Amperometric Titrations

term, “dead-stop end point”) with bi- potentiometric—i.e., “constant current” at two essentially identical electrodes. (234-a)—titrimetry ...
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Amperometric Titrations John J. Stock, University of Connecticut, Storrs, Conn.

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HIS PAPER covers the period from the previous review (232) through October 1965. L-nless otherwise indicated, potentials are with respect to the saturated calomel electrode (SCE). Confusion of biamperometric (older term, “dead-stop end point”) with bipotentiometric-Le., “constant current” a t two essentially identical electrodes (284a)-titrimetry has occurred in a few articles. The inclusion of any bipotentiometric titrations in the present review is accidental. Amperometric titrations are described in two nionographs (233, 293). Berka and his coworkers (22) have reviewed the amperometric titration of organic compounds. A training program that involves amperometric titration has been suggested (SO). Uses of polarization curves in the interpretation of aniperonietric processes (142) and mathematical methods for end point location (5, 68, 125, 126) have been described.

APPARATUS AND METHODOLOGY

After addition of the more concentrated “unknown” T solution, the mixture is titrated with the supporting electrolyte (e.g., KC1) until the current has fallen t o its original value. When the postequivalence line of an amperometric titration plot is unsatisfactory for end point location, possible alternatives are the use of the residual current line (23’4~)or of a preaddition technique (236). The latter involves the addition to the supporting electrolyte of the titrand T’ (e.g., Fe+9 in amount approximately 30% of that in the sample. After noting the current (z), the “unknown” amount of T’ is added and the solution is titrated (e.g., with Hgz+2) until the current is less than z. Intersection of the pre-equivalence and “current = d’lines gives the end point. Several new alternating current titration techniques have been described (31, 156, 247). One of these involves phase-angle measurement (156) and another the use of an indicator ion (247)* ACID-BASE REACTIONS

The theory, methodology, and uses in amperometric and other electroanalytical processes of graphite electrodes have been reviewed (15, 51). A rotating platinum electrode (RPE) immersed in I r K I (228) or acidified Khfn04 (285) has been used as a reference in amperometric titration. The “fixed electrode, rotating cell” principle (234b) has been used in titrations a t two platinum electrodes of dissimilar sizes (249). Kies (106) has discussed biamperometry at amalgam electrodes and has described a cell with concentric grooves to contain the amalgam. Various electronic devices for amperometric (162, 164) and biamperometric ( 8 , 131) titration have been reported. Several groups of workers have described automatic (25, 63, 143, 154, 176) or continuous (14, 47) amperometric devices. Bruckenstein and Johnson (32) have described coulometric diffusion layer titrations at a rotating platinum ringdisk electrode system. The current at the disk is increased linearly with time until the rate of titrant generation exceeds the maximum flux of the titrand to the electrode. The excess of titrant is measured amperometrically a t the ring. Oscillopolarographic end point location has been used in “dilution titration” (166). In this, the current due to a dilute standard solution of the titrand T (e.g., Cd+2) is first noted.

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Hydroquinone, pyrogallol, l-nitroso2-naphthol, and dimethylaniline have been used as amperometric indicators in the titration, a t a stationary platinum electrode, of HC1, picric, or toluenesulfonic acid with NaOH or KHIOH (199). Acetic acid and some other organic acids were titrated with KaOH. No external e.m.f. is needed when the “reference” electrode is platinum in saturated Hg2(K03)2. Weak acids in water (201) and in ethanol (200, 202) were titrated with “40H and Et*” (202) or NaOH (ZOO), respectively. Hydrogen peroxide indication can be used in the titration of strong or weak acids (197) and in the analysis of mixtures of HC1 with AcOH or iso-butyric acid (198). Tertiary amines (e.g., nicotine) and salts (e.g., AcONa) in AcOHAczO have been biamperometrically titrated with HC104 a t antimony electrodes, or at platinum electrodes after adding quinhydrone (286-288). Tungsten or aluminum electrodes were less satisfactory (288). The change with pH of the tensametric peaks of methyl orange or thymol blue has been used to follow the titration of HC1 with KOH (26). Dimethylformamide was found to be the most suitable solvent in the high-frequency amperometric titration of aliphatic dicarboxylic acids with methanolic KOH (120).

PRECIPITATION AND COMPLEXING REACTIONS

Methods Involving Silver. Cyanide-thiocyanate mixtures have been analyzed by R P E Agh’O, titration to give cyanide plus thiocyanate; titration after masking with HCHO Cygives thiocyanate alone (152). anide-chloride mixtures were first titrated to the cyanide end point. h second end point was obtained after adding methanol and gelatin (87). The titration of 10-3JI cyanate in 25% methanolic 0.1M KSO, containing gelatin had an error within 1% (86). The temperature must be below 5” C. Mixtures of cyanate with cyanide, thiocyanate, or chloride gave a 2-stage curve, cyanate being titrated in the Internally gensecond stage (85). erated silver ion has been used in the biamperometric titration of cyanide or halide ions in molten LiN03-KN03 eutectic mixture (27). The amperometric titration of bromide-chloride mixtures with AgNOp has been examined and applied to halogen determination in organic compounds (237). Bromide ( 2 ) and iodide ( 1 ) in drugs have been titrated (RPE) with figso,. The AgSOs titration of K I and of mercaptobenzothiazole a t a stationary platinum electrode has been reported (128). Silver ion in dilute containing a trace of K2Crz0, has been titrated biamperometrically with KI (111). Excess of titrant causes iodine liberation. Titration with K I a t a rotating platinum anode has been used to determine silver in crude copper (172). The reaction between silver ion and orthovanadate (210) or metavanadate (209) has been studied amperometrically and is suitable for vanadium determination, Titration (RPE) of KBPh4 in aqueous acetone with AgYO3 has been used for the rapid determination of potassium in cement (73). Bozsai and Mosonyi have described the Agn‘Oo titration (RPE, zero potential) of theophylline (28) and theobromine (29) in pharmaceutical compositions. The titration of - l O - 3 X thioacetamide in a pH 9.5 NH3 buffer [dropping mercury electrode (DbIE), -0.4 volt] usually has an error of less than 2y0 (189). Usatenko and his coworkers have reported the titration (RPE) of silver with 2,4-dithioburet, l-phenyl-2,4-dithioburet (270), and ethylenethiourea (2imidazolidinethione) ($67). Titration

with thionalide in the presence of Bi( N 0 3 ) ~as amperometric indicator has been used to determine silver in coppersilver alloys (284). The determination of sulfhydryl groups in whole blood (213), blood serum (195, 213, 300), milk proteins (308), of reduced glutathione in red cells (72),of disulfide groups in chorionic gonadotropin preparations after sulfitolysis (253), and a study of the urea denaturation of bovine serum albumin ( 9 9 ) , are recent examples of the use of the important Ag-SH titration. Glutathione was found the most reliable standard for titration in a tris(hydroxymethy1)aminoethane buffer of p H 7.4 (167). Usual methods gave inaccurate determinations of sulfhydryl groups in germinating seeds, so preparative operations were done in the presence of excess AgN03. This was titrated with Shol’ts glutathione solution (12.4). (615) has used a rotating pair of indicator electrodes and NaNO2 as indicator in the titration of sulfhydryl. Reduction with triphenylphosphine in aqueous methanol at room temperature and amperometric titration with Agh T o 3 have been used to determine aromatic disulfides (83). Alkyl disulfides are incompletely reduced, but both these and aromatic sulfides can be determined if tributylphosphine reduction is used (84). Methods Involving Mercury. Although 0.01N mercury(1) was determined by direct titration with, or back titration of, KI, only back titration succeeded with 0.001N Hg(1) ( 5 6 ) . RIercury(1) reacts with unithiol in 2 : l ratio and may be titrated with this reagent (226). Bagbanly and his coworkers (12) have concluded that small amounts of mercury(I1) can be titrated with Reinecke’s salt. RIercury(I1) in -0.2N HzS040.005N KzCrz07 has been biamperometrically titrated with KI. Alternatively, the sample was added to excess buffered Na2S203,which was back titrated with 0.01N HgCL (110). Mixtures of silver and mercury(I1) ions have been analyzed by first titrating both ions together by the K I method. After removal of silver as AgC1, mercury is determined by the Ka2Sz03 method (211). To analyze sulfidethiosulfate mixtures that may contain sulfite, sulfate, chloride, or nitrite, sulfide in one aliquot is biamperometrically titrated with Cd(Ac0)z. Another aliquot is boiled with H3B03, treated with HCHO, and titrated for thiosulfate with HgClz (108). Conversion to thiosulfate by heating with Ka2S03, destruction of excess sulfite with HCHO, and titration with HgClz have been used to determine sulfur in activated carbon and sulfide ores (109). The amperometric titration of mercury(I1) with ethylenethiourea has been

reported. Since mercury is complexed first, mixtures of mercury and silver ions can be titrated (267). Lotareva (127) has improved Usatenko’s anodic sodium diethyldithiocarbamate titration of mercury. The procedure was used for the determination of mercury in ores and organomercury compounds, Mercury(I1) has been titrated with 2,4dithioburet a t a p H of 1 to 3. Excess titrant gives an anodic current a t the R P E potential of +0.5 volt. Mercury in ores can be determined by this method (639), or by titration with potassium ethylxanthate (880). .4n HCl medium of pH 0 to 2 is recommended for the titration of mercury with l-phenyl-2,4-dithioburet (270). Titration of mercury with thionalide has been carried out a t a potential of +1.1 to $1.2 volt (281, 284). iLlercury(1) and mercury(I1) present together in 2N H2S04have been titrated with unithiol (226). This titrant has been used for the determination of mercury in ores (166). Another possible titrant for mercury(I1) is thioacetamide (248). Mercury(I1) titration at a D l I E (zero potential) has been recommended for the determination of Acaprin [N,N’bis - (N - methylquinoliny1urea)methylsulfate] (229). The amperometric titration of sulfhydryl groups with HgC12 a t a rotated mercury pool electrode (zero potential us. the mercury-Hg12 electrode, or -0.23 volt us. SCE) has been recommended for protein studies (218). An alternative is biamperometric titration a t mercury pool electrodes (applied e.m.f., E , 0.025 to 0.1 volt) (219). Studies of the denaturation of albumin (99) and of disulfide bonds in 7-globulin (39) have involved titration with HgClZ. The relation between sulfhydryl and disulfide content and wheat quality has been described. Titration with ethylmercury(I1) chloride was carried out a t a D M E with forced drop rate (254). Titration with methylmercury(I1) iodide has been used to show that eucalyptus kraft lignin contains only traces of sulfhydryl and disulfide (159). Interchain disulfide bonds in y-globulin have been determined after reduction by titration with phenylmercury(I1) hydroxide (39). Methods Involving Lead. Addition of KNOI and pyridine and titration with P b ( N 0 3 ) ~a t a D M E have been used to determine 0.03 to 0.3 mg. of COz in 20-ml. portions of aqueous solutions (186). Titration of sulfate with Pb(N08)2 has been used to determine so3 in cement (216) and sulfur in organic substances (231). Several workers have automated this titration (80, 1.43, 154). Sulfate and chromate have been titrated a t a rotating platinum disk electrode that measures the oxidation current of lead ion (36). Sulfate has been titrated with Pb-

(0Ac)z a t a R P E and a platinumKMn04 reference electrode (285). Lead has been titrated with K4Fe(CN)6 a t a platinum wire-platinum foil electrode system (249). Sulfate in therapeutic serums has been determined by addition of excess Pb(?;03)2 and back titration of the filtrate with K4Fe(CN)6 (4). Lead in mixtures with thallium(1) has been titrated in 1M KNOB with K4Fe(CN)6 a t a DRIE potential of -0.4 volt (89). Alkylchlorosilanes in RIeOH-benzene that is 0.3M in LiN03 have been titrated with Pb(dcO)z. Lead chloride is precipitated (116). Ozaki and his coworkers (167) have found that 10-5~lf lead in KK03-ascorbie acid medium can be titrated with EDTA a t a mercury-drop convection electrode. The biamperovetric titration of lead a t lead amalgam electrodes has been reported (106). Precipitation as PbW04, dissolution of this in alkaline tartrate, and titration with EDTA have been used to determine tungsten in minerals (35). Methods Involving Hexacyanoferrate(I1). Amperometric titration with CazFe(CS)6 has been used to determine potassium in sylvinites. A salt bridge of saturated C a s 0 4 is used, and the 60% ethanolic medium is seeded with CaK2Fe(CK)8 (250). Songina’s anodic K4Fe(C?rT)Gmethod has been applied to the titration of calcium in drugs ( 3 ) . The titration of zinc with K4Fe(CN)e has been performed with the aid of a platinumKbIn04 reference electrode (285), biamperometrically in the presence of copper, zinc, aluminum, manganese, and iron (227), and by superimposition of an a x . ripple on the -1.02-volt D M E potential (77). Schilt and Nowak (218) have compared K 4 F e ( C N ) ~ and tetracyano-mono-1,lO-phenanthrolineferrate(I1) as amperometric titrants for zinc a t a stationary platinum “convection” microelectrode. The latter titrant has the better solution stability, gives better precision, and permits the titration of 10-6111 zinc. Calcium in solutions prepared from plant ashes and soils has been determined by addition of CdC2O4 and titration of dissolved cadmium with K4Fe(CN)6 (228). Biamperometric titration ( E = 0.250 volt) of thallium (111) with K4Fe(CN)8in the absence of supporting electrolyte has shown that the sharp end point occurs a t a thallium (111) to hexacyanoferrate(I1) ratio of 5 to 4 (307). Titrations that involve lead (4, 89, 249) or uranyl (203) ion and K4Fe(CN)6 have been reported. Manganese a t concentrations of about 0.2 mg. in 30 ml. has been titrated with NarFe(CN)6 (251). Methods Involving Molybdenum and Tungsten Species. Lanthanum nitrate has been titrated with VOL. 38, NO. 5 , APRIL 1966

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NazMo04, and vice versa, without supporting electrolyte and a t a D M E potential of -1.5 volts (108). A potential of -1.95 volts was used for the direct and reverse titration of cerium (111) nitrate with NazMo04 (206). Titrations involving thallium(1) sulfate and alkali polymolybdates have also been reported (206). Molybdate ion has been determined by titration of EDTA a t a rotating tantalum anode, and by addition of excess EDTA and back titration with standard zinc or molybdate solution (316). Direct titration with EDTA (194, 315) has also been used. The titration of molybdate with bis(4-dimethylaminopheny1)methane has been (carried out in the presence of zinc, manganese, cobalt, and nickel (169). Pyrogallol has been titrated with phosphomolybdic acid a t a rotating platinum anode (193). Gupta has reported the titration of copper(I1) (76), cerium(II1) (74), and thallium(1) (76) with Na2W04. After suitable extraction, Coptis alkaloids have been titrated with silicotungstic acid (82). Various heteropolyacids of tungrten have been used to titrate cinchonine and other alkaloids (180). Methods Involving EDTA or Analogous Reagents. Copper(I1) has been titrated with E D T A a t a rotating platinum anode (194) or biamperometrically (299). The latter method was used for the determination of copper in ores and in alloys with silver, zinc, tin, aluminum, and silicon (295). An e.m.f. of 1.4 to 1.6 volts was applied in the biamperometric titration of 10 to 100 pg. of copper in 20 ml. with 5 X 10-4-7w EDTA (297). Several groups of workers have described the successive titration of calcium and magnesium in mixtures. Calcium is titrated with EDTA a t pH 11.75, with 0.130 volt applied to the platinum cathode and silver amalgam anode. Titration to a second end point is continued after change of p H and applied e.m.f. to 9.60 and 0.210 volt, respectively (192). Biamperometric titration at graphite or platinum electrodes has also been used (304). Another method involves amperometric titration in a pH 10.5 ethanolamine buffer a t a mercury pool electrode of potential +0.020 volt (145). Calcium is titrated with ethylene glycol bis(2aminoethyl ether)-iL’,N,iY’,N’-tetraacetic acid (EGTA), then EDTA is used to titrate magnesium. The anodic current. increases sharply at each end point. The method has been used for blood serum and urine (146), and for water, cement, and soil (196). Strontium has been titrated with EDTA (194). Sulfate has been determined by addition of excess BaC12 and back titration with EDTA (252). Sulfur and zirconium in organic compounds have been determined by a 454 R

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method that involves fusion with Nap COa and dissolution of the melt in HCl. An aliquot is adjusted to pH 3 and zirconium is titrated with EDTA. Zirconium in a second aliquot is complexed by the exact amount of EDTA, then sulfur is determined as sulfate by the BaClrEDTA technique (252). Mixtures of zinc with either iron(I1) or cadmium have been titrated with EDTA a t a DME (137). Cadmium has been titrated with EDTA a t a mercury-drop convection electrode (167). EGTA has been used to titrate cadmium in the presence of zinc in ammoniacal medium (59, 155). Copper (11) amperometric indication permits the D M E potential to be lowered from -0.9 to -0.3 volt. Titration in the presence of dissolved oxygen is then feasible (59). Titration in a pH 5 acetate buffer decreases interference by magnesium and alkaline earth elements. The successive titration of calcium and cadmium is possible in 1.5M ammonia (59)* The biamperometric titration of thallium(II1) with EDTA is reported to be highly selective with fluoride as masking agent (303). Thorium has been biamperometrically titrated with EDTA by use of the indicator system iron (111)-EDTAliron(I1)-EDTA, and thorium in uraninite has been determined by this method (261). The titration can be carried out coulometrically (662). Several studies have involved the titration of lead with EDTA (35, 106,167). Amperometric titration with EDTA has been used to analyze mixtures of vanadium(II1) and vanadium (IV) (267). Piperazine salts have been determined by precipitation by excess KBi14 and titration of the supernatant solution with EDTA (306). Molybdate (315),phosphomolybdic acid (194), and manganese(I1) (137) have been amperometrically titrated with EDTA. Iron(II1) has been amperometrically titrated with EDTA a t a D M E (137) or a rotating tantalum electrode (314). The titration can be run biamperometrically a t platinum or graphite electrodes (2996, 198, 302). This method has been used for iron(II1) determination in high-carbon slags (301). Nickel has been titrated with EDTA at a rotating platinum anode (194) and by an a x . polarographic technique that use7 hexamminechromium(II1) as indicator ion (247). The current decreases as nickel is complexed and then increases rapidly as the chromium-EDTA complex is formed. This complex exhibits a current peak at the chosen potential of - 1.25 volts. Methods Involving Other Organic Compounds. The amperometric titration of formaldehyde with serum proteins has been used to study the protein-formaldehyde reaction (40). Arsenic(II1) in 20% ethanolic 0.1M

Na2SO4has been titrated with tartaric acid a t a DME potential of -1.25 volts (60). The current rises during titration, but is not greatly affected by excess titrant. Niobium in solutions obtained from niobium steel or wolframite has been titrated with pyrocatechol (115). This titrant has also been used for titanium and tantalum (658) and for the analysis of mixtures of vanadium(II1) and vanadium(1V) (256). Titration a t p H 1.5 gives total vanadium, while only vanadium(1V) is titrated a t pH 3.1. Copper(I1) has been titrated with resacetophenone (126) and with 2’,3’,4’-trihydroxychalcone (244).

Amperoinetric titration with 1,2cyclohexanedione dioxime, a t a RPE of zero potential, has been used to determine palladium (88). Zirconium has been titrated with cupferron (685) or neocupferron, which is also a titrant for titanium (65). Another titrant for these two metals, for gallium (64), and for cerium (292) is N-benzoylphenylhydroxylamine. Addition of excess of this reagent and back titration with CuS04have been used to determine thorium and lanthanum (292). Pyridine bases have been determined in bismuth-containing medium by titration with KI (186). 8-Quinolinol (oxine) has been used to titrate molybdate (31, 130) and variow metal ions (31). The titration of thorium and uranium(V1) with 8-hydroxyquinaldinic acid has been described (265). Unsatisfactory results were obtained in the titration of lead or iron(I.11). A method for the titration of copper(I1) B-ith tetraphenyloxalamidine has been used for samples of brass (168). Zirconium (183) and hafnium (181,182) have been titrated with Flavazine L. Tartrazine is another titrant for hafnium (181,182). Bromopyrogallol red has been used as a titrant for uranium(V1) (256). Titrations with organic compounds that contain active sulfur groupings have been given considerable attention, especially by Russian workers. Methods that involve such compounds and silver, mercury, or lead have already been discussed. Copper(I1) in ammoniacal tartrate medium has been titrated with sodium diethyldithiocarbamate (DETC) (167). Khen thallium(II1) is titrated, a thallium-DETC complex is formed first, but decomposes to give the thallium(1) compound (868). The titration of thallium with hexamethylenedithiocarbamate is more sensitive than the titration with DETC. Potassium ethyland isoamylxanthates form thallium (111) coinplexes that dissolve in more titrant to give thallium(1) compounds (269). Titration with potassium ethylxanthate has been used to determine thallium in alloys and ores. Titration with thiourea (13, 179), phenylthiourea

($79), 1,l-dimethyl-3-p-chlorobenzenesulfonylthiourea (279), and 2,4-dithioburet (240) has been used for the determination of palladium in metal concentrates and slimes. Sodium glycollate in acid, neutral, or alkaline medium is oxidizable a t a platinum elect'rode and may be used as a titrant for some metals (174). On titration with unithiol, gold(II1) is reduced and precipitated as a gold(1) complex that redissolves as more titrant is added (225). This titration has been used to determine gold in concent,rat'es. Another titrant for gold is 1phen~l-2~4-dithioburet(270). Titration Rith diinercaptothiopyrones has been used t o determine copper in ores, granulated nickel, and aluminum and zinc alloys (10). With lead as amperometric indicator, bismuth in fusible alloys has been titrated with potassium ethylxanthate (280). Another titrant for bismuth is thionalide (281, 284). This reagent has also been used to titrate copper in ores and alloys (282, 2 8 4 , antimony (282, 2 8 4 , and palladium in deposition sludges (283). 0-Resorcylidenethiosemicarbazone has been used to titrate copper, nickel, and cobalt in the presence of cadmium (230). Usatenko and his coworkers have ext,ensively studied titrations with 8mercaptoquinoline. Determinations with this titrant of copper (%$I), gold (WS), cadmium (274 , indium (276), palladium, and iridium (272) have been described. To determine copper, zinc, and iron in aluminum alloys, the sample is suitably dissolved and the pH of an aliquot of the solution is brought to 0.5 to 1. Separate end points for iron and copper are obtained on titration with 8mercaptoquinoline. After pH adjustment to 4.5 to 5.5 and addition of NaF, a second aliquot is titrated to obtain the sum of copper and zinc (277). The same titrant has been used to determine copper in metal distillation residues, copper and zinc in brass or bronze, copper and iron in duralumin (276),and molybdenum in steels (242). A combination of precipitation and reduction reactions allows iridium(1V) , palladium(11), iron(III), and copper(I1) to be differentially titrated (271, 278). 411 end points are obtained from the same titration curve, Precipitation with sodium tetraphenylborate and either back titration of excess reagent with thallium(1) (24) or addition of acetone to the precipitate and its titration with .4gXO3 (73) have been used to determine potassium in cement or other technical products. Tetraphenylborate amperometric titrations of compounds such as KC1, amphetamine sulfate, and hexadecyltrimethylammonium bromide have been improved by constant-rate titrant addition and continuous recording of cur-

rent (221). Precipitation with excess tetraphenylborate and biamperometric back titration with .4gso3 have been used to determine r\TH&03 in mixtures with urea (107). Oxalate precipitation along with rare earth elements, ignition, dissolution and amperometric titration with thoron, have been used to determine thorium in monazite (260). The titration medium contains S H 2 0 H .HCl, which reduces cerium(1V) and iron(III), preventing their interference. Uranium(V1) has been titrated with aqueous ethanolic Arsenazo I11 solution (255). Although the titration of 4 x to 2 X 10-2M perchlorate with tetraphenylstibonium sulfate is precise to within 1.570, titrant standardization under conditions approximating those of an actual determination is to be recommended (147). Chloride, chlorate, nitrate, phosphate, and sulfate do not interfere. Miscellaneous Titrations. Germanium(1V) in iYH40H-XH4C1 medium has been titrated with 11gS04 a t a DhIE potential of -1.6 volts (48). Arsenic(V) interferes, but arsenic(III), silicate, and borate do not. 13iamperometric titration with Cd(OXc)2 has been used to determine sulfide in the presence of sulfite, sulfate, chloride, and nitrite (108). The titration of alkylchlorosilanes with Cd(XOs)? is based upon the precipitation of CdCL from the anhydrous AcOH medium (116 ) . Titration with ortho-, meta-, and pyrovanadate has been used to study compound formation with thallium(1) (807). This ion has been determined by titration in X a X 0 3 medium with pyrovanadate (207) and, in alkaline medium (pH 11.5), with K2Cr04 (89). Lead does not interfere in the chromate method. Uranium(V1) in KC104 medium has been titrated with orthovanadate (144). Titrations such as that of CuS04 with Cr2(S04)3 have been used to study the reactions of copper salts with those of chromium(II1) (163). Titration with FeCh at a R P E has been used to determine phosphates in rustproofing solutions (261) and fluoride in etching baths (129, 162). A procedure for the titration of fluoride with Th(N03)d has been described (80). Titration with Iz has been used to study starch-t.ype polysaccharides (114), the determindion of amylose (16), and the adsorption of I, on starch (49). Zirconium has been biamperometrically titrated with fluoride, using iron(II1) as indicator ion (220). The titration of uranium(V1) with N a F has been used to illustrate a new a x . technique (31). Cadmium in plating baths has been determined by suitable pretreatment, addition of pyridine, and titration with KSCN (133). The titration of calcium with Na2Se03 has been described (43). Cations such as barium

that form insoluble selenites interfere. Amperometric titration in fused KSOs has been used to study precipitate formation between IYd(N03)3and K,SO, or KOH (290). OXIDATION-REDUCTION REACTIONS

Methods Involving Iron. =1 relative error of less than 2% has been found in the amperometric or biamperometric titration of cerium(1V) in 0.8-1.2K HzS04 with FeS04 (291). Titaniuin(1V) has been determined by reduction, collection in FeNH4(S04)2, and biamperometric titration of iron(I1) with cerium(1V) (2W0). The sy>tems iron (11)-cerium (IV) and iron (11)-manganese(VI1) have been used t o illustrate phase angle titration (156). Biamperometric titration of vanadate with electrolytically generated iron(I1) has been used to determine 0.001% or more of vanadium in TiC1, (192). Conversion to vanadate and titration with iron(I1) at a RPE ha.. been used to determine trace amounts of vanadium in steels and cast irons (259), and also vanadium yesent as carbides in steels (263). Filenko has described iron(I1) amperometric (53) and biamperornetric (54) titration methods for the determination of vanadium, chromium, and manganese in alloy steels. 13iamperornetric titration was used R hen only chromium and manganese were determined (56). A standard deviation of only 29 p.p.m. has been obtained in the ampeiometric titration of K2Cr2O7with electrolytically generated iron(I1) (132). Addition of excess 1Iohr qalt to reduce gold (111) and back titration with K2Cr207 have been used to determine gold in solutions made from crude copper (172). llicrogram quantities of chromium in mixtures of fluoride salts have been determined by dissolution of the sample, oxidation to chromium(V1) with Ago, and titration with 1Iohr's salt at a pyrolytic graphite electrode (PGE) ( 9 ) . Amperometric and other end point methods for the titrimetric assay of highpurity plutonium have been found to give essentially equal results (306). A relative standard deviation of 0.03%, on over 800 samples containing 10 to 20 mg. of plutonium, has been reported for the Seils method, which involves amperometric titration with FeS04 (21). The biamperometric titration of Fe(C104)~ in anhydrous -1cOH with Pb(OAc)4 (176) or IC13 (177) has been described. Submillimolar concentrations of iron (111) in HC104-KSCN medium have been titrated with HgC104 at a RPE (236). Reduction with zinc amalgam and biamperometric coulometric titration with iron(II1) have been used to determine from 1 t o 1090 pg. of titanium per ml. of solution (223). hlilligram quantities of iron(II1) have VOL. 38,

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been biamperonietrically titrated with electrogenerated vanadium(II1) (263). Cranium has been determined by suitable dissolution, passage through a Jones reductor, and R P E amperometric titration with hlohr’s salt (245). -1mixture of uranium(II1) and uranium (Is’) is titrated. The current is anodic before the firrt end point and cathodic after the secoiid one. Aniperometry a t the D l I E appears to be superior to RPE ainperometry or biamperometry as an end point method in the titration of uranium(1s’) with iron(II1) a t room temperature (62). Pashchenko and Songina (178) have titrated submilligram amounts of gold (111) with K4Fe(CN)6. Thallium(1) (103), chromium(II1) ( S I $ ) , and cobalt (11) (142) have been titrated with K3Fe(CN),. The titration of chromiuni(II1) is performed in 12.5N S a O H containing a trace of T1(x03)3 a5 catalyst. Glucose in a flowing system has been continuousl~7determined by pumping in glucose osidase-KrFe(CN) 6 solution and amperometrically measuring the K3Fe(CN)6 that is formed (23). Hydroquinone ha5 been used to titrate K3Fe(cs)6in saturated XaHCO3 (106). Nonferrous Methods Involving Cerium, Titanium, Vanadium, Chromium, and Manganese. From 0.05 to 10 fig. of uraniuni(1V) per ml. in 1Ji HZSO4-lX H3P04 has been titrated nith Ce(HS04)4 at a PGE of potential +0.5 volt (316). Few common ions interfere in this titration. The amperometric titration of nitrite (2%) and the biamperometric titration of promethazine (19) r5ith cerium(1V) have been reported. Cerium(1V) has been titrated with oxalic acid (224,291), ascorbic acid (220), and cupferron (138, 291). Poor reproducibility in the direct or reverse titration of cerium(1V) with neocupferron has been reported (138). Reduction, addition of excess cerium(IV), and biamperometric back titration with ascorbic acid have been used to determine titaniuin(1V) either alone or admixed with vanadate and iron(II1) ($20). Uranium(V1) in LTOzhas been titrated with electrogenerated titanium (111) (246). Titanium(1V) in HzS04 and vanadium(1V) in HzS04-H3P04 medium have been titrated with vso4 (66). Vanadiuiii(I1) has also been used to titrate molybdate in HCI or H2S04a t a platinum electrode, or in HaPo4 a t a DLIE (78). hlolybdenuin(V) is formed in the first case, and molybdenum(II1) in the second. Titration in 5N H2S04 has been used to determine molybdenum in ferromolybdenum. Electrogenerated vanadium(II1) has been used as a biamperometric titration for vanadate, dichromate, and permanganate (263). Vanadate and dichromate have also been titrated with hydroquinone a t a R P E (106). Agasyan and his coworkers (7) have concluded

456 R

ANALYTICAL CHEMISTRY

that biamperometric titration with vanadate is one of the best methods for determining uranium(1V). Dichromate has been used to titrate tin(I1) in formate medium a t a DnlE (46) and pyrogallol a t a RPE (193). I n the titration of dichromate with electrogenerated molybdenum (V) , biamperometric curves with E = 0.3 volt were sharper than the amperometric curves at a platinum electrode of potential +0.9 volt (52). The aniperometric titration of dichromate in 0.7N HNOj has been described ($12). The titration of manganese(I1) with K l l n 0 4 has been discussed in several papers (69-71, 142) and has been used to determine manganese in zinc electrolytes (69, 7 1 ) . Addition of oxalic acid, dissolution of the precipitate in 7 N H2S04and titration with KMn04 have been used to determine total rare earths (224). Scandium has been determined by addition of excess il’-benzoylphenylhydroxylamine and back titration with KRln04 (64). Methods Involving Chlorine. Quercetin ($67, caffeine (93), theobromine, theophylline (94),and phenyl butazone (97) have been biamperometrically titrated with electrogenerated chlorine. Electrolytic reduction of nitrate t o ammonium ion, addition of KBr and biamperometric titration with XaOC1 have been used to determine total nitrogen in xH4N03 (113). Primary amides have been titrated in 20% dioxane-121 HC1 with Ca(OC1)2 a t a RPE of potential $0.4 volt (184). A potential of +0.3 volt was used in the titration of nitrite (&), hydrazine sulfate, arsenic(III), or ascorbic acid (44) in citrate buffers with chloramine T. Ceriuni(1V) , vanadate, and dichromate have been determined by addition of excess hydrazine sulfate, arsenic(III), or ascorbic acid and back titration with chloramine T (44). This titrant has been used for salts of aminosalicylic acid (319). Free residual chlorine in water has been titrated with sodium arsenite a t a gold electrode (67). Low results in the titration of 0.1 and 0.5 p.p.m. of chlorine with phenylarsenoxide may be due to incompleteness of reaction and loss during stirring (160). Titration with phenylarsenoxide has been used to evaluate active-chlorine bleaching agents (204). Methods Involving Bromine. Electrogenerated bromine has been used t o titrate micromolar concentrations of arsenic(II1) by the ring-disk technique (32) and thiocyanate ion biamperometrically (42). Bismuth has been determined by conversion to BiCr(SCS)6, dissolution of this precipitate, and titration of thiocyanate (42). Biamperometric titration with electrogenerated bromine has been used to determine furan in tetrahydrofuran (Sit?), 2-phenyl-l,3-indandione in the presence of lactose (loo),quercetin (96),

and anthranilic acid (79). From 0.1 to 1 mg. of copper, zinc, cobalt, or nickel has been determined by precipitation as anthranilate, dissolution in HC1, and titration of anthranilic acid (41). Copper has also been determined by titrating the dissolved anthranilate at a RPE (79). Other organic compounds that have been biamperometrically titrated with electrogenerated bromine include 4- and 5-azaindan-1,3-dione derivatives (168), phenylbutazone (97), hydrochlorides of chlorotetracycline and oxytetracycline (98), dihydralazine (96), tetramethyllead, and tetraethyllead (178). h platinum wire cathode and cylindrical anode were used in the automatic coulometric determination of low bromine numbers of hydrocarbons (134). Back titration of excess of electrogenerated bromine with electrogenerated copper(1) has been used to determine methyl vinyl ketone (517). Bromine in MeOH (119) or AcOH (118, 119) has been used to titrate unsaturated organosilicon compounds. Vinyl monomers (266) and aniline (139) have been titrated in acidified KBr with KBr03 a t a RPE. Biamperometric titration with KBr03 was used for the determination of 2-phenylindane1,a-dione (100). Molybdate has been determined by addition of excess 8quinolinol and back titration with KBr03 at a vibrating platinum electrode (130). Solutions of organic sulfides with a primary or secondary alkyl group have been standardized (238), and sulfonamides (18) and barbituric acid derivatives (20) have been determined by biamperometric titration with KBr03 in the presence of KEr. Submilligram quantities of ammonium salts (38, 121) and sulfamic acid (121)have been biamperometrically titrated in borate buffer with electrogenerated hypobromite. Urea, or the sum of urea plus KH4NO3, has been biamperometrically titrated in saturated KHCOI a t 60’ to 70’ C. with KOBr (107). Methods Involving Iodine. The biamperometric titration of IZ with xazSz03, or the reverse, has been applied t o the determination of hydrogen peroxide (37), microgram amounts of hydrogen sulfide (187), iodide and thiosulfate ions in the presence of each other (112), carbon-carbon double bonds (go), milligram quantities of formic acid obtained in the S a I 0 4 oxidation of saccharides ( I I ) , amine oxides and peroxides (81), and cyclohexanone oxime (179). Microgram amounts of organic iodocompounds have been determined by oxygen-flask combustion, oxidation of the resulting iodide to iodate, addition of excess Xa2Sz03and biamperometric titration with KIOI (148). Hydroquinone has been used to titrate KIO3 in 5X HC1 at a RPE (106).

The biamperometric titration of tin HC1 with KIO, gave three end (11) in 5A17 points, indicating the respective oxidations of tin(I1) to tin(IV), iodide to 12,and Iz to IC12- (57). Arsenic(II1) (57) and ascorbic acid (151) have also been titrated with KlOs. Biamperometric titration of liberated If with electrogenerated tin(I1) has been used to determine selenium(1V) (264). To determine selenium in copper refining sludge, this is dissolved in HXO3 and the selenium is separated by paper electrophoresis. Total arsenic in glasses has been determined by dissolution in HC1-HF mixture, reduction of arsenic (V) with iodide, removal of iodine on an anion exchange reiin, and amperometric titration of arsenic(II1) at a platinum electrode with electrogenerated iodine (309). Passage through the exchange resin also removes antimony(III), which othervc-ibe interferes. If the reduction step is omitted, only arsenic(II1) is determined. Similar titrations in tartrate medium have been used to determine total antimony and antimony(II1) in glasses that also contain arsenic (310).

Hydrazine has been determined by biamperometrically til rating a K r S208-KI mixture (91). The reaction has been used for the indirect determination of PbOLand M n 0 2 (92). The direct biamperometric titration of niicrogram amounts of H2S with electrogenerated I2requires close control of p H and of titration time (187). 2,3-Dimercaptopropanol (102) and potassium ethylxanthate (101) have also been titrated with electrogenerated If. Thallium(II1) has been titrated in 0.3 to 0.5LVH2SOawith K I a t R R P E of potential +0.8 volt (104). Titrations, in anhydrous AcOH, of unsaturated organosilicon conipounds with IC1 (117) and of mercury(1) , arsenic(III), antimony(III), and Na2S03 with IC13 (177) have been described. Interest has continued in nontitrimetric determinations that are based upon changing the kinetics of iodineproducing reactions. Catalysis of the iodide-H702 reaction has been used to determine microgram quantities of molybdenum at a RPE (214). Biamperometric indication was used in all of the following examples. Af olybdenuni and tungsten ( 2 5 X in CdS and molybdenum ( 2 2 X in LiF single crystals have been determined by the iodide-H202 method (33). Germanium a t a concentration of 0.1 to 2.5 pg. per ml. has been determined by its effect on the iodide-molybdate reaction ( 1 4 2 ) . Catalysis of this reaction by H 2 0 2i b the basis of automatic methods for the deterniiiiation of galactose (170) and for the assay of glucose oxidase (171). LIicrogram amounts of iron(I1) have been determined by catalysis of the iodide-persulfate re-

artion (140). Iron(III), reduced by iodide in the reaction mixture, can be similarly determined with slightly less accuracy. hlaterials in which water has been determined by biamperometric titration with Karl Fischer reagent include aliphatic ketones ( H ) , low polymers of formaldehyde (150), white sugars (1 7 ) , refrigerant gases and propellant niixtures (63),and other organic substances (34). Xew apparatus has been developed for the automation of this titration (63, 175). Electrogenerated reagent has been used to titrate submilligram quantities of water (188) and in the continuous indication or control of the water content of a stream of liquid sample (14). Other Reactions. Reduction to molybdenum(II1) and titration with CuSOd at a RPE has been used to determine molybdenum in steels (259). Cystine has been titrated a t a DME with copper(I1) in the presence of excess ascorbic acid (243). Reducing sugars in refinery liquors have been determined by a biamperometric Lane-Eynon titration (311). Tetramethyllead and tetraethyllead haxe been titrated with (178). electrogenerated iiiercury(1) Antiniony(II1) in 251 KOH-O.05JI EDTA has been titrated nith HgC12 (294). Although arsenic(II1) interferes, titration is poscible in the presence of tin(1I). Thallium(II1) has been titrated n i t h ascorbic acid (10/t), potasiiuni ethylxanthate (269), and dimercaptothiopyrones (123). The DNE ainperonietric (6) and bianiperoinctric (176) titrations of arsenic(II1) in anhydrous .IcOH with P ~ ( O A Chave )~ been described. The biamperometric titration has also been used for Xa2S03 and T\",SCX (176). Uraniuni(V1) in an acetate buffer containing pyridine has been biamperometrically titrated with aqcorbic acid (217). Ruthenium(1V) has been titrated with hydroquinone a t a RPE (190). This electrode has been used in the titration of wbniillimolar concentrations of nitrite with sulfamic acid (2%). Biamperoinetric titration with XaXOs has been used to determine various aromatic amines (149, 211), hydrazides (21I), sulfonamide- in pharmaceuticals ( I S ) , sodium benzenesulfinate (61), and 4-aniinobenzoylacetonitrile (60). Various aromatic amines and phenols have been titrated with m- or p-nitrobensenediazonium chloride a t a DNE (136) or 17 ith p-wlfobenzenediazoniuin chloride a t a vibrating copper anodeplatinum electrode combination (135). LITERATURE CITED

(1) Abramov, AI. K., Aptechn. Delo 1 1 , 62 (1962). ( 2 ) Ibid.. 13. 38 (1964). ( 3 ) Abramov, lf. K.,' Semina, Yu. G., Ibid., 13, 58 (1964).

(4) Abramov, AI. K., Teodorovich, I. L., Ibid., 13, 66 (1964). ( 5 ) Adamek, P., Uoleial, J., Zj.ka, J., Collection Czech. Chem. Commun. 28, 2131 (1963). (6) Adamek, P., Doleial, J., Zfka, J., Microchem. J . 8 , 1 (1964). ( 7 ) Agasyan, P. K., Nikolaeva, E. R., Demina, L. A., Zavoclsk. Lab. 30, 1434 (1964). ( 8 ) Alonso, C. R., Rev. Fac. Farm . Univ. Central Venezuela 4, 133 (1963). (9) Apple, R . F., Zittel, H. E., h A L . CHEW36, 983 (1964). (10) Arishkevich, A. LI., Usatenko, Yu.

I., T r . Dnepropetr. Khim.-Tekhnol. Inst. 1962 (16), p. 47; CA 61, 1254b

(1964). (11) Babor, K., Kalac, Y.j Tihlarik, K., Chern. Zvesti 18, 913 (1964). (12) Bagbanly, I., A41ekperov, A,, Nadzhafova, K., Azerb. Khim. Zh. 1963 ( l ) , 51; C A 59, 12165g (1963). (13) Bardin, 11. B., Balandina, N. S., Todorova, 0. I., Zh. Analit. Khim. 19, 1228 (1964). (14) Barendrecht. E.. U. S. Patent 3,131,133 (Cl. 2 0 4 1 ) (-4pr. 28, 1964). (15) Barikov, I?. G., Songina, 0. A., Zaoodsk. Lab. 30, 5 (1964). (16) BelIiller, J. S.,,,"L\lethods Carbo-

hydrate Chemistry, R . L. Whi-tler, ed., p. 165 Academic Press, Xew York, 1964.

(17) Bennett, R. G., Runeckles, R. E., Thompson, H. hI., Intern. Sugar J . 66, 109 (1964). (18) Beral, H., llurea, L., Rlatigearu,

lI., Cuciureanu. E.. Farinacia (Bucharesi) 12, 245 ('1964); CA 61,' 6867g

(1964). (19) Beral, H., Wermescher, B., Murea,

L., Cuciureanu, E., AIadgearu, AI., Rev. Chiin. ( B i d m r e s t ) 16, 105 (1965); C d 63, 9749b (1965). (20) Beral, H., IVermescher, B., Llurea, L., lIadgearu, AI., Cuciureanu, E., Pharm. Zentralhalle 103, 112 (1964). (21) Bergstresser, K. S., JVaterbury, G. R.,C . S. At. Energy Comni. LA-

3091 (1964). (22) Berka, A,, Doleial, J., Zj.ka, J., Chemist-Analyst 53, 122 (1964); 54, 24 (1965). (23) Blaedel, W. J., Olson, C., ANAL. CHEM. 36, 343 (1964). (24) Bluemel, G., Freiberger Forschungsh. A 267, 333 (1961) (Pub. 1963). (25) Blyakh, G. I., Gorelkiiiskii, Yu. V.,

Grinman, I. G., Shulyar, B. N., L.S.S.R. Patent, 159,685 (Dee. 28, 1963). (26) Bodyu, \-. I., Kozlova, I. V,,Sister, Yu. D., Lyalikov, Yu. S., Zh. Analit.

Khim. 18, 659 (1963). (27) Bonibi, C. G., Fiorani, AI., l l a z z o c chin, G . A., J . Electroanal. Chem. 9 , 4,57 (1965). (28) Bozsai, Q., Llosonyi, L., Pharm. Zentralhalle 103, 250 (1964). (20) Bozsai, I., lIosonyi, AI., Acta Pharni. Hung. 34, 246 (1964); C A 62, 12982b (1965). (30) Breant \I., Robin, J., Chim. Anal. ( P a r i s ) 4$, %5 (1965). (31) Breyer, B., Beevers, J. R., Hayes, J . W., Proc. Australian Conf. Elcctrochenz., l s t , Sidney, Hobart, Australia

1963, p. 275 (1965). (32) Bruckeiistein, S.,Johnson, D. C., A s . 4 ~ CHEN. . 36, 2186 (1064). (33) Bulgakova, A. >I., Zalyubovskaya, N. P., Zh. Snalit. Khim. 18,1475 (1963). (34) Campiglio, A Fannaco (Pavia), Ed. Sei. 20, 570 ( l & ) . (35) Chang, T.-H., Tsao, F.-Y., Shu, S.-AI., Hzta Hsueh Hsveh Pao 30, 230 (1964); CA461, 6392c (1964). (36) Chovnyk, X. G., Rutberg, L. G., Alemaskina, G. A., U.S.S.R. Patent 159,302 (Dee. 7, 1063). VOL. 38, NO. 5, APRIL 1966

457 R

' Listv 57. 156 (1963'1. ' ' (48) firanitskaya, R.' AI., Iashvili, E. V., Zh. Analit. Khzm. 19, 1031 (1964). (49) Duelin, V. I., Kazarov, V. I., Ibid., 18, 1016 (1963). (50) Elenkova. N.. Todorova. G.. Anal. dhim. Acta 29. 364 119631. ' (51) Elving, P.' J., Fried; I., Turner, W. R., U.S. At. Energy Comm. COO1148-84 (1964). (52) Feldman, F. J., Christian, G. D., Anal. Chim. Acta 33,266 (1965). (53) Filenko, A. I., Zavodsk. Lab. 29, 1423 11963'1. (54) Filenko,' A. I., Zh. Analit. Khim. IO. -ins 11964) (5ij'Fifeiko, A. I., l i k r . Khim. Zh. 31, 225 (1965); CA 63, 2377e (1965). (56) Filipczuk, H., Zeszyty Nauk. liniv. Lodz. Ser. I I 10. 185 (1961): ,, CA 61. 7707f (1964). (57) Fiorani, hl., Bombi, G. G., Freddi, R., Ric. Sci. Rend., Sez. A 3, 749 (1963). (58'1 Fischer, F., Schiene. R.. Z . Chem. 4, 69 (1964). (59) Flaschka, H., Speights, R., Anal. Chim. Acta 28, 433 (1963). (60) Fleszar, B., Chem. Anal. (Warsaw) 9, 223 (1964). (61) Fleszar, B., Ibid., 10,49 (1965). (62) Florence, T. M., Shirvington, P. J., ANAL.CHEM.37,950 (1965). (63) Francis, H. J., Sawyer, P. O., Mzcrorhem. J . 8, 139 (1964). (64) Gallai, Z. A., Alimarin, I. P., Sheina, S . 31.)Zh. Analit. Khim. 18, 1442 (1963). (65) Gallai, Z. A., Alimarin, I. P., Sheina. 5 . M..Norozova. L. A,. Ibid. 19, 1464 (i964j. (66) Gallai, Z. A., Xlaranovskaya, T. Ya., Ibid., 18,924 (1963). (67) Ghelberg, N. Rr.j Igiena (Bucharest) 13. 63 (1964): CA 62,328h (1965). (68) 'Goldman, J. A., Meites, L., Anal. Chim. Acta 30, 280 (1964). (69) Gordienko, V. I., Kovalenko, P. X., Ivanova, Z.I., Peredovye Metody Khim. Tekhnol. i Kontrolya Proizv. (Rostovon-Don: Rostovsk. Univ.) Sb. 1964, p. 113; C A 62, 12433h (1965). (70) Gordienko, V. I., Kovalenko, P. N., Ivanova, Z. I., Ukr. Khim. Zh. 30, 801 (1964); CA 61, l5341e (1964). (71) Gordienko, 1'. I., Kovalenko, P. N., Ivanova, Z. I., Zavodsk. Lab. 30, 31 (1964). (72) Grimes, A. J., A'ature 205, 94 (1965). (73) Grubitsch, H., 2 . Anal. Chem. 209, 313 (1965). (74) Gupta, C. M., Bull. Acad. Polon. Sci.. Ser. Sci. Chim. 13. 167 11965). (75) Gupta, C. AT., Indian J. Chem. 3, 39 (1965). \----,-

~

I

458 R

,

ANALYTICAL CHEMISTRY

(76) Gupta, C. M., Naturwissenschuften 5 0 , 545 (1963). (77) Gupth, S. L., Sharma, S. K., J. Electroanal. Chem. 8, 478 (1964). (78) Gusev. S. I.. Nikolaeva. E. M.. Zh. ' Analit. Khim. 19, 715 (1964). (79) Hargis, L. G., Boltz, D. F., Talanta 1 1 , 5 7 (1964). ( 8 0 ) Hitchen, A., Can. Mining Met. Bull. 58, 641 (1965). (81) Hoft, E., Schultze, H., J . Prakt. Chem. 19,260 (1963). (82) Hsu, L.-H., Chou, T.-H., Yao Hsueh Hsueh Pao 12, 171 (1965); C A 63, 2388a (1965). (83) Humphrey, R. E., Hawkins, J. M., ANAL.CHEM.36, 1812 (1964). (84) Humphrey, R. E., Potter, J. L., Ibid.. 37. 164 (1965). (85) Ikedi, S.,~ Nishida, G., Bunseki Kagaku 13, 133 (1964). (86) Ikeda, S., Nishida, J., Ibid., p. 433. (87) Ikeda, S., Xishida, G., Yoshida, T., Ibid., p. 690. (88) Ivonina. 0. h l . Zh. Analit. Khim. 19, 644 (1964). (89) Jain, D. S., Gaur, J. N., Bull. Chem. Soc. Japan 37,995 (1964). (90) Jedlinski, Z., Paprotny, J., Chem. Anal. (Warsaw) 8, 765 (1963). (91) Jovanovic, M. S., Kalinic, M. P., Glasnik Hem. Drustva, Beograd 27, 289 (1962). (92) Jovan&ic, A I . S., hIanojlovic, C. hl., Gudalo, J., Ibid., 25-26, 109 (1960-61). (93) Kalinowska, Z. E., Acta Polon. Pharm. 20, 69 (1963); CA 61, 93559 (1964). (94) Kalinowska, 2. E., Ibid., 20, 193 (1963); CA 62, 1516e (1965). (95) Kalinowska, 2. E., Chem. Anal. (Warsaw) 9, 831 (1964). (96) Kalinowska, Z. E., Kochalska, J., Bcta Polon Pharm. 20., 59 11963): ,, CA 61, 9357f (1964). (97) Kalinowski, K., Fecko, J., Ibid., 21, 247 (1964); CA 62,13849a (1965). (98) ,Kalinowski, K., Piotrowska, A., Ibzd., 20. 199 (1963): CA 62, 1515f (1963). (99) Kapoor, R. C., Vijnana Parishad Anusandhan Patrika 3, 27 (1960); CA 58, 5919j (1963). (100) Karklins, A., Veiss, A., Latvijas PSR Zznatnu Akad. Vestis, Kim. Ser. 1963 ( l ) ,p. 124; CA 60, 28b (1964). (101) Kekedy, L., Makkay, F., Studia Univ. Babes-Bolyai, Ser. Chim. 7, 105 (1962); CA 61, 126419 (1964). (102) Kemula, W., Brachaczek, W., Chem. Anal. (Warsaw) 8,579 (1963). (103) Khadeev, 5'. A., Myalkovskaya, S. G., A'ekotorye Vopr. Khim. Tekhnol. i '

~

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1963,p. 143;-~~-61;'3Og (ig64). (104) Khadeev, V. A., Poluektova, S. N., Ibid., 1963, 174; CA 61, 1266h . p. (1964). (105) Khadeev, V. A,, Yudin, K. A,, Ibid., 1963,p. 135; CA 61,30h (1964). (106) Kies, H. L., J . Electroanal. Chem. 8, 325 (1964). (107) Kiss, S. A., Chem. Anal. (Warsaw) 8, 529 (1963). (108) Kiss, S. A., Magy. Kem. Lapja 18, 145 (1963). (109) Kiss, S.A.,Ibid.. 19, 169 (1964). (110) Kiss, S. A., 2. Anal. Chem. 194, 104 (1963). (111) Kiss. S. A , . Ibid.. 195. 249 11963).

(113) Kleinova, J., Kadic, K., Rezac, Z., Ibid., 199,35 (1963). (114) Kobayashi, T., Kobayashi, N., Aar. Biol. Chem. (Tokuo)27.438 11963). (115") Xomolova, ~. G.,-Tserkovnitskaya, I. A., Zavodsk. Lab. 30, 1329 (1964).

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I 1 964) \ - _ - -

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WORKcarried out with partial support of the U. S. Atomic Energy Commission (Contract AT-(30-1)-1977).