Anal. Chem. lQ84, 56,63R-68R (1888) Smith, 8. J.; Ross, R. M.; Ayers, C. R.; Wills, M. R.; Savory, J. J. Liq. ChrOmatOgr. 1983,6 (7), 1265-1272. (1898) Smith, S. L.; Blshara. R. H.; Drummond, G. E. J . Llq. Chromatogr. 1081,4 (12), 2205-2212. (1908) Soclc, H.; Gaberc-Porekar, V. Fresenius’ 2.Anal. Chem. 1981,309 (2). 114-116. (1918) Sonnino, S.; Ghldonl, R.; Chlgorno, V.; Masserlnl, M.; Tettamanti, G. Anal. Blochem. 1983. 128 (l), 104-114. (1928) Soundararajan, 0.; Subbalyan, M. Indian J . Chem., Sect. A 1983, 22A (4). 311-315. (1938) Soundararajan, G.; Subbaiyan, M. Indian J . Chem., Sect. A 1083, 22A (5),402-406. (1948) Soundararajan, G.; Subbaiyan, M. Indlan J . Chem., Sect. A 1983, 22A (5),399-401. (1958) Spahn, H.; Mutschler, E. J . Chromatogr. 1982,232 (I), 145-153. (1968) Spillman, T.; Cotton, D. 8.; Lynn, S. C.; Bretaudlere, J. P. Clln. Chem. (Winston-Salem, N.C.) 1983,2 9 (2), 250-255. (1978) Srlvastava, K. C.; Awasthi, K. K. J . Chromatogr. 1983, 275 (I), 61-70. (1988) Srlvastava, S. P.; Chauhan, L. S.; Reena J . Liq. Chromafogr. 1982, 5 (6),1081-1095. (1998) Srlvastava, S. P.; Kamlesh; Gupta, V. K. J. Liq. Chromafogr. 1983, 6 (I), 145-153. (2008) Srlvastava, S. P.; Reena Anal. Lett. 1982, 15 (A5), 451-457. (2018) Stahl, E.; Giatz, A. J . Chromatogr. 1982,240 (2), 518-521. (2028) Stahl, E.; Glatz, A. J. Chromatogr. 1982,243 (I), 139-143. (2038) Stahr, H. M.; Domoto, M. A&. Thln Layer Chromafogr., [Proc. Blenn. Symp.], 2nd 1980 1982,403-412; Touchstone, J. C., Ed.; Wiley: New York.
(2048) Stahr, H. M.; Klnker, J.; Nlckolson, D.; Hyde, W. J. Llq. Chromafogr. 1082,5 (6),1191-1200. (2058) Stahr, H. M.; Pfelffer, R.; Hyde, W. J . Liq. Chromafogr. 1982,5 ( 6 ) , 1181-1190. (2068) Stepanek, J. J . Chromafogr. 1083,257 (2), 405-410. (2078) Stopher, D. A. Mefhodol. Surv. Eiochem. Anal. 1083, 12, 65-67. (2088) Stubblefield, R. D.; Kwolek, W. F.; Stoloff, L. J . Assoc. Off. Anal. Chem. 1982,65 (6),1435-1444. (2098) Studer, A.; Traltier, H. HRC CC,J . High Resoluf. Chromafogr. Chromatogr. Commun. 1982,5 (IO), 581-582. (2108) Sulochana, G.; Kalavathy, R.; Padmanabhan, L. Indian J . Med. Res. 1982, 7 6 , 281-283. (2118) Sundholm, E. 0. J . Chromatogr. 1983,265 (2), 285-291. (2128) Szabo, A.; Rabai, G. Anal. Chem. Symp. Ser. 1982, 10,433-439. (2138) Szepesl, G.; Dudas, K.; Pap, A.; Vegh, 2.; Mlncsovlcs, E.; Tylhak, T. J . Chromafoar. lQ82.237 11). 137-143. (2148) &pes1 G.; Molnar, J. Chromatographia 1981, 14 (12), 709-711. (2158) Taklno, Y.; Odanl, T.; Tanlzawa, H.; Hayashl, T. Chem. Pharm. Bull. 1982. 30 (6).2196-2201. (2168) Tasl-Toth, E.; Polyak, 8.; Boross, L.; Feher, T. Anal. Chem. Symp. Ser. 1982. 10, 473-475. (2178) Tewari, S. N.; Sharma, J. D. Bull. Narc. 1983,3 5 ( 1 ) , 63-67. (2188) Thlerry-Palmer, M.; Gray, T. K. J. Chromafogr. 1983.262, 460-463. (2198) Thomas, M. H.; Epsteln, R. L.; Ashworth, R. 8.; Marks, H. J. Assoc. Off. Anal. Chem. 1083,66 (4), 884-892. (2208) Tiffany, J. M. J . Chromatogr. 1982,243 (2), 329-338.
---.--
%
I.
(2218) Tomingas, R.; Grover, Y. P. Fresenius’ 2.Anal. Chem. 1982,313 (5),414-416. (2228) Tonelll, D.; Gattavecchla, E.; Breccia, A. J. Chromafogr. 1983,275 ( l ) , 223-228. (2238) Tonelli, D.; Gattavecchla, E.; Gandolfl, M. J . Chromafogr. 1982,231 (2), 283-289. (2248) Lehnert, W.; Ropers, H. H. Clln. Genet. 1982,22(1),25-29. (2258) Torok, I.; Paal, T. L. J . Chromafogr. 1982,246 (2), 356-359. (2268) Touchstone, J. C.; Hansen, G. J.; Zelop, C. M.; Sherma, J. Adv. Thin Layer Chromatogr., [Proc. Bienn. Symp.] 2nd 1980 1082, 219-228. Touchstone, J. C., Ed.; Wlley: New York. (2278) Touchstone, J. C.; Levln, S. S.; Dobbins, M. F.; Beers, P. C. J . Liq. Chromafogr. 1983,6 (l), 179-192. (2288) Travesset, J.; Such, V.; Gonzalo, R.; Gelpl, E. HRC CC, J . High Resoluf.Chromatogr. Chromafogr. Commun. 1981,4 ( l l ) , 589-590. (2298) Tsao, F. H.; Zachman, R. D. Clin. Chlm. Acta 1882, 116 (l), 109-1 20. (2308) Uchlyama, S.; Uchlyama, M. J . Chromafogr. 1983,262, 340-345. (2318) Van den Ende, A.; Raedecker, C. E.; Malruhu, W. M. Anal. Eiochem. 1983, 134 (I), 153-162. (2328) Van Genderen, H. H.; Van Brederode, J.; Nlemann, G. J. J . Chromat w r . 1983,256 (I), 151-153. (2338) Vaskovsky, V. E.; Khotlmschenko, S. V. HRC CC,J . High Resoluf. Chromafogr . Chromatogr . Commun . 1982,5 (1 I), 635-636. (2348) Ventalchalam, R.; Stahr. H. M. A&. Thin Layer Chromafogr., [Proc. Bienn. Symp.] 2nd 1980 1982,463-468. Touchstone, J. C., Ed.; Wlley: New York.
(2358) Vonderheld, C.; Funk, W.; Hille, J. Proc. Inf. Symp. Insfrum. High Perform. Thin-Layer Chromatogr.,2nd 1982,209-219, Kaiser, R. E.; Ed. (2368) Vukuslc. I . J . Chromafogr. 1082,243 (l), 131-138. (2378) Warfleld, R. W.; Malckel, R. P. JAT, J . Appl. Toxicoi. 1983,3 (l), 51-57. (2388) Watklns, T. R. HRC CC,J . High Resolut. Chromatogr. Chromatogr. Commun. 1982,5 (2), 104-105. (2398) Wesley-Hadzlja, B.; Mattocks, A. M. J. Chromafogr. 1082,229 (2), 425-432. (2408) Wilson, I. D.; Blelby, C. R.; Morgan, E. D. J . Chromafogr. 1982. 242 (l), 202-206. (2418) Wlnsauer, K.; Buchberger, W. Chromatographia 1981, 14 (1 I), 623-625. (2428) Wintersteiger, R. J . Liq. Chromafogr. 1082,5 (3, 897-916. (2438) Wlnterstelger, R. Mlkrochim. Acta 1082,2 (3-4), 279-287. (2448) Winterstelger, R.; Wenninger-Weinzierl, G. Fresenius ’ 2. Anal. Chem. 1981,309 (a), 201-208. (2458) Wu, J. T.; Knight, J. A. Clin. Chem. (Winston-Salem,N . C . ) 1982,28 (1 I), 2337-2338. (2468) Wu, J. T.; Mlya, T.; Knight, J. A. Clln. Chem. (Winston-Salem,N E . ) 1983,2 9 (4), 744-745. (2478) Wuersch, P.; RouIet, P. J . Chromatogr. 1982, 244 (I), 177-182. (2488) Yamaguchl, Y. J . Chromatogr. 1082,228, 317-320. (2498) Yamaguchi, Y. J . Liq. Chromafogr. 1982,5 (6),1163-1170. (2508) Zhou, L.; Shanfleid, H.; Zlatkis, A. J . Chromafogr. 1982, 239, 259-264. (2518) Zlrlng, 8.; Shepperd, S.; Kreek, M. J. Int. J . Pept. Protein Res. 1983,22 (1). 32-38.
Functional Group Analysis Walter T. Smith, Jr.,* and John M. Patterson Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055
The analytical methods discussed in this review have been selected from the literature which has become available to the reviewers from Dec 1981 through Nov 1983. Acids. Free fatty carboxylic acids in fats and oils can be determined as their methyl esters by gas chromatography. The acids are converted into their tetramethylammoniumsalts during transesterification of the glycerides with tetramethylammonium hydroxide and collect in the glycerol layer which separates. After neutralization of the excess base with methanolic HCI, the salts are converted into their methyl esters in the GC injection port after injection (75). A fluorescence method for the determination of carboxylic acids involves their conversion to the ester by reaction with 4-hydroxymethyl-7-methoxycoumarin in the presence of ethyl azodicarboxylate and Ph3P. Both aliphatic and aromatic acids react within 15 min at room temperature (41). Treatment of citric acid and cis- and trans-aconitic acids with dicyclohexylcarbodiimidein the presence of acetic acid produces fluorescent species which can used in the determination of these acids. At the 50-mmol level, the standard 0003-2700/84/0356-63R$O 1.SO10
deviations ranged between 5.26 and 6.75% ( 17). A spectrophotometric method for the determination of formic acid at levels of 0.001% or greater in isopropylphenol depends upon its reduction with magnesium to formaldehyde followed by condensation with phenylhydrazine. After oxidation with K,Fe(CN),, the absorbance of the formazane is measured (3). Trialkylsulfonium and trialkylselenonium salts of carboxylic acids are converted into carboxylic esters on pyrolysis in a gas chromatograph injector and the esters determined by gas chromatography. The carboxylic acid is added to a solution of sulfonium or selenonium hydroxide and an aliquot of the solution is injected (13). A water-soluble carbodiimide (l-ethyl-3-(3-dimethylaminopropy1)carbodiimide)catalyzes the reaction of carboxylic acids in aqueous media with 2-nitrophenylhydrazine to form the hydrazide which is then determined spectrophotometrically in alkaline media (47). Carboxylic acids and their salts may be determined by a spectrophotometric procedure after reaction with chloranil 0 1984 American Chemical Society
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FUNCTIONAL GROUP ANALYSIS
in a dimethylformamide-methyl ethyl ketone solvent. Relative standard deviations for 12 monobasic and 4 dibasic carboxylic acids were 0.007-0.035 (89). Carboxylic acids have been determined by a gas chromatographic-mass spectrometric method after their conversion to the tert-butyldimethylsilyl derivative. The report discusses the applications and limitations of the method (124). An ion chromatography analysis of carboxylic acids without the suppressor system allows the determination of acids in commercial products without a pretreatment process (48). The conversion of fatty carboxylic acids in lipid mixtures to their carbon-14 labeled esters followed by scintillation chromatography has been used to determine free carboxylic acids in such mixtures. When BF3 is used as esterification catalyst, only 0.5% of the esters were transesterified (7). An enantioselective method for the determination of 2halopropanoic and 2-halobutanoic acids involves the use of bacterial 2-halo acid dehalogenases followed by an analysis of the halide ion released. One dehalogenase interacted only with the L acid while another dehalogenase interacted with both the D and L acids (81). A gas chromatographiemass s ectrometric method for the determination of carboxylic aci s involves their conversion to the naphthalenemethyl and cyclohexanemethyl esters using substituted diazomethanes. The report describes the synthesis of 1-naphthyldiazomethaneand cyclohexyldiazomethane (20). Acid Azides. Hydrolysis of acid azides in potassium hydroxide solution produces potassium azide. This latter compound gives a red complex with Fe(I1). Acyl, phen 1methanesulfonyl, and diphenylphosphoryl azides can be l e termined in this way. Aryl and alkyl azides do not interfere (102). Alcohols. Derivatization of alcohols with a fluorescent reagent allows their determination in the lower pmol range using a thin-layer separation procedure. In the presence of a triethylenediamine catalyst, 1-naphthylisocyanate converis primary and secondary alcohols into their carbamates within 30 min and tertiary alcohols within 2 h (123). A spectrophotometric determination of tertiary alcohols is based on the red color produced on treatment of the alcohol with vanillin and sulfuric acid (51). An indirect procedure has been used for the determination of eth lene glycol. After oxidation of the glycol with excess periodte, the unreacted periodate is reduced to iodide. The iodide is titrated with silver ion using an iodide-selective electrode (15). The association of hydroxyl groups in polymers with tetrahydrofuran is the basis of a hydroxyl content determination in polymers. The hydroxy-tetrah drofuran association complex absorbs strongly at 3450 cm-9 thus allowing an infrared analysis of hydroxyl (57). The hydroxyl content in coal has been estimated by acetylation with carbon-14 labeled acetic anhydride. The acetylated sample is burned and the carbon-14 in C02is related to the hydroxyl content (104). Fourier transform infrared spectrometry has been applied to the determination of hydroxyl content in coal. Reproducibility of the spectra obtained is *5% (105). Hydroxyl groups in polymers which are soluble in dimethylformamide can be determined by using the imidazole-catalyzed esterification with pyromellitic dianhydride. In the procedure described, a known quantity of butylamine is added and then titrated potentiometrically (60). The imidazole-catalyzedpyromellitic dianhydride and the p-toluenesulfonic acid catalyzed acetylation methods were compared in the determination of hydroxyl roups in polymers. The two methods both gave reproduci%leand equally accurate results (24). A differential rate method has been employed for the determination of binary mixtures of butanediols. The diols were treated with Ce(1V) and the reaction was quenched with an excess of oxalate. The excess oxalate was titrated amperometrically with Ce(1V) (71). Hydroxyl groups in wood were determined by a deuterium exchange method. The extent of isotope dilution of the DzO was determined by interferometry (115). Aldehydes and Ketones. A new technique for the determination of trace amounts of aldehydes and ketones has been developed in which the carbonyl compounds are preconcentrated at the surface of an electrode followed by analysis
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ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
by differential pulse voltammetry. A modified platinum electrode, with absorbed allylamine on the surface, preconcentrates the carbonyl compounds by way of imine formation (4). An electrochemical detector in the reductive mode has been
used in conjunction with a liquid chromatographic procedure for the analysis of carbonyl compounds after conversion to phenylhydrazine derivatives. Limits of detection of formaldehyde, acetaldehyde, acetone, and acrolein ranged from 54 to 99 pg (53). The determination of a number of aromatic aldehydes a t concentrations of 10-8-10-7 M has been accomplished by a fluorometric procedure in which the aldehyde is treated with 4,5-dimethoxy-1,2-diaminobenzenein dilute acid. The fluorescence is developed by the addition of alkali and stabilized by the addition of 2-mercaptoethanol (83). Fluorescence detection coupled with reverse-phase highperformance liquid chromatography permits the analysis of aldehydes at the 28 pmol level with a standard deviation of k2%. Precolumn derivatization of the aldehydes is accomplished by reaction with dimedone (5,5-dimethyl-1,3-cyclohexanedione) (79). The quantitative oxidation of benzaldehyde in a benzenewater system with KMn04 complexed to dicyclohexyl-18crown-6 ether is the basis of a determination of benzaldehyde. The oxidation requires a molybdate catalyst. Unreacted permanganate in the aqueous layer is determined spectrophotometrically after reaction (90). Formaldehyde and chloral hydrate have been determined by alkaline hypoiodite oxidation. The iodide thus produced is oxidized to iodate which in turn is determined by differential pulse polarography (108). Acetaldehyde reacts with diazotized orthanilic acid in the presence of alkaline sodium sulfite to produce a pink-red color which is related to the concentration of the aldehyde. The relative errors for the method for a concentration range of 10-180 pug vary from -0.2 to +5.2% (32). Formaldehyde, alone or in the presence of formic acid, can be determined in microquantities (detection limit, 50 ng/L) by the use of an immobilized enzymatic oxidation. The hydrogen peroxide formed is analyzed by a chemiluminescence method (95). A procedure based upon the Skraup synthesis has been used to detemine trace amounts of acrolein with high selectivity (methyl vinyl ketone and crotonaldehyde interfere slightly). The sample, concentrated by collection on molecular sieves, is heated with o-aminobiphenylin the presence of 2.5 M H2S04 and the product determined fluorometrically (109). A combined collection and derivatization device has been described for the determination of aldehydes in automobile exhausts. The derivatizing reagent is 2,4-dinitrophenylhydrazine (68). Airborne formaldehyde reacts with p-hydroxybenzoicacid hydrazide to form nucleating crystals. After development, optical measurement of the enlarged crystals can be related to the formaldehyde concentration (59). A report describing the development and evaluation of various methods for the monitoring - of formaldehydehas been published (73). Amines. A nickel oxide electrode svstem has been developed for the detection of amines u6ng a flow injection technique (49). A detection limit of a few nanograms was found for glycine. Natural abundance carbon-13NMR spectroscopy has been used to analyze mixtures of mono-, di-, and trialkylammonium chloride (29). The method is reported to be rapid and not to involve heat and extremes of pH. Enzyme electrodes based upon peroxidase or glucose oxidase have been found to be useful for the analysis of aromatic amines which activate the enzyme (62,63). The detection limit is 0.02-0.6 pM. A thermal-energy analyzer used for the gas chromatographic analysis of N-nitroso compounds has been modified for the determination of amines and ammonia (97). New methods for the production of the absorbing species for the spectrophotometric determination of amines continue to be developed. cis-a,P-Dinitrostilbene is used in the determination of primary and secondary amines in a spectrophotometric procedure (27).
FUNCTIONAL GROUP ANALYSIS
chromatcgraphy or HPLC (122). Both primary and secondary aliphatic amines react within 10 min. A high-performance liquid chromatography procedure for the determination of tertiary aliphatic amines uses a pcstcolumn derivatization which involves reaction of the amine
The structure of the abeorbing species produced in the reaction of rimary amines with ascorbic acid has been determined (67. The spectrophotometric determiaation of aromatic amines usually involves diazotization followed hy coupling. is used as the In a micro method.. &hvdroxvauinoline . .. coupling agent (28). In another studv. the relative merits of H-acid (%amin* .
.,.
~~~~~~
~
naphthyl)ethylenediamine as coupling agents were in"&gated (&%. Structural effects of the amine on the production of color were examined. The coupling of benzenediazonium chloride with N-(ln a p h t h y l ) e i h y l e k d i e is recommended as a procedure for the determination of trace quantities of aniline (86). The optimum conditions for the coupling of the diazonium d t s of 2-, 3-, and 4aminophenol. rn- and pphenylendnmine, 2.4,s and 2,4,&trichloroaniline. and 2,4,5,6tetrachloroaniline with N-(1-naphthy1)ethylenediamine have been described. The coupled products are determined spectrophotometrically (87). Secondary amines can be determined fluorometrically at m o l L levels by a reaction with 2-methoxy-2,4-diphenyl-3(W- anone to give a nonfluorescent product. This product is converted into a fluorescent material by reaction with taurine (82). Another procedure for secondary amine analysis involves conversion of the amine to a primary amine with NaOCI. The rimary amines are then converted into fluorescent material y reaction with o-phthalaldehyde and mereaptoethanol (46). Nanogram levels of nonultraviolet absorbing amines and quaternary ammonium ions can be determined by a liquid chromatographic method hy using a naphthalene-2-sulfonate counterion (42). Trinitrohenzenesdfonic acid is reported to be an ideal precolumn derivatizing agent for the HPLC determination of alkylamines (14). Either electrochemical of W detection may be used. In another study in which the derivatizii agents, trinitrobenzenesulfonic acid, 2.4dinitrofluorobenzene. and 2chlore3,5-dinitropyridinewere compared, it was found that trinitrobnzenesdfonic acid wan superior to the othera in the determination of amines (54). Reaction of primary and secondary amines with 4 - 6 methylbenzothiazol-2-yl)phenylisocyanate produces highly fluoreacent carbamates which can be separated by thin-layer
tl,
E
The citric acid-acetic anhydride reaction has also been applied to the determination of triethylenediamine samples in air. The limit of detection was 1 mg/m3 of air (113). An ion chromatography method has been developed for the detection of ethylenediamine in aqueous or alcohol solutions. The limit of detection is less than 1 ppm (I2). Another method for the determination of ethylenediamine is based on ita reaction with phthaldehyde and 2-mereaptoethanol. Secondary and tertiary amines do not interfere hut certain primary amines, such as 1,8propanediamine, do (44). A chemiluminescence method for the determination of ethylenediamine is based upon the observation that Schiffs hasea increase the catalvtic activitv of maneanese salts in oxidation of luminol hy Lydrogen peroxide. 6etection limits of ue/mI. .. 0.014.02 _ " , ~are ~ ronorted ~ - - ~ 174). ,~ . ~,. The possible detection of aliphatic dinmines with ninhydrin has h e n investigated. Very low yields of the absorbing species were obtained with diamines containing two through five methylene groups (35). A complexometric titration procedure has been developed for the determination of o-aminophenola hut not the m- or p-ammophenola. Microamounta of the aminophenol are titrated with standard copper sulfate or nitrate using a capper ion selective electrode (101). The optimum volume ratio of the mixed solvent methyl cellosolve-propylene carbonate was determined for the pctentiometric tritration of purines and purine derivatives with perchloric acid. The relative standard deviations for nine derivatives and nine binary mixtures were OS-1.5% (116). Nanomole concentrations of N-chloramines have been d e tected by reaction with ~imethylamino-I-napht~enesulfinic acid. The highly fluorescent sulfonamide thus produced is determined by high-performance Liquid chromatography (IOOJ. Amino Acids. The fluorescence intensity of dansyl derivatives and o-phthnhldehyde-2-mercaptoethanolderivatives of amino acids is increased H-20-fold in the presence of surfactant micellar systems. Cationic hexadecyl- or dodecyltrimethylammonium chloride and N-dodecyl-N,N-dimethylammonium-3-propanel-sulfonic micelles are effective in the dansyl case while the nonionic Brij 35 or T X LOO and anionic sodium dodecyl sulfate are effective for the ophthalaldehyde-2mercaptoethanol method (103). For postcolumn fluorometric detectiun of amino acids, 7-chloro-4.nitrobenze2-oxa.l,3-diazole (NBD-CI)appears to he a suitable reagent, especially for proline and hydroxyproline (1%).
Chelating amino acids such as EDTA, DCTA, EGTA, and DTPA have been determined in microgram amounts hy a potentiometric titration method which relies on the inhibitory effect of these substrates on the Cu(ll)-catalyzed periodate thiosulfate reaction (112). Aromatic Hydrocarbons. Shpol'skii spectroscopy and vanations thereon have been used for a variety of polynuclear aromatic hydrocarbons including 9-methylanthracene, 9,IOdimethylanthracene (65)and the monomethylphenanthrenes (SYiJ. The method has also been used with a simple fluorometer which a n be assembled from commercial parts (64).An experimental device having a triplestage cell and a fmt heat exchanger is reported u)optimize determinations and permit rapid crystallization and heating of the samples (92). Laser-excited Shpol'skii spectroscopy, wing a tunahle dye laser appears to be a generally useful technique (127). The synchronous fluorescence technique has been used for the simultaneous determination of carbazole and anthracene in phenanthrene (37). The detection limit for carbazole w a s 0.1% and for anthracene 0.05%. The technique of constant energy synchronous fluorescence, in which the excitation and emission monochromators are scanned simultaneously and a constant energy difference is maintained between the wavelengths. is reported M be an improvement over conventional synchronous techniques (521. The laser twephoton ionization technique has been applied to the determination of a number of polynuclear aromatic ANALYTICAL
CHEMISTRY.
vm. 56. NO. 5. APRIL
1984 6511
FUNCTIONAL GROUP ANALYSIS
hydrocarbons and also to benzophenone and N-phenyl-lnaphthylamine (126). The detection limit is 6 ng/L for pyrene, 0.1 pg/L halogenated anthracenes, and 100 pg/L for benzophenone. The technique is particularly useful for weakly fluorescent and nonfluorescent molecules. A newly developed laser-excited windowless flow cell can be used for simultaneous detection of polynuclear aromatic hydrocarbons by molecular fluorescence and the photoacoustic effect as well as by two-photon photoionization (118). In a spectrofluorometric method, aerosols are fractionated with a low-pressure impactor and the polynuclear aromatic hydrocarbons are extracted ultrasonically into benzene, After concentration, the extracts are spotted and developed on a TLC plate and the benzo[u]pyrene spot is determined by focusing the TLC plate in the fluorescence excitation beam and measuring the resulting emission while scanning the plate. The detection limit for benzo[u]pyrene in 5 pg (76). A recent study indicates that polynuclear aromatic hydrocarbons on soot are degraded in the presence of NOx and SOX. Conversion to the mononitro derivatives occurs in the presence of NO2 or gaseous HNOB(67). A method for determing nitro derivatives of polynuclear aromatic hydrocarbons uses capillary gas chromatography and electron capture detection. It is suggested that the hydrocarbons can be determined by first converting them to their nitro derivatives (111). Spectrofluorometric data have been listed for a large number of compounds (8,56). Carbodiimides. A fluorometric method using trunsaconitic acid as the reagent permits the determination of as little as 50 pmol of carbodiimides (16). Carbohydrates. The reduction of NADP to NADPH by glucose 6-phosphate has been used in two recently reported sugar determinations. The resulting NADPH is measured spectrophotometricallyat 340 nm. In these procedures several enzymes must be added to the sample to convert fermentable sugars in molasses in the one case (2) and mono- and disaccharides in the other case (5) to the glucose 6-phosphate. Reducing sugars eluted by water from a strong cation-exchange HPLC column were detected by their reaction with arginine at 150 "C (boric acid solution, pH 7) to give fluorescent derivatives. Fluorescence intensity correlated with the concentration of reducing sugar in the 7.5 pg to 75 mg range (77). Anomeric and isomeric mixtures of monosaccharides, disaccharides, alditols, and methyl glycosides are readily separated by HPLC (Partisil5 column, ethyl acetate-hexane) after being fully derivatized with chlorodimethylphenylsilane. The derivatives are stable and UV-absorbing (121). A spectrophotometric method for reducing sugars utilizes the absorbance of the alkaline-reduction products of 2-, 3-, or 4-nitrobenzoic acid or 3-nitrobenzenesulfonic acid. Interference from moderate amounts of carboxylic acids, alcohols, and urea is negligible but aldehydes and sulfides interfere (98).
The range of Lever's colorimetric reagent (alkaline hydroxybenzoic acid hydrazide) (66) is greatly enhanced y using scintination colorimetry (80). The developed, colored solution is placed in a scintillation vial along with a miniature vial containing a carbon-14 or tritium source in a conventional scintillation medium. The decrease in total counts caused by the colored solution is an accurate measure of the sugar concentration. The usual colorimetric method could determine D-glucose only at 1mg could be measured. The carbon-14and tritium probes are equally accurate in the 0-200 pg range but the curves are not linear. 2-Amino-2-deoxyhexosescan be converted to their pyridoxal derivatives, which can then be precipitated as Co(II) complexes by addition of an excess of Co(I1). After filtration, the excess Co(I1) is determined by atomic absorption spectrometry (78). a-,p-, and y-cyclodextrins have been determined spectrophotometrically by measuring the decrease in the absorbance at 550 nm of a phenolphthalein solution (pH 10.5) when the cyclodextrin is added. Linear calibration curves were obtained for 0-50, 0-300, and 0-3000 pg/mL of a-,0-, and y-cyclodextrin, respectively (117). Ethers. Nonionic polyoxyethylene can be determined by oxidation with vanadium pentaoxide in H SO4 solution with a precision of 2-3%. The excess Vz05is determined poten-
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ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
tiometrically with iron(I1) ion (22). Ultratrace levels of nonionic polyoxyethylene in the presence of cationic surfactants in water can be determined through the use of an extraction with excess potassium picrate in CH2C12. The potassium complex of the polyoxyethylene is concentrated in the CH2C12layer (31). Methoxy groups in vanillin, p-methoxybenzophenone, 1methoxynaphthalene, dioxane lignin, lignosulfuric acid, and sulfite liquor were determined by an initial reflux with sulfuric acid followed by gas chromatographic analysis of the methanol produced (14)). Methyl tert-butyl ether in gasoline has been determined by attenuated total reflectance and transmission IR spectrophotometric methods (36) and by a reversed-phase liquid chromatographic method using a differential refractometer detector (107). Nitro Compounds. A simple and rapid procedure for the determination of nitro compounds involves the reduction of the nitro group with cadmium in aqueous HC1. The cadmium ions (6 equiv per nitro group) thus produced are determined by atomic absorption or by titration with EDTA, using a Eriochrome Black T indicator or a cadmium ion selective electrode (43). The color produced on reaction of nitrobenzene with acetone in the presence of KOH has been used for the determination of trace amounts of nitrobenzene in aniline (70). An isolation procedure has been devised for the separation of nitro aromatics from biosludges. The nitro compounds are determined by gas chromatography using a thermal energy analyzer as detector (93). Nitrosamines. Procedures for sample preservation, extraction, and gas chromato raphic analysis were investigated for three nitrosamines (947 N-Nitrosodiethylamine, k-nitrosodibutylamine, and Nnitrosodiamylamine in aqueous media can be determined by differential-pulse polarography. The detection limits at pH 3 are 5-10 ppb (11). It has been found that water-methanol and water-acetonitrile solvent mixtures can be used in the normal-pulsed polarographic determination of both polar and nonpolar nitrosamines. Half-wave potentials become more negative as the organic content of the solvent is increased (99). The determination of total N-nitroso content in cutting fluids requires that nitrite ion be removed before analysis by usin ion exchange or by treatment with iodide or sulfanilamiife. After denitrosation, the NO is determined by its gas-phase luminescence on reaction with O3 (21). A procedure for determining nitrosamines in air by using high-performanceliquid chromatography and thermal energy analyzer detection has been described (40). A discussion of gas chromatographic methods for the separation of volatile nitrosamines has been published (106). In a concentration step used for the determination of nitrosamines in water, Ambersorb XE340 (a carbonaceous absorbent) gave recoveries ranging from 58 to 99% (58). Nitrosamines in the presence of nitrites are first refluxed in a nonaqueous solvent with acetic acid to destroy the nitrite; then HBr in acetic acid is added to convert the nitrosamine to nitric oxide. The nitric oxide is determined by chemiluminescence (119). Organometallic Compounds. 4-Biphenylmethanol, 4biphenylacetic acid, and 4-biphenylcarboxylic acid/ triphenylmethane have been investigated as titrant indicators for the determination of alkyllithiums. Of these, 4-biphenylmethanol gave the sharpest color change at the end point (55). The direct introduction of water-toluene emulsions of methylcyclopentadienylmanganesetricarbonyl into the plasma was investigated for the determination of manganese using an inductively coupled plasma emission spectroscopy procedure. The relative standard deviation was 1-3% at the 0.011-0.028 g of Mn/L level (23). Peroxides. The conditions required for the determination of tert-butyl hydroperoxide in the presence of tert-butyl alcohol and tert-butyl peroxide by carbon-13 NMR spectroscopy have been described. Quantities of 0.5 mol % can be detected (33). Phenols. The determination of phenols by using 4aminoantipyrine continues to be used and studied. In one report 22 monohydric phenols are determined by high-per-
FUNCTIONAL GROUP ANALYSIS
formance liquid chromatograph after derivatization with 4-aminoantipyrine. The metho is applicable to the determination of phenols at the ppm and ppb levels in water (9). In a study of the apparent recoveries of 35 phenols in the 4-aminoantipyrine method the recoveries ranged from 0 to 100% (30). The same investigators found an even wider range of recoveries (>loo%) when they used an ultraviolet spectrophotometric method. Ultraviolet spectra of phenolate ions is reported to provide a simple, reliable technique for phenol determination. When the pH of a phenol solution is raised from 7 to 12, the difference in absorptivity at 291 nm is a reliable measure of the phenol concentration for most common phenols (25). Fluorometric analysis has been recommended for determination of the anion of 1-naphthol (1). For the determination of phenolic hydroxy groups in lignins, the sample is acetylated and then the phenolic acetates are cleaved by pyrrolidine. The resulting acetylpyrrolidine is then determined by gas chromatography. Only phenolic acetates are cleaved by this method. If determination of total hydroxyls in the sample is desired, the acetylated sample can be completely saponified (69). Trace amounts of chloro- and nitrophenols in water are acetylated by addition of acetic anhydride to a large volume of an alkaline aqueous solution. The acetates so formed can be extracted efficiently with small volumes of methylene chloride and determined by gas chromatography (72). Nitrophenols are extracted quantitatively from aqueous solution into benzene at pH 4.7-5.7 in the presence of crown ether (dibenzo-18-crown-6).The absorbawe of the benzene solution is then measured a t 315,325, and 357 nm, respectively, for p - , m-,and o-nitrophenol (91). The response is linear in the 3-15 ppm range. For mixtures of these phenols, simultaneous equations can be developed. A novel method for phenol uses an oxygen electrode with an outer membrane having a layer of yeast cells (Trichoporon cutaneurn) capable of degrading phenol. The rate of consumption of oxygen by these cells is related to the phenol concentration (84). Silicon Compounds. The reaction of silanol groups in silica gel with methyllithium to produce methane has been used for the detection of silanol groups. The methane formed is measured volumetrically (120). An infrared method has been described for the determination of the silicon-hydrogen bond in siloxane-polyether copolymers with a relative error of 5%. Infrared absorptions of the polyether, which complicate the indentification of the Si-H absorption bands in the spectra, were eliminated by using a polyether in the reference cell (129). Alkyl groups bonded to silica gels through a silicon-carbon bond can be cleaved to the alkane through the use of molten KOH in triethylene glycol dimethyl ether. The alkanes are then determined by gas chromatography (39). Thiols. Alkanethiols have been determined at the low ng level by using reversed-phase high-performance liquid chromatography after derivatization. The thiols were converted to the mixed disulfide by reaction with excess 5,5'-dithiobis(2-nitrobenzoic acid) at pH 8 (114). Another method involves a gas chromatographic analysis after derivatization of the alkanethiol. The thiols were precipitated with silver ion, converted to the anion by reaction with sodium sulfide and derivatized with pentafluorobenzyl bromide (125). Volatile thiols were determined by trapping in suitable absorbent solutions and then analyzed potentiometricallywith a sulfide ion selective electrode (38). The reduction in the absorbance of diphenylpicrylhydrazyl as a result of reaction with alkanethiols has been used to determine the thiols with an average relative error of 1-270. Thiophenols and derivatives react more rapidly than do the alkanethiols in this reaction (50). A photometric determination of thiols is based on the color developed when an acetic acid solution of the thiol is treated with p-aminodimethylanilie in the presence of ferric chloride and K,Fe(CN), (26): The use of 1,2,4-trinitrobenzenehas been recommended for the 2,4-dinitrophenylationof thiols in the presence of amines. Although the reagent reacts quantitatively a t pH 8.5 and 30 "C with both thiols and amines, the rate of reaction with thiols is -lo4 times faster (110).
B
Unsaturation. Acrylates and methacrylates have been determined with a relative error of 15% using a differential rate method. The binary mixtures are treated with lauryl mercaptan and the excess is titrated with silver ion using an ion-selective electrode (88). The problems and conditions required for the carbon-13 NMR analysis of hexane-hexene mixtures have been discussed. The mole percentages of components in the mixture could be determined to f 2 % (34). Miscellaneous. Quaternary ammonium compounds, cationic surfactants, alkaloids, and substances precipitated by the tetraphenylborate ion have been determined by titration with sodium tetraphenylborate using a liquid-membrane tetraphenylborate ion selective electrode (18). The detection of organic substances deposited on a solid support by the use of ozone-induced chemiluminescencehas been investigated. The method appears to be useful for the detection of polyaromatics, N-heterocycles, sulfur compounds, and fluorescent dyes (45). Many polynuclear aromatic compounds containing heterocyclic sulfur in the bay region exhibit fluorescence spectra at cryotemperatures. Fluorescence can be used for the detection of these compounds (19). LlTERATURE CITED
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