Anal. Chem. 1981, 53, 174R-182R (557) Umbach, E., Kulkarni, S., Feulner, P., and Menzel, D., Surf. Scl., 88,
- .- .-.
65 -, 1878
(558) Umeno, M., Yoshlmoto, M., Shimizu, H., and Ameniya, Y., Surf. Scl., 86,314, 1979. (559) Van den Berg, J. A., Verheij, L. K., and Armour, D. G., Surf. Scl., 91, 218. 1980. (560) -Vander Veen, J. F., Smeenk, R . G., Tromp, R. M., and Saris, F. W., Surf. Sci., 79,219, 1979. (561) Van der Veen, J. F., Tromp, R. M., Smeenk, R. G., and Sarls, F. W., Surf. Sci., 82,488, 1979. (562) Van OoiJ, W. J. and Klelnhesselink, A., Appl. Surf. Sci., 4 , 324, 1980. (563) Van Oolj, W. J., Klelnhesselink, A.. and Levenaar. S. R., Surf. Sci.. 89, 165, 1979. (564) Van Strien, A. J. and Nleuwenhuys, B. E., Surf. Sci., 80,226, 1979. (565) Varma, M. N. and Baum, J. W., Energy Res. Abstr., 4 , Abstr. No. 30942, 1979. (566) Vasquez, R. P. and Grunthaner, F. J., Surf. Sci., 99, 681, 1980. (567) Vedrine, J. C., Prallaud, H., Meriaudeau, P., and Che, M., Surf. Sci., 80, 101, 1979. (568) Venables, J. A.. Derrien, J., and Janssen, A. P., Surf. Sci., 95,411, 1980. (569) Venables, J. D., McNamara, D. K., Chen, J. M., Sun, T. S., and Hopping, R. L., Appl. Surf. Sci., 3 , 88, 1979. (570) Verheij, L. K., Van den Berg, J. A., and Armour, 0. G., Surf. Sci., 84, 408, 1979. (571) Verhoeven, J. A. T., Appl. Surf. Sci., 4 , 242, 1980. (572) Verhoeven, J. A. T. and van Doveren, H., Appi. Surf. Sci., 5 , 361, 1980. (573) Wada, M., Konishi, M., and Nlshikawa, O., Surf. Sci., 100,439, 1980. (574) Walmsley, D. G., Nelson, W. J., Brown, N. M. D., and Floyd, R. B., Appl. Surf. Sci., 5 , 107, 1980. (575) Wang, C. and Gomer, R., Surf. Sci., 90, IO, 1979. (576) Wang, C. and Gomer, R., Surf. Sci., 91,533, 1980. (577) Weber, M. F., Shanks, H. R., Bevolo, A. J. and Danielson, G. C., J . El8CtfOChem. SOC., 127,329, 1980.
(578) Weiss, M., Ertl, G., and Nitschke, F., Appl. Surf. Sci., 3 , 614, 1979. (579) Welssman, D. L., Shek. M. L., and Spicer, W. E., Surf. Scl., 92, L59, 1980. (580) Welkie, D. G., Lagally, M. G., and Palmer, R. L., J. Vac. Sci. Tecbnol., 17,453, 1980. (581) White, H. S. and Murray, R. W., Anal. Chem., 51,236, 1979. (582) Wler, L. M. and Murray, R. W., J . €lecfrocbem. Soc., 126,817, 1979. (583) Willlams, E. D., Chan, C.-M., and Welnberg, W. H., Surf. Sci., 81, L309, 1979. (584) Williams, E. D. and Welnberg. W. H., Surf. Scl., 82,93, 1979. (585) Wllliams, F. L. and Nelson, G. C., Appl. Surf. Scl., 3 , 409, 1979. (586) Willis, R. F., Surf. Sci., 89,457, 1979. (587) Wit, A. G. J., Bronckers, R. P. N., and Flult, J. M., Surf. Sci., 82, 177, 1979. (588) Wittberg, T. N., Hoenlgman, J. R., Moddeman, W. E., and Salerno, R. L., Appi. Surf. Scl., 4 , 531, 1980. (589) Wohlmuth, M. and Bechtold, E., Appl. Surf. Sci., 5 , 243, 1980. (590) Wollckl, E. A., I€€€ Trans. Nucl. Sci., NS26, 1800, 1979. (591) Yamada, Y. and Yoshida, K., Surf. Sci., 86, 161, 1979. (592) Yamamoto, F. and Yamakawa, S.,J . folym. Scl., folym. fhys. Ed., 77,1581, 1979. (593) Yanagihara, T., Surf. Scl., 86,62, 1979. (594) Yaney, P. P. and Becker, R. J., Appl. Surf. Sci., 4 , 356, 1980. (595) Yasumorl, I. and Inque, Y., fetrofech(Tokyo), 3 , 317, 1980. (596) Yates, J. T., Jr., Wllliams, E. D., and Welnberg, W. H., Surf. Scl., 91, 562, 1980. (597) Yates, J. T., $., Thiel, P. A., and Weinberg, W. H., Surf. Sci., 82,45, 1979. (598) Yates. J. T., Jr., Thiel, P. A., and Welnberg, W. H., Surf. Scl., 84, 427. 1979. (599) Y u , H. L., Munoz, M. C., and Soria, F., Surf. Sci., 9 4 , L184, 1980. (600) Zehner, D. M., White, C. W., and Ownby, G. W., Surf. Scl., 92,L67, 1980. (601) Zhdan, P. A., Boreskov, G. K., Boronin, A. I., Schepelin, A. P., Wlthrow, S. P., and Welnberq, W. H., Appl. Surf. Scl., 3 , 145, 1979.
Surfactants R. A. Llenado" and R. A. Jamieson Procter and Gamble Company, Ivorydale Technical Center, Cincinnati, Ohio 452 17
This selective review of the analysis of surfactants includes books, symposia, and journals published during the period 1975-1980. The citations are the result of a thorough searching of Chemical Abstracts and several journals devoted to analyses. Several hundred references were screened, reviewed, and sorted prior to preparing the final draft. We focused on the most important advances in the analyses of surfactants, and thus, we did not attempt to provide an allinclusive bibliography.
BACKGROUND Surfactant is shorthand for surface active agent. Surfactants are organic chemicals that, when added to a liquid, change the interfacial properties of that liquid. Surfactants function as wetting, foaming, dispersing, emulsifying, and or penetrating agents. Surfactants are most commonly classi led by whether or not they ionize in solution ...and by the nature of their ionic or electrical charges. Classifications by electric charges (or lack of) include anionic, nonionic, cationic, amphoteric, and semipolar. Anionic surfactants are negatively charged, nonionic uncharged; cationics are positively charged; amphoterics possess both positive and negative charges, while semipolar surfactants are those whose charges are induced in some way. We chose to organize this review based on surfactant types and then by techniques used for analyzing each surfactant type. The discussion that follows is oriented initially toward product application followed by environmental application. It is our belief that the readers would benefit most from this kind of organization. Analytical needs for surfactants cover a broad spectrum ...from quality control during manufacture to the measurement of trace quantities in environmental samples. Consequently, the isolation of surfactants prior to a given analysis requires different approaches, e.g., from detergent
i
174 R
0003-2700/8 1/0353-174R$O 1.2510
Table I. Important Periodical References for the Analyses of Anionic Surfactants type 1. linear alkylbenzenesulfonate (LAS) and branched alkylbenzenesulfonate (ABS) 2. alkyl sulfate (AS) or
sulfated alcohol 3. alkylethoxylated sulfate (AES) or sulfated alkyl ethers 4. a! olefinsulfonate (AOS) 5. alkane and petroleum sulfonates 6. soaps or alkylcarboxylates 7. alkyl sultones and other surfactants
ref 1B-22B, 44B-46B, 47B, 49B-51B, 53B-59B 23B-29B 18B, 24B 3B, 18B 5B, 33B-35B 30B-32B 36B-40B
and toothpaste matrices compared to sewage effluent and sludge. Because of space limitations, we chose not to discuss separately isolation techniques except when the authors of cited papers were clearly espousing the advantages of their respective approaches. There are a number of books, monographs, and review articles that should be consulted by those analyzing surfactants for the first time (IA-34A). Although some of this work was published prior tq the eriod of this review, important references are contained &at establish the need for or validity of the more recent work. During the course of our literature search, it was obvious that the separation techniques as a group contributed most of the recent advances in the identification, study, or analysis of surfactants. We also believe that the near future will see 0 1981 American Chemical Society
SURFACTANTS
-
__
-. - - ..-Table 11. Techniques Used for the Analyses of .
.- -.
Anionic Surfactants technique 1. two-phase titration, nonaqueous titration, turbidimetric, and volumetric analyses 2. gas chromatography 3. thin-layer chromatography 4. liquid chromatography 5. spectroscopy/ spectrophotometry
Robel A. Jamiwm~W e d hb B.S. da gree hom me UnivaoW of Rhode Is!and. Kkgstm. RI. In 1965 and was awardad a Ph.0. In 1971 trm Purdwt UnkersW where he waked wkh PTOI~SSMS. P. Perone. He began his IndusMal anaWCBl dremlstw CBreer In Faod DiVloion of Racter 6 Oam ble In 1971. In 1977 he became s~ctiMl head In Envhonmental Safety Department of PbG where he has been rarponsC ble fa me development 01 analvtlcal mem ods and environmental late intamallon of detnrpent-related materla1s.
6. radiometry
ref 2 1 4 48, 7B, 9B, 10B, 16B, 178. 34B. 39B
18A, lB, 3B. 19B. 208, 24B,33B, 388 5B, 36B, 37B,48B 358. 37B353B,54B, 55B-59B 17A, ZOA, 11B, 13B, 14B, 18B, 22B, 23B, 268, 31B, 32B, 40B. 44B, 45B,46B.47B, 4RB. 49B. 50B 12B
7. polarography
- .I
8. potentiometry
-
raoid advances via the use of multinuclei maenetic resonance spkctroscopy and the development of suifactant specific sensors/electrodes.
ANIONIC SURFACTANTS General. Anionic surfactants are currently manufactured in more than 2 X ld pound quantities per year (6A). Anionics comprised about 80% of all surfactants manufactured worldwide. It is not surprising, therefore, that the bulk of published literature on surfactants would deal with the analysis or characterization of anionics. Numerous books have been published dealin with the analysis of anionic surfactants (IA-4A); those by L e n (1A) and Cross (ZA) are especially recommended. Table I summarizes articles pertaining to s ific anionic surfactants. T h e number of published papers (%-59R) roughly parallels the manufactured quantities of the individual anionic surfactants. Thus. alkylbenzenesiilfonate has been the most widely studied surfactant followed by the alcohol sulfates, alkylethoxylated sulfates, n-olefin sulfonates, etc. Acronyms commonly used to descrihe these anionics are as follows: LAS. linear alkylbenzenesulfonate; ABS, branched alkylbenzenesulfonate; TBS, tetrapropylene alkylbenzenesulfonatee;AS, alkyl sulfate; AES, alkylethoxy sulfate; AOS, a (alkyl) olefinsulfonate. Although currently standard procedures in many surfactant laboratories, extensive research activities continue on twophase titrations, nonaqueous titrations, and other volumetric analyses (see Table 11) primarily because these techniques are reliable and easy to use for product development application. These older reference techniques, however, are slowly being replaced with newer more specific techniques such as gas chromatography, high-performance liquid chromatography, thin-layer chromatography, and mass spectrometry. Polarography and ion-selective membrane electrode potentiometry are opening new areas of research for rapid and selective anionic surfactant analysis. Nuclear magnetic resonance spectroscopy is an emerging and active field with numerous potential applications. We have listed references for each of these important techniques for the analysis of anionic surfactant in Table 11. Several volumetric methods for analyzing anionic surfactants have been reported (Table 11). Typical relative standard deviation for this type of analyses is 5 5 % with a detection limit of 225 mg/L. For example, the concentrations of al-
9.thermal analyses 10.nuclear magnetic resonance spectroscopy 11. mass spectrometry
__
~~~~~
~
42B, 43B
~~
kylbenzenesulfonates and alkyl sulfates were volumetrically determined by first titrating against a standard acid with a Bromphenol Blue-Acid Chrome Dark Blue indicator, hydrolyzing the mixture in concentrated HCI under reflux, and titrating again in the presence of the Same indicator (4R). Ono e t al. (7R) used poly(44nyl-1 ntylpyridinium bromide) to turbidimetrically determine z u m dodecylbenienesulfonate. The end poind was determined from transmittance a t 420 or 680 nm. Analogous nephelometric titration of alkylbenzenesulfonate has been carried out by using standard cetyltrimethylammonium bromide without any indicators (IOR). Sodium sulfate does not interfere. Nonaqueous titration of alkylbelenesulfonic acid in detergent intermediates has heen done with standard cyclohexylamine ( 9 R ) . A twophase titration method has been developed for analyzing alkybenzenesulfonate in which the excess quaternary ammonium salt is made partially soluble in CHCl and then titrated with standard sodium tetraphenylboron. $he method has been further modified (17R). Cas chromatographic analyses have been used for alkylbenzenesulfonate in different matrices, such as tap water ( I R ) and household detergent (3R). Alkylbenzenesulfonate has been converted to the thiol derivative (38)and then analyzed by GC using an OV-101 glass capillary column. Alkylbenzenesulfonate has been treated with SOCl in DMF to prepare a sulfonyl derivative, treated with MeOk to prepare methylakylhenzene, and determined by gas chromatography ( 1 9 R ) . Rranrhed and linear alkylbenzenesulfonates were distinguishable using 2% silicone OV-101 columns and flame photometric detectors. Watanahe e t al. (2OR) used PCI, to convert linear alkylbenzenesulfonate to the corresponding sulfonyl chloride followed by a9 chromatography. A method for determining al&ylbenzenesrilfonatebased on UV spectroscopy has heen developed (58)with relative errors of 2%. Ion association of alkylhenzene sulfonate and methylene hlue derivatives form the basis of a spectrophotometric analysis for alkylbenzenesulfonate ( I I R ) . In R similar spectrophotometric fashion, Azure A dye (13R. 22R) and Methyl Yellow (14R) have been used to measure alkylbenzenesulfonates. Clementz (12A) developed a radiometric method of determining alkylaromatic sulfonates in crude oil. The procedure is based on the formation of a stahle, chloroform-soluble complex between sulfonates and "Fe-labeled ferroin. An emerging technique for the rapid monitoring of surfactant is potentiometry with selective membrane electrodes. Hoke (6R) prepared an electrode selective for a pentadecylbenzenesulfonate. The active material is a nylon (ELVAMID 8064)membrane impregnated with the complex salt of penANALYTICAL CHEMISTRY, VOL. 53. NO. 5. APRIL 1981 * l75R
SURFACTANTS
tadecylbenzenesulfonic acid and Hyamine 1622. The resulting electrode responds to surfactant activity (concentration) from the critical micelle concentration down to lo-' M. The electrode has been used as an endpoint indicator for the potentiometric titration of alkybenzenesulfonate. The results by this method compare favorably with the methylene blue method (MBAS). Chloride ion was reported to interfere. Ivanov (8B)described a potentiometric method of analyzing alkylbenzenesulfonate using a similar approach. Ciocan (15B)described the potentiometric titration of sodium dodecylbenzenesulfonate with cetyldimethylbenzylammonium chloride. End points were determined with Ruzicka-type electrodes filled with dodecylbenzenesulfonate-ferroin complexes in o-dichlorobenzene-n-decanol solvents. A coated Pt wire electrode sensitive to dodecylbenzenesulfonate anion has been developed (21B). Zephiramine cation was ion-paired with dodecylbenzenesulfonate and then extracted in nitrobenzene. A comelt of naphthalene with nitrobenzene extract was solidified on a Pt wire electrode. Electrode performance characteristics were described. A few methods developed for alkylbenzenesulfonate are also applicable to alkyl sulfates (4B,11B, 18B). The determination of alkyl sulfates and their respective alkyl carbon distribution in deter ent formulations by gas chromatography has been reportecf (24B). The alkyl homologue distribution is determined by derivatization to alkyl iodides prior to GC analysis. A spectrophotometric method based on the development of a blue CHC13 layer when alkyl sulfate is extracted with methylene blue has been developed (23B). The cationic dyes Remacryl Blue B and Remacryl Red 2BL have also been used for the extractional spectrophotometric determination of lauryl sulfate (26B). A liquid membrane surfactant-sensitive electrode has been reported (25B) that is capable of detecting lo4 M sodium dodecylsulfate. Another ion-selective electrode sensitive to Cs-Clo alkyl sulfate has been described for monitoring the content of alkyl sulfate surfactants in process solutions and wastewaters (27B). Another paper described the preparation of a dodecyl sulfate electrode using as the active element a solution of cetylhexyldimethylammonium dodecylsulfate in nitrobenzene (29B). The analysis of alcohol ether sulfates by gas chromatography has been reported by Sones et al. (24B). The relative amounts of alkyl ether sulfates in mixtures separated from detergent formulations are determined by acid hydrolysis to give ethoxylated alcohols which are then converted to alkyl iodides and subjected to gas chromatography. The signal suppression of the differential pulse polarography can be used as the basis for measuring polyaminocarboxylic acids (30B). Mehrotra, et al. used infrared and thermal analysis to study rubidium soaps (31B). Also, by infrared spectroscopy, the concentration of aliphatic acid in surfactant mixtures was determined at 1710 cm-' (32B). Polarography (41B)was used to determine 0.1-10% di-2octylmaleate and di-2-octylfumarate in di-2-octylsulfosuccinate, sodium salt, with a relative standard deviation of 0.02%. The polarographic response of the esters was determined in aqueous EtOH and anhydrous DMF. In a method for lipophilic group analysis (33B),1,4-diisopropyl-6-naphthalenesulfonate is desulfonated by fusion with KOH a t 270-280 "C for 1 h under nitro en to form 1,4-diisopropyl-6-naphthol. Gas chromatograp ic analysis showed no reaction byproducts. Desulfonation with H3P04is not suitable for the analysis because of side reactions. Thin-layer chromatography and ultraviolet spectroscopy are used to determine sodium 1,8-dibutyl-4-naphthalenesulfonate (5B). The concentration of alkanedisulfonate can be determined by two-phase titration with Hyamine in water-chloroform containing phenolphthalein indicator (34B). Zornes et al. reported on the use of high-pressure liquid chromatography for the separation and quantitation of monoand disulfonates. The HPLC technique gave information on the sulfonate composition that was not obtained by traditional wet chemistry methods (35B). Long chain solutions have been analyzed by thin-layer chromatography (36B). Two-dimensional thin-layer chromatography with isopropyl ether and chlorinated solvent mixtures gave an exclusive sultone area, as well as added sensitivity.
a
176R
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
Saturated and unsaturated 1,3-and saturated 1,4-sultones were separated from anionic surfactants by ion-exchange chromatography, concentrated by thin-layer chromatography, and determined by high-performance liuqid chromatography bv comparing retention times and peak areas with reference c6mpo;nds (37B). O'Connell reported the analysis of coconut oil diethanolamide by gas chromatography after preliminary trimethylsilylation (38B). Stognushko et al. reported the analysis of the products of the esterification of higher fattv alcohols and maleic anhvdride (39B). Sodium bis(2-ethylhexy1)sulfosuccinate was determined potentiometrically with cetyldimethylbenzylammonium chloride as titrant (15B). Colorimetric determination of microquantities of dodecyldi(aminoethy1)glycine were described in which the reacid and action products of 1,2-naphthoquinone-4-sulfonic glycine were formed and the absorbance determined a t 505 nm or a complex of bromocresol purple and glycine were formed and the absorbance determined at 588 nm (40B). The mass spectrometry of quarternary ammoniohexanoates (42B) and hydroxyammoniocarboxylates (43B) have been reported by Sanders, et al. (42B) and Keough, et al. (43B), respectively. Environmental. The release of surfactants to the environment has required the development of sensitive analytical methods for their determination a t trace levels in a variety of sample matrices. Several excellent reviews in this area are available (20A, 31A, 32A). Of particular note is the review by Waters and Taylor (20A),which deals with colorimetric procedures for anionic surfactants in wastewater. The most commonly used and accepted method for anionic surfactants is the MBAS method (Methylene Blue Active Substance) as developed by Longwell and Maniece (44B). Methylene blue (MB) is a cationic dye that forms a salt with an anionic surfactant. This salt is readily extracted into CHC13 forming a blue color which is easily quantitated by absorbance at 652 nm. Since several substances in the environment, both organic and inorganic, cause a positive interference in this method, much effort has been devoted to improving sample cleanup procedures. Wickbold (45B),for example, indicated that ositive interferences in the Longwell-Maniece method coul be reduced by usin a sublation step to isolate anionic surfactants. The methof was applied to surface water and drinking water to demonstrate the improved selectivity. Uchiyama (46B), after initially extracting alkylbenzenesulfonate as the MB complex, reextracted the anionic surfactant back into an aqueous solution for subsequent quantitation by absorbance a t 222 nm. Oba et al. (18B) used an infrared technique to quantitate anionic surfactants in sewage and river water. Anionics were first extracted into CHC13 as the MB complex. Following extraction, anionic sulfates were hydrolyzed and then anionic sulfonates were released from the MB complex by ion exchange. The free anionic sulfonates were converted to the sulfonyl chloride derivatives for quantitation by IR. Absorbance bands a t 640,618, and 524 cm-l were used to identify and quantitate LAS, ABS, and AOS, respectively. Total anionic sulfate was determined by the difference in the MBAS value before and after hydrolysis. Hellmann (47B)has investigated the presence of anionic surfactants in suspended sediment, sediment, and sewage sludge. Anionics were extracted from dried samples with CH OH/2 N HC1 or CHBOH 2 N NH3, isolated initially by subtation and then as their IdB complex. The MB complex was purified by a two-step thin-layer process and finally quantitated by IR or colorimetry. Hellmann (48B) has also evaluated common procedures used to release the anionic surfactant from its MB complex. He found chromatography on silica gel will free the anionic surfactant without a structural change. On the other hand, acid extraction of CHC13-MBAS solutions was shown to release the anionic surfactant but cause a significant change in the IR spectrum of alkylbenzenesulfonate. Alkylsulfonates were unaffected. Cationic metal complexes have been used as reagents for the determination of anionic surfactants. Crisp et al. (49B) used the bis(ethy1enediamine) copper(I1) ion to form ionassociation complexes with anionic surfactants that are extractable into CHC13. Anionic surfactants were quantitated Y
;P
SURFACTANTS
indirectly by determination of copper via colorimetry or atomic absorption. Later Crisp et al. (50B)lowered the detection limit of this ap roach by using flameless atomic absorption. LeBihan andPCourtot-Coupez(5IB)also utilized flameless atomic as the absorbtion but used trit.,(o-phenanthroline)copper(II) cationic metal complex. Using the sensitive flameless technique, Crisp et al. (50B)reported a detection limit of 2 pg L for LAS. LeBihan and Courtot-Coupez (5IB),using smal er sample volumes, reported a very easy determination of anionics at the 10 pg/L level. These methods, which were applied to fresh, estaurine, and marine waters, are simple and appear to be more selective than standard colorimetric procedures. The direct determination of anionic surfactanb in effluents and biodegradation test liquors using electroanalytical techniques has been reported by Kozarac et al. (52E) and Cosovic and Hrsak (2B). In the work by Kozarac et al. (52B) surfactant quantitation was based on the measurement of the polarographic current maximum of Hg(I1) and of the capacity current by the Kalousek commutator technique. Both techniques are based on the effect of surfactant adsorption on the electrode surface. The Kalousek commutator technique was found to be superior to the polarographic maximum procedure because it was less sensitive to nonsurfactant organics and because it was applicable to the simultaneous determination of anionic and nonionic surfactants. All samples reported contained more than 2.0 mg L of anionic and nonionic surfactants. Cosovic and 14rsa (2B) monitored the biodegradation of LAS and T B 9 in synthetic sewage by using the Kalousek technique. Results were in good agreement with MBAS results that were run on the same samples. The newest analytical technique to be applied to the determination of anionic surfactants in waste and surface waters is high-performance liquid chromatography. Takano et aY. (53B, 54B) Concentrated ABS as the MB complex and chromatographed it on a silica gel column with detection at 225 nm. In the chromatographic process, the anionic surfactant is released from MB (which remains on the column) and separated as a protonated species in the solvent used. Recovery in river water waB 96.7% and a detection limit of 0.05 mg/L was reported. I-Iashimoto (55B) using a somewhat similar approach separated the MB complex by ion exchange prior to chromatography on silica gel. Gloor et al. (56B,57B) used reversed-phase HP1X to separate and quantitate LAS homologues as ion pairis using trimethylammonium as a counterion. Using only filtered samples, the authors detected about 1 mg/L LAS in raw wastewater and none in river water. The detection limit was 0.1 mg/L. Giger (58B) reported a reversed-phase HPLC technique where only solvent programming (35-75% CH&H in water) was used to elute LAS homologues. The detection limit was 0.1 m /L. Finally, Taylor and Nickless (59N developed a reversecfphase HPLC method based on ion pairing usin cetyltrimethylammonium ions. Samples were concentrated 6 y using XAD-4 resin. The method was used to follow the biodegradation of LAS.
i
k
NONIONI[C SURFACTANTS General. Nonionic suirfactants comprise the second most important class of surfactants after the anionic class (6A). The importance of nonionic surfactants is evidenced by the numerous publications covered by this review. Two important books dealing with nonionic surfactants have been published ( I A , I I A ) as well as numerous review articles (IC-6C). Most of the articles covered by this review dealt with the analysis of nonionic surfactants resulting from the condensation reaction between ethylene oxide and fatty alcohols or alkylphenols to form saturated or unsaturated ethers. The remaining types of nonionic surfactant covered in this review are conveniently categorized as shown in Table 111. The discussion that follows is arranged by techniques (see Table IV) (IC-72C). Foir nonionic surfactant analysis,. gas chromatography appears l o be the most important technique followed closely by high-performance liquid chromatography. One review paper (3C) discusses the use of several techniques-capillary gas chromatography, high-performance liquid chromatography, ,gel chromatography, and nuclear magnetic resonance spectroscopy-for the chemical analysis of ethoxylated alcohols and ethylene oxide-propylene oxide copolymer. Nichikova and co-workers (7C) reported on the analysis of
Table 111. Important References for the Analysis of Nonionic Surfactants nonionic type 1. reaction product between ethylene oxide and fatty alcohol R-O( CH,CH,-O),H
2. reaction product between ethylene
oxide and alkylphenols R-Ph-0-j
CH,CH,O),H
3. reaction product between ethylene
oxide and propylene oxide with
4. reaction products of fatty acids
with mono- and difunctional amines R-CON( C,H,OH) or
ref
2 c , a c , lOC, 1 2 c , 16C, 17C, 2 2 c , 24C, 25C, 29C, 31C, 33C, 36C, 39C, 40C, 44C, 51C, 52C, 53C, 54C, 56C-72C 2C, 7C, 14C, 17C, 27C, 28C, 30C, 35c, 37c, 39c, 45C, 51C, 52C, 56C-7 2C 3C, 17C, 43C, 55C-72C
2C, 11C, 13C, 17C, 34C, 41C, 50C, 52C
R-COOC,H,NHC,H,OH 5. reaction products of ethylene
15C, 17C, 21C
R-COO( CH,CH,O),H 6. sulfate, phosphate, and other
15C
oxide with fatty acids
esters of poly( ethylene glycol) monoalkyl ethers R-O( CH,CH,O),-X where X = SO,, PO,, OAc, etc. 7. reaction products of ethylene oxide with polyhydric alcohol or fatty acid-sugar esters
17C, 21C, 23C, 26C
Table IV. Important Techniques for the Analysis of Nonionics techniques 1. gas chromatography 2. high-performance liquid
ref
7C-l5C, 63C, 70C, 71C l C , 3C,16C-20C, 72C
chromatography
3. mass spectrometry 4. thin-layer chromatography 5. other type chromatography 6. UV-VIS spectrophotometry
2c 21C-28C, 64C, 67C 3C, 29C-31C 32C-41C, 56C, 58C-62C, 67C 7. infrared spectroscopy 20C, 23C, 30C, 42C-44C, 67C 8. X-ray fluorescence 42C, 45C, 57C 9. nuclear magnetic resonance 3C, 23C, 28C, 30C, 46C, 67C 10. potentiometry 42C, 47C, 48C, 51C, 56C 11. polarography 49C, 50C, 69C 12. atomic absorption 52C-54C. 65C. 66C
alkylphenols using gas chromatography with a flame ionization detector. The group separation of monoalkylphenols from diakylphenols was achieved on a temperature programmed (120-280 OC) 2-m column packed with 5% SE-30 on Chromaton N AW. The isomeric monoalkylphenols formed from the individual a-olefins were separated from each other at 190 "C on a 3-m column packed with 15% di(ethy1ene glycol) succinate on Chromaton N AW HMD5. The relative error was 6%. The olarity index of 39 nonionic surfactants was determined gy gas chromatography. With several homologous series of surfactants, a correlation was observed between the polarity index and the HLB value, dielectric constant, and surface tension of the surfactants. The polarity index was independent of the gas chromatographic parameters such as ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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SURFACTANTS
temperature, carrier, flow velocity, and column size (9C). The extraction of the nonionic surfactant-p-tertC~H&~H~O(CHzCHzO)nH-by various organic solvents was studied by gas chromatography. Of the solvents tested, 1,2dichioroethane appears to be best. The results were independently confirmed by a spectrophotometric technique (IOC). O'Connell ( I 1C) described a gas chromatographic method for analyzing coconut oil diethanolamide preparations containin byproducts and unreacted starting materials. The methoi requires preliminary trimethylsilylation. By application of this procedure, O'Connell showed the absence of 1,4piperazinediethanol and monoester amides but not hydroxyethylaminoethyl esters and diester amides. Kaduji and Stead ( I 2 C ) reported the determination of poly(oxyethy1ene) nonionic surfactant by hydrogen bromide fission followed by gas chromatography. The method appears to be applicable to detergent products. Fatty acid alkanolamides were determined by gas chromatography of trimethylsilylated alkanolamides prepared from the fatty amides and N,O-bis(trimethysily1)acetamide or by gas chromatography of the trimethylsilyl derivates of the acids and diethanolamine obtained by the hydrolysis of the amides (13C). The isomeric distribution of the nonionic surfactant poly(ethylene glycol) mono(4-(1,1,3,3-tetramethylbutyl)phenyl] ether was compared by gas chromatography and thin-layer chromatography (14C). The sulfate, phosphate, and fatty acid esters of poly(ethylene glycol) monoalkyl ethers were treated with the mixed anhydride prepared from p-toluenesulfonic acid and acetic anhydride to cleave the ester and ether links, and the reaction products were separated by gas chromatography to identify the hydrophobic groups of the ester type surfactants and distinguish between the types of surfactants (15C). Reviews of the analysis of nonionic surfactants by highperformance liquid chromatography have been written ( I C , 3C). Esters prepared from the nonionic surfactant-ethylene oxide alkanol condensate- and 3,5-dinitrobenzoyl chloride were separated by high-performance liquid chromatography and detected by a UV detector. The chromatographic column was packed with LiChrosorb RP-2 (5u) and kept at 50 "C. The mobile phase was 6:4 MeCN-water (16C). Nonionic surfactants and emulsifiers were analyzed by high-performance liquid chromatography on a column packed with Porasil. Alkylphenoi-, fatty acid-, fatty alcohol-, fatty amine-, and fatty amide-polyglycol ethers and ethoxylated and propoxylated products used in washing, cleaning, polishing, and auxiliary technical agents; fatty acid glycerides themselves and esterified with HOAc, citric, lactic, tartaric, and diacetyltartaric acid; and fatty acid esters with sorbitan, polyglycerol, and sugar used in foods and cosmetics were analyzed. Isooctane/iso-PrOH (99:1), iso-PrOH, and EtOH/H20 (9O:lO) were used for gradient elution. The separations were monitored by using a UV detector. The alkylphenolpolyglycol ethers and fatty acid esters were monitored by measurin the absorbance at 276 and 220 nm; respectively. The PO yglycol ethers not containing a UV chromophore were converted into their 2,5-dinitrobenzoyl esters and the absorbance was monitored at 254 nm. The emulsifiers were separated according to their hydrophilic properties. The retention times were longer and the more polar eluents were used for the more hydrophilic components (17C). Nakamura and Matsumoto reported on the use of highspeed liquid chromatography in the analysis of surfactants in cosmetics (18C, 19C). The analysis of carboxymethylated ethoxylates (21C) was reported by Kunkel. Carboxymethylated surfactants-R(OCH2CH2).0CH2COONa, where R = C12-18,and n = 310-are useful in petroleum recovery by waterflood. Kunkel determined these surfactants in aqueous and oil samples by thin-layer chromatography. After TLC separation, the plates are quantitated by using Dragendorff s reagent and reflectance measurements. Enrichment and pretreatment with macroporous ion exchangers enables determination in the microgram range. Semicroprepipitation with Dragendorff s reagent and photometric determination of bismuth can also be used to measure carboxymethylated ethoxylates, but only at somewhat higher concentrations and relatively high degrees of ethoxylation.
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Ascending thin-layer chromatography on silica gel with 1002.5 CHC1,-EtOH as the moving hase and Dragendorff s reagent as the developer was u s e f for determining poly(ethylene glycol) in oil well waters and in petroleum (22C). The method could also be used to approximate the molecular weight of the surfactant because as the Rf decreases the molecular weight increases. Satisfactory separation was also observed when A1203 or Silchrom S 80s was used as the stationary phase. Bergueiro and co-workers studied the composition of the sorbitan esters (Spans) and ethoxylated sorbitan esters (Tweens) by thin-layer chromatography, infrared spectroscopy, and nuclear magnetic resonance spectroscopy (23C). Aqueous solutions of poly(ethy1ene glycol) monodecyl ether were fractionated by column chromatography. A 3-g sample was suspended in 25 mL of PhMe on a 2.8 X 30 cm column packed with silica gel, washed with PhMe, and eluted with 60:40:1.5 (by vol.) MezCO-PhMe-H,O. Collected fractions were spotted on silica gel-Cas04 plate, developed with Me2CO-PhMe-HzO system, visualized with Dragendorff's reagent, and compared to standards (24C). The chromatographic method is used to separate the acetate ester of ethoxylated alcohols containing 0-12 oxyethylene groups. The separation depends on the number of oxyethylene grou s and is independent of alkyl chain length. Quantitation is ac ieved by spectrodensitometry. Analysis time is 19 min per sample (25C). The chemical composition and sucrose content of commercial sucrose monostearate and sucrose distearate were determined by thin-layer chromatography on silica gel with 3:2.2 PhMe-AcOEt-96% EtOH (26C). Nonionic surfactant determination by channel thin-layer chromatography has been described (27C). The amount of nonionic surfactant was determined from the length of the spot which appeared after spraying with a modified Burger reagent, and a silica gel thin-layer channel eluted with 90:457 CHC13-MeOH-H20 mixture a t 15 "C. The analysis of the ethylene oxide adducts of cardanol and 3-pentadecylphenol by thin-layer chromatography and nuclear magnetic resonance spectrometry has been described (28C). Danes and Casanovas (2C) described the use of mass spectrometry for the analysis of nonionic surfactants. The mass spectra of unseparated nonionic surfactants (coconut diethanolamides, ethoxylated fatty alcohols, akylphenols, fatty amines, or fatty acids) indicate the type of nonionic surfactant, aliphatic or aromatic character, and the presence or absence of nitrogen in the molecule. The degree of ethoxylation is estimated from the inlet temperature required to produce a good spectrum. An interesting and efficient method for enriching and concentrating dilute solutions of nonionic surfactants and separating them from cationic and anionic surfactants has been reported (29C). In the method, polyoxyethylene nonionic surfactants are retained by a ligand exchange process on a form. Several elution chelating exchanger in [CO(NH~)~OH,]~+ systems are tested; the most efficient was 1:l NH3/EtOH. Commercial nonylphenol useful for the manufacture of nonionic surfactants is separated into four fractions by column chromatography and characterized by infrared, nuclear magnetic resonance spectroscopy, and gas chromatography (30C). Anthony and Tobin described an immiscible solvent extraction scheme for polyethoxylate nonionic surfactants (31C). The surfactant is extracted with benzene and the surfactant and polyglycol material are salted out into CHCl3. The two species are recovered separately in a sequential extraction method. In the determination of nonionic surfactants, a method based on the use of ammonium cobaltothiocyanate gives better results than a potentiometric method with Dragendorff s reagent and a spectrophotometric method with phosphotungstate (32C). ' The quantitative determination of hydroxyethylated surfactant by treating with potassium tetraiodoplumbate at pH 12-14 was reported (33C). Schwarz and co-workers (34C) described the analysis of the condensation products of fatty acids or their methyl esters with aminoethylethanolamine. The quantitative oxidation of the hydroxyethylaminoethyl group by periodate is used for the direct determination of the secondary nitrogen.
R
SURFACTANTS
The interference of free polyethylene glycol in the colorimetric determination of small amounts of ethoxylated nonylphenol with Iz-KI has been studied (35C). Poly(ethy1ene glycol) interference can be avoided by its extraction, by addition of electrolytes to the solutions to be analyzed, or by raising the temperature (36C). Waters and Longman (37C) reported a modification.of the Wickbold procedure for the determination of nonionic surfactants. Separately, Hennequin and Lerenard ( 3 8 c ) statistically evaluated the original and modified Wickbold procedures. They found that in the final step of bismuth measurement, the spectrometric and potentiometric methods are equivalent. The accuracy of the complete method was 10-15%. A method for the determination of nonionic surfactant (alkyl or alkyl phenyl ethers of poly(ethy1ene oxide) in air has been described (39C). The method consists of drawing a known volume of air through a filter, extracting the filter with 1:4 EtOH-HzO mixture, adding a color reagent, and spectrophotometric determination a t 490 nm. The reagent was pre ared as follows: 1.3'%iodine, 2.5% KI, 9% HC1, 10% Ba81z in water. In another colorimetric approach (40C), poly(ethy1ene glycol) or its derivative is treated with HC104 and NaIO to cleave the polymer chains3 and produce HCHO which is listilled and determined colorimetrically. The acidimetric and spectrophotometric analysis of products of the cyclocondeneation reaction of higher fatty acids with polyethylene polyamines (41C) has been reported. Hellmann described a trace analysis for nonionic surfactants whereby the nonionic surfactants are adsorbed on clay minerals, e.g., bentonite, and eluted by solvents such as a 1:l mixture of CHCl,-MeOH. The extract is further separated by silica gel chromatography to remove unwanted foreign substances. The quantitation is then carried out with spectroscopy, X-ray fluorescence, and potentiometry (42C). Infrared spectroscopy has been used to measure the level of nonionic surfactants U?OC,23C, 30C) by coupling it with chromatographic techniques. Oxyethylene and oxypropylene groups on poly(oxyalkylene) are determined by IR absorption at 1380 and 1350 cm-'. Since these peaks overlap, the molar absorption coefficients for each group a t each frequency were determined for calibration purposes. The determination requires 5- 10 min and has a relative error of *6% ( 4 3 2 ) . The determination of 1 w t % polyglycol surfactant in nylon 6 by attenuated total reflectance IR has been developed (44C). X-ray flurescence spectroscopy has been applied to the analysis of nonionic surfactants (42C, 45C). Klima and coworkers (45C) described the linear relationship between the concentrations of surfactants, such as hydroethylated alkylphenols in samples of cleaning compounds, and the molybdenum ion concentrations in precipitates obtained by treating these nonionic surfactants with phosphatomolybdic acid. The molybdenum concentrations in the precipitates were determined by X-ray fluorescence spectrometry. The procedure involved the precipitation, filtration through MF-Millipore membrane, and scintillorn~etryof the precipitate directly on the membrane. Nuclear magnetic resonance spectrometrv has been amlied to the analysis and characterization of nonionic surfact'ants (3C. 23C. 28C. 30C). Analytical potentiometry has been used to quantitate nonionic surfactants in solution (42C, 47C, 48C). Molydophosphoric acid is useful as a reagent in the determination of nonionic surfactants b y potentiometric titration with a cathode polarized platinuin electrode. In the preferred method, the excess molybdophosphoric acid is titrated with the surfactant. There is a linear dependence between the surfactant concentration and the concentration of molybdophosphoric acid in the 10-80 mg surfactant range. Tungstophosphoric acid is not useful as a reagent (47C). Sugawara and cow-workers (48C) described the potentiometric and biamperometric titration of nonionic surfactants with standard K4Fe(CNI6. The polarographic determination of tergitol 08 has been described (49C). Ethoxylated fatty acids and oxyethylated fatty amides form solid coimplexes with molybdophosphoric acid which can be isolated and determined by polarography (50C). ~
Holmqvist (51C) reported on the determination of alkylphenol and alkyl alcohol based nonionic surfactants by a derivative chrono otentiometry method. The adsorption of surfactants at a ropping mercury electrode was examined and found suitable for analytical urposes. The size of the identation in the dE/dt curve a t t e potential of desorption was used for the quantitative estimation of the surfactant. A crude classification of surfactants was possible on the basis of the shape and size of the d E / d t curve. The quantitative determination of nonionic surfactants b atomic absorption procedures has been proposed (52C, 5 3 5 54C). One of the pro osed methods is based on the precipitat,ion of ethoxylatecfnonylphenol,ethoxylated oleylamine, and ethoxylated dodecyl alcohol as the surfactant-Ba(Bi1 )z complex, and its dissolution in tartrate solution, followed ky bismut,h determination by atomic absorption (520. The other method (53C, 54C) applicable for poly(ethy1ene glycol) is based on cobaltothiocyanate complex formation in benzene, followed by the determination of cobalt in the organic phase by flameless atomic absorption spectrometry. Environmental. The most widely used method for analysis of polyoxyethylene nonionic surfactants, such as polyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl ethers, in wastewater and surface water is known as the Wickbold procedure (56C). In this procedure nonionics are isolated by sublation into ethyl acetate. After evaporation, the residue is dissolved in water, and the nonionics are precipitated by treatment with a modified Dragendorff reagent (KRi14BaClz-glacial acetic acid). The precipitate is dissolved in an ammonium tartrate solution and bismuth determined potentiometrically. Various modifications have evolved since its development. Materials responding to the Dragendorff rea ents are called Dragendorff Active Substances (DAS). Hefimann (57C) determined the bismuth content of the precipitate directly by X-ray fluorescence analysis of the filtrate collected of filter paper. Waters and Longman (37C) determined the bismuth concentration of the dissolved precipitate by formation of the bismuth-EDTA complex and detection at 263.5 nm. The detection limit of this procedure was 0.025 mg/L and the procedure was shown to results comparable to the original Wickbold procefi::uce The second most widely used method for nonionic surfactants is a colorimetric procedure based on the formation of a complex between a nonionic and ammonium cobaltothiocyanate which is readily extracted into solvents such as benzene (58C). Quantitation is by absorbance measurementa at 320 nm. Substances reacting positively to this reagent are called Cobalt Thiocyanate Active Substances (CTAS). The detection limit for both the CTAS and DAS procedures is about 0.1 mg/L. Boyer et al. (59C) have evaluated the CTAS and BAS procedures and found both yield comparable results in wastewater, surface water, and in biodegradation test liquors (river die-away study). Both procedures utilized the unique sublation procedure developed by Wickbold (60C). The CTAS procedure was critically reviewed by Nozawa (61C). Favretto et al. (8C, 62C) have developed a colorimetric procedure for nonionic surfactants based on the formation of an adduct between the nonionic and an alkali picrate reagent. The adduct i s extracted into 1,Zdichloroethane and the absorbance at 378 nm was used to quantitate the surfactant. The initial procedure used sodium picrate (62C) but this was replaced by potassium picrate (8C) because it formed a stronger adduct which was less sensitive to the presence of anionic surfactants. These authors (63C, 64C) used GC and TLC to characterize the range of applicability (poly(oxyethy1ene) chainlength) of this method. Materials responding to the potassium picrate reagent are called Potassium Picrate Active Substances (PPAS). The method is stated to be more sensitive than the CTAS Drocedure and it can detect shorter chain poly(oxyethy1ene) components which can not be precipitated in the Wickbold BAS method (64C). Other methods that are based on the formation of adducts between nonionics and metal complexes have been developed. Crisp et al. (65C) have used potassium tetrathiocyanatozincate which forms an adduct that is extractable into 1,2-dichlorobenzene. Zinc is reextracted back into an aqueous acid solution and determined by atomic absorption. The method has been tested in freshwater, seawater, and estuarine water. Chlebrecki and Garncarz (66C) used excess molybdophosphoric acid to precipitate nonionic surfactants. The
B
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residual, unprecipitated molybdenum was determined by atomic absorption. Nonionics were detected in carpet factory effluent but not in surface water. The detection limit was 0.05 mg/L. LeBihan and Courtot-Coupez (54C)used flameless atomic absorption to determine cobalt extracted in the CTAS procedure. Sensitivity was about 10 pg/L. The method was applicable to riverwater and seawater. Jones and Nickless (67C)have proposed a method involving the separation and concentration of nonionics using XAD-4 resin. When applied to wastewater and river water samples, several cleanup steps were required ( 6 8 0 Isolated fractions were evaluated by TLC, IR, UV, and NMR to identify types of nonionics. Kozarac et al. (69C) used electroanalytical techniques to determine anionic and nonionic surfactants in sewage and laundry effluents (see anionic discussion). Hellmann (42C) has investigated the analysis of nonionic surfactants adsorbed to sewage slud e and bentonite. He found that a solvent mixture of CH30&/C2H50H/CHCl3/HC1 (concentrated) a t 1:1:1:1 ave complete recovery of nonionics adsorbed to bentonite. Eomplete recovery from sludge was not established. Wee (70C)has developed a gas chromatogra hic method for nonionics in wastewater and river water. Polygxyethylene) alkyl ethers were concentrated by extraction, purified by silica el chromatography, and cleaved by HBr to yield alkyl romides which were quantitated by gas chromatography. Wee reported a detection limit of about 0.5 pg/L in river water. Tobin et al. (71C)used a similar approach to follow the biodegradation of poly(oxyethy1ene) alkyl ethers. HPLC has been used by Cassidy and Niro (20C)and Otsuki and Shiraishi (72C)for the analysis of nonionic surfactants. Cassidy and Niro used molecular sieve columns to analyze nonionics and their degradation products in industrial effluents. Size fractions were collected and analyzed by IR. Otsuki and Shiraishi used reversed-phase HPLC for analysis of poly(oxyethy1ene) alkylphenyl ethers in river water. Nonionics were preconcentrated on the column and eluted with a methanol-water gradient. Recoveries in distilled water a t 1 and 0.05 mg/L were excellent. Field desorption mass spectrometry was used to confirm the presence of poly(oxyethylene) nonylphenyl ether in a small stream polluted by mainly domestic wastes.
6
CATIONIC SURFACTANTS General. Cationic surfactants comprise approximately 6% of the total production of commercial surfactants (6A). A number of books ( I A , 4A, 14A) have reviewed the analysis of cationic surfactants. Many analysis techniques have been reported (10-190). The most common procedure for cationic surfactant determinaton is by colorimetry (10-70). Malat (ID)described the direct determination of 1-carbethoxypentadecyltrimethylammonium bromide (KPTB). The method depends on color formation between the cationic surfactant and thiocyanate in chloroform. Catamin AB in rosin-turpentine products was determined photometrically at 540 nm following reaction with Brilliant Red 5 SKh d e in AcOEt (20). Kawase anJYamanaka ( 3 0 ) developed a continuous solvent extraction method for the spectrophotometric determination of cationic surfactants. The method is based on continuous extraction of the surfactant ion-pair complex with Orange 11. Good spectra and identical molar responses were obhned with seven types of cationic surfactants using MeOH and the Orange I1 reagent. Fatty amines were determined in mixtures with quarternary ammonium surfactants by changing the pH of the aqueous phase. Cationic surfactants in several commercial products were determined and the results agreed with those obtained by the two-phase titration. The detection limit was 5 uM and the capacity - was 10-20 samples/h with a precision of >1.5%. Cationic surfactants, e ., myristyldimethylbenzylammonium chloride and dohgecylpyridinium chloride were determined in water and wastewater a t concentrations of 1.5-6.0 pg by a scheme including ion-exchange separation, coloration by a modified Dragendorff reagent, and evaluation colorimetrically by comparison with standards. Different methods for determining cationic surfactants are reviewed (40).
The cationic surfactants-cetylpyridinium
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
benzyldimethylmyristylammonium chloridewere determined spectrophotometrically with methyl orange in the presence of nonionic or amphoteric surfactants. The cationic surfactants react with methyl orange and decrease the absorbance of methyl orange. The maximum absorbance is observed a t 462 nm and the absorbance is constant a t pH 6.0-8.0 ( 6 0 ) . Cationic surfactants can be extracted in benzene as the surfactant cobaltothiocyanate com lex and then measured by colorimetric or flameless atomic a sorption determination of the cobalt (70). The cationic surfactant-cetyldimethylbenzylammonium chloride-can be analyzed by UV spectrophotometry (80). The extraction and fluorometric determination of anthracene-2-sulfonate ion pairs was used for the determination of quarternary ammonium and alkylpyridinium halides a t 104-10-5 M concentration with methylene chloride, chloroform, and benzene as the organic phases (90). The fluorescence of the alkylpyridinium ion pairs was quenched in solvents of low dielectric constants. A polarorgraphic method is proposed for the determination of cationic surfactants (100)and is based on the decrease of the polarographic maximum of the oxygen wave of the solutions. The chromatographic separation of nine primary aliphatic amines was achieved by soap thin-layer chromatography (detergents on silanized silica gel) (110). Many separations that cannot be effected with either ion-exchan e or reversed-phase chromatography were accomplishe by this method. The gas chromatogra hic analysis of antistatic additives has been reported (1207. l-Aminoethyl-2-nonyl-2-imidazoline and i b 2-alkyl analogue are readil separated from the amides by gas chromatography (130). Tyhis cationic surfactant is used in detergent compositions. Quaternary ammonium containing surfactants were degraded (Hoffman reaction) in refluxing DMF-NaOMe mixture to give mainly a-olefins and alkyldimethylamines, and the homologue distributions of the compounds were determined by gas chromatography. The method was used for the determination of quarternary ammonium chlorides and alkyldimethylammonio&ane carboxylates and sulfonates (140). Environmental. Two laboratories have reported improved analytical methods for cationic surfactants in biodegradation test liquors and wastewaters. Waters and Kupfer ( 5 0 ) described a colorimetric method based on the reaction of disulphine blue, an anionic dye, with cationic surfactants. Quantitation was by absorbance measurement, a t 628 nm, of the chloroform extracted complex. Interestingly enough, the authors used an anionic surfactant to aid in the isolation and concentration of the cationic surfactant. After isolation, the cationic surfactant was released from the anionic surfactant by ion exchange and then treated with disulphine blue. Recovery of cationic surfactants from biodegradation test liquors was generally better than 95% and the limit of detection was 1 pg. The method has been tested in nutrient solutions, distilled water, and synthetic sewage but cannot be applied to waste and surface water samples due to other naturally occurring disulphine blue active materials. Michelsen (40,150)has developed a method for cationics in wastewater based on thin-layer chromatography and quantitation by densitometry. Cationics are isolated by sublation and released from ion-association compounds by ion exchange. The eluted cationic surfactant is separated by thin-layer chromatography and detected by spraying with Dragendorff reagent. Recovery of cationic surfactants in tap water and wastewater ranged from 98 to 113%. The limit of detection was about 0.002 mg/L when applied to sewage wastewater and industrial wastewater. Several other researchers have published methods for cationics but most deal only with analysis of standard solutions. de Zeeuw et al. (160)have developed an ion-pair TLC procedure using iodide or bromide as counterions. Nakae et al. (170) have developed a HPLC method for alkylbenzyldimethylammonium chloride and alkylpyridinium halides using a styrene divinylbenzene column and HCIOl in MeOH as a solvent. Detection was by UV absorbance at 220 nm. Kawase and Yamanaka ( 3 0 ) reported an ion-pair solvent extraction procedure using Orange I1 reagent. Finally, Parris (180)reported a reversed-phase HPLC method for cationics based on ion-pair chromatography using p-toluenesulfonic
;
f
SURFACTANTS
acid. The reported detection limit was 0.1 pg.
AMPHOTERIC SURFACTANTS There were few papers on amphoteric surfactants. Tanako et al. ( I E )reported on the analysis of amphoterics by reaction gas chromatography on the basis of the Hoffmann degradation reaction. Dmitrieva et al. (2E) determined amphoteric surfactants by potentiometric titration. Sanders et al. (42B) and Keough et al. (43B) reported on the mass spectrometry of quaternary ammoniohexanoates and quaternary hydroxyammoniocarboxylates, respectively. Parris (18D)used reversed-phase high-perforrnance liquid chromatography for the direct analysis of sulfobletaine amphoteric surfactants.
ACKNOWLEDGMENT The assistance of Rosemarie Blanchet and Beverly Pratt, technical information specialist, is gratefully acknowledged. LITEIRATURE CITED BOOKS, REVIEW ARTICLES, LECTURES, AND SYMPOSIA
(1A) Rosen, M. J. and Goldsmith, H. A. "Systematic Analysis of Surface Active Agents", Wiley-Interscience, New York, 1972. (2A) Cross, J., Ed. "Anionic Surfactants Chemical Analysis", VoL 8, Surfactant Science Series, Marcel Dekker, Inc., New York, 1977. (3A) Wlckboid, R. "The Analysis of Tenside", Chemische Mare, Germany, 1977. (4A) Hummel, D. "Identification and Analysis of Surface Actlve Agents by Infrared and Chemical Methods". Interscience, New York, 1962. (5A) Mittal, K. L., Ed., "Solution Chemistry of Surfactants", Plenum Press, New York, 1979, Vol. Iand 11. (6A) Frost and Sullivan, "Household Cleaning Products-USA", Frost and Sullivan Inc., New York, 1979. (7A) "McCutheon's Detergents and Emulslfiers", 'Mc Publishing Co., New Jersey, 1980, Annual, International edition. (EA) Sittig, M. "Detergent Manufacture", Noyes Data Corporation, New Jersey, 1979. (SA) Japanese Industrial Standards Committee, "Testing Methods for Synthesis Detergents" JIS-K3362, Japanese Standards Association, Tokyo, 1978. (10A) Soap and Detergent Association "A Handbook of Industry Terms", SDA, New York, 1979. (1IA) Schick, M. J., "Nonionic Surfactants", Vol. 1 Surfactant Science Series, Marcel Dekker, Inc., Nuvv York, 1967. (12A) Rosen, M.J., "Surfactants and Interfacial Phenomena", J. Wiley & Sons, Inc.. New York, 1978. (13A) Cutler, W. G. and Davis, R. C. "Detergency Theory and Test Methods", Vol. 5, Part 2, Surfactant Science Series, Marcel Dekker, Inc., New York, 1975. (14A) Jungerman, E., "Cationic Surfactants", Vol. 4, Surfactant Science Series, Marcel Dekker, Inc., New York, 1970. (15A) W. Linfleld, "Anionic Surfactants-Organic Chemistry", Vol. 7, Surfactant Science Series, Marcel Dekker Inc., New York, 1975. (16A) Gabriel, D. M. and Mulley, V. J., "Detection, Separation, and Isolation of Anionic Surfactant" in "Anionic Surfactants-Chemical Analyses", Cross, J., Ed., Marcel Dekker, Inc., New York, 1977, p. 1. (17A) Gabriel, D. M. and Mulley, V. J., Identification by Absorption Spectroscopy Techniques", in "Anionic Surfactants-Chemical Analyses", Cross, J., Ed., Mar& Dekker, Inc., New York, 1977, p. 91. (18A) Uno, T. and Nakagawa, T., "Gas Chromatography for the Analysis of Anionic Surfactants" in "Anionic Surfactants-Chemical Analyses", Cross, J., Ed., Marcel Dekker, Inc., Wew York, 1977, p. 109. (19A) Koenlg, H. "Nuclear Magnetic Resonance Spectrometry of Anionlc Surfactants" in "Anionic Surfactants-Chemical Analysis", Cross, J., Ed., Marcel Dekker, Inc., New York, 1977, p. 141. (20A) Waters, J. and Taylor, C. F. "The Colorimetric Estimate of Anionic Surfactants" in "Anionic Surfactants-Chemical Analysis", Cross, J., Ed., Marcel Dekker, Inc., New York, 1977, p. 193. (21A) Heinrath, E. "The Volumetric Estimation of Anionic Surfactants", in "Anionic Surfactants-Chemical Anaivsis". Cross. J.. Ed.. Marcel Dekker. Inc., New York, 1977, p. 221 (22A) Commlttee D-12 Handbook,, ASTM D-12-12, "Analysis of Soaos and Other Detergents:, 1972. (23A) Tr-Mezhdunar. Kongr. Poverkhn - Akt. Veshchastvam, 7th 1978, 1 (1977) (Proceedings - International Congress on Surface Active Substances, Moscow). (24A) Koenig, H., Frezenius 2.Anal. Chem., 293(4), 295 (1978). (25A) Kunkei, E., Tenside Deterggnts, 17(5), 247 (1980). (26A) Arpino, A., Riv. Ital. Sosi'anze Grasse, 52(12), 645 (1975). (27A) Kunzmann, T., Siefen, Oele, Fette, Wachse, 102(1), 22 (1976). (28A) Nakagawa, T., Yukagaku, 24(9), 618 (1975). (29A) Nakagawa, T., Yukagaku, 24(10), 691 (1975). (30A) Anghel, D. F., Popescu, G., Niculescu, F., Tenslde Detergents, 17(4), 171 (1980). (31A) Goulden, P. D. "Environmental Pollution Analysis", L. C. Thomas, Ed., Hegden & Sons, Ltd., 1978, p. 144-147. (32A) Kunkel, E., Tenside Detergents, 17, 247 (1980). (33A) Longman, G. F. "The Analysis of Detergents and Detergent Products", John Wiley & Sons, 1975.
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(34A) Longman, 0. F., Talanta, 22, 621 (1975). ANIONIC SURFACTANTS (18) Imaida, M.,Suminoto, T., Miyano, K.,Yoshida, A., Osaka-Furitsu Koshu Eisei Kenkyusho Kenyu Hokoku, Shokuhin Eisel Hen, 10, 63 (1979). (28) Cosovic, B., Hrsak, D., Tenside Deterg. 18(5), 262 (1979). (38) Matsutani, S.,Shige, T., Nagai, T., Yukagaku, 28(11), 847 (1979). (48) Ivanov. V. N., Neftepererab. NBftekhim (Moscow) (7). 49 (1979). (58)Vardloana, E. Y., Vaselovskaya, N. V., Benenfeld, V. M., Chumaevski, E. V., Dzhagatspanyan, R. V., Tr-Mezhdunar. Kongr. Poverkhn-Aki. Veshchastvan, 7th 1, 537 (1977). (68) Hoke, S. H., Collins, A. G., Reynolds, C. A., Anal Chem., 51(7), 859 (1979). (78) Ono. T., Miyata, H., Toei, K., Bull. Chem. SOC.Jpn., 52(2), 425 (1979). 188) Ivanov. V. N.. Stoanushko. D. P.. Nefteoererab. Neftekhim (Moscow), ' (7), 41 (1978). (98) Yamaguchl, S.,Nukul, S., Kubo, M.,Konishi, K., J . Am. OIl Chem. SOC.,55(3), 359 (1978). (108) Ivanov. V. N., Gorina, N. I., Stognushko, D. P., Tember, G. A., Volkov, I.A., Masio-Zhir. from-St., (S), 24 (1977). (118) Toel, K., Fujii, Hideyo., Anal. Chim. Acta, 90(1), 319 (1977). (128) Clementz, Davld M., Anal. Chem. 49(8), 1148 (1977). (138) Wang, L. K., Ross, R. G., Inf. J . Environ. Anal. Chem. 4(4), 285 (19761. (148) Fabre, H., Kamenka, N., J. Pharm. Be@.,31(5), 467 (1976). (158) Clocan, N., Anghel, D. F., Anal. Lett., 9(8), 705 (1976). (168) Wang, L. K., Yang, J. Y., Ross, R. G., Wang, M. H., Water Res. Bull., 11(2), 267 (1975). (178) Wang, L. K., Panzardi, P. J., Schuster, W. W., Awenbach, D. E., J . Envlron. Health, 38(3), 159 (1975). (188) Oba, K., Miura, J., Sekiguchi, H., Yagi, R., Mod, A., WaterRes., 10(2), 149 (1976). (198) Imaida, M., Suminoto, T., Yada, M., Yoshida, M., Koyama, K., Kunita, N., Shokuhin Elselgaku Zasshi, 16(4), 218 (1975). (208) Watanabe, S.,Nukiyama, M., Takagi, F., Ilda, K., Kalse, T., Wada, Y., Shokuhin Eiseigaku Zasshi, 16(4), 212 (1975). (218) Kataoka, M., Kambara, T., Denki Kagaku Oyobi Kogyo Butsuri Kagaku, 43(4), 209 (1975). (228) Wang, L. K., Panzardi, P. J., Anal. Chem., 47(8), 1472 (1975). (238) Perov, P. A., Bogoiepov, A. V., Kozhanov, 8. P., Tolkacheva, 0,A., Neftepererab Neftekhim (Moscow) (E), 42 (1979). (248) Sones, E. L., Hoyt, J. L., Sooter, A. J., J. Am. Oil Chem. Soc., 56 (7), 689 (1979). (258) Anghel, D. F., Ciocan, N., Popescu, G. Tr. Mezhdunar. Kongr. Poverkhu-Akt. Veshchestvam, 7th 1976, l,524 (1976). (268) Yaneva, S.,Borlsova-Pangarova, R. Talanta, 25 (5),279 (1978). (278) Rakhamanlko. E. M., Starobinets, G. L., Laevskaya, G. A,, Vests! Akad. Navuk BSSR, Ser. Khim. Navuk (9, 80 (1976). (288) Anghel, D. F., Popescu, G., Nlculescu, F., Tenside Detergents, 17(4), 171 (1980). (298) Popa, G., Geafar, B . , Luca, C., Rev. Chim. (Bucharest), 25(9), 748 (1974). (308) Christmann, W., Lukaszewski, Z.,Neeb, R., Frezenius Z. Anal. Chem., 302(1), 32 (1980). (318) Mehrotra, K. N., Saroha, S. P., J . Indian Chem. Sac., 56(5), 466 (1979). (328) Gerasimova, N. T., Krut, V. V., Perov, P. A., Neftepererab. Neffekhim (Moscow), (3, 42 (1978). (338) Kanno, S.,Hanzawa, Y., Baba, H., Ogawa, A., Takahashi, T., Yukagaku, 29(4), 265 (1980). (348) Liebscher, G., Eppert, G., 2.Chem. 19(2) 69 (1979). (358) Zornes, D. R., Willhite, G. P., Michnick, M. J., SOC.Pet, Eng. J., 18(3), 207 (1978). (368) Wolf, T., McPherson, 8 . P , J . Am. Oil Chem. SOC., 54(9), 347 (1977). (378) Macmillan, W. D., Wright, H. V., J . Am. Oil Chem. SOC.,54(4), 163 (1977). (388) O'Connell, A. W., Anal. Cbem., 49(6), 835 (1977). (398) Stognushko, D. P., Ivanov, V. N., Tember, G. A., Getmanskaya, Z. I., Usatenko, Y. I., Maslo-Zhir. Prom-St., (3), 24 (1977). (408) Asahi, Y., Hayashibara, M., Takeda Kenkyusho Ho, 34(2), 148 (1975). (418) Zhdamarov, 0. S.,Zhdamarova, V. M., PotaDenko. S. G.. Zh. Anal. Khim., 30(5), 996 (1975). (428) Sanders, R . A., DeStefano, A. J., Keough, T., Org. Mass Spectrom. 15(7), 348 (1980). (438) Keough, T., Destefano, A. J., Sanders, R. A,, Org. Mass Spectrom. 137). 351 (1980). (448)' Longwell, J. and Maniece, W D., Analyst (London), 80, 167 (1955). (458) Wickbold, R., Tenside Detergents 13, 32 (1976). (468) Uchiyana, M., Water Research, 11, 205 (1977). (478) Hellmann, H., Fresenius 2. Anal. Chem. 295, 393 (1979). (488) Helimann, H. Fresenius Z. Anal. Chem. 294, 379 (1979). (498) Crisp, P. T., Eckert, J. M., and Gibson, N. A,, Anal. Chim. Acta 78, 391 (1975). (508)Crisp, P. T., Eckert, J M., Gibson, N. A,, Klrkbright, G. F,, and West, T. S.,Anal. Chim. Acta 87, 97 (1976). (518) LeBihan, A. L., and Courtot-Coupez, J., Anal. Lett. 10, 759 (1977). (528) Kozarac, Z.,Zutic, V., and Cosovic, B., Tenside Detergents 13, 260 (1976). (538) Takano, S.,Yagi, N. and Kunihiro, K., Yukagaku 24, 389 (1975). (548) Takano, S., Takasaki, C., Kunihiro, K., and Yamanaka, M., Yukagaku 25, 31 (1976). (558) Hashimoto, S., Sakurai, K., and Nagai, T., Benseki Kagaku 25, 839 (1976). (568) Gloor, R., and Johnson, E. L., J . Chromatogr. Sci. 15, 413 (1977).
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
181 R
Anal. Chem. 1981, 53, 182R-214R (578) Gioor, R., Johnson, E. L., and MaJors, R., Varian Pub/. #35, 1977. (588) Giger, W., Staub, E., and Schaffner, L., ACS Abstr., April 1979. (598) Taylor, P. and Nickiess, G., J. Chromafogr. 178, 259 (1979). NONIONIC SURFACTANTS
(1C) Daiichi Kogyo Seiyaku Kogyo K.K., Daiichi Kogyo Selyaku S h a h , 404, 10 (1979). (2C) Danes, E. J., Casanovas, A. M., Tenslde Deterg., 18(6), 317 (1979). (3C) Vonk, H. J., Van Weiy, A. J., Van der Ven, L. G. J., De Breet, A. J. J., Van der Maeden, F. P. B., Biemond, M. E. F., Venema, A,, Huysmans, W. G. B., Tr.-Mezhdunar. Kongr. Pov8rkhn.-AM. Veshchestvam, 7th, 1, 435 (1977). (4C) Yamanaka, M., Yukagaku, 27(12), 821 (1978). (5C) Daradics, L., Rev. Chem. (Bucharest), 29(8), 764 (1978). (6C) Kirby, 0. H., Barbuscio, F. D., Metzger, W., Hourihan, J., Cosmef. Perfum., go@), 19 (1975). (7C) Nichikova, P. R., Rud, A. N., Tember, G. A,, Getmanskaya, 2. I., Ivanov, V. N., Zerzeva, I. M., Martynushkina, A. V., Neffepererab. Neffekhirn (Moscow),(3), 46 (1979). (8C) Favretto, L., Stancher, B., Tunis, F., Analyst(London),103(1230), 955 f,l .P-7.R-1,. (9C) Broniarz, J., Wisniewskl, M.. Szymanowskl, J., Abh. Akad. Wiss. DDR 1976. 125 119771. (IOC). Stancher, B., Tunis, F., Favretto, L., J . Chromatogr.,131, 309 (1977). (11C) O'Conneii, A. W., Anal. Chem., 49(8), 835 (1977). f12C) Kaduii. 1. I.. Stead. J. B.. A n a h t (London). lOl(12061. 728 (19781. ~, (l3C) Oka, 'H., Kojima, T.; Bunsekl Kigaku, 25(11), 757 (1976). (14C) Stancher, B., Gabrlelii, L. F., Favretto, L., J. Chromatogr.,111(2), 459 (1975). (15C) Tsuji, K., Konoshi, K., J. Amer. Oil Chem. SOC.,52(3), 106 (1975). (16C) Nazawa, A,, Ohnuma, T., J. Chromafogr. 187(1), 261 (1980). (17C) Brueschweiier, H., Miff. Geb. Lebensmlffelunters. Hyg., 88(1), 46 (1977). (18C) Nakamura, K., Matsumoto, I., Yukagaku, 26(8), 464 (1977). (19C) Nakamura, K., Matsumoto, I., Nlppon Kagaku Kalshl, (E), 1342 (1975). (20C) Cassidy, R. M., Niro, C. M., J. Chromatogr., 126, 787 (1976). (21C) Kunkel, E., Tenside Deterg., 17(1), 10 (1980). (22C) Safiuiiina, L. A,, Asanbaeva, D. N., Shtangeev, A. L., Tr. Bashk. Gos. Nauchnoissled. Proektn. Inst. Neff. Prom.-Sf., 53, 64 (1978). (23C) Bergueiro, J. R., Bao, M., Casares, J. J., Ing. Quim., 10(115), 275 (1978). (24C) Kofanov, V. I., Kiimenko, N. A,, Zavod. Lab., 43(6), 668 (1977). (25C) Fischesser, G. J., Seymour, M. D., J. Chromatogr., 135(1), 165 (1977). (26C) Vertyullna, L. N., Subbotina, A. I., Leonov, M. R., Bobinova, L. M., Trofimov, N. N., Tr. Khim. Khim. Tekhnoi., (3) 112 (1975). ( 2 7 0 Goretti, G., Liberti, A., Petronio, B. M., Rlv. Itai. Sostanze Grasse, 52(5), 165 (1975). (28C) Subbarao, R.,Harigopal, V. P., Feffe, Selfen, Ansfrichm., 77(5), 197 119751 (29C) Carunchio, V., Liberatori, A., Messina, A,, Petronio, B. M., Ann. Chim. (Rome), 69(3), 165 (1979). f30C1 Werner. G.. Tenside Detero.. 16151. 247 (1979). b i c j Anthony, D. H. J., Tobin, R: s., &ai. them., 49(3), 398 (1977). (32C) Mancini, P., Racaneiii, E., Riv. Merceol, 17(2), 219 (1978). (33C) Parkhomovskii, V. L.. Dubrovskaya, N. Y., Otkryriva Izobret. Prom. Obraztsy Tovarnye Znaki, (17), 152 (1979). (34C) Schwarz, G., Leenders, P., Pioog, U., Feffe, Seifen, Ansfrichm., 81(4), 154 (1979). (35C) Sanchez, L. J., GarciaDomlnguez, J. J., Invest. Inf. Text. Tensiascfovos. 2014). 349. 119771. ..., - . ,, ~ ~ . . (36C) Sanchez, L. J., Sohns, C., Comelles, F., Invesf. Inf. Text. Tensioactovis, 20(3), 243 (1977). (37C) Waters, J., Longman, G. F., Anal. Chlm. Acta, 93, 341 (1977). (38C) Hannequin, C.,Lerenard, A., Analusis, 3(3), 177 (1975). (39C) Manaeva, A. I., Iiina, L. A., Bratchin, V. V., Vasiienko, G. V. Gig. Tr. Prof. Zaboi, (2),56 (1980). (40C) Huber, W., Froehike, E., Tenside Deterg. 12(1), 39 (1975). (41C) Krut, V. V., Enina, 0. N., Safina, L. G., Chistyakov, B. E., Neffepererab. Neftekhim. (Moscow),(I), 42 (1977). (42C) Heiimann, H., Frezenius 2.Anal. Chem., 300(1), 44 (1980). ( 4 3 3 Perov, P. A., Tember, G. A., Volkov. Y. M., Gerasimova, N. T., Neftepererab. Neftekhlm. (Moscow),(2), 47 (1979). (44C) Haensei, B., Otto, C.,Faserforsch. Textilfech., 28(2), 81 (1977). (45C) Klima, Z.,Winkler, W., Gega, H., Przegl. Wlok., 31(6), 297 (1977). (46C) Prati, G., Vicini, L., Seves, A,, Jus, A., Arpion, A,, Mezhdunar Kongr. Poverkhn-Akt. Veshchesfvam, 7th 1976, 1, 470 (1977). - r
\ . - . . I .
\ . - . - I .
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(47C) Vinnikov, Y. Y., Kostareva, L. A., Zh. Anal. Khim., 53(3), 547 (1980). (48C) Sugawara, M., Maruyama, K., Kambara, T., Bunseki Kagaku, 24(9), 598 (1975). (49C) Lipchinski, A., Nikoiova, V., Frezenlus 2. Anal. Chem., 291(3), 223 (1978). t5OC) Gega, H., Wojcik, Z., Moniuk, D., Przegl. Wlok., 31(7), 352 (1977). (51C) Hoimqvist, P., Anal. Chim. Acta, 90(1), 35 (1977). (52C) Giacobetti, S.,Lagana, A., Petronio, 8. M., Russo, M. V., Riv. Ita/. Sostanze Grasse, 55(8), 176 (1978). (53C) LeBihan, A., Courtot-Coupez, J., Analusis, 6(8), 339 (1978). (54C) Lebihan, A., Courtot-Coupez, J., Anal. Lett., 10(10), 759 (1977). (55C) Chlebicki, J. and Garncarz, W., Tenslde Detergents, 15(4), 187 (1978). (56C) Wickboid, R., Tenside 9, 173 (1972). (57C) Helimann, H., Fresenius ZAnal. Chem. 297, 102 (1979). (58C) Greff, R. A., Setzkorn, E. A., and Leslie, W. D., J. Am. Oil Chem. SOC.42, 180 (1965). (59C) Boyer, S.L., Guin, K., Kelly, R., Mausner, M., Robinson, H., Schmitt, T., Stahi, C.,and Setzkorn, E., Env. Sci. Techno/. 11, 1167 (1977). (60C) Wickboid, R., Tenside 8, 61 (1971). (61C) Nozawa, A., Oknuma, T., and Sekine, T., Analyst(London) 101, 543 (1976). (62C) Favretto, L., and Tunls, F., Analyst(London) 101, 198 (1976). (63C) Favretto, L., Stancher, B., and Tunls, F., Analyst (London) 104, 241 (1979). (64C) Favretto, L., Stancher, B., and Tunis, F., Analyst (London) 105, 833 (1980). (65C) Crisp, P. T., Eckert, J. M., and Gibson, N. A,, Anal. Chim. Acta 104, 93 (1979). (66C) Chiebreckl, J., and Garncarz, W., Tenside 17, 13 (1980). (67C) Jones, P., and Nlckless, G., J . Chromafogr. 158, 87 (1978). (68C) Jones, P., and Nickiess, G., J. Chromafogr. 156, 99 (1978). (69C) Kozarac, Zutlp, V. and Cocovic, B., Tenside 13, 260 (1976). (70C) Wee, V. T., Advances in the Identification and Analysis of Organic Pollutants", L. H. Keith, Editor, in press. (71C) Tobin, R. S.,Onuska, F. I., Brownlee, B. G., Anthony, D. H. J., and Comba, M. E., Wafer Res. 10, 529 (1976). (72C) Otsuki, A., and Shiraishi, H., Anal. Chem. 51, 2329 (1979). CATIONIC SURFACTANTS
(ID) Maiat, M., Frezenius 2. Anal. Chem., 297(5), 417 (1979). (20) Masiennikov, A. S.,Shiikina, M. A., Lesokhim. Podsochka, (9), 10 (1979). (3D) Kawase, J., Yamanaka, M., Analyst (London), 104(1241), 750 (1979). (4D) Michelsen, E. R., Slefen, &/e, Feffe, Wachse, 104(4), 93 (1978). (5D) Waters, J., Kupfer, W., Anal. Chim. Acta, 85(2), 241 (1976). (6D) Nishida, M., Kanamori, M, Ooi, S., Miyagishi, S., Yukagaku, 25(1), 21 (1976). (70) LeBihan, A., Courtot-Coupez, J., Analusis, 4(2), 58 (1976). (ED) Wang, L. K., Aulenbach, D. B., Langley, D. F., Ind. Eng. Chem. Prod. Res. Dev., 15(1), 68 (1976). (9D) Zapior, B., Keilner, A., Czapklewlcs, J., Chem. Anal. (Warsaw),20(4), 823 (1975). (10D) Baloiu, L. M., Popescu, M., Cretu, S., Rev. Chim. (Bucharest), 30(8), 799 (1979). ( I I D ) Lepri, L., Desideri, P. G., Heimier, D., J. Chromatogr., 153(1), 77 (1978). (12D) Pustavaiova, L. M., Bogosiovskii, Y. N., Makarov, G. V., Tr. Mosk. Khim. Tekhnol. Inst., 88, 50 (1975). (13D) Batukova, G. I., Davydov. V. D., Rodimushklna, N. E., Suchkov, V. V., Koiomiets, B. S.,Kurlyaninova, L. P., Zh. Anal. Khim., 32(7), 1482 (1977). (14D) Takano, S.,Takasaki, C.,Kunihiro. K.. Yamanaka. M.. J. Amer. Oil Chem. SOC.,54(4), 139 (1977). (15D) Micheisen, E. R., Tenside Detergents, 15, 169 (1978). (16D) De Zeeuw, R. A., van der Loan, P. E., Greving, J. E., van Mansveit, F. J. W., Anal. Leff.,9, 831 (1976). (17D) Nakae, A., Kunjhiro, K., Mato, G., J. Chromatogr., 134, 459 (1977). (18D) Parris, N.. J. Li9. Chromafogr. 3, 1743 (1980). (19D) Kawase, J., Anal. Chem., 52, 2124 (1980). AMPHOTERIC SURFACTANTS
(1E) Takano, S.,Kuzukawa, M., Yamanaka, M., J. Amer. Oil Chem. SOC. 54, 11, 484 (1977). (2E) Dmitrieva, L. F., Koiomiets, B. S., Maksimikhina, T. I., Kudryavtseva, M. I., Shcherbik, L. K., German, V. K., Suchkov, V. V., Maslo-Zhir. PromSt., (6), 22 (1975).
Water Analysis M. J. Fishman," D. E. Erdmann, and T. R. Stelnheimer U.S. Geological Survey, Federal Center, MS 407, Denver, Colorado 80225
This nineteenth literature review of analytical chemistry applied to water analysis covers the period from October 1978 182 R
through September 1980. The present review follows the plan of previous reviews, the last of which appeared in ANALYTICAL
This article not subject to US. Copyright. Published 1981 by the American Chemical Society
