Organic elemental analysis - ACS Publications

Organic Elemental Analysis T . S. Ma, Department of Chemistry, Cify Universify o f New York, Brooklyn, N . Y. 7 12 10 Milton Gufterson, Chemistry laboratory, Joe lowe Co., Division of Consolidated Foods Corp., Englewood, N . 1. 0763 1

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PRESEKT PAPER is concerned with recent developments on quantitative analysis of the elements in organic compounds and material. T h e literature and information which came to the attention of the authors after t h e preparation of their last biennial review (170) in October 1967, u p to October 1969 have been surveyed. Some salient points are noteworthy: After promotion for several years (168, 169), the instrument manufacturers have firmly planted their automatic or semiautomatic elemental analyzers in t,he field. h recent survey has revealed that six American firms (56, 57, 120, 188, 199, 236, 241) are actively competing for the market. The senior author has visited a number of laboratories in which the commercial automatic machines are installed and has interviewed the microanalysts who are in charge of them. Where these machines are in continuous operation, the users as a rule are very happy with the new acquisition. They did not hesitate to report, however, t h a t they had spent considerable effort and time to modify the apparatus in order to produce correct results. Some of the alterations and innovations have been published (76, 8.4,151, 191, 192, 213), but many practicing analysts keep the information to themselves. It should be not'ed that these sophisticated machines have been designed and constructed by engineers who are not expected to be familiar with the chemical principles aiid specific requirements of quantitative organic analysis. The fact that many autoniatic analyzers are lying idle in t,he laboratories is not necessarily the fault of the manufacturers. At the present time, ready made instruments are available for carbon-hydrogen, nitrogen, and oxygen determinations. Apparatus for automatic determination of the other elements are being investigated (18, 94, 297). There has been a shift of emphasis on the types of organic elemental analysis. For many years the major work load of organic microchemists was concerned with the determination of the elements, especially carbon aiid hydrogen, in new compounds produced in the research laboratories. Recently, because of the popularity of research in elucidation of molecular structures and reaction mechanism?, the demand for analysis of new organic compounds aiid pure samples has diminished to some extent. On the other hand, the upsurge of interest in enviroiiniental studies and pollution HE

problems has focused attention on trace analysis of organic compounds in complex systems. For instance, methods for t h e determination of sulfur or nitrogen in petroleum have been evaluated. The procedures for pesticide residue analysis, which are based on the determination of halogen or phosphorus, have been under intensive study. T h e aim of the microchemist, as mentioned in a previous review (167) is to obtain the desired information using the minimum quantity of working material. For trace analyses, the ideal method would be to mineralize t h e whole sample and single out the particular element for measurement. This is usually not feasible, however, and a separation step becomes necessary. I n this case, it is important to prevent loss of the organic compound during preliminary treatment of the sample. T h e realm of organometallics has been expanding steadily. Since this group of compounds is known to be unstable, sensitive to the atmosphere, and difficult to be obtained in pure form, precautions should be taken while handling the sample for elemental analysis. Other organic compounds that merit special attention are those with high contents of fluorine or phosphorus, because they teiid to resist complete decomposition. CARBON AND HYDROGEN

I n order to develop a rapid, automatic or semi-automatic method for carbon and hydrogen in all types of organic compounds, research continued on instrumentation along with variations in combustion techniques and tube fillings. Kreutzer (152) described the design and functions of a number of different types of apparatus. Culmo (60) developed a n automatic analyzer yielding good results on a variety of organic compounds. Kunz (154) rendered the Perkin-Elmer 240 Elemental Analyzer fully automatic by the addition of a simple apparatus. Graham (102) utilized a Polypak gas chromatographic colunin with the F & M Model 185 Analyzer allowing for the use of electronic integration for improved resolution of component peaks. Macdonald and Turton (172) and Olson (191) modified the tube fillings for the Perkin-Elmer Analyzer (Xodel 240) and the Coleman C-H Analyzer (Model 33), respectively, for carbon and hydrogen in highly fluorinated substances. Derge (65) tested each stage of the F&M C H N Analyzer. The results for over

60 compounds were in agreement with theoretical values. Dugan and Aluise (89) described a n apparatus based on the uncatalyzed, dynamic flash-combustion of the sample in a n oxygen-helium at,mospherea t 1060-1080° C in a quartz tube. Scheidl (215) recommended a n improved tube filling for the F&M C H N Analyzer which gave better results for some compounds than the catalyst supplied by the manufacturer. Walisch and Schafer (254)used magnesium oxide in the tube filling for removal of fluorine and phosphorus. The rate of combustion in the automatic analyzer had to be slowed for phosphorus-containing compounds because of their slow pyrolysis. Herrmaiin and Leger (119) developed a n improved automat'ic microanalyzer having a length of only about 70 cm and in which complete combustion takes only 5 minutes. Turtnovsky (2.43,244) modified his apparatus for the automation of the gravimetric method for carbon aiid hydrogen by providing a cooling trap between the absorption tubes which were separated by a vessel containing manganese(1V) oxide for the absorpt'ion of oxides of nitrogen. Francis (84) suggested cooling the absorption tubes to eliminate errors caused by temperature fluctuat'ion. Sato, Takahashi, and Ohkoshi (212) wrapped the sample in aluminum foil for rapid combustion. The oxidation of the foil produced a localized temperature of 1700 "C. Sels and Demon (221) described a n improved absorption train for rapid carbon and hydrogen determination by a gravimetric procedure. Abramyan, Kocharyan, and Megroyan (3) used the thermal decomposition product' of potassium permanganate as a combined combustion catalyst and universal adsorbent for the gravimetric det'erminatioii of carbon and hydrogen. Pietrogrande and Dalla Fini (202) employed AigM.n04 and C0304 catalysts in series to reduce analysis time. Marzadro, Farina, and Settimj (176) reduced nitrogen oxides to free nitrogen to eliminate the high hydrogen values obtained in certain compounds containing cyano groups. Pella (196) eliminated the need for absorbents for nitrogen oxides by a two-stage decomposition: static pyrolysis under nitrogen aiid dynamic oxidation in a stream of oxygen. The oxides were autoreduced to free nitrogen. Padowetz (193) studied the efficacy of various tube fillings for the absorption of halogens and sulfur. T h e total amount of these elements just

ANALYTICAL CHEMISTRY, VOL. 42, NO. 5, APRIL 1970

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quantitatively absorbed by the filling was determined. Bartels (15) passed combustion products over a layer of CeOz, which removed halogens, to prevent inactivation of combustion catalysts in dealing with compounds of high boiling point. Awad, Gawargious, and Hassan (10) passed the combustion vapors over a IO-cm layer of silver wool for highly chlorinated or brominated compounds. The sample was placed in a silica capsule which was then inserted in a silica combustion tube. For complex compounds containing tin halides, Bazalitskaya and Dzhamaletdinova (19) recommended ignition of the sample mixed with a MgO-CuO catalyst. For organofluorine compounds, Abramyan and Karapetyan (1) used as combustion reagent the decomposition products of silver permanganate; Helesic (117) proposed Cos04 as combustion catalyst in a method for these compounds in which the F-containing oxidation products were absorbed by a layer of magnesium oxide. Kasler (144) used magnesium oxide as part of the tube filling analyzing phosphorus-containing compounds. For mercury containing compounds, Abramyan and Kocharyan (2) utilized as catalyst the thermal decomposition products of potassium permanganate. Uhle (848) recommended CoaOa on pumice as combustion catalyst for organosilicon compounds. For polymeric compounds containing boron and silicon, Celon and Bresadola (46) employed a catalyst consisting of MnOZCr~03-1110~kept a t a temperature of 1060 "C. The gaseous products were reduced over copper a t 500 "C and determined by gas chromatography. Gawargious and Farag (92) and Saran, Khanna, Banerji, and Zaidi (211) described improved combustion techniquesfor steroids and triterpenes. For explosive compounds Campbell, Harn, Monk, and Petrie (40) recommended mixing the sample with copper or cobalt oxide while Wright (267) proposed dry combustion with certain precautions. Some other combustion techniques have been studied. Schwarz-Bergkampf (217) combusted samples in empty tubes and mathematically determined the optimum temperature. For compounds containing sulfur or nitrogen, this temperature was 1400 "C. Pecar (194) suggested that closed flask combustion could be adapted for the determination of carbon and hydrogen by using magnesium foil to wrap the sample. Saharovici and Pascal (110) used the closed flask technique for the determination of carbon. T h e 0.1N sodium hydroxide solution as absorbent was titrated with 0.1N H C I solution and errors within +0.3y0 were obtained. Goldstein (100) absorbed the liberated CO2 in barium chloride solution, collected the precipitated barium carbonate, dissolved the precipitate in stan106R

dard acid solution, and titrated the excess acid. Culmo and Fyans (61) described a technique for handling liquid samples which involved the use of a n aluminum pan in which the sample was hermetically sealed. Campbell (39) weighed hygroscopic samples in aluminum foil capsules which were then dried to constant weight. A number of improvements have been proposed in the final determination of carbon and hydrogen. Mishchenko and Rodicheva (181) trapped the evolved C02 and H 2 0 in tubes containing silica gel and Molecular Sieve SA, respect'ively. The tubes were heated and the gases determined with the use of a katharometer. Kainz and Wachberger (138) determined the COn after combustion by means of a thermal conductivity detector connected to a digital computer. The H 2 0 which was previously retained by a layer of CaC19-silica was then released by heating the layer and led to the detector. Kainz, Zidek, and Chromy (142) determined the Cos and H 2 0 conductimetrically. Campiglio (41) titrated the C 0 2 produced after combustion by a nonaqueous technique. The C02 was absorbed in dimethylformamide and titrated automatically using 0.02N tet,rabutylammonium hydroxide. Schoniger (215) was able to chemically increase the amount of COZ obtained aft'er combustion. The COZ was reduced to CO over platinized carbon a t 900 "C and then oxidized by passage over CuO a t 500 "C to give t'wice the original amount. This process could be repeated sixteen times until finally the COZ was collected in a cold trap and t'itrated. For the determination of hydrogen only, hllinko and Hermann (183) mixed the sample with sulfur before combustion in a stream of oxygen. The SO2 produced was oxidized to SOo which reacted with the HzO to yield sulfuric acid, which was determined alkalinietrically. Ishii, Hirose, liori, and Kat0 (129) determined hydrogen in organic liquids by scattering of thermal neutrons. Ishii, hfori, and Hirose, (130) improved the method with reference to collimation of the neutron beam and use of a graphite reflector. Continued interest has been show1 in t>hedeterminat,ion of carbon and hydrogen in radioactive samples. Tykva (247) studied the errors in the simultaneous determinations of carbon-14 and tritium by means of an internal gas counter. The same author (246) investigated t h e detection efficiency of a flow-proportional counter for these same isotopes. Kainz and Rachberger (141) determined carbon-14, tritium, and sulfur-35 by converting them into their oxidation products by burning in oxygen, absorbing each individually, and counting by liquid scintillation. Scott


and Kennally (818) sealed the sample in a tube filled with oxygen. After combustion and cooling in liquid nitrogen, the carbon-14 and tritium were determined by liquid scintillation assay. Rudran and Kamath (209) employed wet oxidation of the sample to liberate C02 which after purification was absorbed and counted by liquid scintillation. Kainz and Wachberger (140) recommended a n instrumental compensation technique for the quenching effect of other elements in the determination of carbon-14 and sulfur-35. Eckstein and dttalla (71) used nuclear magnetic resonance analysis for carbon-13. Hamada and Kawano (115) suggested improvements in a dry combustion method for carbon-14. Since nitrogen dioxide, SOs, and halogens interfere in the determination of tritium using liquid scintillation counting, Kainz and Wachberger (137) eliminated interfering products by precipitation with hydrazine hydrate. Yamazaki, Ishihama, and Kasida (259) applied the closed flask Combustion method to the determination of tritium. The activity of the water solution was measured by liquid scintillation counting. For the simultaneous determination of deuterium and tritium, Garnett and Sollich-Baumgartner (90) employed combustion followed by reduction and determination of deuterium by mass spectrometry and tritium by a vibrating reed-electrometer technique. Starcuk and Cupak (229) determined tritium by combustion and conversion of 3H20 to 3H by reaction with CO and CaO. The mixture of 3H and CO was transferred to a counting device for measuring the radioactivity. Rauch and Tykva (206) after combustion, converted the H20 produced to hydrogen by reaction with CaH2. The activity of the gas was determined in a hydrogen-filled gas counter. Kachur and Shutko (135) employed a mass spectrometric technique for deuterium. Eisenberg (75) also used mass spectrometry for the determination of deuterium. The sample was oxidized under vacuum using HgC12 to produce 2HC1 which was then converted to deuterium by reduction over zinc. NITROGEN

Emphasis continued on rapid and automated methods both for dry combustion and wet ashing techniques. Olson and Knafla (191) described methods for the rapid determination of nitrogen in fluoro-compounds using a modified commercial analyzer. Merz (17 7 ) completed an analysis in about 2.5 minutes. The sample, covered with cupric oxide powder, mas burned in oxygen and the gaseous products were swept, into a n aut,omatic nitrometer where the volume of nitrogen mas recorded on a digital counter or printed

out. Bostoganashvili and Turabelidze (27) modified the Dumas method by combusting the sample mixed with cupric oxide in a silica tube containing the same oxidant a t 700-750 "C, thereby reducing the time for a determination by a factor of about seven. Borda and Hayward (26) obtained good results for "reversed capsule" technique. Ehrenberger (73) burnt the sample in electrolytic oxygen a t 950 "C. The combustion gases were passed over CuO a t 900 "C and copper a t 500 "C and the nitrogen was measured volumetrically. For the analysis of nitrated oils, Butkiewicz (3'7) mixed t'he sample with Cos04 and used combustion a t 500 "C in a n atmosphere of CO,. Schulz (216) compared the nitrogen values obtained by using the Technicon Kjeldahl automatic analyzer with the standard Kjeldahl procedure for milk products and found the variations to be statist'ically negligible. Strukova and Fedorova (230) determined nitrogen by the Kjeldahl method without, distillation of ammonia. The digestion mixture was treated with sodium tetraphenylborate and the precipitate dried and weighed. T h e precision was +0.370 but potassium, mercury, and copper interfered. Lebedeva and Novozhilova (159) described improvements in the Kjeldahl-Nessler micro method. Friend (87) measured the liberated ammonia in a Kjeldahl reaction by using a Conway micro-diffusion cell. Diedering (66) investigated the Kjeldahl procedure in which digestion mit,h acetanilide as cont,rol in the presence of sucrose was performed. Recoveries were 957, and the elimination of the sucrose was proposed. For ring nitrogen in heterocyclic compounds without' N-N linkages, hIorita (184) digested the sample in coned &So4 and 5 N C l - 0 3 . Some nitric: acid \vas produced which mas trapped in alkaline solution and the entire mixture was reduced with Devarda alloy, followed by Kjelclahl distillation. Chwaliliski and Brozsfek (55) found that the standard Kjeldahl method yielded low results in benzohydroxamic acid. Preliminary reduction with zincHCll gave quantitative rmults. Ilunke (70) compared the Kjeldahl and Dumas methods for nitrogen in 1)olyacryloaitriles. The standard deviations were k0.227, and + O . l O ~ o for the Dunias and Kjeldahl techniques, respectively. Norris, Carson, Shearer, and Jopkiewicz (185) made a similar study comparing the automated Dumas arid Kjeldahl methods in agricultural materials. The Kjeldahl method was more precise, but the Dumas method using a commercial analyzer required less space and fewer reagents. Gehrke, Kaiser, and Ussary (93) employed a spectrophotometric method for nitrogen in fertilizers. T h e nitrogen was converted into ammonia, and the solution

was treated in a n Autoilnalyzer with sodium phenoxide and NaClO to produce a blue color. Glebko, Clkina, and Vas'kovskii (98) also determined the nitrogen spect,rophotometrically. After sealed tube digestion of the sample, the color was produced by the thymol-hypobromite react'ion. OXYGEN

Xot too many papers concerned with the microdetermination of oxygen have been published since the last review Those that have, are basically improvements in the direct, method. Belcher, Ingram, and llIajer (21) studied the volatile products of the pyrolysis of many organic compounds by the Cnterzaucher method by the technique of mass spectrometry. Their findings were discussed with reference to the analytical implications. Barton and Xash (16) modified Steyermark's direct, gravimetric method so that a determination could be completed in thirty minutes. T h e method was not applicable to compounds containing phosphorus and fluorine. Pella (195) compared helium to argon and nitrogen as a carrier gas. The use of helium gave low results. Gel'man and Grigor'yan (95, 96) used reduced nickel as a component for filling the reaction tube to absorb sulfur-containing products of the pyrolysis. Kuck, Andreatch, and X o h n s (153) after pyrolysis of the sample, determined the CO in the combustion gas by using a nondispersive infrared gas analyzer. Culmo (59) converted a Perkiii-Elmer C H N analyzer to a n oxygen analyzer by changes only in the combustion train. The sample was pyrolyzed in helium a t 950 "C; platinized carbon was used to convert oxygen to CO. T h e resulting gases were passed over copper a t 900 "C to remove sulfur, and then Ascarite, and finally through copper oxide at 610 " C ; and the CO, formed was recorded in a thermal conductivity bridge. Ishii, Mori, and Hirose (231) employed activation analysis with 14-MeV neutrons by using gold as internal standard for the nondestructive determination of oxygen. The activity ratio of to 197A1uwas measured by gammaray scintillation spectrometry. This ratio was proportional to the oxygen content. 1Ilinko and Gacs (182) used a radiometric method for both oxygen and hydrogen. The hydrogen was converted to water by oxidation and the oxygen by hydrogenation. The water was then converted to carbon monoxide in the presence of 14C and after oxidation, the activity of the collected gases \vas measured. HALOGENS

Modifications and improvements to the closed-flask technique for halogencontaining compounds continue t,o draw

more interest than conventional techniques although several papers dealing with tube combustions have appeared. Hozumi and Tamura (123) developed a n automatic recording microanalyzer based upon the principle of optical integration of vapor phase iodine. After combustion of the sample and coilversion of the halogen to iodine, the maximum deflection of a recorder pen was simply interpret,ed to the quantity of halogen in the sample. Raspanti (205) combusted the sample in oxygen with the use of a platinum catalyst. The halogens were absorbed in a NahsOs-HC104 solution and titrated mercurimetrically using diphenylcarbazone as indicator. For iodine Campiglio (42) vaporized the sample a t 900 "C in nitrogen and combusted the gases in oxygen at' 600 "C. The combustion products were absorbed in alkaline solution and the iodine was determined titrimetrically. Ehrenberger, Gorbach, and Hornmel (74) employed an oxy-hydrogen combustion allparatus. The gaseous products were cooled in a spiral condenser, mixed with a n absorption solution, and then entered a graduated flask where aliquots were taken for analysis. Kuus and Lipp (155) studied t h e closed flask method of combustion. They recommended that combustion be carried out on a platinum support in the preseuce of a threefold amount of sucrose. Lebedev, Korobkina, and Vereshchinskii (160) proposed the addition of E D T h to the sample for complete combustion of saniples containing high contents of chlorine. Awad, Gawargious, Hassan, and X i l a d (1I ) described improved procedures for closed-flask combustions. For aromatic compounds, the absorption medium must contain alkaline H202or acidified NaKO2 solution. Aliphatic compounds must be mixed with glucose or benzoic acid, and liquids were sealed in a Sellotape bag before combustion. Chudakova and Simongauz (52) recommended the use of potassium nitrate as additional oxidant and sodium sulfite in alkaline solution as reducing absorbent. Celon and Bresadola (47) used sodium borohydride in the absortiing solution. To improve the sensit,ivity of the potentiometric titration of the halides, Havacek and Swam (116) replaced the aqueous absorbing solution with a 95% methanolic solution and employed the same solvent for t,he titrant (0.01S XgNO3). Habashy, Gawargious, and Faltaoos (110) determined the liberated halides by a polarographic tehnique. Prokopov (204) decomposed chlorine-containing samples in a closed flask and then caused iodine to be liberated which was titrated with sodium thiosulfate solution. For iodine-containing compounds, Pitre and Graiidi (200) absorbed the products of combustion directly in 0.015 HgC104. After the addition of 0.01.Y K I , the solu-


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tion was back titrated with 0.005N HgC104. Fukamauchi and Ideno (88) precipitated the liberated iodine as CUI, dissolved the collected precipitate in acid solution, and determined C u 2 +spectrophotometrically using ethylenediamine, by the standard-addition method. Liberation of the halogens by methods other than combustion have drawn some interest. Liebmann, Hacker, and Hennings (163) treated the sample with sodium-biphenyl reagent for chlorinated pesticides and titrated the chloride ion potentiometrically. Czech (62) used the same basic reagent and employed automatic coulometric titration. Ionescu, Vaganescu, and Bojthe (128) refluxed halogenated nitrobenzenes with pyridine and titrated the mixture with 0.01N Hg(NO& and diphenylcarbazone as indicator. Voegeli and Christen (250) employed piperidine in propane-1, 2-diol and titrated the halide potentiometrically with silver nitrate. Various modifications and improvements have been proposed for the determination of fluorine. Bussmanii and Hanni (36) reviewed the methods available for fluorine in drugs and recommended the following technique: the sample was ashed in the presence of calcium hydroxide and the residue distilled. Fluoride in the distillate was determined colorimetrically with SPADXS [3-(4-sulfophenylazo)chromotropic acid]. 1Ialysz (2 7.5) employed closed flask combustion and titrated the fluoride with thorium nitrate or EDTA solution. Other authors have iniproved the closed flask method. Cheng (48) mixed the sample with potassium chlorate before combustion and titrated the absorbing solution with 0.01N thorium nitrate solution in the presence of arsenazo I as indicator. Maryakina (271) added excess standard thorium nitrate solution to the fluoride solution and titrated the excess reagent conductimetrically with 0.05N N a F . Oliver (190) used water as absorbent and titrated the solution with 0.02A; Th(N03)1, using Solochrome cyanine R and methylene blue as indicator. The titrant was standardized empirically by burning standard fluorine compoundc. The interference of phoq h orus was eliminated by precipitation with qilver. Larina and Gel'nian (158) employed a difference-spectrophotoinetric method for fluoride after combustion based on the decrease in the extinction of the thorium-arsenazo I complex due to the presence of fluoride ion. Light and Mannion (164) titrated the fluoride ion potentiometrically using a fluoride ion electrode. It has been reported (147) that the optimum conditions for the use of these electrodes may be complicated by the use of polyvalent titrants which lead to the formation of more than one complex with fluoride ion. Selig (220) combusted the sample in a bomb with 41

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oxygen and determined fluorine gravimetrically as lithium fluoride. Wheeler and Fauth (255) decomposed the sample with sodium-biphenyl reagent and titrated the fluoride in the aqueous extract with thorium nitrate solution. England, Hornqby, Jones, and Terrey (77) used a nondestructive technique based on irradiation of the sample with 14-MeV neutrons. Good results were obtained but some metal chelates interfered. SULFUR, SELENIUN, PHOSPHORUS, A N D ARSENIC

Various methods have been described for the determination of sulfur in organic compounds which present some difficulties because of the presence of other elements. Budesiiisky and Vrzalova (33) combusted the sample in oxygen and absorbed the products in hydrogen peroxide. The sulfur in the form of sulfate ion was titrated with barium perchlorat,e solution using dibromosulfonazo I11 or dimethylsulfonazo I11 as indicator. Basargin and Xovikova (17) employed closed flask combustion for compounds containing phorphorus and arsenic. Hydrogen peroxide was used as absorbent and a barium salt as titrant with nitchromazo as indicator. Mikhailov and Taraseiiko (179) used the same titrant and indicator for organophosphorus cornpounds but fused the sample in a bomb with sodium peroxide. Before titration, the sodium ion was removed by passage through an ion-exchange resin. Balodis, Comerford, and Childs ( I S ) burned the sample containing phosphorus in a closed flask with hydrogen peroxide as absorbing solution. The phosphate ion was masked with ferric ion, the excess being titrated with E D T A (sulfosalicyclic acid as indicator) and the sulfur determined by titration with 0 . 0 2 4 barium chloride using thoron I-methylene blue as indicator. For orgaiiotin compounds, Chromy and Srp (50) titrated a solution of the sample with 0.05N o-hydrosymercuribenzoic acid in the presence of thiofluorescein-sodium sulfite as indicator. Wroiiski and Bald (258) decomposed the sample in a glass tube and converted the sulfur to hydrogen sulfide by hydrogenation. The gas was absorbed in alkaline solution and t,itrated continuously using 0.01.V sodium o-hydroxymercuribenxoate and dithizone as indicator. Frazer and Stump (85) hydrogenated the sample in a silica bomb and the hydrogen sulfide produced was converted to hydrogen over uranium metal at, 800 "C. The hydrogen was measured manometrically. For compounds containing halogen, a mixture of hydrogen and ammonia was used for the initial reaction to convert any hydrogen halide into the lion-interfering amnionium salt. A standard method iiivolving bomb combustion with oxygen and


gravimetric determination of sulfur as barium sulfate has been published (32). For selenium in organic compounds, Srp (227) ignited t h e sample in a closed flask, and converted the selenium into the Se(V1) oxidation state. For t h e filial determination, reduction using hydrazine sulfate and iodimetric titrat,ioii were employed. Kuus and Lipp (156) eniployed a permanganimetric method for the same element' after combustion of the sample. For phosphorus, Scroggins (219) described a closed flask procedure applicable to problem compounds. Combustion took place in a mixture of oxygen and nitrogen oxides and t h e flask and its contents \vere heated before opening for complete conversion of phosphorus to orthophosphate which was determined spectrophoton3etrically as t'he molybdenum blue complex. Hunter (126) also decomposed the sample by a closed flask technique using oxygen. Absorption took place in ammonia solut;on and the phosphorus was determined by titration with O.OIAr lead nitrate using dithizoiie as indicator. Halogens and sulfur interfered. Lindner and Edniundssoii (165) heated t h e sample with a mixture of sulfuric and nitric acids and a catalyst containing sodium molybdenate and perchloric acid. T h e phosphorus was determined spectrophotometrically as t h e molybdovanadophosphate complex. Griepink and Slaniiia (106) oxidized the sample with nitric and perchloric acids in a Kjeldahl flask. After adjustment of the p H , the solution was titrated electromet'rically using lanthanum nitrate as titrant. Diuguid and Johnson (68) also employed a Kjeldahl wet digestion method using nitric acid-perchloric acid mixture for a wide variety of organophosphorus compounds which were difficult to oxidize, with good results. Terent'eva and Smirnova (239) fused the sample wit'h sodium fluoride and potassium pyrosulfate for difficultly decomposable compounds. For arsenic, Perez-Bustamante and Burriel-Xarti (198) decomposed the samples in chloric acid and then reduced the .Is(V) to As (111) with iodide. Finally the .Is(III) was titrat,ed with iodine solution. Griepink and Krijgsinan (104) employed closed flask combustion using alkaline peroxide solution as absorbent. The arsenic was then titrated with 0.01,V lead nitrate until t h e pH remained constant. Terent'ev, Volodina, and Fursova (237) demonstrated that the oxides of nitrogen produced during closed flask combustions from impurities in the oxygen, interfered in t'he determination of arsenic and must be removed. ORGANOMETALLICS

Jenik (133) reviewed methods for t h e determination of important element's in

organometallic sandwich-type compounds. Included were colorimetric or chelatometric techniques for iron, aluminum, mercury, bismuth, titanium, and cobalt. Goldstein (99) described methods for t h e determination of t h e metallic portion of various naphthenates. T h e sample \\-as hydrolyzed with 312' nitric acid, t h e iiaphthenic acid removed by filtration, and t h e metals were determined by chelatometric titration using E D T A solution. For boron, Fedotova and Voronkov (82) heated t h e samples (complexes of heterocyclic nitrogen-compounds with boron trifluoride) with barium or calcium chloride and distilled off t h e liberated triniethyl borate and HC1. T h e boron was titrated with 0.05N NaOH in t h e presence of mannitol. Kelly (146) determined t h e boron content of amine-borane adducts by hydrolysis with dilute mineral acid followed by alkalimetric titration in the presence of mannitol. Shanina, Gel'man, and Mikhailovaskaya ($82) decomposed boron-containing samples b y bomb fusion with K O H a t 800850 O C . T h e boron in the extract of t h e nielt was determined spectrophotometrically a t 415 nni with azomethine H. Debal and Levy (64) compared the open-tube and closed flask combustion methods for boron and concluded that t h e latter, followed b y potentionietric titration of the mannitol-borate complex gave the best results. Yeh (260)developed a general method for t h e determination of mercury in all types of organomercury compounds. T h e sample was digested Ivith a mixture of potassium permanganate and concentrated nitric and sulfuric acids. B y means of a second-derivative spectrophotonietric titrator coupled to a n automatic buret, the Hg(I1) was determined by the Volhard Method. Shibazaki and Koibuchi (223) decomposed t,he mercury-contaiiiiiiK sample with concd H1S04-fuming H S O I and determined t h e mercury spectrophotometrically a t 460 a m by decolorization of the Fe(II1)S C S complex. Terent'eva and Uernatskaya (22%) recommended a graphite electrode impregnated with paraffin wax for the aniperometric tit ration of zirconium with EDT.1 solution. Strukova and Kirillova (232) determined aluniii i u ~ nin organometallic compounds containing silicon or phosphorus by bomb fusion with sodium peroxide and then adding E D T L 4 solution to t h e acidified extract and back titration of the excess reagent' with cupric sulfate solution in the presence of catechol violet. For the same element, Terent'er, Bondarevskaya, Gradskova, and Kropotova (236) employed bomb fusion with sodium peroxide and deterniined t h e aluminum spectrophotometrically with aluminon. If t h e sample also contained silicon, it was determined spectrophotometrically in a separate aliquot by means of reac-

tion with molybdenum blue. Burroughs, Kator, and Attia (34) converted silicon-containing samples to a readily hydrolyzed fluorinated species b y combustion in t h e presence of a fluorocarbon. T h e silicon was determined spectrophotometrically after reaction with ammonium molybdate. For thallium, Terent'eva, Vinogradova, and -4kimov (240) decomposed t h e organic sample with concentrated sulfuric acid containing Tl(1) hydrogen peroxide. After reduction with iron, t h e Tl(1) was determined by a polarographic technique. Schlunz and Koster-Pflugmacher (214 ) employed X-ray fluorescence for t h e determination of germanium. Arsenic was added as internal standard. Kalinovskaya and Sil'vestrova (143) determined chromium in organic complexes by a photometric technique involving reaction with diphenylcarbazide. T h e sample was deconiposed with a mixture of concd HSOoKC103 and then treated with ammonium persulfate. A standard method ( S I ) has been published for lead in petroleum compounds, involving extraction by refluxing with concd HC1, and precipitation of t h e lead as the chromate. Strukova and Kotova (233) determined phosphorus and iron in organometallic compounds by fusing t h e sample in a bomb with sodium peroxide. I n one aliquot of t h e solution of t h e melt, t h e P043+ was titrated with standard lanthanum nitrate solution, t h e iron being masked with sulfosalicylic acid. I n a separate aliquot, t h e iron was determined photometrically with sulfosalicylic acid. For copper, Reznitskaya and Burtseva (207) digested t h e sample with concd HzS04 and determined the C u 2 + either complexometrically with EDT.1 solution or iodimetrically. Stapfer and Dworkin (228) determined antimony and sulfur in antimony trimereaptides by a titrimetric method based on iodine oxidation. Geyer and Seidlitz (97) described a polarographic method for tin in dialkyltiii compounds. Chromy and Vrestal (51) used a complexometric method for tin in organotin compounds. T h e sample was digested with a mivture of concd sulfuric and nitric acids, excess 0.05J1 E D T A solution added, and back titrated with 0.0551 C u 2 +solution in the presence of a coinplexometric indicator, e.g.,

l-(2-thiazolylazo)-2-naphthol.

Strukova, Kashiricheva, and Lapshova (231) decomposed organopalladiuni complexes by bomb fusion with sodium peroxide. T h e P d 2 +was reduced to the free metal with sodium formate and determined gravimetrically. SIMULTANEOUS DETERMINATION OF SEVERAL ELEMENTS

-1number of papers have been published dealing with t h e simultaneous determination of carbon, hydrogen, and

nitrogen, and that of carbon, hydrogen, and t h e halogens. Separations of t h e elements were often based on chromatographic techniques although other methods such as t h e use of external absorbents have been described. For t h e simultaneous determination of carbon, hydrogen, and nitrogen, Foissac (83) examined critically t h e factors affecting the operation and accuracy of a n automatic analyzer. Chumachenko and Pakhomova (53) decomposed the sample in a sealed vessel attached to a chromatograph. Oxidation t'ook place over nickel oxide a t 900-950 "C, t h e water produced was converted to acetylene b y absorption on calcium carbide, and the combined reaction products were separated on a column of activat'ed charcoal and measured by a thermal conductivity detector. Kainz and Wachberger (136) also employed thermal conductivity measurement, modifying a previously published method. T h e sample was combusted in oxygen, the excess oxygen was retained 011 copper which also reduced oxides of nitrogen. Water was absorbed on ChC12silica sand and COz on Molecular Sieve 5-1. The nitrogen was detected first, the peak-area signal being aut'omatically integrated with digital read-out. T h e carbon dioxide and water were then desorbed in turn and similarly detected. Chumachenko and Pakhomova (54) studied t h e efficacy of various oxidants for organic substances in inert gas st,reanis applicable to the simultaneous determinat,ion of carbon, hydrogen, and nitrogen and showed that nickel oxide was superior. Frazer and S t u m p (86) described the use of a digital computer in a manometric procedure for these elements. Peniiington and 3Ieloan (197) analyzed the combustion products of the sample (CO1, ;V, and SO2) on a copper column packed wit'h silicone oil on Chromosorb P. Gel'man (94) described a combustion technique for compounds containing carbon, hydrogen, nitrogen, and other elenients in which some of t h e products of combustion were collected on absorbents situated within t h e combustion tube. Water, oxides of nitrogen, and carbon dioxide were absorbed on anhydrous potassium chlorate, K2Cr207H 2 S 0 4 on silica gel, and hscarite, respectively. For halogens and sulfur, the hot gases were cooled and collected on silver a t 425 or 575 and 750 "C, respectively. Mercury was collected on gold or silver foil at 0'. For the simultaneous det'ermiriatioii of carbon, hydrogen, and halogens, Xmbramyan, Kocharyan, and Megroyan (5) absorbed halogens and hydrogen halides resulting from combustion of the sample on the thermal decomposition product of potassium permanganat,e. Chlorine and bromine were (determined by titration with mercuric nitrate solution using diphenylcarbazone


109 R

as indicator and iodine b y titration with silver nitrate solution, eosine as indicator. Carbon and hydrogen were determined gravimetrically in t h e conventional manner. Abramyan and Megroyan (6) modified t h e above method in t h a t a simpler apparatus and technique were used. T h e same technqiue ( 7 ) was used for samples containing sulfur in addition to carbon, hydrogen, and halogens. The sulfur was absorbed with the halogens onto the thermal decomposition product of potassium permanganate. The sulfur was titrated with barium nitrate solution with thoron I as indicator. For compounds containing mercury instead of sulfur, these authors ( 8 ) adsorbed this element on fine-grain metallic bismuth and determined it gravimetrically. T h e other elements were determined as previously described. Gawargious and Farag (91) combusted the sample with oxygen in a n empty or packed tube. T h e halogen was absorbed on a silver gauze roll a t 550 "C connected externally between the combustion and water absorption tubes. Hadzija (113) proposed silica gel as a n external absorbent for chlorine in t h e simultaneous determination of carbon, hydrogen, and chlorine and t h e same absorbent (114) for halogens and sulfur. H e also found that manganese dioxide (112) was a suitable absorbent for chlorine or bromine. Fedoseev and Chernysheva (81) determined carbon and halogens in a single sample by pyrolysis, followed by ignition in a stream of oxygen. Halogens were absorbed on moist K I and C02 on Ascarite. For carbon and iodine, Campiglio (49) decomposed the sample by combustion in a stream of oxygen and passed the combustion gases through BaCrO4 a t 600 "C. Iodine was condensed in a dry ice t r a p and determined titrimetrically by t h e method of Leipert. Carbon dioxide was absorbed in dimethylformamideethanolamine and titrated automatically with tetrabutylammonium hydroxide solution. For the simultaneous determination of fluorine with other elements, Novozhilova and Gel'man (187) recommended the use of a silica tube for the pyrohydrolysis of the magnesium fluoride formed during a determination of carbon, hydrogen, and fluorine based on a previously published method. Abramyan, Megroyan, Sarkisyan, and Galstyan ( 9 ) modified their previous method in that crushed silica was used as absorbent. T h e fluorine was dissolved from t h e absorbent with HXO3-aq H202 and titrated with thorium nitrate solution. Gagnon and Olson (89) determined carbon and fluorine by a procedure involving combustion with an oxyhydrogen flame applicable to t h e most stable fluorocarbons. Horacek and Pechanec (122) combusted organic samples containing sulfur and fluorine in oxygen and 110R

absorbed the products in water. Bromine was added to oxidize any so32-to sod2-. The sulfate was titrated with 0.01M Ba(C10& using thoron as indicator and t h e fluoride in the same solution with 0.005M La(NO&, haematoxylin as indicator. Gutbier and Diedrich (109) used closed flask combustion for the simultaneous determination of fluorine and chlorine (or bromine and iodine) in organic compounds. T h e Fwere titrated with 0.01N thorium nitrate solution and t h e C1- (or B r - and I-) with 0.01N Agh'O3 solution potentiometrically. T h e simultaneous determination of a variety of other elements has been reported. Beuerman and Meloan (23) combusted the sample in oxygen to produce CO,, SO2, chlorine, bromine, and iodine. T h e gases were collected in a liquid nitrogen or dry ice t'rap and then separated by gas chromatography, using two separate columns. Detection was by matched thermistors. For carbon, hydrogen, and sulfur, Abramyan, Kocharyan, and Megroyan (4) burned t h e sample in oxygen and absorbed the oxides of sulfur on the t'hermal decomposition product of potassium permanganate. Carbon and hydrogen were determined gravimetrically in the usual way and sulfur titrimetrically with barium nitrate solution using thoron-methy1 blue as indicator. Hadzija (111) for the same elements, combusted the sample in a stream of oxygen using t h e thermal decomposition product of silver permanganate as a source of oxygen and as absorbent for the oxides of sulfur. T h e carbon and hydrogen were determined conventionally while the sulfur was determined gravimetrically as benzidine sulfat'e. Utsumi, Machida, and I t o (249) employed closed flask combustion for the simultaneous determination of chlorine and sulfur in organic compounds. T h e chlorine and sulfur were determined colorimetrically in the absorbing solution by the addition of Hg(SCN)2 and Fe(N03)3 for C1- and BaCrOd suspension for SOa2-. Klimova and Vitalina (150) decomposed the sample by bomb fusion. T h e melt was extracted with peroxide solution, and sulfur and boron were determined titrimetrically with barium nitrat'e solution and sodium hydroxide solution in the presence of mannitol, respectively. Celon (46) employed closed flask conibustion for the simultaneous determination of chlorine, bromine, and iodine. An aliquot of t,he sodium borohydride absorbing solution was titrated for total halogen with 0.0LV Hg(C104)2and successive aliquots were oxidized to bromate and iodat'e for t h e determination of t h e respective halogens. For the simultaneous determination of chlorine (or bromine) and sulfur, Pietrogrande and Dalla Fini (201) combusted the sample by the closed flask technique and titrated the C1- with


0.01N Hg(C104)~in the presence of diphenylcarbazone. T h e solution was then further titrated with 0.02LV Ba(C104)~ using thoron I-methylene blue as indicator. SUBMILLIGRAM SAMPLES

Most of the papers on analysis using submilligram samples described refinements and modifications to existing procedures in order to obtain the desired accuracy. Merz and Pfab (178) report,ed their experience in a n industrial research laboratory in which for the past five years many of the elements in organic compounds have been determined on less than one milligram of sample. The methods used were suitable for routine purposes and exhibited t h e same degree of precision as ordinary microanalyses. Griepink and Krijgsman (109) modified a method for t h e combustion of samples in a closed flask. The sample and ignition strip were placed on a layer of collodion in a black porcelain dish and covered with a drop of collodion solution. The resulting sample packet was stripped from the dish and burnt as usual. Binkowski and Levy (24) incorporated cerium dioxide and silver-impregnated pumice in t,he combustion tube for the analysis of carbon, hydrogen, and nitrogen in conipounds containing phosphorus and fluorine. They also recommended t h a t the temperature of combustion be raised to 1050-1100 "C. Hozumi and Umemot,o (124, 195) improved a method for the decimilligram determination of nit,rogen by sealed tube Combustion. T h e volume of water delivered from a piston buret to replace the volume of nitrogen was corrected by allowing for the difference between the meniscus of nitrogen over potassium hydroxide solution and over Ivater. Griepink and Terlouiv (108) digested nitrogen-containiiig samples in a sealed t,ube with coiicd &Sod. hfter passage through a n ion-exchange column, the ammonia was titrated potentiometrically with 2.9m.lP HC104. Metal ion? interfered with the determination. For the decimilligram deI, Kalisch and termination of the sample in a Marks (253) pyr . stream of helium and converted the oxygen to COz by passage over a nickel carbon catalyst and copper oxide. h f t e r removal of halogens, hydrogen halides, and H2S, and water, the residual gases consisting essent'ially of COz and nitrogen were detected by a katharometer in a bridge circuit. The COzwas absorbed and the final digital counter reading was proportional to the nitrogen content. Belcher. Dryhurst, and Macdonald (20) pyrolyzed the sample and converted the oxygen to carbon monoxide by passage through platinized graphite wool. The carbon monoxide was measured by thermal conductivity.

Walisch and Humme (151) combusted sulfur-containing samples in a n empty tube fitted with nozzles and eddy chambers. T h e resulting sulfate solution was t'itrated automatically with barium chloride solution using carboxy-arsenazo indicator a t 645 nm. Griepink, Slanina, and Schoonman (107) digested sulfur containing samples with C a C r z 0 7in anhydrous H3P04. After reducing with tin, the solution containing HzS was heated and t h e product absorbed in 0.0151 (or 21nJI) CdS04. T h e liberated sulfuric acid was t,itrated with 0.0141 N a O H (or 2mJ1 KaOH). Campiglio and Pel1 (44) determined sulfur by a conductometric procedure developed for microanalysis and, using the ultramicro balance, achieved equal accuracy for decimilligram samples. Kirsten, Danielson, and Ohreii ( 149) developed a special apparatus for t h e determination of chlorine. T h e sample was combusted in a vertical silica tube connected to a titration vessel containing sodium hydroxide as absorbent. T h e C1- was titrated by an automatic differential electrolytic potentiometric method using 0.005S XgxO3 as titrant. List and Tolg (166) heated bromine-containing samples in hydrogen a t 900 "C and absorbed the evolved H B r in acetic acid. T h e bromine was then titrated potentiometrically. For iodine, Griepink and Sandwijk (105) placed the sample between layers of polymethylmethacrylate and employed closed flask combustion. T h e iodide was titratcd with 0.002N -4g?;O3 by a polarization t'echnique. Walisch and Jaenicke (252) combusted halogen-coiitaiiiiiig: samples in a stream of oxygen and absorbed t h e products in nitric acid solution containing hydrazine sulfate as reducing agent. T h e absorption solution was fed into a vessel and titrated aniperometrically with silver ion. T h e total current consumed was shown by a digital counting device. For phosphorus, Christopher and Fenne11 (49) examined a number of methods for mineralization of the sample and concluded that the most suitable method involved open-tube digestion with HC104-H,S04. T h e Pod3- was determined spectrophotometrically a t 315 mi as molybdenum blue or molybdovanadophosphate. Kirsten (148) recommended a mixture of HN03-HC104H2S01 for digestion and determined t h e phosphorus spectrophotometrically as molybdenum blue a t 308.5 nm. TRACE ANALYSIS

T h e importance of this section is revealed by the numerous papers published concerned with the detection and estimation of trace amounts of the elements in organic materials. Egan (72) described a method for carbon in which the sample was ignited in oxygen and the resulting carbon dioxide was ab-

sorbed in barium hydroxide solution. T h e carbon dioxide normally present in air has caused interference in detecting microgram quantities of carbon and t h e technique involved t h e use of self-sealing rubber stoppers and hypodermic syringes and needles for the complete exclusion of air. Blazejczak and Van Der Weide (25) developed a semiautomatic apparatus which included a gas chromatograph, for t h e determination of organic carbon in rocks. Cropper, Heinekey, and Westwell (58) determined organic matter in aqueous plant streams by injecting the aqueous sample into a combustion tube containing CaO at 850-900 "C. T h e liberated C 0 2 was reduced t o methane with hydrogen over a nickel catalyst a t 300-350 "C. The methane was determined in a gas chromatograph using a flame ionization detector. Holm-Hansen, Coombs, Volcani, and Williams (121) digested lipids extracted from algae with K2S208-H3P04 in a sealed ampoule and determined the COZ content b y IR gas analysis. For trace nitrogen in organic materials, Wineburg (256) used a microcombustion technique. Oita (189) decomposed t h e sample b y catalytic hydrogenation and determined the nitrogen with a coulometric detector. Smith, Cooper, Rice, and Shaner (225) percolated petroleum distillates through a column containing H 2 S 0 4 on pumice and a mixture of ZnC12-FeC13. T h e contents of t h e column were digested in a Kjeldahl flask, the ammonia was liberated, collected in concd H3B03 solution, aiid determined spectrophotometrically a t 655 n m after conversion into iiidopheiiol blue. Jones (134) digested the sample with perchloric acid and measured the nitrogen spectrophotometrically a t 635 nm by t h e addition of phenol-sodium nit'roprusside-XaClO in buffered solution. Sloane-Stanley (224) used a similar method for t h e estimation of trace amounts of nitrogen in lipids. Gouverneur, Snoek, and Heeringa-Kommer (101) combust'ed the sample in a n oxyhydrogen flame and absorbed t h e nitrogen oxides in ?;aC102 on alumina. The absorbent, a a s treated with aq H?02, S a O H solution, and Devarda alloy and the ammonia was steam distilled and determined by acidimetric titration. Lewandowski, Madrowa, and Skirbiszewski (162) decomposed the sample by vvet oxidation and collected t h e liberated K H 3 in 0.002N HC1. -4liquots of this solution were passed through paper strips impregnated with a strongly basic anionexchanger, and the areas occupied by the excess of acid were revealed with methyl red and compared to those produced by standards. For sulfur-containing compounds, Majewska (173) compared wet oxidation to closed flask combustion and concluded that the latter procedure was more reliable. For trace amounts.

the S042- were reduced to S2- and determined spectrophotometrically as methylene blue. A standard method (30) has been published for trace amounts of sulfur in petroleum products. After combustion of the sample, t h e sulfur was det'ermined by a t'urbidimetric method. For sulfur in fats, Baltes (14 ) hydrogenated the sample (10-50 g) over Raney nickel and t h e liberated H2S was distilled into a n absorbing solution which mas titrated continuously with mercuric acetate solution in t h e presence of dithizone as indicator. blank determination was necessary. Turuta, Crisan, and Pal (645) also employed hydrogenation over Raney nickel catalyst and distilled the H2S into 0.01J1 cadmium acetate. T h e absorbent solution was titrated with 0.01M EDTA\ in t,he presence of Eriochrome black T and t h e result compared to a blank determination. Podorozhanskii, Zeidlits, and E r u (203) demonstrated t h a t a previously published method was not suitable for trace amounts of sulfur in tetralin. Jaworski and Chromniak (152) reduced sulfur in mixtures containing olefins, with Raney nickel catalyst and titrated the liberat'ed HzS with 0.01.V mercuric acetate (dit>hizone as indicator). Their apparatus was so designed t h a t sample vapors repeatedly came in contact with the catalyst. Farley and Winkler (80) converted trace amounts of sulfur into HzS by vaporization of the sample in a stream of hydrogen and pyrolysis a t 1200 "C over platinum. T h e products were absorbed in zinc acetate solution and t h e sulfur determined spectrophotometrically as methylene blue a t 667 nm. Xegina, Krasheninnikova, and hfikhailina, Ratnikova, and Dokuchaeva, (186) determined small amounts of sulfur and chlorine in polymeric materials by combustion of up to 25-g sample in a special apparatus. T h e final products were absorbed in dilute sodium carbonate solution and analyzed by known titrimetric or photometric methods. Belisle, Green, and Winter (22) described a flow-through closed flask combustion procedure permitting the analj,sis of larger samples necessitated by low concentrations of the element being determined. Bowen (28) decomposed a variety of samples by heating them with a mixture of K3O3-T\'a?lTo3. T h e technique was applicable t o trace analyses of sulfur, halogens, and most metals. I t was not suitable for the determination of mercury. For the determination of t'race amounts of halogens. Dirscherl (67) combusted the sample in oxygen in a tube containing W O ~ - V Z O ~T. h e combustion products were absorbed in hydrogen peroxide solution and titrated with 0.01N Hg(C104)? using diphenylcarbazone as indicator. Kainz and Wachberger (139) burnt the sample in a


111 R

jet and titrated t h e absorbed products potentiometrically with silver nitrate solution. Maltese, Clenientini, and Mori (174) pyrolyzed the sample a t 350 "C and then burnt the products in o,xygen at' 825 "C. T h e halogen (chlorine) was absorbed in aqueous Hz02Ka2COs and determined either spectrophotometrically or by potentiometric titration. For chlorine in vinyl chloride polymers, Leuteritz and Brunner (161) employed X-ray fluorescence using a tritium source. Results were reproducible to *0.2% chlorine. Bramlitt (29) used a gamma-gamma coincidence counting technique after neutron activation of the sample for chlorine in terphenyls. For trace amounts of fluorine, Miller and Keyworth (180) decomposed liquid hydrocarbon samples with sodium biphenyl and extracted with water. T h e aqueous extract was passed through a cation exchange resin and the fluoride was titrated conductimetrically with lanthanum acetate. Ioiiescu and Popescu (127) determined fluorine compounds in air photometrically a t 530 nm with Alizarin red-thoron reagent. The extract of the fluorine compounds was reacted in a special cell designed to prevent loss of HF, with concd AgC104HClO4 reagent. Dah1 (63) decomposed the sample in a n oxygen-filled bomb containing sodium tartrate solution and after extraction determined the F- spectrophotometrically with a composite Ta-malachite green reagent at 630 nm. Taves (234) studied the effect of silicone grease in the determination of trace amounts of fluorine based on a diffusion method. Ke, Regier, and Power (146) developed a method for as low as 2 ppni of fluoride in biological samples based on a nonfusion distillation technique followed by a n ion-selective membrane electrode measurement. Henry (118) ashed foodstuffs in the presence of magnesium acetate, and distilled the residue into sodium hydroxide solution. The absorbent was titrated with 0.5 mJ4 Th(X03)d in the presence of Alizarin red S.Bache and Lisk (12) used a microwave-powered helium plasma unit to fragment and excite compounds eluted from a gas chromatograph. The emission response was quantitative for bromine, chlorine, iodine, phosphorus, and sulfur. For trace amounts of phosphorus, Rison, Barber, and Wilkniss (208) used activation analysis with fast neutrons. Two procedures were given for the elimination of the interference of aluminum. Buyanova (38) determined trace amounts of phosphorus in methyltrichlorosilane by a colorimetric method. The sample was hydrolyzed with nitric acid; silicon was removed by evaporation with HF, and arsenic by reaction with K*SOd-HCl to form the volatile AhClr before the Pod3- were determined by the standard heteropoly-blue 112 R

method. Lambdin and Taylor (157) extracted trace amounts of copper from petroleum distillates with biscyclohexanone oxaldihydrazone. T h e copper complex was measured colorimetrically. For trace amounts of cadmium, Truffert, Favert, and Le Gall (242) digested the sample with sulfuric acid and added bromine to convert Fe(I1) to Fe(II1). The cadmium was extracted with dithizone solution, and determined colorimetrically with Cadion 2B [1-(4-nitro-lnaphthyl)-3-4(4-phenzlazophenyl) triazen]. Engler and Tolg (78) determined microgram amounts of selenium adsorbed on filter paper by burning the paper in a n oxygen filled silica flask. The products were absorbed in alkaline peroxide solution and the mixture finally distilled. The H2Se was then collected in sodium hydroxide solution and titrated potentiometrically with O.lmJ4 lead acetate (silver selenide electrodes). For the same element, Smoczkiewiczowa, Augustyniak, and Meissner (226) digested the sample with molybdic acid-H*S04-HC104 and determined the selenium colorimetrically with o-phenylenediamine. Ewan, Baumann and Pope (79) used a similar digestion mixture and precipitated the selenium with arsenic. The precipitate was dissolved and the selenium determined by measuring the fluorescence produced with naphthalene-2,a-diamine. Burton, Love, and Mercer (36) described a procedure for the determination of strontium-90 in biological materials; 8-hydroxyquinoline was used for the separation of ytt rium-90. LITERATURE CITED

(18) Basson, W. D., Stanton, D. A., Bohmer. R. G.. Analvst. 93. 166 (1968). (19) Bazaiitskaya, V.- S., ' Dzhamaletdinova, XI. K., Zavod. Lab., 33, 427 (1967). (20) Belcher, R., Dryhurst, G., Macdonald. A. 11. G., Anal. Lett., 1, 807 (1968): (21) Belcher, R., Ingram, G., Majer, J. R., Mikrochim. Acta, 1968, 418. (22) Belisle, J., Green, C. B., Winter, L. D., -4x.i~.CHEM.,40, 1006 (1968). (23) Beuerman, D. R., Meloan, C. E., Anal. Lett., !, 195 (1967). (24) Binkowskl. J.. Levv. R.. Bull. SOC. ' Chim. Fr., 1968, 4289." (25) Blazejczak, J., Van Der Weide, B. >I,, Bull. Cent. Rech. Pau, 2, 163 (1968). (26) Borda, P., Hayward, L. D., ANAL. CHEM.,39, 548 (1967). 127) Rostonanashvili. V. S.. Turabelidze. - D. G-., f r . Inst. Farmakohkhim., Akad. S a u k Gruz. SSR 1, 36 (1967). (28) Bowen, H. J. M.,A N ~ LCHEM., . 40, 969 (1968). 129) Bramlitt. E. T., ibid., 38, 1669 (1966). (30) British Standards Institution, B.S.

____

42.50.

IWR

(31) Ibid., B.S. 2878: 1968. (32) Ibid., B.S. 4454: 1969. (33) Budesinsky, B., F'rzalova, D., Chemist Analyst, 5 5 , 110 (1966). (34) Burroughs, J. E., Kator, W. G., Attia, A. I., ANAL. CHLM.,40, 657 (1968). (35) Burton, J. D., Love, R . ll.,Mercer, E. R., Analyst, 91,739 (1966). (36) Bussmann, G., Hanni, W., Pharm. Acta Helv., 42, 41 (1967). (37) Butkiewicz, K., Chem. Anal. (Warsaw), 12, 1329 (1967). (38) Buyanova, L. AI,, Itv. Sib. Otdel. Akad. iYauk SSSR, 1967, 176. (39) Campbell, A. D., Xzkrochim. Acta, 1968, 833. (40) Campbell, A. D., Harn, L. S., IIonk, R., Petrie, D. R., ibid., p 836. (41) Campiglio, A,, Farmaco, Ed. Sci., 22, 196 (1967). (42) Ibid., p 245. 143) Camoidio. A., Mikrochim. Acta, 1968, 166; ' (44) Campiglio, A,, Pell, E., ibid., 1969, ~

(1) Abramyan, A. A,, Karapetyan, A. G., Izv. Akad. dl'auk Arm. SSR, Khim. .Vauk, 19, 855 (1966). ( 2 ) Abramyan, A. A,, Kocharyan, A. .4., zbzd., 20, 515 (1967). (3) Abramyan, A. A,, Kocharyan, A. A., Megroyan, R . A,, ibzd., 19,849 (1966). (4) Ibzd., 20, 25 (1967). (,j) Ibzd., p 29. (6) ilbramyan, A. A,, Rlegroyan, R . A., ibzd., p 191. (7) Abramyan, A. A., Rlegroyan, R. A., Arm. Khim. Zh., 21, 111 (1968). (8) Ibid., p 115. (9) Abramyan, A. A., Negroyan, R . A., Sarkisyan, R. S., Galstyan, G. A., Izv. Akad. 1Yauk Arm. SSR, Khim ll'auk, 19, 859 (1966). (10) Awad, W. I., Gawargious, Y. A., Hassan, S. S. &I., Mtkrochim. Acta. 1967, 847. (11) Awad, W. I., Gawargious, Y. A., Hassan, S. S. AI., Milad, iV.E., Anal. Chim. Acta, 36, 339 (1966). (12) Bache. C. A.. Lisk. D. J.. ANAL. CHEM.,39, 786 (1967). (13) Balodis, R. B., Comerford, A,, Childs, C. E., Microchem. J., 12, 606 (1967). (14) Baltes, J., Fette Sei& Anstrichm., 69, a12 (1967). (15) Bartels, U., Chem. Tech., Berlin, 19,

696 (1967). (16) Barton, H. J., Sash, C. W., Microchem. J., 12, 568 (1967). (17) Basargin, N. N., Novikova, K. F., Zh. Anal. Khim., 21, 473 (1966).


467

(45) Celon, E., ibid., 1969, 592. (46) Celon, E., Bresadola, S., ANAL. CHEM.,40, 972 (1968). 147) Celon. E.. Bresadola. S..Mikrochim. Acta, 1969,441. (48) Cheng, F. W.,ibid., 1967, 110.5. (49) Christopher, A. J., Fennell, T. R . F. W.,Microchem. J . , 12, 593 (1967). (50) Chromy, V., Srp, L., Chem. Listy, 61, 1509 (1967). (*51) Chromv. V.. Vrestal. J.. ibid., 60, \~

'

~

1537 (1966).

( 5 2 ) Chudakova, I. K., Simongauz, A. >I., Zh. Anal. Khzm., 22, 409 (1967).

(53) Chumachenko, AI. X., Pakhomova, I. E.. Dokl. Akad. Sauk SSSR, 170, 12.5 (1966). (54) Chumachenko, AI. X., Pakhomova, I. E., Izv. Akad. Sauk SSSR, Ser. Khim., 1968, 235. (53) Chwalinski, S.,Brzostek, Chem. Anal. (Warsaw), 12, 723 (1967). (56) Coleman Instruments, Rlaywood, Ill., Bull. B-273A (1969). ( 5 7 ) Ibid., Bull. B-291B (1969). (58) Cropper, F. R., Heinekey, D. AI., Westwell, A., Analyst, 92, 436 (1967). (59) Culmo. R..Mikrochim. Acta, 1968, 811. (60) Ibid., 1969, 175. (61) Culmo, R., Fyans, R., ibid., 1968, 816. (62) Czech. F. P., J . Ass. 0.1% Anal. Chem., 51, 568 (1968). ,

I

(63) Dahl, W. E., AXAL. CHEM., 40, 416 (1968). (64) Debal, E., Levy, R., Bull. Soc. Chim. Fr., 1969, 1779. (65) Derge, K., Chemikerzeitung-Chem. Appar., 90,283 (1966). (66) Diedering, P., Mschr. Brau., 20, 268 11967). (67) Dirscherl, A., Mikrochim. Acta, 1968, 316. (68) Diuguid, L. I., Johnson, N. C., hi‘icrochem. J . , 13, 616 (1968). (69) Dugan, G., Aluise, V. A,, ANAL. CHEhf.,41, 495 (1969). (70) Dunke, hI., Faserforsch. Tcrt Tech., 18. 123 11967)

(73) Ehrenberger, F., Z . Anal. Chem., 228, 106 (1967). (74) Ehrenberger, F., Gorbach, S., Hommel, K., British Patent 1,098,407 (June 16, 1965). (75) Eisenberg, F., Jr., Anal. Biochem., 17, 93 (1966). (76) Ellison, RI., Analyst, 93, 262 (1968). (77) England, E. il. U.,Hornsby, J. B., Jones, W. T., Terrey, D. R., Anal. Chiin. Acta, 40, 365 (1968). (78) Engler, R.,Tolg, G., Z . Anal. Chem., 235, 151 (1968). (79) Ewan, It. C:, Baumann, C. A,, Pope, A. L., J . Agr. Food Chem., 16, 212 11968). (80) Farley, L. L., Winkler, R . A,, AXAL. CHEM., 40, 962 (1968). (81) Fedoseev, P. iV.>Chernysheva, T. E., Zw. Vvssh. L’cheb. Zaved.. Khim. Khzm. Tckhoi., 10, 1024 (1967).’ (82) Fedotova, L. A., Voronkov, &I. G., Zh. Anal. Khzm., 22, 1431 (1967). (83) Foissac, L., Chzm. Anal., 48, 354 ilYfifi\ .___

(84) Francis, H. J., Jlzcrochem. J . , 14, 432 (1969). (85) Frazer, J. IT., Stump, R . K., X z k r o chim. .lcta 1967. 651. (86) Zbid., 1968, ’1326. (87) Friend, A. B., Inform. Quim. Anal. Pura Apl. Ind., 21, 175 (1967). (88) Fukaniauchi, H., Ideno, R., J . Phawn. Soc. Japan, 87, 1025 (1967). (89) Gagnon, J. G., Olson, P. B., AXAL. c:HlI., Acta Pharm. Jugoslav. 16, 151 (1966).


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(195) Pella, E., Mikrochim. Acta, 1968,13. (196) Ibid., 1969, 490. (197) Pennington, S., hleloan, C. E., ANAL.CHEM.,39, 119 (1967). (198) Perez-Bustamante, J. A., Burrielhlarti, F., Inform. Quim. Anal. Pura Apl. Ind., 22, 25 (1968). (199) Perkin-Elmer Corp., Norwalk, Conn., Bull., Model 240 Elemental Analyzer, 1969. (200) Pitre, D., Grandi, M.,Xikrochim. Acta. 1967. 347. (201) Pietrogrande, A., Dalla Fini, G., ibid., p 1168. (202) Zbid., 1968, 228. (203) Podorozhanskii, 11. 1I., Zeidlits, E. M., Eru, I. I., Zavod. Lab., 33, 697 i1967). (204) Prokopov, T. S., Mikrochim. Acta, 1968, 675. (205) Raspanti, G., 2. Anal. Chem., 225, 24 (1967). (206) Rauch, P., Tykva, R., Chem. Listy, 61, 1669 (1967). (207) Reznitskaya, T. V.,Burtseva, E. I., Zh. Anal. Khim. 21, 1132 (1966). (208) Rison, 11. H., Barber, W. H., Wilkniss, P., ANAL. CHEM., 39, 1028 (1967). (209) Rudran. K.. Kamath. P. R.. Microchem. J . . 11: 481 119661. ’ (210) Saharoiici, R., Pascal, P., Rev. Chim. (Bucharest) 17, 560 (1966). (211) Saran, J., Khanna, P. N., Banerji, S., Zaidi, S. B. N.. Nzkrochim. Acta. 1968, 1124. (212) Sato, T., Takahashi, T., Ohkoshi, S., Japan Analyst, 16, 309 (1967). (213) Scheidl, F., Microchem. J . , 13, 155 (1968). (214) Schlunz, AI., Koster-Pflugmacher, A., 2. Anal. Chem., 232, 93 (1967). (215) Schoniger, W., Mzcrochem. J., 11, 469 (1966). 1216) Schultz. R. B. T.. Z . Lebensm.Cnters. Fokch., 134, 353 (1967). (217) Schwarz-Bergkampf, E., Mikrochim. Acta, 1967, 1001;

(218) Scott, B. F., Kennally, J. R., ANAL. CHEM.,38, 1404 (1966). (219) Scroggins, L. H., Microchem. J . , 13, 385 (1968). (220) Selig, W., Z . Anal. Chem., 234, 261 (1968). (221) Sels, F., Demon, P., Mikrochim. Acta, 1969, 530. 12221 Shanina. T. RI.. Gel’man. K. E.. Mikhailovskaya, V.‘ S., Zh. Anal: Khim., 22, 782 (1967). 1223) Shibazaki, T., Koibuchi, hI., J . Pharm. Soc. Japan, 88, 140 (1965). (224) Sloane-Stanley, G. H., Biochem. J., 104, 293 (1967). (225) Smith, A. J., Cooper, F. F. Jr., Rice, J. O., Shaner, W. C., Jr., Anal. Chim. Acta, 40, 341 (1968). (226) Smoczkiewiczowa, A., Augustyniak, J., hleissner, W., Chem. Anal. (Warsaw), 12, 629 (1967). 1227) Sro. L.. Chem. Prum.. 17. 390 (1967): 12281 Stanfer. C. H.. Dworkin. R. D.. A ~ A LCHI&., . 40, is91 (1968j. (229) Starcuk, Z., Cupak, LI., Chem. Listy, 60, 1543 (1966). (230) Strukova, hl. P., Fedorova, G. A., Zh. Anal. Khzm.. 21. 509 11966). (231) Strukova, Ai. P:, Kashiricheva, I. I., Lapshova, .4. A., ibid., 22, 1110 (1967). (232) Strukova, hl. P., Kirillova, T. V., ibid., 21, 1236 (1966). (233) Strukova, hl. P., Kotova, V. N., ibid., 22, 1239 (1967). (234) Taves, D. R., ANAL. CHEM.,40, 204 (1968). (235) Technicon Corp., Tarrytown, N. Y., Bull. CHNO Analyzer, 1969. (236) Terent’eva, A. P., Bondarevskaya, N. A,, Gradskova, N. A,, Kropotova, E. D., Zh. Anal. Khim., 22, 454 (1967). (237) Terent’eva, A. P., Volodina, AI. A., Fursova, E. G., i b i d . , p 640. (238) Terent,’eva, E. A., Bernatskaya, 31. V., ibid., 21, 870 (1966). ~

(239) Terent’eva, E. A., Smirnova, N. N., Zavod. Lab., 32, 924 (1966). (240) Terent’eva, E. A., Vinogradova, E. N., Akimov, N. P., ibid., 34, 414

__

(1968\. ~ - -

(241) Thomas, A. H., Philadelphia, Pa., Bull., hlodel 35 hlicro C-H Analyzer, 1969. (242) Truffert, L., Favert, M.,Le Gall, Y., Ann. Falsij. Expert. Chim., 60, 27.5 11967). (243) Trutnovsky, H., Mikrochzm. Acta, 1968, 97. (244) Trutnovsky, H., Z . Anal. Chem., 232, 116 (1967). (245) Turuta, A., Crisan, T., Pal, M., Reo. Chim., 18, 306 (1967). (246) Tykva, R., Collect. Czech. Chem. Commun., 32, 2001 (1967). (247) Tykva, R., Int. J . Appl. Radzat. Isotopes, 18, 45 (1967). (248) Uhle, L., 2. -4nal. Chem., 231, 194 (1967). (249) Utsumi. S.. hlachida. W.., Ito., S.., Japan Anaiyst,’l6, 674 (1967). (250) Voegeli, P., Christen, F., Z . Anal. Chem., 233, 175 (1968). (251) Walisch, W., Humme, G., Mzkrochtm. Acta, 1968, 748. (252) Walisch, R., Jaenicke, O., ibid., 1967, 1147. (253) Walisch, W., Xarks, W., ibid., p. 10.51

(2;4YWalisch, W., Schafer, K., ibid., 1968, 765. (255) Wheeler, P. P., Fauth, M. I., AKAL.CHEM.,38, 1970 (1966). (256) Wineburg, J. P., ibid., 40, 1744 (1968). (257) -%right, H., Explosirsto$e, 14, 274 (1966). (258) Wronski, hl., Bald, E., Chem. Anal. (Warsaw), 12, 863 (1967). (259) Yamazaki, 11.) Ishihama, H., Kasida, Y., Znt. J . A p p l . Radiat. Isotopes, 17, 134 (1966). (260) Yeh, C. S., Microchem. J . , 14, 279 (1969).

Chemical Microscopy G. Cocks,

George

T(W

Cornell University, lfhaca, N . Y.

iii this series covered the two-year period from January 1965 through December 1967. Some earlier articles and books omitted from previous reviews are included in this review. I t is the purpose of this review to report on articles and books of potential interest to those mho use the microscope to solve chemical problems. However, because “chemical problems” are so diverse, and because the microscope is used in so many fields, it was necessary to restrict this review in several ways. KO attempt has been made to report publications in the fields of biochemistry, petrography, or metallography unless they were deemed to be of direct interest to cheniists or chemical engineers. The chemical applications of electron microscopy are the subject of a separate review, and they are not reHE PREVIOUS RCVILW

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0

port’ed here. References to publications in the fields of optics and crystallography are included if they appear to be of interest to chemical microscopists. Past reviews in this series have included a section on meetings and symposia. Because meetings and symposia have become so numerous, and because of the desirability of reducing length of this review, reports of meetings and symposia have been omitted. Printed proceedings of meetings or published articles based on papers presented a t meetings are reported. The great’ diversity and number of publications of possible interest’ to chemical microscopists makes it impossible to find and review all of them. Therefore the author would appreciate comments or suggestions, particularly with regard to the omission of important published art’icles.


BOOKS OF GENERAL INTEREST

A book entitled “The Microscope, A Practical Guide” (1%) has been written by ?Seedham. This book and a third edition of Barer’s excellent “Lecture Notes on the Use of t,he Xicroscope” (9) proyide an introduction to microscopy for beginners. Barer’i book has been expanded by including appendices on phase-cont’rast microscopy, and on the use of research type illuminators. Fraii~oiiJs “Progress in Microscopy” has been translat’ed into German by Ludwig (54). The translator has also included revisions of the sections on phase and interference microscopy. Two more books iii the series entitled “hdvances in Optical and Electron llicroscopy” ( I f ) have appeared. Volume 2 contains four chapters of direct interest to light microscopists.

Organic elemental analysis - ACS Publications

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