Water Analysis M. W . Skougsfad and M. 1. Fishman
U. S.
Geological Survey, Denver, Colo.
T
HIS NINTH review
of the literature of analytical chemistry applied to water analysis is based on material published within the two-year period ending August 1960. The present review follows the general pattern of previous reviews, the last of which appeared in April 1959 (9). Other reviews of the analytical chemistry of water or of certain aspects of water analysis have been published. The Journal of Water Pollution Control Federation prepares a n annual literature review which includes a section on analytical methods. Reviews published in 1959 ( 3 ) and 1960 (4) include more than 180 references to published analytical procedures. Jones ( 5 ) reviewed modern analytical methods for boiler feed water, including methods for carbon dioxide, dissolved oxygen, PI€. conductivity, silica, copper, iron, and carbonates. A review of current analytical methods in the field of pollution was presented by Pettet (8). Methods covered include organic carbon, combined nitrogen, several heavy metals, detergents, cyanides, and phenols, as well as the commonly determined constituents. The review also contained a discussion of sampling techniques. RIaurel ( 7 ) discussed standardization in water analysis and presented French criteria for water quality standards. He included a comparison of French and American methods and, in a series of appendices, data and report forms useful in presenting chemical and biological analyses, chemical computations, tables of cations and anions, and graphs of water mineralization. Kroner, Ballinger, and Kramer (6) reported on the evaluation of laboratory methods for analysis of heavy metals in water, an activity of the Analytical Reference Service of the Robert A. Taft Sanitary Engineering Center. This report tabulates and discusses the analytical results obtained by 17 different laboratories for 7 heavy metals in a reference sample. Where two or more different methods R-ere used for a single constituent, a comparison of results obtained by the different methods is included. The eleventh edition of “Standard Methods for the Examination of Water and Waste Water,” ( I ) published jointly by American Public Health 138 R
ANALYTICAL CHEMISTRY
Association, American Water Works Association, and Water Pollution Control Federation, represents a major expansion of the previous edition. Many changes in specific methods and addition of several new sections and new test procedures have been included in the new edition. The manual includes standard and tentative methods for physical, chemical, and biological analysis of natural and treated water, sewage and treatment plant effluent, and industrial wastes. A second edition of the American Society for Testing Materials “Manual on Industrial Water and Industrial Waste Water” ( 2 ) contains more than 60 ASThl standard and proposed methods for the examination of water, including waste water and process water. Many of these methods are either new or revised. This new edition also contains an expanded introductory section on the general requirements of industrial waters and a discussion of the problems involved in sampling and analysis. ALKALI METALS
Flame photometric methods are most commonly used for determination of alkali metals. Nevertheless a number of other methods have been proposed for the determination of these elements. Kobrova’s (15A) review of methods for determining rubidium and cesium in mineral waters includes a list of 86 references. Ganchev (6A) described a microgasometric method for the determination of potassium. Small amounts of potassium were separated as insoluble potassium perchlorate. By determining the amount of oxygen released by the thermal decomposition of the precipitated perchlorate, an accurate estimate of the potassium concentration of the sample was possible. For 0.3 mg. of potassium the deviations were less than =t1%. Best results were obtained when the solutions to be analyzed contained 5 to 10 times as much sodium as potassium. Hara (8A) reported on the use of potassium or sodium iodobismuthate (111) as a reagent for the gravimetric and volumetric determination of small amounts of cesium. Large amounts of
rubidium were found to interfere as well as large amounts of other alkali chlorides. The removal of the larger part of these latter salts prior to determination of cesium was recommended. Ishibashi and Hara (11.4) re-examined the dipicrylamine method for the determination of potassium and concluded that complete precipitation of the potassium dipicrylaminate can best be achieved by shaking the reaction vessel in an ice bath during reprecipitation. By this method, they determined potassium concentrations in samples of sea water. Ievins and Peinberga (10.4) determined potassium in the range of 0.01 to 0.25 mg. per liter by coprecipitation with ammonium tetraphenylborate. The precipitation was accomplished by adding sodium tetraphenylborate solution dropwise to 1 liter of sample solution adjusted to p H 5 with AcOH and NHaCl. The precipitate obtained was dissolved and reprecipitated before final weighing. Large excesses of most common cations and anions did not interfere. C U + ~ ,Cof2, P b 7 ? , and F e f 2 interfere and were either complexed or removed. A field kit for detcrmining potassium in natural water by hoth volumetric and turbidimetric comp1c.x cobaltinitrite methods was designed by Reznikov and Nechaeva (2ZA). Samples containing low concentrations of potassium were analyzed by comparing the turbidity of the sample containing precipitated potassium-sodium cobaltinitrite with standards or with a specially prepared cclluloid scale. Samples containing larger amounts of potassium R-ere analyzed by an oxidation titration of the precipitated complex. Several colorimetric methods have been proposed for determining small amounts of potassium, rubidium, and cesium. An indirect colorimetric procedure, suitable for small amounts of potassium, was described by Wonova and Kerkenyakova (19-4). The method is based on the precipitation of potassium bismuth thiosulfate and colorimetric determination of bismuth in the precipitate. Accuracy for 10 to 100 fig. of potassium is i 2 % . A simple colorimetric method was described by Palous, Pavelka, and Mara (IOA) wherein the decoloration of yellow dilituric acid (5-nitrobarbituric acid) is proportional
to potassium concentration. Absorbance mas measured a t 420 mp. Hara ( 9 A ) described a colorimetric procedure for determining 10 to 45 pg. of cesium in the presence of up to 4 mg. of potassium or rubidium. Iodobisniuthic(II1) acid reagent was added to an evaporated and dried sample residue. The resultant precipitate mas extracted with nitric acid and the acid solution treated with KCN-NH,OH solution, dilute nitric acid, and a dithizone-chloroform solution. Absorption of the chloroform layer was measured a t 500 nip. Rubidium and cesium were determined colorimetrically by Cherkesov ( S A ) . These elements were precipitated with hexanitrohydrazobenzene, the precipitate dissolved in acetone, and the absorbance measurements made on the resulting solution. The majority of papers dealing with methods for the alkali elements relate to flame photometric techniques. Many investigations have been concerned with interference studies, the use of radiation buffus, or removal of interferences. Some papers reported on advances in illstrumentation particularly in the iliwlopment and application of recordiiig fl:imc photometers. C;iisy:itr;knl,a ( 7 A ) reported a method for tictermining lithium. rubidium, and cc>ium in thc homogeneous residues obtxincd b!, evnporation of natural water samples. Tlsing an air-acetylene flame, 0.003yc rubidium and cesium, and 0 . 0 0 0 5 ~lithium ~ were determined with a probalile error of +15 to 2070’,. 13oroivic.z (1A ) analyzed several mineral n-aters of different types for sodium, potassiuni. lithium, and calcium using both standard and flame photometric m t h o d s . He obtained good results for lithium, sodium, and potassium for waters with a total minera! content of 1200 p.1J.m. or lcss. The interference effects of from 20 to 2000 p.p.m. of sc~diuni: pot:issiriin~ magnesium, and :i!uniinuni on the flame photometric tieterrniii:ition of lithium was stutlicd by Xivto (18-4). Uzumasa, X ~ S L Iand , 85co (?;A) addcd aluminum sulfate t o tlic analysis sample to suppress interForcnce from up t o 1000 p.p.m. of calc,iuni, am1 were able to determine 1 to 10 p.p.m. of !ithiurn with an accuracy of -x: 55;. I7:iloriI Talenti, and Suroini (%A) u c ( d a solution sxturated Iritn respect to SaC’1. KCI, CaCl?, and llgC:!2 as a sj)cetro:.iicriiic,:II buffer t o minimize i:i (,omposition of natural v:iriatiiuu, content of the sample,, plotting intrrlsitj readings against potmsium added, and extrapolating the straight h e obtained through the Y-axis to the X-axis. The distance froni this point to the origin indii.ated the concentrst ion of potassium in the sample. For pot trations greater than 20 :,.p.ni., the calibration curve was n(Jt, a straight line. Yukanovic (3014) investigated the effect of several organic solveiits on the emission characteristics of lithium and reported that certain solvcnts significantly increased the sensitivity. A flame photometer using a liquid fuel \vas described by Kisilwskii rind Tyutpnnikor-a (f &l). An air-gasoline or air-benzene w p o r flame was used. Fuel and air Kere miscd in a carburetor and burned in a btainless steel burner. Interference filters were used to isolate characteristic emission h i e s of sodium, potassium, and lithium, and the calcium oxide hands. The analytical range was 1 to 40 p.p.m. of sodium or potassium, 15: to 1000 p.p.ni. of lithium and 65 to 3,500 p.p.m. of calcium for &termining the salt content of boiler feed water. Zagrodzki and Zsorska (%A) described an automstically recording flame photometer. Factors affecting the flame photometric emission of rubidium in a n air-
acetylene flame were studied by Shellenberger et al. (84A). Rubidium emission a t 780 mp was found to be enhanced by increasing concentrations of potassium. This effect, and a general increase in background, were controlled by adding excess potassium and by using lithium as an internal standard. They also found that sodium enhanced and magnesium depressed rubidium emission. Several other analytical methods have been reported for the determination of the alkali metals, including spectrographic, polarographic, and chromatographic techniques. Pisarev and Ivanova (21.4) reported a spectrographic method for the determination of sodium, potassium, calcium, and magnesium in solutions. Bot’h a low-voltage (3000 volt) spark or an alternating current arc were used, the former Rith a “fulgerator” to introduce the solution directly into the spark, and the latter with a flat-end graphite electrode on which the d u t i o n had been evaporated. The upper electrode in each case was copper. Barium and cobalt were used as internal standards. The analytical range i n the spark was 0.002 to 0.05y0 for cakiiim, 0.002 to 0.5% for magnesium, arid 0.4 to O.5yGfor potassium. I n the alternating current arc, potassium could be determined down to 0.009%. The errors observed ranged from + 5 to =k13.7%. A standard addition techni!i: e ::nd a. system of simultaneous equations obtained by adding known anioiints of sodium and potassium to the analyzed solution and re-exposing the sample were described hy Egorov and Koralev (416). Junkes and Salpeter (1211) pointed out the advantage of measuring line-widths rather than line-densities in the spectiograp!iic determination of lithium, potassium, calcium, and strontium. The analytical curves are similar to d by density measurements a.nd iiava) t,hi. advantage that a n almost uiilimitcci interr-a1 of intensities c:in be covered with little loss of precision of measurenimt. Calibration curves and techniques n-cre described for determining lithium, 1 to 1000 mg. per liter; potassium, 2 to 10,000 mg. per liter; strontium, 25 to 5000 nig. per liter; and calcium, 50 to 1500 mg. per litrr. hfedek aud Valeska (1616) determined rubidium and cesium spectrographically in the range of from 1X to 1 x 10-5mole and 1 X 10-4 to 3 X IOp5 moie, respectively. The samples were sprayed into an air-acetylene flame. Schober and Gutmanri (2SA) determined lithium, rubidium, and cesium polarographically in 80% isopropyl alcohol solvent and 0.1-11 tetraethylhydroxylamine supporting e l d r o l y t e . The quantitative accuracy ivas within h 5 % . Half-wave potentials were observed to be -2.37 volts for lithium, VOL. 33, NO. 5, APRIL 1961
139 R
-2.03 volts for cesium, and -1.97 volts for rubidium. Kalvoda (13A) discussed alternating current polarography with an oscillographic present’ation of de/dt against E. Using a dual ray tube, titration of a n u n k n o ~ nsample was continued until its curve matched the curve of a known solution. Several ions were determined, including sodium and potassium in concentrations of the order of to IO+N. These elements were first separated a t a stationary mercury electrode and then deterniincd in the amalgam. Zyszczynska-Florian and Chomik (3Brlj employed a paper chromatographic method to determine lithium, rubidium, and cesium in brines. By ascending chromatography they were able to tictcJrmine 0.15 to 1.1 mg. of litliiiini y r liter in post-crystallization lye. Ilubiiliuin and cesium were detected b s ~ descending paper chromatography. The sensitivity of a sodium-aluminoolectrode to rations comin irrigation w t e r s and in water extracts of .soils was studied by l3orvvr (Rd). The electrode, insensitive to calcium and rnignesiuni ions, but srnsitivc. to sodium, potassium, and hydrogen ions, was used to determine sodium by first diluting the sample (to reduce the tot>alcation concentration to 10 mcq. p p r liter or less), adjusting the pH to approximately 7, and removing pckissium by precipitation with sodium trtr,zphenylborate. Results obtained with the electrode agreed closely with det,errninations made by flame photornetry. Smales arid Webster ( 2 5 4 ) described a stable isotope dilution method for dc!t(,P,rniningrubidium in sea water and ic rocks. 130th rubidium and lithium could be determined; rubidium to a concentratinn of 1 p.p.m. in a 1-nig. sample. HP.RDNES5, ALKALINE EARTH METALS
Complexonietric titrations with (ethylenrdinit’ri1o)tetraacetic acid and similar chelating agents are fnvorrd for determining water hardness and the common alkaline earth metals in water. Goetz and Smith (IBB)made a thorough htridy and evaluation uf methods for determining water hardness, including a comparison of results obt,ained by gr>ivimrt,ric and volumetric mrthods. h r d n e s s values obtained gravimetrically can be very accurate but require crrnsiderable time per analysis. Titration with stlindard soap solution yields results which ma,y be inaccurate and which are not reproducible. A greater part of their rcport deals with comparisons of t,he newer volumetric chelating reagents and a crit,ical study of t,he various factors affecting the accuracy of the determinations. including buffer 140 R
ANALYTICAL CHEMISTRY
systcn-is, pH adjustirit cators. Complexonietric m ~ t h o d s lo7 tiir determination of calcium ;tnJ mngnesium h a w t w n critical Mattioli, De RuLcrtis, (Z7B). In developing a precise and accilrat’e procedure for determining calcium and magnesium, Liwis and hlelnick (2,4131 studied the severzl uilibria, including copreriomenn, involved at the Pquivhlence poiilt in EDTA titrations for these elemcnts. A number of niodificutioris of commonly employed complexomrtric methods have been reportcd. Stengel and Riemer (44B) described the modification necessary to convert :t photometer for use in the photometric end point detection in the EDTA titration of calcium with murexide indicator and c b f calcium plus magnesium with Eriochrome Black T. To determine low concentrations of calcium in the presence of greater amounts of magnesium, van Schouwenburg (,$OB) added Carbocel to the titration solution. This addition prevents the formation of insoluble magnesium hydroxide which strongly adsorbs calcium murexide and causes serious errors in the determination of calcium. Vol’f (48Bj Pliminated interferences due to Hg+2,Pb+*, and Zn+2 by adding Unitol (sodium 2,3-dimercaptopropanesulfonate) to t8hetitration solution. This reagent forms stable complexes with thest, ions without intcrf::riiig with the determination of c n l h n and magnrsiurn in an r,mrrJonin buffered solution with Chromogen Black indicator. Busev and Petrenko (4B) reviewed the entirc subject of complexometric indicators. Korenman, Ganina, and Leifer (1BB) described the use of Acid Monochrome Bordeaux C as ai1 indicator for the determination of calcium, either colorimetrically or by complexometric titration with Trilon B. The indicator gives a product of different color with each of the alkaline earth elements arid is an extremely sensitive reagent for calcium. Colorimetrically, calcium can be determined in the presence of up to 50 times as much barium or strontium, and up to five times as much magnesium. Calcium titrations were carried out by buffering a small (5- to 10-ml.) volume of sample with concentrated ammonia solution, adding 5 to 10 drops of the indicator (prepared urated aqueous solution), and titrating to a yellowviolet end point with l’riion B. Omega Chrome Fast Blue 2G was proposed by El Raheem (SB)as an indicator for the EDTA titration of calcium, magnesium, and manganrse a t p H 10. The change is from bright blue to red or violet. The indicator does not form complexes with aluminum, cadmium, copper, lead, or
zinc t i t pH 10, b:it can be used in tiic titration of Iiickrl. icitd, and cadniiuin, undei rcguhtpti caditions oi pH urxi Moustafa (iOBj
I Raheniesample. According to Goltlstclir, (1SB) a sharp end point changr from pink to yellow is observed vihen glyo. bis(2-hydroxyanil) is used as the in _cator for the EDTA titration of cnlciuip. A mixed indicator, Hydron 11, CORsisting of Acid Chrome Dark Green C! and X:iphthol Yellm S was usrd hv Mustatin and Kurchkova j32B) for t h determination of calcium in the presencr of magnesium. Thcj color change ii. from bright pink to green. Jankowit,~ and Eidcy (SOB) found that the use oi Eriochrome Red I3 gave sharp accuratt end points in the EDTA titration of calcium. hlagon, l-(2-hydrosyphcnylazo) - 2 - hydroxy - 3 - (2,4 - dimethylphenylcarbonol) naphthaline, was found by hlaier (2bB) to be a satisfactory indicator for the determination of small amounts of magnesium. Large amounts of calcium interfered and required removal by precipitation as calcium tungstate. A field method for measuring water hardness was developed by Gundlach, Koch, and Stovesand (l4B). The determination is carried out by adding tablets containing titrant (disodium EDTA), indicator, and buffer. The number of tablets required to produce a color change in the indicator is a measure of the hardness of the water. Caicium mey- also be determined separately by adding a few drops of NaOH solution and murexide indieator, follon.ed by the addition of the titration agent, again in tablet form, until the solution color changes from red to violet. Application of an siit,omaticspectrophotometric titrator to the determination of total hardness, calcium, and magnesium has been described by illalmstadt and Hadjiioannou (26B). -4 standard EDTA titration was employed to titrate total quantity of calcium plus magnesium. Calcium alone was determined by titration a t pH 13 Iyith Calcon indicator, and magnesium determined by difference. The commercially available apparatus automatically stops the titrations at the equivalence point. Accuracy and reproducibility of analyses are equal t o those obtained by the
5ioni.r imnu:tI titrations. llukheriicc. rjc+, and Bhattncharjee (3181 :L method for the dctermination of 1v:iti.r hardness and also for dc>ttmiinirii. ~nnpnceiuni, calcium, :inti bnrinni ious in solution by high frequency titration. The titrant used IKIS 3tanci:ird sodium osalate which prccipitatcs lmth h r i n m and cakiuni. 3Iagnesium ivas dett~rminctl with sodiuiii hydroside. 1 w:is tic!tcrniined by titra s t a n d u d suIE:ttc solution. for total liardni'ss :igeed within li?& rvitll .i-he.; ol>taincd l ~ ythe standard :AX* JI sol:ition procedure. Pasovsk;~yn .%BI iijiIo\Vc*tl the F:D'F-\ titration onrluctoiiic.tricn!~~ to iletcrniinc w.ntt,r The samplt. is buffrred ,,vitlr .in ~ ~ ~ n i n i ~ n i1iiiflc.r ; i i ~ a lsolution and itr:ittd \\it11 stnnd:ii.ii 9.1X disodium D'!~.I ~00I~itio11. Isliihars :md Takcuchi ( 1 7 8 ) used a s t nnrl riri i 5olution of tc t i,;!soi lii iin ~:,hris;l)h:Ltc, to dctemiiic>the li;idn \ v a k r . The titrant n-a+ firvt stnn izcd xgtiinst a c;ilcium ~~hloriilc solutiix tration. \17ati,rs m p l e s to pH 10 nith an riium chloric!e soiution, :Eriochronic Black 1' V A S nddrd RS jndicntor :idthe titrs*iori with standard ~ ! ~ o ~ ~ h o ? j isolution h s t i ~ co!itinuc.d to a lor chaiiye of red to blue. d method detcinining ca!cium, niapnesiuni. and hardnrss of rvat (loniplcsoii 111 TTRS rl 1; i (13) , .I neiv system for describing the linrcln~~ssof water was proposed by ?opov ( 3 6 8 ) . The suggested units of iirement arc Inilligram~ciuivnl~~ts ix'r iter, escept for water of w r y lorn h:>iliness where gmima-eqaix-alent+ :Ire :i.*i.[l. On this scale, 3 water of 0 to 1.5 ,i!il!inl.arn-equivaler!t pcr 1itc.r is classisoit, o soft nfiti,r 1.5 to 3, a t w:itt>r 3 t o 4.5.n niodervatrr 1.6to 6.5. a1:d $: hard 11. \Tatclr oi more chan 1 1 milligr~irii-c~c~iii~~alerits I,(';. litibr is very linrd. Ca1cii:n: WIS determined by Ringhorn. Pensar. and Wanninen (SHB) Jn the ;)resmer rJf magnesiiini h!. titrating with IZGTA f~th>-lenegi i.tIier) trtraacrtic R :IS an intirrrct intlicitor. 3Iagnesium i n sea x t t e r and brines \vas determined spectrophotometricnjl~ h y OKatii ar;d Hiroi (3.iH) using xylidyl liiue n-kiictl forms a colorwi complex with riiagnwium in &oliolic solution. Maxi:n;ini ahwrption of the rwqent o c ~ t r at s iil3 c i diiie ~ at 510 mp a'czorption is due to t h e reagent-mngnesium compleu :ind to unrencted reagexiit. UndiBr soiiie eontlitions sodium arid c.nlciurfi in tcrfere. T7-.r...m;.iii quantities of calcium (-1to 2.4 ~g ) \vc.re deterniincd by Leclerc and van 13encilcn (2SB) b y precipitating caicium phosphate, rrdissolving the
also stiidicd the effect of in eliminating interferences of a number of snbstances including aluminum, phosphate, sulfate, and silica. If the lanthanum-aluminum ratio is 12.5 t o 1 (by weight) or greater, the interference is eliminated. Romero (3L.R) found that serious interference in tlie detcrinination of calcium occurred iv1ic.n :iluminum and phosphate were t . He rc~ommcndedremoval of
wrrect only for sodium, hw :mdj-zing pot:ible 'ivater iir irrig:it~oii >\(:ltcr. .\ sr biiii'cir wis t!s(~iby 17alnri.-1' snvoiiii (.$6/j, to niininiize iri!i,tlerrnces in the flr i l t c jiliritu~nc~triccic.tvrr:iin:~tion of (2aIcili:ii iii n ; l t o r . Their iiictiiurl wis ary
+mxnr,
11
titrating n.ith :in :iliiali ,pliatc :ind iiilic;n.i:ig the I C 1:reciiJitntion of calcium phosphate \ith i frequent' flame photometric r r a d i n p , the amount of calcium J
', aluminum almost >vas also observed
u n i or stroritium :yere c i e t ~ ~ ~ n i by ned ct flame photomerry by XakajiniaJ ata, and -4mnnc :3b'). Their $error
darium and strontium were determined in hot, spring waters by Iiarvakanii M I f 3 ) asing a ~pectrograpl~~ic rnf%hod. The residrie obtained hy ev,tdporation of the FXI in a n alternating cur volts, 5 amperes, for 60 seonds. Tungsten W R S used as a n internal standard. 'The range for quantitative detection was from 0.001 to 0.05% of the residue. Scott and Ure (4.123) determined magVOL. 33, NO. 5, APRIL 1961
* 141 R
nesium spectrographically using the porous cup spark method and a direct reading attachment on a small quartz spectrograph. Solutions containing up to 24 p.p.m. of magnesium were analyzed a t a rate of 40 determinations per hour with a relative standard deviation of about *2%, Strontium was added as an internal standard. Small quantities of barium in natural waters contaminated by industrial wastes were determined by Dzhaparidze ( 7 B ) . The turbidity formed by adding sulfuric acid was compared with standards; 1 p.3.m. of barium could be detected. Selivanova and Zubova (42s)described a polarographic method for the determination of strontium. The determination of beryllium is important, chiefly because of the exceedingly toxic properties of this element and its compounds. Beryllium, unlike the other elements of the alkaline earth group, does form intensely colored compounds which provide sensitive colorimetric tests for its presence. Colonmetric, fluorometric, indirect titriIndric, and neutron activation methods have been reported for determining beryllium. Adamovich ( I B ) pointed out that Alizarin Blue Black B, a commonly used reagent for the colorimetric determination of beryllium, is unstable in ammonia and in sulfuric acid, and that the photometric characteristics of its beryllium complex in ammoniacal solutions change on standing. Beryllium forms a colored complex with ammonium aurintricarboxylate at p H 6, and can be used, according to Mukherjii and Dey (SOB), to determine beryllium in the concentration range of from 0.5 to 100 3.p.m. Most metallic ions, however, interfere. Bose, Srinwasulu, and Rao (SB) determined parts per million concentrations of beryllium with the colorimetric reagent gossypin, a glycoside of the flavanol gossypetin. In disodium EDTA solutions of p H 7 , the absorbance of the complex at 450 mp follows Beer's law. Aluminum, thorium, and the rare earths do not interfere although uranium does interfere. An extremely sensitive fluorometric method was developed by Sill and Willis (43B). By careful control of pH, and by the use of a buffer system, an internal acid-base indicator, complexing agents, and a permanent glass fluorescence standard, they were able to detect as little as 0.0004pg. of beryllium. Venkataratnam and Rao determined beryllium polarographically at concentrations up to 8 X 10-3M, using a n acid lithium chloride supporting electrolyte. Beryllium, in both solid and aqueous samples, was determined by Milner and Edwards ($OB) who measured the photoneutron flux produced when the sample was irradiated with neutrons from a Sb1*4 source. The presence of
142 R
ANALYTICAL CHEMISTRY
any material which absorbs thermal neutrons interferes.
Up to 20 mg. of chromic and cobaltous ions do not interfere. The red complex formed by Fe+3 and IRON, MANGANESE, ALUMINUM, AND catechol in neutral or weakly acid soluCHROMIUM tion was used by Smith (SZC) to determine from 0 to 15 p.p.m. of iron. A number of n w reagents Ilaw been The complex was formed in 1 hour in a proposed for the spectrophctametric and phosphate-buffered solution and abcolorimetric determination of small sorbance read a t 580 mp. Beer's !aw i s amounts of iron. Gupta and Sogani valid up t o 15 p.p.m. of Fe+3. Vana(OC) investigated 3-hydroxy-1-phenyldium interferes seriously but 5 p.p.ni. 3-methyltriazine as a reagent for Fe+3. of aluminum and up to 0.4 pap.m. of The greenish blue chelate complex copper, nickel, manganese, and tungformed in the p H range 3.1 to 4.5 has an steii do not interfere. Majumdar and absorption peak a t 425 mp, and is sensiSavariar (2OC) determined iron by tive to less than 1 p.p.m. of iron. measuring, a t 590 mp, the absorbance of Lukasik-Rardzinska and Popowicz a solution containing the blue complex (1OC) have described a colorimetric formed between Fe +3 and 2-hydroxy-3method based on the complex formed in naphthoic acid. The optimum p H for alkaline solution between Fe+3 and formation of the complex was 2.9 to 3.1. sodium p-aminosalicylate. The sample Although the complex is soluble in solution, containing from 0.005 to 0.075 water, the excess reagent is not and mg. of Fe+3, was neutralized and must be held in solution by adding buffered to a p H of 9 to 10 with a 2% gelatin. The optimum concentration borax solution. Five milliliters of a 10%;. range for the method was 4 to 20 p.p.m. solution of the color-forming reagent of Fe+3. Rao (29C) determined Fe*3 was added and the solution heated at spectrophotometrically with aqueous 60" C. for 15 minutes. The solution resorcinol, measuring the absorbance st was cooled and its absorbance measured 450 mp and a t an optimum p H of 2.9. a t 420 mp. Copper and zinc do not Beer's law applied over the range of 14 interfere. A modified 4,7-diphenyl-l,lO-phenan- to 79 p.p.m. of Fe+3. Ferrous ions do not interfere but certain other cations throline method for determining iron do. in high purity water was described by Shigematsu and Tabushi (302)deterKnapp (17C). By using redistilled mined 0 to 2 p.p.m. of Fe+3 by measurn-hexyl alcohol as the estraction solvent ing absorbance a t 410 mp of a butyl and by eliminating sources of conalcohol extract of the complex formed tamination, he was able to obtain stable, between Fe+3 and dibenzoylmethane. water-white blanks and to eAtend the An aliquot of the sample was adjusted range t o 1 p.p.b. Six samples were to a p H of 2.5 to 3.0 and 0.5ml. of 5% analyzed in 30 minutes or l w . 3.3dibenzoylmethane in acetone was added. Dimethbxybenzedine Ras used by VasThe maximum color formation was siliades and Manoussakis (S6C) to deterachieved in 20 minutes or less a t 70" C. mine ferric ions. Absorbance of the The complex was extracted with 20 ml. red complex formed at a p H of 2.5 to 3, of butyl alcohol and its absorbance was measured a t 450 my. Ferrous ions measured with the reagents as a referdo not react with the reagent. Nitrite ence. Molybdenum, titanium, and copdoes not interfere if its concentration is per interfere seriously as does more thar. less than that of ferric ion. High con100 pg. of chromic ion. centrations of chromate, dichromate. Tabushi (S4C) extracted the Fe+3and iodide do interfere. acetyl-acetonate complex with butyl Tropolone reacts with excess Fe+3 to acetate and found that absorbance of give a green 1:l complex but gives a the chelate compound in the organic brown-red 1:3 complex if an excess of solvent followed Beer's law for 0.5 to tropolone is present. These complexes 10 p.p.m. of iron. Butyl acetate exwere used by Oka and Matsuo (25C) tracted the complex completely at p H for mutually determining Fe+3 and 6 to 8. Titanium, chromium, bismuth, tropolone in solution. The 1 : 3 comand large amounts of uranium and plex formation is complete over the pH copper interfere in the determination. range of 1.3 to 8.5 and shows absorption Oi (24C) determined 0 to 10 p.p.m. of peaks a t 425, 550,and 590 mp. Beer's Fe+3 by measuring the absorbance of a law is valid at concentrations of F e f 3 up chloroform extract of the red-violet to 0.07 pg. per ml. Khopkar and De complex of iron and salicylaldehyde( 1 6 0 determined Fe+3by extracting an ethylenediamine. The extraction was acidified sample with a 0.15M solution made at p H 5 and absorbance of the of 2-thenoyltduoroacetone in benzene. chloroform solution read a t 495 mp. At The absorbance of the red Fe+3-chelate 0.5 p.p.m. of Fe+3, the accuracy was is measured at 460 mp and compared k2%. Copper, cyanide, fluoride, and with absorbances of known solutions. EDTA interfere. Holdoway and Beer's law holds over the range 1 to Willans (11C) proposed tris(o-hydroxy10 p.p.m. of Fe+3. Several ions interpheny1)phosphine as a colorimetric fere, including copper, silver, nickel, reagent for Fe+3. This reagent forms a manganese, aluminum, and phosphate.
red-violet coniplcx with Fe t 3 in 0.3 to 2.SS nitric acid solutions. 'f'tie complex, stable in the acid solution for a t least 16 hours, has a n absorption masimuni bctxeen 530 and 559 mp. Ceric ion is the only cation which intcrferes seriously with the deterniiriation, although acetate, borate, sulfate, phosphate, nnd fluoride interfere to some extent. The disodium salt tif 1,2-diaminocyclohexantetraacetic acid (Al>C:'L'-Sa2) was proposed by llartiriez and Xcndoza (,"IC) as a reagent for determining Fe+*, l h e colored chelate solution obeys Beer's law. Another chelating agent, bis(2-aniinoethyl tether of ethylene glycol-S, .Y, N ' , A"'-tt.traacetic acid (EGTA) \vas investigated by llnrtinez and I'az Cnstro (32C). In this method a n aliquot of the Fe+3 solution was mixed with 1 ml. of the reagent, and the mixture diluted until homogeneous. .it pII 5 the absorbance (at 430 mp) followed Iker's law for 3 to 100 p.p.m. of I?ef3. At pH 4, Beer's law held for 5 to 140 p.p.m. Copper, nickel, manganese, cobalt, fluoride, and cyanide interfere, as do large amount,s of phosphatc,. Borate, acetate, nitrate, chloride, and bromide do not interfere. Alniassy and Kavai (ZC) determined iron in mineral waters by means of two organic reagents, aniline and bipyridine. F e r * was oxidized to FeL3 with nitric acid. Aniline ( 5 ml.) vias added and the solution buffcred with 15% sodium acet,ate solution. Bipyridine was then added as the color-forming reagent. Interferences, particularly of cobalt, nickel, and manganese, in the 2,2'-bipyridine method were studied by GratCabanac ( Z j . These ions were found to cause no interference if the ratio of the concentration of the interfering ion to concentration of iron did not exceed 15 for cobalt, 22 for nickel, or 80 for manganese. These ratios were the same whether in sulfate, wetate, or chloride solutions. A stable, standard color-comparison solution, consisting of a mixture of 0.05% Bismark Brown, 0.0005% fuchsin, 80% glycerol, and 2y0 carboxymethyl cellulose solution in distilled water, was proposed by Sugiura and Nagasaka (332)for the preparation of reference standards for colorimetric determination of iron in water. A titrimetric method, based on titration of Fe+3 with Trilon B, was used by Yakimets and Bashkirtseva (37C) to determine iron in a variety of materials including water. The titration was carried out in acid (pH 1 to 2) solution with potassium thiocyanate as the indicator. .4n aliquot of the water sample was acidified, and a small amount of ammonium persulfate added to oxidize the iron. The solution was then boiled for 2 minutes, cooled to 50' to 60' C., and 5 ml. of 40% potas-
yanate added. If less than iron is present, the titration is riiadc with 0.0036N Trilon 13, a t 0.1 to 5 nig. of Fe, O.OlN, and a t more than 5 mg., 0.05S. The following ions a t coricentrations indicatcd do not interfere: aluminum, 10 p.p.ni.; niangsnese, 10 p.p.m.; zinc, 50 p.I;.ni.; calcium and magnesium, 100 1i.p.m.; phosphate, 35 p.p.m.; sulfate and chloride, 1000 p.p.m. Ilndcrwood (S5C) determined fractional milligram amounts of Fe+ in 100 nil. of solution by titrating with ethylenediaminebis(o - hydroxyphenylacetic acid). The titrations were made in acid (pH 3) solutions and thp end point detected photometrically. Many metals do not interfere. Microgram amounts of iron were determined by reducing the sample volume and titrant concentrations; larger (milligram) amounts were determined by changing to a wave length of lesser sensitivity. Small quantities of manganese were determined photometrically by Bankovskis, Ievins, and Luksa (SC) by measuring the absorbance of the stable complex formed between manganese and 8-mercaptoquinoline (thioxine). The complex, insoluble in water, was extracted with benzene, chlorobenzene, toluene, or xylene, and the absorbance a t 413 mp compared with standards. Alkali and alkaline earth metals and aluminum, chromium, zirconium. thorium, titanium, and lanthnriurn dv not interfere. The addition of potassium cyanide masks interference caused by iron, cobalt, nickel, and palladium. Lead, zinc, cadmium, titanium, vanadium, and tin interfere and require removal bpfore determining manganese. Manganese from 0.05 to 8 p.p.m. was determined by Karanovicli (ISC) by visual colorimetric comparison of standards and samples treated with saiicylalo-aminophenol. An aliquot of the sample was treated with 10% ammonium chloride solution, 4 drops of a o.05y0 alcoholic solution of the color-forming reagent, and 0.2 ml. of 2074 sodium hydroxide. Ten minutes later, 0.3 ml. of 4oy0 formaldehyde was added and the color comparison made immediately. Alkali metals do not interfere nor do the following, provided their concentrations do not exceed that of manganese by the amounts indicated : arsenic, cadmium, 200: 1 ; silver, molybdenum, 100: 1; zinc, aluminum, and mercury 50:l. Chromium and barium a t 100:1, and iron, nickel, magnesium, and barium a t 50: 1 can be tolerated if their effect is masked by Seignette's salt. If lead is present, the determination can be made only in strongly alkaline solution. In this case, the sensitivity is greatly decreased and cobalt and copper interfere. Yuen (38C) determined traces of manganese by oxidizing M n f 2 to hfnO4- with potassium periodate, and measuring J
the absorbance at 620 nip of a malachite green solution formed by permanganate oxidation of the rcagent, leucomalachite green. The dct~rrninationof both manganese and iron by atomic absorption spectroscopy was described by Allan ( I C ) . The iron line a t 2453.3 A . and the manganese line a t 2794.8 A. \wrc the most sensitive. Two polarographic procedures for determining manganese have recently been reported. Catherino and 1Ieites (4C) measured the diffusion current of the anodic wave of Mn+Z in a sodium hydroxide-sodium tartrate solution. The polarographic measurement n n s made after controlled potential eleetrolysis of the sample solution, a step necessary to ensure conversion of all manganese to the $ 2 oxidation state and to remove or render innocuous other possible interfering ions. The method was claimed to be sinil~le,accurate, and specific. Manganese a t concentrations of from 2 X 10-4 to 7 X 10-3.V (about 10 to 400 p.p.m.) r i a determined by Issa et al. ( 1 3 0 . They oxidized l l n to hIn+3 and stabilized the higher oxidation state with the addition of triethanolamine. They found a straight line relationship between measured diffusion current and concentration over the concentration range noted above. A committee of the American K a t e r Works Association recommended a method for determining total chromium in xatcr, particularly in m t c r containing an appreciable amount of organic mattcr ( I J C ) . The method involves reduction of hcsnvalent chromium ivith sodium sulfite, destruction of organic matter by evaporation to fumes with concentrated nitric acid, and finally reosidizing chromium with a slight excess of permanganate. Excess permanganate was destroyed rvith sodium azide, the chromate reacted with diphenylcarbazide, and the resulting color compared visually with standards treated identically. Alternatively the absorption may be measured photometrically a t 540 mp. A reagent blank is required. At 0.15 mg. of chromium per liter the average deviation is 1070, but may approach 20 to 40% a t lower concentrations. Rlercury, iron, and vanadium interfere under certain conditions. Kravtsova (1SC) determined chromium colorimetrically, both visually and photometrically, with carmoazine reagent. This reagent, the disodium salt of 2-(sulfo-l-naphthylazo)-l-naphthal4-sulfonic acid, permits visual detection of 3 pg. Gf chromium per liter and photocolorimetric detection of 0.2 pg. per liter. The photocolorimetric error was *2%. No other ions interfere. The sensitivity of the 1-naphthylamine method for chromium may be increased VOL 33, NO. 5 , APRIL 1961
143 R
(arc)
tenioid; a c c o i h g to Polyanskii by cstracting the colored complex with isoamyl alcohol. The sensitivity of the tieti:rmiriL:tinn i m s 0.1 ing. of chromium per liter. f)ackhani (MC) made an evaluation era1 absorptiometric methods for aluminum, ineluding hematoxylin, Alizarin Red S, and aluminon methods. The hematoxylin method was considered unsatisfactory because of the variation in sensitivity with aluniinum concentration, although its sensitivity was very good for low concentrations of aluminum. The Alizarin Red S method lacked sufficient srrisitivity bui. was satisfactory in other r c q r c t s 'l'he aluminon method as pruposed by Pclole and, Segrove (2SC) was recommended as having the best over-all accuracy and sensitivity. Packham suggested certain niodifications in the Poole and Segrove method, including a provision for removing fluoride interference. The aluminon method was also studied in detail by Shull ( S I C ) , and modifications and improvements were incorporated to improve its accuracy, sensitivity, and reproducibility. The improved method provides for elimination of interferences due to ferric iron, chromium, fluoride, and metaphosphate ions. Glycolic acid was added to inhibit interference of iron, normal phosphate, chromium, titanium, and certain other ions and an acid-fusion was included to eliminate fluoride and metaphosphate interference. Alternatively, metaphosphates may be destroyed by boiling with sulfuric acid. Up to 10 mg. of sulfite per liter and up to 0.5 mg. of chlorine per liter caused no interference. Sulfite and chlorine in excess of these concentrations were removed by t r y t m e n t with hydrogen peroxide and sodium thiosulfate, respectively. The limit of detection was 0.02 p.p.m. Methods for determining aluminum anti phosphate in surface water wvre described by Entz (SC). Using an aluminon procedure he determined from 12 to 33 pg. of aluminum per liter in lake and stream samples. Both iron and aluminum were extracted from a large volume of sample solution and determined simultaneously by Motojima and Hashitani (2SC). Three milliliters of 1% 8-quinolinol solution in acetic acid were added to an aliquot of sample containing not more than 100 pg. of iron nor more than 50 pg. of aluminum. Extraction was made with chloroform a t p H 5.2 to 5.5 and absorbance measured a t 470 mp (iron) and 390 mp (aluminum). Guerrcschi and Romiat ( E )prepared empirical correction curves for simultaneous spectrophotometric determination of iron and aluminum by the hematoxylin method. The curves were applied to total concentrations of iron and aluminum up to 0.30 pg. per ml. Iron and aluminum in sea water were 144 R
ANALYTICAL CHEMISTRY
determined s i m u l t a n ~ o i iby ~ ~iIashitani ~ and Yamanioto (10 what lengthy procetii ment of a 1-liter e:mpic~ with hydrochloric acid and herj.ilium sulfate solution, filtration, and addition of a 1% solution of 8-quinoliriol to a portion of the resulting filtratix. After adjustment of the 211 to 5.0 t u 5.5, the8-quinolinolates of iron, aluminum, copper, and nickel wero removed with potassium cyanide soiution and the absorbance of the orgmic phase measured a t 390 and 470 mp. (~onccntrationsof aluminum and iron in sea water samples ranged from 5 to 252 pg. per liter and from 4 to 156 pg. per liter, respectively. As little as 0.04 pg. of aluminum per liter was detected by Ishibashi, Shigematsu, and Xishikawa (1%') using a fluorometric method. They added 0.1% Pontnclirome Blue Black R solution and :rmmoniuni ac aliquot, adjusted the pH of the solution to 4.8 with sulfuric acid or ammonia, warmed the solution for 10 minutes, eoolcd it, and measured its fluorescence with a fluorimeter having a 600-mp filter. Calcium, strontium, magnesium, beryllium, indium, manganese, fluoride, and phosphate do not interfere. Gallium causes positive errors and cobalt, vanadat,e, and large amounts of copper, titanium, and nickel cause negative errors. Ferric ion cannot be tolerated. Eshelman et al. (SC) combined organic extraction with flame photometry to determine aluminum in a variety of nonferrous and ferrous alloys and in minerals. The sensitivity of thr method is such, however, that it would seem suitable also for determining aluminum in water. Aluminum mas extracted either from an acetate buffered solution adjusted to pH 5.5 to 6.0 with a 0.1111 solution of 2-thenoyltrifluoroacetone in 4-methyl-2-pentanone; or from an acetate buffered solution a t pH 2.5 to 4.5, containing N-nitrosophenylhydroxylamine (cupferron) in 4methyl-2-pentanone. Aspirating an organic rather than an aqueous solution of aluminum into an oxyacetylene or oxyhydrogen flame, resulted in a 100-fold increase in the emission intensity. Both the 396.2-mp line and the oxide band head at 484 mp were used for flame intensity, measurements. The detection limit was about 0.5 pg. per ml. COPPER,
ZINC, CADMIUM, BISMUTH, LEAD COBALT, A N D NICKEL
Two methods for determining microquantities of copper, lead, and zinc, in natural waters were described by Miller and Libina ( 2 5 0 ) . One method was based on the differences in solubilities of copper, zinc, and lead diethyldithiocarbaminates in hydrochloric acid of varying concentration. The other method was based on carbon tetrachloride extractions of dithizone com-
p l e m of these metals h i l i i soIutioi,> oi varying pIt1. lii this metal ditliizop.it,rs w w with carhim t: t: ,ichlmdt! h m weakly ammoniacai soiutiun iii tt .e prcwnce of ammonium citrx e . Lead anti z h c were thcn riwxtraiteii ivith u.01 t o o.mlY hydrochloric n(id and copper ticti,rmined in tlic oi~ganic j ! l ~ s e . 'I'lie - ( T w +matle aikalinc a n d was t h > n aslticd f:, wturn tu the aqueous lu! ~ r .'i'iita nlethod car! Le adaptPd for fie1i.i iise. The I J W of zin diethylditliiocarbaIi~~~te as a si,lcctiv?
per milliliter M ith no iiiterferrnre from iron, mang:lnrde, cob:ill, riirkt,i, or silver. In their stuclim (111 the anai>.ticu! applicatioris of coniple~ons, 1I:irtiI:ez and lleiidoza (P2Dj investiqatcd 1.2.d i a m i r i o c ~ - c ~ l o h e x a n e - t e t r ~ a c r ~acii: ~~(~ (ADCT) as a reagent for ropiwr. Riley :tiit1 Sinhaseni W L i i detrriuinerl copper in sen water and othcv by reducing copper with hydro hydrochloride and extracting t 0.037, biquinoline in hexanol. To the combined extracts \\-as added a am:-il amourit of 1yo hydroquinontb in ali-oh01 and the solution dilutrd t o volunic n.ith hexanol. Absorban!:e at 540 nip was compared with known solutions g i v a identical treatment. The use of dialkyl nnd dinryi dithiophosphoric acids as andytitxi rcngc!its has been investigated by Euaev and Ivanyutin ( 5 D ) . !,-sing the Iiotnsaiurn salt of diethyl dit~iioI)lios!,hc,ric. acid, they were able to detcrininc 0.Gl.i to 0.1 pg. of copper in the presrriw of other metals. Sicke; diethyl dit'niol,tios!)liats was used by Busev and Ivany1,itin (O'D,; as a very srlcctive and sensitive rc:igent for copper. To tl,~ti~riiiil!e copper in water, they acidjSt-;i 3. 1- t o Biitt,r sample arid ext,mctcti rirrec tirnes wit15 small portions of (.arb and 0.005111 nickei die phate. They were able b\J tietermhe 0.01 pg, of copper at H di!l:tioii of i to 109. AleskoLskii c t al. i2Di an,; . \ I R ~ K ! ~ skii, Miller, and Sergeev ( S D ) b?\-t.!%,ped a field method for conccntratiiig ('CqIFJV?, zinc, silver, and lead, by aciPtirjition on finely divided cation t~schunccniaicrial. Twenty grams of acid-trt7atc.d cation exchanger, Al&. 5Si02,nIIQ0, of particle sine 0.10 to 0.15 mm., w-cs dispersd in 1 liter of sample. Aftcr 20 niinutw the sedirnented particles were scparatcd, washed with 15% hydrochloric. acid anti hot water, and the heavy mrtals dPtermined in the wash liquid by colorimetric methods. They were able to drtermine microgram quantities of these elements. Aleskovskii, Libina, and Alillw ( I D ) also described a laboratory procedure
for concentrating cqmer and lead frcni wati'r with a cation exchange resin. 'The sample was passed through R 50 X 30 mm. coiwrin, coiitaining 1-min. diiirieirr resin, at a rate of 0.6 to 1.0 liter per hour, The adsorbed r-ations were olutcd wit,h hydrochloric a i d :md hot water and the cluatc: evalmnted to near d r y n ~ s sbefore determining lead and copper bj' conventional metiiods. >largerum and San!*icana (2lD'i evidudted several nicthods for deter1ni;iing micro aniounts of zinc in t,he presence of other heavy met'szls. They mended wparation by rvdracting dithieone and the use of bis(2xyetliyl)dithiocar},arnate as a iriasking agent. In this method, zinc is present oniy as the dithizonate and not :as a mixture of two ron:plexes. Zinc, a t cconccntrations of less than 6 p.p.m., was idi+xninid b j Platte and Blarcy iP6D) u s i ~ gZincon !2-carbesy-2'-hy&oxy 5' su1fof~)rmazylbcrizene). C:adniium and manganese interfere to some extent, but most other heavy netals do not. Houghton ( 1 4 0 ) deter.nined 0.5 to 3 p.p.:fi. of zinc in water by a method based 011 tmhereaction of zinc 7,vith Brilliant Green in an acid solution containing thiocyanate. As much as 10 p.p.m. of aluminum and l e d , and 3 p.p.ni. of copper and iron offer no interference. Gusev and Bitort ( l 2 D ) described a iirphelometric method for determining :IS little as 0.09 pg. of zinc per rniiiiliter In water, based on the stable turbidity formed with tiiantipyrylmethylmethane. Popova (26D) determined lead and zinc poiarograyhically after concentrating these and other heavy metals in the field :it the timr. of collecting the sample. Cor;centration w s accomplished by c-,opr"il)itatioii n-ith calcium carbonate, a technique 7,vhirh afforded complete recovery of lead and zinc providing their concmtrations did not exceed 1.5 mg. j)er liter. The calcium carbonate prsci;)itate was dissolvtxd in nitric acid and lead and zinc determined polarographically, lead directly, and zinc: after separation of the lead. The sensitivity of the method was 0.02 mg. per liter. A rapid screening test for cadmium in potable water was described by Lieber (lUU\i. L)ithizone reagent was added to t)he samples and the color compared with standards containing 0.1 to 0.4 p.p.ni. of cadmium. Hexavalent chromium caiises no interference; copper and nickel cause a darkening of the cadmium-dithizonate color. A spectrophotometric method sensitive to 0.05 p.p.m. of cadmium was described by Chavannc and Geronirni (,?Oi. The reagent. 3-(pnitrophenyI)l- phenyla azo phenyl) triaz formed a stable cadmium complex mhose absorption a t 560 mp obeyed Beer's law iip to 0.6 p.p.ni. of cadmium. Cyanide and several cat,ions, especi:ily mercuric
-
-
Arid silve! inn?, interfere to aoiiic extent. Lazarev and iazareva (18D1 vsed Rhodamine il 'co dQterrnine 0 t o 0.6 pg. of zinc per milhhter. The metlmd, based on thr, reaction of cadinium iodide with Rhodamine B t o form CdL jC2B113103N2jb R i not specific Cot* cadmillin znd requires mdtiple dithizone &?ai +ions to separate cadmium from other heavy metals. Interference due to iron l,va$ eliminated by adding ascortric acid. -4 Daper chromatographic separation and &.termination of small aniouds of cadmium w a ~reported by Hermanowicz and Sikorowka (1SDl Gilbert (80) found that the flame photometric detecstion limit for cadmium in a hydrogen& flame was 0.1 p.n.m. using a Brchman Ill' ~pectrophotometcr n i t h photOmiikiT~1i?r attachment Qnantitatire determinations n-ere made by direct comparison of succeqsive dilutions of qample and standard cadmium ~ o l u tion. Interference effects of w w a l ions. including aluminum. iron, copper, and calcium, mere studicd. Jacobs and I'oe (16D) di'wibed the use of S A7'-bis(3-dimeth~laminopropy1Mthiooxamide to simultaneously determine microquantities of copper, cobalt, and nickel. The complexes were formed at a pH of 9.0 + 0 3 by adding 3 ml. of 1.5 X 10-3Jf reagent solution to a sample aliquot and diluting to 25 ml. Thirtv minutes ner? required for maximum rolor development. ilbsorbance wvns measured a t 365, 430, and 500 mp. Molar concentrations were calculated from the measured absorbancies and a series of simultaneous spectrophotometric equations. Palladium interfere., and iron and manganese must be absent. 3lcDowell et a2. (2OD) found that the use of xylene instead of chloroform to extract, the nickel-4-isopropyl-1,2-cycloIiexanedionediouime compleu refidts in significantly increased senGti\ itv in the spectrophotometric determination of nickel. They determined cmcentrations of nickel from 0.005 to 100 p.p.m. in water and other materials. Iron, cobalt, and copper interfere seriously and require special treatment :or niasking or removal. Blund\ and Simpson (40) used the snme chelating agent but used toluene as the orqanic eutractant. Methods for determining nirkel with dimethylglvoxime have been reported by Gregorowicz (IOD) and bv Nieto (24D). Cobalt concentrations from 0.3 to 2.0 p.p.m. were determined by Gupta and Sogani (21D) b j iiieans of the highly selective and spnsitive reagent, sodium-p-(mercaptoacetamido) benzene sulfonate. With cobalt, this reagent gives a stable water soluble complex in the pH range 6.5 to 7.5 with peak absorbance a t 475 mp. I t pH 8.5 to 11.0 a brown complex is formed which has an
~Lbsorptioi~ ninsiriiuni ztl 390 011.1. The systerii (ibrys Iker's law over the concentration range cvitcd and is not infliicnced by the presence of 300 p.p.ni. of aluminum, 200 11.p.m. of zinc and maiiganese, 150 p.1i.m. of coypcr, iron, ~hromiuni,silver, tuiigstt'n, and molybdenum, 2nd 5 p.1i.m. of palladiuni. The use .of the p-nitrophenylhydrazone of iiiacetyl monoximc to determinc microgram amounts of cobalt war; reported by Goldstein and k2spiiioia (BD) and by H u et ctl. j l j U l . A number of elements w r ( ' obsi'rvid to interfere. Khaiifa ( 1 7 D ) desrribed 9 method for determining 0.1 to 1.0 p.p.m. of bismuth tising the reddish violet color of the coiiil~lex formed between biqinuth and thc azo dye, Fast Gray RX. Several cations interfere with the method. MOLYBDENUM, VANADIUM, TITANIUM, AND ZIRCONIUM
X method for deterniining molybdenum in sea arid fresh water has been dewloped by Sugawara, Tanaka, and Okabe (13E). Molybdenum from as much as 5 liters of water was collected by coprecipitation lvith hydrated manganese oxide. The sample was warmed to 70" to 80" C., acidified with hydrochloric acid, neutralized to bromocresol purple with 4N sodium hydroxide and buffered to p I i 3.8 Fyith acetic acidsodium acetate. Small volume.: of manganous sulfate solution and permanganate solution were added with vigorous stirring and the solution heated to 80" C. to hasten coagulation. After cooling and filtering, the collected precipitate was dissolved in a small volume of 2 N hydrochloric acid containing 1 ml. of 1% hydrogen peroxide. The solution was then boiied gently to affect complete solution of the residue and to remove most of the excess HLh. To the cooled solution, 1 ml. of 10% sodium sulfite solution was then added to reduce ferric ions and to further destroy any remaining H20,. Complete removal of H20z and ferric ions was accomplished by adding a small volume of 10% potassium iodide solution and the liberated iodine driven off by heating on a water bath. The final solution volume did not exceed 15 ml. Two milliliters of concentrated hydrochloric acid, 2 ml. of ferrous ammonium thiocyanate solution, and 3 ml. of stannous chloride solution were added and the solution stirred T;igoroiisly. hlolybdenuni thiocyanate was then extracted with two small portions of a 1 to 4 mixture of butyl alcohol and ch!oroforni. The volume of the conibined extracts was adjusted to 10 nil., a few milligrams of solid stannous chloride added to prevent oxidation of ferrous ion, and absorbance measured a t 475 mp and compared with standards. Kuznetsov, Loginova, and Myasoedova (6E) concentrated molybdenum VOL. 33, NO. 5, APRIL 196
naphthol. As little as 10” grams of stannous tin may be detected under proper conditions. These reagents are highly specific for tin. Tin, from 0 to 2.0 pg. per liter, was determined spectrophotometrically by Ishibashi e.! al. (BG), by a n improved phenylfluorone method. Increased reproducibility of color development was observed when tartaric acid was added to the samples. The spectrophotometric determination of germanium with g-(p-dimethylaminophenyl) - 2,3,7 - trihydroxy - 6
-
fluorone was reported by Kazarinova and Vasil’eva (8G). Kononenko and Poluektov (QG) examined the characteristics of four dihydroxy-chromenol dyes as possible reagents for determining microgram quantities of germanium. They reported that the most suitable reagent was 6,7-dihydroxy-2,4-diphenylbenzopyrylium chloride, which in 0.1N hydrochloric acid permits determination of 0.01 to 0.25 pg. of germanium per milliliter. Shakhova and Motorkina (11G) developed a method for determining 0.001 to 1.0 mg. of germanium dioxide, in not more than 10 ml. of solution. ?‘he method is based on the extraction of the germanomolybdic heteropoly acid from acid solution. Several extractions with isoamyl alcohol are required. When arsenic is also present, both heteropoly acids are extracted with a butyl alcohol-ethyl acetate mixture and a later addition of chloroform to this extract returns the germanium complex to the aqueous phase while the arsenomolybdic heterpoly acid remains in the organic phase. A final series of extractions with small portions of isoamyl alcohol permits complete recovery of the germano-polyacid. Absorbance is measured at 428 mp. A polarographic procedure for determining less than 0.4 m o l e per liter of germanium was described by Stashkovs and Zelyanskaya (IdG). Methods for determining gallium, indium, and thallium, and for separating these elements from interfering elements, were discussed by Cherkashina and Vladimirova (JG). Their review of. the analytical chemistry of these elements included a list of 118 references. Karanovich, Ionova, and Podol’skaya ( 7 0 determined 0.04 pg. of gallium per milliliter by extracting, from hydrochloric acid solution of p H 2.4 to 3.2, the blue complex formed by reaction with gallion. Amylacetate or isoamyl alcohol was preferred as the extractant. Interference due to ferric and cupric ions was eliminated by the addition of hydroxylamine and thiosulfate, respectively. A fluorometric method, based on the fluorescence of the reaction product of gallium with 2,2’,4’-trihydroxy - 5 - chloroazobenzene 3 - sulfonic acid, was described by Lukin and Bozhevol’nov (IO@. Fluorescence intensity depended on the kind of medium, water or isoamyl alcohol. I n water the sensitivity was 0.01 pg. in 5 ml. and in the alcohol 0.005 pg. in 5 ml. Gilbert (6G) determined 10 to 250 pg. of indium with a precision of 1.0% or better by flame photometry. He RCommended the indium line at 4511 A. and an oxygen-hydrogen flame as being most suitable. With a Beckman flame photometer equipped with a photomultiplier radiation detector, he observed a detection limit of 0.01 p.p.m. of indium. Emission a t 4511 A. was
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VOL. 33,
NO. 5,
APRIL 1961
147 R
directly proportionid to concentration up to 100 p.p.m. RARE EARTHS, URANIUM, A N D THORIUM
Flame photometric nwthods have recently been proposed for determining lanthanum and the rare earths. A review of the analytical behavior of these elemerits in the flame, illeluding 131 references, was recently prppared by Dvorak and Rezac ( 2 H ) . Menis, Rains, and Dean ( i f f determined ) lanthanum by mpasuring its flame emission intensity at 743 or $90 mk. At thwe nave lengths the interferences of a number of elmients nere found to be sonien hat less than a t shorter !save lengths. The use of an alcoholic medium also increased tolrrance for diverse ions. Analysis bj nicans of the standard addition technique was recommrnded. These same investigators (5”)have also reported a method for determining niicrogrnrii quantities of lanthanum by selective extraction n i t h a 0.1-1f solution of 2-theno~-ltrifluoroacetone in 4-methyl-%pentanone and determining lanthanum in the organic phase by flame photometry. The extraction was best accomplished from a 1Jf acetate solution buffered a t pH 5 . Of 18 elements tested, only titanium and aluminum were found to interfere when present in amounts greater than the lanthanum. Fluoride and phosphate prevent extraction of lanthanum. The emiwion intensity of the 743-mp band was 100-fold greater in the ketone solution than in an aqueous solution, and a sensitivity of 0.050 pg. of lanthanum per milliliter per scale division was achieved. Rains, House, and Menis (8fI\ investigated the flame spectra of scandium, yttrium, and the rare earths (except cerium and promethium) using the same extractant and solvent. A recording spectrophotom4 e r was used to determine the wave iength 2nd relative intensities of the several spectral lines and bands of these elements. Smith and Chandler (IOH) developed a field method for determining uranium in water in connection with geochemical prospecting. At p H 6, uranium forms a yellow complex with dibenzoylmethane. This complex was extracted with CCla and the color intensity compared nith standards. By this simple procedure, they were able to detect 1 kg. of U308. A field method for determining uranium transfer forms was devised by Yakuleva and Shurshalina (IbH). The method involved dialysis through a semipermeable membrane, dipping the membrane containing the water sample into a beaker of distilled water until equilibrium concentrations were attained on both sides of the membrane. Two days were required for dialysis. By analyzing the solutions a t equilibrium conditions, it was possible to
148 R
ANALYTICAL CHEMISTRY
determine whether the uranium in the samples was in mechanical suspension, colloidally dispersed, or present as ions. Another field method based on fluorescence of uranium fluoride, was described by Milner and Barnett ( 5 H ) . A I-ml. sample, Containing a t least 1 fig. of uranium per liter, was filtered, acidified, and evaporated to dryness on a fluorimeter dish in the presence of magnesium and acetic acid. The residue was then fused with 0.5 gram of Na2C03-SaF-K2C03 flux and t l i ~fluorescmre of the fooled flux compared with similarly prepared standards. To determine as little as 0.1 pg. of uranium per liter, a 100-ml. eample nas evaporated, the residue dissolved, and the pH adjusted to b e h e e n 6 and 7. EDTA was then added and the uranium e-+ tracted aq the 8-quinolinol complex in chloroform. A portion of this extract was then taken for the fluorometric determination. The use of 8-quinolinol as a spectrophotometric reagent for uranium was further described by Motojima, Yoshida, and Izawa ( 6 H ) . They found that uranium S-qninolinolate could be quantitatively extracted from slightly alkaline solution by chloroform. Absorbance of the solution follows Beer’s law for 2 to 40 pg. of uranium per milliliter of chloroform. Up to 100 pg. of many metallic ions do not interfere. Shibata ( 9 H ) proposed I-(2pyridy1azo)-%naphthol as a colorimetric reagent for uranium. This reagent forms a deep red precipitate with uranium in ammoniacal solution. The complex can be extracted with chloroform if sodium chloride or sodium sulfate is first added to the solution. The chloroform extract of the complex was stable and its color obeyed Beer’s law. The addition of EDTA or cyanide eliminates interference of many diverse ions. Pollard, Hanson, and Geary (7H) synthesized 4-0-pyridylaso) resorcinol and investigated its uses as an analytical reagent for determining uranium, cobalt, and lead. They found it to be the most sensitive R ater-soluble reagent for the colorimetric determination of uranium, as well as the first published water-soluble reagent for lead and the most sensitive reagent known for determining cobalt. A polarographic method for determining uranium in natural waters was described by Starik and Starik (1111). The method permitted determination in the range of 2 X to 8 X 10-4ill concentrations with a precision of *2%. The electrode reaction involved reduction of uranium(V1) to uranium(1V) in hydrochloric acid solution. Lead, aluminum, the alkali metals, and phosphate do not interfere with the determination. Vanadium in concentrations exceeding 10% of the uranium concentration does interfere: such solutions
require modification of the method to determine uranium accurately. They found that the reduction of uranium (IVj to uranium(II1) was not satisfactory for the polarographic determination of uranium. Thorium was determined spectrophotometrically by Alimarin, Golovina, and Kuteinikov ( I H ) using quercitin as the color forming reagent. Thorium, but none of the rare earths, forms a colored compound nith this reagent. The yellowish green complex is soluble in n ater-alcohol mixtures or it may be extracted a i t h isoamyl alcohol, butyl alcohol, or amyl acetate. The organic extraction serves to separate cerium from thorium, when this is necessary. The sensitivity of the method was 0.1 pg. per ml. The presence of a 16,000-fold excess of the rare earths does not interfere. B O R O N A N D SELENIUM
The Standard Methods Committee ( 7 4 of the American Water Works Association recommended two methods for determining boron in water, sewage, and industrial wastes. A colorimetric method, using curcumin, requires only 1 ml. of sample, is useful for 0.10 to 1.0 mg. of boron per liter and may, with modification, be adapted to the determination of from 0.025 to 0.20 mg. of boron per liter. The second method, based on an electrometric titration of the complex acid produced when mannitol is added to a neutral solution containing borate, is suitable for determining 0.10 to 5 mg. of boron per liter with a high degree of accuracy. The Committee’s report includes details of both procedures. A method for determining boron with 1,l ’-dianthrimide was described by Rainwatm ( 9 J ) . The method uses the color change, from greenish yellow to brilliant blue, which occnrs in a concentrated sulfuric acid solution containing boric acid and 1,l’-dianthrirnide. The reaction, extremely slow a t room temperature, is complete in 3 hours a t 90” C. Kitrate and bicarbonate, or carbonate, interfere but are satisfactorily removed by evaporating the sample with concentrated sulfuric acid, a step that is necessary anyway, because of the limited solubility of dianthrimide in sulfuric acid containing traces of moisture. Recovery tests made on samples of varied composition and containing from 0.20 to 1.05 mg. of boron per liter indicated a standard error of 0.012 mg. per liter. Danielsson ( 6 4 conducted a systematic investigation of the influence of several analytical factors on the dianthrinlide determination of boron, including sulfuric acid concentration, reagent concentration, boron concentration, and reaction temperature. Suitable conditions were: dianthrimide 0.4 mg. per ml., sulfuric
source emitting light in the region of use of a barium chloride-tartaric acid acid 93 to 95% by weight, boron 0.3 to 420 mp and fluorescence measured at reagent as a means of separating and 1 .O pg. per ml., and a heating time of 1 550 to 600 mp. Cp to 0.5 pg. of seledetermining boron; barium borotarto 1.5 hours at 100" C., or 4 to 5 hours nium was determined with a qensitivity trate is insoluble in ammoniacal solua t 80" C. These conditions were not of 0.02 pg. tion. The precipitate was dissolved necessarily critical and some deviation and the boron determined indirectly by could be tolerated without loss of preeither a colorimetric estimation of cision or sensitivity. CHLORIDE, BROMIDE, AND IODIDE tartrate or a flame photometric estimaCallicoat and Wolszon ( 4 J ) made a tion of barium. The first method n a s critical study of factors affecting the satisfactory for 10 to 180 pg. of boron A new adsorption indicator method determination of boron with carminic while the second method gave satisfor determining salinity of sea water acid and described a procedure for deterfactory results on 4 to 20 pg. A fluowas described by Van Landingham mining 0 to 40 pg. of boron in a rescence method, based on the fluo( 2 3 K ) . Ohlweiler, Meditsch, and maximum of 250 ml. of aqueous solution. rescence of the boronresacetophenone Kuperstein ( I 9 K ) made a critical The recommended procedure gave a n complex, was used by Rao and Apevaluation of several modifications of accuracy of 1 0 . 3 pg. of boron on standthe Volhard method for chloride. For palarju (IOJ)to determine up to 7 mg. ard boric acid solutions. Callicoat, of boric acid per liter in aqueous soluroutine analyses, they recommended a Wolszon, and Hayes ( 5 4 evaluated a tions. modification involving addition of nitromixed resin bed ion exchange technique A procedure for the microdeterminaphenol to the titrated solution. far separation of milligram quantities of tion of selenite was described by The advantages of niercuro- and merboron prior to its determination by the Schulek and Barcza (12J). At a p H curimetric methods for determining carminic acid procedure. They found of about 5 and at room temperature, chloride have been emphasized by that, with a strong acid cation eschange selenite was reduced to colloidal metallic several analysts. Beskov and Slizkovresin and a weak base anion exchange selenium by ascorbic acid, any excess skaya (3%) recommend three methods: resin, the precision obtained on simple or of which was oxidized by bromine. The titration with mercurous nitrate, with complex samples falls within the probmetallic selenium was then dissolved in either ferrocyanide or diphenylcarable error inherent in the carminic acid a potassium cyanide solution, the excess bazone as indicator, and titration with procedure. The accuracy was to some cyanide removed by boiling, and the mercuric nitrate in the presence of extent dependent on the total salt conselenocyanide content of the resulting diphenylcarbazone. Interferences in tent of the samples and hence the prosolution determined by either the tungthe mercurometric method include cedure was most satisfactorily applied state or the distillation method. chromate, lead, zinc, sulfide, sulfate, to those samples whose total salt conA photometric method for determinnitrite, and bichromate. A mercurotent can be controlled. ing 5- to 1OO-pg. amounts of selenium in metric procedure was also described by Murata and Yamauchi (BJ) detersolution was described by Bode and Novikovskaya and Przhevalskii ( I 8 K ) , mined 0.5 to 10 pg. of boron in solution Mosenthin ( I J ) . They precipitated and a comparison of the mercurimetric by extracting the yellow complex formed copper selenide with hydrazine hydromethod with Mohr and Volhard methbetween boron and morin. The sample sulfate from a solution buffered a t a ods was made by Dannenberg ( 5 K ) . aliquot was heated in a platinum dish p H of 4.5 with ammonium citrate. Goldman ( 7 K ) described the use of a with sodium sulfate and evaporated to The precipitated selenide was dissolved modified indicator for the mercuriabout 1 ml. After neutralizing, hydroin nitric acid and the equivalent copper metric chloride procedure which facilichloric acid, oxalic acid, and morin determined spectrophotometrically with tates p H adjustment to the optimum were added and the solution again diethyldithiocarbamate. Silver and lead titration range and sharpens the dievaporated to a small volume. Acetone interfere, and cannot be tolerated. phenylcarbazone end point. The indiwas then added to the cool solution Limited amounts of gold, bismuth, cator was prepared by dissolving 0.25 and sodium sulfate separated. The mercury, molybdenum, tin, and tellugram of crystalline diphenylcarbazone, solution was then heated for 30 minutes rium do not interfere, and large amounts 4.0 ml. of concentrated nitric acid, and at 55" C. to drive off the acetone, of many other common cations do not 0.06 gram of xylene cyanole FF in 100 cooled, and the yellow product extracted interfere. R a y ( 1 I J ) determined trace ml. of 95% ethyl alcohol. Addition of with acetone. Exactly 10 minutes after amounts of selenium colorimetrically by 1.0 ml. of indicator to a 100-ml. aliquot extraction, the absorbance was measured reducing selenium compounds with hot of a potable water generally produces a at 425 mp. hydrochloric acid and hydriodic acid. Spicer and Strickland ( I S J ) described p H of 2.3 to 2.5, found to be optimum The selenium formed combined with three procedures for determining boron for the titration. The indicator color is the liberated iodine to form a colored in residues from distillates collected in blue-green at this pH, light green at pH solution whose absorbance was measthe usual distillation separation of less than 2.0, and deep blue a t p H above ured at 490 mp. Excess iodine was boron. The procedures are based on 3.8. The titration end point color is a removed by adding phenol to form, in the reaction of boron and curcumin definite purple. the presence of mercuric oxide, the under controlled conditions to form Kemula, Hulanicki, and Janowski colorless triiodophenol. The method either rosocyanine or rubrocurcumin. ( I I K ) described a colorimetric method is relatively rapid, accurate to within One of the procedures described profor traces of chloride in water. Di10% of the amount present, and suitvides for nearly quantitative conversion phenylcarbazone reagent and mercuric able for determining 5 to 50 pg. of of boron to rubrocurcumin and is nitrate solutions were added to a selenium. Of mvny possible interfercapable of detecting as little as 0.01pg. of slightly acidified sample and absorbance ing substances studied, only tellurium boron. Because these analyses were all of the solution measured after 30 minwas found to cause serious difficulty. utes. The relationship between abmade on distillates, most interfering Selenium was determined fluorosubstances had already been removed. sorbance and concentration was linear metrically by Watkinson (16J). Seleup to 60 mg. of chloride. A modificaFluoride, in any amount, interferes and nium was complexed with zinc dithiol, must be completely absent. Distillation of a direct spectrophotometric extracted into a 1:1 mixture of ethylene tion of microgram amounts of boron mercuric thiocyanate method was dechloride and carbon tetrachloride, and scribed by Ambuhl ( I K ) . The method without loss was discussed in detail by the fluorescence developed with 3,3'-diwas used for the determination of up Spicer and Strickland (14J). to 20 mg. of chloride per liter, with a aminobenzidine. A toluene extract of Bovalini and Piazzi (2J)and Bovalini, precision of 0.05 to 0.2 mg. per liter. the selenadiazole waa irradiated with a Pucini, and Lo Moro ( S J ) proposed the VOL 33, NO. 5 , APRIL 1961
0
149R
Ammonium ions, sulfate, phosphate, and nitrate do not interfere, although nitrite, mercuric, and ferric ions do interfere with the determination. The potentiometric field determination of chloride ion using a silver-silver chloride electrode was described by Back (ZK). The rugged electrode contains a billet of silver chloride, thus exposing a relatively large surface to the test solution, in contrast with earlier electrodes which expose only a small filament of silver chloride. Used with a standard calomel reference electrode and a sensitive p H meter, this electrode was adequate for rapid determinations of chloride with an accuracy well within the range required for field .determination. A simple, rapid, constant-current potentiometric titration procedure for determining chloride was developed by Freedman ( 6 K ) . Using polarizable platinum electrodes, he was able to determine low concentrations of chloride ion in either aqueous or nonaqueous media. Malmstadt and Winefordner (1OK, 17K) developed a new, extremely sensitive, precision null-point potentiometric technique for determining 0.03 to 30 mg. of chloride per liter of water. Samples of higher concentration may be analyzed by adjusting original sample volume. The procedure consists of rapidly changing the chloride concentration of a water sample until it is identical to the concentration of a known reference solution, while measuring the small differences in chloride concentration of the two solutions by the precision null-point potentiometric technique. The entire procedure including sample preparation, analysis, and calculations, requires only about l minute per sample. Interferences are the same as for standard argentimetric methods. Goldman and Byles (8K) suggested a modification of the standard phenol red method for bromide. The precision of the method, based on the oxidation of bromide and bromination of phenol red in the presence of Chloramine T a t a p H of 4.6 to 4.7, was increased by selecting an optimum time interval between addition of Chloramine T to oxidize the bromide and addition of sodium thiosulfate to reduce Chloramine T. Selection of optimum concentrations of reagents also improves the reliability of the method by eliminating fading of the color. A microdiffusion method for determining bromide and iodide in hot spring waters was developed by Koga ( I S K ) . Iodide in the sample was oxidized by sulfuric acid-potassium dichromate solution and the iodine allowed to diffuse overnight into an inner chamber containing a small volume of potassium iodide solution. Next, the bromide was oxidized by increasing the concentration of dichromate
150 R *
ANALYTICAL CHEMISTRY
and acid, and bromine similarly collected by diffusion into a new portion of potassium iodide solution. The iodine collected was determined colorimetrically with starch, and the bromine collected in the second step was determined by titration with 0.005N sodium thiosulfate solution. Iodide and bromide in oil field brines were determined spectrophotometrically by Collins and Watkins (4K). Iodide was oxidized to iodine with nitrite extracted with carbon tetrachloride, and absorbance measured a t 517 mp. After removal of iodine, bromide was oxidized by hypobromite, the liberated bromine extracted with carbon tetrachloride, and absorbance measured at 417 mg. The method was sensitive to 0.2 and 5.mg. per liter of iodide and bromide, respectively. Rossum and Villarruz (21K) modified the ceric sulfate-arsenious acid method of Lein and Schwartz (15K) and developed a procedure for the routine determination of less than 0.100 mg. per liter concentrations of iodide in water. Iodide ion catalytically accelerates the reduction of ceric sulfate by arsenious acid, the reaction rate being proportional to the amount of iodide present. The reaction can be followed by measuring the absorbance (at 420 mp) of the ceric solution. Substances normally present in natural waters do not interfere. Interferences in the ceric sulfatearsenious acid method were also investigated by Roychowdhury and Gyani (ZZK). They found that, in 10-ml. samples, the following did not interfere: 100 pg. of creatine-zinc chloride, 160 fig. of copper sulfate, 500 pg. of calcium chloride, 245 pg. of magnesium sulfate, 68 mg. of trichloroacetic acid, 500 pg. of urea, and 10 pg. of fluoride. Larger amounts of fluoride, however, interfered seriously. A polarographic method for determining iodide in ground waters was described by Przybylski (20K). Kishko and Shevera (1ZK) determined iodide in solutions spectrographically. They introduced the sample through the lower of a pair of copper electrodes, excited the sample with a low voltage spark discharge, and measured the intensity of the iodine line a t 5875 A. Golubeva ( 9 K ) determined iodide in water by extracting, with ethyl alcohol, the residue obtained by evaporation of from 1 to 3 liters of sample. The alcohol extract was made alkaline, evaporated to dryness, the residue dissolved in water, acidified, bromine water and potassium iodide solution added, and the iodine titrated with 0.001N sodium thiosulfate. Elaborate precautions were observed during initial evaporation of the sample to ensure complete removal of organic matter without loss of iodide. A micromethod for determining the iodide concentra-
tions in drinking water and other materials was described by Gustun (IOK). He titrated iodine with standard thicsulfate solution adding a few drops of phenol to bind any bromine present. Lei and Chou (14K) determined 0.1 to 1 pg. of iodide per liter in water by measurement of the absorbance of the iodine-starch complex. The complex, unstable in sulfuric acid, was stable when phosphoric acid was used to acidify the sample. Iodide was oxidized to iodate with bromine water, the excess of which was removed by the addition of sodium formate. The addition of potassium iodide reduced iodate to iodine. Chloride, bromide, and ferric ions do not interfere. F L U 0 RI DE
The zirconium-alizarin method continues to be widely used for determining fluoride in water. Visintin and Monteriolo (145) after a comprehensive literature survey, concluded that the zirconium-alizarin reagent alone, of those currently available, provides sufficient sensitivity and stability. They made a detailed study of the several analytical factors affecting sensitivity, accuracy, and reproducibility of the ,method. In preparing the reagent, a 2:1 molar ratio of sodium alizarin sulfonate and zirconium oxychloride (ZrOCl2.8H20) in 1.35N sulfuric acid gave best results. Depending on the Concentration of alizarin, the optimum acid concentration was found to vary from 1.05 to 1.80N. The color stability was greatest with 8 X 10-4M alizarin, 4 X 10-4M zirconium, and 1.351V sulfuric acid. They recommended measuring absorbance a t 525 mp. Complete color development is not reached in less than 18 hours, although only a slight error is involved if readings are made earlier. Samples should be kept in the dark during color development and the color density is greater a t 19' to 20' C. than a t higher temperatures; a correction of h0.02 mg. per liter per 2' temperature difference is required. The reagent color does not follow Beer's law. A number of commonly occurring cations and anions were found to interfere, causing values for fluoride to be low. They also evaluated two other fluoride methods but judged them to be less satisfactory than the zirconium-alizarin method. A modified zirconium-alizarin method was used by Tisserand (12~5)to determine fluoride in natural waters. The reagent was prepared in a mixture of equal volumes of 3N hydrochloric acid and 3N sulfuric acid. Any variation in the amount of acid used in preparing the reagent resulted in decreased sensitivity. Absorbance measurements were made a t 530 mp after 1 hour. Inter-
ference from sulfate, chloride, and iron was avoided by evaporating the sample to a small volume, acidifying with sulfuric acid, distilling the sample from silver sulfate, and analyzing the distillate. The method was successfully applied to the determination of from 10 to 100 pg. of fluoride per liter. Quentin and Indinger (1OL)examined several reagents for colorimetric fluoride determination including ferric ion, peroxytitanyl sulfate and several zirconium dye lakes including hemoto,xylin, purpurin, alizarin, and eriochromecyanine. They concluded that the last two yield the best absorbance curves and developed fluoride methods using each of these reagents. Vinnik and Chepelevetskii (1SL) developed a fluorometric titration method for determining 0.047 to 1.145 mg. of fluoride with a maximum error of 0.005 mg. Morin was used as an indicator in the titration of fluoride with 0.001 to 0.002N potassium aluminum sulfate solution. Koros (6L) determined 0.05 to 2.0 mg. of fluoride volumetrically by titration with thorium nitrate a t a p H of 5 to 6 and in the presence of Pyrocatechol Violet. The error was less than 5% of the amount present. A colorimetric method using resacetophenone and ferric ion as the reagent was reported by Lmng and Hsueh (8L). From 0.005 to 1.0 mg. of fluoride per 100 ml. was determined. Sulfide, bicarbonate, cyanide, titanium, and zirconium interfere. In 1OO-ml. samples, 0.1 gram of sodium chloride, 0.2 gram of sodium nitrate, and 2 mg. of sodium sulfate do not interfere. The advantages of lanthanum chloranilate as a reagent for the direct determination of fluoride in water and other materials were pointed out by Fine and Wynne (4L). With this reagent, a fluoride distillation is unnecessary and maximum color is developed in 30 minutes. Optimum fluoride concentration range is from 2 t0.200 mg. per liter. Brownley and Howle (SL)described a spectrophotometric method based on bleaching, by fluoride, of a thoriumphenylfluorone lake. Phosphate interferes when present in excess of 1 p.p.m. Interference of iron and other cations was minimized by passing the sample through a column of ion exchange resin. A similar method involving the lake formed with zirconium and pdimethylarni~ioazobenezenearsonic acid, was de\doped by Kamada and Onishi (6L) for determining 0.02 to 10 p.p.m. of Atioride. The zirconium-fluoride complex releases part of the organic reagent whose absorbance was measured, after filtering to remove unreacted lake. The absorbance was found to be constant for as long as 20 days, but did not follow Beer’s law a t the higher fluoride concentrations. Sulfide and thiosulfate
interfere if present in excess of 2 pap.m. The method was used directly in the analysis of rain, river water, and well water. T o determine fluoride in sea water and in springs, a preliminary separation by distillation or ion exchange was necessary. Szabo, Beck, and Toth (11L) determined fluoride by measuring the fading of a ferric thiocyanate solution. The thiocyanate complex was extracted with amyl alcohol to increase color intensity. Ten micrograms of fluoride could be determined in 50 mi. of sample. A conductometric titration method based on the reaction between fluoride and lanthanum ions was described by Kubota and Surak (7L). Milligram quantities of fluoride can be determined if the total amount of extraneous ions is small. The titration is best applied to the analysis of distillates. These authors also described a steam distillation assembly which facilitates complete separation of the fluoride with a minimum volume of distillate entirely frec of the acid used to volatilize the fluoride. A simplified zirconium-sodium alizarin sulfonate method mas described by Ashley ( I L ) . He found that an alizarin concentration of 0.01 mg. per inl. of lake solution containing zirconium and alizarin in equimolar ratio gave a reasonably deep color for spectrophotometric measurements with 5-cm. cuvettes. Absorbance readings within the p H range 2.86 to 0.66 indicated that the lake could be used a t fairly high concentrations of hydrogen ion, thereby minimizing the effect of free acid in steam distillates containing fluoride ion. Precise measurements, *0.05 pg. per ml., were possible over the range 0 to 1.9 pg. of fluoride per milliliter. T o determine 0.1 mg. of sodium fluoride in the presence of as much as 1 gram of sodium chloride, Moreno and Vila (9L) treated a residue of chlorides and fluorides with a 2:3 volume ratio of water and sulfuric acid and distilled off most of the hydrochloric acid. The rest of the hydrochloric acid was removed with silver sulfate and the fluoride determined as silicon tetrafluoride. Bellack and Schouboe (2L) developed a simple and rapid technique giving an accuracy within 0.02 mg. per liter in the fluoride concentration range of 0.00 to 1.40 mg. per liter. Sodium 2-(psulfonphenylazo) 1,8 - dihydroxynaphthalene - 3,6 - disulfonate - zirconium lake (SPADNS) is decolorized by fluoride, and the decrease in its absorbance a t 570 mp is proportional to fluoride concentration. Free chlorine interferes and must be removed by adding arsenite solution. Aluminum interferes, causing a decrease in absorbance within 15 minutes. When aluminum is present, the absorbance is not measured until after 2 hours,
SULFATE AND SULFIDE
Methods for determining sulfate in water generally fall into three categories: chelatometric titration, spectrophotometric, and indirect flame photometric methods. Xavone ( 1 4 M ) proposed a titrimetric method based on reverse titration of a n alcohol solution of k n o m lead content with the water sample being analyzed. An acidified solution of lead dithizonate is pink. Upon adding sulfate ions, or a water sample containing sulfate, lead is removed from the lend dithizonate and a deep blue color is observed. The titration is best carried out in a solution of p H 3. Calcium interferes and must be removed by a n ion exchange treatment. A direct titration with standard lead nitrate solution and dithizone indicator was used by Nechiporenko (16.41) to determine 0.5 to 50 mg. of sulfate with a n accuracy of 1 to 2%. The chloride content must be no more than seven times the amount of sulfate and the calcium Concentration no more than one third of the sulfate concentration. A simple method for determining sulfate was described by Mukai and Goto ( I S M ) . Sulfate was precipitated with barium chloride in the usual manner. The precipitate was then collccted, redissolved in a measured excess of 0.05A1 E D T A solution, and the unreacted E D T A titrated with 0.05M BaClt solution, using a metal phthalein as indicator. Large amounts of many diverse cations do not interfere. Rumler, Herbolsheimer, and Wolf (18M) suggested that the analysis could be speeded up by using triethanolamine, methanolamine, or sodium hydroxide, instead of ammonia to adjust the p H of the solution prior to the final titration of E D T A with barium. The reagent, barium(ethylenenitril0)tetraacetate, was used by Iritani and Tanaka ( 7 M ) as a precipitant for sulfate ions. The p H of a sample solution was adjusted t o between 9 and 10 with ammonium hydroxide and a slight excess of 0.01 to 0.05M barium-EDTA added. While heating the solution on a water bath, dilute hydrochloric acid was added slowly until a p H of 2.5 to 3 was reached. The resulting barium sulfate precipitate was filtered and washed, the combined filtrate and washings neutralized, an equal volume of ethyl alcohol added, and the excess EDTA titrated with 0.01M barium chloride solution, using metal phthalein indicator. Alternatively, the titration was made with 0.01M magnesium chloride, and Eriochrome Black T indicator. They determined 10 mg. of sulfate with a n error not exceeding 0.1 mg. Effenberger ( 6 M ) determined sulfate in water by D, chelatometric titration method using Cnlcein as indicator. VOL. 33, NO. 5, APRIL 1961
151 R
Calcium wis first determined by EDTA titration. To a second aliquot was added a n amount of 0.1N hydrochloric acid equivalent to the niet,hgl orange alkalinity of the N?-ater, plus a 5% excess. The sulfate was then precipitated as barium sulfatc with a measured excess of standard barium chloride solution. After filtering off the precipitate, the filtrate was made alkaline and titrated with 0.02M disodium EDTA with Calcein indicator. A mean deviation of +0.82% was observed. The interference of heavy metals was eliminated by adding potassium cj,anide and triethanolamine prior to the titration. Sulfate was determined spectrophotometrically by Babko and IIarkova ( 1 M ) using a ferric thiocyanate reagent made up in a pH 2.7 buffer solution containing p-sulfanilic acid and sodium carbonate. Two milliliters of the reagent was added to 0.5 ml. or less of sample, 5 ml. of acetone was then added, and thc absorbance of the solution a t 420 mp compared with st'andards. Fluoride ions interfere as do ferric ion concentrations in esress of 0.5 mg. per liter. These same authors also proposed the use of colored zirconium or thorium complexes for the colorimetric determination of sulfate (2M). A visual comparison method was described using the zirconium complex with Acid Chromium Blue K. From 1 to 60 fig. of sulfate in 2 ml. of sample was determined with a mean relative error of f10%. Alternatively, zirconium or thorium alizarinates were used. Increased sensitivity was achieved by extracting the complex with carbon tetrachloride or ether and by spectrophotometric measurement of the color intensity. Palaty (16111) described methods for sulfate based on measurement of the absorbance of the free indicator reagent, liberated by sulfate from its insoluble thorium or zirconium salts. Several indicators were suggested, including Pyrocatechol Violet for which a procedure was given. From 0.5 to 100 p.p.m. of sulfate were determined. He suggested removing interfering cations by treatment of the sample with a n ion exchange resin or in the case of iron, by reduction with hydroxylamine. Interfering fluoride and phosphate may be removed by precipitation as insoluble lanthanum salts. Iwasaki et al. ( 8 M ) determined as little as 0.02 p.p.m. of sulfate by adding solid barium chromate to the sample to precipitat'e the sulfate and then determining chromate in the filtrate with diphenylcarbazide. Alternatively, the barium chromate may be added as a hydrochloric acid solution, as a suspension in 0.5N acetic-0.0lN hydrochloric acids, or, for the determination of 0.02 to 5 p.p.m. of sulfate, as reprecipitctted, fine grained crystalline barium chromate. Phosphate and ferric ions 152 R
0
ANALYTICAL CHEMISTRY
interfere with the determination. A rapid method for determining sulfate, chloride, and nitrate in a single sample was described by Ceausescu (qJ1). The method is based on conversion, by cation exchange of all salts in the sample to t'heir corresponding acids, determination of total acid by titrating with sodium hydroxide, determination of sulfuric acid by titration with barium perchlorate, and, finally, determination of hydrochloric acid by titration with mercuric nitrate. Sitrate is determined by difference. Phosphate, if present, interferes. Detailed directions for carrying out the complete analysis are given. Indirect flame photometric methods for determining sulfate were described b y B u r r i r l , Ramirez-Mufioz, a n d Resach-M. de Lizarduy (3.11) and by Shaw ( I 9 M ) . Both procedures depend on the addition of a known volume of standard barium solution to precipitate the sulfate, and determining unreacted barium by flame photometry. Strontium may be used in place of barium. Podgornyi (17-11) described a procedure whereby sulfate, total strong acids, and total salt content of natural waters can be determined by means of polystyrene sulfonate cation exchange resins and by trilonometric titrations. The concencentration of sulfate is determined by the difference between the sum of strong acids and the concentration of other mineral acids as well as by titration with standard Trilon B solution. Low concentrations of sulfate in rain and other waters were determined by Johannesson ( 9 M ) with the aid of a cation exchange resin. The water sample was passed through a column of the resin (hydrogen form) to remove all cations. I t was then boiled to remove C02, and, after cooling, hydrochloric acid and a n excess of solid HgO were added. At this point, the conductivity of the solution is due almost entirely to the sulfate and only a small correction is required for chloride and in some cases, nitrate. The method is suitable for determining 1 to 10 p.p.m. of sulfate. A nephelometric, barium sulfate method for determining sulfate in water was described by Vosloo and Sampson ( Z O M ) , who examined in detail the several variables which affect reproducibility and reliability of the method. An amperometric, back-titration method for determining sulfide in water was suggested by Goldman ( 6 M ) . A known amount of standard iodine solution was added to the water sample and titrated, a t a p H of 4, with 0.00564N phenylarsenoxide solution. At the completion of the titration a second, identical amount of iodine was added and the titration repeated. The difference in titrant volumes is equivalent to the sulfide present in the sample. The method was used successfully on sam-
ples containing up to 0.20 p.p.ni. of sulfide. Kat0 and Shinra (10M) dctermined micro amounts of sulfide in water by adding the solid reagent, bis(1-nitroso-2-naphtholato) copper, to a n aliquot of the water sample adjusted to a pH of from 5.2 to 6.4. The reagent reacts with sulfide ions to precipitate copper sulfide and liberate an equivalent amount of 1-nitroso-2-naphthol. After filtering, the p H is adjusted to 9.2 to 12.5 and the absorbance mcasurcd at 366 nip. From 0.1 to 2 p.p.ni. of sulfide in water can be dctcrmincd. .Is little as 0.05 p . p m of ferric ion iiitcrferes. A simple device for determining 2*to 1000 p.p.m. of sulfide was described by Kobayashi ( 1 1 M ) . The device consists of a small glass tube filled with silica gel granules which have been soaked in lead acetate solution and dried. To determine sulfide, a prepared tube was immersed in the sample and the length of color-changed column observed and compared with a xorking curve prepared from standards. The analjks can be completed within 3 minutes, gives 1Oyoaccuracy, and is not seriously hindered by ferric, sulfate, chromate, chloride, or carbonate ions unless their concentrations are fairly high. Mikes and Szanto (1261) determined milligram amounts of sulfate in solution by converting sulfate to chloride by ion exchange and titrating the chloride obtained. Phosphate, chromate, etc., must be absent and the original chloride content of the sample must be determined and subtracted from the total chloride determined after the i w cschange treatment. SILICA, PHOSPHORUS, AND ARSENIC
-4 review of available methods for determining silica in mater, particularly sea water, was prepared by Isaeva (9143. He slso discussed the preparation and stability of silica standard reference solutions. Richer ( 2 0 N ) gave detailed directions for a gravimetric silica procedure in which particular care is taken to reduce to a minimum the possible errors inherent to the determination. Specific instructions were included for carrying out the dehydration, filtering and washing, and final ignition of thc precipitate. A simple, direct determination of silica by the molybdenum blue method was described by Justatowa ( I 2 N ) . Color standards were prepared from potassium chromatr, potassium tetraborate, and picric acid solutions, and sample Rolutions compared n ith the standards in Hehner cylinders. Iwasaki and Tarutani ( f f S ) investigated salt effects on the colorimetric detrrmination of silica and found that the absorption spectrum of the molybdate varies
both with the kind and the concentration of salts present. Color stability was observed to decrease with increasing salt content. The salt effect was greater a t longer wave lengths than a t shorter wave lengths, the effect being greatest in the case of those salts, such as ammonium sulfate, which also exhibit, in themselves, the greatest over-all effect. Sodium chloride solutions were found to exhibit minimum salt effects. Conversion of the unstable p-silicomolybdate to the stable a-form was found by Andersson ( I N ) to give reproducible absorbance measurements and improved color stability, uninfluenced by wide variations of molybdate and salt concentration, and by pH. The conversion is accomplished by heating thv 8-silicomolybdate for 3 hours on a stcani bat,h. The optimum concentration of the ammonium molybdate reagent was O.05MJ and best results were obtained when the sample solution was adjusted to a pH of 1.5 with perchloric acid. The importance of making the absorbance measurements a t exactly 400 i n u iva9 also stressed. Ringbom, Ahicrs, and Sutonen ( S I N ) also desc~ibedt'he conversion of p-silicomolybdate to the a-form and the advantages gained by the conversion. The solution obtained after addition of ammonium molybdate was adjusted to p H of 3.5 to 3.7 with a monochloracetic acidanirnonium nionochloroacetate buffer solution. Tlie conversion was complete in 10 minutes a t 100" C. Absorbance was measured a t 390 mp. Several extraction procedures for the spectrophotometric determination of silica by the molybdenum blue method have been described. Lheureux and Cornil (16%') extracted the aqueous acid molybdate solution first with a butyl alcohol-chloroform mixture and then with butyl alcohol. Ammonium persulfate and ethyl alcohol were added to tlie combined extracts and absorbance mew6urecl a t 400 mp. Large amounts of iron and ammonium ion were found to interfere, as well as redwing substances and hydrogen peroxide Adding boric acid eliminated interference of fluoride ion. Paul and Pover (18N) viere able to make accurate and reproducible colorimetric determinations of 4 c a on samples containing up to 10UO ,zg. of phosphate, by selectively c,xtwcting the phosphomolybdate com! ~ h ~with < ethyl acetate. After the action step, the silicomolybdate in aqueous phase was reduced to rbdenum blue and absorbance measured a t 690 mp. Increased sensitivity of the silicomolybdate method was achieved by donnenschein (14N)b y extracting the amine salt of the molybdenum blue complex with chloroform. Silicomolybdic acid was formed in the usual way, reduced with stannous oxalate, and
converted to a n amine salt by adding oxyethylated dodecylamine. The amine salt was then extracted with chloroform and its absorbance measured at 750 mp. The method permits determination of 2 pg. of SiOz per liter with a n accuracy of &lo%. Special precautions are required to keep the blanks as low as possible. A committee for the Association of American Soap and Glycerine Producers, New York, investigated current methods for determining orthophosphates and condensed phosphates in water. The committee's report, prepared by RIoss ( I Y X ) , pointed out the shortcomings of commonly used methods particularly in regard to the hydrolysis of condensed phosphates during the orthophosphate determination, and also errors caused by the interference of several substances commonly found in water., A modified extraction and hydrolysis procedure was recommended for the determination of orthophos phate, hydrolyzable phosphate, and total P205 content, at level.. as low as fractional parts per million. A rapid method for determining total phosphate in v ater n as dewibed by Robertson ( S S K ) . He examined conditions affecting the reversion of complex condensed phosphates into orthophosphate and determined optimum conditions for affecting complete reversion in the shortest possible time. Several different acids and oxidizing agents, and the effects of a large number of diverse ions on the reversion were investigated. The recommended procedure permits a field determination of total phosphate in 15 minutes. Phosphate concentrations of treated water were determined spectrophotometrically by Beneden ( S N ) . Ammonium molybdate reagent n as added to an acidified sample and the phosphomolybdate complex produced by sulfite reduction in the presence of a trace of hydroquinone catalyst. Fogg and Wilkinson ( 7 N ) determined from 1 to 600 fig. of Pz05in boiler water and effluents by a modified phosphomolybdate procedure. Solid ascorbic acid \%asadded as the reducing agent and a stable molybdenum blue color formed rapidly a t the boiling point of the solution. A number of other materials, including soluble silica, iron, chloride, nitrate, and sulfate, do not interfere when present in moderate amounts. Arsenate must be reduced to arsenite; excessive amounts of nitrate and chloride must be removed. Optimum conditions for determining phophates, using ascorbic acid as the reducing agent for the phosphomolybdate, were also dewribed by Redinger and Schmidt (19N). For 0.6 to 3.1 pg..of phosphorus per milliliter, they recommended 3.5 to 4.0 mg. of molybdate per milliliter, 0.4 to 0.5N sulfuric acid, and 0.025 ascorbic acid solution. All solu-
tions were kept a t 20" C. Kavamura and Xamiki (1SN) examined several factors affecting the molybdenum blue procedure when stannous chloride is used as the reducing agent. They reported optimum sulfuric acid and ammonium molybdate concentrations to be 0.65N and 0.15%, respectively. Maximum color intensity was achieved a t a temperature of 35" to 40" C. Salt errors in the phosphomolybdate method were avoided by Datsko and Semenov ( 6 N ) , who extracted the heteropoly acid n i t h butyl alcohol. Kuhn and Bochem (15N) determined 3 to 50 mg. of PzOs per liter by a simple colorimetric comparison procedure which can be completed in 5 minutes. An acid vanadomolybdate solution was added to the sample solution contained in a test tube and after 5 minutes the resulting color was compared with standaids. The sensitivity may be increased to 0.1 mg. of Pz06per liter if a spectrophotometer is used. Up to 1000 mg. of silica per liter does not interfere. A titrimetric method for determining phosphate concentration was described by Ivanova and Kovalenko (ION). The titration was made with mercuric nitrate by the two-addition method, permitting consecutive determinations of phosphate and chloride. The sensitivity of various reagents incorporated on test papers for detection of arsenic by the Gutzeit method and the effect of antimony on the determination were investigated by Watanuki ( P S N ) . Mercuric bromide gave a different color for arsenic and antimony and enabled detection of 0.1 pg. of arsenic and 10 pg. of antimony. The discolored area on the test paper was proportional to the concentration of arsenic. A simplified Gutzeit test was devised by Roth, Jackson, and Delay (ash'). Dozanska and Czarnodolowa ( 6 N ) proposed three different methods for determining arsenic in sewage and industrial wastes. A modified Gutzeit method was recommended for obtaining a n initial estimate of the amount of arsenic prescnt. Very low concentrations of arsenic, 0.003 to 0.5 mg., are best determined by a colorimetric molybdenum blue method whereas larger amounts are preferably determined titrimetrically. Arsenic in mineral waters was determined by Krapivina (14N) by first collecting the arsenic from 300 to 500 ml. of sample on freshly precipitated ferric hydroxide, dissolving the precipitate v,ith dilute hydrochloric acid, and then adding dilute copper sulfate solution and either sodium hypophosphite or stannous chloride as a reducing agent. The color intensity of the resulting solution was compared with similarly prepared standards. Bastos and Salum (Sly)described a coprecipitation method whereby they VOL 33, NO. 5, APRIL 1961
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were able to determine as little as 0.0005 p.p.m. of arsenic in river water. A large volume of sample was concentrated by evaporation. Ammonia was then added to precipitate hydrated ferric oxide which completely adsorbed the arsenic. The precipitate was dissolved in sulfuric acid, the arsenic reduced to arsine, and determined by its reaction nith gold(II1) chloride. Soos and Selenyi (S6N) described two methods for determining arsenic in mineral naters. By one method, arsenic was converted to arsine by nascent hydrogen and the arsine conducted through silica gel impregnated with mercuric chloride. The intensity of the resulting discoloration was proportional to the quantity of arsenic. Alternatively, the generated arsine was arrested by filter paper impregnated with mercuric chloride and the paper subsequently treated with potassium iodate and sodium hypobromite solutions to recover the arsenic. The arsenic in solution was then determined colorimetrically after the addition of ammonium molybdate, phenol (to eliminate bromide) and a reductant (hydrazine sulfate). Ciuhandu and Rocsin ( 4 X ) determined 1 to 158 pg. of arsenic in 5 ml. of solution spectrophotometrically by passing liberated arsine into a solution containing equal volumes of 0.1M silver nitrate and 0.1M sulfamoylbenzoic acid, and one half volume of molar sodium hydroxide. The resulting solution gave a brown color whose absorbance a t 420 mp was proportional to the quantity of arsenic. A nephelometric method, using a n antipyrinemolybdate reagent, was described by Gusev and Bitovt ( 8 N ) . The method enabled determination of from 0.0 to 2.5 pg, of arsenic and was free from interference of 3000 p.p.m. of calcium, 1000 p.p.m. of magnesium, 50 p.p.m. of manganese or aluminum, and 2 p.p.m. of iron. Phosphate interfered and required removal prior to the anal) sis. Yoshimura ( S Y N ) described a method based on the principle of internal electrolysis to determine 0.2 to 0.5 pg. of arsenic. Arsenic in a sulfuric acid solution was reduced to arsine by hydrogen formed at a platinum mire electrode in contact with a zinc amalgam. The evolved arsenic was reacted with mercuric chloride-impregnated filter paper and the discoloration compared with standards. NITRATE, NITRITE, AMMONIA, A N D ORGANIC NITROGEN
A new simple field test for nitrates in water was described by Robertson and Wachter (26P). Using a portable photoelectric colorimeter and a reduction - diazotization - coupling method, they determined up to 75 p.p.m. of nitrate with a standard deviation of 1 154 R
ANALYTICAL CHEMISTRY
p.p.m. in the 0- to 25-p.p.m. range, and 5 p.p.m. in the 25- to 75-p.p.m. range. Two of the three required reagent mixtures were prepared in pellet form to ensure properly measured and combined reagents and to increase reagent stability. An analysis can be completed in 10 minutes. Coldwell and McLean ( S P ) developed a new sensitive and specific spot test for nitrate ion. Nitrate and diphenylamine, spotted on filter paper and exposed to short wave length ultraviolet radiation produce a yellow color. As little as 1 pg. of nitrate can be detected in 0.01 ml. of solution. Two commonly used methods for nitrate, the phenoldisulfonic acid method and the reduction method, were shown by Greenberg et al. (8P) to lack desired accuracy and reproducibility. To overcome shortcomings of these methods they proposed a method based on the reaction between nitrate ion and brucine to give a colored product. The intensity of color is a function of the concentration of nitrate, although the system does not obey Beer’s law and standards must be prepared simultaneously with the analyses. The brucine procedure is relatively simple and rapid, and consistently yields reliable results. Certain disadvantages of the method were pointed out including the fact that brucine is toxic and that the concentration range is limited to 1 to 10 mg. of nitrogen per liter. Entz (5P) also described a modification of a brucine procedure for determining nitrate in about the same concentration range. Fisher, Ibert, and Beckman ( 6 P ) determined both nitrite and total nitritenitrate in water by controlling the sulfuric acid concentration of the solution in which the brucine-nitrite color is devdoped. At 17% acid only nitrite forms a yellow color a i t h brucine, a t 50% acid both nitrate and nitrite are reactive. Chlorine, chlorides, and other commonly encountered substances do not interfere. Pappenhagen and Looker (24P) also pointed out the shortcomings of phenoldisulfonic acid and reduction methods, and recommended the use of Iiessler’s reagent after reduction of nitrates to ammonia with a n alkaline ferrous sulfate-silver sulfate solution. T n o other reducing techniques were investigated: one utilizing a zinc-copper couple, and the other, aluminum foil. The later technique proved to be unsatisfactory and the zinc-copper couple less satisfactory than alkaline ferrous sulfate-silver sulfate. Their studies indicated that the Nessler’s reagent procedure was superior to the pyridinepyrazalone method for the determination of reduced nitrates. A new direct spectrophotometric method for nitrate determination was suggested by Hartley and Asai (IOP).
They investigated conditions under which nitrate ion and excess 2,6-xylenol reagent react quantitatively to form 4 - nitro - 2,6 - xylenol. Nitration was complete within 5 minutes in sulfuricacetic acid or sulfuric-phosphoric-acetic acid solutions of suitable acid proportions. Absorbance of the resulting solution obeys Beer’s law up to 125 p.p.m. of nitrate. Kitrite and chloride were found to interfere and were removed by the addition of solid sulfamic acid and silver sulfate. Precision of the method, expressed as relative standard deviation, was about 1%. Skorodumov (SYP) proposed a colorimetric method employing a sulfuric acid solution of diphenylamine as reagent for 0.01 to 4.0 mg. of nitrate per liter. The sample was acidified with sulfuric acid. Sodium chloride and acid diphenylamine reagents were added and, after 3 hours the color of the solution compared with standards. A limited amount of nitrite does not interfere: hydrogen peroxide increases the color intensity and bcth sulfite and thiosulfate decrease it. A rapid method for determining less than 0.02 p.p.m. of nitrate was described by Hsu, Wen, and Jen (12P). They acidified the sample with acetic acid, destroj ed any nitrite present, and then added a powdered mixture of barium sulfate, manganous sulfate, zinc, citric acid, sulfanilic acid, and a-naphthylamine. The resulting mixture n-as shaken for 1.5 minutes, centrifuged, and the absorbance of the supernate measured at 515 mp. Prochazkova (S5P) described a similar procedure, reducing the nitrate with hydrazirle in l N sodium hydroxide solution arid in the presence of copper catalyst. Excess hydrazine was removed with acetone before complexing the nitrite with sulfanilic acid and a-naphthylamine. They attained a relative accuracy of less than 2% for 0.01 to 0.4 mg. of nitrate per liter. Directiors for preparing a phenolsulfonic acid reagent and its use in the rapid determination of 2.5 to 20 p.p.m. of nitrate were described by Middleton (SOP). The simple procedure required mixing of equal volumes of sample and reagent, adding 3N aqueous ammonia solution and measuring absorbance immediately a t 426 mp. Matsidaira and Tsuda ( I S P ) described a procedure for determining ammonia and organic nitrogen in sea water. Ammonia was determined indirectly by adding a calculated exceSs of sodium bromate to the sample. Potassium iodide and a known amount of starch solution were then added and the iodine, released by the excess bromate, determined spectrophotometrically. From this, the amount of ammonia originally present was calculated. Organic nitrogen was converted to ammonia and determined in the same u. ay.
Hamaguchi, Kuroda, and Endo (9P) determined both nitrate and nitrite simultaneously by measuring their ultraviolet absorption peaks at 302 and 355 mp, respectively. Other nitrogen compounds do not interfere; aluminum a-as converted to aluminate ion to eliminate its interference. Large amounts of ammonia were removed by acidification. The method was used t o determine 0 to 15 mg. of nitrate and 0 to 4 mg. of nitrite per liter. A total of 71 dyes, all containing primary amino groups, were tested for their reactivity with nitrite ion by Korenriian and Yunina ( I 4 P ) . From mow than 50 which showed a color change, tliey selected Neutral Red, Acid Dark Green C, Direct Blue K , and Direct Diazo Black C as being part,icularly suitable for the detection of nitrite. These dyes will detect 0.33pg. of nitrate per milliliter a t a dilution of 1 : 3 X 106. The reagent N , N , N ' N ' tetrametliylbenzidine, which is oxidized by nitrite to colored diphenoquinone '., k'-bis(dimethy1ammonium chloride), was used by Matrka and Navratil (18P) to determine nitrites. Suranova (28P) desrribed a procedure for determining 0.0342t o 0.684mg. of sodium nitrite per 100 ml.: with the reagent, p-aminosalicylic acid. A stable color formed in 5 minutes. Kristalev and Kristaleva (16 P ) described the use of a pyraeolonc derivative, l-ph~~n~l-3-methylpyrazolone, in determining m a l l amounts of nitrite. A direct co!orimetric method for nitrite, using p-aminobenzoic acid, was described by Nokhov, Udalov, and Khalturin (21P ) . Physostigmine salicylate solution was used by Szepes j29P) for both qualitative and quant,ih t i v e t$,sts for nitrite. Indole was used as a sensitive reagent for nitrite by Ze1ci:ova and Karanovich (YOP). The wnsitivity of their method was 0.3 pg. 2f riitriti. in 40 ml. of solution. Leko md S ~ y 3 l P ) suggested an improved d bawl on the formation of p-nitrosodium dimethylaniline T the rc.?ct,ion of dimethylaniline with i:t;ir'' ic,u. The solution shows a n ab)tion maximum at 460 n:~. Various actcirs influencing color intensity and stability were studied. Ci!)tinium conditions for the colorincttric determination of nitrite with 3,ivanol were investigated by Jirele , I S P ) . He found that the addition of !yogdatin sohition stabilized the color or up to 4 hours. A method for determining small unount>sof ammonia was described by 3ovvther and Large (QP). An alkaline :olut,ionof sodium phenate was added to .he sample solution. This mixture, ieated in the presence of hypochlorite md manganous sulfate, produces, vithin 45 minutes, a colored solution rith maximum absorbance at 625 mp.
The absorbance is directly proportional to nitrite content up to 4 pg. per ml. Atkins (IP)used chloramine T and pyridine-pyrazolone reagent to determine ammonia in sea water. Krieger (16P)described a relatively simple apparatus and method for determining ammonia. The sample was placed in the larger vessel, and 1 ml. of 0.01N sulfuric acid in the smaller vessel, of a Fleury "micro-Schloessing" apparatus. The apparatus was closed and heated a t 37" C. for 30 minutes. The sample was then made alkaline and the system heated a t 37" C. for 24 hours. Ariimonia, which had collected in the acid solution, was then determined spectrophotometrically with Nessler's reagent. Dissolved and suspended organic nitrogen in sea water was determined by R a g a (7P) by first boiling the sample with sodium hydroxide solution, and then adding ferrous sulfate and sulfuric acid and boiling again until white fumes of sulfuric acid appeared. Finally the ammonia was steam-distilled into boric acid solution and titrated with standard hydrochloric acid. Dudova (4P)determined organic nitrogen in ground waters by a preliminary distillation of ammonia with a borate buffer at p H 7.4. Nitratenitrite nitrogen interferes seriously, a 6-fold excess of nitrate resulting in complete loss of organic nitrogen in the determination. He recommended a potassium biiodate solution as the absorbent for ammonia, with subsequent iodometric determination. Ohlweiler and Meditsch ( B P )modified and improved their previously reported ( W P ) indirect absorptiometric method for cyanide in water by substituting diphenylcarbaeone for the p - dimethylaminobenzylidenerhodanine reagent. A cathode ray polarographic technique for determining cyanide ion in water was developed by Hetman ( I I P ) . The method, capable of detecting 0.05 pg. of cyanide per milliliter, is not subject to interference from the usual trace impurities in natural water. A large excess of free chlorine, bromine, or iodine interferes, and sulfide ion, when present, must be removed prior to analysis. OXYGEN A N D OTHER GASES
A number of modifications and applications of the standard Wmkler method for dissolved oxygen have recently been reported. Nusbaum (14Q) pointed out the advantage of substituting solid sulfamic acid in place of concentrated sulfuric acid for final acidification in the Winkler method. Sulfamic acid is nonhygroscopic, less corrosive, and readily adaptable to field kits. Moreover, i t destroys nitrites, making the use of sodium azide unnecessary. He also suggested the use of Niagara soluble starch in field kits to avoid the necessity
of
carrying starch solution.
Bargh
($9) reported a rapid, routine method
for determining micro amounts of dissolved oxygen in water. A 500-ml. sample was collected in a bottle of special design and oxygen determined by the Winkler method. Yamagishi and Konishi (16Q)determined as little as 0.001 p.p.m. of dissolved oxygen in boiler water by observing special precautions in the Winkler procedure. The titration was carried out by the dead-stop end point method and particular care was taken to remove all dissolved oxygen from the reagents used. They thus attained a titration precision of 0.0003p.p.m. in the absence of hydrazine. The precision in the presence of hydrazine was slightly less. Resch (18Q) suggested a photometric indication of the titration end point as a n improvement in the Winkler procedure. Griffiths and Jackman (5Q) performed the final iodine titration potentiometrically, using a platinum indicator electrode and a glass reference electrode. A micromethod for determining 0.003 to 0.02 p.p.m. of oxygen in boiler water was described by Holland (69). Fractional milliliter amounts of sodium hydroxide, manganous sulfate, and acid o-toluidine reagents were added successively to the sample, and the resulting colored solution compared with standards. A microtonometric method for the determination of dissolved oxygen, carbon dioxide, and nitrogen in 0.5 ml. of sample was described by Jones (SQ). A small gas bubble map be equilibrated with t h e sample and subsequently analyzed in 25 minutes. Results for oxygen compare favorably with the micro-MTier method. Alcock and Coates (I&) compared results obtained by the indigo carmine, the Hersch cell, and the 0-toluidene methods. They found satisfactory agreement among the three methods. Mancy and Okun (IS&) developed a polarographic system for automatically srunpling, determining, and recording dissolved oxygen concentrations in water and waste water. They studied the effect of surface active agents on the electrode kinetics of the dropping mercury electrode and found that adsorption of a n anionic surface active film distorts diflusion current measurements in the region of the first oxygen wave. The presence of cationic agents interferes with current measurements in the region of the second oxygen wave, and nonionic surface active agents, in concentrations exceeding 10 mg. per liter, interfere throughout the entire potential range. Determination of dissolved oxygen in natural waters is best carried out at a potential corresponding to the second reduction wave because the most common surface active pollutants are anionic. VOL. 33, NO. 5, APRIL 1961
155 R
T y k r and Karchmer (SYQj developed portable polarographic equipment for determining dissolved oxygen a t the sampling site. Using a horizontallymounted capillary of carefully selected characteristics they achieved a drop time of 0.25 second and a resulting diffusion current relatively insensitive to agitation or to sample flow.. Determinations may be made rapidly to 0.1 p.p.ni. of oxygen in waters of pH 4.5 to 11 and of total salt concentration of 0.001 to 0.05M. Samples containing more or less than this amount of salt may be analyzed after the addition of a special reagent mixture which eliminates difficulties caused by either too high or too low salt concentrations. Karchmer (9Q, roQj made a detailed study of the several factors related to abnormally high currents observed when diwolved oxygen is determined polarographically using a rapid-dropping mercury electrode and the relationship brtneen drop tinie and polarogrxphic current produced by disbolved oxygen. Ahiniproved electrode system for mea>iiring dissolved oxygen was designed by Carritt and Icanwisher (QQ). The system, consisting of a solid phtinum electrode, a silver-silver chloride reference electrode, a thermistor Lvhich provides temperature compensation, arid 0.5X ium hydroxide internal electrolyte, encased in a tight fitting poIj.cthj,lenc membrane, overcomes most of tlie shortcomings of previous polarographic, solid-electrode systems. The membrane, being permeable t o dissolved molecular oxygen but niuch less so to other dissolved substances, minimizes electrode poisoning and permits the electrode t o operate as a selective electrode for oxygen in a wide variety of aqueoiis systems. The unit may be used with recording equipment for continuous measurement or may be incorporated in a portable instrument for field use. llnibuhl (SQj reported on the practical applications of a n Oxytester, designed for the clectrocheniical determination of dissolved oxygen in lakes and activated sludge basins. He described the construction features of the instrument and also of a combination instrument which simultaneously measures dissolved oxygen, t,eniperature, and conductivity. Results of performance tests on a commercial, continuous-recording dissolved oxygen analyzer were reported by hIacklin, Baumgartner, and Ettinger (12Q). Tlie instrument consisted of a pump, a system for aspirating and separating the gas and water, and a standard commercial apparatus for analyzing gases for oxygen. The instrument performed reasonably well in field and laboratory tests and under a variet,) of xater conditions and dissolved oxygen levels. A vrry wnsitive niethod for tictermin-
156 R
ANALYTICAL CHEMISTRY
ing traces of carbon dioxide in boiler feed water was developed by Jennings and Osborn (7Q). Using a 10-liter sa~nplecontaining no more than 1 mg. of carbon dioxide, they were able to obtain an accuracy of *0.003 mg. per liter. The sample is aspirated for 1 hour with COTfree air, the COz absorbed in 0.01X sodium hydroxide and titrated potentiometrically. iitmospheric carbon dioxide must be excluded and particular care taken to keep the blank to a minimum. A nebv instrumental method for measuring the concentration of dissolved hydrogrn in m t e r \vas reported by Kright and Stiteler (24Q). It is based on the fact that the electrical resistance of palladium is changed ivhcn in contact with water containing di-rolved hydrogen, the effect being pru1)ortional to the hydrogen concentration. A colorimetric determination of dissolved hydrogen hased on reduction of an alkaline permanganate solution \vas used by Robinson and Conklin (I9Q) to determine 5 to 50 cc. of hydrogw per kilogram of water, with a standard deviation froni the mean of multiple dcterminations on a single system of =t:j%. Shirley (SOY) described a thcrmal conductivity method for drterniining hydrogen in high-prcsure cooling n-ntcr. LOK concrntrations of chlorine in water were determined spectrophotometrically by Sprirny (BQ). Chlorine dissolved in carhoii tetrachloride shows an absorption maximum a t 335 mp. He was able to detect 1 pg. of chlorine per milliliter. h method for determining both free and combined chlorine in water \vas described by Palin ( I S Q ) . A suitablj- buffered sample solution is titrated with ferrous ion with diethylp-phenylenediamine as indicator. llono-, di-, and triehloramines may also be determined by adding potassium iodide and continuing the titration under specified conditions. A similar procedure for the determination of free chlorine and mono-, and dichloramine in water was described by Yagovoi (MQ). Post and Moore (I?‘&) developed a specific, sensitive method for determining chlorine dioxide in l o v concentrations. Chlorine dioxide reacts, a t a p H of from 4.1 to 4.3, with l-amino-8naphthol-3,6-disulfonic acid to yield a colored solution whose absorbance measured a t 525 mp follows Beer’s law for concentrations up to 1.5 mg. per liter. Chlorine interference was eliminated by the addition of malonic acid. Of a number of other ions studied, only polyphosphates interfered seriously. Oana (15Qj described a rapid and precise method for determining argon in gases and in natural water. The method involves introducing a known volume of gas into a vessel containing a tungstcn filament on \vliich solid metallic calcium ii placed. Heating the fila-
mcnt volatilizes calcium which reacts with all gas components except argon and the other inert gases. hleasuxment of the remanent pressure permits determination of argon in the sample (helium, neon, etc., are usually a small proportion of the total and are therefore neglected). The method was applieii to t,he analysis of many differcnt typtzs of natural waters. Shirley, Pachucki, and Lolos ( S I Q ) described two methods used to determine dissolved argon in niakeuii \\ater of a nuclear reactor. A mass spectrometer was ernplojwl by Kaivakami ( I I Q ) to determine nitrogen, oxygen, neon, and methanc dissolved i n thermal waters. ORGANICS
Buj.dens a n d Ledent ( 3 R ) m:itlt. :L study and comparison of the relat1i.c merits of each of three oxidizing agents commonly used for determining oxj-gm demand of pollutrd n.aters. They concluded that potassium pernianganstc and cwic sulfate \yere about equivaleiir’. A 0 . 2 5 5 1)otnsiiuni chromate solution vias a1.o satisfactory if used viitlioiit silver sulfatc catal!,st. Detection of organic pollution by a photoluiiiinescence nietliotl \vas investigated by Popov (23R). ‘Ihc pl.iotciliiniinesce~i~e of natural IYatcr? i)rotlucrd by ultraT-iolrt radiation of 320 to 400 nip depends alnioqt entirely on t,he prewricc of organic substances. Several factors particularly the pH of the solution, were found to influence tht. e i n i s h n intensity. Fulvic acids occurring in natural waters were determined by Wilson (28R, 29R) by measuring their ultraviolet absorption a t 300 nip. Since ferric ion also absorbs a t this wave length, it was necessary to determine iron and apply a correction t o the observed absorbance. Up to 30 p.p.m. of fulvic acid was found in certain samples; a maximum of 0.6 p.p.m. \vas found in hard well waters. Fulvic acids may also be determined by oxidation with permanganate according to standard procedures. The usefulness of column partition chromatography in the separation and identification of organic acids in natural water samples was demonstrated by Mueller, Larson, and Ferretti (21 R). An alkaline evaporation of the sample, followed by a n ether extraction of the acidified aqueous tesidue, was used to prepare the sample for separation of individual acids or groups of acids on a silicic acid column. The acids were eluted with 1-butanol in chloroform and identified by R, value comparison. on paper chromatography. Bars and Fikhman (1 R ) determined naphthenic acid and humic acid in natural n-atcr hj. extraction of a n acidified sample n-ith benzene or chloroform. Gubina (!.$G)
pointed out the fact that naphthenic wids may precipitate completely from nxter samples kept in storage, partIr:ularl;- if t,he p H of the water is less ilm 6.0. He described a method for cc~l!ei-ting naphthenic acids from water ng freshly precipitated (').XI
i i (Ei'R) examined three coni-
rnori!y employed methods for determin-
i w ;he.m!s. Csing caniples of phenol, . .! ,tnd m-cresols, and tar acids, he ircd r c a l t s obtained by the onailino method, the formation of
of phenol with the aid of 2,6dic.iiloro~enzc~quinonechloraniine. I n sikdine mlution, sodiuni phenolate react:; with this reagent to give sodiuni %,ti-dichlori)i?~Llophenolate, a compound absorbance of the sured directly or, ;irrii.runtc
I
v.e:ult,eci In inrreased
,e;1e-.
Smd! quantitiw of phenol may be )nlawgaptiically using a iurn electrode. However, generally le?:, than satis,>'? of tk.e relative ease of ?oJwiing : i f thc ;iletinuni electrode. +inAib:g nil Frishmnn (11R ) de' b 4 ti; : J prcicPdurc? b ~ xhich rapid t r ~ ~ d h poisoning C R I : be overcome. Iiciting and ancdic polarization rt.:r,tments, a stable electrode was obained which permitted d e t e r m i n h o n if phenol a t concentrations up to 1 0 - 5 ~ n t'urhjd and colored solutions with a n ,vcr:rq~error of 2.5 to 4.7y0. 1
Vaughn (26R) presented a report of a Task Group of the American Water Works Association on Analytical Methods for Synthetic Detergents. The report discusses the effects of syndets on water supplies and considers in detail two commonly used analytical methods for determining alkylbenzenesulfonates (ABS) : the methylene blue method, and the infrared method. A two-step approach to the examination of water supplies for ABS content was recommended. The water should first be tested by the methylene blue method. If results indicate 1.0 p.p.m. or less of ABS,no further analyses are required. If the methylene blue result is high, a sample should be analyzed by the infrared method to determine its true ABS content. Webster and Halliday (2TR) reported a n improved colorimetric method for the determination of ABS conccntrations in river water and sewage. The method is based on earlier methods and includes a n acid hydrolysis, removal of hydrolyzed materials, a n extraction with 1-methylheptylamine to separate the detergent. removal of excess amine by boiling M ith alkali, and finally colorimrtric determination of the detergent with methylene blue. The method is reasonably rapid and provides results which are in good agreement with infrared analyses. Etienne (QR)developed a procedure for determining 0.2-p.p.m. quantities of polyglycolic surface active agents in water. The method is based on precipitation of the phosphomolybdate complex, with precautions to eliminate other surface active agents and nitrogen compounds which would interfere. The method is suitable for determining simple and hydrophilic ethers, and, with modification, the lipophilic ethers. A method for determining benzene in water was reported by Devlaminck (6R). Benzene vapor as displaced from a n acidified sample by entrainment disLillation, nitrated, and the product extracted with methyl ketone. Absorbaxe of the organic phase was measured a t 560 mp. The sensitivity of the method was 0.01 mg. per liter. A method for determining oils in refinery effluents was described by Harva and Somersalo (15R). 4 weighed sample was extracted with carbon tetrachloride, a portion of the organic layer filtered, and absorbance of the filtrate measured a t 260 mp and compared with the absorbance of standards. Istomina (16R) made a comparison of the gravimetric and luminescence methods for determining oil in water and condensate. For highest sensitivity, simplicity and speed of analysis, the luminescence method was preferred. Several light hydrocarbon components of the effluents from synthetic rubber plants were determined by procedures described by Ruzicka (@E).
.4 potentiometric method for determining trichloroethylene in industrial waters was reported by Deyl and Effenberger ( 8 R ) . Ammonium persulfate and nitric acid were added to the sample and the mixture refluxed to volatilize the liberated hydrogen chloride. The HC1 was absorbed in water and titrated potentiometrically with 0.01N silver nitrate. A blank correction for chlorides present must be determined on a separate sample. Johannesson (18R)made a survey of possible methods for determining the bactericidal agents monobromamine and monochloramine in sea water which has been disinfected with chlorine. An amperometric method using a rotating platinum electrode and phenyl arsenoxide titrant was developed and used successfully. Turskii, Mazov, and Samolova (25R) determined resins present in waste M aters by making successive chloroform extractions of a sample made alkaline n-ith sodium hydroxide, d r j ing the extract, and measuring its absorbance. Jayn:e and Reimann ( 1 7 R ) reported a method for determining resins present in the circulating and waste water from a paper-making machine. A v e t combustion technique for determining organic substances in evaporation residues was described by Kleinert (19R). The residue was heated with a solution of potassium iodate in sulfuric acid and the ratio of carbon dioxide formed and oxygen consumed during the reaction was used to determine the nature and state of oxidation of the organic material present in the water. For pure carbohydrates this mtio is 1.000, and for lignin sulfonic acids, it is 0.852. Gubin and Hoffmann ( I S R ) tested the method of Forsblad (10R) on solutions of eight different organic substances and recommended the method for a test of the amount of organic impurities in power plant water. A method for determining dichloronaphthoquinone, a component of fungicides, was proposed by Zakhar'ina ( W R ) . Daisley (4R) developed a sensitive method for the measurement of vitamin Blz ccncentration in sea water. The method is based on a quantitative determination of the chlorophyll produced by a n algae culture grown in contact with a water sample to which a suitable growth medium has been added. Deyl ( 7 R ) described a method for determining hematin in water. ISOTOPIC ANALYSIS.
RADIOACTIVITY
Karapacheva and Rozen (f4S)and Kats and Lapteva (15s) have reported methods for complete isotopic analysis of water. The latter calculated isotope concentrations from differential pycnometric determinations of a reference san-iple and the analyzed sample, while the former authors based their method VOL. 33, NO. 5, APRIL 1961
157 R
on the use of catalytic exchange of oxygen and densitometric measurements. Yakimenko et al. (36s)determined the isotopic composition of several natural sources of water by normalization a t 400" f 10" C. with HI obtained in a single step electrolysis. Normalization was made in a continuous working 13-step isotopic exchange assembly, and the final deuterium concentration was determined by the float method. Analyses were also made (37s) by slow (25-48 days) electrolysis until equilibrium was established between the feed and the gases enriched in HZand 0 1 8 . A simplified float method for determining deuterium in water was deicribed by Baertschi and Thurkauf (IS), who were able to determine 0.1 to 99.9% DzO in water with a precision of 0.01 to 0.00270 DiO. An improved thermal conductivity method for deuterium was reported by Yanagisawa et al. (38s). From 0 to 2% D20 was determined with a n accuracy of =k0.05%by Reaser and Burch (89s) using a Fiske osmometer to measure freezing point elevation. Ceccaldi (6s) investigated the infrared absorption bands used for determining D,O in water and pointed out that the choice of band should be governed by the precision required, the amount of sample available, and the relative concentration of the isotopes. Methods of analysis and results of tritium determination in natural waters were discussed by Schumacher ( 3 1 s ) . Payne and Done (26s) proposed modifications of their previously reported procedure. The modifications result in improved reliability and a n exkended range, and thus permit tracer experiments involving very high dilutions of tritium. Rlerritt (21s) described a method in which tritium is counted as water vapor in a heated proportional counter filled with methane and calibrated with a standard tritiated water sample. The system is simple, rugged, and yields results reproducible within k2Y0 standard deviation. Hazards of radioactive isotopes in food and water and general analytical methods for determining radioisotopes in water, food, and sewage were discussed by Hahn and Straub (9s). Methods for determining very low radioactivity in natural waters were reviewed by Ralkova (288) and specific methods for measuring a-, 8-, and ?-activity were described. The application of gamma-ray spectrometric techniques and volume reduction methods to the determination of low concentrations of radionuclides in water was discussed by Kahn and Reynolds (138). A further discussion of gamma-ray spectrometric systems of analysis and their application to the determination of a number of unseparated isotopes in reactor water was included in a report by Perkins 158 R
ANALYTICAL CHEMISTRY
(87s). blunter (23s) described test methods for assessing radioactivity hazards in industrial waters. General details of a technique using potassium40 as a standard for measurements of p-emission of water residues were described by Bylinkina (5s). A sensitivity of IO-" curie per liter was achieved. Boni (38) developed a n analytical method for the radiochemical separation and quantitative recovery of ruthenium, zirconium, niobium, neptunium, cobalt, iron, zinc, strontium, rare earths, chromium, and cesium from a variety of natural materials including river water. Both anion exchange and precipitation techniques were employed. Recovery of the individual isotopes was, in each case, greater than 95%. Precipitation and extraction methods for isolation of radioactive fission elements were described by Brezhneva et al. Using a n electrodialysis technique with a n ion exchange resin membrane, Owers (36s) achieved, in 2 hours, a 35fold concentration of cesium and strontium in t a p water samples in which these radioelements were to be determined. Higher concentration factors were attained with longer electrolysis. Subsequent radiochemical determinations were simplified by the absence of all anions other than nitrate. Carrierprecipitation techniques for concentrating radioelements mere discussed by Lazarev and Grashchenko (17s). They described specific conditions for achieving optimum results with both ferric hydroxide and barium sulfate precipitates. Ion exchange and precipitation methods for determining strontium-90 in water were described by Orlova (248). The separation and concentration of yttrium-90 and strontium-90 by cation exchange and the determination of these radioisotopes in water was described by Stanley and Kruger (348). Weiss and Lai (358) measured radiobarium in sea water by cocrystallizing barium, and other alkaline earth elements, with potassium rhodizonate, and analyzing the crystallized material by conventional radiochemical procedures. An emergency field test for determining barium-140and strontium-90 in drinking water was described by Melbourne (IOS). The method, a greatly simplified ion exchange method, yields results which are satisfactory for the purpose. Goldin, Velten, and Frishkorn (7s) determined concentrations of radioactive strontium isotopes in both fresh and salt waters by extracting strontium-90 into 2-thenoyltrifluoroacetone and @-countingyttrium-90 activity, and by &counting a strontium carbonate precipitate to determine total radioactive strontium. Their procedure provided for removal of common interferences. Radiostrontium isotope con-
(4s).
centrations were determined on rain and snow samples by Shvedov et al. (92s). h method for determining radiostrontium in sea water was described by Loveridge (18s). Helmholz and Schneider (188) described the chemical separation and specific counting instrumentation developed for the determination of cobalt60 in waste solutions associated with the chemical processing of irradiated uranium. Cobalt-60 was precipitated from solution, separated from the bulk vf interferences, and specifically determined by a combination of gamma energy discrimination and gamma coincidence counting. Hataye (10s) developed a method for determining radium-C and thorium-C in radon-containing, carbonated mineral spring waters. The two isotopes were extracted from a n acid-iodide solution with isoamyl alcohol. Alberti, Bettinali, and Salvetti (1s) measured the concentration of radium-B, radium-D, and thorium-B in natural waters, by 8-counting the residue obtained from a dithizone extract of the sampie. Hataye (11s) used a similar method LO determine radium-B and thorium-B in radioactive spring waters. The need for a n accurate analytical method for the detection and determination of low concentrations of iodine-131 in drinking water and sewage was pointed out by Hahn, Levin, and Friedlander ( 8 s ) . They reviewed the general techniques for concentrating iodine from water, and described procedures for concentration by ion euchange and by precipitation. They also included details of a procedure for decomposing organic substances in sewage samples prior to the determination of iodine-131. Evaluation of the methods, using tap water and sewage samples, indicated that results obtained xere always within the limits of accuracy of a radiometric analysis. The determination of radioruthenium in effluent and in sea water was reported by Loveridge and Thomas (19s). Rickard and Wyatt ($08) also described a radiochemical method for determining fission ruthenium in aqueous solutions. The radioactive content of sea water was determined by Sodd, Goldin, and Velten (338). Various precipitation techniques were used to separate (1) cations, (2) strontium, barium, and radium, and (3) cesium. Miyake and Sugiura (28s) measured the radioactivity of sea water samples by a double ferric hydroxide-barium sulfate precipitation, and achieved an average efficiency of coprecipitation of fission products of about 90%. A new, large-surfaced, windon leqe flow counter for measuring gross radioactivity of water samples by the evaporation method was described by Kiefer and Maushart (16s). Water in large
aluminum dishes placed in the bottom of the casing of the flow counter is evaporated directly with a surface evaporator. The technique offers a n improvement over common methods of evaporation. MISCELLANEOUS
A number of investigators have reported spectrographic methods for water analysis, particularly for the determination of minor elements. Russmann (202') made a comparison of several types of electrodes used in spectrographic analysis of solutions and concluded that a rotating disk, with a Ringsdorff 12 electrode, gave highest reproducibility. A new carbon arc method was reported by Haftka (92'). The method, involving drying 0.03 ml. of sample on a carbon electrode and exciting with a carbon arc, was found to increase the sensitivity for several heavy metals by a factor of lo2 to lo3 over other analytical methods. Nagy and Polyik (142') described two spectrographic methods for determining eleven heavy metals in water. In one method, 25 to 100 ml. of sample was evaporated to dryness, the residue moistened with hydrochloric acid, beryllium added as a n internal standard, and the moist residue transferred to carbon electrodes and excited with a n alternating current arc. Alternatively, the heavy metals were concentrated by multiple extractions of a large volume of sample (250 to 500 ml.) using 8-hydroxyquinolinol-chloroform and dithizone-chloroform. The extracts were combined and evaporated to dryness and the residue analyzed spectrographically as in the first procedure. With the latter method, it was possible to determine 0.8 to 100 pg. of the metal per liter of solution. A review of evaporation methods for spectral analysis of solutions was prepared by Lipis (112'). A spectrographic method for the quantitative analysis of minor elements in natural water was described by Haffty (82'). Twelve milligrams of the sample evaporation residue was mixed with half its weight of powdered graphite and the mixture completely volatilized in a direct current arc of 16 amperes. Matrix effects were minimized by preparing standards of approximately the same composition as the samples being analyzed. Analysis lines and concentration ranges of the working curves are tabulated for 24 elements. Impurities in heavy water were determined spectrographically by Webb (86T),who used a method similar to the copper spark method except that the standards and samples were made up in nitric acid solution and silver electrodes were used. Loginova (122') described a spectrographic method for determining tin, zinc, cadmium, antimony lead,
and arsenic in natural water. A spectroscopic buffer containing ammonium phosphate and sodium, calcium, and magnesium sulfates together with 0.1, 0.1, and 0.5%, respectively, of iron, manganese, and aluminum, was used to minimize the effect of variations in water sample composition on the analytical results. Germanium was added to all samples as a n internal standard. The lower limit of the analytical range was of the order of 10-3 to lo-'%. Ruthenium, rhodium, niobium, and zirconium were determined in sea water by Rose (192'). These metals were coprecipitated with ferric hydroxide, the residue ashed a t 700" C., and the residue analyzed spectrographically. Analysis of synthetic samples indicated good recoveries of all these elements except ruthenium. Atomic absorption spectroscopy is a relatively new analytical technique which appears to offer promise in the field of water analysis. I n contrast with flame photometric methods which are based on emission of radiant energy of a specific frequency by atoms or molecules excited in a high-temperature flame, atomic absorption methods are based on the absorption of resonant wave length radiation by atoms in the ground state, or in some cases in a n already excited state. I n practice, the sample is atomized into a low temperature flame through which radiation of selected wave length is passed. I n proportion to the concentration of the element atoms in the flame, the intensity of the incident radiation will be diminished and can be measured with a suitable radiation detector system. The method has greater scope and generally suffers much less from interelement interference than does flame photometry. A description of this general technique together with some of its applications, limitations, and difficulties, was presented by Menzies (132'). The application of neutron activation analysis techniques to water analysis was described in t x o reports by Blanchard, Leddicote, and Moeller ("., 32'). Irradiation of the water sample, followed by addition of stable elements as carrier, and radioactivity analysis of the chemically separated groups, permits identification and determination of 13 elements, including argon, arsenic, barium, chloride, copper, iodide, potassium, manganese, magnesium, protactinium, rubidium, sodium, zinc, iron, and strontium. The limit of detection in micrograms ranges from 0.00003 for manganesc to 0.45 for iron. Navone (162') developed a mathematical equation for computing the specific conductance of a sample of pmhos per centimeter a t 25" C. when the resistance is measured a t a temperature other than 25" C. The equation requires determination of a cell factor, different for each conduc-
tivity cell employed, by carefully determining the resistance of a standard potassium chloride solution a t several different temperatures from 18" to 30°C. De Xooyer and Smit ( f 6 T ) d i m w e d the determination of total salt content of boiler water from electrical conductivity measurements. Methods for measuring turbidity in water and the preparation of suitable turbidity standards were diqcussed in a report prepared by Rodier and FaivreDuboz (1"). Results of tests with three different instruments and with both resin and diatomaceous carth standards were included in their study. Vadkovskaya and Bakhman (242') cited three different methods for estimating the amount of colloidal material in mineral waters: comparison of the intensity of light scattered by the test and standard solutions, light absorption measurement, and simultaneous measurement of conductivity and interference of light in the solution. These techniques were used to determine colloidal silica, iron, sulfides, and other suspended materials in water samples. A portable, battery-operated sample collector was constructed by Eden and Melbourne (62'). The equipment is designed to collect samples from open channels on a preselected schedule. Greenberg and Navone (62') designed a control chart for use in checking the accuracy of analyses in n ater laboratories. They made a statistical evaluation of the results of 971 mineral analyses performed in two laboratories over a 3-year period. Using the difference between the sum of anions and the sum of cations as a function of the sum of anions, they calculated a set of limits of acceptable variation from the theoretical limit of zero and based on a suggested limit of *1 standard deviation. I n practice the control chart system can be used to detect the presence of assignable causes of variation not onlj of over-all laboratory operation but also of individual chemists, A nomogram for calculating the p H of potable and industrial waters from transitory hardness units ( A ) and free carbon dioxide concentration ( B ,mg./liter) was described by de la Sota (21 2'). The relationship p H = 7.462 log A / B was used for the calculations. Hoemig (102') pointed out the limitations that must be recognized in applying P and M values for the calculation of hydroxidecarbonatebicarbonate equilibria. A reliable calculation of bicarbonate and carbonate concentrations can be made when the p H and total carbon dioxide concentrations are known. Thomas and Lynch (282') made a critical study of the Larson and Henley method for determining low alkalinity of rain water samples and tested the validity of the method for the analysis of waters of a wide range
+
VOL 33, NO. 5 , APRIL 1961
159 R
of alkalinity and salt concentrations. The method vias superior to present referee procedures in that it eliminates errors due to variation of true equivalence point with total alkalinity. Babkin and Epeikina (f 2') made a detailed study of the alkalimetric estimation of dissoived carbon dioxide in boiler water. The usual titrimetric method, reliable only for concentrations of 4 to 5 mg. of carbon dioxide per liter, was modified by sampling and titrating in a vessel which excludes air from contact with the sample. I n this manner, reliable results were obtained for 2 to 5 mg. of carbon dioxide per liter. A mixed indicator, composed of thymol blue and 1naphtholphthalein, was recommended by Thomann and Scherrer (225") for determining free carbonic acid in water. K t h the mixed indicator, the titration end point is clearly discerned and values: of + I p.p.m. of carbon dioxide are distiuguishable in 100-nil. water samples. l l e t h o d ~for field determination of chloride, bicarbonate, :-idfate, calcium, and magnesium were described by Dublyans'kii (42'). Gubeli (72') described a method for determining ultra-traccs of silver iodide in rain water. The residue obtained by evaporating 50 liters of rsin water \vas fused with sodium carbonate and the metallic silver separated by extracting the mp!t with water. The silver was then determined by spot test, using p - dimethylaminobenzilidenerhodanine. Iodide was determined in the alkaline extract by oxidation with ferric ion, distillation in a nitrogen stream in the presence of carbon tetrachloride, and observing the intensity of the color reaction on paper strips treated with sodium fluorescein solution. A scheme for the conductometric analysis of natural water was proposed by Pasoirskaya (I 75"). Total hardness was determined by titration with EDTA: magnesium bj. a similar titration after fixing cnlciuni with oxalate; cal(ium by difference. Sulfate was determined indirectly by titrating the exce.s barium ions reqLiired for precipitntion. Chloride K:E titrated lvith mercuric nitrate, a n d carbonate hardness, in the nbsencr :if phosphates, determined b\- titration nith barium hydroside. The presence of phosphate necessitated precil~itntion nith. barium chloride and wparniion b\r filtration before titrating carbonate hardnc -411 titrations w r e performed conductometricdly. LITERATURE CITED lntroduction
(1j -in\, Public Hcaltli ~ ~ S S O CSew . York 1 9 , ~ sT., . "St>andard hlethods for the Ex:imin:itlon of b'ater,'' 11th ed., 1960; published jointly with .4m, Water Works
160 R
0
ANALYTICAL CHEMISTRY
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(1958). (19C) Lukasik-lvardzinska, H., Popowirz, J., Chern. Anal. (Warsaw) 3, 893-5 (1958). (20C) Majumdar, A . K., Savariar, C. P., Anal. Chim. Acta (in Eng.) 21, 47-52 (1959). (21'2) Martinez, 'F. B., Mendoza, R. R.,
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121-6 (1958). (14D) Houghton, G. I-., Z'ioc. SOC. W a f e r Treatment Rxani. 6, Pt. 1, 60-5 (1 9.57'1
(15Dj'Hu,H., Leu, Y., soong. H., m u , P., Hua Hsueh Hsueh Pao 24, 255-7
(1958). (1GD) Jacobs. W. D., Toe, J. H., Anal. Chim. Acto (in Eng.) 20, 435-43 (1959) (17D) Khalifa,, H... Ibzd.,, 17,. 318-21 (1957). (18D) Lazarev, A. I., Lazareva, 1'. I., Zae'odskaya Lab. 25, 783-6 (1959). 119D) Lieber, JI., Water and Seiaacqe TBorks 105, 374 (1958). 120D) McDowell, B. L., lleyer, A. S., Jr., Feathers, R. E., Jr., White, J. C., ANAL.CHEM.31, 931-4 (1959). 121D) Margerum, D. W., Santacana, F., Zbid., 32, 1157-61 (1960). (22D) RIart,inez, F. B., Mendozs, R.&,
Andes real SOC. espafi. fis. quzm. (Madrid) 55B, 299-304 (1959). (23D) Miller, A. D., Jibins, R. I., Z h w . Anal. Khim. 13, B64-7 (1958). (24D) Kieto, J. O., Bol. inform peti,o/. (Butnos Aires) No. 318, 641-3 (1!)59). (25D) Platte, J. A,, Marcy, V. I f . , ANAL.CHEM.31, 1226-8 (1958). (26Dj Popova, T. P., Shornik Nauch.Tekh. Inform., Ministerstca Geol. i Okhrany Xedr No. 1, 129-30 (1955): Referat. Zhur. Khim. Abstr. KO. 68,688 i l 9.56'1
127Di%ley, J. P., Sinhaseni, P., Analysl 83, 299-304 (1958). (28D) Tanaka, Y . , Ito, K., B7cnvki Kayaku 6, 728-31 (1957) Molybdenum, VanadiJm, Titanium, and Zirconium
Iron, Manganese, Aluminum, and Chromium
(1C) Allan, J. E., Spectrochim. Acta 8 0 0 4 (1959). (2C) Almassy, G., Kavai, M. Z., Magyar KCm. Folydirat 62, 325-6 (1957). (3C) Bankovskis, J., Ievins, A,, Lukm, E., Zhur. Anal. Khim. 14, 222-6 (1959). (4C) Catherino, H. A . , Meites, L., Anal. Chim. Acta (in Eng.) 23,57-65 (1960). (5C) Entz, B., Mag?iar Tudomanyos Akad. Tihanyi Biol. Kutatointezetenek Evkonyce
25, 173-8 (1957-8).
(6C) Eshelman, H. C., Dean, J. A , , Menis, O., Rains, T. C., ANAL.CHm. 31, 183-7 (1959). (7C) Grat-Cabanac, M., Anal. Chim. Acta (in French) 19, 108 (1958). ( 8 C ) Guerreschi, L., Romiat, R., Ricerca SCZ. 29, 2178-85 (1959). (9C) Gupta, H. K. L., Sogani, K.,J . Indian Chem. Soc. 36, 87-91 (1959).
(1OC) Hashitani, H., 1-amamoto, K.. IVippon Kagaku Zasshi 80, 727-31 (1959). (1lC) Holdoway, M. J., Willans, J. L., Anal. Chim. .4cta (in Eng.) 18, 3i6-80 IlQ.6F1~ \ A " Y - , .
(12C:) Ishihashi, M., Shigematsu, T., Xishikawa, Y., Bunseki Kagaku 6, 508-71 (1957). (13C) Tssa, I. M., I s m , R. M., Hewaidy, I. F., Omar, E. E., Anal. Chim. Acta ( i n I3ny.) 17, 434-9 (1957). (14C) J . Am. Water Works Assoc. 50, 832-4 (1958).
Copper, Zinc, Cadmium, Bismuth, Lead, Cobalt, and Nickel
( l D ) , Aleskovskii. V. E . Lihina, R. I., Miller, A . D.. Trudu Leriingrad. Tekhnol. Inst. im.Lensoreto 48, 5-11 (1058). (2D) Aleskovskii, V. B.! Dobychin, S. L., Kedrinskii, I. A , , Miller, -4. D., Mikheeva, -4. I., Mokhov, A. A , , h'azarova, 2 . K.,Ibid., 48, 12-21 (1958). (3D) Aleskovskii, V. B., Miller, A. D., Sergeev, E. X., Trudy Komispii Anal. Khirn., ilkad. 2Va,:ck S.S.S.R., InPt. Geokhim. i Anal. Khim. 8, 217-26 f 1958). \
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(8E) lbid., 22, 158--62 (1360). (9E) Okac, +4., Sommer, L., Anal. Chim. Acta (in Ger.) 15, 345-.% (1956,. (lor)I'eshkova? V. M., Mrl'chakova, N. V., Sinitsyna, E. D., Izcest. T'ysshikh Ccheb. Zavedenii, Khinz 7 Khirn. Tekhnol. 3, No. 1, 72-4 (1960). (11E) Sano, €I., R7tnseki Kugaku 7, 235-8 (1958). (12E) Sano, H., 'I'alanta 2, 187-90 (1059). (13E) Sugawara, K., Tanaka, M., Okabe, S., Bull. Chem. Soc. Japan 32, 221-2
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VOL. 33, NO. 5, APRIL 1961
161 R
Mercury, Silver, and Platinum Metals
( I F ) Beamish, F. E., McBryde, W. A. E., Anal. Chim. Acta (in Eng.) 18, 551-64 (1958). (2F) Chavanne, P., Geronimi, C., Anal. Chim. Acta (in French) 19, 442-7 (1958). (3F) Fiala, S., Vodni hospodarstwi 14, 372-3 f19.59). ,- - - , (4F) Grandi, F., Salvagnini, L., Chim. e ind. (Milan)41, 430-1 (1959). (5F) Hakkila, E. A., Waterbury, G. R., ANAL.CHEM.32, 1340 (1960). (6F) Havrankova, J., Volf, J., Pracovnz lekarstvi 10, 250-3 (1958). (7F) Israel, Y., ANAL.CHEM.31, 1473-5 (1959). (8F) Jacobs, UT.D., Zbid., 32, 512 (1960). (9F) Ibid., 32, 514 (1960). (10F) Jacobs, W. D., Yoe, J. H., Talanta 2, 270-4 (1959). (11F) Karas, V., Pinter, T., Croat. Chem. acta (in Ger.) 30, 141-7 (1958). (12F) Korshunov, I. A,, Malyugina, N. I., Vertyulina, L. N., Trudy Khim. i Khim. Tekhnol. 1, 419-22 (1958). (13F) Lindstrom, O., ANAL.CHEM.31, 461-7 (1959). (14F) Sen, B., Anal. Chirn. Acta (in Eng.) 21,3540 (1959). (15F) Sugihara, T., Nippon Kagaku Zasshi 81, 77-80 (1960). (16F) Surasiti. C.. Sandell. E. B.. Anal. C h h Acta (in Eng.) 22,261-9 (1960). (17F) Ugol'nikov, N. A., Ikonnikova, Z. P., Doklady 7-oi Nauch. Konf. Posvyaschen. 40-Eetiyu Velikoi Oktyabr. Sots. Revolyutsii, Tomsk. Univ. No. 2, 180 (1957); Rejerat. Zhur. Met. Abstr. S o . 21,814 1958). (18F) Wagner, V. L., Jr., Yoe, J. H., Talanta 2. 223-9 (1959). (19F) Xavikc J., Z.'anal: Chem. (in Eng.) 164, 2 5 0 4 (1958) ~
Tin, Germanium, Gallium, Indium, and Thallium
(1G) Anderson, J. R. A,, Costoulas, A. J., Garnett, J. L., Anal. Chim. Acta (in
Eng.) 20, 23642 (1959). (2G) Anderson, J. R. A., Garnett, J. L., Lock, L. C., Ibid., 19, 256-9 (1958). (3G) Cherkashina, T. V., Vladimirova, V. M., Zavodskaya Lab. 25, 1307-18 (1959). (4G) Garnett, J. L., Lock, L. C., Anal. Chim. Acta 17, 574-8 (1957). (5G) Gilbert, P. T., Jr., Spectrochim. Acta 12, 397-400 (1958). (6G) Ishibashi, M., Shigematsu, T., Yamamoto, Y., Inoue, Y., Bunseki Kagaku 7, 473-7 (1958). (7G) Karanovich, G. G., Ionova, L. A., Podol'skaya, B. L., Zhur. Anal. Khim. 13, 43944 (1958). (8G) Kazsrinova, N. F., Vasil'eva, N. L., Ibid.,13, 677-81 (1958). (OG) Kononenko, L. I., Poluektov, N. S., Zhid., 15, 61-8 (1960). (10G) Lukin, A. M. Bozhevol'nov, E. il.,Ibid.. 15, 43-8 (1960). (11G) Shakhova, Z. F., Motorkina, R. X., ikfetody Analiza Redkilch i Tsvet. Metal. (Moscow: Gosudarst. l7niv.l Sbornik 47-57 (1956); Rejerat. Zhur. Met. Abstr. No. 13,682 (1957). (12G) Stashkova, N. V., Zelyanskaya, A. I., Intvest. Sibir. Otdel. Akad. Nauk S.S.S.R. NO.1, 59-66 (1959). Rare Earths, Uranium, and Thorium
(1H) qiirnarin, I. P., Golovina, A. P., Kuteinikov, A. F., Dyull. Nauch Tekh. Znjorm., Ministerstvo Geol. i Okhrany Nedr. S.S.S.R. No. 7, 61-4 (1957). (2H) Dvorak, J., Rezac, Z., Chem. listy 53, 1113-31 (1959).
162 R
ANALYTICAL CHEMISTRY
(3H) Menis, 0.) Rains, T. C., Dean, J. A., ANAL.CHEM.31, 187-91 (1959). 2., Dean, ((4H) Menis, O., Rains, T. C., J. A., Anal. Chim. Acta (in Eng.) 19, 179-89 (1958). (5H) Milner, G. W. C., Bamett, G. A,, U. K. Atomic Energy Authority C/R 2723, 14 pp. (19B8). oshida, H., Izawa, ((6H) Motojima, K., Yoshida, K., ANAL.CHEM.32, 1084-5 (1960). (7H) Pollard, E. H., Hanson, P., Geary, W. J., Anal. Chim. Acta (in Eng.) 20, 26-31 (1959). (8H) Rains, T. C., House, H. P., Menis, 8, O., Zbid., 22, 315-27 (1960). (9H) Shibata, S., Zbid., 22, 479-84 (1960). (10H) Smith, G. H., Chandler, T. R. D. Proc. U . N . Intern. Conj. Peaceful Uses, Atomic Energy, 2nd, Geneva, 2, 148-52 (1858). (11H) Starik, I. E., Starik, A. S., Trudy Radievogo Znst. im. V . G. Khlopina 5, NO. 2, 105-16 (1957). (12H) Yakovleva, M.N., Shurshalina, hl. A., Radiokhimiya 1, 445-9 (1959). '
Boron and Selenium
(15) Bode, H., Mosenthin, H., Z . anal. Chem. 164, 232-41 (1958). (25) Bovalini, E., Piazzi, M., Ann. chim. (Rome) 48, 305-9 (1958). (35) Bovalini, E., Pucini, L., Lo Moro, A., Ibtd., 49, 1046-50 (1959). (45) Callicoat, D. L., Wolszon, J . D., ANAL.CHEM.31, 1434-7 (1959). (55) Callicoat, D. L., Wolszon, J. D., Hayes, J. R., Zbid., 31, 1437-9 (1959). (6J) Danielsson, L., Talanta 3, 138-46 (1959). (75) J. A m . Water Works Assoc. 50, 827-31 (1958). (a)Murata, A., Yamauchi, F., Xippon Kagaku Zasshi 79, 1454-8 (1958). (9J) Rainwater, F. H., J. A m . Water Works Assoc. 51, 1046-50 (1959). (1OJ) Rao, G. G., Appalarju, N., 2. anal. Chem. (in Eng.) 167, 325-9 (1959). (llJ) Ray, E. M., U . S. Atomic Energy Comm. GAT 289, 11 pp. (1959). (125) Schulek, E., Barcza,. L.,. Talanta 3, 27-30 (1959). (135) Spicer, G. S., Strickland, J. D. H., Anal. Chim. Acta (in Eng.) 18,. 231-9 (1958). (145) Zbid., 18, 523-33 (1958). (155) Watkinson, J. H., ANAL.CHEM. 32, 981 (1960). Chloride, Bromide, and Iodide
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(1
