(167) West, P. W., AXAL. CHEM. 34, 104R-lllR (1962). (168) West, P. W., Diffee, J., Anal. Chim. Acta 25, 399402 (1961). (169) West, P. W., Llacer, A. J., ANAL. CHEM.34, 555 (1962). (170) West, P. W., Llacer, A. J., Cimerman, C., Mikrocham. Acta 1962, pp. 1165-1168. (171) West, P. W., Lorica, A. S., Anal. Chim. Acta 25, 28-33 (1961). (172) West, P. UT., lIarDonald, A. hf. G., West, T. S., “Analytical Chemistry 1962,” Elsevier, Amsterdam, 1968. (173) West, P . W., llohilner, P. R., AXAL.CAEM.34, 558 (1962).
1174) West. P. W.. Ordoveza. Fe. Ibid., ‘ p.’1324. ’ 1175) West. T. S.. Anal. Chim. Acta 25. 405-421 (1961).‘ (176) West, T. S., Analyst 87, 630-636 ( 1962). (177) West, T. S., Ind. Chemzst 38, 35-37 81-83 (1962). (178) Willis, J. B., ‘Vatwe 191, 381-382 (1961). (179) Yamaguchi, Koichi, Ueno, Keihei, Talanta 10, 1041 (1963). (180) Ibid., p. 1195. (181) Yamamura, S. S., Wade, >I. A., Sikes, J. H., ANAL.CHEM.34, 1308 ( 1962). (182) Yatsimirskii, K. B., Fedorova, T. I
,
I., Dokl. Akad. Nauk SSSR
143, 143145 (1962). (183) Yoshimori, Takayoshi, Yamade, Tsugihiko, Hongo, Tsutomu, Takeuchi, Tsugio, J . Chem. SOC. Jawnn, Ind. Chem. S e c t . 65, 1808-1811 (1962). (184) Zhivopist?ev, V. P., Chelnokova, 3T. N., 1:ch. Zap. Permsk. Cos. Univ. 19, 87-91 (1961). (185) Zolotavin, V. L., Korznyakova, E. G., T r . Ural’sk. Politekhn. Inst. 121, 9-17 (1962): (186) Zolotov, Yu. A., Zavodsk. Lab. 28, 1404-1408 (1962).
This work Rupported in part by Public Health Service Research Grant A P 00117 from the Division of Air Pollution, Bureau of State Services.
Organic Microchemistry T. S. Ma and Milton Gutterson, Department o f Chemistry, Brooklyn College, City University o f New York, Brooklyn
T
H I S REVIEW, like the previous ones on organic microchemistry, covers only elemental analysis and the determination of organic functional groups and rovers the period from October 1961 to September 1963. l y e mentioned in our last review (255)that the current trend in microchemistry is concerned with the principles and methods of chemical esperimentation using the minimum quantity of working material t o get the maximum amount of chemical information. This trend is particularly significant in the developments in quantitative organic microanalysis during the past two years. Thus, considerable effort has been devoted to the determination of carbon, hydrogen, nitrogen, and other elements in less than 1 mg. of organic material. Simultaneous determination of several elements with one sample-w hich conserves the working material and usually also time-is the theme of many research papers. Since gas chromatography is a tool especially suited for separations on the milligram to microgram range, it is not surprising to find that the organic microchemists are utilizing this technique to perform quantitative analysis of progressively smaller quantities of materials. The applications of gas chromatography to organic elemental analysis are amply documented in the succeeding sections. *\ beginning has also been made to use gas chromatography in microdeterminations of organic functional group’, wch a$ the alkosyl (gal), amino (1.54), alkimino, carbo\j 1, and C-methyl (266) groups. 1Iore actirities in this field are to be elpect ed. dutomation has come to the organic microanalytical laboratory. X number
150 R *
ANALYTICAL CHEMISTRY
of publications have appeared which describe the assemblies for automatic determination of carbon, hydrogen, nitrogen, and sulfur. Several manufacturers (65, 93, 102, 411) have put out commercial models of automatic analyzers. It should be noted that the chief advantage of the automatic apparatus is saving of labor. These machines are recommended for routine analytical work where many samples have to be processed during a short period of time. They are not intended to produce better results than the conv6ntional manuallyoperated assemblies. ELEMENTAL ANALYSIS
Carbon and Hydrogen. Rapid combustions procedures continue t o receive much interest. Pfab (327, 328) pyrolyzed the sample in a slow stream of nitrogen, the products being combusted in a fast stream of osygen a t a jet. h misture of copper oside and silver pumice in the combustion tube ensured complete osidations. Chang, Huang, and Chang (58) employed a combination of preliminary pyrolytic oxidation and catalytic combustion using silver permanganate as catalvst. Oda and co-workers (304, 306) described a n apparatus containing a preheated double combustion tube. The sample, placed in the inner tube, is combusted almost instantaneously a t 800°-850” C.; complete osidation is obtained by passing the gaseous products over copper oside with a current of osygen. Imaeda and co-workers (179) combusted the sample in a current of air a t 750°-800” C. Porous copper oside was used as osidant while porous silver was a n escellent absorbent for halogens and oxides of
IO, N .
Y.
sulfur. U t s u i , Yoshikawa, and Furiiki 1282) employed combustion with a stream of nitrogen mised with electroIvticallv generated osygen. Meyer and Vetter (27.9) used Co304 as catalyst and precipitated MnOz to remove nitrogen osides in a procedure employing combustion with dry osygen a t 6.50” C. Klimova and Antipova (214) inserted a flash heater of relatively large size in front of the combustion train ensuring complete decomposition of the sample within 2 to 3 minutes. Ingram (173) used closed flask combustions. The flask was modified to contain a quartz chamber. The sample was drawn into the chamber with a magnet and ignition was with osygen which uas passed through the apparatus during combust ion. The development of these rapid techniques inevitably lead to attempts to automate the entire procedure. Maker (263) described a commerciallyavailable unit in which the combustion tubes are vertically mounted and include motor-driven furnaces. Malissa and Pel1 (261) used a packed combustion tube although their studies indicate that empty tube combustion is feasible. Electrolvtic cells automatically record the conductance of a n absorbing solution at constant gas pressure for the quantitative measurement of carbon, hydrogen, and sulfur. The results of the determination of these elements simultaneously by their apparatus are encouraging. Gustin (135) combusted the sample in a slow stream of osygen, surrounding the organic compoiind by copper oside which eliminated sample explosions. The procedure is similar to Dumas nitrogen techniques. The final sweep with oxygen is rapid. The time for a deter-
mination is about 10 minutes. Knobloch, Knobloch, and Mai (218) developed a n autom:ttic combustion apparatus for serial determinations of carbon, hydrogen, and nitrogen. From 26 to 32 combustions t a n be performed daily by one operator utilizing 2 parallel tubes and Vecera's rapid method with cobaltic oxide as ratalyst. Simon, Sommer, and Lyssy (384) described a fully automatic method in which each stage of the determination is discussed and reviewed. Most of the above procedures employ a conventional finish. Luskina and coworkers (653) combusted the sample rapidly in a closed tube with CuO and helium. The combustion products were chromatographed on a column of tritolyl phosphate on fire brick. Sommer and co-workws ( 3 9 4 ) swept t h e products of combustion into a n evacuated system of two katharometers fitted with V-tubes containing magnesium perchlorate and soda asbestos. Signals from thermal conductivity cells were proportional t o t,he carbon and hydrogen contents. Vecera (430, 431) employed rapid c o m b u h o n over cobaltic oside followed by detection of t h e combustion gases by a thermal conductivity cell. The water produced was first reduced t o hydrogen with iron foil. Haber and Gardner (,'39) determined the water produced by combustion of the sample electrolytically. The carbon dioxide was measured similarly after treatment with a lithium hydroside catalyst at 250" C. to yield water. Kliniova and *\nisimova (212) investigated compounds which would react with water t o givv HCl. Phenylborondichloride was found best. The carbon dioxide was absorbed in sodium hydroxide solution, tlarium chloride solution added, and titrated with HC1 solution. Kuck and co-workers (235) employed infrared abso:ption for determining the carbon dioxide produced by the conventional combustion of organic compounds. Water WLS converted t o hydrogen over calcium hydride and t'he gas was detected by thermal conductivity. The technique is of special value in the diagnosis of hidden errors in microcombustions (636). Many modifications in the procedure for carbon and hydrogen have been described for those compounds which may otherwise cause difhulties. Campbell and Macdonald ( 5 4 ) combusted fluorine containing samples in a tube with a side ' a r m containing M g O pellets. The- combustions temperature was 820"-850" C. b u t in some cases it was necessary t o raise the temperature t o 950" C. Lebedeva, Nikolaeva, and Orestova (244) employed a silver vanadate catalyst at 500' C. for t h e combustion of monom1:ric and polymeric compounds cont:tining fluorine. Ingram ( 1 7 4 ) studied the errors inherent '
in the combustion of organic fluorine containing compounds and concluded t h a t SiF4 is formed and carried t o the COa absorption t'ube. This can be eliminated by including N g O in the silver gauze packing. Funasaka, Ando, and Murase (112) also employed MgO for t h e same type of compounds, as a zone between two layers of copper oside all a t 800' C. Pechanec and Horacek (317) developed a special silver sponge for the absorption of mercury vapor in t h e cool zone of the combustion tube. Gawargious and Macdonald (116) studied the rapid combustion of organometallic compounds. Cobaltic oxide was a satisfactory catalyst, but tungstic oxide had t o be added t o samples containing zinc, alkali metals, and phosphorus, while special precautions were necessary for those compounds containing arsenic or mercury. T h e same authors (118) recommended careful volatilization at 900" C. for siliconcontaining compounds and a tube filling of MgO t o avoid t h e formation of stable volatile silanes or S i c . For thermally stable compounds, especially organoboron samples, Butterworth ( 5 3 ) proposed combustion at 1300' C. obtained by induction heating. Ebelling and Malter ( 8 9 ) proposed a silver vanadate packing which demonstrates a great capacity for compounds containing sulfur and halogens. Zabrodina and Levina (453) employed a n external absorption tube a t room temperature packed with copper for the absorption of halogens. A number of investigators have concerned themselves with the processes involved in organic combustions. Ingram (175) advocated a simple method of direct ignition in escess of oxygen in a chamber a t 850" C. under closed system conditions. Gawargious and Macdonald (117) compared the efficiency of a number of catalysts for the empty tube combustion technique. Cobaltic oxide was most satisfactory for general work. Horacek, Pechanec, and Korbl (160) studied the efficiency of catalyst,s in the combustion of carbon monoxide, heptane, and benzene by noting lowest temperature a t which a given catalyst system gives quantitative results. Klimova and Antipova (213) reported t h a t decomposition of organic compounds by rapid technique proceeds layer by layer, not throughout the mass of the compound. Kainz and Xlayer in a series of papers reported their studies on absorptions of nitrogen oxides. The factors governing the absorption by manganese dioside (191) and t.he importance of the length of packing and gas flow rate (192) were given. The use of lead peroside (193) and mistures of lead peroside and manganese dioside (194, 195) es1)ecially as esternal absorbents were recommended. Seivrnan and 'Tomlinson
(298) reported on t h e use of a n external absorbent' for nitrogen osides. They pointed out the importance of preventing condensation of the water before i t enters the absorption tube due t o the solubility of the nitrogen oxides in water. Kainz and H-orwatitsch (187) studied the efficiency of empty tube combustion as related to temperature and recommended a minimum of 750" C. They also studied combustion over copper oxide. The concentration of the combustion vapors in the gas flow is important (188) and the Pregl method which produces low concentrations is recommended for empty tube combustions. The same authors also studied the different effects of oside and metal catalysts (190) on the combustion of organic compounds including the retention of combustion vapors (189) on various metal oxides. Copper oside gave the least retention. Mitsui and eo-workers (283) recommended silver granules for the absorption of halogens and sulfur oxides. Their capacity was the same as Ag wool b u t t h e granules are most convenient t o use. Thomas (418) described a simple apparatus for winding silver wire for use in combustion tubes. Ronzio (355) reported on the use of stainless steel absorption tubes. Rush and Miller (358) proposed barium isopropyl methylphosphate as a stable, rigorous standard. The compound is refractory, and is useful also for determinations of barium, phosphorus, and alkoxy1 groups. X number of procedures have appeared for either the determination of carbon or hydrogen. Vecera (434) designed a combustion tube which is connected by means of a glass capillary to the COS absorption tube in the weighing room. hllinko (688) pyrolyzed the sample in a stream of ammonia a t 1150" C. to yield hydrogen cyanide which is absorbed in methanolic KOH and t,itrated with 0.02N silver nitrate solution. Dunston and Griffiths ( 8 8 ) modified a previously-described method for carbon based on met combustion. Holmes (155) described a test, tube fitted with a ground-glass stopper and short, side a r m useful for adding nitric acid or ot'her oxidant during wet combustmion procedures for organic compounds. Maros and eo-workers ( 2 6 8 ) presented a modification of their technique for carbon based on distillat,ions and titration of COS. Vecera, Lakomy, and Lehar (436) measured the COz from the combustion by the change in electrical conductivity of a barium hydroxide absorbing solution. Olson, Houtman, and Struck ( 3 0 9 ) determined hydrogen by absorption of the water produced by combustion in a cell containing PSOS. The water is determined by continuous electrolysis VOL. 36, NO. 5 , APRIL 1964
151 R
using either constant-potential or constant-current silver coulometry. Mlinko (987) used an iodimetric finish after the water was absorbed in CS,to produce H S . Soucek (395) used coulometry for the determination of hydrogen after combustion over silver permanganate. Belcher and co-workers (27) determined hydrogen in organofluorine compounds. The combustion is at 900" C. with MgO pellets to absorb fluorine compounds. The water can be absorbed conventionally or titrimetrically by t h e liberation of HCI from 8-ethyl-8-methylglutaryl chloride. Greenfield and Smith (127) absorbed the water in a conductimetric cell containing sulfuric acid. The assay of the radioactive isotopes of both carbon and hydrogen have been reported. Kelly, Peets, and Buyske ($05) employed closed flask combustion. The absorbing solution was dissolved in a toluene-phosphor and counted. Dobbs (85) used a similar combustion technique but injected a liquid scintillator into the flask. .In aliquot was withdrawn for counting. Mlinko and Szarvas (289) converted the I4CO2 to methane before counting. Crespi and Katz (68) used the infrared absorption peaks of water a t 1.66 and 1.44microns for the determination of deuterium. Tamiya (410) modified a method for deuterium. Aft'er combustion in sealed tube, the water is converted to hydrogen and analyzed by mass spectrometry. Horacek (157) used rapid combustions and determined the deuterium content of the water produced by densimetric isotope analysis by the falling drop method. Garnett, Hannan, and Law (115) reported a modification to the gas counting procedure for tritium. Petukhov and Guseva (326) determined deuterium by a refractometric method. Oxygen. Ehrenberger (91) described a special furnace for heating a 2'-shaped combustion tube. T h e vertical portion contains the carbon catalyst a n d the a p p a r a t u s is designed to prevent sooty deposits. Bobranski and Sidorowicz (35) offered improvements in the Schiitze method. Quartz tubes may cause errors in t'hat SiO, 2C = Si 2CO. Supremax glass can be used with a catalyst containing platinum and palladium and a temperature of 750" C. Campiglio (55) described a control circuit for a furnace capable of maintaining a temperature of 1120" 1" C. Salzer (363) proposed a conductimetric finish for oxygen determinations in which halogens, nitrogen, and sulfur do not interfere. Kapron and Brandt (BOO) prevented the formation of metal oxide3 in the combustion of organo-metallic compounds by mixing the sample with lead chloride or cuprous chloride. Pesez and Bartos (325) reduced t,he iodine produced by the re-
+
*
152 R
ANALYTICAL CHEMISTRY
+
action of carbon monoxide and IzOs with potassium borohydride and titrated I- potentiometrically with standard Ag+. Novak and Slavik (301) proposed an electrometric method for measuring the oxygen content of gases. Suchanec (404) presented two methods for oxygen. One involved heating, in a stream of nitrogen over copper oxide, while the other employed pyrolysis at 920" C. in a stream of helium, the CO being absorbed at -78" C. and determined by gas chromatography. Compounds containing phosphorus and fluorine give poor results. Guldner and Beach (153) pyrolyzed the sample in a n open graphite crucible in a stream of heliu'm a t a temperature of 1650"-1800" C. heating by high frequency induction. The carbon monoxide formed was converted into COS and determined conductimetrically. Cruikshank and Rush (70) reported on the determination of oxygen in fluorine-containing compounds. Errors are caused by reaction of fluorine with silica in combustion tube. The use of a platinum tube was promising, while coating quartz tube with carbon was unreliable. The use of magnesium nitride to absorb F or HF was not recommended. Pansare and Mulay (315) pyrolyzed the sample in a stream of nitrogen, employing platinum-rhodium as catalyst, and converting CO to CO, with copper oxide a t 300" C. Mlinko (285) used a n improved ter Meulen procedure: sample passed over palladium, then nickel, and finally copper to yield water. The water is converted to nitrogen as follows:
HzO
+ Ba (OCN),
NH,
.?$ Nz. 520'
The nitrogen is determined volumetrically. Beck and Clark (20) encapsulated the sample in graphite forming a miniature reaction vessel. Heating in a stream of argon over a n oxidation reagent produced CO2 which was measured conductimetrically. Haraldson (140) investigated the pyrolysis of sulfur-containing compounds at various temperatures by the use of gas chromography. CS,,HzS, and SO? were produced in amounts in agreement with known equilibrium constants. Imaeda, Kinoshita, and X z u t a n i (178) described the preparation of porous black silver and porous copper as abqorbents for iodine. Steele and Meinke (398) utilized activation analysis for the determination of oxygen. The sample sealed in polyethylene was bombarded with fast neutrons and the intensity of the emitted x-rays was measured. Zonov (466) decomposed the sample by using high frequency discharge and then obtained the isotopic composition of the CO produced by mass spectrometry.
Nitrogen. Rapid a n d automatic modifications of t h e D u m a s procedure continue t o receive emphasis. Dorfman and eo-workers (86) described the construction and operation of a n automatic apparatus in which the sample is combusted over CO, in one furnace at 825" C., while oxides of nitrogen are reduced over copper in another a t 525" C. Vecera (451, 452) combusted the sample in a stream of CO, using CorOc as oxidation catalyst. The nitrogen evolved after passage of the vapors over hot copper was determined by thermal conductivity. Sternglanz and Kollig (400) evaluated a commercial automatic nitrogen analyzer and recommended that refractory compounds be fused with V2OS in a platinum sleeve and then combusted a t 900" C. Brown (44) proposed a modification in the timer of the same initrument to change the course of a cycle. Mizukami and Miyahara (292) were able to perform 32 analysis in 7 hours by a n arrangement of eight combustion tubes axially about the center of the furnace. Kakabadse and Manohin (I96) modified the packing for the rapid determination of nitrogen in fluorine-containing. compounds. The combustion tube was packed with CuO-Cu, then N a F , and finally Xg wool. Heating was performed with four furnaces and the CO, stream was passed over catalytically-decomposed hydrogen peroxide to yield oxygen. Selenium was incorporated in the KOH solution to prevent foam and bubbles sticking to the side of the nitrometer. hbramyan, Kocharyan, and Karapetyan (4) used NiO both as packing and to blend with the sample, halving the time necessary for the PreglDumas procedure. Modifications of the "slow" procedure have been reported. Fodor-Varga (103) reduced the copper oxide with methanol by heating in a stream of CO obtained by passing COz over hot carbon. Browne and Polya (46) recommended slow purging to minimize the errors in the nitrogen determination of certain 1,2,4-trizoles. Buckles, Rush, and Corliss (48)made a careful study of the entire procedure. improved tube filling consisted of nickel oxide/Cu ' copper oxide. The main furnace was kept a t 800" C. and the sample burner a t 900" C. Rigorous standards were advocated, in particular cystine. MeGillivray (275) described a simple oxygen generator which ensured desired rate of flow of oxygen in the carbon dioxide stream. Block, Morgan, and Siggia (37) utilized the technique of differential reaction rates to determine mixtures of two compounds by measuring a t intervals the volume of nitrogen released during the micro-Dumaas procedure. Simek and Tesarik (583)studied the combustion products of the micro-
Dumas procedure by gas chromatography. Slow combustion with a gradual increase in temperature was desired. Reitsema and Allphin (360) determined t h e KOz and COZ produced during combustion to obtain the C-to-N ratio. If CO2 is used as carrier gas, the nitrogen can be determined with a n accuracy equal to t h a t of the Kjeldahl determination. Parsons, Pennington, and Walker (316) combusted the sample in a carbon criicible using silver permanganate and (bopper oxide as catalysts. The cartjon dioxide and water were absorbed and the nitrogen was swept into a gas chromatographic column with helium and detected by thermal conductivity. Kjeldahl and other wet combustion procedures continue to be of interest. Baker (16) studied the influence of various metal catalyt,ts on the microKjeldahl determination. A mixture of mercuric oxide (20 mg.), K2S04 (2.25 grams) and concentrated HzS04 (1.5 ml.) was found to be best. Albert ( 6 ) proposed bismercaptoacetate as a reducing agent for compounds containing nitrogen-to-oxygen bonds. For pyridine compounds, Terent'ev and Luskina (414) digested the srtmple in a flask fitted with a condenser using CrC13 and a mixture of CuS04, SeOz, and K2S208plus concentrated H2S04. Kasagi and Ito (204) eliminated the distillation step by adding to a n aliquot of t h e digest, chloramine-T and pyrazolone reagent and, after adding cC14, measuring the extinction of the organic layer a t 460 mp. iiskraf, Bhatty, and Shah (15) reduced oxygen-to-nitrogen linkages with glucosth, and after the digestion step added KBr and excess 0.02.N NaOC1. The excess was reduced with 0.0lN As203 which was back titrated with the standardized 0 . 0 2 s NaOCl. Hashmi, Ali, and Umar (I@') added NaOBr solutions to the digest and determined the excess by iodometric titration. Radmacher and Hoverath (342) digested the sample with metallic lithium. Set0 (372') described a simplified apparatus for the phosphoric and iodic acid decomposition of nonvolatile nitrogen coripounds. After digestion over COZ, the nitrogen was determined in a Van Nyke nitrometer. Shamri ( 3 7 4 ) and eo-workers proposed a mixture of CaO and NaOH (1: 11) for the digestion applicable to heterocyclic compounds. Sulfur. Xovikova, Basargin, a n d Tsyganova (302) empl3yed closed flask combustion and titration of the sulfate with 0.02.V Ra(&@a)2solution and a new indicator-carboxyarsenazo [3-(0arsenophenylazo) - 6-(c-carboxyphenylazo) - 4,5 - dihydroxynaphthalene2,7-disulfonic acid]. Lebedeva and Novozhilova (242) u6,ed closed flask combustion with alka ine peroxide as
absorbent. The solution was evaporated to near dryness in the presence of a small amount of platinum black and finally titrated with 0.02N B a (NO& using Alizarin Red S as indicator. Dixon (82) employed closed flask combustion and direct titration of Sodzin the presence of methylene bluemethyl red. When other elements besides C and 0 were present, conductimetric titration with barium acetate was used. Kirsten, Hansson, and Nilsson (220) titrated the sulfate directly with lead nitrate, or after separation on a column contai ing aluminum oxide and cation-exchange resin. Fabre (9$) used 0 . 0 1 S lead nitrate as titrant and Thoron as indicator. Ellison (92) proposed closed flask combustion, followed by reduction with acidified hydriodic acid in a stream of nitrogen gas, the products being collected in KaOH solution. To this solution after acidification was added excess iodine solution which was back titrated with 0.025 KazSzOa. Malissa and Machherndl (260) made a systematic investigation of the closed flask combustion method and reported no correlation for sulfur content, standard deviation, and nature of S-bonding. Mergroyan and Tonakanyan ( 2 7 7 ) combusted the sample in a quartz tube at 8i)O'-900° C. without catalysts. The issuing gases were absorbed in hydrogen peroxide solution which after boiling was titrated acidimetrically. M a n y other elements interfered. Sudo, Shimoe, and Tsujii (406) proposed a platinum catalyst which facilitated the oxidation of sulfur-containing compounds. The absorption of the issuing gases on electrolytic silver was quantitative at 390"-410' C. Swift ( 4 0 7 ) combusted the sample in a platinum boat; t h e products of combustion were drawn through a platinum cylinder containing silver wool. The gain in weight of this cylinder gives the sulfur content of the sample. Okuno, Morris, and Haines (308) proposed hydrogenation and gas chromatography for volatile sulfur-containing compounds. The sample was injected into a stream of hydrogen flowing over a platinum catalyst. The HzS gas was condensed and vaporized into the gas chromatograph. Beuerman and Meloan (32) combusted the sample in oxygen, condensed the SO2 produced in liquid nitrogen and later vaporized the gases into a chromatographic. column with helium as carrier and a thermistor detector. For compoundq containing mercury in addition to sulfur, Pechane (320) absorbed the combustion gases over Rln2@3. The MnSO, waq extracted and titrated complexometrically using (ethylenedinitrilo)tetraacetic acid ( E D T A ) . Jenik and Kalous (183) compared the closed flask combustion
with mineralization using M g metal. The hydrogen sulfide produced by the latter technique was determined colorimetrically. Shaw ( 3 7 5 ) employed wet combustion and indirect flame photometry for sulfur in biological fluids. Halogens. Closed flask combustions have received much attention not only in methods b u t in t h e design of apparatus. Favorskaya and Lukina (96) saturated the filter paper with potassium nitrate solution prior to ignition for compounds with high halogen contents. Mizukami, leki, and Kasugai (290) used aqueous ammonia as absorbent and removed interferences by boiling before titration with silver nitrate solution. Wang, Tuan, and Ch'i (444) proposed alkaline peroxide solution as absorbent and titration of the halides with 0.01N mercuric nitrate using diphenylcarbazone as indicator. Wielopolski, Krajewski, and Swierkot (447) determined chlorine in organic compounds conductimetrically aft'er t h e closed flask combustion. Tomlinson (421) recommended a combustion tube procedure for liquids, refractory substances, and for those compounds with high halogen contents as the closed flask technique may give incomplete combustion. Recommended specificat'ions for the combustion flask have been published (66). Weir (445) described a compact igniter and safety shield for the flask, consisting of a shield of acrylic resin with a hinged lid and a Teflon t h u m b screw to hold the stopper in place. Kusenko and Cardone (239) modified the Thomas-Ogg lamp safety igniter to permit the stopper to be held in place conveniently during the ignit'ion. (126) Gouverneur and Eerbeek developed a simple shield of wire gauze for the safe ignition of the sample in the flask. Ferber, Holubec, and Crick (98)described a device for flushing of the flask with oxygen, in which a n aspirator is used to evacuate the flask. Ogg, Kelly, and Corinelly (307) suggested t h a t either of two approaches are feasible for safe, oxygen-filled flask combustion, namely electrical ignition or by use of radiant energy. Pechanec (319) combusted halogen compounds containing mercury conventionally and absorbed the mercury and halogens on the decomposition product of KMnO,. After the mercury was distilled off, the halides were extracted with water and titrated mercurimetrically or argentimetrically. Pella (324) recommended aqueous bisulfite as absorbent after combustion of the sample in a stream of oxygen. Bromine could be determined in the presence of chlorine by absorption in hypochlorite solution to form bromate. Dirscherl and Erne (81) combusted the sample a t 1000" C. and absorbed the produczts in hydrogen peroxide solution. Titration VOL.
36, NO. 5 , APRIL 1964
0
153 R
using mercuric perchlorate solution and diphenylcarbazone as indicator was employed for C1- or Br-. Ehrenberger (90) determined iodine by decomposition with oxygen and burning the vapors in a n oxy-hydrogen flame. The iodine was absorbed in bromine solution and de termined by Li epert 's method. Mlinko (286) proposed hydrogenation for halogens in organic compounds. T h e sample was pyrolyzed at 800' C. with hydrogen and NHs gases in a tube containing nickel to absorb C and H2S. The ammonium halides were absorbed in a tube containing glass wool. The increase in weight of the tube was determined. Mizukami, Ieki, and Kasugai (291) dispersed the electrostatic charge on the absorption funnel containing silver granules in t h e combustion method for halogens by cooling the funnel i n humidified air. Klimova and Merkulova (215) described the preparation of finely divided silver useful for absorbing halogens or sulfur. Shah and Jabbar (373) decomposed the sample with sodium in a nickel capsule in a sealed tube. T h e products were dissolved, passed through a n ionexchange column, and the resulting HC1 titrated acidimetrically. Hennart (146) proposed a n indirect chelatometric finish after fusion of the sample with sodium peroxide or closed flask combustion. The same author (146) used the technique for iodine in the presence of other halogens. It was necessary first to reduce the iodine to iodide which was precipitated with a known amount of Pd+2. The excess of Pd +2 was determined by the chelatometric method. Pristavka (337) described procedures designed to prevent losses of halogens and other elements during the mineralization of organic compounds. A number of other methods for halogens have appeared, Chambers, Musgrave, and Savory (67) devised a special apparatus for weighing and transferring gases and volatile liquids which were shaken with a biphenylsodium-dimethoxymethane complex t o yield sodium halides, the latter being determined by the oxycyanide method. For tetrabromoethane, Alon and coworkers (9) em1)loyed dehydrohalogenation with ethanolic 1)otassium hydroxide solution. The bromide was determined iodimetrically or nel)helometrically. Matsuda and l l a t s u d a (274) titrat'ed alkyltin halides with silver nitrate solution by the high frequency method. For organicalljr-bound chlorine, Griffin (131) proposed iron-55 x-ray absor1)tion using conventional 1)roportional-counting facilities. Several techniques have been proposed for fluorine-containing compounds. Konovalov (222) described closed flask combustion using calcium chloride solution as absorbent to liberate
154 R
ANALYTICAL CHEMISTRY
HC1 which was titrated acidimetrically. Compounds containing other elements aside from carbon and hydrogen in addition to the fluorine were not tested. The closed flask and oxy-hydrogen flame techniques were compared by Levy and Debal ( 2 4 8 ) . The oxyhydrogen flame method was more precise and universal but the flask was simpler and less costly. Lebedeva and co-workers (245) used the flask combustion and titrated Fin buffered solution with 0.025n' Th(xo3)4using Alizarin Red S as indicator. Ferrari, Geronimo, and Brancone (100) employed flask combustion with a colorimetric finish, reacting the fluoride with Eriochrome cyanine R and ZrO Cl2 solution. After flask combustion, Trutnovsky (422) titrated the fluoride with 0.00531 Ce(II1) in the presence of murexide-naphthol green B. Abramyan and Sarkisyan (3) mineralized the sample with potassium permanganate in a sealed tube. The fluoride was titrated with thorium nitrate solution using sodium alizarin-sulfonate as indicator. Francis (105) described a bomb machined from stainless steel useful for alkali metal fusions. A list of 14 halogenated and four sulfur-containing compounds recommended as test substances has been published ( 6 7 ) .
posed digestion with concentrated HzS04-HN03 in a Kjeldahl flask for 1
minute. Kan, Kashiwagi, and Tanabe (198) demonstrated that the ammonium molybdophosphate precipitate turned black on heating a t 500" C. but its weight remained constant. They reported that heating for 10 minutes is sufficient. MacDonald and Stephen (268) described closed flask combustion for phosphorus and sulfur. Alkaline hypobromite was used as absorbent. The was precipitated as quinoline molybdophosphate and the precipitate determined by dissolving in excess alkali. Ryadnina (360) modified a closed flask combustion method in t h a t nitric acid solution was used as absorbent, and after boiling to convert PzOsto H3P04,a colorimetric finish was employed using (SH4)2 hf004 in the presence of basic bismuth nitrate and ascorbic acid. Liddell ( 2 4 9 ) discussed the application of the closed flask combustion to petroleum products for the determination of phosphorus, sulfur, and chlorine. The phosphorus wa5 determined colorimetrically using (h"4)6lfOi024 in the presence of hydrazine. Jenkins (184) applied x-ray fluorescence analysis to the determination of phosphorus, sulfur, and chlorine in volatile liquids, Phosphorus, Mercury, and Arsenic, Chumachenko and Uurlaka ( 6 1 ) deAbd and co-workers (1) determined mercury in pharmaceutical preparations composed the organic sample with by adding E D T A to the digested sample potassium metal in a micro bomb. The and titration of the excess with 0.OlN potassium phosphide was oxidized with ZnS04 in the presence of Solochrome permanganate solution t o Po4-3which Fast Navy 2R. Kondo (222) decomwas titrated amperometrically using posed the sample in a nickel crucible in uranyl acetate solution. Hozumi and Mizuno (169) digested the sample with the presence of CuO, Cu, iron, and CaO. A gold plate on top of the crucible abconcentrated H2SO4-HK03 mixture and sorbed the mercury and was subemployed an indirect complesometric sequently weighed. Pechanec and Horfinish. The PO4C3was precipitated with acek (318) combusted the sample over excess h l g + 2 which was titrated with E D T A using Eriochrome black T as nitrogen, absorbed the combustion products onto the decomposition product of indicator. Horacek (156) proposed a K M n 0 4 , and absorbed the mercury on titrimetric finish after mineralization d v e r sponge. Mitsui, Yoshikawa, and of the sample, using 0.01N La(N03)3 Sakai (284) employed combustion over in the presence of Chrome Azurol S. nitrogen containing a suitable amount of Kondo (220) decomposed the sample in a microbomb using sodium peroxide. electrolytically generated oxygen and absorbed the mercury vapor on silver The Po4-3 was titrated with uranyl acetate solution a t 95' C. The entire granules. Stefanac (399) employed flask comprocedure took 1 hour and alkaline bustion for organic compounds conearth metals did not interfere. Ditaining arsenic. Sodium acetate soluPietro. Kramer, and Sassaman (78) tion was used as absorbent and the modified the micro-Carius procedure for arsenite and arsenate ions were prephosphorus by adding KC1 to the tube cipitated with silver nitrate solution. to avoid deposition of a residue conThe precipitate was treated with K2Nitaining phosphorus on the sides of the (CN)( solutions and the displaced Ni+2 tube. was titrated using EDTA solution and Abramyan, Sarkisyan, and Balyan murexide as indicator. Puschel and ( 5 ) employed sealed tube oxidation with potassium permanganate. The 1'04-3 Stefanac (339) used alkaline peroxide as absorbent and titrated the arsenate ions was precipitated with (NH4)6Moi024. directly with lead nitrate solution and The precipitate was dissolved in ex4-(2-pyridylazo)resorcinol or 8-hydroxycess alkali which waq determined by 7 - (4 - sulf - 1 - naphthy1azo)quinolineacidimetric titration. In the gravi5-sulfonic acid (SNAZOXS) as indimetric method of Lieb and Wintersteiner, Kan and Kashiwagi (197) procator.
Other Elements. Potassium was determined by a n ndirect chelatometric method described by Sousa (396). After precipitation with perchlorate and conver4on to chloride, Ag+ was added, and the precipitate was treated with K21Ji(CN)4solution. The liberated Ni+, was titrated using E D T A solution and murexide as indicator. Bladh and Gedda ( 3 5 ) precipitated the potassium with sodium tetraphenylborate solution and determined the excess of reagent by turbidimetric titration using cetyltrimethylammonium bromide solution as titrant. Jenik and Jurecek (182) decomposed the sample with magnesium metal and determined silicon colorimetricall:; as the molybdenum blue complex. Dunstan and Griffiths (87) propowd wet oxidation using alkaline K2S20ssolution for nonvolatile boron-containing compounds. T h e boric acid was determined alkalimetrically after addition of mannitol. Pierson (330) evaluated six procedures for the determination cif boron in organic compounds. Sharp end points in the alkalimetric titration in the presence of mannitol were achiev3d by controlling type and degree of initial oxidation depending upon t h e structure of the compound. Thn, Hesse, a i d Neuland (17'1) proposed closed flask combustion for compounds containing selenium. The selenium in the form of H2Se0s was determined iodimetrictlly. Simultaneous Determination of Several Elements with One Sample. hlaresh and co-workers (264) utilized gas chromatography for the simultaneous determination of carbon, hydrogen, and nitrogen. Cmventional combustion was employelj and the combustion products including acetylene from the reaction of w t t e r with calcium carbide were condensed on silica gel a t liquid nitrogen temperatures. The C02,N2,and CzHzgases were volatilized into a gas chromatograph containing silica gel. Nightingde and Walker (300) proposed rapid combustion in a high-frequency induction furnace eliminating the necesqity for a liquid nitrogcn trap for CO!, N,, and CzH2. These gases were separated on a column of Linde 5.1 Moleculw Sieve. Frazer (106) employed a bomb combustion technique and measured the CO,, Hz, and Sz gases volumetrically in a gasburet. Frazer and Crawford (107) described improved procedures for the above-mentioned gas volumetric method. Tarent'ev and Luskina (4f3) reduced certain nitrogen compounds with zinc and thcn eniployed digestion with sulfuric and chromic acids to yield CO, which was absorbed in Ascarite. The nitrogen in the rosidue was determined bv the Kjeldahl procedure. Abramyan and Atashyan ( 2 ) described a new absorbent for halogens in their simultaneous del ermination with
carbon and hydrogen. A tube containing antimony was placed between those for the absorption of water and carbon dioxide. Gutbier and Rockstroh (136) absorbed the halogens in a tube containing -Igwool activated with nitric acid solution and maintained a t 580' C. Onoe, Furukawa, and Otsuka (311) offered a n improvement in a previously-described method for the simultaneous determination of C, €1, halogens, and sulfur. Lebedeva and Kramer (241) combusted the sample in a stream of oxygen over Co304as catalyst and determined C, H, and mercury simultaneously by collecting the metal on silver-impregnated pumice. Pechanec (321) employed the decomposition product of d g h 4 n 0 4as catalyst and collected the mercury in a tube containing silver sponge and wool. Beuerman and Meloan (33) extended their previous gas chromatographic method to include the separation of COZ and SO, to permit their simultaneous determination. Rittner and Culmo (353) determined C and H by the standard Pregl-type procedure and determined boron by alkalimetric titration of aqueous solution of the residue. Pel1 and hlalissa (323) subjected organic compounds containing carbon and SUIfur to slow combustion; the products were trapped and determined by the relative-conductimetric method. From the stepwise increase in conductivity various fractions of the organic compounds could be analyzed. Terent'ev, Luskina, and Syavtsillo (415) determined carbon, silicon, and aluminum simultaneously. After wet combustion of the sample, CO, was absorbed in a soda lime tube and the silicic acid in the residue was converted to Na2SiFG and determined volumetrically. The aluminum was separated by electrolysiq on a mercury cathode and determined complexometrically. .A number of procedures have appeared for the simultaneous determination of elements in organic compounds but not including carbon and hydrogen. Belcher and Fildeq (22) determined chlorine, bromine, and iodine in the presence of each other after rapid combustion. The same authors (23) extended the method to include sulfur in addition to the halogens. Bondarevskaya and co-worker? (39) employed bomb combustion for the elements fluorine, silicon, and chlorine. Aqueous aliquotq were I\ ithdrawn for the titrimetric determination of each separately. Rittner and Culmo (354) treated the sample with concentrated HzS04 and catalysts and determined boron, nitrogen, and phosphorus separately in aqueouq aliquotf. White (446) proposed closed flask combustion for sulfur and chlorine in organic compounds. T h e SO4-, was titrated using 0.02N Ba(C104), as titrant and Thoron-
methylene blue as indicator, and the C1- was t'itrated in the same solution using mercuric nitrate solution and diphenylcarbazone as indicator. Hozumi (164) employed a funnel containing two chambers, one of which is filled with .\gI and the other with .ig granules for the absorption of halogens after combustion of organic compounds. From the decrease in weight of the silver iodide tube and increase in weight of the ot'her, the percentage and kind of halogens could be calculat,ed. Yoshikawa and Mitsui (452) absorbed halogens and sulfur on silver gauze which was weighed before and after combustion of the sample. The gauze was dissolved electrolytically and the SO4+ determined by complexometric titration. Hozumi and Mizuno (168) absorbed the halogens and sulfur in KOH solution in a funnel containing glass beads. ;in aqueous extract, was titrated potentiometrically using .Ag;1'03 solution for halogens, followed by complexometric titration for S04-2. Luskina, Terent'ev, and Syavtsillo (252) decomposed organic samples containing silicon and phosphorus with KzSzOs or H202 solution in concentrated H 2 S 0 4 . The silicic acid was coagulated using gelatin, filtered off, and determined separately. The phosphorus in the filt,rat,e was measured colorimetrically. Determination below the Milligram Range. Kirsten, Hozumi, a n d S i r k (211) and Hozumi and Kirsten (167) combust,ed decimilligram amounts of organic compounds containing carbon, hydrogen, and nitrogen in a sealed tube and measured the volume of the gases produced in t'he same tube over mercury under varying conditions for t,he simultaneous determinat'ion of the elements. Ralisch ( 4 4 1 ) for the same elements burned the sample in a continuous helium-oxygen stream and separated and determined the resulting C o n , H 2 0 , and Nzby gas chromatography. Belcher, Campbell, and Gouverneur (24) described a general procedure for Kjeldahl digestion with or without, pre-reduction w i n g a mercury catalyst for microgram amounts of organic compounds. Kanchukh (1.99) used a colorimetric ninhydrin method for nitrogen after digestion. Rottcher, van Gcnt, and Pries (40) proposed colorimetry after the addition of KaOC1 with manganese sulfate as catalyst to sulfuric acid digestion mixtures. Dixon and Shuel (83) described a special apparatus for the distillation of microgram amounts of XH3 after Kjeldahl digestion. Kirsten and Hozumi (208, 209) used sealed tube combustion and subsequent volumetric measuremmt of the nitrogen in the same tube for microgram amounts of samplr. The samr authors (166) and Hozumi (163) obtained the nitrogen content from the w i g h t of displaced mercury. VOL. 36, NO. 5 , APRIL 1964
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A number of ultramicro procedures have appeared for halogens in organic compounds. Kirsten (207) described two simple and rapid techniques in which diffusion is used for the absorption of the combustion products. Zak and Uaginski (454) used automated end point detection for microgram amounts of iodine. Oelschlager (306) proposed modifications to a previously-published method for fluorine while Soep (390, 391) determined the element colorimetrically after combustion of a cut-out spot after paper chromatographic separation. Uelcher and co-workers (26) employed flask combustion and titration with mercuric nitrate solution (diphenylcarbazone as indicator) for microgram amounts of chlorine, and a similar technique for sulfur (26) employing titration with barium perchlorate and Thoron as indicator. Dirscherl and Erne (79) proposed empty-tube combustion for the simultaneous determination of sulfur and halogens. The gaseous products were absorbed in peroxide solution and determined titrimetrically. Bhattacharyya, Uhaduri, and Banerjee (34) proposed complexometric titration for determining small amounts of phosphorus. Fennel1 and Webb (97) used sealed tube digestion and colorimetry with 1,lo-phenanthroline for microgram amounts of iron. FUNCTIONAL GROUPS
Oxygen Functions. Using t h e previously-published technique of infrared spectrometry, Anderson and Duncan (10) and iinderson, Herbich, and Zaidi (13) have investigated the causes of anomalous Zeisel alkoxyl reactions in certain compounds. Urancone (42), in a discussion of organic functional group analysis in industry, reported t h a t depending upon the structure of the compound some anomalous results may occur in alkoxyl determinations. Hozumi and Hazama (165) tested the alkoxyl apparatus recommended by the Committee on Microchemical Apparatus of the American Chemical Society and found incomplete removal of HI in the scrubber and some retention of alkyl iodide in the apparatus. Water was as suitable as a n y other wash liquid. Karpitschka (201) attributed the anomalous behavior of substituted pyrimidyl - trimethylammonium chlorides in the alkoxyl determination to some reaction of the N-methyl group with H I to form methyl iodide. Lebedeva and Pisaenko (243) determined alkoxyl groups in high molecular weight compounds by a modified Viebock and Schwappach method with good results. Klimova and Zabrodina (227) refluxed the sample with potassium iodide and phosphoric acid. Ascarite was used as the scrubbing agent. d description of 156 R
ANALYTICAL CHEMISTRY
the Zeisel apparatus with ground-glass joints and of the Friedrich apparatus has been published (43). Mitsui (280) presented a simple gravimetric method for the microdetermination of alkoxyl groups in which the purified alkyl iodide is absorbed onto a type 13-X molecular sieve. hlitsui and Kitamura (281) simultaneously determined alkoxyl groups from methoxyl through propyl by absorption on silica gel and subsequent volatilization into a gas chromatograph. Fukuda (111) combusted the alkyl iodides from methoxyl and ethoxyl groups to COz and iodine and absorbed each separately. From the molar ratio, the type and amount of each group could be calculated. hnderson and Duncan (1l ) differentiated esters and acetals from ethers by a total alkoxyl determination and by refluxing with hydrochloric acid. The method is not universal as ethers with unusually labile linkages also react. Crompton (69) determined alkoxide groups in organo-aluminum compounds by spectrophotometric determination of the alcohol liberated on treatment of the compound with acetic acid. Klimova and Zabrodina (216) determined carbonyl groups on a micro scale by oximation with a reagent consisting of ",OH. HC1 partially neutralized with triethanolamine. After standing the free base was determined alkalimetrically. Albertsson and Samuelson (7') precipitated the hydrazone in alkaline solution with hydrazine hydrochloride. The precipitate was separated, taken into solution, and p-dimethylaminobenzaldehyde added as a colorimetric reagent. Schmorak and Lewin (370) used the cyanohydrin method for carbonyl groups in starch. Ruch, Johnson, and Critchfield (357) proposed hydroxyammonium formate as an oximation reagent for carbonyl-containing compounds. Hennart (147) described modifications to a previously published method for the volumetric determination of oic-diketones. Burger, Gaizer, and Schulek (51) investigated the determination of hydroxylamine by oxidation with bromine chloride, potentially useful for determining excess reagent in carbonyl group determinations. Cochran and Reynolds (64) employed photometric titration using sodium borohydride for certain aldehydes (end point: disappearance of carbonyl band under ultraviolet light). Uudesinsky (49) determined reducible organic compounds including aldehydes by treating the sample with the mercury(I1) salt of EDT.l. The liberated E D T A was titrated complexometrically. Solymosi (393) described a ferricyanimetric titration of formaldehyde with osmium tetroxide as catalyst. Probsthain (338) proposed a number of volumetric methods for the determination of free
formaldehyde in thiourea resins. Sarrach (366) pointed out that the 2thiobarbituric acid test for aldehydes in irradiated samples must take into account the formation of peroxide, which would interfere. Plessing, Concha, and Brieva (333) presentedsome useful reagents for the determination of the aromatic aldehyde group. Jaulmes and Hamelle (180) suggested the addition of E D T A to the bisulfite solution in its iodimetric determination as air oxidation of S03-' is catalyzed by traces of copper. Burroughs and Sparks (52) investigated the iodimetric determination of acetaldehyde bisulfite and recommended the addition of isopropyl alcohol to prevent air oxidation and the inclusion of ,an alkaline borate buffer solution shortly before the end point. Crummett (71) proposed a spectrophotometric nitrite method for the primary hydroxyl group content of poly(oxypropy1ene) glycols. Stetzler and Smullin (401) determined the hydroxyl number of polyoxyalkylene ethers by acid-catalyzed acetylation. Gutnikov and Schenk (137) also used acid-catalyzed acetylation but converted the product to a hydroxamic acid which was determined colorimetrically. Vioque and Maza (440) proposed a similar colorimetric method for microgram quantities or organic compounds. Quattrone and Choy (340) recommended potentiometric titration to a set p H for the back titration of excess acetic anhydride in the microdetermination of primary alcohols. Karpov (202) determined methanol by oxidation with dichromate while L i p parni (250) proposed a colorimetric finish after oxidation of ethanol with mercuric oxide. Frei (108) oxidized hydroxy acids with potassium permanganate and determined the excess reagent by titration with a ferrous salt. Meluzova and co-workers (276) determined mixtures of primary and secondary alcohols by use of absorption spectra in the ultraviolet and infrared regions. Maros, Perl, and Schulek (266) differentiated aldonic acids and sugar dicarboxylic acids by the determination of carbon dioxide and formaldehyde formed by periodate oxidation. Huber and Gilbert (170) employed direct titration of phenols by bromine. The end point was detected by constant-current potentiometry. Ginzburg and Flegontova (122) proposed amperometric titration a t the rotating platinum electrode for phenolic groups in epoxy resins, employing K13rO3-KDr solution as titrant. Delgado (76) applied the coulometric technique to the bromination of phenols. Silin (382) presented a bromimetric and colorimetric method for bisphenol. Griffin
(f 30) employed a n isotope dilution technique for the determination of the same compound. M a and Yang (257) developed a radiochemical method for the microdetermination of tannins. The uranium complex of the polyhydroxy phenols is precipitated and the beta activity of thl. precipitate is meaiured. Pandya and Haldar (314) determined phenol. in aqueous solution by thermometric titration with alkali. Veno and Tachikawa (437) investigated various cathodes for the cerimetric titration of quinol. DeMarco and Marcui ( 7 7 ) offered soine improvements for the colorimetric (determination of salicylic acid. Friedemann, Weber and Witt (109) and Salova and h n t o n o v a - ~ ~ n t i p o v a (362) investigated the use of alkaline ferricyanide solution for the determination of reducing sugars. Malmstadt and Pardue (2629, and Guilbault and co-n orkers (132) presented enzymatic methods for glucose. Gallois (113) described a new electronic automatic yaccharimeter. The carboxyl group has been determined by decarboxylation followed by gas chromatography ( 2 5 6 ) . Several papers have been p iblished dealing with oxidative determination of the carboxyl group. Suzuki (406) proposed coulometric titration with electrolytically-generated manganese (111) and iron(I1) ion.. Mathur, Rao, and Choa dhary (271) determined formic acid by catalytic oxidation with ceric sulfate. Rao (344) used nitroferroin as indicator in titration? with the same reagent. This group of workers also (347, 348) proposed methyl orange as a n indicator in cerium(1I‘)titrations of oxalate. Polak, Pronlc, and den Boef (535) investigated the oxidation of certain acids stepwise with acidic permanganate and thon with alkaline manganate solution. Rao, Rao, and l l u r t y (348) emplo:;ed ammonium hexanitratocerate for rhe oxidation of oxalic and mandelic acids a t room temperature. Maros, Pinter-Szakacs, and Schulek (269) oxicized formic acid with mercuric chloride and determined the evolved COz by absorption in barium hydroxide solution. Muramatsu, Iwasaki, and Kojima (296) determined carboxylic end groups in poly(chlorotrifluorethy1ene) by infrared spectrophotometry. Dartos ( 1 7 ) used p-nitrophenacyl bromide as a colorimetric reagent for microgram amounts of carboxylic acids. Osterud and Prytz ( 3 1 2 ) employed polarography for the determination of aliphatic esters. The hydroxamic acid wave from the equilibrium mixture of the .ample with alkaline hydroxylamine is reproducible and proportional to the ester concentration. Formates have been determined by near-infrared spectrometry ( 3 3 6 ) and by oxidation with
iodine (439). Verma and Bose (438) estimated malonates by oxidation with iodine although a number of other compounds interfere. Inczedy and Gimesi (f7W) titrated diethyl malonate and its substituted derivatives in ethylenediamine sdution using potassium methoxide. A three-component mixture of the compmnds could be resolved by proper cheice of solvent. Hessler and Xlarsen (150) simplified the method for determining acid and saponification values of waxes with the aid of fluorescent indicators. Gore and Gupte (124) extended their previous method for the microdetermination of acetyl groups to 0or S-acetyl. Illewmer and Mlinko (278) determined acetyl and azido groups simultaneously. The acetic and hydrazoic acids produced by hydrolysis were titrated conventionally and then the azido ions were titrated cerimetrically. An alpha-acyl group introduced into lactones or lactams produced a bathochromic shift in the ultraviolet absorption spectra used by Buchel and Korte (47) for its determination. Onoe (310) improved Wiesenberger’s method for the determination of acetyl group by using dioxan as solvent and 50y0 sulfuric acid as saponification reagent. Pokorny and co-workers (334) compared several methods for the determination of peroxide groups in cosmetic products. Shurygin (380) analyzed benzoyl peroxide in the presence of free chlorine. Wolfe (448) determined hydroperoxides by reaction with a stable TiC1, reagent and spectrophotometry of the reduction product. Karvanek, Pokorny, and Janicek (203) presented iodimetric and colorimetric methods for active oxygen in washing powders. Decimilligram amounts of epoxyethane were determined by Jaworski, Zielasko, and Gasior (181) by hydrolysis and oxidation to formaldehyde n hich was treated with chromotropic acid. Kosenko (224)described a polarographic procedure for the simultaneous determination of ethylene and propene oxides. Obruba (303) proposed reaction with hydrogen iodide for the microdetermination of oxyethylene groups. The liberated iodine was determined by titration with thiosulfate solution. Pitter (552) described a colorimetric procedure for nonionic polyoxyethylene type surfactants. Seher (3’71) reacted polyoxyalkylene glycols with sodium tetraphenylborate and determined the complex precipitate by rnercurimetiic titration. Bolt man and lleroza (41) determined acetals and other compounds containing combined acetaldehyde groups by hydrolysis and colorimetric determination of the liberated acetaldehyde. Litvinenko and co-workers (251) proposed a general method for the microdetermination of
acid anhydrides. The samples were reacted with m-chloroaniline, and the excess amine was titrated potentiometrically with sodium nitrite solution. Hennart and Vieillet (149) determined acid chlorides by titration with perchloric acid in nonaquenus solution before and after the addition of mercuric acetate. Terent’ev (416) reacted acid halides (and sulfonyl halides) with an amine (hexamine) and determined the excess reagent by nonaqueous titration. Nitrogen Functions. Differential determination of alkimino groups by gas chromatography has been reported (266). Ishidate and eo-workers described dielectrometric titrations of amines using picric acid (176) and toluene-p-sulfonic and trichloroacetic acids (177). The titrations were followed by a high frequency circuit and were dependent on the difference in dielectric constant between the reactants. Hoffmann and Lysyj (154)determined primary amino groups by nitrosation followed by the analysis of the gaseous products by gas liquid chromatography. Usami (426) reacted diphenvlamine with mercuric acetate to give a product which exhibited a polarographic wave R hose height was proportional to the original concentration of the amine. Kuffner, Sattler-Dornbacher, and Humer (237) analyzed the reineckates of aliphatic amines by titration using silver nitrate solution and dichlorofluorescein as indicator. A report on the recommended specifications for the Van Slyke manometric apparatus has been published (402). Various amines were determined titrimetrically by Dafttary and Haldar (72) using either acids or sodium nitrite solution and thermometric detection of the end point. Quentin (341) and Higgins and Drinkard (151) proposed methods for the determination of ethylenediamine in the presence of other nitrogen-containing compounds. Moore and Dithl (295) recommended the addition of bisulfite solution to the perchloric acid digest of amino compoundq to prevent loss of nitrogen during distillation. Smith, Worrell, and Sinqheimer (389) investigated the amperometric titration of amine salts with sodium tetraphenylboron (TPB). Either anodic depolarization at the dropping mercury electrode or electrochemical oxidation of TPB ion a a s employed. In some caseq reqidual titration of the excess reagent with potawium iodide )\-as applied. Maros, P e d , and Schulek (267) determined certain amino alcohols by oxidation \tith periodate to yield formaldehyde and ammonia. Ruch and Critchfield (356) acetvlated nuxtures of amines and titrated the tertiary amine potentiometrically using 0.01S HC10,. l l a t r k a , Podqtata, and Sagner (273) studied the influence of temperature on the course of nitrite titration of VOL. 36, NO. 5 , APRIL 1964
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primary aromatic amines. Khomutov and Eberil (206) recommended certain conditions for the potentiometric titration of aniline by bromination. Delgado (76) employed bromination by the coulometric technique for aromatic amines. H e reported that the influence of p H was dominant and listed the recommended p H and bromine equivalents per mole for various amines. A number of reductimetric procedures have appeared for nitro and other reducible nitrogen groups in organic compounds. Tiwari and Sharma (419, 4%’) used titanous sulfate solution for the reduction of nitro compounds and titrated the excess reagent with alum or ferric sulfate solution and potassium thiocyanate solution as indicator. The use of a buffer solution containing acetic acid-potassium citrate made the reduction almost instantaneous. Fauth and Roecker (95) investigated the reduction of gem-di and tri-nitro compounds with titanium (111) chloride. Rigid control of the reaction conditions was necessary for reproducibility. Hovak and eo-workers (162) reduced nitro and nitroso compounds with concentrated HzS04-Cr0,. The liberated nitric acid was reduced with Devarda’s alloy to K H a which was distilled and determined titrimetrically. Juracek (186) investigat’ed the wet oxidation of organic nitrogen compounds with chromic acid. From the various products obtained, the simultaneous determination of several forms of nitrogen in a complex compound is possible. Pietrzyk and Rogers (331) investigated the effects of surface active agents on the half-wave potentials obtained in the polarographic reduction of aromatic nitro compounds. hlaricle (166) determined certain reducible organic compounds by coulometric generation of biphenyl radical ions. The reaction was followed potentiometrically and is not of general applicability because of side reactions. Ramachandran (343) employed sodium borohydride reduction followed by colorimetry for 2,4-dinitrophenylamino groups. Shinozaki and Okamoto (37’7) determined nitroglycerin by selective reduction with ferrous salts and back titration of the excess reagent with permanganate solution. Kulev and Kristalev (238) reported a photometric procedure for p-nitrothiobenzoic esters. Levitsky and Norwitz (247‘) proposed infrared spectrometry for the determination of nitrocellulose. Studeny and Uhrova (403) presented a new modification in the bromimetric determination of urea. Zarembo and Watts (455) detrrmined the carbodiimide function by reaction with oxalic acid to form disubstituted ureas. The excess arid was titrated in nonaqueous solution using sodium 158 R *
ANALYTICAL CHEMISTRY
methoxide. Uno and Miyajima (425) treated quaternary ammonium salts with methyl orange solution to form a colorless complex and titrated with 0.01N K2Cd14 to yield a red color. Berlin and Robinson (SO) precipitated quinine with dilituric acid and weighed the precipitate in a thermobalance. Danek (73) determined certain alkaloids colorimetrically, after precipitation as Reinecke’s salt. Tur’yan and Smekalova (424) reported an indirect polarographic method for cyclohexanone oxime and certain other compounds. Hennart and S’ieillet (148)proposed chelatometry for the volumetric determination of vie-dioximes. Dmitrieva and Bezuglyi (84) determined azobutyronitrile in polymers by polarography a t the dropping mercury electrode. Theivagt (41 7 ) employed methoxy-mercuration for the determination of cyclopropylamides. The samples were reacted with a methanolic mercuric acetate reagent and the excess reagent determined. Grekov and Shvaika (129) proposed potentiometric titration \\ith sodium nitrite for substituted oxadiazoles. Hlanka (56) reacted pyridine with cyanogen bromide and the product after hydrolysis was determined colorimetrically. Guriev and co-workers (134) employed high frequency titration for the determination of melamine with cyanuric acid. Singh, Sahota, and Gupta (385) used potassium periodate as a volumetric reagent for the estimation of organic derivatives of hydrazine. Grekov and hfarakhova (128) determined hydrazides of aliphatic acids by potentiometric titration with sodium nitrate solution. Sulfur Functions. Several methods for the determination of sulfur functions on the 0.1 meq. scale have been evaluated (256). Wronski (450) proposed mercurimetric titration of aliphatic thiols usingo-hydroxymercuribenzoic acid a$ titrant and thiofluorescein as indicator. Bruck and Baily (46) employed conductimetric titration with silver nitrate solution for mercapto groups in polycaprolactam fibers. Kolthoff and Eisenstadter (219) studied the application of the amperometric method to the mercurimetric titration of sulfhydryl groups. Palmer (313 ) used mercuric perchlorate as titrant for thiols, with either potentiometric or visual detection of the end point. Carr and 13it-.\lkhas (56) reported that the high results found in the argentiinetric titration of mercapto acid.; \\as due to the formation of insoluble polysilver salts (.\gS-RCOO;\g). Usami (427) dptermined phenothiazine in vinyl acetate by an indirect polarographic met hod. JVroniki (451) reported the use of sodium o-hydroxymercuribenzoate for the titration of thiourea and sulfides In
thiocyanates. For thiourea, Ginzburg (121) proposed a polarographic method at the rotating platinum electrode. Singh, Verma, and Saran (586, 587) used iodine chloride to ovidize the sample, while Koshkin (225) titrated the sample solution with mercuric nitrate solution using copper l-phenylthiosemicarbazide as indicator. Bukharov and Sysoeva (50) proposed bromatometric and mercurimetric titrations for thiourea and Lesz and eo-n-orkers (246) developed a n indirect complexometric method for thiourea and thioacetamide. For the latter compound, Claeys and eo-workers (62) employed oxidation with NaOBr in weakly alkaline solution and titrimetric determination of the excess reagent. Alicino (8) studied the applicability of the Zeisel alkoxyl procedure to the determination of S-alkyl groups. In general the method is valid but requires a much longer time and depends on the configuration of the rest of the molecule. .Inderson and Zaidi (12) applied their infrared spectrometric method to the reaction products of thio-alkyls and hydriodic acid. M a n y of these compounds do not yield alkyl iodides or release other volatile products. Thus the Zeisel alkoxyl procedure cannot be recommended as a general procedure for thioalkyls. Walisch, Hertel, and Ashworth (44.9) determined sulfonyl chlorides in the presence of the corresponding sulfinyl and sulfenyl chlorides by potentiometric titration with sodium sulfide solution. Procedures for the determination of isothiocyanates have been proposed by Venkataraghavan and Rao (436) and Stankoviansky, Rusina, and Szabadosova (397). Rronski (449) reported the direct titration of hydrolyzable sulfur using o-hydroxymercuribenzoic acid as titrant with thiofluorescein or Gal’pern, dithizone as indicator. Girina, Luk’yanitsa (114) have improved the iodometric potentiometric procedure for organic sulfides. Mathur, Rao, and Kachhawaha (272) reported the potentiometric titration of sulfonamides using butyl nitrate solution. Ruzicka and Kotoucek (369) determined some thiazines and thiazones by direct potentiometric titration with ascorbic acid solution. Unsaturated Functions. Horacek and Pechanec (159) described a modified Warburg manometer for the determination of double bonds by catalytic hydrogenation. Hartley and Hobson (141) determined the iodine value of fatty extracts of wool by a gravimetric procedure. The sample was reacted with bromine in a platinum dish and the product weighed after volatilization of the reagent. 13aumann and Gilbert (19) proposed constant-current potentiometry for the coulometric deter-
mination of bromine iiumbers. Be1en’skii and Baraboshina (28) studied microanalytical hydrogenation and described hydrogenation vessels and manometers and proposed a copper-palladium catalyst. Dassler ( 7 4 ) determined a diene by heating the mmple in a closed tube with maleic anhydride, the excess reagent being determined by iodometry. Philipp, Bartels, and Hoyme (329) compared available methods for olefinic linkages and concluded t h a t the addition of S03-2 with subsequent titration of hydroxyl groups most suitable for the analysis of vinyl monomers. Schmalz and Geiseler ( 3 6 9 ) proposed modification of reaction conditions for the analysis of olefinic material with perbenzoic acid to prevent side reactions with free iodine. Gorokhovskaya and Geller ( 1 2 5 ) , Geher and Vago (120), Horacek ( 1 5 8 ) , and Majewska and 1Jrbanowicz ( 2 5 9 ) have described polarographic or amperometric methods for monomeric and polymeric unsatura ;ed compounds. Bencze ( 2 9 ) proposed a colorimetric method for allyl chloiide in the atmosphere. Chen ( 5 9 , 6 0 ) and Johnson and Shoolery ( 1 8 5 ) have used the technique of nuclear magnetil. resonance for determinatisns of unsaturated compounds. Siggia, Hanna, and Serencha (38f)described the USP of differential reaction rates to analyzs mixtures of unsaturated compounds Gutterson and M a (138) determined mono-substituted acetylenic compounds on a micro scale by ionaqueous titration. The sample was reacted with silver perchlorate liberating perchloric acid which was titrtted with 0.01A’ tris-(hydroxymethy1)- aminomethane using martius yellow-crystal violet as indicator. Tur’yan ar d Romanov ( 4 2 s ) employed amperometric titration using Ag for the determination of acetylene. A solution of the sample had to be used as titrant rather than the reverse due to losses of sample during degassing. Usami ( 4 2 8 ) also used a polarogrsphic method for acetylene, applying it t o t h e adduct of the sample with mercuric acetate. Miscellaneous Functions. A number of nonaqueous titration procedures have been described for compounds with acidic properties. Cluett (63) studied the use of tetrabutylammonium hydroxide as titrant and butylamine as solvent for the titration of substituted phenylureas. Fijolka and Lenz (101) compared butyltriethylammonium hydroxide as titrant for weak acids to sodium methoxide. One advantage i s , its solubility in organic solvents while a disadvantage is the instability of the 0.OlN solution. Korenman, Perepletch ikova, and Etlis (223) and Rink and Riemhofer ( 3 5 2 ) described some indicators for the nonaqueous titration of arids. Procedures
have been proposed for acidic groups in humic acid ( 1 4 ) , for acylamidines @ I ) , and for lead styphnate (388). Reynolds, Little, and Pattengill (351) proposed a n ,V,N-dimethyl fatty amide (Hallcomid M-12) as a differentiating solvent for titrations with tetrabutylammonium hydroxide solution. Kreshkov, B y kova, and Kazaryan (228) resolved mixtures of acids containing u p to five compounds by titration with tetraethylammonium hydroxide. Shibazaki (376) dissolved acidic samples in diethylamine on a column of sea sand. Steam was passed through the column and the amine tied u p by the sample was distilled off and titrated. Hotz (161) described a n apparatus for titrations under anhydrous conditions. Ferrari and Heider ( 9 9 ) purified dimethylformamide by passage through a mixed resin bed and molecular sieves. Vallant (422s) determined acid numbers on a micro scale b y a n iodometric procedure. I n a series of papers (229, 231, 235, 234) Kreshkov and co-workers studied solvents and titrants for differential titration of bases and their mixtures with salts and acids. Ethyl methyl ketone was especially recommended as solvent. M u t h and co-workers (297) presented a nonaqueous titration method for aromatic AT-oxides in acetic anhydride. Wang and Hunter (443) described the titration of certain alkaloids with perchloric acid after their absorption on ion-exchange pellets added to t h e solution. Sokolowski and Kolka (392) titrated nitrogen glycosides potentiometrically using 0.01N HC104. Shkodin and co-workers ( 3 7 9 ) resolved mixtures of bases in acetic acid by conductimetric titration. Shkodin and Karkuzarki ( 3 7 8 ) described a n antimony electrode for titrations in acetic acid and its mixtures with acetic anhydride. Safarik (361) proposed p-toluenesulfonic acid as titrant and dichloromethane and colorobenzene as solvents for the determination of certain bases. Sano (364, 365) used the same titrant for the differential titration of amines by electrometric titration. Higuchi and co-workers (152) described a modification to their previously-published procedure to titrate very weak bases such as amides. Hitchcock and Elving (153) used a Lewis acid (aluminum chloride) for titration of organic bases by a high frequency technique. Mohilner and Reynolds ( 2 9 3 ) used dispersed sodium metal for the selective determination of active hydrogen. Amines and esters do not react. Martin and J a y ( 2 7 0 ) determined active hydrogen by reaction of the sample with diborane and determination of the increase in pressure manometrically. Pechanec and Horacek (322) reacted the sample with lithium aluminum hydride in a modified N’arburg ma-
nometer for the determination of active hydrogen. Gore and Gupte (123) compared four methods for the Cmethyl determination and recommended oxidation with Cr03-H2S04 in a sealed tube. Schenk and Ozolins (367) proposed tetracyanoethylene as a reagent for aromatic hydrocarbons, detecting the end point of the titration photometrically. Schenk, Santiago, and Wines (368) considered the reagent to be analogous t o metal-EDTA complexes and studied the usefulness of the pi-complexes of the reagent with aromatic hydrocarbons, aryl ethers, and phenols. A number of other methods have appeared which are concerned with hydrocarbon groups (254, 349, 4 0 9 ) . Rao and Rao (345) converted triphenylmethane dyes to carbinol bases and employed cerimetric titration for their determination. Kreshkov and co-workers in a series of papers (226, 227, 230, 232) presented a number of methods for the analysis of silicon-containing organic compounds. Fritz and Burdt (110) proposed reaction with bromine for SiH and SiCeH6 groups. Franc and Wurst (104) and Garzo, Till, and Till (119) determined silanes by application of gas chromatography. Terent’eva proposed a polarographic method for aluminum in alumino-organosiloxanes ( 4 1 2 ) . Hennart presented chelatometric methods for alkylmagnesium halides (144) and aluminum alkyls ( 14 3 ) . Molinari and co-workers (294) used gas chromatography for the analysis of organomagnesium compounds. Uernstein (Sf) applied gas chromatography to the analysis of phenyllithium, while Tagliavini, Belluco, and Riccoboni (408) proposed coulometry for the determination of hexaethyldilead in the presence of tetraethyllead. Nezu ( 2 9 9 ) used amperometric titrations for the determination of tetraphenyl-phosphonium chloride. 13ass (18) presented a colorimetric method for certain alkyl phosphites. Lada (240) used a n indirect method for the determination of water in certain organic compounds. Cobaltous chloride solutions was added to form a precil~itatewith water. The precipitate was separated, dissolved in water, and ~ complexometricallg. the C O + titrated Dirscherl and Erne (80) described a simple apparatus for the microdetermination of water in organic compounds by the Karl Fischer method. LITERATURE CITED
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ANALYTICAL CHEMISTRY
(307) Ogg, C. L., Kelly, R . B., Connelly, J. A,, Microchem. J . , Symp. Ser. 2, 427 (1962). (308) Okuno, I., Morris, J. C., Haines, W. E., ANAL.CHEM.34, 1427 (1962). (309) Olson, E. C., Houtman, R. I,.) Struck, W. A,, Microchem. J . 5, 611 (1961). (310) Onoe, T., Japan Analyst 9, 479 (1960). (311) Onoe, T., Furukawa, C., Otsuka, H., A n n . Rep. Takamine Lab. 11, 100 (1959). (312) Osterud, T., Prytz, M., Acta Chem. Scand. 15, 1923 (1961). (313) Palmer, T . A,, Dissertation Abstr. 22, 3366 (1962). (314) Pandya, P. K., Haldar, B. C., J . Sei. Ind. Res., India, B. 21, 503 (1962). (315) Pansare, V. S., Mulay, V. S . , Mikrochim. Acta 1961, 606. (316) Parsons, M. L., Pennington, S.N . , Walker, J. M., ANAL.CHEW 35, 842 (1963). (317) Pechanec, V., Horacek, J., Collection Czech. Chem. Commun. 27, 232 (1962). (318) Ibid., p. 239. (319) Pechanec. V.. Ibid.., 27., 1702 (1962). , , (320) Zbid., p. 1817. (321) Ibid., p. 2009. (322) Pechanec, V., Horacek, J., Ibid., 26, 1805 (1961). 1323) Pell. E., Malissa., H.., Talanta 9, ' 1056 (1662)' (324) Pella, E., Mikrochim. dcta 1962, 916. (32.5) Pesez, M., Bartos, H., Bull. SOC. Chim. France 1961, 1191. (326) Petukhov, G. G., Guseva, T. V., Z h . Analit. Khim. 17, 140 (1962). (327) Pfab, W., Z . Anal. Chem. 187, 354 (1962). (328) Ibid., 190, 414 (1962). (329) Phillip, B., Bartels, U., Hoyme, H.. Faserforsch. Textiltech. 12. 581 (1461). " (330) Pierson, R. H., ANAL.CHEM.34, 1642 (1962). (331) Pietrzyk, D. J., Rogers, L. B., Ibid., 34, 936 (1962). (332) Pitter, P., Chem. Ind. (London) 1962, 1832. (333) Plessing, B. C., Concha, E., Brieva, A. J.. Rev. Real Acad. Cienc. Exact. Fis. .cat. Madrid 55, 681 (1961). (334) Pokorny, J., Karvanek, M., Pokorna, V., Janicek, G., Sb. Vysoke Skoly Chem.-'l'echnol. v Praze Oddil P'ak. I'otravinareske Technol. 1960, 319. (335) Polak, H. L., Pronk, H. F., den Bocf, G., Z . Anal. Chem. 190, 377 (19(;2). (336) Powers, R. M., Tetenbaum, M.T., Tai, H., ANAL.CHEM.34, 1132 (1962). 1337) Pristavka., D.., Chem. Zvesti 15. 865 (1961). (338) Probsthain, K., Z. Anal. Cheni. 187. 104 11962). (339) 'Puschel, R., Stefanac, Z., Mikrochim. Acta 1962, 1108. (340) Quattrone, J. J., Jr., Chou, T., Mzcrochem. J . 6. 259 11962). (341) Quentin, R: J., ANAL:CHEM.34, 1170 (1962). (342) Itadmacher. W.. Hoverath, A., Gliceckauf 96. 1146 11960,. (343) Ramachahdran, L. K.,'ANAL.CHEM. 33, 1074 (19Gl). 1344) Itao. K. B.. 2. Anal. Chem. 184. ~
(345) Itan, 6. G., Itao, X . V., Ibid., 188, 8!) (1962). (346) Ilao, G. G., Rao, P. V . K., Murty, K . S..'l'alanta 9. 835 (1962). (347) liao, V. P. it., Suryanarayana, A., Z . Anal. Chem. 191, 200 (1!)62). (348) Rao, V. P. R., Satyanaraynna, I)., Suryannrayann, A,, Ibid., 191, 202 (1962).
(349) Rashkes, Y. V., Zh. Analit. Khim. 17, 627 (1962). 1350) Reitsema. R. H.. Allohin.' X. L.. A ~ A LCHEM.' . 33. 355'1 1MAl). , (351) -Reynolds, C.' A:, Little, J., Pattengill, hl., Ibid., 35, 973 (1963). (352) Rink, M., Riemhofer, M., Pharm. Ztg. Ver. Apotheker-Zt . 107,462 (1962). (353) Rittner, R. C., 8ulmo. R.. ANAL. CHEM.34. 673 11962) (354) Ibid., '35, 1268 (1963). (355) Ronzio, A. R., Microchem. J . 5 , 607 (1961). (356) Ruch, J. E., Critchfield, F. E., ANAL.CHEM.33, 1569 (1961). (357) Ruch, J. E., Johnson, J. B., Critchfield, F. E., Ibid., 33, 1566 (1961). (358) Rush, C. A , , Miller, J. I., Microchem. J . , Symp. Ser. 2, 449 (1962). (359) Ruzicka, E., Kotoucek, M., 2. Anal. Chem. 180, 429 (1961). 1360) Rvadnina. A. M.. Zauodsk. Lab. 27; 465 (1961). (361) Safarik, L., Mikrochim. Acta 1963, 26. (362) Salova, A. S., Antonova-Antipova, I . P., Lakokrasochnye Materiuly i ikh Prinaenenz'e 1960, 55. (363) Salzer, F., Mikrochim. Acla 1962, 835. (364) Sano, H., J . Pharm. SOC.Japan 81, 1310 (1961). (365) Ibid., p. 1313. (366) Sarrach, D., Xaturwissenschaftm 49, 394 (1962). (367) Schenk, G. H., Ozolins, M., A 4 ~ ~ ~ . CHEW33, 1562 (1961). (368) Schenk, G. H., Santiago, M., Wines, P., Ibid., 35, 167 (1963). (369) Schmalz, E. O., Geiseler, G., 2. Anal. Chem. 190, 233 (1962). (370) Schmorak, J., Lewin, M., ANAL. CHEM.33, 1403 (1961). (371) Seher, A,, Fette, Seifen, Anstrichmittel 63, 617 (1961). (372) Seto, J., Japan Analyst 9, 669 \
-
~
-
~
i 1m). \ - - - - /
(373) Shah, R . A,, Jabbar, S. A., Pakistan J . Sei. Ind. Res. 5, 162 (1962). (374) Shamri, Y. F., Khyl'ko, 0. K., Saootsns'ka. Y. B.. Ukr. Biokhim. Zh. 34: 443 11962). (375) ShaCollection Czech. Chern. (lommun. 26, 2298 (1961). (431) Ibid.. Talanla 8 . 446 11961). (432j Ibid.; Collectidn Czech. Chem. C‘ommun. 26, 2308 (1961). (433) Ibid.,Mikrochini. Acta 1962, 896. (434) Ibzd., p. 891. (435) Vecera, If., Lakomy, J., Lehar, L., Collection Czech. Chena. Comniun. 27, 1033 (1962). (436) Venkataraghavan, R., Rao, C. N. It., Chemzst Analyst 51, 48 (1962).
(437) Vena, K., Tachikaws, T., Japan Snalyst 9 , 873 (1960). (438) \‘erma, R. hl., Bose, S., J . Indian Cheni. SOC.38, 899 (1961). (439) Ibid., Anal. Chim. :letu 27, 176 (1962). (440) Vioque, E., hlaza, AI. P., Grasas Aceites (Seuille, S p a i n ) 13, 207 (1062). (441) Walisch, W.,Trans. Y . Acad. sei. Ser. I I 25, 603 (1963). (442) Walisch, W.)Hertel, I > . F.,Ashnorth, 11. R. F., Chini. Anal. 43, 234 (1961). (443) Wang, S. M.,Hunter, I{. IV., J . Pharm. Sei. 50. 265 11961). (444) Wang, C.LI.’, Tuan, H.,’Ch’i, H.-Y., Chem. Hull. Peking 1962, 53. (445) JVeir, H. E., Microchern. J . 6 , 109 (1962). (446) White) 1). C . $ AIifmchirrz. Acta 1962, 807. (447) Wielopolski, .4., Karjewski? J., Swierkot, J., Chcni. Anal., Warsou, 7, 1139 (1962). (448) Wolfe, C., ANAL @HEM. 34, 1328 (1962). (440) IVronski, &I., A n a l y s t 86, 543
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(4%) I d i d . , Chem. Anal., Il‘arsaw 6 , 859 (1961). 1451) l b z d . . 7. 1009 11962). (452) Yoshikawa, K.; Mitsui, T., Japan Analyst 10, 723 (1‘361). (453) Zabrodina, A . S., Levinn, S. Y . , Zh. Analit. Khim. 17, 644 (1962). (454) Zak, B., Baginski, E. S.,ANAL. CHEU. 34, 257 (1962). (455) Zarembo, J. E., Watts, I f . M., Jlicrochem. J . , Synip. Ser. 2, 591 (1962). (456) Zonov, Y. A., Zh. Analit. Khim. 17, 502 (1‘362).
Chemical Microscopy George G . Cocks, Bcrtfelle Memorial Institute, Columbus, Ohio
T
previous revicw in this series by Coven and Cox (73) covered the two-year period ending in October 1961. This review covers the two-year period ending in October 1063, b u t also contains references to a few earlier publications, and to some publications in November and December of 1963. It is obviously impossible to review all of the publications in which chemical microscopy has pla] ed a n important role. Therefore, no attempt has been made to cover publications in the biological, metallurgic>al, and geological applications of micrcscopy, except for those which seemed to be of general interest to chemical microscopists. Electron microscopy is not included, as it is the subject of a, separate review. An attempt has beer made to include references to publications in the fields of optics and crystallography which are of potential interest to chemical microscopists. HE
MEETINGS AND SYMPOSIA
T h e first iimerican meeting of the Royal Microscopical Society was held in April 1963 in celebretion of the ter-
centenary of the microscope in living biology. Although this meeting was primarily concerned with biological applications, a number of papers of general interest were presented. Among these were “Converters and Vidicons” by G. 2. Williams, “Staticons” and “Interference hlicroscopy and the Living Cell” by R . Barer, “Flying Spot Scanners” by P. O’B. hlontgomery, “Fluorescence hIicroscopy and the Living Cell” by D. Wittekind, “Phase Microscopy and the Living Cell” by G. G. Rose, “The Synthesis of New Methods Incorporating Microscopes for the Analysis of hlolecular Behaviour of Cells” by K. R. Porter, and “Photo Materials for Recording Low Light Intensity through the Microscope” by E. H. Land. T h e series of symposia sponsored by McCrone Research Institute was continued, with “Micro-62” being held in Chicago and “Micro-63” in Ihighton, England. The papers presented in the “Micro-63” meeting are being published in The Microscope and Crystal Front, which recently changed its name from The2 Microscope and Entomological Monthly. The American Society for Testing
and Materials (ASThI) sponsored a Symposium on Interference Microscopy at its June 1962 meeting in .itlantic City. The chairman was P. Bartels. A year later, in June 1963, the ASTN sponsored a Symposium on Resinographic Methods which was organized by T. G. Rochow. Eighteen papers on various aspects of resinography were presented. .Isa result of the interest in resinography demonst,rated at this symposium, the ASTN is taking steps to organize a new Committee E-23 on Resinography. ,In organizational meeting is planned during the national meeting to be held in Chicago, June 21-26, 1964. The Se\v York Microscopical Society has held two meetings concerned with chemical microscopy. The first was a symposium on Teaching l\Iic:roscopy, held in New York City February 1 and 2, 1963, under the chaimianship of T. G. Rochow. ‘ h e l v e papers were present,ed. On May 3. 1963. a 8ymposium on development of l‘cstilt Microscopy was held under thc rlii,wtion of F. Morehead. Ai Colloque International sur les Processus de Suclkation 3ur les Reactions des Gaz eur le5 116taus ct ProhVOL. 36, NO. 5, APRIL 1964
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