Amperometric, bipotentiometric, and coulometric titration - Analytical

Anal. Chem. 1982, 5 4 , 1 R-9 R

Amperometric, Bipotentiometric, and Coulometric Titration John T. Stock University ,of Connecticut, Storrs, Connecticut 06268

vantages of reagent generation by anodic dissolution of metals (151) have been explored. Kinetic parameters and current efficiencies for the generation of manganese(II1) (27)and of chlorine (28) have been examined by rotating disk electrode voltammetry. A parameter, Q, has been proposed for the quantitative appraisal of the quality of coulometric titrations (26). A formula for curves obtained in coulometric titration to a twin-electrodeend point has been reported (143). The development of the triangleprogrammed titration technique has continued with evaluations of the titration curves (192,193)and of a procedure for complete coulometric titration in flowing solutions (190).

This survey covers the period from the previous review (274) through Oct 1981. The order of treatment is the same as in that review. Unless otherwise specified, potentials are with respect to the saturated calomel electrode (SCE). Olga Songina’s extensive studies on the applications of amperometric titrimetry have made her a leading authority in this field. The appearance of the third edition of her book (272) is therefore a major event. Interest in titrimetry in nonaqueous or essentially nonaqueous media has Continued to grow. Fleviews concerning the amperometric (166) and the coulometric (114) aspects have appeared. The proceedings of a conference on coulometric analysis (225),a study aid to this field (123),and a massive review of the coulonnetric literature from 1967 to 1972 (152) have been published. Other reviews deal with general aspects (36,66, log),advances in the electrogenerationof coulometric titrants (2),use of electrogenerated trivalent manganese compounds (11),analysis of organometallic compounds (30),coulometric elemental (organicandysb (315),titration of rhenium(VK1) (M), analysis of drinking water (68), indicator electrodes for highly dilute solution (293),and detectors for continuous-flow coulometry (2?87). The relative electrode sensitivity, defined as the ratio of the difference between indicator and residual currentcl to the product of residual current and concentration, has been proposed as a measure of the electrode zipplicability in amperometric titration (100).

ACIDI-BASE REACTIONS The purity of pH-standard KH phthalate has been certified by potentiometric titration with electrogenerated hydroxyl ions (173). Precise acid-base coulometric titration has also been used to assay high-purity sulfamic acid and Na2C03(20). Computer control was used in the coulometric potentiometric titration of H3P04and HCl(207). Continuous titration with internally generated hydroxyl ion has been used in the automatic determination of low concentrations of HC1 in gases (37). The capacity of ion-exchange resins (101) and autoprotolysis constants for H20, MeOH, and ethylene glycol (96) have been determined by coulometric titration. Titration with electrogenerated LiOH of HOAc that has been isolated by steam distillation has been used to determine the acetyl group in acetanilide (296). Oxygen in organic compounds has been determined by pyrolysis to form CO. This is oxidized by Iz05and the resulting C02 is absorbed in 5% Ba(C104)2of pH 9.7. This solution is then coulometricallytitrated with hydroxyl ion to return the pH to its initial value (194). A somewhat similar principle has been used to determine oxygen in uranium carbide (106). The d.etermination of oxygen in organic compounds by automated coulometric titration of COz enables 23 samples to be handled in 4 h (148). Automatic coulometric titration following combustion in oxygen has been used to determine carbon and sulfur in a single metal sample (18). Traces of oxygen in steel have been determined by high-frequency melting in a graphite crucible, oxidation of the resulting CO by hot CuO, and coulometric titration of COz (111). An automatic coulonnetric carbon analyzer has been used to determine Na2C03and CaC03 by treatment with HC1 and titration of the liberated C02 (197) and the carbon content of CaC03and MnCO,, obtained as corrosion byproducts (198). Conversion to CO anid then to COz for coulometric titration has been used in the simultaneous determination of oxygen and mercury in inorganic and organic compounds (203). Formic acid has been determined by oxidation with mercury(I1) acetate and automatic coulometric titration of the resulting COz (226). Coulometry was one of the techniques involved in a critical evaluation of methods for the determination of traces of carbon in zirconium (168). The photooxidation of organic substances is sensitized by Ce(S04)z (121). The method can be used to determine organic carbon in water by coulometiricallytitrating the COzthat is produced

APPARATUS AND METHODOLOGY Amperometric titration apparatus for water examiination (214),automatic operation (302),determining trace impurities in gases (160),obtaining im roved reproducibility (129),and intermittently adding fixed)quantities of titrant (260) have been described. A pulsed chronopotentiostatic technique in which the connection of a stationary electrode to the SCE alternates between direct and by way of a current source is reported to give results as accurate as obtainable with a dropping mercury electrode (DME) or EL rotating platinum electrode (RPE) (270). New coulometric titrators employ pulsed current (164) or are compensated for drift (65). Others are computer controlled (207),digitally controlled (292),use high-sensitivity end point detection (112),have an improved design for external generation of alkaline titrant (136),operate automatically with a diode-modulation amplifier to galvanically separate indicator and generator systems (140), and automatically perform dual-intermediate titrations (275). Permselectivemembranes of high resistance have been used for reagent generation with well-defined pulses of current (248,249). The development of coulometric instrumentation in Hungary has been described (54). A thin-layer cell with a gas-porouswall has been developed to monitor ppm levels of SOz (34). Hydrodynamic biamperometric end-point detection in coulometric titrimetry has been accomplished by use of a sandwich-type thin-layer cell (57). The diffusion-layer technique, in which an electrogenerated species le€t over after reaction with the test substance is determined at ti second electrode, is the subject of a patent

(122). The coulometric titration of weak bases in glycol solvents has been examined (95). Biamperometric indication at bismuth electrodes and glass-SCE potentiometricindication gave agreeing results in a study of the coulometric titration of organic acids in various organic solvent systems (131). Biamperometric titration in HOAc with pyridine or an alkali acetate has been used to determine HC104and H2S04in the presence of an excess of H3PO4 (73). PromethazineHCl and similar acid pharmaceuticals have been coulometrically titrated in 90% dimethyl sulfoxide (DMSO) medium (170).

(5).

Coulometric titration techniques that are rapid and accurate

(184),permit high-precision assay of primary standards (19,

20, 169, 173) and which have been applied to the determination of phase diagrams of multicomponent system13(305) have been reported. Factors that govern the accuracy of the results of automatic coulometric titration have been examined (266). The electrogeneration of reagents for drug control (301), improvements in a method for remote determination d u r a nium in intensely radioactive solutions (206), and the ad0003-2700/82/0354-1 R$06.00/0

0

1982

American Chemical Society

1R

AMPEROMETRIC, BIPOTENTIOMETRIC, AND COULOMETRIC TITRATION

Biamperometric indication at bismuth electrodes has been used in the coulometric determination of naproxen in a MeOH-Me2C0 medium (80). An automatic apparatus for the determination of carbon and hydrogen in organic compounds involves flash combustion and retention, by freezing, of the HzO thus formed while the CO is absorbed and coulometrically titrated in 9 1 DMSO-Hzb medium. The HzO is then caused to react with carbonyldiimidazole, giving a second batch of CO, that is then titrated (113).

PRECIPITATION AND COMPLEXING REACTIONS Methods Involving Silver. The effect of dissolved oxygen on the shape of the curves obtained in the amperometric titration of chloride with AgNOB at a graphite electrode has been investigated (158). An electrode prepared from fused AgBr-AgI-Ag,S has been used in the argentometric amperometric titration of chloride in sulfate-containing soils (269). Silver in silver-gallium-sulfur semiconductor material has been determined by amperometric titration with KI (137). The same titrant, in conjunction with a cerium(1V)-arsenic(111)or cerium(1V)-antimony(II1) catalyst, has been used to determine submilligram amounts of AgN03 (72). The amperometric titrations of silver with phenylmercaptoaceticacid (257) and with thiosalicylamide (15) have been described. Copper-silver ternary alloys with zinc, cadmium, or nickel have been analyzed by amperometrictitration with 8-mercaptoquinoline. Silver is titrated in 6 N HzS04, while titration in 2 N HOAc gives the sum of silver and copper. Nickel and zinc are titrated in HOAc-NaOAc medium. The cadmium content is obtained by difference (259). The effect of the medium on the selectivity of 8-mercaptoquinoline as a titrant for silver and some other metals has been examined (280). An investigation of 5-sulfo-8-mercaptoquinoline as a titrant for silver and other metals has shown that this compound has a smaller range of use in amperometry than 8mercaptoquinoline itself (40). Dissolution in HN03, adjustment of the solution to pH 10, and amperometric titration with AgNO, have been used to determine metallic selenium (116). The same titrant has been used to determine H,SeO, (117).

With W03 as combustion aid in moist oxygen, total chlorine in coals and other materials has been determined by titration of HC1 with electrolytically generated silver ion (298). Biamperometric, rather than potentiometric, indication is recommended for the coulometric titration of chloride in a method for the determination of chlorine in organic peroxy compounds (132). The workup in a method for the microcoulometric determination of total involatile and volatile organochlorine compounds in water involves continuous extraction with i-Pr ether or hexane, concentrationof the extract, and combustion in oxygen (69). Extraction, saponification, and coulometric titration have been used to determine organochlorine compounds in wastewater samples (126). Total organohalogenshave been titrated following solvent extraction and pyrolysis (299). The elimination of nitrogen, sulfur, and phosphorus interferences in the combustion-microcoulometric determination of chlorine in petroleum products has been studied (156,178). Some applications of coulometric chloride determination in pharmaceutical analysis have been described (107).

A method for the determination of metallic sodium in sodium tetrahydroaluminate involves treatment with lbromobutane,extraction of NaBr with HN03, and coulometric titration with silver ion (153). Volatile thiols in natural gas have been determined by absorption in ethanolic AgN03-NH3-NH4N03,addition of KI equivalent to the total AgN03, and iodide-ion-selectivepotentiometrictitration of the residual iodide with electrogenerated silver ion (77-79). Coulometric titration with silver ion has been used to determine halogens in organometallic and heteroorganic compounds after oxygen-flask decomposition (165)and in organosilicon compounds after fusion with Na20z(32). Absorption on active carbon, pyrolysis, and coulometric titration with silver ion are features of a patented method for the determination of organic halides in solid, liquid, and gaseous samples (283). The automatic coulometric titrations of microgram amounts of sulfide (39) and of thiols in kerosene (10) have been described. A coulometric method by which only cysteine in its mixtures with methionine is measured amperometrically has 2R

ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982

been reported (254). In a method for the determination of dithiooxamide with electrogenerated silver ion, direct titration in NH3-NH4N0, medium is used. A second method involved treatment with I,-CC14 in alkaline solution and titration of the liberated iodide ion. The second method is the more sensitive but is less selective than the first (115). Methods Involving Mercury. Submilligram amounts of HgCl, and Hg(N03), have been determined by catalyzed amperometric titration with KI (72). Mercury(I1) has been amperometrically titrated with thiosalicylamide (15),5-sulfo-8mercaptoquinoline (40),and, biamperometrically, in DMSO medium with EDTA (92). The use of thionine as a photoredox indicator in performing the titration with EDTA, or with 1,2-diamino-N,N,N’,N’-tetraacetic acid (DCTA), has been reported (262). The microdetermination of cerium(II1) by a method that involves coulometric titration with mercury (11) ion has been reported. Bipotentiometric indication at mercury electrodes is used. A small excess of EDTA is added to the sample. Then the excess EDTA and the EDTA displaced from the cerium(111)-EDTA complex by malic acid are titrated (186). A precision of 0.1-0.2% in the determination of submilligram amounts of americium(II1) is reported for a coulometric titration that involves reaction with Hg(I1)-EDTA complex and reduction of the liberated mercury(I1) ion at a mercury electrode (21). Methods Involving Lead. Sulfuric acid in mixtures with p-chlorobenzenesulfonic acid has been determined by amperometric titration in H20-Me2C0 medium with Pb(N03), at a DME potential of -0.6 V (309). A vibrating graphite electrode has been used in the amperometric titration of lead-copper mixtures with EDTA (133). The EDTA titration of lead has been performed with iodine as photoredox indicator (263) and, at high precision, with ac polarographic end-point detection (273). Optimum conditions have been found for the amperometric titration of lead with triethylenetetraminehexaacetic acid (TTHA), based on either the cathodic current of the metal ion or the anodic current of TTHA (233). The results of amperometric titration of lead with (NH4),C204at a stationary solid electrode in a pulsed chronopotentiostatic system are reported to be as accurate as those obtained at a DME or RPE (270). Methods Involving Hexacyanoferrate. K,Fe(CN), has been used as amperometric titrant for zinc and cadmium at a wax-impregnatedgraphite-platinum electrode system (267) and for zinc at a pulsed solid stationary electrode (270). Zinc has also been determined by coulometric titration with hexacyanoferrate(I1)to a biamperometric end point (47). Th ac oscillographic polarographic titration of hexacyanoferrate(I1) with zinc ion has been studied (304). Holmium has been amperometrically titrated in a 60% ethanolic medium with K4Fe(CN), by measuring the anodic current of the titrant at an RPE potential of +0.8 V vs. the mercuroiodide electrode (285). A similar technique has been used for the titration of neodymium (286). The hexacyanoferrate(I1) titration of zirconium, thorium, and uranium(V1) by voltammetry at constant high resistance has been reported (108). Methods Involving EDTA or Analogous Reagents. Optimum conditions have been found for the amperometric titration with TTHA of copper, zinc, cadmium, lead, and nickel, based on the reduction current of the metal ion. If the anodic current of TTHA is measured, the technique can be extended to include the determination of magnesium, calcium, and aluminum (233). Thionine has been used as photoredox indicator in the amperometric titration of mercury(I1) with EDTA or DCTA (262). The applications of Safranine T as amperometric indicator in EDTA titrimetry have been studied (237). An indirect method for the determination of cerium(II1) involves the bipotentiometrictitration of displaced EDTA with electrogenerated mercury(I1) ion (186). A coulometric method for the determination of americium(II1) involves the measurement of mercury(I1) ion displaced from its EDTA complex (21). The iodine-iodide system has been used as photoredox indicator in the amperometric titration of calcium, zinc, cadmium, cerium(III),lead, iron(III), cobalt, and nickel (236, 263). Less than 0.001 % of calcium in analytical-grade compounds such as KOH or NaC104 can be determined by amperometric titration with TTHA, with lead ion as amperometric indicator (232). Zinc has been used as indicator ion

AMPEROMETFIIC, BIPOTENTIOMETRIC, AND COULOMETRIC TITRATION

and nickel, have ben titrated with EDTA by applying 0.5 V between platinum electrodes (87).Monoethanolamine (S0.05 M) improved the solubilitv of EDTA in PrOH and did not

in the dopolarographic titration of calcium with (ethylene glycol)bis(B-aminoethyl ether)-NJVJV',N'-tetraacetic acid (EGTA). A 40-fold excem of magnesium does not interfere. The method was used to determine calcium in limestone (135). The normal and differential pulse polarcgaphic oxidation of mercury in the presence of various chelons has been examined (124). These studies have led to a method for the consecutive pulsed-mode amperometric titration of low concentrations of calcium and magnesium in water samples. Calcium is titrated first with EGTA and then EDTA is used to titrate magnesium (125). A medium containing EDTA copper salt is used in a patented procedure for the coulometric determination of the total hardness of water (271). A dropping indium amalgam electrode has been developed for the EDTA amperometric titration of zinc and other metal ions in the presence of high halide ion concentrations (58). A thin-film mercury electrode was used in the ac oscillopolarographic titration of zinc with EDTA (304). The purity of recrystallized disodium EDTA dihydrate has been determined by precise coulometric titration with zinc ion. Addition of excess EDTA and coulometric back-titration was used to assay high-purity aluminum (284). A method for the successive titration of cadmium and zinc with EGTA makes use of a carbon paste electrode that is maintained at +0.85 V w. a platinum cathode. Calcium-EDTA complex is added after the cadmium end point and the titration is continued to determine zinc (204,250). Amperometric titrimetry and polarography were used in a study of the system containing cadmium, cobalt, and TTHA (176). Amperometric titration with EDTA has been used to determine gallium in sulfur-containing semiconductors (137). Anodic EDTA oxidation at a PhO, electrode has been proposed as a modified amperometric indication procedure in the high-precision coulometric titration of gallium and indium in semiconductor compounds (98,991. Yttrium and lanthanum in alloys and glasses have been determined by amperometric titration with diethylenetriaminepentaaceticacid (DTPA) at a graphite electrode that is held at +1.3 V vs. the Ag/AgCl electrode (74). A weight buret was used in the high-percision ac polarographic titration of lead with EDTA (273). The amperometric titration of EDTA with Bi(N0 )3 at a stationary bismuth electrode has been reported (153. Square-wave amperometric titration, based on the direct anodic oxidation of mercury in the presence of excess EDTA, has been used to determine total available heavy metals in water samples (276). Zirconium in the microgram range has been determined by addition of iron(II1)-EDTA couple and coulometric titration of the released iron(II1) with iron(I1)-EDTA. Sulfosalicylic acid was used as spectrophotometric indicator (187). Gevorgyan and his co-workers have extensively studied complexometric titrimetry in nonaqueous media A procedure for the EDTA biamperometric titration of mercury(I1) in DMSO medium can be used for mercury determination in materials that are hard to dissolve in H20 (92). Thorium and certain lanthanides have been similarly titrated in HOAc with [nitrilotris(methylene)]triphosphonic acid (81,141). Biamperometric titration in HOAc medium with magnesiumEDTA has been used to determine cations such as of copper, bismuth, and nickel in binary and ternary mixtures with palladium (86). Propanol appears to be a versatile medium for complexometric titrimetry. With NH40Ac or KOAc as supporting electrolyte, submilligram amounts of copper have been titrated a t copper or platinum electrodes (90).Magnesium and calcium (82),as well as copper, cadmium, iron(III),

I

interf&e with the determiiation of copper and various other metal ions (84). Indium in salt mixtures imitating nonferrous metal sulfide ores, separated by masking and by extraction into CHCI,, has been determined by EDTA biamperometric titration in pmpanolic KOAc (91). A similar medium was used in the titration of indium, scandium, and praseodymium (88). Methods Involving Other Organic Compounds. The biamperometric titration of hismuth(II1) with chloranilic acid has been reported (53). RPE titration with Eriochrome Cyanine R has been used to determine vanadium(1V) (219) and chromium in steels and other materials (216,218,220). Vanadium(II1). vanadium(N), and titanium(II1) in the same solution have been titrated with gallocyanin at pH 1-2, pH 2.2-2.8, and pH 3.0-5.0, respectively (215, 217). Milligram amounts of copper in a pH 4.5 acetate buffer have been titrated with l-hydroxy-2-acetonaphthone at a potential of 4 . 4 V. Nickel can be titrated in a pH 8.5 ammonia buffer if a potential of -1.4 V is used (227). The titration of nickel has also been performed amperometrically with 1,2-cycloheptanedione dioxime (heptoxime) ( I 72) and oscillopolarop a p h i d y with dimethylglyoxime (303). The amperometric titration of indoxine with nickel has been used to determine this metal ion (134). A study of the oxidation of N cinnamoylpbenylhydroxylamiuea t a graphite electrode has led to the use of this reagent as amperometric titrant for gallium, scandium, yttrium (7.9, and lanthanum (205). In the titration of vanadium species with salicylhydroxamicacid, the graphite electrode was held a t a potential of +1.0 V (97). Various derivatives of pbthalanilic acid have been reported to be highly selective amperometric titrants for thorium (256). An amperometric titrimetric method for the determination of zinc involves the formation of a ziucthiocyanatelobeline mmplex (265).Titration with potassium iodotriiodothallate(1) a t a DME potential of 4 . 7 V has been used to determine opium and Strychnos alkaloids (228). The amperometric titration of HCHO with diethylenetriamine has been described (177). Milli am amounts of copper have been amperometrically titrateifst the RPE with ammonium dithiocarbamate (43). Amperometric titration with sodium diethyldithiocarbamate has been used in the analysis of mixtures of copper with lead or thallium(1) (133). Lead in gunmetal and in lead ore has been determined by DME titration with 1,5-his(benzylidene)thiocarbohydrazone (261). Complexes of sodium pentamethylenedithiocarhamate with copper, nickel, and iron(II1) have been prepared and the coulometric titration of this reagent has been examined (161). Thiocarbohydrazide has heen suggested as a titrant for a number of cations (56). Chromium(II1) in 1 N "0,-Me,CO medium has been titrated a t a graphite electrode with 3-(diethylamino)methyl2,6-dimercapto-1,4-thiopyrone.A 1 N HNO,-l H H,P04 medium was used for the titration of chromium(V1) (294). A rapid method for monitoring the composition of thermocouples involves the determination of platinum, palladium, and indium without preliminary separation. Amperometric titration of two aliquots of the solution with methyldimercaptothiopyrone is involved (9). Thallium in alloys and in dusts has been determined by titration of thallium(II1) with thiounithiol(55). Phenylmercaptoacetic acid has been used to titrate copper, silver, iron(III),and cobalt (257). Another titrant for copper and cobalt is o-hydroxy-4-benzamidothiosemicarbazide, which can also be used to determine manganese(I1) and nickel (282). RPE titration with thidicylamide has been used to determine silver, gold(III), mercury(II), and palladium(15). Tuugstophosphoric acid has been used to titrate methylene blue in HCI medium (278). An accelerated method for the analysis of silver-copper alloys that contain zinc, cadmium, or nickel involves amperometric or biamperometric titration with 8-mereaptoquinoline (259).A study of the reaction of this reagent with gold(II1) has led to a method for the determination of gold in the presence of various other ions. For goldiridium ratios from 21 to 1:5, differential ampemmetric titration can be used to determine gold in the presence of iridium(1V) (281). O p timum conditions have been reported for the titration of nickel in alloys and steels, as well as of various other metal ions (280). Ruthenium(IV1, reduced by 8-mercaptoquinoline to ruthe-

-

ANALYTICAL CHEMISTRY. VOL. 54. NO. 5, APRIL 1982 3 R


nium(III), then reacts with the reagent in 1:l ratio. An amperometric titration method for the determination of ruthenium in a zinc-based catalyst was developed (23). Indium in catalysts has been determined by RPE amperometrictitration with 8-mercaptoquinoline (24). Although apparently less generally useful than the parent compound, 5-sulfo-8mercaptoquinoline can act as titrant for silver, mercury, gallium, and palladium (40). The anodic voltammetric curves of sodium diethyldithiocarbamate in PrOH medium have been studied to evaluate the suitability of this reagent as an amperometric titrant (93). A similar study in N,N-dimethylformamide (DMF) has elucidated the conditions for the amperometric titration of transition metals (94). With 0.2 M NH40Ac as supporting electrolyte in DMF, gold(II1) and palladium have been titrated with sodium diethyldithiocarbamate (83). Titration in HOAc medium with thioacetamide has been used to determine palladium in binary and ternary mixtures (86). Palladium in HOAc and its mixtures with inert solvents such as CHC13 has been amperometrically titrated with rubeanic acid (89). By use of 0.2 M KOAc as supporting electrolyte in HOAc, palladium has been biamperometrically titrated with lead diethyldithiocarbamate (85). Miscellaneous Titrations. In a study of the solubility of thorium molybdate, the lowest value was found in NH40Ac solutions, suggesting possible use in amperometric titrimetry. Back-titration of molvbdate bv Th(N03, could be used in the determination of phosphate (42). ~Sul%illigramamounts of PdCl2 have been determined by catalyzed titration with KI ( 72).

OXIDATION-REDUCTION REACTIONS Methods Involving Iron Species. Titration with iron(I1) generated in H2S04-H3P04medium is the basis for a rapid coulometric method for the determination of gold (202). Thionine has been used as photoredox indicator with chloride ion as bridge ligand in the iron(I1) titration of thallium(II1) (171). Coulometric titration with iron(I1) has been used to determine vanadium in ferrovanadium (61). A method for the determination of the aldehyde functional group involves oxidation in 38% H SO4 with K2Cr207and coulometric titration of excess oxiiant with iron(I1) (296). A similar coulometric titration of excess K2Cr207has been used to determine uranium in active process solutions (49). The amperometric titration of uranium in low-grade ores has been achieved by the FeKH3P04reduction method (110). Uranium has been assayed by a method that involves dissolution along with high-purity iron in H202-H2S04,addition of Ce2(S04)3, and electrolytic reduction to produce U(IV), Fe(II), and Ce(111). Constant current is then used to quantitatively oxidize U(1V) to U(V1) and Fe(I1) to Fe(II1). After crossing the end point, this is determined potentiometrically by precise back-titration (179). Terbium has been determined in the presence of other lanthanides by conversion to Tb407 and reaction with MnS04 to yield manganese(II1). This is amperometrically titrated with Mohr's salt (139). Submilligram quantities of iron(I1) have been coulometrically titrated with manganese(II1). Coulometric back-titration of excess manganese(II1) with iron(I1) was used to determine oxalic acid (12). Nitrogen oxides from the pyrolysis of nitro oligomers have been determined by reaction with permanganate and coulometric back-titration with iron(I1) (185). A study of the coulometric titration of manganese(VI1) with iron(I1) has shown that amperometric end point detection is advantageous with respect to sensitivity, precision, and possibility of automation (253). A slightly acidic 1M NaBr and 0.05 M iron(II1)-EDTA medium has been used in the iron(I1) coulometric titration of platinum (127). Iron(I1) has been coulometricallv titrated with aold(II1) (41) and also by a simplified method"that permits ihe determination of iron in aluminum (312). Iron(II1) oxidizes cobalt(I1) in a medium containing picrolonic acid and forms iron(I1) (51). Coulometric potentiometric titration of the iron(I1) thus released with cerium(1V) has been used to determine cobalt in steels (52). m-Nitrobenzoic acid has been determined by titanium(II1)-iron(I1) dual-intermediate coulometric titration (48). A platinum-graphiteelectrode system (268)and a system of one untreated SnOz electrode and another that has received successive treatment with HN03, KI, and FeS04 (138) have 4R


been used to follow the titration of iron(I1) with cerium(1V). The zero-current bipotentiometric Sn02system has also been applied to the titration of iron(I1) with dichromate and with permanganate (138). Amperometric titration with KzCr207 has been used to determine iron(I1) in oxidized pellets of iron ore concentrates (67). In the copper@)coulometric titration of a mixture of vanadium(V) and iron(III), the potential drop for reduction to vanadium(1V)is followed by another that corresponds to the reduction of iron(II1) to iron(I1). This principle has been used to determine vanadium and iron in ferrovanadium and in other materials (147, 196). Optimum conditions have been found for 100% current efficiency in the generation of tin(I1) in SnCl,-KCl-HCl medium and have been applied to the coulometric titration of iron(II1) (235). The amperometric titrations of iron(II1) with ascorbic acid (62) and with 0phenylenediamine (71) have been described. The titration of a mixture of cerium(II1) and cobalt in alkaline medium by use of the K3Fe(CN),-K4Fe(CN), couple has been carried out at a platinum-graphite electrode system (267). Tungstate has been determined by reduction to tungsten(V) with bismuth amalgam and amperometric titration with K3Fe(CN),(162). This titrant has also been used to determine p-aminodiphenylamine and certain of its Nsubstituted derivatives (295). Hexacyanoferrate(II1)has been potentiometrically titrated in alkaline medium with tin(I1) that was generated externally (14) and biamperometrically titrated with N2H6HS04using methylene blue as photosensitizer (264). Ferrocene and its 4-alkyl derivatives have been coulometrically titrated with copper(I1) that was generated from CuC104in MeCN (159). Nonferrous Methods Involving Cerium, Titanium, Vanadium, Chromium, and Manganese. Antimony in ores and concentrateshas been determined by coulometric titration of antimony(II1) with cerium(1V) (46).Oxidation with Ce(c104)4, followed by addition and cerimetric amperometric back-titration of excess of Na2C204,forms part of a procedure for the analysis of n-PrOH-i-PrOH mixtures (64). The biamperometric titrations of hydroquinone with cerium(IV), vanadium(V), and chromium(V1) have been described and applied to the analysis of mixtures of vanadium(V) with cerium(1V) or chromium(V1) (231). A platinum-graphite electrode system has been used for the cerimetric titration of thallium(I),vanadium(IV),and cobalt in aqueous solutions and of ascorbic acid, hydroquinone, and various potassium alkyl xanthates in MeCN medium (268). Hydrogen in steels has been determined by a method that involves anodic dissolution in Na2S04solution containing 2,2,6,6-tetramethyl4-hydroxypiperidinyl-1-oxy1 (R-1 tanol) and amperometric back-titration of excess R-1 tanol with Ce(S04)2(144, 145). Cerium in thin CeFz-ZnS films has been determined by coulometric titration of cerium(1V) with chromium(I1) (3). Coulometric titration with titanium(II1) has been applied to drug control (301) and to the determination of aminophenoxazinium dyes such as Meldola Blue and Nile Blue A (277). Titanium in bauxite has been determined by procedures that involve amperometric titration of titanium(II1) with methylene blue or of titanium(1V) with BzPhNOH (290). A study of the voltammetry of vanadium(1V) in nonaqueous solutions has shown that vanadium(II1) electrogenerated in HOAc can be used for the coulometric titration of certain inorganic and organic substances (149). In the iodometric amperometric determination of vanadium(II1)at pH 3.8-4.0, a 100-fold excess of vanadium(1V) does not interfere. Differential determination of the two species is possible because a change of pH permits a determination of their sum (63). Uranium determination, based on automatic coulometric titration of uranium(1V) with vanadium(V),has been evaluated (167)and scaled down to handle low uranium levels (181). VOSOl in dilute H2S04has been used in the electrogeneration of vanadium(V) for drug control (301). Coulometric titration with copper(1) has been used to determine vanadium in silicovanadium (61) and also vanadium and iron in the same solution (147, 196). Vanadium(V) has been titrated coulometrically with tin(I1) (235) and amperometrically with ascorbic acid (62). In inert atmosphere, the titer of 0.1 N tin(I1)-glycerol is stable. Biamperometric and bipotentiometric indication can be used in the titration of the tin(I1)-glycerol complex with


K2Cr20,~H202 and certain other oxidants can also be determined (6;O). The coulometric titrations of chromium(V1)for the precise assay of K Cr207(169) and with tin(I1) that is generated in SnCl,-K&l-HCl solution (235) or, externally, from tin amalgam (14) have been described. The RPE titrations of chromium(V1) with ascorbic acid (62) and with 1-naphthylamine (300) have been examined. The RPE amperometric titrations of 1Hz02,thiosulfate, and thiocyanate with mangmese(II1) pyrophosphate (174) and of manganese(II1)with thiosalicylic acid (21;) have been reported. The electrochemical generation of the manganese(II1) diphosphate complex in H2S04solution lhas been studied and applied to the coulometric titration of submilligram quantities of hydroquinone (12). In a study of the generation of manganese(II1) from manganese(I1) at various electroldes, the maximum efficiency of 99.91% was obtained at a gold electrode in 7.5 M H2S04(27). Conditions have been described for the quantitative electrogeneration of manganese(II1) in a medium of propionic acid and for the manganese(II1) biamperometric coulometric titration of compounds such as hydroquinone and 2-aminophenol(212). Thiomalic acid has been coulometrically titrated with manganese(II1) in HOAc medium (209). Zero-potential RPE amperometric titration with KMn04 has been used to determine monovalent phosphorus in H3P02 and NaIIzP02(103-105) and H202in NaF-H2S04 medium (120). Titration with KMn04 in the presence of fluoride has also been used to determine microgram amounts of ascorbic acid (102). RI’E amperometric titration in H3P04-H2S04 medium, when permanganate is reduced to manganese(III), has been used to determine sulfur-containing organic compounds such as cysteine and 2-mercaptobenzothiaz~ole(22). A DME a t zero potential was used in the titration of 4,4’dinitrostilbene.2,2’-disulfonic acid in NaHC03 solution with KMn04 (13). Thiamine bromide has been determined by a method ithat involves amperometric titration with KMn04 at a graphite electrode (142). Addition of NaOH, BaC12, and KMn04,followed by bipotentiometric back-titration of excess permanganate with TlC104(223), has been used to determine 1,2,3,4-tlhiatriazole-5-thiolate (195). Methods Involving Chlorine and Bromine Species. Titration at a platinum-graphite electrode system with dichloramine-Tin the presence of KI has been used to determine ascorbic acid in tablets and the like (224). The determination of low concentrations of chlorine species in water by amperometric titration with phenylarsine oxide has been further studied (33, 214). In a study of the electrogeneration of chlorine at a glassy carbon electrode, a maximum current efficiency of 99.99% was obtained with the H2S04concentration ait 1 M (28). Chlorine was used as oxidizing titrant, with coplper(1) as the reducing titrant, in a coulometric method for the determination of platinum(I1) and platinuin(1V) in their mixtures (155). A method for determining organochlorine compounds in industrial environments involves combustiion and oxidation of the HC1 to chlorine, which is then determined by continuous coulometry (229). Submilligrarn amounts of ammonium ion have lbeen determined by thermal NaOH decomposition of (NH4)&r04pr metal ammine complex, absorption of the liberated NH3 in NaBr-borate solution and coulometric titration with hypobromite ion (1!?9). Automatic coulometric hypobromite titration hlas been used to determine ammonium ion and urea in the presence of various salts. After titration of ammonium ion at room temperature, the titration is continued at 80 “C to deterinine urea (244). Coulometric titration with hypobromite has been used to determine nitrogen in silazanes by prior hydrolysis to liberate NH3 (31),sulfur compounds such as thiosulfate, tetrathionate, and dithiocarbamates (188)and 2-mercaptobenzothiazole (146). In the selective KBrO, amperometrictitration of arsenic(II1) and antiinony(lII),two aliquots of sample are used. ‘Fitration in the presence of KI in 1 M H2S04 measures antimony only. The sum arsenic plus antimony is obtained either by using KBr in place of KI or by omitting salt addition and raising the H2SO4 concentration to 6-8 M (50). A dual-intermediatetitanium(II1)-bromine process has been used for the determination of iron (40). The related bromine-coloper(1) process has been used in the automatic coulometric titration of submilligram quantities of aniline (275). Arsenic(II1) in the sub-ppm range has been coulometrically

titrated with bromine in a thin-layer cell (57). Flow coulometry with a ring-disk electrode has been tested by the titration of arsenic(II1) with bromine (70). Daidzein has been determined by generation of excess bromine, addition of excess arsenic(III), and continued generation of bromine to a biamperometric end point (306). The determination of ppm amounts of SO2 by reaction with electrogenerated bromine in a thin-layer gas-porous cell has been reported (34). Bromometric titration by the triangle-programmed electrolysis technique has been applied to the analysis of flowing solutions of small volume (191). In an examination of the coulometric titration of platinum(II), biamperometric indication was preferred for 60 ~g or smaller amounts of platinum (45). The conditions fix the coulometric titration of arsenic(II1) and antimony(II1) with bromine generated in HOAc have been investigated (210). In the coulometrictitration of hydrazines in HOAc medium, the sample was added after bromine approximately equal to 90% of the expected titer had been generated (211). Paeonol(307) and catechin (308) in Chinese herb drugs have been biamperometrically titrated with electrogenerated bromine. A procedure for the analysis of mixtures of cysteine, qystine, and methionine involves determination of the sum of the three compounds by coulometric titration with bromine (254). The presence of pyridine generally gave better results in the bromometric coulometric titration of various anilines (288) and alkylanilines (289) in aqueous HOAc. ‘l‘hioglycollic acid and NazS204in their mixtures have been determined biamperometrically by the coulometric titration of one aliquot with bromine and a second with iodine (200). Bromine that was generated and detected on a ring-disk electrode has been used to titrate dithiaalkanediols in MeOH-H20-KBr medium (255). N-Bromosuccinimidehas been used as amperometric (313) and biamperometric (314) titrant for substances such as arsenic(II1)and Na2S:203 and as amperometrictitrant for KSCN (4, 314). Methods Involving Iodine Species. Iodine has been used as amperometric titrant for HCN in a pH 8.2 borate buffer (59). Coulometric titration of SO2with iodine has been used to determine total sulfur in waters (35), in coal and other materials (297), in hydrocarbons (189) and for the rapid determination of sulfur in organic and some inorganic compounds by use of an automatic microanalyzer (208). A method for the simultaneous determination of thiourea and thiocyanate is based on the differing induction effects on the rate of the iodine-NaN3 reaction (128). Arsine has been determined in the presence of hydrogen by reaction with HgC1, in MeOH, treatment of the As(HgC1,) precipitate with iodine, and amperometric back-titration with Na2Sz03(251). A similar back-titration has been used in the determination of free chlorine in ClCN (2,52). Cobalt(II1) in oxide catalysts has been determined by a process based on treatment with KI and biamperometrictitration of the liberated iodine with Na2S?O3 (163). Thiocarbamyl sulfenamides and other vulcanization accelerators have been determined by iodine liberation and amperometric titration with Na2S203(16, 17). Tellurium in organic substances has been determined by combustion to form Te02,dissolution in “OB, addition of KI and then of 0.005 M Na2S20 and biamperometric coulometric titration of excess Na2S28, (8). Oxides and battery material have been analyzed for nickel in different oxidation states by mixing with KI, dissolving in dilute H2S04, and titrating the liberated iodine with 8mercaptoquinoline at pH 1.5-2.0 to measure nickel(II1). The pH is then made approximately 10 and titration is continued to an end point that gives total nickel (258). Hydroxylamine salts have been amperometrically titrated at the RPE potential of +0.6 V with KI03 (238). Mixtures of NzH4 and NHzOH have been analyzed by RPE titration in NaC1-HC1 solution with KIO,. Addition of KBr after the NzH4 end point enables the titration to be continued to a second end point (2:?9). An analogous procedure has been used to analyze mixtures of HCHO and its oxime. The oxime is titrated first and then excess of NHzOH (which does not interfere) is added and the newly produced oxime is titrated (240). The RPE KI03 titrations of hydroquinone in 4 M HC1 at 10 OC and of p(methy1amino)phenol in NaC1-2 M HCl at 25 O C have been described (243). In KBr-HC1 medium, only hydroquinone in its mixture with p(methy1amino)phenol is titrated with KIO,. Both compounds in a second aliquot can ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982

5R


be titrated in the presence of HC1 and NaC1, thus permitting the differential determination of the two organic compounds (242). Sulfanilamide and certain of its derivatives have been determined in KBr-HC1 medium by titration with KI03 (118). For determination of small amounts of iodide in the presence of high concentrations of bromide and chloride ion, bromine is used to oxidize iodide to iodate, HOAc, NazS203,and KI are added and the excess of Na2Sz03is biamperometrically titrated with KIO,. The method was used to determine iodide in brines and seawater evaporates (291). The amperometric determination of trace amounts of osmium by its catalysis of the arsenic(II1)-periodate reaction has been studied (6). Masking of periodates with ammonium molybdate has been used to determine iodates in the presence of periodates by amperometric titration with KI at approximately 10 OC (241). Biamperometric titration with Karl Fischer reagent has been used to determine H 2 0 in Na2HP04 (7) and in the products obtained by fusing muscovites with Si0 (310). Karl Fischer reagents in which pyridine is replaced by an amine such as diethanolamine so that the SOz:aminemolar ratio is 1:l react rapidly, with improved precision and accuracy (245, 247). Such a reagent was used to determine HzO in cysteine hydrochloride monohydrate by a double biamperometric titration (246). The determination of small amounts of HzO by titration with electrogenerated Karl Fischer reagent has received considerable attention. Several reports, some of which are patents, describe improved coulometric electrolyte solutions (38, 182, 183,221,222). Others deal with the use of a single-compartment titration cell (279), automatic coulometry (29,292),and end-point drift correction in automatic titrations (65). Applications include the determination of H20 in solvents such as MeOH and DMF (213),solutions for nylon fiber production (38), solids (1301, polyamides (175), and technical-grade polyacrylamide (180). In a study of the conditions for drying bauxites for chemical analysis, H20 was determined coulometrically (311). Oxygen-containingimpurities in LiH have been determined by treatment with EtOH, methylsulfuric acid, and HI to convert oxygen into HzO and coulometric titration of this with Karl Fischer reagent (154). In the coulometric titration method for determining hydrogen in fluoride-containing slags, the H,O resulting from combustion of the sample in oxygen _is measured ( 1 1 4 . Other Reactions. Coulometric titration with copper(1) has been used to determine water-soluble oxygen and silver in various materials (150). The photosensitized amperometric titration of copper(I1) with NzH4has been described (264). Copper(I1) generated in MeCN has been used to investigate the oxidation of hydroquinone and various thiols (159). Conditions for the electrogeneration of silver(I1) and the applications to drug control have been described (301). Gold(II1) has been used as coulometric titrant for compounds such as ascorbic acid and phenazine sulfate (41). The biamperometric titration of gold(II1) with hydroquinone has been used to determine gold in quartz, pyrites, and ilded jewelry (230). In a study of process acceleration by bri ge ligands, silver has been amperometrically titrated with tin(I1) (171). SnClz in glycerol has been used as titrant for aromatic nitroso compounds in HC1-saturated EtOH (234). Stannite electrochemically generated from tin amalgam has been used to biamperometrically titrate mercury(II), arsenic(V), and bismuth(\') in 10 M NaOH at 100 OC (14). Coulometric titration with tin(I1) generated from SnC14in acid solution has been used to determine molybdenum(V1) in steel analyses (235) and, with photometric end point detection, arsenic in semiconductor alloys by prior formation of molybdoarsenic acid

d

(201).

Lead(1V) generated in HOAc medium has been used to titrate ethyl thioglycolate and thiosalicylic acid (209). The amperometric titration of thallium(II1) with thiosalicylic acid has been described (25). Sodium p-aminosalicylate has been amperometrically titrated with NaNOz in the presence of KI (1). Intermittent generation of oxygen, controlled by change in pressure, has been used to determine the BOD of water held at constant temperature in a closed system (76). LITERATURE CITED

(1) Abramov, M. K.; Medvedskaya, N. Ya. farmatsiya (Moscow) 1980, 2 9 , 46-47; C A , 94, 36435a (1981). (2) Agasyan, P. K., ref 225, pp 3-12.

6R


(3) Akhmadeev, M. Kh.; Pashinkina, G. 2 . ; Zotova, V. N. Sb Nauchn. Tr., Vses Nauchno-Issled. Inst. Lyuminoforov Osobo Chist. Veshchestv 1977, 15, 51-55; CA, 91, 221873t (1979). (4) Akhrnedov, G.; Zhdanov, A. K.; Sldorov, Kh. Doki. Akad. Nauk Tadzh. SSR 1980, 23. 184-186; C A , 93, 125122t (1980). (5) Albery, J.; Wood, P. British Patent Appl. 2 045 943 (Ci. G01N27/44), 05 Nov 1980. (6) Alekseeva, I. I . ; Khvorostukhina, N. A.; Rysev, A. P.; Khornutova, E. G. Z h . Anal. Khim. 1980, 35, 505-510; C A , 93, 363442 (1980). (7) Aleshkina, T. S.; Yuzhallna, L. V. Khim. Prom-sti., Ser: Metody Anal. Kontrolya Kach. Prod. Khim. Prom-sti. 1980, (2), 23-25; C A I 93, 36396t (1980). (8) Anisimova, G. F.; Klimova, V. A. Z h . Anal. Khim. 1980, 35, 607-609; C A , 93, 36461k (1980). (9) Arlshkevich, A. M.; Kutsenko, L. M.; Pitsyk. 0. I.; Dzhigota, A. D.; Fedash, T. G. Metall. Koksokhim. 1979, 6 1 , 100-103; C A , 92, 1 4 7 9 3 ~ (1980). (10) Barbelet, M.; CauJolle, J. P.; Scramoncln, C.; Thlbault, E. Fr. Demande 2438391 (Cl. GOlN27/42), 11 Apr 1980; C A , 93, 152998q (1980). (11) Barek, J.; Berka, A.; Jakubec, K. Chem. Listy 1979, 73, 1027-1035; CA, 92, 33189w (1980). (12) Barek, J.; Berka, A.; Jakubec, K. Microchem. J . 1979, 24, 454-462. (13) Ibid., pp 495-502. (14) Basov, V. N.; Agasyan, P. K.; Vlkharev, B. G. Vestn. Mosk. Univ., Ser. 2 : K h h . 197g, 20, 456-458; C A , 92, 51289h (1980). (15) Basu, A.; Mazumdar, M.; Shome, S. C. J. Indian Chem. SOC. 1980, 5 7 , 1156-1158. (16) Basu, D. K.; Adhlkari, 6.; Pal, D.; Chaudhurl, A. K. Taianta 1980, 27, 671-672. (17) Ibid., 1981, 28, 262-264. (18) Benevol'skli, A. S.; Ivanov, Yu. A. Zovod. Lab. 1980, 46, 790-793; C A I 93, 197008h (1980). (19) Berclk, J.; Cakrt, M.; Hladky, Z., ref 225, pp 155-164. (20) Bercik, J.; Cakrt, M.; Hladky, 2.; Barnoky, L.; Mathiasova, A. INSYMET '76, (Int. Symp. Metro/.), 3rd 1978, 55-60; C A , 93, 36331t (1980). (21) Bergey, C.; Fouchard, L. Talanta 1979, 26, 445-450. (22) Bessarabova, I.M.; Songlna, 0. A. I z v . Akad. Nauk Kaz. SSR,Ser. Khim. 1980, (l), 73-75; Anal. Abstr., 39, 68123 (1980). (23) Bessarabova, I. M.; Songina, 0. A,; Plotnikova, E. V. Z h . Anal. Khim. 1980, 35, 1644-1646; C A , 93, 214893n (1980). (24) Bessarabova, I . M.; Songlna, 0. A.; Urasheva, Zh. M. Zavod. Lab. 1981, 47, 23-24; C A , 94, 1 8 5 0 0 6 ~(1981). (25) Bessarabova, I. M.; Songlna, 0. A,; Zakharova, L. V. Khim. Khim. Tekhnol. (Alma-Ata, 1962-) 1977, 22, 41-48; CA, 92, 121204~(1980). (26) Blshop, E., ref 225, pp 13-34. (27) Blshop, E.; Cofre, P. Analyst (London) 1981, 106, 429-432. (28) Ibld., pp 433-438. (29) Bizot, J.; Bolesse, M.; Beze, J. F. Actual. Chim. 1980, (9), 31-33; C A , 94, 95153e (1981). (30) Bondarevskaya, E. A.; Krlilova, T. V.; Buyanova, E. V.; Kropotova, E. D. Flz.-khim. Metody Issled. Elementoorgan. Soedin ., M , 1980, 107-1 17; C A , 93, 197196t (1980). (31) Bondarevskaya, E. A.; Krlllova, T. V.; Buyanova, E. V.; Sakovets, 0. P. Zh. Anal. Khim. 1980, 35, 755-757; C A , 93, 47595h (1980). (32) Bondarevskaya, E. A.; Potsepklna, R. N.; Kudryashova, L. M. Zh. Anal. Khim. 1979, 34, 2364-2368; C A , 92, 1907961 (1980). (33) Brooks, A. S.;Seegert, G. L. J. Water Poliut. ControlFed. 1979, 5 1 , 2636-2640. .. ... -.. .. (34) Bruckensteln, S.;Tucker, K. A.; Glfford, P. R. Anal. Chem. 1980, 52, 2396-2400. (35) Brull, E. E.; Golden, G. S.Anal. Chim. Acta 1979, 110, 167-170. (36) Burangey, S.V.; Dhaneshwar, R. G. Indian Chem. Manuf. 1980, 18, 10-12. (37) Bursa, S.;Wleczorek, A.; Stanisz-Lewlcka, M.; Kicinska, M.; Zarudskl, J.; Bursa, J. Pomiaty, Autom., Kontrola 1981, 27, 22-23; C A , 95, 107807g (3981). (38) Bykova, L. N.; Galltsyn, A. D.; Bogoslovskll, V. V.; Novikov, A. V. Khim. Volokna 1980, (3), 54-55; C A , 93, 96633c (1980). (39) Cakrt, M.; Berclk, J.; Hladky, Z.,ref 225, pp 175-182. (40) Cera, L.; Bankovskil, Yu. A. Latv. PSR Zinat. Vestis, Kim. Ser. 1981, (3), 31 1-315; C A I 95, 90519q (1981). (41) Chateau-Gosselin, M.; Christian, G. D.; Patrlarche, G. J. J. Pharm. Selg. 1980, 35, 19-23; C A , 92, 203655q (1980). (42) Chatterjee, S.S. Fert. Techno/. 1979, 76, 133-134. (43) Chatterjee, R.; Guha, D.; Chatterlee, S. S. Proc. Indian Acad. Sci. (Ser.): Chem. Sci. 1981, 90, 11-18. (44) Chavdarova, R. I z v . Khlm. 1979, 12, 87-96; C A , 92, 51237q (1980). (45) Chavdarova. R. Dokl. Solg. Akad. Nauk 1979, 3.7, 1683-1686: CA, 92, 190734n (1980). (46) Chazova, L. A. Izv. Sev.-Kavk. Nauchn. Tsentra Vyssh. Shk., Estestv. Nauki 1980, (l), 58-61; C A , 93, 178875~(1980). (47) Chazova, L. A,; Lopatin, 8. A. I z v . Sev.-Kvak. Nauchn. Tsentra Vyssh. Shk., Tekh. Nauki 1979, 7 , 99-102; C A , 91, 221918m (1979). (48) Chen, Tung-Yueh; Kang, Fei-PI; Chang, Plen-Hsueh. f e n Hsi Hua Hsueh 1977, 5 , 369-371; C A , 94, 57432n (1981). (49) Chitnls, R. T.; Talnikar, S. G.; Paranjape, A. H. J. Radioanal. Chem. 1980, 59, 15-21. (50) Chokina, N. Yu.; Zakharov, V. A,; Songina, 0. A. Z h . Anal. Khim. 1979, 34, 1993-1998; C A , 92, 87428s (1980). (51) Clement, G.; Paris, M. R. Anal. Chlm. Acta 1979, 110, 219-225. (52) Ibld., pp 227-232. (53) Cortinez, V.; Baudlno, 0.; Marone, C. Aflnldad 1979, 3 6 , 495-498; C A I 93, 60421t (1980). (54) Darnakos, T.; Havas, J., ref 225, pp 199-210. (55) Danilenko, E. F. Vopr. Khim. Khim. Tekhnol. 1979, 5 4 , 96-100; C A , 92, 68957x (1980).

.

AMPEROMETRIC, BIPOTENTIOMETRIC, AND COULOMETRIC TITRATION (56) Deshmukh, 0. S.; Kulkarnl, A. 0. Indlsrn J. Chem., Sect. A 1981, 20A, 314. (57) De Soto Perura, M. A.; Curran, D. J. Anal. Chim. Acta '1980, 779, 251-261. (58) Dieker, J. W.; Van der Linden, W. E.; Den Hoef, 0. Talanta 1979, 26, 973-975. (59) DI, R. I.; Akhmedzhanova, S. A.; Gladyshev, V. P. Zavod. Lab. 1979. 45. 88'7-889: C A I 92, 5 1358e (1980). (60) Dolezal, J.; Housal, M.; Zlma, J. Mlcrochem. J . 1981, 26, 280-287. (61) Dresoher, A.; Kucharkowski, R. Fresenius' 2'. Anal. Chem. 1979, 298, 144- 149. (62) Dzarkheshevn, 2. T.; Songina, 0. A,; Bekturova, 0. 6.; Zakharov, V. A. I z v . Akad. Nauk Kaz. SSR, Ser. Khim. 1979, (6),40-44; CA, 92, 103738~(1980). (63) Dzarkesheva, 2. T.; Zakharov, V. A.; Songlna, 0. A.; Bekturova, G. B. Zh. Anal. Khim. 1981. 36, 289-290; C A , 94, 2 1 8 9 5 5 ~(1981). (64) Dzieslec, J. Chem. Anal. (Warsaw) 1979, 24. 917-920; CA, 92, 157302!x (1980). (65) Eppstein, L. 6.; Kroeger, J. K.; Llndblom, K. A. British Patent Appl. 2021 785 (CI. (301N27/44) 05 Dec 1979. (66)Ewlng, G. W. Am. Lab. (Falrfeld, Conn.) 1981, 73 (8), 16, 18. 20, 22. (87) Fedorov, A. A; Chernyakhovskaya, A. I.; Lamtsova, V. A. Zavod. Lab. 1981, 4 7 , 13-15; CA, 95, 90507) (1981). (88) Frahne. D.; Gal, J. V.; Deuschle, A. LaborPraxis 1980, 4(8), 28-37; CA, 94. 70133311 (1981). (69) Frltschl,' U.; Frlischl, G.; Kussmaul, H. 2. Wasser Abwasoer Forsch. 1978, 7 7 , 165-170; Anal. Abstr., 37. 61-137 i(1979). (70) Fujlnaga, T.; Qkazakl, 8.; Hlral. H. Buli. Insf. Chem. Res., Kyoto Univ. 1979, -57, 376-380. (71) Furnlca, M. Bui. Inst. Politeh. Iasi, Sect. 2 : Chim. Ing. Chim. 1979, 25, 35-36; CA, 92, 208369j (1980). (72) Gaal, F. F.; hbramovlc, 8. F. Talanta 1980, 27, 733-740. (73) Gaal, F. F.; Budmlmlr, M. V.; Horvat, R. 1.; Canlc, V. D. G/as. Hem Drus. 19eograd 1980, 45, 49-56; CA, 93, 249372~(1980). (74) Gallal, 2. A.; Shelna, N. M.; Ollferenko, (3. L.; Baranchlkova. N. A.; Stasiunas, E. Irl. Zavod. Lab. 1980, 46, 392-394; C A , 93, 60473m (1980). (75) Gallal, 2. A.; Shelna, N. M.; Svedlene, N. TezlsyDok/.-V.es. Soveshch. Polyarogr., 7th 1978, 82; C A , 93, 15668t (1980). (76) Ganlner, H. Fresenius* 2.Anal. Chem. 1879, 299, 42-45. (77) Garat, T.; SZIJCS, M.; Devay, J. Hung. Sci. Instrum. 1979, 46, 17-20; CA , 9% 11 9 3 9 9 ~(1980). (78) Garail, T.; Szucs, M.; Devay, J. Magy. Kem. Foly. 1980, 86, 289-293; C A , 93, 152631q (1980). (79) Garcil, T.; Szucs, M.; Devay, J., ref 225, pp 211-219. (80)Gawrych, 2.; Szyszko, E. Acta Poi. Pharm 1979, 36, 569-573; Anal. Abstr., 39, 2E29. (81) Geviorgyan, A. M.; Khadeev, V. A.; Kostylev, V. S. Doki. Akad. Nauk Uzb. 8SR 1979, (I), 45-46; CA, 92, 103738a (1980). (82) Ibid. 1979, IS), 48-49; C A , 93, 88040s (1980). (83) Ibid. 1979, (e), 23-24; C A , 93, 66041t (1980). (84) Gevorgyan, A. M.; Khadeev, V. A.; Kostylev, V. S.; Khadeeva, L. A. Dokl. Akad. Nauk Uzb. SSR 1980, (e),43-45; C A , 94, 219008h (1981). (85) Gevorgyan, A. M.; Khadeev, V. A.; Kostylev. V. S.; Nadoi'skil, M. Ya. Doki. Akad. Nauk Uzb. SSR 1978. (5), 43-44; C A I 92, 332979 (1980). (86) Gevorgyan, A. M.; Khadeev, V. A.; Talipov, Sh. T.; Kostylev, V. S. Uzb. Khim. Zh. 1979, (4), 13-17; C A , 92, 5 1 3 6 3 ~(1980). (87) Ibid. 1980, (2), 76-77; CA 93, 87991r (1980). (88) Ibid. 1980, (5), 58-60; CAI 94. 57572h (1981). (89) Gevwrgyan, A. M.; Tallpov, Sh. T.; Khadeev, V. A.; Kostylev, V. S. Zh. Anal. Khim. 1979, 34. 1791-1794; CA, 92, 6 8 9 4 6 ~(1980). (90) Gevwrgyan, A. M.;Tallpov, Sh. T.; Khadeev, V. A.; Kostylev, V. S. Zh. Vses. Khlm. 0 - v a . 1979, 2 4 , 658-660; C A , 93, 18450b (1960). (91) Gevorgyan, A. M.; Tallpov, Sh. T.; Khadeev, V. A.; Kostylev, V. S.; Khadeava, L. A. Z h . Anal. Khim. 1980, 35. 1921-1924; C A , 93, 2302162 (1980). (92) Gevorgyan, A. M.; lallpov, Sh. T.; Khadeeva, L. A.; Kostylev, V. S.; Mukhamedzhanova, D. V. Zh. Anal. Khim. l 9 8 l , 36, 893-895; C A , 95, 90468x (1981). (93) Gevorgyan, A. M.; Talipov, Sh. T.; Khadeeva, L. A.; Kostylev, V. S. Uzb. Khim. Zh. 197'9, (8). 84-65; CA, 93, 18436b (1960). (94) Gevorgyan, A. M.; Tallpov, Sh. T.; Khadeev, V. A,; Kostylev, V. S.; Mukhamedzhanova, D. Zh. Anal. Khlm. 1980, 3 5 , 2026-2028; C A , 93, 230136~(1980). (95) Glab, S.; Hulanlcki, A., ref 225, pp 221-230. (96) Glab, S.; Hulanlckl, A. Talanta 1981, 28, 183-1613. Tserkovnitskaya, I.A. Ory. Reagenty (97) Grigor'eva, M. F.; Slesar, N. I.; Anal. Khim. 1980, 3, 17-21; CA, 94, 1 1 3 8 7 1 ~(1981). (98) Gruundler, P., ref 225, pp 231-237. (99) Gruendler, P'. Anal. Lett. 1981, 74 ( A 3 ) , 163-173. (100) Gruendler, P.; Boettger, T. Chem. Anal. (Warsaw) 1980, 25, 10891096; C A , 95, 107818m (1981). (101) HaJos, P.; Inczedy, J. J . Chromatogr. 1980, 2U7, 193-197. (102) Hammam, A. M.; Idrlss. K. A. J. Indian Chem. SOC. 1981, 58, 140- 142. (103) Hammam, A. M.: Idrlss. K. A.: El-Koml. Z. R. J. Indian Chem. SOC. 1980, 57, 83-65. (104) Hemmam, A. M.; Iilrlss, K. A.; El-Komi, 2. R. J. Chern. Technoi. Blotechnol. 1980. 30. 509-512. (105) Hammam, A. M.; Idrlss,-KrA.; Seleim. N. M.; El-Komi, .Z.R. Mikrochlm. Acta 1980, 7 , 221-228. (106) Hrnda, M.; Maeda, A.; Yahata, T.; Hoshlno, A. Nlppon Genshlryoku Gakkaishi 1979, 27, 738-743; C A , 92, 33347w (1980). (107) Hanko, A.; Jozan, M.;Szasz, G., ref 225, pp 239-249. (108) Hart0 Casbno, A.; Sanchez Batanero, P. Mnidad 1980, 37, 421-424 C A , 94, 2021 12q (1981). I

I

-

(109) Hasty, R. A. Lect. Notes-Sch. Pure Appi. Electrochem. 1979, no. 8 . (1 10) Hitchen, A.; Zechanowltsch, G. Talsrnta 1980, 2 7 , 383-389. ( I 11) Ho, Yung-Nlen; KO, Shen-Hul; Chao, Chen-I; Tuan, Yung-Shen Kang T'leh 1980, 75, (5), 51-52; CA, 94, 184881h (1981) (112) Hong, Jong Guk; Ro, Yong Suk Punsok Hwahak 1981, (I), 3-6; CA, 95, 34741u (1981). (113) Houde, M.; Champy, J. Microchern. J . 1979, 24, 300-309. (114) Hulanlckl, A,, ref 225, pp 85-106. (115) Ikeda, S.; Motonaka, J.; Nakabayashl, Y. Bunseki Kagaku 1979, 28, 527-531; CA, 91, 203890s (1979). (116) Ikeda, S.; Satake, H.; Koyama. T. Bunseki Kagaku 1979, 28, T51T53; CA, 92, 689891 (1980). (117) Ikeda, S.; Satake, H.; Shlnohara, H.; Takelchi, K. Bunseki Kagaku 1981, 30, T35-T39; CA, 94, 184959q (1981). (118) Ikeda, S.; Satako, H.; Shlmomura, S. Nlppon Kagaku KaishlI981, (4), 521-525; C A , 95, 49495r (1981). (119) Inokuma, Y.; Ochlal, T.; Kusumoto, Y. Trans Iron Steel I n s t . Jpn. 1980, 20 (3). 878. (120) Issa, 1. M.: Hamrnam, A. M.; Ghandour, M. A. Egypt. J. Chem. 1977 (Pub. 1979)' 20, 339-345. (121) Ivanov, T N.; Atanov, A. N. Zh. Anal. Khim. 1980, 35, 588-592; CAI 93, 384803 (1980). (122) Ivanov, T. N.; Atlanov, A. N. U.S.S.R. Patent 734556 (Cl. GOIN31/16), 15 May 1980; CAI $3, 230341m (1960). (123) Ivanov, Yu. M.; Komolova, N. G.; Shartukov, 0. F. "Principles of Potentiometric and Coulometric Analysis: Study Aid"; Leningr. Tekhnol. Inst.: Leningrad, 1978; C A , 91, 2 0 3 8 2 1 ~(1979). (124) Jackson, L . L.; Osteryoung, J.; Osteryoung, R. A. Anal. Chem. 1980, 52, 66-70. (125) Jackson, L. L.; Osteryoung, J.; O'Dea, J.; Osteryoung, R. A. Anal. Chem. 1980, 52, 71-75. (126) Jaeger, W.; Hagenmeler, H. 2. Wasser Abwasser Forsch. 1980, 73, 86-69; CA, 93, 101248n (1980). (127) Jedral, W., Hulanlckl, A,, ref 225, pp 251-258. (128) Jedrzejewskl, W.; Ciesielski, W. Chem. Anal. (Warsaw) 1979, 2 4 , 861-866; CA, 92, 1572182 (1980). (129) Jilek, J. Swiss Patent 818272 (Cl. GOlN31/16), 15 Jul 1980; CA, 93, 230254k (1980). (130) Jones, F. E. Anal. Chem. 1981, 53, 1955-1957. (131) Jovanovlc, M. S.; Vucurovlc, B. D., ref 225, pp 259-267. (132) Kalavska, D.; Kozakova, E.; Groidlova, A,; Revus, M.; Irova, M. Ropa Uhiie 1980, 22, 388-394; CA, 93, 197228e (1980). (133) Kamenko, V. A.; Kamenko, R. S.; Khomlch, E. V. Khim. Khim. Tekhno/. (Mlflsk) 1980, 75,3-8; CA, 93, 2 1 4 6 8 3 ~(1980). (134) Kannan, R.; Nareyan, R. Trans. SAEST 1980, 75, 77-80. (135) Kao, Hung; Weng. Yun-Rong; Yin, Chang-qulng Chem. J. Chinese Unlv - .. . I.9- 8- 1., 111 , 37-42 -. (136) Kashkan, 0. V.; Zakharova, 2. A.; Kuleshov, V. I.Zh. Anal. Khlm. 1979, 34, 1323-1326; CA, 91, 2 0 3 7 1 5 ~(1979). (137) Kas'yanenko. G. R.; Lukianets, I. G. Zavod. Lab. 1979, 45, 600-801; CA. 93. 18444c 11980). (136) Kekedy, L.; Korrnos, F. Talanta 1979, 26, 584-588. (139) Kemeleva, N. G.; Zainkovskaya, L. M.; Songlna, 0. A. Zavod. Lab. 1979, 45, 700-701; CA. 91, 186024t (1979). (140) Keurlngsinstltuut voor Waterleldingartikelen (KIWA) N.V. Neth. Appl. 78 01, 376 (CI GOlN27/44) 09 Aug 1979. (141) Khadeev, V. A.; Gevorgyan, A. M.; Tallpov, Sh. T.; Kostylev, V. S. Zh. Anal. Khim. 1979, 34, 1114-1 120; CAI 91, 167620h (1979). (142) Khrenova, D. Kh.; Tsukanov, Yu. V.; Brutko, L. I.; Gallai, 2. A,; Sheina, N. M. Khim.-farmi'h. 1980, 74, (IO), 105-107; CA, 94, 5 3 0 4 8 ~(1981). (143) Kim, J. W.; Ro, J. H.; Kim, T. J. PunsokHwahak 1980, (I), 13-17; CA, 93, 160534a (1980;1. (144) Klyachko, Yu. A.; Gvazava, V. A. Zh. Vses. Khim. 0 - v a . 1980, 25, 710-711; CA, 94, 40876n (1981). (145) Klyachko, Yu. 14.; Gvazava, V. A.; Larlna, 0. D.; Pakhomova, E. G. Zavod. Lab. 1981, L77(7), 15-16; CA, 94, 113891a (1981). (146) Komarek, J. Zb. Stud. Ved. Odb. Pr. (Slov. Vys. Sk. Tech. Bratislave, Chemlckotechnol. Fak.) 1979, 111-112; CA, 92, 103804~(1980). (147) Komissarova, T. E.; Pakhomova, T. M.; U.S.S.R. Patent 709991 (Cl. G01N27/42), 15 Jan 1980; C A , 92, 157249k (1980). (148) Kopyckl, W.; Fruisse, D.; Blnkowskl, J. Chem. Anal. (Warsaw) 1980, 25, 829-839; CA, 95, 54376g (1981). (149) Kostromln, A. I.; Abdullln, I. F.; Agasyan, P. K. Zh. Anal. Khim. 1981. 36, 681-686, C A , 95, 5 4 1 1 4 ~(1981). (150) Kostromln, A. I; Abdullln, A. F.; Dmetriev, A. L.; Badretdinova, G. Z. Zh. Anal. Khim. 1981, 36, 884-888; CA, 95, 90467w (1981). (151) Kostromln. A. I.; Akhmetov, A. A.; Abdullln, I.F. Zh. Anal. Khlm. 1979, 34, 1243-1246; CA, 91, 185887q (1979). (152) Kostromln, A. I; Badakshanov, R. M.; Evgen'ev, M. I.; Makarova, L. L.; Badretdlnova, G. 2.; Mosolov, V. V. Eiektrodyne Protsessy Adsorbtslya lg78, 2, 38-110; (>A, 91, 221714s (1979). (153) Kotova, V. N.; Larikova, G. G.; Shimlcheva, N. A,; Tagirova, N. A,; Antipova, 0. A. Zh. Anal. Khim. 1981, 36, 880-883; CA. 95, 9 0 4 6 6 ~ (1981). (154) Kotova, V. N.; Ilarikova, G. G.; Zamyatnlna, N. I.; Dykina, L. P. Zh. Anal. Khim. 1979, 34, 1651-1653; CA, 92, 14791v (1980). (155) Kovalenko, N, L.; Vershkov. V. A.; Kozhukhovskaya, G. A,; Mal'chlkov, G. D. Zh. Anal. Khim. 1980, 35, 1161-1164; CA, 93, 180591s (1980). (156) Koyano, K. Niosekl Rebyu 1980, 22, 180-187; CA, 93, 242268f (1980). (157) Kozulina, M. M.;Lepln, Ya. K.; Songlna, 0. A. Khim. Khim. Tekhnol. (Alma-Ata, 7962-) 1977, 22,38-41; CA, 92, 121203b (1980). (158) Kozulina, M. M.; Lepln, Ya. K.; Songina, 0. A. Zavod. Lab. 1981, 4 7 , 8-9; CA, 94, 185002j (1981). (159) Kratochvll, 6.; AI-Daher, I.M. Taianta 1980, 27, 989-992. I .


7R

AMPEROMETRIC, BIPOTENTIOMETRIC, AND COULOMETRIC TITRATION (160) Krlchmar, S. I. Zh. Anal. Khim. 1980, 35, 969-975; C A , 93, 60328t (1980). (161) Kudela, S.;Garaj, J.; Hofbauerova, H.; Kettmann, V. Collect. Czech. Chem. Commun. 1980, 45, 800-809. (162) Kulev, I.; Vldeva, M. God. Vlssh. Khim.-Tekhnoi. Inst., Burgas, Bulg. 1978, 73,pt. 1. 103-110; C A , 94, 24368t (1981). (163) Kuznetsova, A. S.;Malakhov. V. V. Khim. Prom.-st., Ser.: Metody Anal. Kontrolya Kach. Prod. Khim. Prom-stl. 1979, (12), 8-10; C A , 92, 226006t (1980). (164) Kyoto Electronics Mfg. Co. Ltd. Jpn. Kokai Tokkyo Koho 81 37,548 (Cl. G01N27/42) 11 Apr 1981. (165) Larlna, N. I.; Gel’man. N. E. Zh. Anal. Khim. 1981, 36, 795-797; C A I 95, 72779v (1981). (166) Lebedeva, M. I.; Borlsova, R. V.; Volodlna, N. A. Zh. Anal. Khim. 1979, 34, 1369-1361; C A , 91, 203622f (1979). (167) Lewis, K. Report 1980, NBL-294. (168) Leyendecker, W.; Serrini, G. Comm. Eur. Communities, (Rep .) EUR 1979, EUR 6424. (169) Li, Cheng-Tung; Shen, Yu. Fen Hsi Hua Hsueh 1978, 6,347-351; CAI 92, 225955q (1980). (170) Livertoux, M. H.; Besslere, J. Talanta 1981, 28, 81-88. (171) Lopez Gonzalez, A.; Sierra Hernandez, M. T.; Sierra Hernandez, M. I.; Sierra Jiminez, F. An. Quim. 1979, 75, 529-535; C A , 91, 1 6 7 8 6 0 ~ (1979). (172) Macarovlci, C. G.; Horak, J.; Varhelyl, C.; Benko, A. Stud. Univ. Babes-Bolyai, (Ser.) Chem. l980,25, 71-75; C A , 94, 149619g (1981). (173) Malkova, E. M.; Levchenko, Yu. N.; Katyshev, V. N.; Grlshakova, T. E. Izmer. Tekh. 1981, (4). 58-59; C A , 95, 17706u (1981). (174) Mallela, S. P.; Khandelwal, B. L. J. Indian Chem. SOC. 1979, 56, 796-797. (175) Malyshev, A. I.; Khainson, A. B.; Khachapurldze, N. A,; Bondarevskaya, E. A.; Kropotova, E. D.; Migachev, G. I. Zh. Anal. Khim. 1980, 35, 1314-1318; C A , 93, 205439s (1980). (176) Masuda, Y.; Nakamori, T.; Sekido, E. Nectrochim. Acta 1981, 26, 427-494 .-. .- .. (177) Matsuda, T.; Ito, S.;Nagal. T. Bunseki Kagaku 1980, 2 9 , 804-806; C A . 94. 57648n - - 11981\. (178) Matsuzaki, A.; Koyano, K. Anal. Chem. 1980, 52, 146-149. (179) Merclny, E.; Pattyn-Fauville, G.; Swennen, L.; Duykaerts, G. Anal. Chim. Acta 1981, 729, 113-124. (180) Mezentseva, V. F.; Basov, V. N.; Agasyan, P. K.; Rusakova, V. P.; Volkov, A. 2 . Zavod. Lab. 1981, 4 7 , 10-11; CA, 94, 2 0 9 6 5 5 ~(1981). (181) Mitchell, W. G.; Lewis, K. NBS Spec. Pub/. ( U S . ) 1980, 562, 140-146. (182) Mltsubishi Chemical Industries Co., Ltd. Jpn. Kokal Tokkyo Koho 80 67,650 (Cl. GOlN27144) 21 May 1980; C A , 93, 1 9 7 1 7 8 ~(1980). (183) Ibld. 80 98,350 (Cl. G01N27/44) 26 Jul 1960; C A , 94, 40905w (1981). (184) Mltsubishi Petrochemlcal Co., Ltd., Jpn. Tokkyo Koho 80 48,253 (CI. GOIN27/44) 04 Dec 1960; C A , 94, 202194t (1981). (165) Mladenov, I.; Mltev, S.;Markov, M.; Todorov, S.;Uzov, Kh.; Kolov, N. Sb. Dokl .-Nats. Konf. Mladife Nauchni Rab Spets . “Neft Khlm .“, 7st , 7976(Pub. 7977). Sekts. Org. Sint. 160-164; C A , 93, 151435s (1980). (186) Mo, Jin-Yuan. Hua Hsueh Hsueh Pa0 1980, 38, 293-296; C A , 94, 10653v (1981). (167) Mo, Jin-Yuan; Lln, Zhi-Qlng. Hue Hsueh Hsueh Pa0 1980, 38, 387391; C A , 94, 113795~(1981). (186) Mocak, J.; Hofbauerova, H.; Bustln, D.; Garaj, J., ref 225, pp 279-287. (189) Moore, R. T.; Clinton, P.; Barger, V. Anal. Chem. 1980, 52, 760-765. (190) Nagy, G.; Feher, 2.; Toth, K.; Pungor, E. Hung. Sci. Instrum. 1979, 46 119801 . - , 5-15. - .- * C -.A. . 93. .-, 60282v -----, (191) Nagy, G.; Feher, 2.; Toth, K.; Pungor, E. Magy. Kem. Foly. 1979, 85, 321-326: C .A . 91. 167757t (1979). (192) Nagy, G.; Feher, 2.; Toth,‘K.; Pungor, E.; Ivaska, A. Talanta 1979, 26, 1143-1 153. (193) Nagy, G.; Lengyel, 2.; Feher, 2.; Toth, K.; Pungor, E. Magy. Kem. Foly. 1981. 67, 119-125; C A , 94, 218906n (1981). (194) Nakajima, M.; Sakural, H.; Sakai, A.; Imaeda, K.; Ohsawa, K.; Kurikl, T. Bunseki Kagaku 1980, 29, 744-749; C A , 94, 76055h (1981). (195) Neves, E. F.; Pollto, W. L.; Tamura, T.; Franco, D. W. Anal. Lett. 1979, 72 (A7). 741-752. (196) Nikolaeva, L. N.; Komlssarova, T. E.; Pakhomova, T. M. Zh. Anal. Khim. 1980, 35, 1148-1151; C A , 93,1 7 8 8 8 7 ~(1980). (197) Nishlna, K. Jlgyo Galyo-Nagano-ken Seimitsu Kogyo Shikenjo 1979 (Pub. 1980), 96-98; C A , 95, 7 2 5 9 1 (1981). ~ (198) Ibid., pp 99-102; C A , 95, 72592d (1981). (199) Nonomura, M. Tokyo-toritsu Kogyo Gijutsu Senta Kenkyu Hokoku 1981, (IO), 116-120; C A , 95, 347532 (1981). (200) Oganesyan, L. B.; Kon’kova, N. F. Zh. Anal. Khim. 1980, 35, 19951999; C A , 94, 10746e (1981). (201) Oganesyan, L. B.; Ogareva, M. 9.Zh. Anal. Khim. 1979, 34, 17641767; C A , 92, 68947u (1980). (202) Oganesyan, L. B.; Ogareva, M. B.; Kon’kova, N. F.; Avdeeva, F. N. Zh. Anal. Khim. 1981, 36, 262-265; C A , 94, 2 1 8 9 5 1 ~(1981). (203) Ohsawa, K.; Suzukl, K.; Imaeda, K. BunsekiKagaku 1981, 30, 300304; C A , 95, 54154h (1981). (204) Ohzekl, K.; Schumacher, E.; Umland. F. Fresenius’ Z . Anal. Chem. 1979, 294, 352-355. (205) Ollferenko, 0. D.; Gallal, 2. A.; Sheina, N. M.; Svedlenne, N. Vestn. Mosk. Univ., Ser 2 : Khlm. 1980, 21, 400; C A , 93, 160654q (1980). (206) Palamalai, A.; Thankachan, T. S.;Balasubramanian, G. R. India, A . E . C . . React. Res. Cent.. lReD.) RRC 1979. RRC-39. (207) Pap, T.; HaJos, P.; Inczedy: J: Magy. Kem. Foly. 1981, 8 7 , 3-6; C A , 94. 149598~(1981). (208) Paroutaud, P.; Cousin, 6.; Fraisse, D. Microchem. J . 1980, 25, 267-280. r

-

.-

\

-

-

I

.

.

..---,-

._..

8R


(209) Pastor, T. J.; Vajgand, V. J.; Antonljevic, V. V. Gias. Hem. Drus. Beograd 1979, 44, 651-656; C A , 92, 226164t (1980). (210) Pastor, T. J.; Vajgand, V. J.; Antonljevlc, V. V. Anal. Chim. Acta 1980, 720, 357-360. (21 1) Pastor, T.; Vajgand, V.; Antonljevic, V.; Ciric, I., ref 225, pp 289-298. (212) Pastor, T. J.; Vajgand, V. J.; Kicovic, Z.;Ciric, I.Glas. Hem. Drus. Beograd 1980, 45, 213-219; C A , 94, 40954m (1981). (213) Pawlowski, W.; Jedral, W. Chem. Anal. (Warsaw) 1980, 25, 151153; C A , 93, 125203~(1980). (214) Payne, J. T. J. Water Pollut. Control Fed. 1979, 57, 2540-2544. (215) Perevoshchikov, V. A.; Perevoshchikova, V. V. U.S.S.R. Patent 684421 (€3. G01N27/04), 05 Sep 1979; C A , 91, 203845f (1979). (216) Ibid. U.S.S.R. Patent 767033 (Cl. COIG37/00), 30 Sep 1980; C A , 94, 24489h (1981). (217) Perevoshchlkov, V. A.; Perevoshchikova, V. A,; Kormishlna, Zh. A. U.S.S.R. Patent 710952 (Cl. COlG23/00), 25 Jan 1980; CA, 92, 140146b (1980). (218) Perevoshchlkova, V. V. Khim. Prom-st., Ser.: Metody Anal. Kontrolya Kach. Prod. Khim. Prom-sti. 1981, (3), 29-31; C A , 94, 167054~ (1981). (219) Perevoshchlkova, V. V.; Perevoshchikov, V. A. U.S.S.R. Patent 715477 (Cl. COIG31/00), 15 Feb 1980; C A , 92, 2 0 8 4 8 7 ~(1980). (220) Perevoshchlkova, V. V.; Tserkovnitskaya, I.A. Zh. Anal. Khim. 1980, 35, 1525-1529; Anal. Abstr., 40, 46166 (1961). (221) Petrov, S. I.; Bogoslovskii, V. V.; Galltsyn, A. D. U.S.S.R. Patent 785718 (Cl. G01N27/42), 07 Dec 1980; C A , 94, 131706~(1981). (222) Petrov, S. I.; Galitsyn, A. D.; Kasperovich, V. L. Zh. Anal. Khim. 1980, 35,2195-2198; C A , 94, 953920 (1961). (223) Pollto, W. L.; Neves, E. A.; Franco, D.W.; Tamura, T. Simp. Bras. Eiectroquim. Hectroanal., (An.), 7st 1978, 127-132; C A , 93, 18458k (1980). (224) Prasad, 8. 8.; Singh, T. B. Acta Poi. Pharm. 1979, 36, 729-731; C A , 93, 225680s (1980). (225) Pungor, E.; Ed. Coulometric Analysis. (Proceedlngs of a Conference Held at Matrafured, Hungary, 17-19 October, 1978). Akad. Kiado, Budapest, 1979; C A , 91, 186074j (1979). (226) Raines, D. A.; Huffman, E. W. D. Microchem. J . 1979, 24, 479-483. (227) Rao, N. V. K. N.; Balakrishna, V. V.; Raju, N. A. Indian J . Chem., Sect. A 1980, 79A, 607-608. (228) Rao, N. V. R.; Tandon, S.N. Taianta 1980, 27, 449-450. (229) Rasputnis, I.Gig. Tr. Prof. Zabol. 1979, (E), 56-58; C A , 92, 10486b (1980). (230) Reddy, G. S.; Rajan, S. C. S.;Reddy, Y. K. J. Eiectrochem. Soc. India 1979, 26, 221-223. (231) Reddy, G. S.;Reddy, Y. K. J . Eiectrochem. SOC. India 1980, 29, 137- 139. (232) Rubel, S.;Wojciechowski, M. Anal. Chim. Acta 1979, 709, 67-72. (233) Ibid. 1980, 775, 69-60. (234) Ruzicka, E.; Paleskova, M.; Jilek, J. A. Collect. Czech. Chem. Common. 1980, 45, 1677-1663. (235) Sanchez-Pedreno. C.; Aibero, I,; Gracia, L. An. Quim. 1979, 75, 232-237; C A , 91, 2218212 (1979). (236) Sanchez-Pedreno. C.; Garcia, M. S.;Sierra, M. T.; Sierra, M. I.An. Qulm., Ser. B 1980, 7 6 , 281-284; C A , 93, 197113~(1980). (237) Sanchez-Pedreno, C.; Perez Trujillo, J. P. Afinidad 1981, 38, 241-244; C A , 95, 125433m (1981). (238) Satake, H.; Ikeda, S.Bunseki Kagaku 1979, 28, 468-473; C A , 91, 186031t (1979). (239) Satake, H.; Ikeda, S . Nippon Kagaku Kaishi 1979, (lo), 1322-1326; C A , 91, 221952t (1979). (240) Ibid. 1980, (5), 717-721; C A , 93, 36466r (1980). (241) Satake, H.; Ikeda, S.;Tanaka, M. Nippon Kagaku Kaishi 1981, (E), 1260-1264. .-. . . -. . , CA -. . , 95. 108046~ ... . .. (19811. -, (242) Satake, H.; Sakaguchi, N.; Ikeda, S. Nippon Kagaku Kaishi 1980, (9), 1358-1362; C A , 93, 197236f (1980). (243) Satake, H.; Sakaguchl, N.; Ikeda, S.Bunseki Kagaku 1980, 29,532536: C A . 94. 57644h 11961). (244) Schilbach, U.; Klrmse, E.’M. Chem. Anal. (Warsaw) 1978, 23, 10251028; Anal. Abstr. 3 7 , 4026 (1979). (245) Schoiz, E. Fresenius’ Z . Anal. Chem. 1980, 303, 203-207. (246) Ibid. 1981, 305, 416. (247) Ibid. 1981, 306, 394-396. (248) Schumacher, E.; Hackmann, 9.Fresenius’ 2. Anal. Chem. 1980, 304 350-357. (249) Ibld. 1980, 304, 358-361. (250) Schumacher, E.; Ohzekl, K.; Umland, F. Anal. Chem. Symp. Ser. 1980, 2 , 189-197. (251) Seidelmann, U. Fresenius’ Z . A m i . Chem. 1980, 302, 196-198. (252) Ibid. 1981, 305, 355-357. (253) Semenov, I.A,; Komarova, N. I.Zh. Anal. Khim. 1981, 36, 11041106; CA. 95, 143475f (1981). (254) Sement, E. G.; Glrard, M. L.; Rousseiet, F.; Chemla, M. Ann. Pharm. Fr. 1979, 3 7 , 509-514; C A , 93, 173803n (1980). (255) Sement, E. G.; Moiroux, J. Anal. Len. 1979, 72(874), 1411-1422. (256) Sharma, C. L.; Arya, R. S. Taianta 1979, 26, 577-578. (257) Sharma, C. L.; Singh, A. K. Indian J . Chem., Sect. A 1980, 79A. 175-177. (258) Sharonlna, R. M.; Suprunovlch, V. I . ; Pirozhok, S. N. Zavod. Lab. 1979, 45, 993-995; C A , 92, 51386n (1980). (259) Shevchenko, Yu. I.; Pit‘ozhok, S. N.; Suprunovich, V. I. Vopr. Khim. Khim. Tekhnol. 1979, 54, 103-107; C A , 92, 68958y (1980). (260) Shin Kosumoso Denki K. K. Jpn. Kokai Tokkyo Koho 80 76,945 (CI. GOIN27126) 10 Jun 1980); C A , 93, 230273r (1980). (261) Shome, S.C.; Majumdar, M.; Basu, A.; Mitra, P. C. J. Indian Chem. SOC.1981, 58,801-803.

-.

\ . - -

Anal. Chem. 1982, 5 4 , 9 R - 1 9 R (262) Sierra, F.; Cebrlan, A,; Hidalgo de Cisneros, J. L. H. Aflnldad 1979, 3 6 , 515-517; CA, 93, 6 0 4 2 3 ~(1980). (263) Sierra, M. T.; Soledad Garcia, M.; Isabel Sierra, M.; Sierra, F. An. Qulm. 1979, 7 5 , 517-522; C A , 91, 1 6 7 7 9 4 ~(1979). (264) Sierra Hernandez, M. I.; Sierra Hernandez, M. T.; Lopez Gonzaiez, A,; Sierra Jiminez, F. An. Oulm. 1979, 7 5 , 528-528; C A , 91, 1 6 7 8 5 9 ~ (1979). (265) Sikorska-Tomicka, H.; Nytko, K.; Judsz, D. Zesz. Nauk. folltech Slalostockiej, (Ser.): Mat., Flz., Chem. 1979, 5 , 163-177; CA, 93, 31853e (1980). (266) Slmakin, 0. A.; Kuznetsov, 0. F.; Chernov, A. V. Report 1979, NHAR1l(370); C A I 93, 197064~(1980). (267) Slngh, T. B.; Prasad, B. B. J . Nectrochem. SOC. India 1979, 28, 99-101. (268) Ibld. 1980, 29, 141-144. (289) Skobets. E. M.; Abarbarchuk, I. L.; Drokov, V. G,;Iosipchuk, B. V. Ukr. Khlm. Zh. (Russ. Ed.) 1981, 4 7 , 455-459; CA, 95, 72401s (1981). (270) Skobets, E. M.; Kosmatyi, V. E. Ukr. Khim. Zh. (Russ. Ed.) 1981, 47, 241-243; C A , 95, 17454k (1981). (271) Small Business Promotion Corp. Jpn. Kokai Tokkyo Koho 80 128,147 (Cl. G01N27/44), 03 Oct 1980; CA, 94, 36067g (1981). (272) Songina, 0. A.; Zakharov, V. A. "Amperometrlc Tltratlon~",3rd ed.; Khlmiya: Moscow, 1979; CA, 93, 1971650 (1980). (273) Spivakovskii, V. B.; Dovgopol, 0. S.;Makovskaya, G. V.; hfiolsa, L. P. Zh. Anal. Khlm. 1979, 34, 1681-1686; Anal. Abstr., 38, 48131 (1980). (274) Stock, J. T. Anal. Chem. 1980, 5 2 , 1R-9R. (275) Stook, J. T. Anal. Chlm. Acta 1981, 124, 85-90. (278) Stojek, Z.; Osteryoung, J. Anal. Chem. 1981, 5 3 , 847-851. (277) Stuzka, V.; Lukas, I.Chem. Zvesti 1980, 3 4 , 197-202; C A , 93, 967761, (1980). (278) Stuzka, V.; Ruzlcka, 0. Mikrochlm. Acta 1980, 2 , 77-83. (279) Sudo, T.; Mlyake, N. Jpn. Kokal Tokkyo Koho 80 24,652 (CI. GOlN27/44), 21 Feb 1980; CA, 93, 364289 (1980). (280) Suprunovich, V. I.; Pirozhok, S.N.; Shevchenko, Yu. I.; Kullkovskaya, Zh. 8. Vopr. Khlm. Khlm. Tekhnol. 1979, 5 5 , 45-50; C A , 92, 1400799 (1980). (281) Suprunovich. V. 1.; Shevchenko, Yu. I . 2 h . Anal. Khlm. 1979, 3 4 , 513230 (1980); CA, 92, 51323q (1980). (282) Swaml, Y.; Gupta. D.;Mohm, M.; Swaml, M. P.; Rana, V. B. Acta Clem. Indica, (Ser.) Chem. 1980, 8 , 23-24. (283) Takahashi, Y.; Moore, R. T.; Joyce, R. J. Ger. Offen. 2934561 (Ci. COlB9lOO), 06 Mar 1980; CA, 92, 226178a (1980). (284) Tanaka, T.; Hona. K.; Yoshimorl, T. Bull. Chem. SOC.Jpn. 1980, 5 3 , 661-683. (285) Tokusheva, G. T.: Volkova, L. D. Kompleksn fererab frlr. Nedefltsltnogo Syr'ya Kirg. Probl. Ekol. 1978, 154-159; CA. 94, 167840q (1979). (286) Tokusheva, 0. T.; Lavkina, L. Ya. Kompleksn. fereab. frir. Nedefltsitnogo Syr'ya Klrg. frob/. Ekol. 1978, 159-163; C A , 91, 2 0 3 7 0 8 ~ (1979). (287) Toth, K.; Nagy, G.; Feher, Z.; Horvai, 0.;Pungor, E. Anal. (Chim.Acra 1980, 114, 45-48,

(288) Truedsson, L. A. Talanta 1979, 26, 493-498.

(289) Truedsson, L. A.; Smith, B. E. F. Talanta 26,487-491. (290) Tserkovnitskaya, 1. A.; Diaby, L. Vesfn. Leningr. Univ., Fiz., Khim. 1980, (2), 96-99; CAI 93, 1064152 (1980). (291) Tsonkova, S.;Kulev, I.Zavod. Lab. 1981, 4 7 , 24-25; C A , 94, 113907k (1981). (292) Umemoto, K. Bull. Chem. SOC.Jpn. 1981, 5 4 , 2017-2022. (293) Umland, F.; Schumacher, E.; Bartels, U.; Sefzlk, F. Forschungsber. Landes Nordrheln- Westfalen 1979, 2896; CA, 92, 208247t (1980). (294) Usatenko. Yu. I.; Dryuk, L. F. Vopr. Khim. Khim. Tekhnol. 1980, 59, 84-88; CA, 94, 1139061 (1981). (295) Usvyatsov, A. A. Medvedeva, I. M.; Slavnova, A. S.; Genklna, E. V. Zavod. Lab. 1980, 4 6 , 795-797; CA, 93, 215076k (1980). (296) Uzov, Kh.; Mitev, S.;Lyubcheva, M.; Todorova. D. Sb. Dokl.-Nets. Konf. Mladite Nauchnl Rab Spets. "NettKhlm.", 1st 1976 (Pub. 1977). (Sekts. Org. Slnt.), 142-146; CA, 93, 197222~(1980). (297) Van Grondelle, M. C.; Zeen, P. J. Anal. Chlm. Acta 1980, 116, 335-343. (298) Ibid., pp 397-401. (299) Van Steenderen, R. A. Lab. Pract. 1980, 29,380-385. (300) Vartanyan, S.V. Arm. Khim. Zb. 1981, 34, 23-27; CA, 94, 149641h (1981). (301) Vlre, J. C.; Chatrau-Gosselin, M.; Patriarche, G. J. Mlkrochlm. Acta 1981, 1 , 227-239. (302) Volkov, A. 2.; Agasyan, P. K.; Basov, V. N.; Basueva, G. A. Zavod. Lab. 1980, 4 6 , 589-592; CA, 93, 125052~(1980). (303) Weng, Yun-Rong; Chern, Tzun-Rong; Kao, Hung Kao Teng Hsueh Hsiao Hua Hsueh Msueh f a 0 1981, 2 , 117-121; CA, 94, 1 8 4 9 7 9 ~ (1981). (304) Weng, Yun-Rong: Wu, Cal-Yu; Zhang, Wen-Bin; Gao, Hong Nan-ching Ta Hsueh Pao, Tzu Jan K ' o Hsueh 1980, (I), 53-60; CA, 94, 407920 (1981). (305) Weppner, W.; Li-chuan, Chen; Piekarczyk, W. 2. Naturforsch., A , 1980, 35A, 381-380; CAI 92, 221712k (1980). (306) Xu, Lin-Xln; Llu, Ai-Ru. Yao Hsueh Hsueh f a 0 1979, 14, 35-38; CA, 92, 82485y (1980). (307) Ibld. 1980, 15, 184-188; C A , 94, 7806s (1981). (308) Ibid. 1980, 15, 836-640; C A , 94, 9 0 4 3 5 ~(1981). (309) Yakovleva, A. V,; Zhltomlrskll, A. N. Khlm. from-sf., Ser.: Mefody Anal. Kontroka Kach. Prod. Khlm. from-sti. 1979, (lo), 57-58; CA, 92, 140100g (1980). (310) Yamaya, K. Anal. Chlm. Acta 1979, 110, 233-243. (311) Yoshimori, T.; Asano, Y.; Hattorl, Y. Talanta 1979, 26, 527-530. (312) Yutse Broadcasting and Recording Equipment Works, Fen Hsl Hua Hsueh 1978, 6 , 240-241; CA, 92, 190654m (1980). (313) Zhdanov, A. K.; Akhmedov, G. Zh. Anal. Khlm. 1980, 3 5 , 609-812; C A , 93, 36352a (1980). (314) Zhdanov, A. K.; Akhmedov. G.; Saidov, A. Uzb. Khim. Zh. 1981, (2), 13-15; C A , 95, 34717r (1981). (315) Zuo, Yu-Mln Hua Hsueh Tung f a 0 1980, (3), 151-157: CA, 93, 125173k (1980).

.

.

I

.

Analytical Electrochemistry: Theory and Instrumentation of Dynamic Techniques Dennis C. Johnson Department of Chemistry, Iowa State University, Amm, Iowa 5001 1

This review is written in accordance with my perception that my audience consists, in the main, of individuals with interest in electrochemical methods for the quantitative, qualitative, and kinetic characterization of chemical systems rather than an interest restricted to the subject of the analytical methodology of electrochemistry. Furthermore, it is my perspective that the purpose of this review is to highlight trends and significant developments rather than to provide a critical commentary on the literature. The literature cited is that abstracted in C.A. Selects: Electrochemical Reactions and Analytical Electrochemistry, 91 (23)to 95 (22),published by Chemical Abstracts Service. The citations are organized within six sections according to recent ractice (25A). Initial screening and selection of articles were Eased on the abstracts accompanying the citations. For publications deemed significant but which could not be reviewed, due to language or

lack of availability, the Chemical Abstracts reference is included. The scope of citations in Books and Reviews is somewhat broader than the title subject for the purpose of informing electroanalytical chemists of useful resources providing comprehensive coverage of the broader discipline of electrochemistry. References located for published reviews of books are also cited.

BOOKS AND REVIEWS Bard and Faulkner (2A) produced a much-needed, longawaited, scholarly, and up-to-date text surveying the many aspects of theory rind application in analytical electrochemistry. Their text offers a robust treatment of the subject with numerous illustrations which will make this a highly valued resource for the electrochemist and analytical chemist alike. I recommend caution, however, in the choice of this text for

0003-2700/82/0354-9R$06.00/00 1982 American Chemical Society

QR

Amperometric, bipotentiometric, and coulometric titration - Analytical

Recommend Documents