Anal. Chem. 1982, 5 4 , 58R-62R
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 1979 through Nov 1981. Several topics are not listed under the classifications which follow but are of general interest. A new book on the determination of elements and groups has been published (7). Absorption spectroelectrochemistry may be useful for analytical procedures involving oxidation-reduction systems. Compounds which have been studied include 4-amino-4’methoxydiphenylamine, tris(5-nitro-1,lO-phenanthroline)iron(I1) perchlorate, and 4,4’-diamino-3,3’-dimethylbiphenyl (102). Room-temperature phosphorescence gives promise as a new analytical technique (72). Multiplex gas chromatography (74)and functional group analysis of interferometric data from gas chromatography/Fourier transform infrared spectroscopy (108) are also topics of current interest. Several pentafluorophenyldialkylchlorosilanes are described as versatile derivatizing agents for use in gas chromatography with electron-capture detectors (76). The use of ion-selective electrodes and sodium tetraphenylborate as titrant permits potentiometric precipitation titrations of a variety of water-soluble cations such as quaternary ammonium salts, alkaloids, dyes, and other organic bases (88). Organic analysis via phosphorimetry has been reviewed recently (107). Acids. Techniques for converting acids to esters for subsequent determination by chromatography include the use of a poly(crown ether), poly(methacryloylaminobenzo-15crown-5), as a catalyst for preparing p-bromophenacyl esters of lower alkanoic acids for gas chromato aphic determination (43) and the use of potassium fluorig as catalyst for the preparation of phenacyl, p-bromophenacyl and p-phenylphenacyl esters for determination by high-performanceliquid chromatography (57). Both methods give high conversions at room temperature. For the preparation of methyl esters, the use of trimethylsilyldiazomethane is recommended as a safer reagent than diazomethane (33). For the determination of a variety of acids and phenols in water, extractive alkylation with tetrabutylammonium ion as counterion and pentafluorobenzylbromide as alkylating agent is used to prepare the samples for glass capillary _ gas _ chromatography (26). In Dolvmers having a low carboxvl content (0.1-0.002 mol %) tlie Earboxyl grckps are esterfied with 9:anthryldiazomethane and determined by IR (55). A spectrophotometric determination uses a water-soluble carbodiimide, l-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate, to convert acids to hydroxamic acids (95). Visual titration of otherwise insoluble acids is possible when the titration is carried out in a system containing cationic micelles (73). Conductometric titrations with 0.1 M N,N’-diphenylguanidine as the titrant in 2-methoxyethanolgive comparable precision and accuracy to that obtained for titration of carboxylic acids in nonaqueous solvents and is also useful for determination of phenols and aromatic nitro compounds (77). For preparing derivatives of 1,2- and 1,3-diols suitable for gas chromatography, ethylphosphonothioic dichloride (CH3CH PSC12)has been found useful. The cyclic derivatives can be ietected a t the low picogram level with an N-P detector or with a flame photometric detector. The derivatives also produce characteristic mass spectra which mi ht be useful in GC-MS work. The reagent also forms useful ferivatives with 1,2- and 1,3-aminohydroxy compounds and with p- and yhydroxy acids (75). Alcohols. 1,2-Diols (and a-amino alcohols) have been titrated potentiometrically with a special liquid-membrane 58 R
type periodate ion-selective electrode (48). In a different procedure, both aliphatic and phenolic 1,2-diolsare oxidized by excess potassium periodate. The excess is precipitated as lead periodate and determined by atomic absorption (96). 13C NMR has been utilized satisfactorily for the determination of the primary hydroxyl groups of polyols used in urethane manufacture (51). The hydroxyl content of similar polyols has also been determined by treating the poly01 with excess phenyl isocyanate, followed by reaction of the excess isocyanate with excess dibutylamine which is then determined by titration with hydrochloric acid (5). Aldehydes and Ketones. A fluorescence method developed for the determination of aromatic aldehydes (66)involves the conversion of the aldehyde to a naphthothiazole by reaction with 2,2’-dithiobis(l-aminonaphthalene). Carbonyl compounds present in nanogram levels can be determined by derivatization with 2,4-dinitrophenylhydrazine (28) followed by high-performance liquid chromatography. The use of N,”-diphenylethylenediamine as a derivatizing reagent has allowed the determination of aldehydes in air (69). The imidazolidines are detected by gas chromatography or by gas chromatography/mass spectrometry (70). The determination of carbonyl compounds in the presence of aliphatic aldehydes frequently involves a pretreatment in which the aldehydes are removed. For such a removal, it has been reported that aqueous sodium 6-aminohexanoate (67) is superior to the sodium bisulfite method. In another procedure involving a gas chromatogfaphic determination of carbonyl compounds, the aliphatic aldehydes are selectively removed by N-isopropyl-N’-phenylphenylenediamine which has been added to the stationary phase (23). A photometric method for the determination of aliphatic aldehydes has been developed in which the absorbance of the reaction product of the aldehyde, diethylamine and chloranil is measured at 640-60 nm (64). Aromatic aldehydes, ketones, and formaldehyde do not interfere. This method has been extended to the determination of acetals (63). The acetals are hydrolyzed with dilute HC1 and the aldehydes determined photometrically. An investigation of the mechanism of the formation of the colored species (18) in the determination of aldehydes with the Nash (60) and Sawicki reagents (86) resulted in the development of an automated fluorescence method for the determination of formaldehyde using 4-amino-3-penten-2-one (17). Methods which have been used for the analysis of formaldehyde in air and in forest products have been reviewed (31). Formaldehyde in the presence of amine resins and lacquers has been determined by treatment with excess sodium sulfite (32) followed by iodometric titration of the excess. An evaluation of the 4-hexylresorcinol procedure for the determination of acrolein shows that this method gives low values for acrolein (35) and that the magnitude of the deviation depends on the time of storage of the mixed reagents. Amines. The sulfur trioxide-dimethylformamide adduct has been used as the titrant in a conductometric determination of amines using dimethylformamide as solvent (115). Primary, secondary, and tertiary aliphatic amines exhibited inflection points whereas other amines did not. A chemiluminescent method has been developed for the determination of aliphatic secondary and tertiary amines in the ranges of 0.2-0.6 and 0.1-0.45 mol/mL, respectively (11). The chemiluminescence arises from a benzoyl peroxide oxidation of the amine in chloroform or acetone. The change in absorbance of T complexes of tertiary amines as a function of time has been used to determine amine concentrations (99). Recoveries ranged from 98 to 103%. Determinations of tertiary amines in the presence of primary and secondary amines were made possible by a prior treatment
0003-2700/%2/0354-58R$06.00/0 0 1982 American Chemical Society
FUNCTIONAL OROUP ANALYSIS
IlllncLs and Indiana Unkersny. He was a Ully Fdbw at Indiana In 1944-1946 and a Fek Fund postdcctaal Fellow at Chicago In 1946-1947. He Is e m OT C o a of~ OW 100 publicanons in sciemc journak. During 1963-1964. hs was vklIlng professor and cha~rman 01 me Deoartment of Chemlsby at me Unkersny of Libya. Trlpoll, and In 1965-1966 was a Fulbrlght-Hays vl&hIg pmlewn at Unlverstiy 01 Beirut. Lebanon.
me American
of the sample with acetic anhydride. The formation of amine complexes with cobalt and thiocyanate ion is the basis of an amine determination (58). The complex concentration is determined by measuring cobalt in the complex by atomic absorption s ectrometry. A differential reaction rate metbmfwas used to determine mixtures of aniline and ita derivatives down to concentrations of 10.' M (981. The colnr develomd from the reaction of the
a function of time. Primary aliphatic amine groups in polymers have been eatimated by a modified Van Slyke procedure (112). Relative standard deviations ranged from 2.8 to 4.3% depending on concentration. Sulfenamide mixturw ohtained from the reaction of primary and secondary amines with 2,4dinitmbmnesulfenyl chloride can be readily separated by using Silufol plates (65). After elution from the plates, the sulfenamides are determined photometrically. A fluorometric method for the determination of secondary amines involves an initial reaction with fluorescamine followed by beating a t 70 OC with leucylalanine (59). The procedure is reported to be more sensitive than other methods for sec. ondary amines using fluorescamine In the fluoreacamine Drocedure for determining orimarv aromatic amines, the p r o h u r e gives poor results irthe oGhb position is substituted with methyl or phenyl groups (100). The failure is attributed tu inhibition of the reaction of the amine with fluorescamine by steric factors. The extent of oxidation of Metol with various oxidizing agents such as KIO,, K,Fe(CN),, K&O,, and chloramine T is dependent on the concentration of an aromatic amine catalyst (80).The reaction is the basis of a determination of primary aromatic amines. A number of spectrophotometric methods have been developed for the determination of amines which differ essentially in the method used in the production of the absorbing species. In one approach, primary and secondary amines were converted to enamines by reaction with o-formyl-o-hydroxyacetophenone (44). Tertiary amines do not interfere. In another method, aniline was determined hy diazotization followed by coupling with N-(1-naphthy1)ethylenediaminein acidic media (62). The reaction of methylamine with phenol in the presence of alkaline hypochlorite results in the production of a blue~~~~
~
~~~~~
~
~~~~
~~~~~~~
~
~~~~~~~
colored material whose intensity can be related to the concentration of the methylamine (13). The lower limit of detection was about 0.5 ppm. The color produced on reaction of amines with sodium 1,2-naphthoquinone-4-sulfonateis the basis of a spectrophotometric method for the determination of these compounds (85). Amines in industrial emissions with concentrations greater than 0.4 ppm could be determined by this method. An analysis and separation of primary and secondary amines by high-performanceliquid chromatography is based on their reaction with phenyl isocyanate (9) to form disubstituted ureas. Amines down to the 1-ng level can be detected hy this method. A derivatization reagent for amines has been prepared by condensing homovanillic acid with N-hydroxy8uccinimide (89). The chief advantage of the resulting amide derivative is its high response to electrochemicaldetection used in reversedphase liquid chromatography, Amino Acids. Several reports describe methods for determining the relative amounts of enantiomers of a given amino acid. In one method, the enantiomers are separated on a reversed-phase chromatographic column using an aqueous mobile phase which contains the Cu(I1) complex of L-aspartylcyclohexylamide (29). In another procedure, the enantiomeric amino acid is converted to diastereomericdipeptides by reaction with the N-carboxy anhydride of bleucine or L-phenylalanine. The dipeptides are then separated by reversed-phasechromatographyon Nucleosil 5CI8(94). Optical purity and composition of mixtures of amino acids and their methyl esters can be determined after their reaction with the cobaltic complex of N8"-ethylenebis(acety1acetonimine)a t pH 7 to give colored species with different absorption spectra for the acids and the esters. The rotatory powers of the esters and acids are enhanced to different extents and polarimetry or CD measurements provide for determination of optical purity without actual separation (92). NMR can also be used for determining the enantiomeric composition of amino acid methyl esters. The esters are converted to their trifluoroacetyl derivatives and dissolved in CDCI, Peak separation is obtained by adding europium heptafluorobutyrylcamphorate (79). The free amine content of amino acids and peptides supported on polystyrene resins can be determined by reaction with salicylaldehyde and measurement a t 315 nm of the resulting Schiff base (15). The fluorescence produced when phenylthiohydantions derived from amino acids are treated with N-chloro-1-(dimethy1amino)naphthalene-&sulfonamide sodium salt provides the basis for determination of these derivatives (116). Aromatic Hydrocarbons. Shpol'skii spectrometry continues to be applied usefully to the determination of aromatic hydrocarbons (16, 113,114). Other techniques used include quantitative Fourier transform/NMR spectroscopy (40). fluorescence line narrowing spectrometry (IO),and the application of the method of rank annihilation to fluorescent multicomwnent mixtures (37).
A recent book discusses the analytical chemistry of polycyclic aromatic compounds (52). Carbodiimides. Reaction of carbodiimides with aqueous aniline hydrochloridegives N-phenylguanidine,which can be determined readily due to its large UV absorbance a t 230 nm. In a less sensitive method, the carhodiimide converts acetic acid to its anhydride which can then be determined colorimetrically as ferric bydroxamate (109). Esters. Cellulose triacetate and cellohiose octaacetate have been analyzed for acetate content by aminolysis with pyrrolidine followed by gas chromatographic determination of the acetylpyrrolidine formed (56). Isocyanates. Toluene diisocyanateand presumably other volatile isocyanatescan be determined hy observing the change in oscillation frequencyof piezoelectric quartz crystals coated with polyethylene glycol (3).The method appears to be useful for the detection of isocyanate vapors down to the level of 0.02 ppm. A high-pressure liquid Chromatographic determination of methyl isocyanate involves the collection of the methyl isocyanate on an ion exchange resin, reaction with fluorescent reagent, and analysis by chromatography (104). ANALYTICAL CHEMISTRY. VOL. 54, NO. 5. APRIL 1982 5 S R
FUNCTIONAL GROUP ANALYSIS
Nitro Compounds. Nitroalkanes undergo enzymatic decomposition with nitroalkane oxidase to form nitrite, carbonyl compounds and hydrogen peroxide. An analytical procedure for the determination of nitroalkanes is based upon this reaction followed by the spectrophotometric analysis of one of the products formed (97). Both aromatic and aliphatic nitro compounds have been analyzed to within an error of +0.3% by a pyrolytic procedure in an oxygen atmosphere (34). The nitrogen oxides and nitrogen-containing products were converted into NO2 by passage over P b 0 2 and the NOz was determined iodometrically. A reductive method has been used for the determination of nitrobenzene and chloronitrobenzene in air and in urine (20). After conversion of the nitro compounds to the corresponding anilines, the anilines were analyzed spectrophotometrically after coupling with sodium 1,2-naphthoquinone4-sulfonate. Aromatic nitro compounds at picomole levels in mixtures have been determined with a precision of 11% using an initial gas chromatographic separation followed by detection with a thermal chemiluminescence (TEA) detector (50). Nitrosamines. A denitrosating mixture which is useful in the presence of large amounts of water has been developed (27). An acid mixture of glacial acetic acid and concentrated H3P04 or H2S04containing 0.1-5 wt % of Br- or I- is used. A review, containing 31 references, of the methods used in nitrosamine determination has appeared (14). Methods employing a TEA detector are emphasized. Nitrosamines in mixtures with nitramines can be determined by gas chromatography using a TEA detector (106). However, the analysis fails if GLPC peaks are unresolved because both nitrosamines and nitramines respond to the TEA detector. Nitrosamines in the presence of amines were successfully analyzed by using gas chromatography with a TEA detector without prior cleanup or isolation (71). The determination of nitrosamine in diesel engine emissions makes use uf a phosphate-citrate buffer system or a Thermo-Sorb/N cartridge (30). After extraction of the traps, the extract was analyzed by gas or liquid chromatography using a TEA detector. Because of possible interferences by other nitrogen compounds, the identity of nitrosamines should be confirmed by mass spectroscopy. N-Nitroso derivatives of amino acids were determined by conversion to their methyl esters with diazomethane followed by gas chromatographic separation on an OV-17 column (83). An alkali flame ionization detector, a thermal energy analyzer detector, and the Hall electrolytic detector (pyrolytic mode) were evaluated for the gas chromatographic analysis of nitrosamines in wastewater (82). While each detector exhibited equivalent efficiencies,the Hall detector was reported to have some advantages for routine monitoring. The possible use of a polarographic detector for the analysis of nitrosamines by high-performance liquid chromatography was investigated (105). Nitroso Compounds. The procedure of Hegedues previously described for the analysis of nitro compounds (34) was also employed for the determination of nitroso compounds. A titrimetric procedure has been developed for the analysis of aromatic nitroso compounds (84). The sample was dissolved in ethanolic hydrogen chloride and titrated with SnClz in glycerol to an amperometric, potentiometric or visual end point. The relative error was less than 3% and nitro compounds did not interfere. N-Oxides. A pyrolytic procedure has been used for the determination of alkyldimethylamine N-oxides in which the sample is decomposed at 150-340 OC and the alkene produced detected by gas chromatography (21). Organometallic Compounds. A titrimetric procedure for the determination of organometallic compounds involves the dropwise addition of a sec-butyl alcohol titrant containing N-phenyl-1-naphthylamine(8). The initially produced yellow-orange color disappears at the equivalence point. The procedure offers no advantage over the other methods in the analysis of alkyllithium compounds but is reported to give more reliable endpoints in Grignard reagent analyses. Other procedures for the determination of alkyllithium reagents involve the addition of the alkyllithium to a substance which develops an intense color at the equivalence point. In 60R
ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
one such procedure, the compound titrated was 1,3-diphenyl-2-propanone tosylhydrazone in tetrahydrofuran (54) while in another method, the solution titrated was 2,5-dimethoxybenzyl alcohol in ether, benzene, or tetrahydrofuran (110).
Oxiranes. The reaction of oxirane groups in epoxy resins with a quaternary ammonium bromide followed by potentiometric titration with HCIOl is the basis of the determination of the oxirane content (87). Acetic acid is the preferred solvent. In a titrimetric procedure for the determination of oxirane content in cycloaliphatic epoxy resins using HBr as titrant and crystal violet as indicator, chlorobenzene was found to be a superior solvent (46) to the usually employed glacial acetic acid. Peroxides. Acyl peroxides in the presence of peresters, other peroxides, and hydrogen peroxide were determined by reaction with hydroxylamine at pH 7 followed by formation of the iron(II1) complex (45). The complex was determined spectrophotometrically. By carryin out the hydroxylamine reaction at pH 14, both peresters andthe diacyl peroxides can be determined. Reaction conditions and the effect of possible interfering substances were investigated in the determination of organic peroxides by NJV’-di-2-naphthyl-1,4-phenylendiamine (24). Infrared spectroscopy has been used to determine cumene hydroperoxide in the presence of its reaction product and phosphites (117). Phenols. A gravimetric method, which is regarded as being more useful than bromination or nitration methods for the determination of phenols involves the formation of addition compounds between phenols and chromic anhydride (42). By use of optimum reaction conditions and a calibration curve, the method gives results within 2% relative error. Derivatization of phenols results in improved detection of these com ounds by gas chromatography. Sensitivity has been improved y use of a bromination procedure coupled with the use of an electron-capturedetector (38). Quantitative recovery of phenols from aqueous samples via gas chromatography was achieved by use of an acetylation procedure (19). The esters of the phenols were obtained by adding excess of acetic anhydride to the aqueous solution of the phenols containing sodium bicarbonate. The use of an internal standard, o-ethylphenol, is recommended for the gas chromatographic determination of phenol in urine (103). Trace levels of phenols in water have been determined by high-pressure liquid chromatographywith standard deviations of 0.3-1.0% (81). It has been found that sulfite and sulfur dioxide interfere with color development in the 4-aminoantipyrine spectrophotometric method for the determination of phenol (61). Modifications in the procedure which result in improvement of the detection of phenols by this method are discussed. Silicon Compounds. An infrared method for the determination of silanol groups in phenylsilicone resins has been developed (111). Band assignments were verified experimentally. Sulfonates. A critical review of the methods used in the analysis and separation of sulfonates has been published recently (49). The absorbance at 564 nm of ion-association compounds between sulfonates (and sulfates) and l-methyl-4-(-4-dimethylaminopheny1azo)pyridinium iodide has been used to determine these compounds spectrophotometrically (36). Sulfonic Acids. A gas chromatographic procedure for the determination of sulfonic acids is based on their conversion to thiols which are then determined using a 3% OV-1 on Chromosorb W column (68). The sulfonic acids were converted to sulfonyl chlorides with PC15 followed by reduction to thiols with LiA1H4. Sulfonium Compounds. Methods of determining the sulfonium group have been reviewed (4). Thiols. A simple method for the determination of thiols in the presence of organic sulfides and disulfides involves reaction of the thiol with 2-chloro-1-methylpyridiniumiodide in the presence of excess triethylamine (6). The HC1 released reacts with the triethylamine and the excess triethylamine is determined by titration with HC1 to a Bromothymol Blue end point.
Yl
FUNCTIONAL GROUP ANALYSIS
By observing the extent to which the peroxidase-catalyzed oxidation of o-dianisidime by hydrogen peroxide is inhibited by thiols, it is possible to determine thiols in the concentration range of 10"-10-8 M (22). Heterocyclic sulfur compounds also react. Thiols have been found to undergo exchange with thiols bound to a polysaccharide by a dithiol linkage. When the displaced thiol is chemilluminescent, the concentration of the displaced thiol and hence the concentration of thiol in the sample can be determined (53). The method is sensitive to 5 pmol. A silver iodide electrode was found to give best results in a potentiometric titration of thiols with silver nitrate in methanol-water mixtuires (47). A colorimetric determination of thiols involves treating the thiol sample with p(dialky1amino)phenylmercury acetate followed by diphenylcarbazone (12). Thiols in the presence of sulfides and disulfides in lubricating oils have been determined by a potentiometric titration with silver ammoniate Eiolution (101). The sulfides were determined by potentiometric titration with KI03 and the disulfides determined as thiols after catalytic reduction. Amino acids containing thiol groups were separated by high-performance liquid chromatography and detected fluorimetrically after separation by reaction with N-(9acridiny1)maleimide (9,?). The formation of yellow bismuth salts of thiols is the basis of a colorimetric deterimination of thiols (91) in air. The detection limits are 4-1.000 mg/m3. Thiols in air have been detected down to 0.2 ppm by measuring the decrease in absorbance observed when the thiol is added to a solution of diphenylcarbazone complexed with a mercury(I1) salt (39). Thioamidss. The extent to which sulfur compounds (thiourea, dithiocarbamate) catalyze the azide-iodine reaction has been used as a method to determine these compounds (78). A modified Coleman N analyzer is used to estimate the liberated nitrogen. Unsaturation. A review containing 71 references discusses the addition of thiocyanogen and other pseudohalogens to unsaturated fatty acids (90). Chromatography colurnns prepared from sulfonic acid resins in which sulfonic acid protons have been partially replaced with silver ions have been found to be effective in the separation of unsaturated fatty acids and glycerides (1). The extent of replacement of' the available protons in the sulfonic acid groups by silver ion affects peak shapes during elution and elution times. The above procedure has been applied to the separation of mixtures of methyl &,trans-, and truns,trans-12,15-0~tadecadienoates and of mixtures of methyl trans,&- and, cis,&- 12,15-octadecadi1snoates (2). Monounsaturated glycerides in palm oil have been determined by gas chromatographic analysis of the methyl esters of azelaic acid glycerides obtained by esterification of acids produced by a permanganate-periodate oxidation (25) of the glycerides. Unreacted vinyl acetate in poly(viny1 acetate) has been determined by titration with potassium bromate-potassium bromide in the presence of HCl in acetic acid (41). LITERATURE CITED (1) Adlof, R. 0.; Emken, E. A. J. Am. 011 Chem. SOC. 1980, 57,276-8. (2) Adlof, R. 0.; Rakoff, H.; Eniken, E. A. J. Am. OilChem. SOC.1980, 57, 273-5. (3) Alder, J. F.; Isaac, C. A. Anal. Chim. Acta 1981, 729,163-74, 175-88. (4) Ashworth, M. R. F. Chem. Sulfonium Group 1981, 1, 79-99. (5) Baccei. L. J.; Malofsky, B. Po/ym. Prepr., Am. Chem. SOC.,Div. Polym. Chem. 1979, 20, 492-5. Chem. Abstr. 1981, 94,66123q. (6) Bald, E. Talanta 1980, 27,281-2. (7) Bance, S. "Handbook of Practical Organic Micro-Analysis: Recommended Methods for Determlnlng Elements and Groups"; Horwood: Chichester, England, 1980. ( 8 ) Bergbreiter, D. E.; Pendergrass, E. J. Org. Chem. 1981, 46,219-20. (9) Bjorkqvlst, B. J. Chromatogr. 1981, 240, 109-14. (10) Brown, J. C.; Duncanson, J. A., Jr.; Small, 0. J. Anal. Chem. 1980, 52, 1711-15. (11) Burguera, J. L.; Townshend, A. Talanta 1979, 26, 795-8. Teternlkov, L. I.U.S.S.R. 726,473 S Apr 1980, Appl. (12) Busev, A. I.; 2,538,713, 26 Oct 1977. Chem. Abstr. 1980, 93,6 0 6 2 6 ~ . (13) Carr, J. D.; Dass, C. Anal. Lett. 1981, 74,815-24. (14) Castegnaro, M.; Walker, I:. A. Analusls 1980, 8 , 125-9. (15) Chou, Y.-S.; Chien, H.4. Sheng Wu Hua Hsueh Yu Sheng Wu Wu Ll Chin Chan, 1978, 22, 12-14. Chem. Abstr. 1981, 94,8 4 4 7 8 ~ .
(16) (17) (18) (19)
Colmsjoe, A. L.; Oestman, C. E. Anal. Chem. 1980, 52, 2093-5. Compton, B. J.; Purdy, W. C. Anal. Chim. Acta 1980, 179,349-57. Compton, B. J.; Purdy, W. C. Can. J. Chem. 1980, 58, 2207-11. Coutts, R. T.; Hargesheimer, E. E.; Pasutto, F. M. J. Chromatogr. 1979, 179,291-9. (20) Dangwal, S. K.; Jethani, B. M. Am. Ind. Hyg. Assoc. J. 1980, 47, 847-50; Chem. Abstr. 1981, 94,106328t. (21) Degtyarev. V. A.; Pisarev, V. T.; Galbova, N. D. U.S.S.R. 681,367, 25 Aug 1979. Chem. Abstr. 1979, 97,203902~. (22) Dolmanova, I.F.; Popova, I. M.; Skekhovtsova, T. N. Zh. Anal. Khim. 1980, 35, 1201-5; Chem. Abstr. 1980, 93, 1 9 7 2 2 0 ~ . (23) Evans, M. B. Chfomatographia 1980, 73,555-6. (24) Ferracini, V. L.; DeLima, C. G. Analyst (London) 1981, 706, 574-83. (25) Ferrenbach-Bouvron, C. Rev. Fr. Corps Gras 1981, 28, 117-21; Chem. Abstr. 1981, 94,194004~. (28) Fogelqvist, E.; Josefsson, B.; Roos, C. HRC CC,J. High Resolut. Chromatogr. Chromatogr. Commun. 1980, 3,568-74. Chem. Abstr. 1981, 94,180377a. 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Kinetic Determinations and Some Kinetic Aspects of Analytical Chemistry Horacio A. Mottola Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078
Harry B. Mark, Jr" Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 4522 1
The basic organization of the 1980 Review (1) has been retained for this report. Papers included in this review have been selected from reports which appeared in the literature since the 1980 review through approximately November 1981. Again catalytic determinations comprise the largest number of references, backing up the same trend established through the years. Coincidentally also again, as in the 1978-1980 period, roughly 10 times as many applications of catalysis have been published as applications of differential reaction rate methods. An interesting departure with respect to previous reviews is the increase in the number of contributions discussing kinetics in solvent extraction.
BOOKS AND REVIEWS Following the trend of an academic increased interest in kinetic determinations, the subject is being now frequently incorporated in textbooks, even for undergraduate training (2). Three rather specific areas of analytical chemistry (chromatography, flameless atomic absorption spectroscopy, 62 R
0003-2700/82/0354-62R$06.00/0
and continuous-flow analyses) were chosen to illustrate the role that kinetic principles play in the understanding of the fundamentals of these analytical approaches (3). Exposure of students in analytical courses to these concepts is considered to provide them with a better understanding of fundamentals behind analytical techniques, put kinetics in analytical chemistry in a better perspective, and improve the mind of the student on creative thinking. The first review on kinetic methods of analysis in the Chinese language, containing 387 references, was published in 1978 ( 4 ) . Kinetic methods in organic analysis have been reviewed by Antonovskii (5) and by Kreingol'd et al. (6). A review on catalvtic methods in the German language - - has been authored by Muller (7). Nikolelis and Hadjiioannou have recently discussed the analytical use of inhibition, activation, and promotion of metal-ion-catalyzed reactions in trace analyses (8). Some theoretical principles (with emphasis on enzymatic methods) for kinetic determinations have been reviewed by 0 1982 American Chemical Society
