Kinetic Aspects of Analytical Chem stry Ronald A. Greinke Union Carbide Corporation, Carbon Products Division, Parma Technical Center 12900 Snow Road, Parma, Ohio 44 130
Harry B. Mark, Jr." Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 4522 1
This review surveys the literature from December 1973 through November 1975. Papers pertaining to mechanistic and kinetic studies of reactions were not included unless the results of the study were applied to kinetic analysis. The format is similar to the 1974 Annual Review. This survey classifies the recent literature according to general kinetic papers, catalyzed reaction rate methods, uncatalyzed reaction rate methods, differential reaction rate methods for the analysis of mixtures, and instrumental, computer, and miscellaneous kinetic methods.
GENERAL KINETIC PAPERS Several general kinetic papers were published during the period. Mottola ( 1 ) reviewed the use and application of catalytic and differential reaction rate methods. Kinetic methods for the determination of osmium and ruthenium were reviewed by Shlenskaya, Khvostova, and Kadyrova ( 2 ) . The determination of organic ligands by their modification of the rate of metal-catalyzed reactions was reviewed by Mottola ( 3 ) .The ligand modification effects were divided into three categories: inhibition, true metal-complex catalysis, and promotion. Recent editions of analytical textbooks have expanded chapters on the kinetic approach for quantitative determinations ( 4 , 5 ) . CATALYZED REACTION RATE METHODS The application of catalyzed reactions for the determination of a single species in solution is again by far the most frequently applied area of kinetic analysis. The highly sensit,ie and, in some cases, specific determinations are unique advantages that catalyzed reaction rate methods offer to analysts. A number of variations of the catalytickinetic difference method were described by Weisz and coworkers (6-8). With this technique, the catalyzed reaction proceeds simultaneously in two separate mixtures, one containing a standard amount of catalyst, and the other containing an unknown amount of catalyst. The difference in signals between the two systems can be related to the concentration of catalyst in the unknown solution. In one case ( 6 ) ,the difference method, followed by thermometry and conductometry, was employed to determine copper which catalyzed the reduction of iron(II1) with thiosulfate. In another variation ( 8 ) , a quotient method of evaluation was presented for the reaction between cerium(II1) and arsenic(II1) catalyzed by iodide and osmium. The calibration graph produced is independent of temperature. The kinetic difference method, based on Landolt-type reactions, was described ( 7 ) for the determination of molybdenum, vanadium, and iodide. A variety of inorganic cations and metals were assayed by catalyzed reaction rate methods. Tarumoto and Freiser ( 9 ) reported that arsenic(II1) can function as an auxiliary catalyst in the osmium catalyzed redox reaction of bromate with iodide. Arsenic in human lung tissue was determined after low temperature ashing. A kinetic method for arsenic(V), described by Statsenko (101, was based on the enhancing effect of arsenic(V) on the reduction of molybdotungstate by ascorbic acid. Chromium was catalytically determined by several procedures. The oxidation of o-dianisidine by hydrogen peroxide, catalyzed by chromium(VI), was studied by Kneebone and Freiser ( 1 1 ) . Chromium, as low as 0.001 pg, was determined in industrial atmospheres. Dolmanova et al. (12) used the same reaction for the determination of 0.018 ppm chromium(II1) in gallium arsenide. An improved method
for chromium by the o-dianisidine-hydrogen peroxide reaction was also reported by Dolmanova et al. ( 1 3 ) ,who employed 4-aminobenzoic acid or 4-picoline to enhance the catalytic activity of chromium. Kreingol'd et al. (14) described a kinetic method for chromium(V1) in silica based on its effect on the oxidation of 2-aminophenol by hydrogen peroxide. The rate of reaction of diphenylcarbazone with hydrogen peroxide is proportional to the concentration of cobalt. By using this reaction, Dolmanova and workers (15, 16) determined cobalt as low as 0.02 ng per ml. From 26 phenolic compounds tested, 2-hydroxybiphenyl was chosen as the best activator for this reaction (16). Dubovenko and Beloshitskii (17) determined micro amounts of cobalt(I1) by a kinetic method which involved the chemilurninescenee reaction of lucigenin with hydrogen peroxide. A number of catalytic methods for copper were reported. Pantel and Weisz ( 1 8 ) have shown that copper can catalyze the chemiluminescent reaction between luminol and hydrogen peroxide. L-Histidine inhibits the reaction. The sensitivity of the quenching action of copper(II), as reported by Drokov and Dubovenko ( 1 9 ) ,on the reaction of hydrogen peroxide with lucigenin can be improved by introduction of cobalt(I1). McGlothlin and Purdy (20) devised a procedure for copper(II), which catalyzes the decomposition of hydrogen peroxide. Rychkova and Dolmanova (21)used the copper(I1)-catalyzed oxidation of quinol by hydrogen peroxide for the determination of trace copper in power-station water. Fel'dman and Matseevskii (22) described a copper(I1) kinetic method based on the oxygen consumed in the oxidation of titanium chloride, the rate of which is proportional to copper(I1). The copper(I1)-catalyzed redox reaction of hexacyanoferrate(II1) and cyanide was the basis of a kinetic method reported by Lopez-Cueto e t al. (23). Iridium catalytic methods were reported by several workers. Sheherbov et al. (25) described the fluorometric determination of iridium which catalyzes the reduction of cerium(1V) by either antimony(II1) or arsenic(II1). The reduction of cerium(1V) by mercury(1) is also catalyzed by iridium. By using this reaction, Fedotova et al. (26) determined as low as 0.2 pg of iridium in industrial materials. Tikhonova, Yatsimirskii, and Kudinova (27) used the iridium-catalyzed oxidation of mercury(1) by manganese(II1) for the assay of as little as 10 ng of iridium. The oxidation of luminol, catalyzed by iridium(IV), was the basis of a kinetic method presented by Lukovskaya et al. (28). Several papers by Bonchev and workers (29, 30) described the determination of iron in blood serum. The methods are based on the oxidation of p-phenetidine hydrochloride by hydrogen peroxide, catalyzed by iron(III), and with the use of 1,lO-phenanthroline as an activator. Rychkova and others (31, 32) reported kinetic methodsfor the assay of iron in drinking and boiler water. The approaches employed were either the oxidation of 0 - toluidine (31) or p-phenetidine (32) with KI04, catalyzed by iron(111). The catalysis by iron(II1) of the photo-oxidation of methyl orange in the presence of oxalic acid was used for the determination of 1 to 4 pg of iron in nickel (33). Manganese was assayed by a large number of catalytic methods. Fukasawa and Yamane (34)described the kinetic determination of manganese in tantalum and niobium metals after concentration of manganese by ion exchange. After concentration, manganese catalyzes the oxidation of malachite green by periodate. This same reaction was also used by Fukasawa et al. (35) for measuring trace amounts ANALYTICAL CHEMISTRY, VOL. 48, NO.
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of manganese in high purity sulfur. After combustion of the sample, 5 ppb of manganese could be measured. Morgen et al. (36) developed a method for 5 to 50 ng of manganese in natural water, based on its attenuation of the fluorescence of a beryllium-morin complex. Abe and Takahashi (37) have shown that manganese(I1) catalyzes the oxidation of anthraquinone dyes by hydrogen peroxide. Manganese was assayed kinetically in zinc and cadmium compounds by Gregorowicz et al. (38) on the basis of its catalytic effect on the oxidation of 0-dianisidine by periodate. A kinetic method for manganese(I1) was proposed by Sanchez-Pedreno and Arias ( 3 9 ) .Manganese catalyzes the reaction between chromium(V1) and EDTA. Micro amounts of manganese were determined by Tiginyanu and Oprya ( 4 0 ) ,who used the manganese catalyzed oxidation of iodide by periodate. The mechanism of the oxidation of aromatic amines with periodate, catalyzed by manganese(II), was studied by Dolmanova et al. (90). A method was proposed for determining down to 0.08 ng of manganese(I1) per ml. A kinetic method for mercury in urine and fish was proposed by Rohm and Purdy ( 4 1 ) . Mercury catalyzes the reaction between Fe(CN)64- and 1,lO-phenanthroline. Four procedures (42-45) were reported for molybdenum based on its catalytic effect on the oxidation of iodide by hydrogen peroxide. In the first, Feys, Devynck, and Tremillon (42) followed the reaction by an enthalpimetric method. Molybdenum in plants was measured by Bradfield and Stickland (43) in the second. A mathematical model of this reaction was constructed and the optimum analysis conditions were selected by Ruzinov ( 4 4 ) .In the final procedure, Altinata and Pekin (45) followed the rate of the reaction with an iodide-activity electrode. Jost et al. (46) described the determination of molybdenum(V1) from its catalytic enhancement on the reduction of bromate by iodide. The standard deviation and the minimum detectable amounts of molybdenum were compared to four other methods. A kinetic method for molybdenum in sea water was proposed by Kuroda and Tarui (47). They employed the stannic chloride-iron(II1) tartrate reduction reaction catalyzed by molybdenum. Yamane et al. (48) assayed molybdenum by using the reaction between methylene blue and hydrazinium sulfate. A variation of the Landolt-type reaction was reported by Weisz and Pantel (49) for the determination of molybdenum. For the catalyzed oxidation of iodide with hydrogen peroxide, thiosulfate served as the Landolt reagent. Two similar kinetic methods for nickel in rare earth metal oxides (50) and in tantalum and niobium pentoxides (51) were described by Yurikova and Dzhumoshev (50) and by Dolmanova et al. (51). The nickel-catalyzed reaction of diphenylcarbazone and hydrogen peroxide was utilized in both cases. Alekseeva et al. (52) devised a kinetic method for niobium and tantalum. These metals catalyze the oxidation of potassium iodide by hydrogen peroxide. Many investigators applied catalyzed reactions for osmium determinations. Mueller and Otto (53) used the catalytic effect of osmium and ruthenium on the oxidation of 1-naphthylamine by nitrate. By judicial choice of inhibitors, activators, and reaction conditions, both osmium and ruthenium can be determined in each other’s presence. Khvostova et al. (54) also applied 1-naphthylamine-nitrate reaction. A detailed study by Burgess and Ottaway (55) of the osmium-catalyzed reaction of arsenic(II1) with potassium bromate allowed a mechanism to be proposed and the optimum osmium analysis conditions to be selected. The method has a detection limit of ppm. Alekseeva et al. (56),who also used the arsenic(II1)-bromate reaction catalyzed by osmium, monitored the reaction rate by measuring the diffusion current for the reduction of evolved bromine a t a rotating platinum electrode. Konishevskaya et al. (57) determined osmium by its catalytic action on the oxidation of p-phenylenediamine with hydrogen peroxide. Traces of osmium were assayed by Alekseeva et al. (58)who used the iodide-ClOn- reaction. A kinetic method for osmium was proposed by Lukovskaya and Terletskaya (59), who employed the catalytic oxidation reaction of luminol with hydrogen peroxide. Pilipenko and Terletskaya (60) described the determination of platinum, rhodium, and iridium based on their en88R
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hancement of the reaction of lucigenin, hydrazine, and oxygen. Many methods were outlined for ruthenium. Alekseeva et al. (61) based their catalytic method on the oxidation of ferroin by periodate, enhanced by ruthenium. The method of Goncharik, Yatsimirskii, and Tikhonova (62) used the ruthenium catalyzed oxidation of p - anisidine with manganese(II1) sulfate. Kinetic determinations of ruthenium which enhanced the oxidation of either mercury(1) or diphenylamine by cerium(1V) were reported by Tikhonova et al. (63). Kalinina and Boldyreva (64) applied the catalytic action of ruthenium on the oxidation of o-dianisidine with periodate to assay ruthenium in ores at the 0.01- to 0.1ppm range. The reactions of copper(I1) and periodate ( 6 5 ) , iron(II1)-thiocyanate and thiosulfate ( 6 6 ) , iodide and hydrogen peroxide (67),p- benzoquinone and manganese(II1)pyrophosphate ( 6 8 ) ,and silver(1) and iron(I1) (69) are all enhanced by trace amounts of ruthenium. Two methods were described for determining selenium. The method of Markova and Kapian (70) used the selenide or selenourea-catalyzed reduction of silver bromide in a photographic plate by p-methylaminophenol-hydroquinone developer. Klochkovskii and Neimysheva (71) based their catalytic method on the reduction of nitrate by iron(I1)-EDTA,enhanced by Se03*-. A kinetic method for silicon was proposed by Morozova and Il’enko ( 7 2 ) .Silicon catalyzes the oxidation of iodine by Mood2-. Many researchers reported catalyzed reactions for silver determinations. The oxidation reaction of sulfanilic acid by potassium persulfate, enhanced by silver, was frequently applied (73-75). Aleksiev’s et al. (74) method was used to assay silver in human saliva, while Mueller’s and Otto’s (75) method was automated for continuous silver determinations. After extracting silver into nitrobenzene, Mueller et al. (76) quantitatively determined silver by measuring its effect on the oxidation of bromopyrogallol red by persulfate. Hadjiioannou et al. ( 7 7 ) automatically titrated silver with iodide and made use of the Sandell-Kolthoff indicator reaction for end-point detection, in which a trace excess of the titrant, iodide, acts as a catalyst for the reduction of cerium(1V) in the presence of arsenic(II1). As low as 0.01 ppm of silver in granite and other natural materials was assayed by Miller and co-workers (78, 79) who employed the silver-catalyzed oxidation of manganese(I1) with persulfate. When adding ethylendiamine as an activator, Jasinskiene and Rauckiene (80) observed a 100-fold increase in silver catalyzed oxidation of certain azo compounds by persulfate. Datta and Das (81) determined traces of silver and gold, which catalyzed the rate of decomposition of potassium ferrocyanide in the presence of 2,2‘bipyridyl. Chemiluminescence kinetic methods for titanium(1V) and hafnium(1V) were developed by Dubovenko and Bilochenko ( 8 2 ) .These metals catalyze the reaction of luminol and hydrogen peroxide. A kinetic method for paratungstate B, described by Wolff and Schwing (83),was based on the enhancing effect of tungstate on the iodide-bromate reaction. Pilipenko and Pavlova (84) quantified uranium(V1) by its catalytic effect on the reduction of Victoria blue by titanium (111). Yamane et al. (85) investigated the vanadium-catalyzed oxidation of chromotropic acid by bromate and developed a method for as little as 5 ng of vanadium. Costache and Sasu (86, 87) reported kinetic methods for vanadium, which enhanced the reaction between bromate and either bromopyrogallol red (86) or Bordeaux Red (87). Vanadium in steel ( 8 7 ) was determined. Kataoka and Kambara (88) used an iodide selective electrode for following the vanadium-catalyzed oxidation of iodide by ClOs-. Vanadium(V) in high purity water and aluminum sulfate was assayed by Kreingol’d et al. (89). Vanadium catalyzed the oxidation of 1hydroxy-3-methyl-1-phenylureawith potassium bromate. The inorganic anions, iodide, cyanide, and sulfide were quantified by catalyzed reactions. Truesdale and Smith ( 9 1 ) , employing the iodide-catalyzed reaction of cerium(1V) with arsenic(III), determined 20-100 pg of iodide per liter in river water. A detailed mathematical approach was made to obtain the most suitable form of calibration
Ronald A. Grelnke, Raw Materials Research Scientist for the Carbon Products Division, Parma Technical Center, Union Carbide Corporation, Parma, Ohio, received his B S degree from the University of Illinois in 1963, and his M S and Ph D in analytical chemistry from the University of Michigan in 1965 and 1967, respectively Dr Greinke joined Union Carbide Corporation in 1967 as an analytical chemist in peracetic acid and peracetic acid derivatives production for the Chemicals and Plastics Division at South Charleston, West Virginia In 1971, he became head of analytical research and development at the Parma Technical Center His research interests includes kinetic methods of analysis, gas chromatography, thermal analysis, polynuclear aromatic hydrocarbon analysis. and environmental analysis He has published research papers in these areas, is a co-author of the book "Kinetics in Analytical Chemistry," and the chapter "Analytical Chemistry of Carbon" which will be published in the "Treatise of Analytical Chemistry" Dr Greinke is a member of Sigma Xi and was past chairman of the Cleveland Analytical Topics Group, ACS Harry E. Mark, Jr., Professor of Chemistry and Chairman of the Analytical Chemistry Division, Department of Chemistry, University of Cincinnati, received his B.A. degree from the University of Virginia in 1956 and his Ph.D. degree from Duke University in 1960. He was a postdoctoral research associate at the University of North Carolina (with C. N. Reilley) from 1960 to 1962 and at the California Institute of Technology (with F. C. Anson) from 1962 to 1963. He was a member of the staff of the Department of Chemistry at the University of Michigan from 1963 to 1970, Visiting Professor of Chemistry at the Universite Libre de Bruxeiles, 1970, and joined the staff at the University of Cincinnati in 1970. His research interests are in electrochemistry, surface chemistry, kinetic methods of analysis, environmental analytical problems, and instrumentation. In addition to research papers, he is the coauthor of the books "Kinetics in Analytical Chemistry," "Activated Carbon: Surface Chemistry and Adsorption from Solution,'' and "Simplified Circuit Analysis; Digital-Analog Logic." He is also a coeditor of the monograph series "Computers in Chemistry and Instrumentation" and a member of the Editorial Board of Analytical Chemistry, Analytical Letters, Chemical Instrumentation, and Talanta.
graph. The effects of changes in temperature, reaction period, and spectrophotometric variables are discussed. Ke et al. (92) assayed iodine in serum, and Lauber (93)measured iodide in thyroid hormones both by using the same arsenic(II1)-cerium(1V) reaction. A kinetic study of the photochemical reaction between phenosafraine (3,7-diamino-5phenylphenazinium chloride) and EDTA was described by Sierra and co-workers (94). These authors found that the reaction is strongly inhibited by iodide and subsequently developed a method for its determination (95).Jasinskiene and Umbraziunaite (96) quantified iodide based on its catalysis of the oxidation of azo dyes by hydrogen peroxide. An indirect kinetic determination of cyanide was set up by Gregorowicz et al. (97). Ludwig and co-workers (73) assayed sulfide, which inhibits the silver-catalyzed reaction of sulfanilic acid and persulfate. Dutt and,Mottola (98) reported a kinetic method for oxalic acid in biological fluids. This acid accelerated the initial reaction rate of the ferroin-chromium(V1) indicator reaction. The temporary nature of the acceleration of the ferroin-chromium(V1) by oxalic acid and other species was further studied (101).These authors described the acceleration phenomenon as "promotion" and not catalysis, since the rate modifying species became inactive either by destruction or by complexation with the generated chromium(II1). By judicious choice of reaction conditions and by employing initial reaction rate measurements, they quantified microgram amounts of oxalic and citric acid, vanadium(IV), arsenic(III), chromium(VI), hexacyanoferrate(III), and molybdenum(V1) (101). Dutt and Mottola (99) also observed that the ferroin-chromium(V1) reaction, accelerated by oxalic acid was preceded by an apparent induction
period in the presence of uric acid. The kinetic mechanism occurring during this induction period and a method for uric acid in human blood serum and urine was subsequently published (99).As many as 50 chromium determinations in a one-half hour period were achieved by Dutt and Mottola (102) who used the transient oxidation-reduction signal of the ferroin-chromium(V1) system. The chromium(VI) was added to a reaction mixture containing ferroin and oxalic acid. A transient redox signal was generated because oxalic acid first acts as an accelerator for the ferroin oxidation to ferriin and then acts as a reducing agent of the generated ferriin. Semenyuk and Razumova (100) quantified micro amounts of carboxylic acid by using the acid catalyzed reaction of benzoyl fluoride with p-anisidine. Some organic compounds bond hydrogen ions, and some ligands chelate metal ions in a manner to lower the reduction potential of the hydrogen ion and metal ion a t an electrode surface, which results in a catalytic polarographic prewave. As in past years, may papers again were published which report the measurement of polarographic catalytic currents for the sensitive and selective quantification of metal ions, ligands, and organic compounds. Chikryzova and Kiriyak (103, 105) observed that a catalytic polarographic current, proportional to the molybdenum(V1) concentration, is formed a t a DME in a solution of molybdenum(VI), glucaric acid, and potassium chlorate. Sharipova and Songina (104) titrated molybdenum(V1) with lead(11) in the presence of hydrogen peroxide and found the end point of the titration by measuring the catalytic current of the reduction of peroxo complexes of molybdenum(VI) a t a DME. The polarograms of aqueous solutions of bromate were shown by Toropova et al. (106)to have a catalytic wave in the presence of traces of molybdenum(V1). The wave was proportional to molybdenum concentrations in the range of 0.1 to 0.4 ng per ml. Budnikov and co-workers (107) found that the catalytic current of the reduction of hydrogen ions a t a DME in the presence of cobalt(I1) complexes of dithiocarbamates was proportional to the concentration of cobalt. A method was proposed by Stepanova and Sinyakova (108) for determining micromolar amounts of niobium by polarography in citric acid medium with measurement of the catalytic wave of chlorate. Polarography of a solution of rhodium(II1)-thiosemicarbazide complexes by Ezerskaya and Kiseleva (109)resulted in formation of a catalytic hydrogen wave that was proportional to microgram amounts of rhodium. Manok and co-workers (110) showed that the second polarographic wave of uranium(VI), due to the reduction of uranium(V) to uranium(III), is enhanced in the presence of chlorate. The kinetic current, believed to result from the re-oxidation of uranium(II1) to uranium(1V) by the chlorate, was used in the quantification of trace amounts of uranium. Tur'yan and Strizhov (111, 112) reported the polarographic determinations of oxalic acid (111) and phthalic acid (112) by means of the catalytic waves for indium oxalate and indium phthalate formed in a chlorate medium. Lopex Fonseca, Sanz Pedrero, and Tutor (113)made use of the catalytic prewave current of cobalt(I1)-thiamine disulfide in a chloride-borate-boric acid medium for the determination of thiamine in pharmaceutical preparations. Catechol was assayed by Zaitsev e t al. (114),who observed that polarograms of the reduction of tin(1V) in the presence of chlorate and catechol show catalytic waves proportional to catechol.
UNCATALYZED REACTION RATE METHODS If a suitable equilibrium or nonkinetic method is available, the use of uncatalyzed reactions for the determination of a single species in solution is not recommended owing to lower accuracy. If the reaction employed for the nonkinetic determination is either slow, reversible, or involves an additional interfering consecutive reaction, then an initial reaction rate kinetic method becomes advantageous. Several inorganic anions were determined by uncatalyzed reactions. Beckwith, Scheeline, and Crouch (115) investigated the kinetics of formation of 12-molybdophosphate from molybdenum( VI) and phosphate in strong acid solutions by stopped-flow methods. The obtained rate laws and mechanisms gave insights to the optimum conditions for ANALYTICAL CHEMISTRY, VOL. 48, NO. 5, APRIL 1976
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phosphate determinations by an initial reaction rate method. An initial reaction rate method for phosphate was also reported by Dorokhova et al. (116), who measured the formation rate of molybdovanadophosphoric acid. Karayannis and co-workers (117) studied the iodate-arsenite reaction in strong acid solutions by stopped-flow spectrophotometric techni ues. An initial reaction rate method for arsenic in the 10-2 to M range resulted in a f3% relative standard deviation. Based on kinetic and analytical studies on the oxidation of thiocyanate by chromic acid in aqueous sulfuric acid medium, Muralikrishna and Bapanaiah (11 8 ) developed an uncatalyzed kinetic method for thiocyanate. Thallium(II1) oxidizes 4,4’-dihydroxydiphenyl (DHDP) quantitatively. Chloride and bromide form a strong complex with thallium(II1) which does not oxidize DHDP and hence, results in a lowering of the observed rate constant. Mentasti and Pelizzetti (119) used these facts for developing an uncatalyzed kinetic method for chloride and bromide. A variety of organic compounds were determined via uncatalyzed reactions. Karayannis (120) kinetically quantified ascorbic acid by measuring the reaction with 2,6-dichlorophenolindophenol with a stopped flow technique. Karayannis and Kordi (121) presented a study of the reaction between biuret, hypochlorite, and phenol. The results of this investigation yielded an initial reaction rate method for biuret in the to M range. Ethylene-, propylene-, and butylene glycol were determined by automatically measuring the reaction rate with periodate. Efstathiou and Hadjiioannou (122) used a perchlorate ion selective electrode to follow the reaction. Bissett et al. (223) kinetically measured 2-oxohexoses by reaction with cysteine. Nitroglycerin was assayed in tablets by measuring the initial reaction rate with methanolic sodium hydroxide (124). Kinetic methods for catechol, resorcinol, and quinol was presented by Rao (125). Bromide and bromate reacted to form bromine. The generated bromine immediately reacted with the phenol. After all the phenol was monobrominated, the excess bromine bleached methyl orange. The time required for bleaching was related to the amount of phenolic compound. Kurzawa and Krzyminska (126) described a kinetic procedure for sulfathiazole by reaction with sodium azide and iodine.
DIFFERENTIAL REACTION RATE METHODS The differential reaction rate approach is a useful tool for the in situ simultaneous determination of two- and three-component mixtures with closely related chemical properties. During the two-year period, several new differential reaction rate approaches were described, and the determination of many two-component mixtures of organic compounds and inorganic cations were reported. Connors (127) described an analogy between kinetics and spectrometry. He proposed that multicomponent mixtures could be analyzed, just as in absorption spectrometry, by establishing systems of simultaneous equations. The optimum frequencies for the measurements can be determined by inspection of the “kinetic spectra” of the individual reactants. De Oliveira and Meites (128) reported a new general technique in interpreting the data obtained in differential kinetic analyses. The approach, which is based on the simultaneous evaluation of four parameters (the concentrations and the pseudo-first-order rate constants of the faster and slower reacting species) by obtaining differential thermometric data, was applied to a mixture of methyl and propyl acetates. Kreshov et al. (129) resolved binary mixtures of olefins in monomer and polymer composition based on differences in reactivity of the double bonds toward mercury(I1) acetate in methanol. Mixtures of organic nitrogen compounds were determined by reaction with chromic acid. The monitoring of the nitrogen evolved as a function of time allowed Kozak and co-workers (130) to resolve a mixture of azobenzene and 2,3-dimethyl-1phenylpyrazolin-5-one. Yonekubo and co-workers (131133) developed several differential reaction rate systems for metal ions. Germanium(1V)-silicon(1V) (131), titanium(1V)-vanadium(V) (132), and zirconium(1V)-niobium(V) (133) mixtures were resolved by differences in the rates of reduction of the metal-heteropoly acids. A differential reaction rate determination of a surface layer of bari90R
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um orthotitanate in barium titanate powder, a raw material for capacitors and piezoelectric ceramics, was reported by Murata and Omatsu (134). The principle is based on large differences in the rate of dissolution in acetic acid. The method was free from the effect of particle size of barium titanate because it was based on the change of the rate of dissolution. The kinetic analysis of mixtures by the Method of Proportional Equations was applied by Yatsimirskii et al. (135) for the determination of dysprosium, holmium, and ytterbium. The xylenol orange complexes of these rare earth metals react a t different rates with EDTA. Kloosterboer (136) outlined a variation of the differential kinetic analysis of cations, which was first described by Margerum (137, 138). Margerum’s method involved measurement of rates of exchange of metal complexes of trans-1,2-diaminocyclohexane N,N,N’,N’-tetracetic acid (Cy) with copper(11). This multidentate ligand exchange proceeds via exchange with hydrogen ions. In Kloosterboer’s (136) modification, the pH continuously decreases during the analysis, which increases the rate of exchange. The advantages are: large difference in rate constants does not cause a long duration of the reactions; since all reactions are slow a t a high pH, there is enough time for thorough mixing of the reactants and no stopped flow apparatus is necessary.
INSTRUMENTAL COMPUTER, A N D MISCELLANEOUS KINETIC METHODS In the past two years, there has been a great deal of research dealing with instrumentation, automation, data handling, detectors, etc., which have been applied to kinetic measurements and/or analysis or which could be potentially applied to kinetics. Weisz and coworkers (139-142) have developed four different instrumental approaches to the so-called steadystate or “stat” methods of catalytic kinetic analyses. In the “stat” methods, an external means of keeping one of the reactants or reaction products a t a constant preset value is employed. The rate a t which the reactant is added or the product removed is measured. They have developed a “POtentiostat” method where the concentration of the reagent to be kept constant is monitored potentiometrically (139). The potentidmetry measurement circuit is coupled to an automated buret and the reagent is automatically added to maintain the potential of the solution a t the preset value. They demonstrate the system’s applicability to the determination of thorium, vanadium, and iodide. They also have developed similar automated concentration “stats” which used optical absorbance (“absorptiostat”) (140), dual polarized amperiometric (“biamperostat”) (141) and luminescence intensity (luminostat) (142) monitoring. They applied these methods for the analyses of iodine and molybdenum (140,141 ), catalase and copper (140,142) and manganese (141). Efstathiou and Hadjiioannou (143) have designed an automated potentiometric reaction rate method for the determination of vicinal glycols using a perchlorate ion selective electrode. They employ the variable-time approach and report that various glycols in the lov3 M range can be determined with relative errors of about 0.7% and measurement times of only about 15 to 150 seconds. Dutt and Mottola have devised a novel but simple flow-through cell and flowthrough loop system for repetitive and continuous injection determinations (144). All the necessary reagents are contained in a single reservoir and are continuously circulated a t constant flow, through the electrolysis cell. An aliquot of the species to be analyzed is injected into the flow stream rapidly and participates in a very rapid redox reaction which changes the concentration of the monitored species. A subsequent but slower reaction regenerates the monitored species chemically. Numerous example systems are described. Truesdale and Smith (145) have developed an automated catalytic rate method for iodide or iodate in river waters. These authors carried out an excellent comprehensive study of the reaction mechanism and all the effects of experimental variables which could lead to erroneous results which warns the potential user of the technique of all possible pit falls. Townshend has presented a discussion of the design and advantages of total automation which results in the improvement in the accuracy and precision of kinetic analyti-
cal measurement as compared to equilibrium methods (146). A computer automated reaction rate system for the catalytic determination of thyroid hormones has been developed by Knapp and Leopold (147). T h e sensitivity limits are in the 0.1-ng range and the sample throughput is about 36 per hour. Mousa and Winefordner have developed a new phase resolved phosphorimetry technique (148). They showed that phosphorescence emission and excitation spectra of molecules which exhibit extreme overlap can be phase-resolved into the spectra of the individual components. The fluorescence emission was also shown to be phase-resolved from the phosphorescence emission. The precision and accuracy for several synthetic bimolecular (148) and drug mixtures (149), (species with different life times) were excellent and the technique appears to be very promising as an analytical technique and as a method of determing phosphorescence life-times. Wilson and Miller (150) have developed a computer-controlled laser phosphorimeter. Although this instrument was used for the determination of life times of mixed phosphorescent species, the time-resolved and component-resolved spectral data could obviously be used analytically. Another area of instrumental research that has shown exceptional growth over the past two years and that has tremendous potential for use in kinetic based analysis has been the development of rapid scanning spectrophotometers. Wightman et al. (151) have described a computer controlled rapid scanning stopped flow apparatus based on the modification of a frequency scanning type optical system (Harrick Scientific RSS).Mark e t al. (152) have also presented the design of a computer-controlled rapid scanning system based on the Harrick RSS. Similar computerized rapid scanning stopped-flow systems have been developed by Dye and coworkers (153, 154). Other (frequency scanning) computerized rapid scanning spectrophotometer designs have been described by O'Keefe and Malmstadt (155) and D. J. Johnson e t al. (156). Strojeck and co-workers have designed a derivative mode rapid scanning spectrophotometer (157) and Miller e t al. (158) have developed a computerized real time system for microsecond-range acquisition and processing spectrometric kinetic data. Milano and coworkers (159, 160) have developed and evaluated a dispersive type rapid scanning spectrophotometer which employs a Vidicon array detector system. There have been three recent review articles which deal with the subject of detecting devices for measuring fast optical systems which are important for the development of rapid scanning instruments. Lytle has written a comprehensive evaluation of the applicability and limitations of phototubes (161) and Talmi has written two excellent papers on TV-type multichannel (array) detectors (162, 163) which indicate that future breakthroughs in this type of detection will lead to very fast rapid scanning instruments. There have been several papers on improved instrumentation in relaxation methods for measuring fast reaction. An improved pressure-jump apparatus has been described by Knoche and Wiese (164) and Pate1 and coworkers (165). Kruzan and Stoehlon have devised a relatively simply digitizing interface for use in relaxation experiments to improve sampling and give on-line processing of the data (166). An optical rotation detection system for temperature-jump apparatus has been developed by Sana et al. (167).
A number of automated and/or computerized measurement systems have been recently developed which could be adapted to kinetic measurement and analysis or illustrate important techniques in on-line computer instrumentation. Zynger has described an automated stepping differential calorimeter (168). Wampler and DeSa (169) have designed LITERATURE CITED
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Electron Microscopy Michael Beer Department of Biophysics, The Johns Hopkins University, Baltimore,
During the past two years, high resolution scanning microscopes have appeared both through manufacturers and assembly in research laboratories. So far, few actual applications have been reported. .Important progress has been made in specimen preservation and the development of electron microscopy designed to avoid radiation damage. These and other results will be briefly reviewed here.
INSTRUMENTS Conventional transmission electron microscopes (CEM) continue to be the principal instruments for obtaining high resolution structural information on biological and even nonbiological materials. During recent years, manufacturers have incorporated into them beam tilting arrangements to allow dark field microscopy, and coils to allow operation in the scanning mode utilizing either transmitted br secondary electrons. Often field emission guns are available as attachments. These are differentially pumped to the necessary vacuum of about Torr with the column at the more usual pressure of perhaps Torr. With such an addition, high resolution Scanning Transmission Electron Microscope (STEM) operation should be possible. Several manufacturers now offer STEM instruments. In ones marketed by AEI and Vacuum Generators, only the gun is a t very high vacuum while the remainder of the column has rubber gaskets and is pumped by diffusion pumps. Siemens offers an instrument capable of perhaps
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2-3 A iesolution, ultrahigh vacuum throughout, computer coupling, and energy analyzer for the transmitted electrons. At present, it is not clear if ultrahigh vacuum will be necessary in the column for the determination of the final detail. For microscopes used as microprobes, the energy of the x-ray fluorescence can be determined by energy dispersive spectrometers. The theoretical and experimental aspects of this field were the subject of a recent conference and its proceedings, which are now published (32),are an excellent report on the present status of the field. Some electron microscopes built for research purposes merit mention. A high resolution STEM at Johns Hopkins University (28) has produced clear images of single atoms. At Cornel1 University, a conventional optics transmission electron microscope with 100-keV beam, superconducting lenses, and ultrahigh vacuum throughout is being tested (18). An electron microscope built a t the Oak Ridge National Laboratories also uses conventional optics and superconducting objective lens (30).
SPECIMEN DAMAGE Electron microscopes now exist which have resolution capabilities near the length of a ckiemical bond. What then prevents electron microscopy from deducing the complete chemical structure of a molecule or an assembly of molecules? For biological materials, there are two difficulties ANALYTICAL CHEMISTRY, VOL. 48, NO. 5, APRIL 1976
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