(204) Wallach, D. F. H., Surgenor, D. M., Soderberg, J., Delano, E., ANAL. CHEM.31, 456-60 (1959). (205) Watts, H. L., Ibid., 32, 1189-90 (1960). (206) Weiss, H. V., Lai, Ming G., ANAL. CHEW32, 475-8 (1960). (207) Weisz, H., "Microanalysis by the Ring Oven Technique," Pergamon Press, 1961. (208) Weisz, H., Mzkrochinz. Acta 1960, 703-5. (209) Weisz, H.,West, P. IT7., Mtkrochim. Acta 1960,584-5. (210) Wenger, P. E., KapBtanidis, I., Janstein, W. von, JILkrochim. Acta 1960,961-6.
(211) West, P. W., ~ A L CHEY. . 32, 71-9 (1960). (212) West, P.W., Diffee, J., Anal. Chim. Acta 25, 399-402 (1961). (213) West, P. W., Lorica, A. S., Anal. Chem. Acta 25, 28-33 (1961). (214) West, P. W., Weisz, Herbert, Gaeke, G. C., Lyles, George, ANAL. CHEM.32. 943 (1960). (215) West,' T. S:,Anhl. Chim. Acta 25, 301-12 (1961). (216) Ibid., pp. 405-21. (217) Weisenberger, E., Mikrochim. Acta 1960, 946-60. (218) Will, Fritz, 111, ASAL. CHEM.33, 1360 (1961).
(219) JTilliams, J. P., Microchem. J . 4 187-93 (1960). (220) Willis, J. B., ANAL.CHEM.33, 556 (1961). (221) Wilson, A. L., ilnalyst 86, 72-4 (1961). (222) YatsimirskiI, K. B., Chen. listy 54, 795-805 (1960). (223) Young, J. P., White, J. C., Ball, R. B., ANAL. CHEW32,928 (1960). (224) Ziegelhoffer, A, Hubka, M., Foglsinger, G., Chem. Zvesti 15, 158-60 (1961). (225) Zolotavin, V. L., Sannikov, Yu. I., T r u d y liral'sk. Politekh. Inst. 1959,
228-33.
Review of Fundamental Developments in Analysis
Organic Microchemistry T.
S. M A and MILTON GUTTERSON
Department of Chemisfry, Brooklyn College, Cify Universify o f New York, Brooklyn 7 0, N. Y.
T
review follows the last one (196) published without any duplication of references. It covers the original contributions in microdeterminations of the elements and functional groups that came to the attention of the authors during the period from October 1959 through September 1961. d s in the past, microdeterininations of physical constants and qualitative organic microanalysis are not included. The rei~iewprepared by Cheronis (60) is recommended to those who are interested in the latter topic. Weinstein and Wanless ( S l y ) , and Kiberly and Drake (380) have surveyed the recent developments in physical constant measurements. Since complete elemental analysis of a n organic substance became possible after the perfection of micromethods for determining oxygen and fluorine, the attention of tlie research workers in quantitative organic mic7roanalysis has been directed to the simultaneous determination of several elements with one sample, extension of functional group micromethods, rapid procedures and automatic operations, as me11 as quantitative analysis bflow the milligram scale. This is in line with the new concept of microchemistry which is concerned ith the principles and methods of chemical ehperimentation using the minimum quantity of material t o get the maximum amount of chemical information. HIS
ELEMENTAL ANALYSIS
Carbon and Hydrogen. Dorfman and Robertson (66) described modifications t o their previously published semi-
automatic procedure. The movable furnace was automatically controlled and nitrogen oxides were absorbed by manganese dioxide. The time for a determination was reduced to 15 minutes. T'ecera, Vojtech, and Synek (321) used automatic combustion with stepwise switching on of combustion zones in the presence of cobalto-cobaltic oxide as catalyst t o reduce the time to 3 to 8 minutes. Marzadro (209) combusted the sample in a short tube a t 690" C. using a cobalto-cobaltic catalyst with the oxides of nitrogen absorbed in a Pregl-type absorption tube. Arventiev, Leonte, and Offenberg (10) proposed short tube combustion in a rapid current of air and passed the vapors over a catalyst of 20% cobalto-cobaltic oxide on asbestos at 650" to 700" C. Kuck, Berry, and Barnum (184) described a n improved microcombustion furnace. The heating element \vas made of Kanthal wire and the ceramic material was constructed from commercial cordierite (magnesium aluminum silicate) lined with 0.003inch platinum foil. Stuck (290)has modified a previously described procedure employing a titrimetric finish for the determination of carbon, reducing the time t o 10 to 15 minutes. Greenfield (99) used I'regl combustion with the absorption tube replaced by a conductimetric cell for carbon determinations on 1-mg. samples. Gel'man and Van (91) employed the conductimetric method for both carbon and hydrogen using Pregl combustion. The water evolved mas reduced t o carbon monoxide over platinum and carbon black and thence to carbon dioxide over copper oxide.
Gas chromatography has been utilized for C-H determinations. Dusmalt and Brandt (68) and Sundberg and Maresh (293) converted the water formed in the combustion of the sample into acetylene with calcium carbide and determined the carbon dioxide and acetylene by thermal conductivity measurements. Vogel and Quattrone ($14) passed the carbon dioxide and water vapors directly into the chromatographic system for measurement. The accuracy for carbon was not as satisfactory as by the Pregl method while for hydrogen it was better. Cacace, Cipollini, and Perez (4.2) continuously oxidized gas chromatographic effluents over copper oxide, then converted the water to hydrogen gas using finely divided iron, and finally obtained the area under the carbon dioxide and hydrogen peaks with a n auxiliary column. Juvet and Chiu (140) employed closed flask combustion for the deterniination of carbon, using standard sodium hydroxide solution as absorbent, and back titrating the excess n-ith standard 0 . W acid. Cheng and Smullin (49) modified the method by using barium chloride solution to precipitate the carbon dioxide. The precipitate was dissolved in standard acid solution which was back titrated with standard base. Kainz and Horm.titsch (144-147) in a series of papers studied the factors affecting the oxidizing efficiency of tube fillings, their capacity, the use of mixed catalysts, and the deactivation which occurred on heating with oxygen. Probably the best catalyst is a copper oxide-cobalto-cobaltic oxide combinaVOL. 34, NO. 5, APRIL 1962
111 R
tion formed by heating a t 500" C. a mixture of copper oxide and cobaltous nitrate. Horacek, Iiorbl, and Pechanec (123) evaluated the efficiency of 28 catalysts and recommended CO&, CozO3 and silver, or Fez03 plus precipitated CuO. Vecera, Snobl, and Synek (308) studied the kinetics and mechanism of the catalytic rapid determination of carbon and hydrogen. Of the various catalysts studied, C0304 was recommended with a flow rate of oxygen of 12 cc. per minute, reducing the time for a determination to several minutes. Their apparatus was capable of complete automation. S'ecera and Snobl (307)studied the use of manganese dioxide for the absorption of nitrogen oxides. A gel [nfnO(OH)z]was found most efficient. Onoe (237-9) investigated a number of external absorbents for the oxides of nitrogen and concluded that n h O z and silica gel Rere the best. The nature of the absorption by n h O zand the dependence of its capacity on the method of preparation Fvere also studied. Active NnOz prepared from >Ins04 and K,lIn04 was recommended. Wood (322) devised a rapid method for fluoro-organic compounds. The SiF4 that formed on combustion was absorbed in an external tube packed with sodium fluoride and silver wool and maintained a t 270" C. Scott and coworkers (270) used a semimicro manometric method. The carbon dioxide and water were condensed, the carbon dioxide in a liquid nitrogen trap, and then each was vaporized separately into a mercury manometer. A list of 38 recommended test substances for the microdetermination of C and H has been published (128). Christman and Paul (51) described an anticoincidence counter to improve gas-proportional counting for the determination of C14and tritium after the dry combustion of organic compounds. Jeffay and Alvarez (134) absorbed the COZ after combustion of the sample containing CI4in ethanolamine solution. An aliquot was transferred to a solution containing a scintillator for counting. Buchanan and Corcoran (31) combusted the sample in a sealed tube with CuO, AlnO,, and CuCl2. The tube was opened in a vacuum system and the volume of C 0 2 measured while the Cl4 content wns obtained in a gas-proportional counter. Busellu, RIarzadro, and Rossi (41) described a combustion apparatus and manometric system for the rapid gas-proportional counting of C14. Kienitz and Riedel (160) employed combustion in a Liebig tube, the nitrogen oxides were reduced over copper, and the evolved carbon dioxide was measured in a vacuum apparatus. The C14 content was then determined in a gas-proportional counter after dilution with methane. 1 12 R
ANALYTICAL CHEMISTRY
The deuterium content of organic compounds was determined by Jones and MacKenzie (139) by the use of a n infrared spectrophotometric technique. Taniiya (29295) combusted the sample and reduced the mater to hydrogen over zinc and platinum. The gas was examined in a mass spectrograph for its deuterium content. Piibyl (248, 249) used beta-radiation for hydrogen determinations in liquid hydrocarbons. The deuterium content of water was measured by Arnett and com-orkers ( 9 ) by reaction with calcium hydride. The deuterium which was liberated was determined in a gas chromatograph by thermal conductivity using hydrogen as the carrier gas. Simon, Daniel, and Klebe (273) oAidized the sample in a glass bomb with potassium perchlorate. The carbon dioxide containing C14 \vas pumped off into a vacuum system and counted. The residue was treated with zinc amalgam and the evolved hydrogen was measured similarly. A novel method for deducing the chemical composition of a sample was proposed by von Ardenne, Steinfelder, and Tummler (315). The electronaddition ionization technique of mass spectrometry was used to determine the CI3 to CL2ratio from which the number of carbon atoms in a molecule could be predicted. Oxygen. Kirsten (161) described a simplified and rapid method for the direct determination of oxygen. The carbon monoxide produced was reacted a i t h anhydro-iodic acid and the reaction products were absorbed and weighed in a tube containing Ascarite and Dehydrite. Sulfur and halogens were previously absorbed in a liquid oxygen trap. Gel'man, Wang, and Bryushkova (92) reduced the time for an analysis to 10 minutes by a rapid flow of the inert gas, a greater length of catalyst, and automatic movement of the furnace. The carbon dioxide finally produced was determined by measurement of the conductivity of the alkaline adsorbent. Mizukami and Ieki (226) reacted the carbon monoxide produced after the decomposition of the sample nith anhydro-iodic acid in a glass funnel. The loss of neight of the funnel mas used to determine the oxygen content. Korshun and Bondarevskaya (176) proposed preliminary pyrolysis of the sample with nitrogen a t 900" to 1000" C. The oxides produced 11ere converted to carbon monoxide by passage through a 5-em. length of carbon. The gas was then oxidized to carbon dioxide over cupric oxide. Fbdmacher and Hoverath (269) eliminated the interference of sulfur, which, because of the formation of carbon disulfide, would yield carbon dioxide, by incorporating a layer of copper beyond the combustion furnace. RIizukami,
Ieki, and Numoto (227) described an improved purification train for eliminating the last traces of oxygen from nitrogen gas by the use of Raney nickel. Nitrogen. A number of rapid methods for the Dumas determination of nitrogen have been described. Gustin (106) employed an automatic setup capable of six determinations an hour. Features are magnetically stirred POtassium hydroxide solution, two furnaces, one a t 850" C. filled with cupric oxide and the other a t 400" to 500" C. with copper and cupric oxide, and measurement of the nitrogen gas in a 5-ml. capacity syringe. Canal and Alemanni (49) used t n o nitrometers for semimicro determinations. Levy and Cousin (198) modi5ed the Schoniger apparatus, including a simplified gas flow, replaceable packing, and movable electric furnaces. Leger 1190) described an apparatus and simplified procedure suitable for both micro- and semimicrodeterminations. An apparatus has been patented (240) which consists of tn-o concentric tubes filled with cupric oxide wire partially reduced with hydrogen gas before combustion of the sample. The British Standards Institution (30) has published the specifications for the standard apparatus for micro Dumas determinations. A modified nitrometer using plastic components has been described by hlitsui (224) and by Miller and Latimer (221). Stehr (284) proposed a technique for calibrating nitrometers by introducing nitrogen gas into the instrument with a microburet. Eder (71) observed the gas flow in the nitrogen combustion train acoustically by clipping a wire to the bubble counter and feeding the signal to an amplifier and speaker. Kainz and Hainberger (143) described an automatic apparatus for the determination of nitrogen by Pregl's method. Gore and Kulkarni (36) reported that pure cupric oxide was unsatisfactory as a paching a t 730" C. Therefore a second roll of copper gauze was placed within the end of the hot zone. Trutnovsky (301) combusted the sample in oxygen produced from the reaction of manganese dioxide and hydrogen peroxide, with the excess oxygen entering a guard tube containing copper powder at 550" C. Vecera and Synek (309, 310) combusted the sample in carbon dioxide and oxygen, the latter being obtained from the electrolysis of a solution of sulfuric acid. The hot gases (750" to 900°C.) were passed over a packing of CoaOa on corundum and thence over copper a t 500" to eliminate the residual oxygen. Kirsten (163) studied the use of various metal oxides (CuO, KiO, and CoaOJ for the tube packing. Narita and
Ishii (230) combusted the sample in a platinum boat with MnOr for 10 minutes in a furnace a t 950" C., 5 additional minutes were used to expel all the nitrogen gas. The combustion tube could be connected to two nitrometers. Kainz and Kasler (163) investigated the nitrometer gas evolved during combustion and found some methane present using Dumas combustion a t 700" C., no methane using the Pregl technique, and considerable methane with automatic combustion. By raising the temperature of the automatic combustion to between 850" to 900" C., all traces of methane were eliminated. Hochenegger (122) described a simple and easily constructed device for producing pure carbon dioxide from potassium carbonate and sulfuric acid to be used for Dunus nitrogen deterniinations. Hubsch and Kehring (126) compared the Kjeldahl and Dumas procedures for saniples of animal origin and found both to be of equal precision. They recommended the use of 307, hydrogen peroxide to shorten the Kjeldahl digestion time. Cepciansky and Chromcova (47) suggested a new digestion mixture for Kjeldahl nitrogen composed of sulfuric and phosphoric acids plus cupric sulfate monohydrate and selenium powder. Bradstreet (28) digested the sample rvith sulfuric acid and sucrose and then added potassium sulfate and selenium. For pyridine compounds, a mixture of sulfuric and phosphoric acids was employed. The procedure was not applicable to aliphatic secand tert-nitro compounds. Fojtova and Purs (80) described a digestion flask ivith the neck bent a t an angle of 135 degrees which was more satisfactory than the conventional Kjeldahl flask. Milner and Zahner (2.23) used 0.01N sulfaniic acid with boric acid in the receiver for the titration of traces of ammonia using methyl red-alphszurin as indicator. Durcl; (39) eliminated the distillation step after digestion with sulfuric acid and hydrogen peroxide. An aliquot was treated with Kessler solution and the absorptivity a t 450 mp compared to a calibration curve. Sulfur. The closed flask combustion technique has cont'inued to receive the most interest. Steyermark rind con.orkers (286)reported that the oxygen flnsk technique yielded theoretical results for sulfhydryl and sulfonamide groups while the Carius method gave low results. Tickers and Kilkinson (313) concluded that the flask combustion technique using titration with barium perchlorate gave results comparable to standard methods. However, this titrant was not satisfactory for compounds with a high proportion of nitrogen. Soep and Demoen (281) compared three methods for the volumetric determination of sulfate after
the combustion-titration with barium perchlorate and thoron as indicator, with barium nitrate and sodium aliaarinsulfonate as indicator, and with lead nitrate and dithizone as indicator and found the latter procedure to be the best. Steyermark and coauthors (286) used dilute sodium hydroside solution as the absorbent. After combustion, the solution was treated with fuming nitric acid or bromine and titrated with 0.01N barium chloride and tetrahydroxyquinone as indicator. Khite (318) removed interfering cations with an ion exchange column and then titrated the sulfate with lead nitrate using dithizone as indicator. Bartels and Hoyme (15) used an indirect complexometric finish after the closed flask combustion. Excess barium chloride solution was added and back titrated with EDTA. Boos (24) developed a similar technique using flask combustion with hydrogen peroxide solution as the absorbent. Flask combustion followed by precipitation of sulfate with barium perchlorate, and measurement of the activity of the precipitate was used to determine sulfur-35 (110). Alazor, Meisel, and Erdey (215) reacted the sample in a test tube with molten potassium. After the excess metal was destroyed, the solution was titrated in the dark using O.OIN [Fe(CX)e]- 3 with lumiiiol as indicator. The same authors (214) compared a number of methods for the microdetermination of sulfur. Ishidate and Kimura (129) combusted the sample using Pregl's method, absorbing the sulfur dioxide in hydrogen peroxide, and titrated the solution with EDTA in the presence of excess barium ions. Dixon (64, 65) absorbed the sulfur on electrolytic silver and then after extraction of the silver sulfate with hot water, titrated the silver ions with standard potassium iodide solution. A similar procedure (291) employed titration with 0.OlN XH4SCiY for the determination of the silver ions. Halogens. A number of modifications of the closed flask combustion technique have been described. Martin and Deveraux (204) used electrical ignition. Eder (76) modified the stopper to contain a glass loop to hold the sample in a roll of filter paper. Bennewitz (20) combusted liquids in thin-walled bulbs rn rapped in filter paper. The oxygen flask method was used by Olson and Krivis (234) for chloride. The end point was detected coulometrically using electrolytically generated silver ions. Haslam, Hamilton, and Squirrel1 (116, 117) used a flask modified both for electrical firing by remote control and for potentiometric titration. The absorbent contained sodium hydroxide and sodium
bisulfite and the chloride ions were titrated autoniatically with 0.01N silver nitrate solution. Cheng (48) used potassium hydroxide and hydrogen peroxide as the absorption solution and titrated the halogens in ethyl alcohol solution using 0.02N mercuric nitrate a s titrant and diphenylcarbazone as indicator. White (319) proposed essentially the same conditions with close control of the apparent p H of the solution before titration. In the presence of sulfur, barium chloride solution was added before the titration. Kewman and Tomlinson (231)employed a potentiometric finish after flask combustion using 0.0LV silver nitrate solution. Sokolova, Orestova, and Sikolaeva (18.2) employed 0.01N mercuric nitrate or perchlorate for chloride or bromide using diphenylcarbazone as indicator. Iodine was determined iodometrically after conversion to iodate. Fildes and hlacDonald (79) employed a mercurimetric finish or oxidation with hypochlorite for bromine and with bromine for iodine. In both cases the bromate or iodate were determined iodometrically. Cook (57) proposed oxygen flask combustion with solid sodium nitrate added to the sample. Chloride and bromide were titrated with mercuric nitrate (0.025N) using diphenylcarbazone as indicator, and iodide similarly in the presence of pyridine after reducing free iodine and iodate with hydrazine solution. Lysyj (195) used a spectrophotometric finish for chloride. After flask combustion, mercuric chloranilate !vas added and the liberated chloranilic acid measured colorimetrically. Johnson and Vickers (138) reported that the closed flask combustion technique as applied to the determination of iodine in pharmaceutical substances was suitable for routine work. Jenik, Jurecek, and Patek (136) determined iodine by decomposition of the sample with magnesium, conversion of the iodide to iodate, and subsequent titration of iodine mith 0 005N sodium thiosulfate. The error in the method due to elementary carbon was eliminated by adding Alfa ions (1%). Potassium fusion to decompose the sample was used by LIazor, Meisel, and Erdey (216). The halogen was deterrnined by titration with 0.01 to 0.002-V silver nitrate using Variamine 131ue as indicator. Uukina and RIoizhes (38) employed a similar technique but finished by adding excess silver nitrate solution and back titrating with potassium iodide solution using starchiodine as indicator. Kirsten (166) determined halogens by treatment with sodium nitrite solution, destruction of the excess, and potentiometric titration using silver nitrate solution. The sample was decomposed either by the oxygen flask method or by combustion combined with hydrogenation. VOL. 34, NO 5 , APRIL 1962
113 R
Ishidate and Kimura (130) absorbed the halogen evolved by micro Carius combustion in sodium bisulfite solution. The halide was precipitated as the silver salt, collected, and dissolved in KZNi(CK)d solution. The liberated S i + 2 was titrated with 0.03N EDTA solution. Abramyan and Sarkisyan (1) used sealed tube combustion with potassium permanganate (300" to 500' C. for 1 hour). dfter the destruction of the excess permanganate and addition oi hydrogen peroxide, the halide was titrated with standard mercuric nitrate solution using diphenylcarbazone as indicator. Meier ($17 ) employed combustion in a quartz tube at 1050" C. The gases were passed through a packing of silver iodide liberating iodine which was determined volumetrically after conversion to iodate. Sulfur interfered. Decomposition of the sample in a metal bomb with sodium peroxide, followed by titration of the iodide using 0.01N mercuric nitrate solution and diphenylcarbazone as indicator, was proposed by Urrutia, Ramirez, and Aguayo (304). Coulson and Cavanagh (58)described an automatic chloride analyzer employing coulometric titration. Maruyama and Sen0 (208) used flame spectrophotometry, combusting the sample in the presence of cupric nitrate, and measuring the band spectra of cuprous chloride. Martin and Floret (806) decomposed the sample by preliminary pyrolysis with hydrogen, followed by combustion with oxygen. The evolved gases were absorbed in a known volume of a standard solution, the nature of which depended upon the substance to be determined. Steyermark and coworkers (887) employed a modified flask combustion technique for fluorine compounds. The fluoride-containing solution was titrated photometrically with 0.01N thorium nitrate using sodium alizarinsulfonate as indicator. In the presence of mercury, phosphorus, or arsenic, prior steam distillation was necessary. Kondo (173) decomposed fluorine containing organic compounds in a micro bomb and titrated the adjusted solution !\it11 0.01-Y aluminum chloride and Eriochrome Black T as indicator. Sass, Eeitsch, and Morgan (264) liberated the fluoride from phosphoroand phosphonofluoridates by treatment nith sodium ethoside. The fluoride was then determined by titration with thorium nitrate and Alizarin Red S as indicator. Johnson and Leonard (137) proposed oxygen flask combustion and a colorimetric finish €or fluoride after the addition of alizarin coinplexan and ceric nitrate solution. Olson and Shaw (256) added thorium chloranilate after flask combustion, and determined the fluoride spectrophotometrically by comparison to a standard curve. 1 14 R
ANALYTICAL CHEMISTRY
Phosphorus, Arsenic, and Mercury. A number of papers have appeared concerned with the closed flask combustion method for the decomposition of organic compounds containing phosphorus. Kremsbrucker (179) used a colorimetric finish after reaction with ammonium molybdate. Puschel and Wittmann (151) titrated the liberated P04-3 with 0.005N Ce+3 using Eriochrome Black T as indicator. Meier (918) determined the phosphorus indirectly by adding standard lead nitrate solution and back titrating with 0.01.N KHzP04 solution using Eriochrome Black T as indicator. The results were 3 to 5% too low. Dirscherl and Erne (68) reported that these low results were caused by retention of some phosphorus in the carbon left on the platinum gauze. The use of a larger flask was recommended along with the addition of (XI14)~S,08to the sample. Fennel1 and F e b b (?'6), after decomposing the sample with sodium peroxide, determined the phosphorus gravimetrically as the quinoline molybdophosphate. Kirsten and Carlsson (164) described improved procedures for the mineralization of the sample and for spectrophotometric measurement employing amyl acetate as extractant. Bartels and Hoyme (14) compared several methods for the decomposition of the sample and for the determination of phosphorus. Tuckerman and coworkers (308) digested the sample containing arsenic with perchloric acid t o liberate the arsenic which was converted to arsenious acid and titrated with 0.005N iodine solution. h colorimetric finish as heteropoly molybdenum blue was also employed. Fournier (81) refluxed an arsenic compound with aqueous sodium carbonate and determined the arsenic as the molybdenum blue complex. Mercury in organic compounds was determined by Martin and Floret (205) gravimetrically by combustion of the sample and absorption of the mercury on gold leaf, or volumetrically by pyrolysis with hydrogen, followed by combustion with the oxyhydrogen flame and absorption of the gases by bromine solution. After the addition of EDTA solution, the excess was titrated with 0.01N sodium diethyldithiocarbamate. Mercury mas also determined by Hetnarski and Hetnarska (120) by precipitation nith the sodium salt of 2-mercaptobenzothiazole, and titration of the excess reagent with 0.01N iodine solution. Other Elements, Yasuda and Rogers (527) employed oxygen flask combustion, mixing the sample with sucrose, for organoboron compounds. The determination was completed by coulometric titration in the presence of mannitol. Shaheen and Braman (2'71) oxidized the sample with fuming nitric
acid in a sealed tube. After neutralization of the strong acid, mannitol was added and the mannitol-boric acid complex titrated potentiometrically. Flask combustion using sodium hydroxide solution as absorbent was the basis of a method for boron (232). The solution was neutralized to methyl red, mannitol and phenolphthalein added, and the titration completed with 0.02S sodium hydroxide solution. Neier and Shaltiel (219) determined selenium in organic compounds by flask combustion or combustion in a quartz tube followed by reaction with acidified potassium iodide to liberate iodine which was titrated nith 0.01-V sodium thiosulfate solution. Zabrodina and Khlystova (331) described modifications to their procedure for selenium for compounds containing chlorine, bromine, or sulfur. Dingwall and Williams (61) treated an aliquot of the solution resulting from the decomposition of the sample with sulfuric and nitric acids with chloropromazine hydrochloride and measured the absorptiyity a t 420 iiip for selenium. Ceausescu (46) determined sodium by precipitation as sodium zinc uranyl acetate. The precipitate \vas dissolved in water, the solution passed through an ion exchange column, and the liberated acetic acid titrated with standard base. Fedoseev and Grigorenko (7'5) employed magnesium metal for the decomposition of the sample to determine alkali metals. After the decomposition, the solution was titrated with standard acid or ashed to yield the metal sulfates. Silicon was determined by wet oxidation yielding a precipitate of Si02which, after solution, was treated with ammonium fluoride in the presence of standard acid to form the fluorosilicate ion (299). The excess acid was then back titrated. Riemschneider and Petzoldt (255) described a semimicro technique for manganese in organic compounds. Simultaneous Determination of Several Elements with One Sample. Zabrodina and Egorova (330) determined carbon, hydrogen, and halides simultaneously by absorption of the halides on copper after combustioil of the sample. Klimova and Merkulova (166) absorbed the halides on electrolytic silver in a quartz dish a t the end of the combustion tube. Klimova and Zabrodina (169) proposed a procedure for carbon, hydrogen, and nitrogen in which the nitrogen oxides produced during combustion were absorbed on a mixture of potassium dichromate and sulfuric acid on silica gel. The Anhydrone tube was maintained a t a temperature of 75Oto 85" e. to prevent any nitrogen oxide absorption. Margolis and Shevkoplyas (200) employed the same absorbent for the nitric oxides using combustion in a
quartz tube packed with the decomposition product of silver permanganate. -4mino nitrogen was not converted quantitatively to nitrogen oside. Klimova and llukhina (167) determined carbon, hydrogen, sulfur, and halogens on one sample. After combustion the carbon dioxide and water were absorbed as usual. The halogens were absorbed on silver a t 420" C. while the sulfur dioxide was retained by a filling of ConOa,which was extracted nith water and the solution titrated with standard barium nitrate solution. llalissa ( I N ) , in a rapid method for carbon, hydrogen, and sulfur, employed a conductimetric finish for each element. Sfter combustion, the carbon dioxide was absorbed in dilute sodium hydroxide solution. The water evolved \vas converted to acetylene, and finally combusted t o carbon dioxide and measured as above. The sulfur dioxide was absorbed in dilute titanium chloride solution. .4 rapid method (176) has been proposed for the simultaneous determination of carbon, hydrogen, halogens, and mercury. The latter was determined gravimetrically by absorption on silver. In the absence of halogens, Lebedeva and Fedorova (1S9) combusted the sample in a quartz tube containing silver permanganate and determined the mercury volumetrically after absorption in nitric acid solution. Terent'ev and Luskina (297) were able to analyze simultaneously for carbon, halogens, nitrogen, and metals on one sample using wet oxidation with sulfuric acid and CrOa. The gases evolved were passed through a layer of CrOa on Halogens n-ere pumice a t 700" C. absorbed in hydrazine solution and determined by Volhard titration, while the carbon dioxide was absorbed on hscarite. The nitrogen in the residue, fixed as ammonium sulfate, was determined by the Kjeldahl method. Metals were also determined on the residue. The simultaneous determination of carbon, hydrogen, and fluorine (90) was described in which any fluorine retained after combustion is removed by pyrohydrolysis. Chumachenko and Aliroshina (52) employed catalytic destructive hydrogenation for the determination of halides and sulfur. The sample was heated in a stream of hydrogen and the evolved hydrogen halides and hydrogen sulfide were absorbed in 30% potassium hydroxide solution. Aliquots were taken for conventional analysis. Giesselmann and Hagedorn (93) used the osygen flask method for sulfur and either chlorine or bromine. The sulfur was determined by titration with standard barium perchlorate solution and the halide with standard silver perchlorate solution and dichlorofluorescein as indicator. Pella (243) combusted the
sample automatically in a tube fitted with porous platinum frits for halogens and sulfur. The halogens were titrated with mercuric perchlorate solution and diphenylcarbazone as indicator whereupon thorin was added and the solution titrated to the second end point using barium perchlorate solution. Chlorine and bromine were determined simultaneously by Sauciuc (266). Total halogen was determined colorimetrically using Hg(SCX)* and (P\TH&SO4-Fe(S04)3 and after reaction with lead dioxide and sulfuric acid, and filtering, the chloride alone by the same procedure. Greenfield, Smith, and Jones (100) employed Pregl-type combustion in a closed system n-ith hydrogen peroxide solution as the absorbing liquid for halogens. These n-ere determined simultaneously by amperometric titration, varying the conditions for each individual halide. Iionovalev (174) described a procedure for the simultaneous determination of nitrogen, chlorine, and bromine. Eger and Lipke (73) proposed a semimicro method for fluorine and phosphorus. After fusion of the organic sample, the resulting solution was passed through an ion exchange column and each element eluted separately. Gel'man and coworkers (89) analyzed for nitrogen and fluorine simultaneously. The sample was combusted in a silica tube a t 900" C., packed Ii-ith nickel and magnesium oxides in a current of carbon dioxide. The nitrogen was collected in a nitrometer and the hydrogen fluoride liberated from the residue by pyrohydrolysis ith steam. The fluoride was finally titrated with thorium nitrate. Fennel1 and Webb (77) proposed a semimicro technique for determining silicon and phosphorus on one sample. Either sealed tube digestion with nitric and sulfuric acids, or metal bomb combustion with sodium peroxide was used. In the former, the phosphorus was precipitated with nitratopentaminocobaltinitrite and the silicon dioxide weighed directly; in the latter, the phosphorus was precipitated as quinoline molybdophosphate and the silicon dioxide decomposed with hydrogen fluoride. Terent'ev, Fedoseev, and Ivashova (296) decomposed the sample in a test tube with magnesium (or calcium) metal. Nitrogen was determined by titration of NH4+,sulfur by titration with standard iodine solution, and halogens by titration with standard silver nitrate solution. Gray, Clarey, and Beamer (98) used the technique of beta ray back scattering and transmission for organic compounds containing hydrogen, carbon, nitrogen, oxygen, and fluorine. This method is applicable t o liquid samples. Determination below the Milligram Range. Cacace and corrorkers
(42) examined gas chromatographic effluents for carbon and hydrogen analysis. The compounds were combusted continuously over copper oxide to carbon dioxide and water. These gases were then separated by an auxiliary column and determined in a thermal conductivity cell. Microgram amounts of sulfur \%ere determined by Diaon (64) employing the open tube combustion technique. The sulfur oxides mere absorbed onto extracted metallic silver which IWS with nater and the Ag+ titrated potentiometrically 11ith potassium iodide solution. Granatdli (97)proposed reaction with Raney nickel to produce hydrogen sulfide nhich was titrated with mercuric acetate solution and dithizone as indicator. Gustafsson (105) reduced the sulfate ions t o hydrogen sulfide using sodium dihydrogen phosphate and hydriodic acid. A colorimetric finish was proposed converting the hydrogen sulfide to methylene blue. The yield, however, was only 6570, Robinson (256) employed a flame photometric technique using reference to a standard curve for microgram amounts of sulfur. Gutbier and Boetius (107) devised a miniature Pregl apparatus employing the Dumas technique for microgram amounts of nitrogen and reported reproducible blanks. Roth (261) used Kjeldahl digestion and Nesslerization. The reagents were purified to maintain lo~vblanks. Belcher, Leonard, and West ( I S ) proposed a colorimetric procedure for fluorine. After closed flask combustion, alizarin complexan and ceric nitrate were added to develop a blue color, the absorptivity being measured at 610 mp. Hall (111), after ashing the sample, collected the hydrogen fluoride on filter paper by diffusion. The paper was extracted and the solution titrated with 0.001.V thorium nitrate using sodium alizarinsulfonate as indicntor. Blinn (23) described the preparation of sodium biphenyl reagent useful for the determination of microgram quantities of organic chlorine. A coulometric technique based on internal electrolysis \vas proposed by Kis and Shejtanow (165) for small amounts of iodine, Bottcher, van Gent, and Pries (26) proposed rapid digestion using 7Oy0 perchloric acid in a sealed tube for submicro phosphorus determinations. Gutenmann and Lisk (108) used closed flask combustion for small quantities of mercury. After combustion, extraction with dithizone was employed with a spectrophotometric finish. Born and Riehl (25) determined very small amounts of oxygen in solids by activation. For the simultaneous determination of selenium and mercury, Olson and Shell (236) employed x-ray VOL 34, NO. 5 , APRIL 1962
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fluorescence. Kotrly and Vrestal (177) determined bismuth and lead by titration with 0.001M disodium EDTA in the presence of xylenol orange. The end points were detected photometrically. FUNCTIONAL GROUPS
Oxygen Functions. Budesinsky and Korbl (36) determined acetals, ketals, and vinyl ethers by simultaneous hydrolysis with hydrogen bromide and oxime formation n ith hydroxylamine hydrochloride. The excess hydroxylamine \vas titrated potentiometrically with potassium ferrocyanide. Terent’ev and coworkers (298) reacted anhydrides of carboxylic acids with a secondary amine and determined the excess amine acidimetrically. Gas chromatography has been proposed by Springler and Market (283) for the determination of acetyl and formyl groups. The sample was reacted with methanol and hydrochloric acid to form the methyl acetates and formates which were separated and determined in the chromatographic system. Kainz (142) described the partial automation of the acetyl group deterniination which involved the distillation step. The apparatus consists of a pump controlled by a relay for adding successive amounts of water. Benson and Turner (21) acetylated the sample with radioactive acetic anhydride and measured the specific activity of the separated and purified product. Ludowieg and Dorfman (194) determined microgram amounts of N-acetyl by hydrolysis in a sealed tube nith hydrochloric acid and methanol. The methyl acetate formed was determined colorimetrically as the ferric hydroxamic acid complex. Budesinsky and Korbl (35) studied the errors in the Zeisel alkoxyl determination and recommended the addition of a constant amount of a 2.170 formic acid solution for destroying excess bromine. The use of sodium antimonyl tartrate as a scrubber was advocated. For samples containing sulfur, Sobue, Hatano, and Arai (279) proposed absorption of the alkyl iodide in pyridine rather than silver nitrate solution. The complex formed was determined colorimetrically. Cundiff and hiarkunas (80) also absorbed the alkyl iodide in pyridine but titrated the complex as a weak acid with tetrabutylanimonium hydroxide and azo violet as indicator. KO scrubbers were necessary as the interfering substances were titrated as strong acids. Anderson and Duncan ( 6 ) proposed soda asbestos as a solid scrubber for the Zeisel alkoxyl determination. The same authors (7) employed an infrared spectrophotometric technique to study the reaction variables in the Zeisel 1 16 R
ANALYTICAL CHEMISTRY
method. In a continuation of their study (8),the infrared method was extended t o the simultaneous determination of niethoxyl and ethoxyl groups. Miller, Samsel, and Cobler (22d) determined individual alkoxyl groups from methyl t o butyl by condensing the alkyl iodides in a cold trap. An aliquot was then injected into a gas chromatographic system and the areas of the peaks measured. Fukuda (85-87) described a combustion technique for alkoxyl groups. The alkyl iodide was swept into a combustion tube with oxygen and decomposed to iodine and carbon dioxide which were absorbed and weighed separately, the iodine on silver, and the carbon dioxide on potassium hydroxide. From the ratio of the number of moles of iodine obtained to that of carbon dioxide, the nature of the alkoxyl groups could be ascertained. Hozumi (124) decomposed the alkyl iodide in a tube containing silver granules a t 400’ to 500’ C. which absorbed the iodine. Kainz (141) determined glycol ethers by decomposition n-ith hydriodic acid producing an alkyl iodide and ethylene. The alkyl iodide was determined by the Zeisel procedure and the ethylene measured in a nitrometer. Kretz (182) proposed sealed tube decomposition of the sample using hydriodic acid, followed by steam distillation for higher alkoxyl groups. Guagnini, Vonesch and de Riveros (102) proposed saponification, esterification with formic acid, and distillation of the methyl formate into alkaline hydroxylamine solution for a colorimetric determination using ferric ion for methoxyl groups in pectin. Klimova and Zabrodina (168, 170) determined carbonyl groups by osimation with hydroxylamine hydrochloride in the presence of an aliphatic tertiary amine. The excess amine was titrated with standard 0.02N acid. Budesinsky and Korbl (34) employed oximation with hydroxylamine and titrated the excess reagent with either 0.1N potassium ferrocyanide or iodine solution potentiometrically. Hamann and Herrmann (113) reacted the sample with 2,4-dinitrophenylhydrazine solution, filtered, and determined the excess reagent by iodonietric titration with 0.01N solutions. Zobov, Lyalikov, and Mukhammednazarova (552) titrated carbonyl compounds directly with 2,4-dinitrophenylhydrazine standard solution. The end point was detected amperometrically using ultrasonic vibrations to settle the precipitated hydrazone. Maros and Schulek (203, 303) proposed oxidation of some sugars with periodic acid liberating 2 moles of aldehyde. The bisulfite addition products were formed, decomposed with
potassium cyanide, and the sulfite titrated with standard iodine solution. Sugimatsu and Yahara (292) employed reduction with sodium borohydride for carbonyl groups in cellulose. The excess reagent was determined by the addition of potassium iodate and subsequent titration of iodine with standard sodium thiosulfate solution. Stephens and Teszler (285) estimated low boiling carbonyl compounds by a modified alphe-ketoglutaric acid2,4-dinitrophenylhydrazine procedure. Ralls (253) developed a gas chroniatographic procedure which involved reaction with suitable reagents in a capillary tube and subsequent volatilization of the reaction products directly into the chromatographic system. Hall (111) reacted the carbonyl conipounds with dinniines to form imines which are reducible a t the dropping mercury electrode. Van h t t a ai:d Jamieson (305) used a polarographic technique for the determination of acetone. Pesez (244) reacted the s.,mple with 2,4-dinitrophenylhydrazine iii a colorimetric procedure for niicrogram amounts of carbonyl compounds. Slouf (275) used the reduction of phosphotungstic and phosphomolybdic acids by ketonic groups t o molybdenum blue, and Altshuller and Cohen (4) proposed p-nitrophenyldiazonium fluoroborate for aliphatic aldehydes and ketones as the basis for colorimetric determinations. A number of other colorimetric methods (119, 228, 316) have been proposed for sugars. Kats and Shoikhet (159) suggested an improvement in the Bertrand method for sugars in which Fehling solution L3 was replaced with trihydroxyglutaric acid and sodium hydroside. Lidmari-Safmt and Theander (193) compared the borohydride and copper number methods for sugars. Launer and Tomimatsu (187, 188) investigated the stoichiometry of sodium chlorite with aldehydes and polysaccharides. Patchornik and Ehrlich-Rogozinski (646) determined the benzyloxy group by hydrolysis with hydrogen bromide. The benzyl bromide formed was extracted, reacted with aniline, and the liberated hydrogen bromide titrated with standard 0.01S sodium methoxide solution. Verma and Bose (812) analyzed formates by oxidation nith potassium iodate and iodine, the excess iodine being determined by titration with standard thiosulfate solution. Ma and Gerstein (198) investigated two methods for organic peroxides. In one, reduction with iodide in the presence of ferric ions and titration of the iodine with 0.02N sodium thiosulfate was used and in the other the sample was reacted with excess titanous chloride which was back titrated with 0.025N ferric ammonium sulfate. The iodometric procedure was preferred.
Schenk and Fritz (84,268) described a procedure for compounds containing the hydroxyl group and others with acetylatable hydrogen in which perchloric acid was used as catalyst and ethyl acetate as solvent in conjunction with acetic anhydride. Farkas (74) treated the sample nith dimethyl sulfate, isolated the product, and determined the metliosyl group content in an indirect procedure for hydroxyl groups in lignin. Robinson, Cundiff, and Markunas (257) proposed esterification with dinitrobenzoyl chloride for hydrosyl groups and reported that this method was applicable to some tertiary hydroxy compounds. Benson and Turner (21) employed C I 4 acetic anhydride as the acetylating reagent, and determined the specific activity of the recovered and purified product. Naruta and I w m a (207) studied the use of vanadium osinate while Pesez and Bartos (W&) employed 3,5-dinitrobenzoyl chloride and piperazine as colorimetric reagents for alcohols. Guilbault and iLlcCurdy (103) proposed cerium(1S’) oaidimetry in the presence of silver and manganese as catalysts for polyhydric alcohols. The excess reagent was titrated with ferrous diammonium sulfate (0.01N) and ferroin as indicator. Maros, hfolnarPerl, and Schulek (201) determined 1,2glycols by oxidation with periodic acid to produce formaldehyde which was converted to the bisulfite addition product, decomposed with cyanide, and titrated iodometrically. Henry-Basch and Freon (118) studied the osidation of pentasubstituted glycerols with periodic acid. Rose (259) proposed electrolytic oxidation and ultraviolet absorptiometry of the product for a substituted glycol. Kyriacou (186) employed spectrophotometric titration with a standard solution of acetyl chloride for poly (oxy) propylene glycols. Nitrogen Functions. Kainz, Kasler, and Huber (148-152,154,155) have further reported on the anomalies in the determination of the primary amino group by nitrosation. Studied were the anomalous behavior of compounds containing active methylene groups, of glycine, and other amino acids, of phenols, indole and derivatives, of sulfonic acid and amides, and of pyrolline and osazoline compounds. Ma and Breyer (197) proposed an enzymatic method for the primary amino group. The sample was deaminated with D-amino oxidase in the presence of catalase and the liberated ammonia determined by distillation and acidimetric titration. Primary amines were determined colorimetrically on a microgram scale by Pesez and Bartos (245) and Bartos and Burtin (17). Dubin (67) condensed the sample with 1-fluoro-2,Pdinitrobenzene and differentiated primary from secondary
amines by measurement of the absorptivity a t two different wavelengths. Kratochvil, hiIatrka, and Marhold (178) determined some diamines colorimetrically. Reynolds, Walker, and Cochran (254) analyzed aromatic amines in the presence of aliphatic amines, alcohols, and phenols by ultraviolet spectrophotometric titration using a standard solution of acetic anhydride in pyridine. Mathur, Rao, and Narain (211) employed potentiometric titration with alkyl nitrite for primary aromatic amines. Yokoo ($29) proposed ferricyanide-azotometrp for the determination of a secondary amine in proteins after hydrolysis and reduction. Ashworth (11) proposed a turbidimetric method for hydrazine and organic hydrazines. The sample was reacted with a solution of selenium dioxide and the resulting suspension of selenium measured spectrophotometrically. Singh, Sahota, and Singh (274) employed titration with Chloramine T for organic hydrazines. Olson (233) used electrolytic generation of bromine and coulometric titration for various hydrazines. Clark and Smith (53) determined methyl hydrazine and hydrazine in mixtures by successive titration with Chloramine T and sodium hypochlorite solutions. Jancik, Cinkova, and Korbl (133) titrated a hydrazine derivative (isonicotinic acid hydrazide) potentiometrically using 0.1N potassium bromate, the amount of acid present being critical. hIatrka and Sagner (212) proposed direct reductimetric titration using vanadium(I1) sulfate for azo dyes. Earley and Na (69) determined azo and diazonium compounds and nitroarylhydrazines by reduction with standardized titanous chloride under nitrogen, the escess reagent being back titrated with ferric alum solution and ammonium thiocyanate as indicator. Klimova and Zabrodina (171) analyzed primary and secondary saturated compounds containing nitro groups by reduction with aqueous potassium iodide in acidic solution. The liberated iodine mas titrated with 0.01W sodium thiosulfate solution. Shinozuka and Stock (272) reduced 2,2-dinitropropane with zinc amalgam and determined the nitrite ion colorimetrically. Altshuller and Cohen (3) proposed reaction with nitrous acid as the basis for a colorimetric procedure for primary nitroparaffins. Sawicki and Stanley (267) presented a colorimetric technique for aromatic polynitro compounds. Poethke, Gebert, and Muller (247) studied the gravimetric determination of alkaloids by precipitation with reinecke salt. By adjustment of the acidity either the mono-or di-reinecke salt could be precipitated. Cross, McLaren, and Stevens (59) obtained the picrates of alkaloid bases which were
then extracted n3,h chloroform, decomposed, and the free picric acid determined colorimetrically. Strychnine salts were analyzed by Kuntze and Hadicke (186). The sample solution was passed through a colunin of basic aluminum oxide, the alkaloid eluted from the column, and titrated acidimetrically. hlilligram amounts of barbituric acid and some derivatives (166, Ib7) were determined by coulometric titration using electrolytically generated bromine. Karie (158) has investigated the polarographic behavior of amidines. Yokoo (328) analyzed pyridine and some derivatives by reduction with Iianey nickel in a test tube to form a secondary amine which was determined by application of ferricyanide-azotometry. Colorimetric reactions for pyridine and derivatives have been presented by Roth and Schrimpf (26d), Szen-czuk @ S i ) , and Pesez and Burtin (246). bIetcalfe (2.20) employed a cellulose ion exchange column for the isolation and concentration of quaternary ammonium compounds which were then eluted and determined colorimetrically using bromophenol blue. Sulfur Functions. Wronski (326) employed a complexinietric titration procedure for the determination of thiophene. The sample was reacted n-ith excess mercuric perchlorate solution and back titrated using thioglycolic acid solution (0.02N) and thiofluorescein as indicator. The same author titrated thiourea (325) directly with a reagent consisting of mercuric acetate and aniline in acetic acid solution (trimercurianiline acetate) using p-dimethylaminobenzylidenerhodanine as indicator. Sulfides were titrated separately with o-hydrosymercuribenzoic acid using dithizone as indicator. Banerjee (12) proposed osidation with a standard solution of bromide-bromat’e using starch-potassium iodide as indicator; for the determination of thiourea, Gupta (104) employed oxidation with iodine. Furst (88) used amperometric and polarographic estimation for allylthiourea, 0.01N silver nitrate being the titrant. Budesinsky, Vanickova, and Korbl (37) determined some derivatives of thiourea by reaction with cadmium complexonate to precipitate cadmium sulfide. The free complexon in the filtrate was titrated with standard calcium chloride solution using methylthymol blue as indicator. Fritz and Palmer (83) titrated mercaptans with mercuric perchlorate, the end point being detected spectrophotometrically in the presence of thioMichler’s ketone. Gregg, Bouffard, and Barton (101) determined thiols and aryl trityl sulfides by titration with standard mercuric nitrate solution using diphenylcarbazone as indicator. KoltVOL 34, NO. 5 , APRIL 1962
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hoff and Eisenstadter (178) investigated the use of amperometric titrations a t the rotating platinum wire electrode for mercapto groups, while Stricks and Chakravarti (289) employed polarographic titration a t the dropping mercury electrode. The latter proposed ethylmercuric chloride as the titrant. Bowers and Russell (27) investigated the polarographic behavior of aryl sulfones and sulfoxides. Matrka and Sagner (215) determined sulfonic groups in azo dyes by amperometric titration using benzidine solution. Barnard and coworkers ( I S ) proposed gas-liquid chromatography for the separation and polarographic estimation of thiosulfonates. Unsaturated Functions. Wronski (324) determined allyl alcohol by reaction with mercuric nitrate solution and styrene (323) by treatment with mercuric perchlorate solut,ion. In both cases, the excess reagent was titrated with thioglycollic acid using thiofluorescein as indicator. Bartels and Hoyme(16) employed a complexometric method for acrylate esters. The sample was reacted with mercuric acetate and EDTA, the excess of which was titrated with 0.02N zinc sulfate, using Eriochrome Black T as indicator. Sodomka (280) improved the bromometric method for the estimation of vinyl acetate. Hamann and Herrmann (114) proposed a bromate-bromide reagent with mercuric acetate as catalyst for the determination of unsaturated compounds. The excess reagent was determined by iodometric titration. A bromide monochloride reagent (0.OliV) was used by Burger and SchuIek (40) for maleic and fumaric acids. Ozolins and Schenk (241) determined Diels-Alder active dienes using tetracyanoethylene; the excess reagent was titrated with 0.05,17 cyclopentadiene using phenanthrene as a warning indicator and pentamethylbenzene as indicator. Altshuller and Cohen (6) proposed a colorimetric reaction with p-nitrophenyldiazonium fluoroborate for conjugated diolefins. Franke (82) used mass spectrometry before and after treatment with benzenesulfinyl chloride as a measure of olefinic unsaturation. Smits (278) proposed ultraviolet spectrophotometry for the determination of the iodine number of microgram amounts of sample. Fenton and Crisler (78) used near-infrared spect'roscopy for cis-unsaturation in oils. Miscellaneous Functions. Robinson and coauthors (258) titrated the 3,sdinitrobenzoate ester derivatives of alcohols as weak acids using potentiometric titration with pyridine as solvent and 0.OliV tetrabutylammonium hydroxide as titrant. Hummelstedt and Hume (127) performed photometric titrations of weak acids (mainly phenols) with tetrabutylammonium hydroxide solution as titrant and isopropyl alcohol 1 18 R
ANALYTICAL CHEMISTRY
as solvent. Differential titrations were possible by this technique whereas the potentiometric method yielded a single peak. Wolf (521) employed alkalimetric titration for morphine, determining mixtures of morphine and codeine by prior titration of both as bases. Phenolic esters were titrated as weak acids by Smith and Haglund (877). Belcher, Serrano-Berges, and West (19) studied the submicro titration of carboxylic acids in aqueous solution. Cas0 and Cefola (44) recommended sulfamic acid as a primary standard for organic bases. The purification of dimethylformamide for use in nonaqueous titrations has been described (229). Gutterson and Ma (109) titrated very weak organic bases both potentiometrically and visually using 0.01S perchloric acid solutions. Acetic, propionic, and formic acids and acetic anhydride were used as solvents. Bases with pKb values to 13.5 in water were titratable. Przyszlakowski (250) found anhydrous propionic acid superior to acetic acid as a solvent for the nonaqueous titration of some alkaloids. Budesinsky and Korbl (33) proposed a complexometric procedure for certain organic bases. The sample was reacted with a solution of cadmium iodide and EDTA, after which the excess EDTA in the filtrate was titrated with 0.01M calcium chloride using methylthymol blue as indicator. Mizukami and Hirai (225) reported that neutral solvents were superior to acidic soIvents for the titration of salts of phenothiazine as bases, using perchloric acid solution as titrant. Photometric titrations were used by Connors and Higuchi (65) for such very weak bases as urea and aretamide, and by Hummelstedt and Hume (126) for differentiating mixtures of bases of similar strength. Bezinger, Gal'pern, and Abdurakhmanov (22) differentiated aliphatic amines, aromatic amines, sulfoxides, and carboxylic acid amides from ri single sample by titration with 0.05X perchloric acid solution using acetic anhydride as solvent. Van hIeurs and Dahmen ($06) studied conductometric titrations of organic bases in nonaqueous solvents. Mather and Anson ($10) employed a coulometric technique, generating hydrogen ions a t a mercury electrode in acetic acidacetic anhydride solution for the titration of organic bases. Tuthill, Kolling, and Roberts (SOS) titrated certain alkaloids in nonaqueous solution using visual, potentiometric, and photometric detection of the end point. Streuli (188)employed nonaqueous titrimetry to determine the relative basicities of substituted phosphines. Alicino (2) titrated thiourea as a base in the presence of mercuric acetate using acetic acid as solvent, 0.01N perchloric acid solution as titrant, and either crystal
violet or quinaldine red as indicator Schulek and Endroi-Havas (269) proposed use of pentane saturated with propane and butane gases for creating an inert atmosphere in micro acid-base titrations. A number of methods for determining water in organic compounds have been proposed. Eberius and Bohnes (70) suggested an improved Karl Fischer reagent. Connors and Higuchi (66) used spectrophotometry for the detection of the end point in a Karl Fischer titration. Extraction of the water with an organic solvent and subsequent measurement of its dielectric constant were used for moisture in sucrose (46, 191). Cole and coworkers (64) determined water in organic liquids by continuous coulometry, the water first being stripped from the sample by an inert gas and then collected in a special cell. Jackwerth and Specker (131) used a spectrophotometric method based on the reaction of the water in the sample with lithium chloride and cupric perchlorate. Jahr and Fuclis (132) reacted the sample with tert-butylorthovanadate. In the presence of water, an insoluble vanadate was precipitated, collected, and finally titrated with (KH&S04 FeS04 using the sodium salt of iV-methyldiphenylamine-p-suifonic acid as indicator. Thomas (300) described a modified apparatus for the microdetermination of moisture in organic compounds by the loss in weight on drying. Budesinsky (52) described an apparatus suitable both for semimicro determinations of active hydrogen and for unsaturation by catalytic hydrogenation. Harp and Eiffert (116) proposed exchange with deuterated water, while Giles (94) used exchange with tritiated ethyl alcohol for the determination of active hydrogen. Ryba (26s) determined active methylene groups by condensing the sample with diethyl-p-phenylenediamine. The difference between blank and sample titrations with potassium ferricyanide was used for quantitative measurement. Brandenberger, Maas, and Dvoretzky (29) analyzed methyl groups in alkylbenzenes by digestion in a sealed tube, using a reagent consisting of 2:l 5A' chromic acid-concentrated sulfuric acid solution. After digestion, the acetic acid was steam distilled and titrated with 0.05.1- base. Benzoic acid did not interfere as it was destroyed during the digestion period. Dirscherl and Erne (65)determined hydro-halides of organic bases by titrating directly with 0.01N mercuric perchlorate solution and diphenylcarbazone as indicator. Heyrovsky (121) titrated phenylboron compounds with 0.1N mercuric nitrate or perchlorate potentiometrically or polarographically. Ross and Denney (260) proposed
titration with 0.02N perchloric acid for phosphoranes. Phosphonium salts required the presence of mercuric acetate before titration. Sass and coworkers (265) determined some organophosphorus halidates on a semimicro scale by oxidation with a peroxide reagent. Smith (2’76) reacted dialkylphosphites with cacotheline as the basis of a colorimetric method. Glebovskaya, Maksimov, and Petrov (95) used integral absorption in the region between 13.3 to 13.4 microns for -CHp content in long chain compounds. Suclear magnetic resonance was employrd hy Kubota and Takamura (183) for the analysis of methyl-phenylsiloxane polymers. Kreshkov and coworkers (180, 181) described a number of titrimetric methods for determining alkylchlorosilanes. LITERATURE CITED
(1) Abramyan, -2. A., Sarkisyan, R. S., Izvest. Akad. iyauk. Armyan S.S.R. Khim. A-auki 12,341 (1959). ( 2 ) Alicino, J. F., Microchem. J . 4, 551 (1960). \ -
- - I -
(3) hltshuller, A. P., Cohen, I. R., ANAL. CHERI.32, 881 (1960). (4) Ibid., 32, 1843 (1960). (5) Altshuller, A. P., Cohen, I. R., A n d . Chim. Acta 24,61 (1961). (6) Anderson, D. M. W.,Duncan, J. L., Chem. & Ind. (London) 1949, 1151. (7; Anderson, D. AI. W., Duncan, J. L., l‘alanta 7, 70 (1960). (8) Zhid., 8, 1 (1961). (9) Arnett, E. M., Strem, AI., Hepfinger, N., Lipowitz, J., McGuire, D., Science 131, 1680 (1960). (10) Arventiev, B., Leonte, AI., Offenberg, H., Am. Stzznt. Univ. “Al.I . Cuza,” Iasi, Sect. I 6, 183 (1960). (11) Ashworth, PI. R. F., Jlicrochim. Acta 1961. 5. (12) Banerjee, S. N., J . Indian Chem. Soc. 36, 449 (1959). (13) Barnard, D., Evans, hl. B., Higgins, C;. h1. C., Smith, J. F., Chem. & Ind. (London) 1961, 20. (14) Bartels, U., Hoyme, H., Chem. Tech. (Uerlzn) 11, 156 (1959). (15) Ibzd., 11, 600 (1959). (16) Bartels, ci., Hoyme, H., Faserforsch. u. I’edzltech. 10, 345 (1959). (17) Bartos, J., Burtin, J. F., Ann. phunn. jranc. 17, 144 (1959). (18) Belcher, R., Leonard, M. A., JTest, T. S.,J . Chem. Soc. 1959, 3577. (19) Helcher, R., Serrano-Berges, L., Kest, T. S.,Ibid., 1960, 3830. (20) Bennemita, R., Mikrochim. Acta 1960, 54.
(21) Benson, R.H., Turner, R. B., ANAL. CHEM.32, 1464 (1960). ( 2 2 ) Bezinger, N. S., Gal’pern, G. D., Abduralihmanov, M. A . , Zhur. Anal. Khzm. 16,91 (1961). ( 2 3 ) Blinn, R. C., ~ ~ N A LCHEM. . 32, 292 (1960). ( 2 1 ) Boos, R N., Analyst 84, 633 (1959). ( 2 5 ) Born, H.-J., Riehl, N., Angew. Chem. 72, 559 (1960). (26) Bottcher, C. J., van Gent, C. M., Pries, C., Anal. Chim. Acta 24, 203 11961). ( 2 ? ) Bowers, R. C., Russell, H. D., ANAL. CHEY.32, 405 (1960). (25) Bradstreet, R. B,, Ibid., 32, 114 11960’i.
(26) Brandenberger, S. G., Maas, L. IT.,
Dvoretzky, I., Ibid., 33, 453 (1961).
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~
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(130) Ibid., 8, 739 (1959). (131) Jackwerth, E., Specker, H., 2.anal. Chem. 171, 270 (1959). (132) Jahr, I
