. Fuel, 40 (323), 564-8 (1967). (271) Thiele, H., Freiberger Forschungsh, A NO. 385, 39-60 (1966). (281) Thomas, J., Jr., Benson, G. S., Hieftje, G. SI.,A4mer.Chem. Soc., Div. Fuel Chem., Preprints, 10 (3), 7-14 (1966). (291) Vdovenko, RI. I., Ershina, L. X., Probl. Teploenerg. Prikl. Teplojiz., 1965 (2), 66-73. (301) Vdovenko, 11. I., Gulak, L. A., ibid., 1966 (31, 46-8. (311) Vlasova, N. S., Yovye Issled. Obl. Obogashch. Melkikh Klassov Uglei Rud,
320 R
ANALYTICAL CHEMISTRY
Akad. N a u k SSSR, Inst. Gorn. Dela, 1965. 17-23. (321) Yao, Hsing-I, Acta Foculio Sinica,
6 (21. 151-61 ~-~ - - 1196Fil. (331) Yoshimura, F., Mitsui, S., Nenryo Kyokaishi, 45 (468), 191-7 (1966). (341) Zabavin, V. I., Kleimenova, L. A., Strel’tsova, A. T., Karnaeva, A. V., Surkova. V. L.. Ulanov. N. N..’ K h i m . Tverd. T o d . . 1967 11). 53-60. (351) Ziegeihardt, W.;’ Z. Angew. Geol., 13 (11-12), 599-606 (1967). \ - / I
\ - - - - I
GASEOUS FUELS Reviews
(1J) Altshuller, A. P., ANAL.CHEM.,39, IOR-21R (1967). (2J) Ball, D. F., Steel Times, 192, 159-61 (1966). (3J) Bard, A. J., ANAL.CHEM.,40, 64-73 11968). (4J) Brame, J. S. S., and King, J. G., “Fuel: Solid, Liquid and Gaseous,” 6th Ed., Arnold, London, 1967. (5J) Crisler, R. o., ~ A LCHEM., . 40, 246R-254R (1968). (6J) Crummett, W.B., and Hummel, R. A., ibid., 330R-34R (1968). (7J) Hume, D. N., ibid., 174R-184R il9)Afii j-”--,.
( 8 J ) Juvet, , R. S., Jr., and Dal Nogare, S.,
h d . , 33R-50R (1968). !J9) Kemu. L. J.. Pzweline Enar.. 39 19). 24-28 (i967). ClOJ) Kiser, R. W.,and Sullivan, R. E., ANAL.CHEM.,40, 273-302R, (1968). ( l l J ) Kosugi, IC., Kagaku Kojo, 11 ( 7 ) , 74-81, (1967). (l2J) Lodding, IT. Ed., “Gas Effluent Analysis,” Marcell Dekker, New York, N.Y., 1967. (135) Pietrzyk, D. J., ANAL.CHEM.,40, 194R-22R (1968). (145) Stock, J. T., ibid., 392R-401R (1968). (l5J) Shull, K. I,., and Beardsley, J. D., ibid., 39, 158-161R. (1967). (16J) Toren, E. C., zbid., 40, 402R-411R (1968). (175) Tuemmler, F. D., ibid., 39, 157R158R (1967). (185)’ Wilson, H. N., and Duff, G. ?VI. S., Analyst (London), 92,723-58 (1967). I
.
Gas Chromatography
(1K) Afanas’ev, A. I., Tr. Groznensk, Neft. Nauchn. Issled. Inst., No. 23, 224-8 (1967). (2K) Alekseeva, A . V.,and Fomina, A. I., Gazou. Khromatogr., 3,79-83 (1965). (3K) ,Araki, S., and Kawamura, N., B u n sekz Kagaku, 16, 334-40 (1967). (4K) Aranda, V. G., and Flaquer, J. O., Combustibles, 24, 35-59 (1964). (5K) Aranda, V. G., and Flaquer, J. O., Quim. Ind. (Bilbao), 13, 33-40 (1966). (6K) Abtaf’eva, E. A., T r . Saratou. Inst. Giproniigaz, 5 , 361-6 (1966). (7K) Avon, AI., Dumas, C., Badre, R., and Dutheil, J., Chem. Anal. Warsaw), 50, 84-8 (1968). (810 Bellar, T. A., and Sigsby, J. E., Jr., Environ Sei. Technol., 1, 242-6 (1967). (9K) Bennett, D., J . Chromatogr., 26, 482-4 (1967). (IOK) Beskova, G. S., Russo, L. P., Mamakina, N. G., and Pyatygina, E. S., Gasov. Khromatogr, 5 , 129-31 (1967). (11K) Boer, H., Chem. Weekbl., 64, 13-17 (1968). (12K) Bossart, C. J., and Zinn, T. L., French Patent 1,447,231 (July 1966). (13K) Brhacek, L., Kalandra. O., and Dufek, F., Hutniche Listy, 21, 53-6 (1967).
(14K) Calongne, 8. B., and hloi-ris, J. P., Proc. Annu. Tech. Meet. Exhib., Amer. Assn. Contam. Contr., 4th IV-1, 5p (196.5). ~---_,.
(15K) Chang, T. L., J . Gas Chromatogr., 4, 371-5 (1966). (16K) Chertorizhskii, A. V., and Al’perovich, V. Ya., ibid., 4, 310-16 (1966). (17K) Crawforth, C. G., and Waddington, D. J., ibid., 6 , 103-5 (1968). (18K) Curren, IT. J., German Patent 1,223,176 (1966). (19K) Deur-Siftar, D., Tehnika (Belgrade), 21, 1605-9 (1966). (20K) Doran, T., and Cross, J. P., J . Gas Chromatogr., 4, 260-2, (1966). (21K) Durrett, L. R., and O’Neal, M. J., Jr., U.S. Patent 3,236,603 (1966). (22K) Egel’skaya, L. P., Kolesnikova, R. D., and Pogorelenko, A. A., T r . Probl. Lab. K h i m . Vysokomol. Soedin., Voronezh. Gas Univ., 4, 222-7 (1966). (23K) Ellerker, R., Lax, F., and Dee, H. J., Water Res., 1, 243-5 (1967). (24K) Engelhardt, J., Proc. Conf. Appl. Phys.-Chena. Methods, C h e m . A n a l . (Budapest), 2, 169-76 (1966). (25K) English, P. E., Znstrum. Contr. S s t 40, 90-3 (1967). (264) ‘Ettre, L. S., and Zlatkis, A., “The
Practice of Gas Chromatography,’’ John Wiley and Sons, Ken. York, N.Y., 1967. (27K) Farzane, N. G., and Ilyasov, L. V., Zavod. Lab., 33,560-2 (1967). (2810 Galazyuk, L. ri., Zhurba, A. S., Muradov, A. A., and Sokol, A. I.,
Gaz. Delo, Kauch.-Tekhn. Sb, 1967 ( l o ) ,
15-17. (29K) Gaumann, T., Schriftenrkihe For-
schgemeinsch. Schweiz. Lackjabrikanten,
7, 1-20 (1966). (30K) Giddings, J. C., and Iieller, R. A., “Advances in Chromatography,’’ Vol. 2, Marcel Dekker, Inc., New York, N.Y., 1966. (31K) Giddings, J. C., and Keller, R. A., “Advances in Chromatography,” Vol. 3, Marcel Dekker, Inc., New York, N.Y., 1966. (3210 Giddings, J. C., and Keller, R. A., “Advances in Chromatography,’’ Vol. 4, Marcel Dekker, Inc., New York, X.Y., 1967. (33K) Giddings, J. C., and Keller, R. A., “Advances in Chromatography,” Vol. 6, Marcel Dekker, Inc., Xew York, N.Y., 1968. (34K) Gnauck, G., and Schoen, H., Proc. Conj. Appl. P h y s X h e m . Methods Chem. Anal. (Budapest), 2, 182-8 (1966). (35K) Grasselli, G., and Snavely, LI. K., Piogr. Infrared Spectrosc., 3, 55-74
(1967). (36K) Gray, P. S., British Patent 1,092,919 (1967). (37K) Green, L. E., Facts Methods, 8 , 2-6 (1967). (38K) Habermas, R.E., and Bucska, C. D., Co?nbitstton, 38,31-2 (1966). (391i) Halasz, I., and Heine, E., Advan. Chromatogr., 4, 207-63 (1967). (40K) Iogansen, A. V., and Kurkchi, G. S., Zavod. Lab., 33, 558-9 (1967). 141K) Jones, C. N., ANAL.CHEM., 39, 1858-60 (1967). (4210 Kaishev, Kr., Kkolov, R., and Iioleva. S.. God. K h i m . Tekhnol. Inst., 11, 187-97 (1964). (43K) Klosterman, D. L., and Sigsby, J. E., Jr., Amer. Chem. Soc., Div. Water, d i r Waste Chem., Preprints, 5 , 126-8 ilq65i (44K) Knapman, C. E. H., “Gas Chromatography Abstracts,” Vol. 8, Elsevier, Sew York, ?LT.Y.,1967. (45K) Kuo, C., Fang, K., and Chen, P., Hua Hsueh Tung Pao, 1966,43-5. (4610 Lauent’ev, T’. I., Baranenko, S. E., and hemchenko, S . S., Gaz. Delo, .Yattch.-Tekhn. Sb., 1967 (18), 25-30. \ - - - - /
(47K) Leathard, D. A., and Shurlock, B. C., Advan. Anal. Chem. Instrum., 6, 1-92 (1967). (48K) .Ledy;er, XI “Chromatographic Reviews, Vol. 9, Elsevier, New York, N.Y.. 1967. (49K) Lederer, hf., “Chromatographic Reviews,” Vol. 8, Elsevier, New York, N Y . , 1966. R. J., and Henze, J. C., U.S. ( 5 0 K i Loyd, . Patent 3,330,150 (1967). (5lK) Rfarkasov, P. I., Fonkich, A. G., Androsova. V. 11..Gazov. Khromatoar., 3, 96-8 (1965). (52K) Miesowicz, H., Chem. Anal. (Warsaw), 12, 903-5 (1967). (53K) Moghadam, P. E., Bull. Iranian Petrol. Inst., 22, 754-60 (1966). (54K) Xotizuki, -4,, Furuyama, Y., and Kimata, A,, Koru Taru, 18,42-7, (1966). (5510 Nikolov, R., Kaishev, Jr., and Koleva, S., God. Vissh. Khimikotekhnol. Inst., 12, 255-66 (1!365). (56K) PSosova, N. S., and Shitof, M.D., Tr. Kuibyshevsk. Gos. Nauchn.-Issled. Inst. Neft. Prom., 33, 201-7 (1966). (57K) Ohta, IC, Kagaku No Ryoiki, 20, 431-44 (1966). (58K) Overfield, C. V., and Wnefordner, J. D., J . Chromatogr.,30,339-43 (1967). (59K) Palm, E., Glas. Instrum. Tech., 10, 691-4 (1966). (60K) Papa, L. J., Dinsel, D. L., and Harris, W. C., J . Gas Chromatogr., 6, 270-9 (1968). (61K) Petrovic, K., A’afta (Zagreb), 18, 343-5 (1967). (62K) Pichuzhkin. I-. I.. and Saraeva. V. V., Vestn. Mosk. Vnib. Ser. 11: Khim; 21, 2,5-8 (1966). Jecko, G., Belgian (63K) Pierrard, ---H.,_and , Patent bi1,diLI Il‘Jbb). (64K) Prokop’eva, 11.F., Bukina, V. K., Mar’yanov+kaya, Ii., Sh., and Shemetikhiria. il. A.. Zh. Anal. Khim.. 21. 1098-103 (1966). (65K) Purnell, J.’ H., Annu. Rev. Phys. Chem., 18, 81-98 (1967). (66K) Reinhardt, 11.)Koch, H., and Otto, R., Chem. Tech. (Berlin), 69,42-4 (1967). 167K) Sal’nikova, G. M., and Yashin, Ya. I Gazov. Khronatogr., 4,118-20, (1966). (682) Schupp, 0. E., and Lewis, J. S., “Comuilation of Gas Chromatonrauhic Dflta,” ASTM Data Series Pub. 5S25Ae AST11, Philadelphia, 1967. (69K) Shkatov, E. F., Neftepererab. Nejtekhim. A k a d . Nauk Ukr. SSR, Respub. Meghvedom Sb., 1966 (lo), 36-8. (70K) Skarvada, A , , and Zbytek, P., Ropa Uhlie. 10. 78-82. 84 (1968). (71K) Solomon, P., J . Chromatogr., 30, 593-5 (1967). i72K) Szekely, G., Xacz, G., and Traply, G., Periodica Polytech., 10,231-5 (1966). I73K) Tsitsishvili, T-it-ishvili, G. V., ilndronikashvili, T. C., Chumburidze, T. -4.,and Iioridze. Z. I.. Soobshch. Akad. Nauk. Grit%.SSR, 42, 65-72 (1966). (7410 Valibekov, Yu. V.,Rolotov, G. M,, and Reininn, I. V., Dokl. Akad. Nauk. Tadzh. ”S’R, 10, 35-8 (1967). (75K) Van Huyssteen, J. J., Water Res., 1, 245 (1967). (76K) Walker, J. Q., Hydrocarbon Process. Petrol Rejiner, 46, 122-4 (1967). 177K) Williams. J. E.. and RIcDaniel. E. L.,’French Patent 1,’446,904(1966). ’ (7XIi) Yeatts, L. B., Jr., Attrill, J. E., and Rainey, W.T., Jr., Rept. KO. ORNLTRI-523, 1963. (79K) Yonetani, H., Bunseki Kagaku, 17, 406-1 3 1968). (80Ii) Zlatkis, A,, “Advances in Gas Chromatography,” Preston Tech. Abs., Evanston, Ill., 1967. 181K) Zlatkis. A.. and Kaufman. H. R.. J . Gas Chrokatdor.. 4. 240 il966,. (82K) Zocchi, F., “ib8d.i 6, 1OC-2 ’(1968). (83K) Zocchi, F., ibid., 251-3 (1968). ~~
^ ^
~
Sulfur Compounds
(1L) Austin, R. R., Ann. ZSA Con$ Proc., 19 (2-5-3-64), (1964). (2L) Austin, R. R., ibid., 20 (2-1-1-65), (1965). (3L) Bernardini, R., Spaggiari, PIT. A., and Turtura, L., Riv. Combust., 21, 63-77 (19671. -- \ - -
I
(4L) Fails, J. C., U.S. Patent 3,300,324 (1967). (5L) Katoh, T., Bunseki Kngaku, 15, 909-12 (1966). (6L) Leidnitz, K.,Gas-Wasserfach, 106, 1204-6 (1965). (7L) Nacovskyj W., Technicon Symp. 2nd, 224-7 (1966). (8L) Nacovsky, W., ibid., Combustion, 38, I,1 - 967) - -. ,. (9L) Popl, M., and Weisser, O., Sb. Vysoke. Skoly. Chem. Technol. Praze, Addil Fak Technol. Paliv Vody, 11, 35-38 (1966). (1OL) Risk, J. B., and Murray, F. E., U.S.Patent 3,300,282 (1967). (11L) Schneider, W.,Enerkietechnik, 17, 543-6 (1968). (12L) Schumann, H., Lobenstein, K., and Blaschke. H., British Patent 1.047.700 , , (1966). (13L) Smith, J. F., Hultz, J. A,, and Orning, -4.A., U.S. Bureau of Mines R. I. 7108, (1968). (14L) Williams, A. F., and Lom, W.L., J . Appl. Chem. (London), 17, 179-84 (1967). ,
I
Dew Point, Water, and Suspended Matter
(111) Armstrong, V., Humidity Moisture, Pap. Int. Symp., 1963, 1, 202-4 (pub.
1965). (2M) Asami, T., ANAL.CHEM.,40,648-50 (1968). (3M) Baranenko, S. E., and Krivorotov, A. A,, Gaz. Delo, Nauch.-Tekhn. Sb., 1967 (6), 27-31. (4M) Bisberg, A., Annu. I S A Conj. Proc., 19 (11.2-1-64), (1964). (531) Brewer, A. W., Humidity Moisture, Pap. Int. Symp., 1963, 1, 135-43 (pub. 1965). (611) Cherry, R. J., ibid., 1, 539-51 (pub. 198.5).
(7;\i)-Dartsch, H., German (East) Patent 55,453 (1967). (811) Flumerfelt, G. C., British Patent 1,039,220 (1966). (911) Francisco, C. C., and Beaubien, D. J., Humidity Moisture, Pap. Int. Symp. 1963, 1, 165-73 (pub. 1965). (10M) Freeland, F. L., British Patent 1,058,771 (1967). (1111) Gast, T., “Forschungsarbeiten zur Entwicklung eines Gravimetrischen, Automatisch Registrierenden Konzentrationsmessgeraetes fuer den Feststoffgehalt in Rauch- und Abgasen,” Westdeut. Verlag, Cologne, 1966. (12M) Gonzalez, 11. J., and Lee, A. L., J . Chem. Eng. Data, 13, 172-6 (1968). (1311) Griffin, 0 . G., and Stringfield, C. \I., J. Sci. Instrum., 41,241 (1964). (14M) Hartley, J. L., Chamberlin, J. L., and Huff, W. D., Humidity Moisture, Pap. Int. Symp. 1963, 1, 205-8 (pub. 1965). (1511) Hasko, L., Energia. Atomtech., 20, 453-8 (1967). (16hl) Herrmann, G., Chem. Tech. (Berlin). 18. 304-5 11966). (171Ij Likomskii, V. I., U.S.S.R. Patent 149,917 (1968). (ISM) Leone, 0. J., Humidity Moisture, Pap. In!. Symp. 1963, 1, 635-42 (pub. 1965). (1951) Lueck, IT.,Arch. Tech. Messen, NO. 246, 263-4 (1964).
(20M) Martin, S., Humidity Moisture, Pap. Int. Symp. 1963. 1, 149-54 (pub. 1965). (21M) Paine, L. C., and Farrah, H. R., ibid., 1, 174-88 (pub. 1965). (22M) Smith, C. R., and Free, D., Chem. Eng. No. 202, CE236-43 (1966). (23M) Starshov, I. hl., Voevodkin, Yu. P., and Khalimov. A. A.. Gazov. Khromatogr., 3, 103-6 (1965). ’ (24M) Thiele, T. N., British P a t e n t 1,052,171 (1966). (25M) U‘ylie, R. G., Davies, D. K., and Caw, W.A., Humidity Moisture, Pap. Int. Symp. 1963. 1, 125-34 (pub. 1965). Calorific Volues and Physical Properties
(1P) Armstrong, G. T., U.S. Nat. Bur. Stand. Tech. Note 299, (1966). (2P) Brinke, R., Tech. Ueberwach.,. 9,. 69-77 (1968). 13P) Edmister. W. C.. Hudrocarbon Process, 46, 119123, (1967).(4P) Glushchenko, I. AI., Stal’ Sb. Statei, 1965 (7)666-7. (5P) Hepple, P., “Natural Gas,” Elsevier, Xew York, N.Y., 1966. (6P) Laurien, H., “Taschenbuch Erdgas,” Oldenbourg, Munich, 1966. (7P) Masalov, Ya. F., Teploenerg., 15, 88-90 (1968). (8P) Moore, B. J., and Shrewsbury, R. D., U.S. Bur. &lines. Inform. Circ. 8356, 1967. ’
Sampling
(1Q) .4dams, R. O., Rev. Sci. Instrum., 37, 1243 (1966). (2Q), Bagwell, S. >I., and Pringle, H. P., 0 2 1 Gas. J.,65, 110-13 (1967). (3Q) Barnes, L. K., U.S. Patent 3,289,481 (4 ) Doubek, J., and Hayer, ?*I.,Czecho$oy:ian Patent 124,196 (1967). ( 5 Q ) Kaufmann, W., German (East) Patent 48,082 (1966). (6Q) Kurz, H., German (East) Patent 52,839 (1966). ., V. R., (7Q) Langdon, W. >IIvanuski, Putscher. R. E.. O’Neill. H. J.. and Krupnick, A. C.,’J. Gas Chromatogr., 4, 269-70 (1966). (8Q) Leonard, J. S., Tappi, 49, 84A-85A (1966). (9Q) AIiller, W. M., Chem. Eng. Progr., 61,75-8 (1965). (lOQ) PolSanskii, G. A., Govorov, V. I., and Kalinichenko, P. G., Metallurg, 11, 17-20 (1966). (1lQ) Quigley, J. J., U.S. Patent 3,304,783 (1967). (l2Q) Romer, E., Pomiary, Automat., Kontr., 11, 200-4 (1965). (13Q) Kilka, K., German Patent 1,259,605 11968). (14Q) Williams, H. P., Overfield, C. V., and Wnefordner, J. D., J . Gas Chromatogr., 5, 511 (1967). Orsaf
(1R) Hobbs, A. P., Encycl. Ind. Chem. Anal., 2, 139-57 (1966). (2R) Tsisin, N. A., Gaz. Prom., ll,, 47-8 (1966). (3R) Veiga, C. A,, D’Alessandria, A. V. H., and Barberis, H. H., Anales Asoc. Quim. -4rg., 53, 137-41 (1965). Automatic Analyzers
(1s)Abdrakhmanov,
hl. I., Stakhov, A. A., and Shapiro, M. G., Prib. Sist. Upr., 1968 (2), 53-4. (2s) Ageikin, D. I., Zykov, V. V., Abdrakhmanov, hl. I., Stakov, A. A., Valiakhmetov, G. V., Shapiro, AI. G., and
VOL. 41, NO. 5, APRIL 1969
321 R
Vrachev., V. L., U.S.S.R. Patent 191,888 (1967). (3s) Benz, D. E., Doughty, D. A., and Tibbetts, S. J., U.S. Patent 3,384,746 (1968). (45) Boucher, E. A., J. Chem. Educ., 44, A935-6, A938-9, A942-4, A948, A950, A952, A954, A956, A958, A960, A962, A964. A966 11967). (5s) Bresler, P. I., Opt. Spektroslc., 23, 9i3-9 (1967). (6s) Bresler, P. I., ibid., 24, 132-6 (1968). (75) Dierkes, G., Gas-Waerme, 17, 6-11 (1968). (8s)Dokunina, N. B., and Novitskii, P. V.,U.S.S.R. Patent 192,212 (1967). (9s) Fleming, H., and Schneider, J., German (East) Patent 54,509 (1967). (10s) Hersch, P., U.S. Patent 3,291,705 (1966). (11s) Hummel, H . , German P a t e n t 1,240,307 (1967). (12s)Janac, J., Czechoslovakian Patent 119.136 (1966). (13s) ’Katoen, J., Lueckers, J., and Reints, J., CentreNat2.Rech. Met., 7,3-10 (1966). (148) Kharitonov, T’. P., Zauod. Lab., 33, 902-3 (19671. (15s) Kordesch, K., U.S. Patent 3,258,416 (1066). (16s) Lucero, D. P.. and Krupnick, A. C., ANAL.CHEM.,40, 1222-7 (1968). (17s) Luft, K. F., Kesseler, G., and Zorner, II., and Lazeanu, L., Metrol. A d . (Bucharest), 13. 132-5 (1966). . (24s) Solomons, C., and Hynes, J. P.. U.S. Patent 3.328.277 (1967). (2jS) Tarasevich, 9. ill., Dopou. Akad. Nauk. Ukr. RSR, 30,372-7 (1968). (26s) Tsien, H. C., U.S. Patent 3,301,775 (,---. 1 0671,.
(275) Tsien, H. C., and Horowitz, H. H., C.S. Patent 3,305,458 (1967). (28s) Cniversal Oil Products Co., Xetherlands Patent A4pplication 6,609,823 fj 1- !Mi> - - . ,.
(29s) Vana, J., “Analyzatory Plynu a Kapalin” Sntl., Prague, (1967). (305) Wankowicz, K.. Pomiaru. Automat., Konlr., 12, 418-20 (1966). (31s) Zakharov, I. A., and Aleskouskii, V. B., U.S.S.R. Patent 185,108 (1966).
(5T) Sweetser, P. B., ANAL. CHEM.,39, 979-82 (1967). (6T) Takata, Y.,and Muto, G., Nippon Kagaku Zasshi, 88, 107-9 (1967). Potentiomefric
(1U) Capuano, I. A,, U.S. Patent 3,304,243 (1967). (2U) Janda, &and I., Hrudka, J., Czechoslovakian Patent 116,537 (1965). (3U) Kagasov, V. &I.,and Zharkova, N. A., Koks i Khim., 9,29-33 (1966). (4U) le Petit, G., and Legler, R., German (East) Patent 48,041 (1965). (5C) bloebius, H. H., German (East) Patent 48,083 (1966). Standards
i l l 7 ) ASTY Standards, Philadelphia, Pa.,
1968, Parts 18 and 19, ASTRl (1968).
Colorimetric Miscellaneous
(1T) Hobart, E. W.,Bjork, R. G., and Katz, R., Aiv.4~.CHEW,39,224-6 (1967). (2T) Naatschappij, N. V., Ketherlands Patent Application 6,714,062 (1968). (3T) Pilarciyk, H., Miller, G., and Paterok S., Chem. Anal. (Rarsaff), 12, 899-902 (1967). (4Tj Shimomura, S., Itami, T . , and Kosasayama, il., Tokushima Daigaku Y a k u g a h Kenkyu Nempo, 15, 1-3, (1966).
(1W) Nozhnova, 1‘. V., U.S.S.R. Patent 200,303 (1967). (2W) Rochkind, 11.AI., ANAL.CHEM.,39, 567-74 (1967). ( 3 R ) Sokolov, V. G., Kraplina, Kh. F., Pinsker, A. E., and Slobodyanik, E. K., Koks i Khim., 11, 36-8 (1968). (4K) Zhurov, Yu. A,, LValcch.-Tekh.Sb. Geol. Razrab. Transp. Ispol’z. Prir. Gaza, 5 , 163-3 11065).
