ANALYTICAL CHEMISTRYJ. B. Headridge, T. B. Pierce, and D. M. W. Anderson( J . B. H.: Department of Chemistry, The University, S b m , 10; T. B. P.:Analytical Chemistry Group, A.E.R.E., Harwell; and D. M . W. A,: Department ofChemistry, University of Edinburgh, Edinburgh, 9)1. Introduction.-A most interesting paper on trends in analyticalchemistry in 1965 has been published, these being compared with trends in1946 and 1955.’ The following statement is from that article: “ I n broadcategories, the methods of analysis most commonly encountered in currentpublications are, in descending order, optical absorption and emission,titrimetry, gas analysis (including gas chromatography), electrical methods,radioactivity, gravirnetric methods, and X-ray methods.”One in seventeen of all papers abstracted in Chemical Abstracts 1965 awas on analytical chemistry, the number of abstracts on analytical chemistrybeing about 10,OOO.l Russia, Germany, the United States, Britain, andJapan have, in the last ten years, increased their output of papers on analy-tical chemistry by factors of approximately 4.8, 2-0, 1.7, 1.2, and 1.1 re-spectively.1In 1965, the trend towards the increased use of instrumental methods ofanalysis has continued.There is even greater interest than in 1964 in spectro-scopic methods of analysis and in electrochemical methods, particularlypolarography, voltammetry, and coulometry. Atomic absorption spectro-scopy and spectrofluorjmetry are continuing to receive attention from anincreasing number of analytical chemists.The research effort given to gravimetric methods of analysis is stiUdecreasing, as expected, but solvent extraction as a method of separationbefore solution spectrophotometric, atomic absorption spectrophotometric,and polarographic analysis, is receiving increasing attention.A very largenumber of papers on gas-phase chromatography continue to appear.2. Qualitative Analysis.-Chalmers and Dick have continued to developanalysis schemes based on combinations of solvent-extraction and spectro-photometry; Lyle and Shendrikar have described * the separation of gallium,indium, thallium, germanium, tin, and lead by solvent extraction withN-benzoyl- AT- phenylhydroxylamine .There have been other novel and interesting approaches.The separationand identification of Group I, 11, and IV cations by thin-layer chroma-tography on maize starch has been de~eloped,~ and a similar technique,using circular thin-layer chromatography,6 gives very rapid identification ofgroup I-V cations after group separation has been effected by classicalR. B. Fischer, Anulyt. Chern., 1965, 37, No. 13, 27A.R. A. Chalmers and D. M. Dick, AnuZyt. Chim. Ada, 1965, 32, 117.S. J. Lyle and A. D. Shendrikar, Analyt. Chim. Ada, 1965, 32, 576.M. H. Hashmi, M. A. Shahid, and A. A. Ayaz, Talanta, 1985, 12, 713.a Chern. Abs., 1965, 62 and 63.ti V. D. Canic and S. M. Petrovic, 2. analyt. Chem., 1966, 211, 321; V. D. Canic,S. M. Petrovic, and A. K. Bern, ibid., 1965, 213, 251512 ANALYTICAL CHEMISTRYprocedures.Ottendorfer has devised a method of combining the ring-oven with thin-layer chromatography, and a " slotted oven " for the identifi-cation of anions has been described.8" Co-ordination chain reactions " have been proposed for the examina-tion of ultra-trace quantities of cations that complex with EDTA ; extensionsof this sensitive technique t o other complexing systems seem feasible.Further developments are also likely to arise from the appIication10 ofcatalytic reactions to indicate end-points in titrimetric processes, and fromthe characterisation of some organic compounds by their self-emitted infra-red radiation.llFour novel methods of gas analysis have been proposed: Luis and SB 12have developed simple ultramicro- techniques using a stereoscopic micro-scope; Williams and Findeis l3 have developed " Geiger pulse attenuation ;"and detectors based on (a) electronic emission spectra of organic vapours 1.1and ( b ) the energy required to produce an ion-pair in a vapour ls have beendescribed.An important approach to the concentration of trace elements, offeringscope for development, is based on " precipitation ion-exchange :" thematrix and trace elements are adsorbed on a cation-exchange column, thenthe eluent precipitates the matrix and elutes the traces.16Separations of anions have been based on the use of cadmium acetate 1 7and silver chromate-impregnated paper.ls Freiser et al.19 have foundarylazo-8-quinolinols to form metal chelates at low pH values.The ana,ly-tical uses of compounds containing P=S and P(S)SH groups have beenreviewed,20 and Few 21 has described the colorimetric reactions of steroidswith perchloric acid and aromatic aldehydes.Enzymic analysis will become increasingly important in the future :Bergmeyer z2 has reviewed recent developments, and a technique for main-taining the activity of enzyme preparations has been described.233.Methods of Separation.--Solvent extraction. Details of an automatedthree-phase countercurrent apparatus have been p~blished,~4 and computer7 L. J. Ottendorfer, Analyt. Chim. Acta, 1965, 33, 115.8 M. A. Leonard, S. A. E. F. Shahine, and C. L. Wilson, Mikrochim. Ichnoanalyt.Acta, 1965, 160.D. W. Margerum and R. K. Steinhaus, Analyt. Chenz., 1965, 37, 222.lo H.Weivz and U. Muschelknautz, 8. analyt. Chem., 1965, 215, 17.lIM. J. D. Low, L. Abrams, and I. Coleman, Chenz. Comm., 1965, 389.l2 P. Luis and A. Sh, MikTochim. Ichnoanalyt. Acta, 1965, 621.l3 F. W. Williams and A. F. Findeis, Analyt. Chem., 1965, 37, 857.l4 A. J. McCormack, S. C. Tong, and W. D. Cooke, Analyt. Chem., 1965, 37,l6 J. E. Lovelock, Analyt. Chem., 1965, 37, 583.l8 F. Tera, R. R. Ruch, and G. H. Morrison, Analyt. Chem., 1965, 37, 358; R. R.l7 I. K. Taimni and R. Rakshpal, J . prukt. Chem., 1965, 25, 134.lo 5. Takamoto, Q. Fernando, and H. Freiser, AnaZyt. Chem., 1965, 37, 1249.2o T. H. Handley, TaZanta, 1965, 12, 893.21 J. D. Few, Analyst, 1965, 90, 134.22 H. M. Bergmeyer, 2. analyt. Chem., 1965, 212, 77.23 E. K. Baurnan, L.H. Goodson, G. G. Guilbault, and D. N. Kramer, Analyt.24 H. L. Meltzer, J. Buchler, and Z. Frank, Amzlyt. Chem., 1965, 87, 721.1470.Ruch, F. Tera, and G. H. Morrison, ibid., p. 1565.J. G. Sabo, Chemist-Analyst, 1965, 54, 110.Chem., 1965, 37, 1378J . B . HEADRIDGE, T . B . PIERCE, D . M . w. AXDERSOX 513techniques have been applied 25 in solvent extraction studies involvingtantalum fluoride with isobutyl ketone, N - benzoyl-N-phenylhydroxylamine,or tri-n-octylphosphine oxide. The latter reagent was also used in the deter-mination of zirconium and hafnium in niobium.26 Applications of tri-n-octylphosphine sulphide have also been investigated,z7 and Handley 28 hasused metal di-n-butylphosphorodithioates as solvent extractants. N -Benzoyl-N-phenylhydroxylamine 25 was also used by Lyle and Shendrikar 29in studies with protactinium.Stephen and Townshend 30 have studied the reactions of rhodaminederivatives with many metals, with special reference to the production ofsoluble complexes.Trifluoroacetylacetone has been used in conjunctiouwith ben~ene,~1 chl~roform,~~ or chloroform and isobutylamine 33 for theextraction of widely differing mixtures of cations.Other investigators have studied the separation of molybdenum( VI)from rhenium( N) with pentyl a~etate,~4 and of selenium from telluriumwith ethyl methyl ketone.35 Systematic studies of solvent mixtures for theseparation of the alkaline earths 36 and for the extraction of zinc oxinate 37have been published. Moore 38 has made an extensive investigation of theextraction of actinides and lanthanides, from aqueous solutions of a varietyof organic acids, with high-molecular-weight amines.Other extensivestudies have involved the extraction of palladium and rhodium,39 and thedistribution 40 of 45 elements between 83 yo 2-ethylhexanol-17 yo lightpetroleum and hydrochloric acid of different concentrations. Brooks 4 l hasproposed new techniques, based on liquid-liquid, discontinuous solventextraction, for the determination of trace elements in silicate rocks and insea water; enrichment factors of 400,000 are claimed.Applications of this convenient techniquecontinue to increase ; devices facilitating continuous-flow systems continueto be publi~hed,4~ and methods for increasing reproducibility 43 and pre-venting adsorbent loss 44 have been recommended.Thin-layer chromtttography.25 L.P. Varga, W. D. Wakley, L. S. Nicolson, M. L. Madden, and J. Patterson,seD. F. Wood and J. T. Jones, Analyst, 1965, 90, 125.27 D. E. Elliott and C. V. Banks, Analyt. Chim Acta, 1965, 33, 237.28 T. H. Handley, Analyt. Chem., 1965, 37, 311.2B S. J. Lyle and A. D. Shendrikar, Talanta, 1965, 12, 553.30 W. I. Stephen and A. Townshend, Analyt. Chim. Acta, 1965, 33, 257.31 G. P. Morie and T. R. Sweet, Analyt. Chem., 1965, 37, 1552.32 W. G. Scribner, W. J. Treat, J. D. Weis, and R. W. Moshier, Analyt. C'hetn.,33 W. G. Scribner and A. If. Kotecki, Analyt. Chem., 1965, 37, 1304.34V. Yatirajam and R. Prosad, Indian J . Chem., 1965, 3, 345.35 N.Jordanov and L. Futekov, Talanta, 1965, 12, 371.37 G. K. Schweitzer, R. B. Neel, and F. R. Clifford, Analyt. Chim. Acta, 1965, 33,38 F. L. Moore, Aizalyt. Chem., 1965, 3'7, 1235.39 H. C. Eshelman, J. Dyer, and J. Armentor, Analyt. Chim. Acta, 1965, 32, 411.*O K. A. Orlandini, M. A. Wahlgren, and J. Barclay, Analyt. Chem., 1965,37, 1148.O1 R. R. Brooks, Talanta, 1965, 12, 505 and 511.4 2 T. M. Lees, M. J. Lynch, and F. R. Mosher, J . C'lwontatog., 1965, 18, 595.4 3 L. X. Bark, R. J. T. Graham, and D. McCormick, Talanta, 1965, 12, 122.4 4 31. P. Clapp and J. Jeter, J . Chronzatog., 1965, 17, 558.Analyt. Chem., 1965, 37, 1003.1966, 37, 1136.E. Gagliardi and W. Likussar, Milerochim. Ichnoanalyt. Acta, 1965, 765.514514 ANALYTICAL CHEMISTRYOf the papers dealing with inorganic 45 applications, reference is restrictedhere to the separation of phosphates 46 on circular layers of corn starch, andto the separation of halides 47 and noble metal rhodizonates 48 on silica gel.A larger number of interesting papers were devoted to organic problems.Iodine-quenched fluorescence 49 offers a sensitive method of detection, andspectral reflectance 50 has been recommended for the estimation of amino-acids.Other investigators have studied the separation of ester~,~1 long-chaintertiary a m i n e ~ , ~ ~ quinones 53 on polyamide layers, terpene and sesquiterpenealcohols on silica gel impregnated with silver nitrate,54 and chlorophyll com-ponents on powdered sugar containing 3 yo starch.55 Acridones and phenan-thridones have been separated, and located 56 by fluorescence methodsemploying trifluoroacetic acid fumes and tetraethylammonium hydroxidesolution.Carbohydrate chemists 57, 58 have made extensive use of thin-layertechniques. Roudier 59 has compared the results given by paper chromato-graphy with those obtained for methylated monosaccharides on silica gellayers, and other investigators have published results obtained with celluloselayers,so Kieselgel G with sodium acetate 61 or boric acid,61, e2 and silica gelwith sodium hydrogen ~ u l p h i t e .~ ~Paper chromatography and partition chromatography on columns. Somany Papers were published under these classifisations that a very carefulselection of only the most important, in general terms, had to be made.Hesse 64 has found that the most important causes of change in, and lossof, substances during chromatographic separations are acid/base reactions,oxidation by heavy-metal oxides, autoxidation, and catalytic decomposi-tions by the stationary phase.Thoma a5 has applied regular solution theoryto the problem of selecting solvent components, and concluded that it is45 J. P. Garel, Bull. SOC. chim. France, 1965, 1899.46 V. D. Canic, M. N. Tur&ic, S. M. Petrovic, and S. E. Petrovic, Analyt. Chem.,4 7 E. Gagliardi and G. Pokorny, Mikrokhim. Ichnoanalyt. Acta, 1965, 699.48 H. HranisavljeviB- Jakovljevi6, I. Pej kovi6-Tadi6, and J. Milj kovib-Sto janovi6,49 E. V. Milborrow, J . Chromatog., 1965, 19, 194.50 M.M. Frodyma and R. W. Frei, J . Chromatog., 1965, 17, 131.5 1 J. A. Attaway, R. W. Wolford, and G. J. Edwards, Analyt. Chetn., 1965, 37,5 2 E. S. Lane, J . Chromatog., 1965, 18, 426.53 K. Egger and H. Kleinig, 2. analyt. Chem., 1965, 211, 187.64 E. Stahl and H. Vollmann, Tahnta, 1965, 12, 525.5 5 M.-D. Nutting, M. Voet, and R. Becker, Analyt. Chem., 1965, 37, 445.66 E. Sawicki, T. W. Stanley, W. C. Elbert, and M. Morgan, Talanta, 1965, 12,S. Chiba and T. Shimomura, Agric. and BioZ. Chem. (Japan), 1965, 29, 486.68 G. G. S. Dutton, K. B. Gibney, P. E. Reid, and K. N. Slessor, J . Chromatog.,59 A. Roudier, Bull. SOC. chim. France, 1965, 271.6o D. W. Vomhof Bnd T. C. Tucker, J . Chromatog., 1965, 17, 300.61 P. G. Pifferi, Anulyt. Chem., 1965, 37, 925.62H.Jacin and A. R. Mishkin, J . Chromatog., 1965, 18, 170.6s S. Adachi, J . Chromatog., 1965, 17, 295.84 G. Hesse, 2;. analyt. Chem., 1965, 211, 5.65 J. A. Thoma, Analyt. Chem., 1965, 37, 600.1965, 37, 1576.Mikrochim. Ichnoanalyt. Acta, 1965, 141.74.605.1965, 20, 163J. B. HEADRIDGE, T. B. PIERCE, D . M . w. ANDERSON 515often more profitable to study variations in solvent proportions rather thanchanges in the solvent components. Synthetic computer-generated peakshave been used 66 to investigate the effects of impurities on peak displace-ments and band broadening.decreases the time required forseparations of cations, and high-temperature paper chromatography hasalso led to faster separations.Badami 69 has reviewed reversed-phase partition column chromato-graphy. Berg 70 has inter-connected a series of individual columns, of suc-cessively decreasing volume, with glass couplers to facilitate larger-scaleseparations ; submicrogram amounts of thirteen metals have been separated '1from 50 grams of uranyl nitrate.The separation of fatty acids from C, to C16 has been achieved,52 onpaper impregnated with dimethylformamide, after their conversion intoNN- dimethyl-p- amino benzene- azop henac yl esters .A mercury film on platinum has been used 73 as the stationary phase in achromatographic separation of thallium, lead, indium, and tin in which theretention time depends on the applied potential.Nolecular-sieve chromatography.This technique is clearly in its infancy,and many of the greatly increased number of applications reported in thepast year have been highly specialised and empirical; Photaki has publisheda short Re~iew.~4 Many of the results reported have been obtained 759 76by using the Sephadex range of cross-linked dextrans, and some of the lesshighly cross-linked grades are best used with the reverse-flow technique.'?Column materials other than cross-linked dextrans are available for thistype of chromatography, e.g., silica gel,78 calcium phosphate,79 and theBio-Gel range of polyacrylamides .80Gm chromatography.A very large number of publications involving thistechnique continues to appear, and in this section also a very restrictedselection had to be made.Wilson and McInnes 81 have recommended an integration method ofeliminating errors arising from base-line drift in the measurement of peak66 P.D. Klein and B. A. Kunze-Falkner, Analyt. Chem., 1965, 37, 1245.67 Z. Zhu-Jun,ActaChim.8inkay 1965,31,355; Z.Dey1and J . Rosmus, J . Chromatog.,68D. French, J. L. Mancusi, M. Abdullah, and G. L. Brmnmer, J . Chrmatog.,ssR. C. Badami, Chem. and Id., 1965, 1211.70 0. W. Berg, Analyt. Chem., 1965, 37, 774.71 R. A. A. Muzzrtrelli and L. C. Bate, Tulunta, 1966, 12, 823.7 2 J . ChurGek, F. Kope6rly, M. Kulha*, and M. Jurecek, 2. analyt. Chem.,7 s W. J . Blaedel and J . H. Strohl, Anulyt. Chem., 1965, 37, 64.?OI. Photaki, Chimika Chronika, 1965, 30 A, 1.76 P. Andrews, Biochem. J., 1965, 06, 595.76A. A. Leach and P. C. O'Shea, J . Chromatog., 1965, 17, 245.77 F.Rothstein, J . Chromatog., 1965, 18, 36.781. P. Ting and W. M. Dugger, Analyt. Biochem., 1965, 12, 571.OS S. A. Kibardin, Uspekhi Khim., 1965, 34, 1472.A centrifugal acceleration technique1965, 18, 435.1965, 19, 445.1965, 208, 102.D. M. W. Anderson, I. C. M. Dea, S. Rahman, and J . F. Stoddart, Chem. Comm.,1965, 145; A. N. Schwartz, A. W. G. Yee, and B. A. Zabin, J . Chromatog., 1965, 20,164.81 J . D. Wilson and C. A. J . McInnes, J . Chromatog., 1965, 19, 486516 ANALYTICAL CHEMISTRYareas, and Teitelbauni 82 has discussed some errors that may arise in resultsfrom dual-column chromatographs. Other authors 83, 84 have also consideredsources of error in quantitative analyses, and electronic methods of elimi-nating tailing and of sharpening individual peaks in a gas chromatogramhave been published.85A low-pressure d.c.discharge detector has been described;86 it is simplet o construct and operate, and has a sensitivity comparable with the flame-ionisation detector.Dal Kogare 87 has considered the use of organic solids as adsorbents,and Dewar 88 has indicated some possible advantages of liquid crystals assolvents in gas chromatography. The advantages of operating at low tem-peratures has been Deans has published a useful techniquefor back-flushing columns that eliminates dead-space and stop-cocklubricants .A number of Papers have been concerned with the use of gas chromato-graphy in conjunction with some other technique: Juvet and Turner 91 havefollowed the controlled degradations given by high-intensity mercury radia-tion; several authors, e.g.,92 have continued to devise trapping-systems tocollect g.1.c.fractions for investigation by infrared, ultraviolet, or massspectroscopy ; and there has been increased interest in investigations of thepyrolysis products of natural 93 and synthetic 94-g6 polymers.Tri-fluoroacetylacetonates have been investigated g' with an electron capturedetector, and 2-2 x 10-l2 g. of rhodium can be detected. Juvet and Fisher 98have separated a number of heavy metals as their fluorides, using a thermalconductivity detector fitted with nickel filaments to resist corrosion.Of the organic applications, the use of trimethylsilyl derivatives has ledto advances in the separation of inositols, 99 pentaerythritols,lOO and sugars ;lo1the latter have also been separated after conversion to their alditol acetates.102Other complex natural products to have been investigated include the VitaminTwo papers are likely to lead to important inorganic advances.8 2 C.L. Teitelbaum, Analyt. Chem., 1965, 37, 309.8 3 M. F. Barakat, 2. analyt. Chem., 1965, 209, 384.8 5 J. W. Ashley, jun., and C. N. Reilley, Analyt. Chem., 1965, 37, 686.88M. J, S. Dewar and J. P. Schroeder, J. Org. Chem., 1965, 30, 3485.89 W. A. Van Hook and M. E. Kelly, Analyt. Chenz., 1965, 37, 508.OO D. R. Deans, J. Chromatog., 1965, 18, 477.SIR. S. Juvet, jun., and L. P. Turner, Analyt. Chem., 1966, 37, 1464.szH. T. Badings and J. G. Wassink, J. Clarmtog., 1965, 18, 159.93 S.Glassner and A. R. Pierce, Analyt. Chem., 1965, 37, 525.O 4 R. L. Gatrell and T. J. Mao, Analyt. Chem., 1965, 37, 1294.95 B. Kolb, G. Kemmner, K. H. Kaiser, E. W. Cieplinski, and L. S. Ettre, 2. aizalyt.$ 6 F. G. Stanford, Analyst, 1965, 90, 266.9 7 W. D. Ross, R. E. Sievers, and G. Wheeler, jun., Analyt. Chenz., 1965, 37, 59s.$8R. S. Juvet, jun., and R. I;. Fisher, Analyt. Chem., 1965, 37, 1752.99 Y. C. Lee and C. E. Ballou, J. Chromatog., 1965, 18, 147.B. D. Sully and P. L. Williams, Analyst, 1965, 90, 643.E. R. Fisher and M. M. McCarty, jun., Analyt. Chem., 1966, 37, 1208.S. Dal Nogare, Amlyt. Chem., 1965, 37, 1450.Chenz., 1965, 209, 302.l o o R. R. Suchanec, Analyt. Chem., 1965, 37, 1361.l01 J. S. Sawardeker and J.H. Sloneker, Analyt. Chenz., 1965, 37, 945.lo2 J. S. Sawardeker. J. H. Sloneker, and A. Jeanes, Analyt. Chenz., 1965, 37,1602J . B . HEADRIDGE, T . B . PIERCE, D . M . w. ANDERSON 517D group,lO3 glyceride ~ i l s , ~ ~ ~ and amino-acids as their N-trifluoroacetyl-n-butyl esters .lo5Ion-exchange. Schmuckler 106 has reviewed the properties and analyticalapplications of chelating resins. Although publications in this field in 1965have been largely inorganic in nature, organic topics have included (a;) theseparation of aldehydes in the bisulphite form,l07 ( b ) the separation of amines,particularly diamines, on cation resins loaded with nickel ions,lo8 ( c ) theseparation of monosaccharides by an automated procedure,log and (d ) thepreparation and properties of quaternary cellulose anion-exchangers.llOThe use of liquid ion-exchangers has continued to attract attention:Irving and Damodaran ll1 have determined perchlorate in the presence ofother halogen acids by means of a coloured anion-exchanger; Rao andSastri 112 have separated some elements on silica columns treated with aliquid cation-exchanger.An interesting preliminary report 113 has shownthat liquid ion-exchangers can be used to pre-treat silica gel for use in thin-layer chromatography.Ion-exchange selectivity scales have been published 114 for a large numberof cations, in nitric acid and in sulphuric acid media, on a sulphonated poly-styrene resin. Thiocyanate- based eluants have been used frequently,lI5and several groups of investigators have studied general separations of thealkali meta1s,ll6 the alkaline earths,llT and the rare earths.ll8 More specificapplications have included the determination of rhenium ;l19 the separationof silver ;12* and analyses of bronze,121 silicate rocks,122 and thorium-uraniumand plutonium-thorium-uranium alloys.123Electrophoresis. Gross 124 has published a Review of electrophoresis inlo3 P.P. Nair, C. Buca,na, S. De Leon, and D. A. Turner, AnaZyt. Chem., 1965,lo* T. L. Mounts and H. J. Dutton, Analyt. Chem., 1965, 37, 641.lo5 W. M. Lamkin and C. W. Gehrlre, AnaZyt. Chem., 1965, 37, 383; F. Marcucci,lo6 0. Schmuckler, Talaiata, 1965, 12, 281.lo' K. Christofferson, Analyt. Chim Acta, 1965, 33, 303.lo8 J. J. Latterell and H.F. Walton, Analyt. Chim. Acta, 1965, 32, 101.log L. A. Larsson and 0. Samuelson, Acta Chem. Scand., 1965, 19, 1357.110 R. R. Benerito, B. B. Woodward, and J. D. Guthrie, AnaZyt. Chenz., 1965,37, 1693.ll1 H. M. N. H. Irving and A. D. Damodaran, Analyst, 1965, 90, 443.112 A. P. R'ao and M. S. Sastri, 2. analyt. Chem., 1965, 207, 409.113 U. A. T. Brinkman and G. de Vries, J. Chronzatog., 1965, 18, 142.114 F. W. E. Strelow, R. Rethemeyer, and C. J. C. Bothma, Analyt. Chena., 1965,37, 106.115 A. K. Majumdar and B. K. Mitra, 2. analyt. Chem., 1965, 208, 1; D. J. Pietrzykand D. L. Kiser, Analyt. Chem., 1965,37,233; H. Hamaguchi, K. Ishida, and R. Kuroda,dltalgt. Chim. Acta, 1965, 33, 91.116 E. D. Olsen and R. L. Poole, jun., Analyt. Chem., 1965, 37, 1375; F.Nelson,D. C. Michelson, H. 0. Phillips, and K. A. Kraus, J. Chromatog., 1965, 20, 107; E. D.Olsen, and H. R. Sobel, Takznta, 1965, 12, 81.11' R. Christova and P. Ilkova, Analyt. Chim. Acta, 1965, 33, 434; M. H. Campbell,dnalyt. Chenz., 1965, 37, 262.118 B. L. Jangida, N. Krishnamachari, M. S. Varde, and V. Venkatasubramanittn,Analyt. Chiin. Acta, 1965, 32, 91.119 S. Kallmann and H. K. Oberthin, Analyt. Chem., 1965, 37, 280.lz0 A. V. Rangnekar and S. M. Khopar, Mikrochim. Ichnoanalyt. Acta, 1965, 642.121A. K. De and A. K. Sen, 2. analyt. Chem., 1965, 211, 213.122 A. D. Maynes, Analyt. Chim. Acta, 1965, 32, 211.lZ3 E. A. Huff, Analyt. Chem., 1965, 37, 533.lz4 D. Gross, Analyst, 1965, 90, 380.57, 631.E. Blussini, F. Poy, and P.Gsgliardi, J. Chromatog., 1965, 18, 48751 8 ANALYTICAL CHEMISTRYstabilising media. The more interesting developments have included appli-cations of continuous electrophoretic separation,l25 quantitative filter-paperelectrophoresis by means of reflectance densitometry,lZ6 the identification ofaromatic substances by “ electrophoretic spectra,” 127 and the use of ‘‘ Cel-logel” strips,128 which combine the advantages of both gel and paperelectrophoresis.Thorium, protactinium, and uranium have been separated as theiroxalate ~ornplexes,l~~ and organic applications have included separations ofsugars by high-voltage paper electrophoresis,l30 preparative zone electro-phoresis of proteins on polyacrylamide gels in 8~ urea,131 and the identifica-tion and assay of antibiotics by electrophoresis in agar gel.1324.Gravimetric halysis.-An important series of papers has been contri-buted by Klein and his co-workers, who have studied fundamental aspectsof the co-precipitation of lead with barium sulphate,l33 and also the kineticsof the precipitation by thioacetamide of zinc sulphide and nickel sulphide.134Klein and Swift 135 have further observed that two distinct nucleation pro-cesses may occur in the thioacetamide precipitation of metal sulphides.Other investigators 136 have also studied aspects of the precipitation ofmolybdenum sulphide by thioacetamide.Considerable attention has been paid to precipitation from homogeneoussolution, e.g., of aluminium as basic aluminium benzoate,137 of lead sulphateby sulphamic and of zirconium tetramandelate by hydroxypropylmm1de1ate.l~~ Precipitation from homogenous solution has also been usedfor the determination of barium, strontium, and calcium in barium per-oxide,140 and for the elimination of co-precipitation errors in the determina-tion of nickel with cyclohexane-l,2-dione dioxime.141As was the case last year, there have been very few papers on gravi-metric procedures for anions, although Heslop and Pearson142 have usedradionuclides to study the effect of arsenate and transition metals on theprecipitation of phosphate as ammonium molybdophosphate.Arsenic isalso precipitated under the conditions necessary for the quantitative preci-pitation of phosphorus, and the presence of ferric nitrate inhibits the preci-pitation of phosphorus.125 N.E. Skelly, Analyt. Chem., 1965, 87, 1526.126 A. L. Latner and D. C. Park, CZin. Chim. Ada, 1965, 11, 538.127 J. Franc and W. Kov&3, J . Chromatog., 1965, 18, 100.12s H. Keller and H. Seeger, 2. anaZyt. Chem., 1965, 212, 125.129 E. Merz, 2. analyt. Chem., 1965, 211, 331.130M. Ferencik and I. Ciznar, Chem. Zisty, 1965, 59, 332.1 3 1 P . H. Duesberg and R. R. Rueckert, AmZyt. Bkchem., 1965, 11, 342.132 J. W. Lightbown and P. De Rossi, Analyst, 1965, 90, 89.133 D. H. Klein and B. Fontal, Talanta, 1965, 12, 35.134 D. H. Klein and E. H. Swift, Talanta, 1965,12,349; D. H. Klein, D. G. Peters,135 D. H. Klein and E. H. Swift, Talanta, 1965, 12, 363.136 F. Buriel-Marti and A. Macerira-Vidan, Anales real Xoc.espaii. B’Fia. Quim., 1965,137 R. J. Irving, Talanta, 1965, 12, 1046.138 J. E. IColes, P. A. Shinners, and W. F. Wagner, Talanta, 1965, 12, 297.139 J. C. Rowe, L. Cordon, and W. G. Jackson, Tahnda, 1965, 12, 101.lQo G. Norwitz, Analyst, 1965, 90, 554.141P. D. Jones and E. J. Newmrtn, A d y s t , 1965, 90, 112.1 4 2 R . B. Heslop and E. F. Pearson, Analyt. Chim. Acta, 1965, 33, 522.and E. H. Swift, Tdantu, 1965, 12, 357.61, B, 867J. B. HEADRIDGE, T. B. PIERCE, D . M. w. ANDERSON 519Palladium has been determined with salicyloylhydrazide,l43 and a newreagent, 3,3-diphenylindane-l,2-dione dioxime, has been proposed 144 forthis metal. Christopher and Fennell 145 have studied the determination, asquinoline silicomolybdate, of silicon in organic materials.The preparationof sodium tetrakis-(p-chlorophenyl) borate has been described ;Ia6 it offerspossibilities for determinations of potassium, rubidium, cesium, quaternaryammonium, and protonated basic nitrogen compounds. Rubidium andcmium have also been determined with NN-dimethylethanolamrnonium0r0tate.l~'A new method of precipitating uranium, involving paminobenzoic acidand pyridine in aqueous solution, has been described.148 An interestingmicrogravimetric determination of gold 149 as bis( trimethy1)decamethylene-diammonium tetrabromoaurate(r) allows determination of 700 pg. gold inthe presence of 200-fold excesses of copper and nickel and 50-fold excesses ofother transition metals.5,5'-Thiodisalicylic acid 15* shows promise as a reagent for lead(=),zirconyl(n), indium(m), thorium(Iv), cerium-(m) and -(Iv), and other rareearths.The precipitation of calcium as molybdate,151 and the direct gravi-metric determination of calcium in silicates,152 have been studied.Many other publications in this section appeared during the year, butspace restricts any further mention to the following: the determination ofantimony with 1,2-dim0rpholylcthane,~5~ the determination of thorium inzirconium-hafnium mixtures by aromatic polycarboxylic acids,154 the deter-mination of lanthanum with N - ben~oyl-N-phenylhydroxylamine,~~5 thedetermination of indium with benzenephosphonic acid,156 and the deter-mination of beryllium as a double complex of hexamminecobalt(n1) ion witha di beryllium tricarbonato- complex .I575.Visual Titrations.-As in 1964 most of the progress in visual titrationsfor 1965 has involved redox and complexometric reactions, and rela-tively few papers on acid-base and precipitation titrations have beenpublished.Redox. A saturated solution of hexamminecobalt(1n) tricarbonato-cobaltate(1n) in saturated sodium hydrogen carbonate solution has been usedas a titrant for the determination of iron(@, vanadium(rv), and cerium(m)in acid solution. The hydrated cobalt(1rr) ion is released in acid solution.S. C. Shome and H. R. Das, Analyt. Chim. Acta, 1965, 32, 400.14* L. S. Bark and D. Brandon, Talanta, 1965, 12, 781.145 A. J. Christopher and T. R. F. W. Fennell, Talanta, 1965, 12, 1003.14* F. P.Cassaretto, J. J. McLafferty, and C. E. Moore, Analyt. Chim. Acta, 1965,N. Z. Babbie and W. Wagner, TaEanta, 1965, 12, 105.148 R. Ripan and V. Sacelean, Talanta, 1965, 12, 69.14s M. Ziegler and H. Neygenfind, Mikrochim. Ichnoanalyt. Acta, 1965, 729.150 M. L. Good and S. C. Srivastava, Talanta, 1965, 12, 181.151 K. F. Kharitonovich and M. L. Chepelevetskii, Zhur. anaEit. Khim., 1965, 20,lS2 A. D. Maynes, Analyt. Chim. Acta, 1965, 32, 288.153 E. Asmus and D. Ziesche, 2. analyt. Chem., 1965, 210, 177.154 A. K. Mukherji, 2. analyt. Chem., 1965, 209, 321.lS5 B. Das and S. C. Shome, Analyt. Chim. Acta, 1965, 32, 52.156 A. K. Mukherji, 2. analyt. Chem., 1965, 210, 260.15' G. Gottschalk and P. Dehmel, 2. analyt. Chem., 1965, 212, 380.32, 376.743520 ANALYTICAL CHEMISTRYVisual, potentiometric, or photometric end-point detection may be em-ployed .158Titrimetric methods for the determination of reducing sugars have beenreviewed.159 Benzoquinones and naphthaquinones have been determinedby reacting them with an excess of standard titanium(n1) chloride solutionat room temperature and back-titrating the unreacted titanium(@ withstandard iron( 111) solution, using ammonium thiocyanate as indicator.l60Ozonides in alcohol solution have been quantitatively determined by reactionwith an excess of triphenylphosphine followed by titration of unreactedtriphenylphosphine with standard iodine solution.l6lR i , ,O-0, ,R' R',RZ \o/ '' R2 R23- Ph3P cj.2 ,C=O + PhJPOPhJP + I, HlO Ph3PO 4- 2H1Parathion (diethoxy-p-nitrophenoxyphosphine sulphide) in solid samplesand emulsion concentrates has been determined by reaction with excess ofstandard chloramine-T solution, followed by the addition of potassiumiodide solution and the titration of liberated iodine, equivalent to the un-reacted chloramine-T, with standard thiosulphate solution.162(R),R'PS + 5H,O --+ (R),R'PO + SO,2- + 10H+ + 80Glycerol has been satisfactorily determined by adding copper( 11) chloridein slight excess to the alkaline solution, removing the precipitate of copper(n)hydroxide by filtration, and determining the copper(I1) in the copper(1r)-glycerol complex by adding sulphuric acid and potassium iodide, and titrat-ing the liberated iodine with standard thiosulphate s01ution.l~~A short Review on chelometric titrations has beenpublished 164 and complexometric methods in clinical analysis have beenreviewed.165 The determination of tervalent and quadrivalent metallic ionsby complexometric titration has been reviewed,166 and the effect of nitrilo-triacetate on the standardisation of solutions of EDTA has been examined.lG7The theory of complexometric titrations based on extractive end-pointdetection has been published.168 Further contributions to the theory ofcomplexometric titrations have been reported, and the sharpness of visual,photometric, potentiometric, and amperometric end-point detection hasbeen discussed.16gComplexometric.168 J.A. Baur and C. E. Bricker, Analyt. Chem., 1965, 37, 1461.lSD C. Hennart, Bull.SOC. chirn. France, 1965, 1588.160 T. Gerstein and T. S. Ma, Mikrochim. Ichnoanalyt. Actn, 1965, 170.0. Lorenz, Arzalyt. Chem., 1965, 37, 101.lea V. Laxminarayana and A. R. V . Murthy, Chenaist-Analyst, 1965, 54, 9.lsa J. T. McAloren and G. F. Reynolds, AnaZyt. Chim Acta, 1965, 32, 170.164 C. N. Reilley, Analyt. Ghein., 1965, 37, 1298.166 A. Holasek, 2. analyt. Chem., 1965, 212, 90.166 R. Pi.ibi1, Talanta, 1965, 12, 925.la' R. N. P. Farrow and A. G. Hill, Analyst, 1965, 90, 210.1*8 E. Still, Talanta, 1965, 12, 817.lBS M. Tanaka and G. Nakagawa, Analyt. Chiin. Acta, 1965, 32, 123J. B . HEADRIDGE, T. B. PIERCE, D . M . W . STDERSON 521Interference from iron( 111) in the complexometric back-titration of excessof EDTA or DCTA over zinc, lead, cobalt, nickel, copper, and cadmium a tpH 5-0-5-5, with standard lead nitrate solution as titrant, is prevented byprecipitating the iron as potassium hexafluoroferrate(m) on the addition offluoride and potassium ions.170 It has been reported that the interaction ofXylenol Orange with cetylpyridinium bromide allows the extension of itsuseful range as indicator to pH 11.Under these conditions sharp end-pointsare obtained with Xylenol Orange in the titration of calcium, zinc, man-ganese( II), magnesium, and cadmium in alkaline solutions using EDTA astitrant . l 7 1Calcium in serum and urine has been determined by EDTA titarationusing Hydroxy Naphthol Blue as indicator. Iron, magnesium, copper,phosphate, and bilirubin in concentrations normally encountered in serumand urine did not interfere with the reaction of the indi~ator.17~ Microgramquantities of zirconium have been satisfactorily determined by titration inO~05-2~3~-hydrocholoric acid with standard EDTA solution using MethylThyinol Blue as indicator.The effects of other ions on the titration havealso been rep0rted.l7~The interference by phosphate and fluoride in the mercurimefric titrationof chloride using diphenylcarbazone as indicator has been eliminated by pre-cipitating phosphate and fluoride with thorium nitrate solution before thetitration. Such a titration has been applied to the determination of chlorinein organic compounds containing phosphorus and fluorine after an oxygenflask combustion.l 74 A method based on titration with o-hydroxymercuri-benzoic acid has been described for the determination of aliphatic and aro-matic mercaptans in organic solvents using thiofluorescein as indicator.175Sulphur, carbon disulphide, and other disulphides do not interfere.A new indicator made by coupling diazotised 4-nitro-aniline-2-sulphonic acid with chromotropic acid is suitable for the titrimetricdetermination of sulphate ions with standard barium solution. There is nointerference from a 15-fold excess of phosphate.176Standard solutions of silver nitrate and o-hydroxymercuribenzoic acidhave been used as titrants with p-dimethylaminobenzylidinerhodamine asindicator for the titrimetric determination of chloride, bromide, iodide,thiocyanate, ferrocyanide, tetraphenylboron, thiourea, thiosemicarbazide,diphenylurea, t,hioacetamide, o-phenylenethiourea, ethylenethiourea, 00-diethyldithiophosphoric acid, and mercaptans in acidic aqueous ethanolsolutions.o-Hydroxymercuribenzoic acid forms soluble complexes witht.hese substances and the titrations with this reagent are actually based oncomplexometric rather than precipitation reactions.177-4cid-base. Carbon in iron and steel has been determined by combustionPrecipitation.l i 0 R. Pi.ibi1 and V. Veself, Talanta, 1965, 12, 385.171 V. ChromJi and V. Svoboda, Talanta, 1965, 12, 437.172 G. Cartledge and H. G. Briggs, Clinical Chem., 1965, 11, 521.173 S.-C. Hung and H.-S. Chang, Acta Chim. Sinica, 1964, 30, 492.li4 A. F. Colson, AnaZyst, 1965, 90, 35.l i 5 M.Wronski, 2. analyt. Chem., 1964, 206, 352.176 V. I. Kuznetsov and N. N. Basargin, Zacodskaya Lab., 1965, 31, 538.li7 M. Wronski, Talanta, 1965, 12, 593522 ANALYTICAL CHEMISTRYof the sample in a stream of oxygen, absorption of the carbon dioxide thusproduced in dimethylformamide, and titration of this solution with astandard solution of tetra-n-butylammonium hydroxide in benzene-methanol using Thyrnolphthalein as indicator. An automatic potentio-metric titration can also be employed.1786. Instrumental Titrations.-In 1965 a large number of papers appearedon potentiometric titrations, and amperometric and coulometric titrationsreceived considerable attention, but papers on conductometric, photometric,and thermometric titration formed only a small proportion of all those oninstrumental titrations.Potentiometric titrations. A further contribution to the theory of poten-tiometric titrations in glacial acetic acid has now been published.l7Q Mono-basic acids with pKa values up to 5.5 have been determined in acetonitrilein the presence of their anhydrides by potentiometric titration with a stan-dard solut,ion of tri-n-propylamine in acetone.180 Sulphinic acids and mix-tures of sulphinic and sulphonic acids have been determined with goodaccuracy and precision by potentiometric titration in nonaqueous solventsusing quaternary ammonium hydroxides as titrants ,181Constant-current potentiometric end-point detection with two smallplatinum electrodes has been applied successfully to the determination of10-60 p.p.m.of water in organic solvents using Karl Fischer reagent astitrant and N-ethylpiperidine as catalyst.182 Wranium(vI) has been deter-mined by reduction to uranium(1v) with an excess of iron(=) in 12~-phos-phoric acid solution, followed by potentiometric titration with standardpotassium dichromate s01ution.l~~Milligram quantities of chlorate have been determined in phosphoricacid solution with osmium tetroxide as catalyst by potentiometric titrationwith standard ferrous ammonium sulphate solution. Chlorate is reduced tochloride.184 Chlorate has also been determined by direct potentiometrictitration with standard arsenite with osmium tetroxide as ~ata1yst.l~~Milligram amounts of bromide and iodide have been satisfactorily deter-mined by potentiometric titration with standard lead(1v) acetate solution.lSsThe same titrant has also been employed in the potentiometric titration oforganic sulphides in aqueous acetic acid solution.The sulphides are oxidisedto s~lphoxides.~~~A continuous automated potentiometric titrator with a flow-throughdropping mercury electrode has been described for the precise complexo-metric determination of metal ions at millimolar concentrations.la8 Poten-tiometric end-point detection with a silver indicator electrode and with178 R. F. Jones, P. Gale, P. Hopkins, and L. N. Powell, Analyst, 1965, 90, 623.lSo H. W. Wharton, Analyt. Chem., 1965, 37, 730.181 D. L. Wetzel and C. E. Meloan, Analyt. Chem., 1964, 36, 2474.lS3 G.G. Rao, P. K. Rao, and M. A. Rahman, Tahnta, 1965, 12, 953.lS4 J. Vulterin, Coll. Czech. Chem. Comm., 1965, 30, 1505.Is5 P. K. Norkus, Zhur. analit. Kltim., 1965, 20, 496.186 V. Buzkova, N. Moldan, and J. Zyka, Coll. Czech. Chern. Comm., 1965, 30, 28.M. Tanaka and G. Nakagawa, Analyt. Cltirn. Acta, 1965, 33, 543.E. E. Archer and H. W. Jeater, Analyst, 1965, 90, 351.L. Suchomelova, V. Horak, and J. Zyka, Microchem. J., 1965, 9, 201.W. J. Blaedel and R. H. Laessig, Analyt. Chem., 1965, 37, 1255J . B. HEADRIDGE, T. B. PIERCE, D . M. w. ANDERSON 523EDTA as titrant has been applied to the direct titrimetric determination ofbarium, bismuth, cadmium, calcium, cerium(rv), cobalt(@, copper(n), mer-c u r y ( ~ ) , lanthanum, magnesium, manganese( n), nickel, lead, strontium, andzinc in borate buffer solution after the addition of silver-EDTA complex.A back-titration procedure was used for the determination of aluminium,thorium, thallium(rn), and zirconium.169 Bismuth, indium, and thoriumhave been satisfactorily titrated in 0~2~-monoch~oroacetic acid solution atpH 2 with standard EDTA solution using a ferrous-ferric system as indicatorand potentiornetric end-point detection.1900.01-3 =mole samples of perchlorate have been determined with goodprecision, after reaction with an excess of solid vanadium(1n) sulphate in8M-sulphuric acid in the presence of osmium tetroxide catalyst, followed bypotentiometric tit<ration of the resulting chloride with standard silver nitiratesolution .l 91A high-sensitivity recording conductomet)ric titratorhas been described for the determination of low concentrations of acid orother species in the presence of high concentrations of foreign electrolytes.192An apparatus for automatic, conductometric, acid-base titrations in non-aqueous media has been described.193Amperornetric.The smperometric titration of organic compounds hasbeen revie~ed.1~4Biamperometric end-point detection using lead amalgam electrodes hasbeen applied to the titrimetric determination of lead with standard EDTAsolution.195 Biamperometric titration with two carbon electrodes has beensuccessfully employed for the determination of 1-150 mg. of iron(m) usingstandard EDTA as titrant. Many common metallic ions, and cations, haveno interfering effect on the uetermination.lg6 Biamperometric titration withtwo stationary platinum electrodes can also be used for the determination of1-150 mg.of copper(=) with standard EDTA as titrant.lg7 A rapid methodfor the precise determination of silver in non-ferrous metals by amperometrictitration with sodium diethyldithiocarbamate in ammoniacal medium hasbeen described.ls8 Amperometric end-point detection using a rotatingplatinum electrode has been applied to the precise determination of uranium-(m) by titration with standard iron(m) solution.19QAn automatic amperometric titrator using a stationary mercury electrodehas been described for the titration of sulphate with standard lead nitratesolution.200 Amperometric end-point detection has been applied to theConductometric.lS9 F.Strafelda, (2011. Czech. Chem. Comm., 1965, 30, 2320.190 T. Nomina, T. Dono, and G. Nakagawa, Japan Analyst, 1965, 14, 197.lBID. A. Zatko and B. Kratochvil, Analyt. Chem., 1965, 37, 1560.lg2 T. R. Mueller, R. W. Stelzner, D. J. Fisher, and H. C. Jones, Analyt. Chem.,lo3 W. Boardmas and B. Warren, Chern. a d Ind., 1965, 1634.lg4 A. Berka, J. Doleial, and J. Zyka,, Chemist-Analyst, 1965, 54, 24.Io5 H. L. Kies, J . Electroanalyt. Chern., 1964, 8, 325.lg6 J. VorliEek and F. Vydra, Talanta, 1965, 12, 377.lg7 J. VorliEek and F. Vydra, Talenta, 1965, 12, 671.lo* V. I. Lotareva, Zhur. analit. Khim., 1965, 20, 790.1965, 37, 13.R. F. Syrnpson, R. P. Larsen, R. J. Meyer, and R. D. Oldham, AnaEyt. Chem.,S.A. Myers, jun., and W. B. Swann, Talanta, 1965, 12, 133.1965, 37, 68524 A N ,4 L Y T I C B L C H E MI S TR Ydetermination of inorganic chlorides and bromides in glacial acetic acid usingstandard cadmium nitrate solution as titrant .201 Perchlorate has been deter-mined by amperometric titration with a standard solution of fetraphenyl-stibonium sulphate. There is no interference from chloride, chlorate, nitrate,phosphate, or sulphate.202Both aliphatic and aromatic amines have been determined in a dioxan-water mixture, which is 1~ in hydrochloric acid, by amperometric titrationa t +0.4 v (s.c.e.) using a standard solution of calcium hypochlorite as titrant.The 27-chloroamides are produced in the rea~tion.~03Photometric. A further contribution to the theory of photometric titra-tion curves in the presence of indicators is reported for complexometric andacid-base tit ration^.^^^ The construction and evaluation of a semi-immersionphototitrator has been de~cribed.~O~Iron(m), in the presence of high concentrations of bismuth in solutions ofpH 2-3, has been determined by spectrophotometric titration with standardEDTA solution using sulphosalicylic acid as indicator.The bismuth ismasked with a high concentration of ammonium chloride.206 Photometricend-point detection has been applied to the determination of thiols by titra-tion with standard ammonium chloropalladite solution using p-nitrosodi-methylaniline as indicator.207The application of thermometric titration to redoxreactions has been discussed.208 It has been shown that when acids in ace-tone solution are titrated with non-aqueous alkali solution, a rapid rise intemperature occurs beyond the end-point, owing to the formation of diace-tone alcohol. The method has been applied to the precise determination of2,6-&substituted phenols, keto-enols, and imide~.~O~ Alkylaluminium com-pounds have been satisfactorily determined by thermometric titration, therecommended titrants being di-n-butyl ether, benzophenone, t- butyl alcohol,and isoquinoline.210 Thermometric titration has also been applied to thedetermination of diethylzinc in hydrocarbon solution, with o-phenanthrolineand 8-hydroxyquinoline as titrants.211The principles of coulometric titrimetry 213 and recentdevelopments in this technique 213 have been reviewed.Automatic recordingequipment for continuous coulometric titrations has been described.214The capabilities of a relatively simple coulometric titrator have been assessedThermometric.Coulometric.801 A. P. Kreshkov, V. 9. Bork, L. A. Shvyrkova, and M. I. Apasheva, 2hw. analit.202 M. D. Morris, Aizalyt. Chem., 1965, 37, 977.Z o 3 W. R. Post and C. A. Reynolds, Analyt. Chem., 1965, 37, 1171.304 E. Still and A. Ringbom, Analyt. Chim. Acta, 1965, 33, 50.205 H. Flaschka and J. Butcher, Talanta, 1965, 12, 913.206 H. Flaschka and J. Garrett, Talanta, 1964, 11, 1651.207 H. Haglund and I. Lindgren, Talanta, 1965, 12, 499.208 J. Barthel and N. G. Schmahl, 2. analyt. Chem., 1965, 207, 81.209 G.A. Vaughan and J. J. Swithenbank, Analyst, 1965, 90, 594.210 W. L. Everson and E. M. Ramirez, Analyt. Chem., 1965, 37, 806.211 W. L. Everson and E. M. Ramirez, Analyt. Chem., 1965, 37, 812.212 E. Bishop, Lab. Practice, 1965, 14, 928.*13 V. A. Mirkin, Zavodskaya Lab., 1965, 31, 395.214 T. Takahashi and H. Sakurai, J . Chem. SOC. Japan, Ind. Chem. Sect., 1961, 67,Rhint., 1965, 20, 704.1802J . B. HESDRIDGE, T. B . PIERCE, D . 31. W. ANDERSOX 525for the standardisation of acid solutions. Results of excellent accuracy andprecision were obtained.2150.01-10 mg. Amount's of titanium have been determined by reducing thetitanium to the 3+ state with zinc amalgam and titrating the titanium(Ir1)with electrically-generated iron(m), with amperometric or potentiometricend-point detection.216 Iridium(1v) in the presence of rhodium(n1) wasdetermined by titration with electrically generated iron(I1) or ferrocyanide,with potentionietric end-point detecti0n.~17 Molybdenum(v1) has beensatisfactorily determined by titration with electrically-generated titanium-(111), using amperometric or potentiometric end-point detection.218Silica in glasses, glass ceramics, and refractories has been determined bydirect coulometric titration of an excess of 8-hydroxyquinoline used toprecipitate the silico-12-molybdate complex, with electrically-generated bro-mine using amperometric end-point detection.219 Electrogeneration ofchromium( 11) in 1 -5~-hydrochloric acid with high current efficiency hasbeen achieved by reducing the penta-aquobromochromium(1u) ion.Thechromium(I1) thus produced was used to titrate aromatic nitro-compoundswith fairly good accuracy and precision.220 Protein nitrogen has beendetermined in as little as 1 pl. of serum by direct titration of the ammonia inKjeldahl digests with electrically generated hypobromite, using ampero-metric end-point detection.221The coulometric generation of ethylene glycol bis-(p-amino-ethyl ether)-XN'-tetra-acetic acid from mercury-EGTA complex a t the mercury poolanode has been employed for the titration of calcium in the presence ofmagnesium using potentiometric end-point detection.2227. Quantitative Organic Analysis.-EZementuZ. Vecera 223 and his co-workers have published a submicro-method for the determination of carbon,in which the carbon dioxide evolved is measured conductometrically.Belcher et ~ 6 1 .~ ~ ~ have described a manometric method for the submicro-determination of carbon and hydrogen. The water and carbon dioxideformed are trapped at -80" and - 196" respectively and excess of oxygen ispumped out: the trapped gases are expanded into fixed volumes and theirpressures measured by a piston-type burette system and a photoelectriclevel indicator. The method is free from interferences from nitrogen, sulphur,and the halogens other than fluorine.Another interesting method determines 225 both carbon and hydrogen as2 * 5 E. L. Eckfeldt and E. W. Shaffer, jun., Analyt. Chem., 1965, 37, 1534.?16 Z. Slovak and M. Pribyl, Z . analyt.Chena., 1965, 211, 247.217 N. I. Stenina and P. K. Agasyan, Zhur. analit. Khirn., 1965, 20, 351.E. Binder, G. Goldstein, P. Lagrange, and J.-P. Schwing, Bull. SOC. chim. Prance,219 Y . Su, D. E. Campbell, and J. P. Williams, Analyt. Chint. Acta, 1965, 32, 559.220 D. A. Aikens and M. Carlita, Analyt. Chem., 1965, 37, 459.221 G. D. Christian, E. C. Knoblock, and W. C. Purdy, Clinical Chem., 1965, 11, 413.222 G. D. Christian, E. C. Knoblock, and W. C. Purdy, Analyt. Chem., 1965, 37,233 M. VeEePa, J. Lakom9, and L. Lehar, Mikrochim. Ichnounulyt. Acta, 1965, 674.P. Gouverneur, H. C. E. Van Leuven, R. Belcher, and A. M. G. Macdonald,1965, 2807.29,.Analyt. Chirn. Acta, 1965, 33. 360.*z5 H. S. Haber, D. A. Bude, R. P. Buck, and K. W. Gardiner, Analyt.Chem.,1965, 37, 116526 ANALYTICAL CHEMISTRYwater, after combustion in a quartz tube. Hydrogen is det,ermined codo-metrically as water in a special electrolytic cell; the carbon dioxide from com-bustion is converted into an equivalent amount of water, by means of aspecially prepared charge of lithium hydroxide, and determined in a secondelectrolytic cell.Israelstam 226 has reported a rapid, simple, semimicro-method fordetermining carbon and hydrogen; AZicino 227 has discussed the use of ver-miculite in such determinations.Holmes and Lauder 228 have developed the use of gold to remove mercuryin carbon and hydrogen determinations on organic compounds contain-ing mercury, and a Hungarian paper 229 considered the determinationof carbon, hydrogen, silicon, and germanium in organometallic com-pounds.Gas-chromatographic methods have been given for determinations ofnitrogen 230 and of carbon, hydrogen, and nitr~gen.~~l Monar proposed 232three simple procedures, of general application to organic and many organo-metallic compounds, for micro-determinations of carbon, hydrogen, nitrogen,and oxygen ; with an automatically controlled apparatus, determinations ofthese elements are possible within 11 minutes.Considerable attention has been given this year to the determination ofoxygen on the micro 2a3 and sub-micro 234 scales, and Holt has described 235a new technique, involving a oarbon-reduction bed in an induction-heatedgraphite tube, for the direct determination of oxygen in organophosphoruscompounds.Schoniger has published recommendations based on experiencesof the Unterzaucher procedure over a period of 10 years.23* Belcher, Davies,and West 237 carried out a useful comparison of some of the modifications tothe Schutze method that have been proposed in the past; the main conclu-sions reached were that pyrolysis should be carried out over platinisedcarbon at goo", that both reduced copper and sods asbestos are required toremove interfering vapours, and that the determination should be completedgravimetrically, after conversion of carbon monoxide to dioxide with Schutzereagent a t room temperature.A considerable number of Papers dealt with the determination of elementsother than carbon, hydrogen, nitrogen, and oxygen, and Taubinger andWilson238 recommended the use of 50% hydrogen peroxide for the wetoxidation of organic materials.Rowe 23@ has determined chlorine at less226 S. S . Israelstam, Microchem. J., 1965, 9, 193.227 J. F. Alicino, Microchem. J., 1965, 9, 22.ISo I. E. Pakhomova and M. N. Chumachenko, Izvest. Akad. Nauk S.S.S.R., Ser.2s1 K. Derge, Chem-Ing.-Tech., 1966, 37, 718.2Sa I. Monar, Milcrochirn. Ichnoadyt. Acta, 1965, 208.aasP. M. Mietasch and J. Hor&Eek, Coll. Czech. Chern. Comm., 1965, 30, 2889.2s4 K. Yoshikawa and T. Mitsui, Microchem. J., 1965, 9, 52.235 B. D. Holt, Analyt. Chem., 1965, 37, 751.a36 W. Schoniger, Mikrochim. Ichmandyt. Acta, 1965, 679.R. Belcher, D. H. Davies, and T. S. West, Tahnta, 1965, 12, 43.as8 R. P.Taubinger and J. R. Wilson, Analyst, 1965, 90, 429.259 R. D. Rowe, Analyt. Chem., 1965, 37, 368.T. F. Holmes and A. Lauder, Andy&, 1965, 90, 307.T. Aranyi and A. Erdey, Magyar Kdm. Lap& 1965, 20, 164.Khim., 1965, 1138J . B . HEADRIDGE, T . B . PIERCE, D. M . w. ANDERSON 527than 10 p.p.m. in polybutenes, and other papers concerned with halogens 240have given methods for their simultaneous deterrninafi~n.~~~The determination of sulphur has also attracted the attention of severalin~estigators,~4~ and methods for the determination of sulphur in the pre-sence of and of selenium 244 have also been described. Merzhas published ultramicro-procedures for the determination of sulphur andnitrogen,245 and Belcher et aL246 have studied submicro-methods for phos-phorus and arsenic.Pmctional groups.Many interesting Papers, involving a wide range offunctional groups, were published in this section in 1965. Kaiser247 hassuggested that the results of functional group analyses should be publishedin terms of a " functional number," which he defined.Belcher and his co-workers have published several papers during theyear on the submicro-determination of olefinic ~ n s a t u r a t i o n , ~ ~ ~ deactivatedole fin^,^*^ nitrogen grou~s,~~O acetyl groups,251 thiol groups,252 and on theperiodate oxidation reactions of ~arbohydrates.~5~There have been several publications involving aspects of the determina-tion of alkoxyl groups in specialised c i r c u r n s t a n c e ~ , ~ ~ ~ - ~ ~ ~ and papers on thedetermination of epoxy-c~rnpounds,~~~ ethylene oxide, and oxyalkenegroups.255, 258 Sulphydryl and disulphide groups have been investi-gated,254, 259 and hydroxyl groups still continue to attract attention.26*240 D.Pitr6 and M. Grandi, Mikrochim. Ichnoanalyt. Acta, 1965, 193; E. Pella,241 J. C. Mamaril and C. E. Meloan, J. Chromatog., 1965,17, 23; T. V. Reznitskaya242 J. DokladalovA, Mikrochim. Ichnoanalyt. Acta, 1965, 344; T. Takeuchi, I.243 N. Kramer, Mikrochim. Ichnoanalyt. Acta, 1965, 144.2 4 p Z. Stefanac and Z. RakoviE, Mikrochim. Ichnoanalyt. Acta, 1965, 81.245 W. Merz, 2. analyt. Chem., 1965, 207, 424.216 R. Belcher, A. M. G. Macdonald, S. E. Phang, and T. S. West, J . Chem. Soc.,2 4 7 R. Kaiser, 2. analyt. Chem., 1965, 212, 369.248 R.Belcher and B. Fleet, J . Chem. SOC., 1965, 1740.250 R. Belcher, Y. A. Gawargious, and A. M. 0. Macdonald, J . Chm. Soc., 1964, 5698.251 A. K. Awasthy, R. Belcher, and A. M. G. Macdonald, Analyt. Chim. Acta, 1965,252 R. Belcher, Y. A. Gawargious, and A. M. G. Macdonald, Analyt. Chim. Acta,*j3 R. Belcher, G. Dryhurst, and A. M. G. Macdonald, J. Chem. SOC., 1965, 3964.254 J. A. Magnuson and E. W. Knaub, Analyt. Chem., 1965, 37, 1607.2 5 5 F. Ehrenberger, 2. analyt. Chem., 1965, 210, 424.256 P. Dostal, J. Cermak, and B. Novotna, Coll. Czech. Chem. Comm., 1965, 30, 34;V. A. Klimova, K. S. Zabrodina, and N. L. Shitikova, Izvest. Akad. Naub S.S.S.R.,Ser. Khim., 1965, 178, 1288; A. I. Lebedeva and E. S. Pkarenko, Zhur. analit. Khim.,1965, 20, 630.257 J.Urbanski and G. Kainz, Mikrochim. Ichnoanalyt. Acta, 1965, 60.258 J. R. Kirby, A. J. Baldwin, and R. H. Heidner, Analyt. Chem., 1965, 37, 1306;N. A. Kolchina, Zhur. analit. Khim., 1965, 20, 380; F. W. Cheng, Microchem. J., 1965,9, 270; N. AdIer, J . Pharm. Sci., 1965, 54, 735.259 M. Krsteva, B. V. Alexiev, C. P. Ivanov, and B. Yordanov, Amlyt. Chim. Acta,1965, 32, 465; R. E. Humphrey, A. L. McCrary, and R. M. Webb, TaZunta, 1965, 12,727.260 V. Iyer and N. K. Mathur, Analyt. Chim. Acta, 1965,33,554; R. Harper, S. Siggia,and J. G. Hanna, Analyt. Chm., 1965, 37, 600; K. S. Panwar and J. N. Gaur, AnaZyt.Chim. Actu, 1965, 33, 318; D. D. Singer and J. W. Stiles, Analyst, 1965, 90, 290.ibid., 1965, 369.and E. I. Burtseva, Zhw.analit. Khim., 1965, 20, 225.Fujishima, and Y. Wakayama, ibid., p. 635.1965, 2044.R. Belcher and B. Fleet, Talanta, 1965, 12, 677.33, 311.1965, 33, 210528 AN AL Y TI C AL CH E MIS TRYStroh and Liehr 261 have studied the determination of 0- and N-acetylgroups in sugar hydrazone acetat'es and n.1n.r. spectroscopy has been usedin an investigation of N-methyl groups.262Other papers worthy of note involved determinations of hydrazino-groups,263 alkyl and aryl groups,264 a ~ i d e , ~ ~ ~ the carbonyl group,266 andamino and carboxyl end-groups 267 in Nylon.8. Spectroscopic Analysis.-X- Ray $fluorescence spectroscopy and relatedtechniques. Mass absorption corrections in the X-ray fluorescence analysisof igneous rocks have been discussed,2*8 Experimental conditions and re-sults are reported for the analysis of alloys and compounds of high-meltingmetals by X-ray fluorescence spectros~opy.~~~ Reasonably accurate andrapid analysis for silicon, potassium, calcium, titanium, manganese, and ironin rocks has been achieved using X-ray fluorescence spectrography.Pressedpellets of cellulose-diluted rock powders were used.27oThe X-ray fluorescence determination of strontium in food and bone hasbeen described, where the specimen is mixed and briquetted with an organicbinder. Transmittance measurements on the briquettes with monochro-matic Sr-K, radiation allows a correction to be applied to the fluorescent8r-K, X-rays from specimens of differing X-ray 0pacity.~7l Tin in powdersamples has been determined by two X-ray fluorescence methods. The first,a non-destructive general method, in which thick films are used, is fast butless accurate than the second method, which involves fusing the sample in agraphite crucible with a borate flux after the addition of antimony trioxideas internal ~tandard.~7~ Minor amounts of tantalum in niobium have beendetermined by X-ray analysis with direct electron excitation.The limit ofdetection was 200 p.p.m. and the precision (relative standard deviation) was2% in the o.4-5y0 concentration range.273The determination of oxygen in silicates by soft X-ray spectrophotometryhas been described. For oxygen over the range 44--54%, relative standarddeviations of better than 1 yo have been achieved in routine rock analysis.274Xethods involving the use of plastics have been described for obtaining solidsamples for the X-ray fluorescence analysis of mineral oils and organicsolutions.275 Limits of detection for the X-ray fluorescence analysis ofelements in mineral oils have also been determined.276The technique of internal differential X-ray absorption edge spectrometry261 H.-H.Stroh and H. Liehr, J . prakt. Chem., 1965, 29, 8 .262 J. C. N. Ma and E. W. Warnhoff, Canad. J . Chem., 1965, 43, 1849.263 F. G. Hoffman and D. G. Shaheen, Microchem. J . , 1965, 9, 63.264 J. Franc, J. Dvoracek, and V. KolouSkovh, Mikrochim. Ichnoanalyt. Acta,2 6 5 R. G. Clem and E. H. Huffman, Analyt. Chent., 1965, 37, 366.266 A. P. Terentiev and I. S. Novikova, Zhur. analit.Khiin., 1965, 20, 836.267 R. G. Garmon and M. E. Gibson, Analyt. Chem., 1965, 37, 1309.z6* J. G. Holland and E. I. Hamilton, Spectrochinz. Acta, 1965, 21, 206.z69 E. Lassner, R. Puschel, and H. Sohedle, Talanta, 1965, 12, 871.Z 7 O D. F. Ball, Analyst, 1965, 90, 258.2'1 M. Goldman and R. P. Anderson, Aizalyt. Chena., 1955, 37, 718.2'2 K. G. Carr-Brion, Analyst, 1965, 90, 9.273 C. J. Toussaint and G. Vos, Analyt. Chiin. -4cta, 1965, 33, 279.s74A. K. Baird and B. L. Henke, Analyt. Chem., 1965, 37, 727.Z i 6 G. Rothe and A. Koster-Pflugmacher, 2. analyt. Chem., 1965, 213, 173.276 R. Louis, Z . analyt. Chem., 1965, 208, 34.1965, 4J. B. HEADRIDGE, T. B . PIERCE, D . 31. w. ANDERSOX 529has been described. The results are independent of sample geometry andsurface condition.2i7The automation of data evaluation in quanti-tative spectroscopy has been described.2i8 Voltage fluctuation patternshave been obtained for many elements in the d.c.arc. These recordings giveinformation about sample consumption time, arc stability, and reproduci-b i l i t ~ . ~ i Q In a detailed study, cathode excitation was compared with anodeexcitation under the same conditions for 33 elements in the d.c. arc. It wasconcluded that cathode excitation affords greater precision for a number ofmore volatile elements in a carbon matrix.280 The emission characteristicsand sensitivity in a high-voltage spark discharge between an aluminium- basealloy and graphite counter electrode ha.ve been investigated using time-resolved emission spectrometry.281A general procedure has been described for the determination of elementsin the range O .l - l O O ~ o with a single set of working curves using spectro-graphic analysis of powdered samples by rotating disc-spark technique. Theaccuracies and precisions are reasonable.282 An emission spectrographicmethod has been described for the determination of major elements incements with a relative accuracy of & 1-4%.283 A direct-reading spectro-graphic method has been applied to the analysis of 500 pg. samples of non-metallic materials for aluminium, calcium , chromium , magnesium, man-ganese, phosphorus, silicon, and titanium. The limits of detection are aboutSpectrographic detection limits for many elements in tungsten have beendetermined,285 and a method has been described for the spectrographicanalysis of zirconium, whereby 36 impurity elements are determined simul-taneously with limits of detection of 1 x %.The relativeerrors were 10-20%.286 A spectrographic method has been developed forthe determination of ultramicro-amounts of boron ( X . 0 6 p.p. t housnndmillion) in high-purity silicon tetrachloride and trichlorosilane.28710--200 p.p.m. of oxygen in steel have been determined by automaticemission-spectrography using a high temperature hollow-cathode dischargeto melt the sample and excite the atomic spectrum of oxygen, measurementsbeing made on the oxygen multiplet a t 7772/5 In connexion with theemission-spectrometric determination of oxygen in metals it has been shownthat a master analytical curve for oxygen can be constructed without theuse of standard metal samples.289 The d.c.carbon-arc extraction techniquehas been adapted to the direct-reading determination of oxygen in highEmission spectroscopy.1 pg.280to 1.5 x277 T. J. Cullen, AnaZyt. Chem., 1965, 37, 711.278 H. Franke, K. Post, and W. Schmotz, 2. analyt. Chem., 1965, 212, 269.2 i s J. W. Mellichamp, Analyt. Chem., 1965, 37, 1211.280 R. R. Brooks and C. R. Boswell, AnaZyt. Chim. Acta, 1965, 32, 339.281 J. P. Walters and H. V. Malmstadt, Anabyt. Chem., 1965, 37, 1484.282 M. G. Atwell and G. S. Golden, Analyt. Chem., 1965, 37, 1597.283 Z. G. Hanna and J. M. Ibrahim, Z . analyt. Chem., 1965, 214, 33.284 M. Reckziegel, G.Staats, and H. Brueck, 2. analyt. Chenz., 1964, 206, 113.285 R. Dyck, Analyt. Chem., 1965, 37, 1046.286 0. F. Degtyaxeva and L. G. Sinitsyna, Zhur. anabit. Khim., 1965, 20, 603.287 K. Kawasaki and M. Higo, Analyt. Chim. Ada, 1965, 33, 497.2B8 M. S. W. Webb and R. J. Webb, Anabyt. Chim. Acta, 1965, 33, 138.289 V. A. Fassel and J. W. Goetzinger, Spectrochim. Acta, 1965, 21, 289530 ANALYTICAL CHEMISTRYand low alloy steels having oxygen contents ranging between 0.0048 and0.085 wt.The operating parameters of a spectrographic plasma jet have been evalu-ated, and it has been shown that quantitative analysis can be achieved byplasma spectrophotometry under non-interference conditions in multi-element environments.291 The application of the plasma jet to the spectro-chemical analysis of aqueous solutions has been investigated.292 A stabilizedplasma arc has been employed as an excitation source for the determinationof 10-4-10-3% of boron in petrol.The precision was t3%,293Phme photometry. Recent developments in flame spectrophotometricand atomic absorption spectroscopic analysis have been and a,theoretical treatment to explain the shapes of calibration graphs for flamespectrophotometry has been published.2g5 The use of turbulent flames aslight sources for the analysis of solutions by flame photometry has beeninve~tigated.~~A thorough study has been made of the mutual radiation interferenceeffects of the alkali elements and hydrogen upon the resonance line intensitiesof the alkali elements in flame ~pectrophotometry.~97 The precise deter-mination of sodium in uranium, phosphate, carbonate, and silicate rocks byflame spectrophotometry has been described.The enhancement effects ofother alkali metals were overcome by using a radiation buffer.298 Calciumand potassium in soil extracts have been determined automatically by flamephotometry using a Technicon Auto Analyser. Magnesium and phosphoruswere determined simultaneously using atomic absorption spectroscopy andthe Molybdenum Blue colorimetric procedure respectively.299Aluminium oxide (0.1-60%) in refractory products has been determinedby a flame-photometric procedure after solvent extraction as its acetylace-tonate into chlorof0rm.3~~ Copper and magnesium in blood serum have beensatisfactorily determined by high-resolution spectrophot~rnetry.~~~ Flamespectrophotometry with an oxy-acetylene flame has been satisfactorilyapplied to the determination of trace amounts of palladium and rhodiumafter solvent extraction into 4-methylpentan-%one of the salicylaldoximecomplex and diethyldithiocarbamate complex respectively.302XpectroJluorimetry .Solution spectrofluorimetry as a trace technique ininorganic analysis 303 and the phosphorescence spectroscopy of aromatic andheterocyclic compounds have been reviewed.304 Preliminary investigations290 C. Matsumoto, V. A. Fmsel, and R. N. Kniseley, Spectrochim. Acta, 1965, 21,889.2 0 1 E. H. Sirois, Analyt. Chem., 1964, 36, 2389 and 2394.292 P. A. Serin and K. H. Ashton, Appl.Spectroscopy, 1964, 18, 166.293 M. S . Vigler and J. K. Failoni, AppZ. Spectroscopy, 1965, 19, 57.294 H. Herrmann, 2. analyt. Chem., 1965, 212, 1.295 J. Winefordner, T. Vickers, and L. Remington, AnaZyt. Chern., 1965, 37, 1216.2~ M. E. Britske, Zavodskaya Lab., 1964, 30, 1465.297 E. L. Grove, C. W. Scott, and F. Jones, Talanta, 1965, 12, 327.298 H. Kramer and L. J. Pinto, AnaZyt. Chim. Acta, 1965, 33, 438.Z9@ J. Lacy, Analyst, 1965, 90, 65.300 W. Schmidt, K. Konopicky, and J. Kostyra, 2. analyt. Chern., 1964, 206, 174.3O1 R. L. Warren, Analy8t, 1965, 90, 549.308 H. C. Eshelman, J. Dyer, and J. Armentor, AnaZyt. Chim. Acta, 1965, 52, 411.303 T. 8. West, Lab. Practice, 1965, 14, 922 and 1030.304 M. Zander, Chem.-Ing.-Tech., 1965, 37, 1010J.B. HEADRIDQE, T. B. PIERCE, D . M. w. ANDERSON 531into the application of sensitized P-type delayed fluorescence to organictrace analysis have been made,305 and further applications of quenchofluori-metric analysis (the quenching effect of solvents on fluorescence) for poly-iiuclear compounds have been reported.306Thallium(1) at concentrations 20.01 p.p.m. has been determinedspectrofluorimetrically in concentrated hydrochloric acid-potassium chloridemedium. The effects of interfering elements were thoroughly examined.3070.05-50 p.p.m. of zinc as its complex with dibenzothiazolylmethanehas been determined fluorimetrically in aqueous ethanol solution. Themethod was applied to the determination of trace amounts of zincin cadmium and of minor amounts of zinc in magnesium-base all0ys.~083.6 x 10-4-3.6 x 10-2 p.p.m.of boron as boric acid have been determinedfluorimetrically by making measurements on the complex formed betweenboric acid and 4’-chloro-2-hydroxy-4-methoxybenzophenone in concen-trated sulphuric a ~ i d . ~ O ~A fluorimetric method has been described for the determination of hydro-gen peroxide at the ~ O - * M level. The method is based on the oxidation ofnon-fluorescent diacetyldichlorofluorescein to a fluorescent compound byhydrogen peroxide and p e r o ~ i d a s e . ~ ~ ~ A method has been described for thecontinuous determination of 5 parts of hydrogen sulphide in 1O1O parts ofair to 1 part in lo7. It is based on the reduction of fluorescence, which occurswhen hydrogen sulphide is absorbed into 0.0005% (w/v) tetra-acetoxy-mercurifluorescein in 0.0025 % (w/v) sodium hydroxide s ~ l u t i o n .~ ~ l Aspecific fluorimetric method for the detection of cyanide has been described.As little as 0.5 pg. of cyanide gives a highly fluorescent product with quinonemonoxime benzenesulphonate ester. There is no interference from 30 othercommon anions.312 Further studies on the fluorimetric determination ofcyanide have also been reported.313A spectrofluorimetric method for the determination of oxalic acid inblood and other biological materials has been described. The limit of detec-tion is 0.9 p mole of oxalic acid.314 Microgram quantities of atropine havebeen determined fluorimetrically by means of the fluorescent compoundformed between atropine and eosin?15 Spectrofluorimetric methods havealso been described for the determination of histamine in microgram samplesof tissue or microlitre volumes of body f l ~ i d s , ~ l 6 and of m-hydroxyphenyl-ethylamine (m-tyramine) and its analogues.317 0.01 pg.or more of haemC. A. Parker, C. G. Hatchard, and T. A. Joyce, Analyst, 1965, 90, 1.E. Sawicki, T. W. Stanley, and H. Johnson, Mikrochim. Ichnoanalyt. Acta,G. F. Kirkbright, T. S. West, and C. Woodward, TaZanta, 1965, 12, 517.M. Marcantonatos, A. Marcantonatos, and D. Monnier, AeZv. Chim. Acta, 1965,1965, 178.s08R. R. Trenholm and D. E. Ryan, Analyt. Chim. Acta, 1965, 32, 317.slo A. S . Keston and R. Brandt, Analyt. Biochem., 1965, 11, 1.sll T. R.Andrew and P. N. R. Nichols, AnuZy.yt, 1965, 90, 367.sla G. G. Guilbault and D. N. Kramer, AnaZyt. Chem., 1965, 37, 918.31s G. G. Guilbault and D. N. Kramer, Analyt. Chem., 1965, 37, 1395.s15 S. Ogawa, M. Morita, K. Nishiura, and K. Fujisawa, J . Phrm. SOC. Japan,a16 D. Von RedIich and D. Glick, Analyt. Biochem., 1965, 10, 459.s17 W. F. Coulson, A. D. Smith, and J. B. Jepson, Analyt. Biochem., 1965, 10, 101.48, 194.M. Zarembski and A. Hodgkinson, Biochem. J., 1965, 96, 717.1965, 85, 650532 ANALYTICAL CHEMISTRYprotein in animal tissues has been determined spectrofluorimetrically afterconverting the protein’s haem moiety into its fluorescent porphyrin deri-~ative.~18Procaine, cocaine, phenobarbital, chlorpromazine, and atropine have beendetermined phosphorimetrically in blood serum or urine after extraction withchloroform or ether, evaporation of the solution to dryness, and dissolutionof the residue in a mixture of ethyl ether, isopentane, and ethanol.319 Afterextraction from tobacco and separation by thin-layer chromatography,nicotine, nornicotine, and anabasine have been determined phosphori-metrically in ethanol-sulphuric acid with a precision of 6%.320Atomic absorption spectroscopy.The application of this technique to theanalysis of alloys has been discussed with emphasis on accuracy, detectionlimits, and possible extensions of the method.321 A study of the distributionof atoms in an air-acetylene atomic absorption flame has been rep0rted,~2~background corrections in long-path atomic absorption spectrophotometryhave been discussed,323 and factors affecting the shape of analytical curvesin atomic absorption spectroscopy have been considered.324High-intensity hollow-cathode lamps, which emit resonance lines somehundred times more intense than can be obtained from conventional hollow-cathode lamps, have been developed.s25 An integrating analogue computerhas been described for atomic absorption spectrophotometry with systemsfor which the noise level would ordinarily be excessive for satisfactoryanalysis.The detection limit for calcium using the apparatus was 0.003p .p .m .32sParts per million of magnesium in uranium have been satisfactorilxdetermined by atomic absorption spectroscopy without prior ~eparation,~~and magnesium has been determined in alkali products and aluminium alloysby this technique after solvent extraction of magnesium 8-hydroxyquinolateor 8-hydroxyquinaldate into isobutyl methyl ketone.328 With a nitrogen-oxygen-acetylene flame the limit of detection for aluminium in aqueoussolution by atomic absorption spectroscopy is less than 2 p.p.m.Underthese conditions, the effect of potential interferences has been studied andsatisfactory results are reported for the determination of aluminium inalloys and 0res.32~ Atomic absorption spectroscopy has been employed forthe determination of tin in hydrogen peroxide solution using an oxyhydrogenflame and the 2863 A tin line. Concentrations of tin in excess of 0.05 p.p.m.were satisfactorily determined.330 Selenium has been determined by atomicabsorption spectroscopy with a limit of detection of 1 p,p.m.This technique318 G. R. Morrison, Analyt. Chem., 1965, 37, 1124.318 J. D. Winefordner and M. Tin, Analyt. Chim. Acta, 1965, 33, 61.320 J. D. Winefordner and H. A. Moye, Analyt. Chim. Acta, 1965, 32, 278.321 G. Sonnenmacher and F.-H. Schleser, 2. analyt. Chem., 1965, 209, 284.322 C. S. Ram and A. N. Hambly, Analyt. Chem., 1965, 37, 879.323 S. R. Koirtyohann and E. E. Pickett, Analyt. Cbm., 1965, 37, 601.324 I. RubePka and V. Svoboda, Analyt. Chim. Acta, 1965, 32, 253.325 J. V. Sullivan and A. Walsh, Spectrochim. Acta, 1965, 21, 721.326 E. A. Boling, Analyt. Chem., 1965, 37, 488.327 J. R. Humphrey, Analyt. Chem., 1965, 37, 1604.528 M.Suzuki, 1%. Yenagisawa, and T. Takeuchi, Talanta, 1965, 12, 989.329 M. D. Ames and P. E. Thomas, Analyt. China. Acta, 1965, 32, 139.330 E. J. Agazzi, Ataalyt. Chem., 1965, 37, 364J . B. HEADRIDGE, T. B . PIERCE, D . RX. W. ANDERSOX 533was applied with good results to the determination of selenium in wheat andgalena.331Atomic absorption spectroscopy has been applied to the determination ofchromium after extraction of chromium( VI) into isobutyl methyl ketone.With an air-hydrogen flame the detection limit was 0.006 p.p.m. of chro-mium.332 A method has been described for the direct determination of0.05-10~0 of iron in aluminium alloys using atomic absorption spectro-scopy. After a solvent extraction of iron with isobutyl methyl ketone, aslittle as 5 p.p.m.of iron in high-purity aluminium can be determined.333Copper in sea-water has been satisfactorily determined by atomic absorptionspectroscopy after extraction of the copper-ammonium pyrrolidine dithio-carbamate complex into ethyl acetate and spraying of the organic extract intothe flame.334 Zinc in biological materials has been determined with goodaccuracy and precision by direct atomic absorption spectrophotometry. Thelimit of detection was 0.002 p.p.m. of zinc in s0lution.~~5 Traces of copper,chromium, iron, lead, and silver in used lubricating oil have been satisfac-torily determined by atomic absorption measurement of solutions of the oilin 4-methylpentan-2-0ne.~~6Atomic fluorescence flame spectrometry has been applied to the deter-mination of zinc, cadmium, mercury, gallium, indium, and thallium usingimproved equipment.The limits of detection for zinc and cadmium are0.0001 p.p.m. and 0.0002 p.p.m. respectively.337Ultraviolet and visible spectrophotometry . Very few Papers of a generalnature were published, although Ramaley and Enke 338 have proposed theuse of isomation, in which standard solutions and a calibration curve arereplaced by one standard solution.Heteropolyacids have been studied from two different viewpoints :Chalmers and Sinclair 339 have studied the determination of arsenic, ger-manium, and phosphorus ; Billman et aZ.340 have used 12-molybdosilicic acidfor the determination of carbonyl compounds. Diphenylpicrylhydrazyl maybe used 341 for the analysis of amines, and isonitrosoacetanilide has beenreported 342 to give a specific reaction with palladium in acidic media, and avery sensitive reaction with cobalt in ammoniacal solution.The determination of aluminium has been the subject of several interest-ing Papers.West et have described a simple and rapid method for the331 C. S . Ram and A. N. Hambly, Analyt. Chirn. Ada, 1965, 32, 346.332 F. J. Feldman and W. C. Purdy, Andyt. Chim. Acta, 1965, 33, 273.333 A. Atsuya, Japan Analyst, 1965, 14, 592.334 R. J. Magee and A. K. M. Rahman, TaZanta, 1965, 12, 409.335 K. Fuwa, P. Pulido, R. McKay, and B. L. Vallee, AnaZyt. Chem., 1964, 36,336 J. A. Burrows, J. C. Heerdt, and J. B. Willis, Analyt. Chern., 1965, 37, 579.337 J. M. Mansfield, J.D. Winefordner, and C. Veillon, AnaZyt. Chem., 1965, 37,338 L. Ramaley and C. G. Enke, Analyt. Chern., 1965, 37, 1073.339 R. A. Chalmers and A. G. Sinclair, Analyt. Chim. Acta, 1965, 33, 384.310 J. H. Billman, D. B. Borders, J. A. Buehler, and A. W. Seiling, AnaZyt, Chern.1965, 37, 264; J. H. Billman and A. W. Seiling, Analyt. Ghim. Acta, 1965, 33,561.3*1 G. J. Papariello and M. A. M. Janish, AnaZyt. Chem., 1965, 37, 899.343 R. M. Dagnall, T. S. West, and P. Young, Analyst, 1965, 90, 13.2407.1049.F. Buscarbns and F. Buscarhs, jun., Analyt. Chirn. Acta, 1965, 32, 568534 ANALYTICAL CHEMISTRYdetermination of as little as 0.001% aluminium in steel, and Pakalns 344 hasreported that Chromeazurol is a more satisfactory reagent than EriochromeCyanine R or Aluminon.A methods5 for determining antimony in therange 0.02-1.6 p.p.m. depends on the reduction of a molybdate aggregatea t pH 1-4. Thierig and Umland 346 have claimed that the use of Sulphonazo-111 gives the most sensitive and selective method available for determina-tions of barium. Determinations of boron with Diamino-Crysazin 347 andbarium chloranilate 348 have been described.Several methods have been proposed for determining copper, involvingSolochrome Azurine B.S. ,349 biscyclohexanone 0xalyldihydrazone,~~0 neo-cupr0ine,~~1 Acid Alizarin Black S.N. ,352 and Aminomethylazo III.3S3 Butlerand Forbes 354 have concluded, from a comparative study, that Dithizoneis to be preferred to Neocuproine or biscyclohexanone oxslyldihydrazonefor determinations of copper.Pike and Yoe 355 have studied the deep-blue stable chloro-complexesformed by cobalt in dimethylformamide.Two groups of investigators havestudied the determination of lanthanides.356 Methylthymol Blue has beenproposed 357 as a colorimetric reagent for magnesium.Stobart 35~4 has described a method for the determination of 3 p.p.m. oflead in heat-resistant alloy steel; West et have used 4-(2-pyridylazo)-resorcinol as a reagent for lead in steel, brass, and bronze.Belcher, Ramakrishna, and West 360 have found Bromopyrogallol Redto give the most sensitive visible-range spectrophotometric method proposedto date for niobium(v); Patrovsky361 has determined niobium with 4-(2-thiazoly1azo)-resorcinol .Platinum, palladium, and other noble metals have been investigated byseveral groups of workers,362 and Beamish 3133 has given a critical evaluationof colorimetric methods for these metals.Other elements for which interesting methods have been proposed are3 4 4 P.Pakalns, Analyt. Chim. Acta, 1965, 32, 57.345 R. M. Matulis and J. C. Guyon, Analyt. Chem., 1965, 37, 1391.346 D. Thierig and F. Umland, 8. analyt. Chem., 1965, 211, 161.347 A. R. Eberle and M. W. Lerner, Analyt. Chem., 1965, 37, 1568.248 D. R. Peterson and J. R. Hayes, Analyt. Chm., 1965, 37, 306.849 U. Tandon, S. N. Tandon, and S. S. Katiyax, Talantu, 1965, 12, 639.35O K. R. Middleton, Analyst, 1965, 90, 234.s 5 1 C. L. Luke, Analyt. Chim. Ada, 1965, 32, 286.35aM. Hosain and T. S. West, Andyt.Chim. Acta, 1965, 33, 164.353 B. Budesinsky and K. Haas, 2. analyt. Chem., 1965, 214, 325.354 E. J. Butler and D. H. S. Forbes, Andyt. Chim. Actu, 1965, 33, 69.365 L. Pike and J. H. Yoe, Tulanta, 1965, 12, 657.357 J. Metcalf, Andyst, 1965, 90, 409.368 J. A. Stobart, AnuZyst, 1965, 90, 278.359 R. M. Dagnall, T. S. West, and P. Young, Talunta, 1965, 12, 589.360 R. Beloher, T. V. Ramakrishna, and T. S . West, Tulunta, 1965, 12,681.S S l V . Patrovsky, Tahnta, 1965, 12, 971.363 C. F. Bell and D. R. Rose, Tulunta, 1965, 12, 696; M. A. Khattak and R. J.Magee, $M., p. 733; S. C. Srivastava and M. L. Good, Analyt. Chim. Acta, 1965,32, 309.363 F. E. Bemish, Talanta, 1965, 12, 743 and 789.W. J. Maeck, M. E. Kussy, and J. E. Rein, Analyt.Chem., 1965, 37, 103; B.Budcsinsw and K. Haas, 2. analyt. Chem., 1965, 210, 263J . B . HEADRIDGE, T. B . PIERCE, D . M. W. ANDERSON 536phosphorus,364 rhenium,365 thallium,366 thorium,367 uranium,368 and vana-dium( v) .36Infrared spectrophotmnetry. An automatic device, allowing up to 25samples to be run a t one loading, has been described.370A number of papers have described amlyses in which infrared measure-ments have been combined with some other technique, e.g., with X-rayfluorescence,371 thin-layer ~hrornatography,37~ gas ~hromatography,~7~ orfilament pyrolysis.374Several useful new sampling techniques that were described included theuse of silver chloride d i ~ k s , ~ 7 ~ the dispersion of samples in solid antimonytrichloride,376 and the use of molten sulphur as a s0lvent.~77 Auxiliaryinstrumentation devices worthy of note included a potassium wedge forcompensation purp0ses,~7~ variable-angle reflection attachments,379 and asimple semimicro-cell3130 for spectral reflectance measurements.Magee and Gordon381 continued their studies of chelates with a studyof the different forms of the uranium chelates of 8-hydroxyquinoline in theregion 5000-250 crn.-l, and methods were given for the determination ofpyrethrum extracts 382 and cationic surfa ce-active agent~.~*3Near-infrared measurements were used to determine 384 ammonia, carbondioxide, and water a t elevated temperatures and pressures, and analyses ofbutadiene polymers were made by combining the information from near-idrared and n.m.r.analyses.385Nuclear magnetic resonunee. Flockhart and Pink 386 have reviewed theanalytical applications of nuclear and electron magnetic resonance. Readand GoldsteinSS7 have described an integration method of increasing thea64 T. Salvage and J. P. Dixon, Analyst, 1965, 90, 24; W. Pilz, Mikrochim. Ichno-analyt. Acta, 1965, 34.A. K. De and M. S. Rahaman, Talanta, 1965, 12, 343; E. N. Pollock and L. P.Zopatti, Analyt. Chim. Acta, 1965, 32, 418.366 G. F. Kirkbright, T. S. West, and C. Woodward, Takznta, 1965, 12, 517; L. G.Hargis and D. F. Boltz, Analyt. Chem., 1965, 37, 240.a67 P. Kusakul and T. S. West, Analyt. Chim. Acta, 1965, 32, 301.s6sP. Spacu, F. Popea, and C. Tohaneanu, 2. analyt. Chem., 1965, 214, 338.369 0. Budevsky and L.Johnova, Talanta, 1965,12,291; J. A. Dougherty and M. G.370 N. L. McNiven, P. Hoffman, and G. Scrimshaw, Analyt. Chem., 1965, 37, 778.371 S. D. Kullbom, W. K. Pollard, and H. F. Smith, Analyt. Chem., 1965, 37, 1031.37a R. N. McCoy and E. C. Fiebig, Analyt. Chem., 1965, 37, 593.I. Schmeltz, C. D. Stills, W. J. Chamberlain, and R. L. Stedman, Analyt. Chem.,3 7 4 G. Lindley, Lab. Practice, 1965, 14, 826.376 L. L. Pytlewski and V. Marchesani, Analyt. Chem., 1965, 37, 618.376 H. Szymanski, K. Broda, J. May, W. Collins, and D.. Bakalik, Analyt. Chena.,3 7 7 T. K. Wiewiorowski, R. F. Matson, and C. T. Hodges, AnaEyt. Chem., 1965,378 H. McCormiclc, E. L. Deeley, and J. Tadayon, Nature, 1965, 207, 474.37s W. N. Hansen, Analyt. Chem., 1965, 37, 1142; N.J. Harrick, ibid., p. 1446.3B0 R. W. Frei and M. M. Frodyma, Analyt. Chim. Acta, 1965, 32, 501.3B1 R. J. Magee and L. Gordon, Talanta, 1965, 12, 445.383 J. H. N. Byrne, W. Mitchell, and F. H. Tresadern, Analyst, 1965, 90, 362.383 J. T. Cross, Analyst, 1965, 90, 315.384 J. G. Koren and A. J. Andreatch, Analyt. Chem., 1965, 37, 256.38b A. J. Durbetaki and C . M. Miles, Analyt. Chem., 1965, 37, 1231.386 B. D. Flockhart and R. C . Pink, Talanta, 1965, 12, 529.387 J. M. Read, jun., and J. H. Goldstein, Analyt. Chem., 1966, 37, 1609.Mellon, Analyt. Chem., 1965, 37, 1096.1965, 37, 1614; R. A. Edwards and I. S. Fagerson, ibid., p. 1630.1965, 37, 617.37, 1080536 AXALYTICAL CHEMISTRYsensitivity of n.m.r. measurements, and Brame 388 has devised a trap/cellwhich facilitates the examination of gas-chromatography fractions by n.m.r.spectroscopy.Reilley 389 has obtained information regarding the lability of the indi-vidual metal-ligand bonds formed when a multidentate complexing agentreacts with a metal ion; Kula has also shown the suitability of n.m.r.spec-troscopy for studying solution equilibria of metal ~helates,~~* and for deter-mining hydration numbers.391 Goodlett 392 has proposed the use of in situreactions (e.g., with reactive isocyanate) to characterise alcohols and glycolswithin the n.m.r. sample tube.9. Electrical Methods.--PoZurography. Reviews have been published onthe state of polarographic direct-current methods and their instrumenta-tion,393 on recent advances in polarography in Japan,394 on the polarographicanalysis of inorganic substances,395 and on the application of oscillographicpolarography in organic ~hemistry.~96 Cathode-ray polarography (potentialsweep chronoamperometry ) of anions has been discussed,397 and investiga-tions on the determination of mixtures by potential sweep chronoampero-nietry have been reported.398Details of an operational-amplifier, a.c.polarograph with admittancerecording have been published,399 and a controlled potential square wavepolarograph has been described.400 An apparatus for the continuous re-cording of cell respiration has been developed. It is based on the polaro-graphic determination of oxygen.401Polarographic reduction waves, suitable for analytical purposes, havebeen obtained for tin (IV) in perchlorate, tartrate, citrate, and ammoniacalsolutions in the presence of 3-mercaptopropionic a ~ i d .~ O ~ Tin( IV) in boiling1M-sodium hydroxide has been quantitatively reduced by sodium borohy-dride to tin( II), which was then determined polarographically using thereduction wave of half-wave potential - 1-15 v (~.c.e.).~03 The polarographicbehaviour of 35 ions in lM-ammonium fluoride solution adjusted to pH 7has been investigated, and a selective polarographic method for lead hasbeen reported.404 Trace amounts of lead in stainless steels have been deter-mined by differential cathode-ray polarography following a solvent-extractionseparation.405 5-500 p.p.m. of bismuth and lead have been determined388 E.G. Brame, jun., Analyt. Chem., 1965, 37, 1183.389 C. N. Reilley, Analyt. Chem., 1965, 37, 1298; R. J. Day and C. N. Reilley, ibid.,39O R. J. Kula, Analyt. Chern., 1965, 37, 989.391 R. J. Kula, D. L. Rabenstein, and G. H. Reed, Analyt. Chem., 1965, 37, 1783.3 9 2 V. W. Goodlett, Analyt. Chem., 1965, 37, 431.393 H. W. Niirnberg and G. Wolff, Chern.-Ing.-Tech., 1965, 37, 977.394 N. Tanaka, E. Itabashi, and T. Ito, J . Electrochena. SOC. Japan, 1964, 32, 119.395 I. V. Pyarnitskii, Zavodskaya Lab., 1965, 31, 6.396 G. K. Budnikov, Uspekhi Khirn., 1964, 33, 1371.3Q7 R. C. Rooney, J . Polarographic SOC., 1964, 10, 49.398 R. A. Osteryoung and E. P. Parry, J . Electroanal.yt. Chem., 1965, 9, 299.J. W. Hayes and C. N. Reilley, Analyt. Chern., 1965, 37, 1322.* 0 ° E.B. Buchanan, jun., and J. B. McCarten, Analyt. C’laent., 1965, 37, 29.401 P. G. Blunder and M. Modolell, Z. analyt. Chem., 1965, 212, 177.402 X. L. Phillips and R. A. Toomey, Analyt. Chena., 1965, 37, 607.403 D. H. Evans, Analyt. Chem., 1964, 36, 2435.404 A. G. Hamza and J. B. Headridge, Talanta, 1965, 12, 1043.405 R. C. Rooney, Analyst, 1965, 90, 545.1965, 37, 1326J. B. HE9DRIDGE, T. B. PIERCE, D . M. W. AKDERSON 53'7polarographically in copper-base alloys using an acidic tartrate base elec-trolyte, after solvent extraction as diethyldithiocarbamate complexes frominterfering elements . O6Small amounts of tellurium in cartridge brass and in white cast iron havebeen determined by cathode-ray polarography in 1.5~1-phosphoric acid asbase electrolyte.407 Trace amounts of iodide have been determined by theircatalytic effect on the polarographic reduction of indium(m).Other halidesand certain sulphur and nitrogen compounds exhibit a similar catalyticeffect.408Differential cathode-ray polarographic methods have been described forthe accurate determination of iron, nickel, manganese, zinc, cobalt, andcopper in ferrite materials.409 Pulse polarography has been applied to thedetermination of 0.5-50 p.p.m. of nickel and vanadium in petroleumsto~ks.~lO Small amounts of copper(n) in steels and cast irons have beendetermined by polarography in 0~5~-trioxyglutaric acid a t pH 12 as baseelectrolyte.411 Copper concentrates have been analysed for zinc after itssolvent-extraction separation from copper, iron, cobalt, cadmium, nickel,chromium, and mangane~e.41~ Molybdenum has been determined in niobium-base alloys by a quick polarographic method, the base electrolyte beingO*Ei~-hydrofluoric acid-0.5~-sulphuric acid.413 Trace amounts of rheniumin ores, slags, etc., have been determined polarographically after a separationof rhenium from other elements by steam distillation as rhenium heptoxidefrom concentrated sulphuric acid solution.414 A polarographic method hasbeen described for the determination of microgram amounts of gold in bloodand serum after the separation of gold from copper and iron by solventextraction.415 Different'ial cathode-ray polarography has been applied tothe determination of europium in solutions of lithium chloride and iodidewith a precision of 0.1~o.416Small amounts of methanol have been determined by oxidation to for-maldehyde with potassium permanganate in orthophosphoric acid followedby polarographic reduction of the formaldehyde to methanol at 50°.417Polarographic methods have also been described for the determination ofcrotonaldehyde in vinyl acetate,418 of benzotriazole in inhibited ethyleneVolturnmetry.The glassy carbon electrode has been investigated as anindicator electrode in voltammetry. In operation it compares very favourablyand of Sevin, 1 -naphthyl-N-methylcarbamidate.420406 C. H. McMaster, Canad. J. Chern., 1965, 43, 405.407 E. J. Maienthal and J. K. Taylor, AnaZyt. Chem., 1965, 37, 1516.408 A. J. Engel, J.Lawson, and D. A. Aikens, Anulyt. Chem., 1965, 37, 203.40g E. L. Bush and E. J. Workman, Analyst, 1965, 90, 346.Q1o D. D. Gilbert, AnaZyt. Chem., 1965, 37, 1102.411 E. G. Chikryzova and S. Ya. Mashinskaya, Zawodskaya Lab., 1966, 31, 26.412 J. Jankovsky, 2. analyt. Chem., 1965, 213, 84.413 J. B. Headridge and D. P. Hubbard, Analyst, 1965, 90, 173.414 R. Geyer, G. Henze, and H. Meutzner, 2. C?Len,., 1964, 4, 433.415 G. D. Christian, Clinical Chem., 1965, 11, 459.416 V. Verdingh and K. F. Lauer, Aizalyt. Chim. Acta, 1965, 33, 469.*I7 M. Ranny, Analyst, 1965, 90, 664.418 J. Pasciak, 2. analyt. Chem., 1965, 213, 111.419 S. Harrison and G. L. Woodroffe, Analyst, 1965, 90, 44.420R. Engst, W. Schnaak, and H. Woggon, 2. nnalyt. Chem., 1965, 207, 30.538 ANALYTICAL CHEMISTRYwith pyrolytic graphite and other solid ele~trodes.4~1 Voltammetric datahave been reported for inorganic ions with boron carbide electrodes422and a carbon paste electrode suitable for voltammetry in non-aqueous sol--snts has been described.423 A rapid voltammetric method based on thereduction of vanadium(v) to (IV) at a platinum electrode has been describedfor the determination of vanadium ( >0-01%) in steels.Common componentsof steel do not interfere.424Carbon dioxide in gas mixtures has been determined by saturating dime-thy1 sulphoxide with the gas mixture and measuring the current associatedwith the voltammetric reduction of carbon dioxide on an amalgamatedplatinum ele~trode.4~~ Many amines have been determined by voltammetricoxidation at a rotating platinum ele~trode.4~~The theory of anodic stripping voltammetry with a plane, thin mercury-film electrode has been An electrode consisting of mercurydeposited on graphite has been employed to obtain very sharp currentpeaks in anodic stripping ~oltamrnetry.4~8 The theoretical and analyticalcharacteristics of derivative measurement techniques have been evaluated€or reversible electrodepositions at the hanging mercury drop electrode usingelectrolysis with linearily varying potentia1.429 Derivative techniques havealso been applied to'anodic stripping v~ltamrnetry.~~~ It has been shownthat &.c. voltammetry at stationary electrodes, when applied to strippinganalysis, produces a significant increase in sensitivity over direct strippinganal~sis.~3~Anodic stripping voltammetry has been applied to the determination of5-1000 p.p.m.of copper in iron and stee1,4a2 ultramicro-amounts of antimonyand bismuth in germanium and germanium tetra~hloride,4~~ lead in blood,acopper, lead, and cadmium in biological materialsYa5 zinc in sea-water 436and mercury(I1) at a carbon-paste electrode ( < l a 2 5 x 1 0 - 5 ~ ) 437 and at awsx-impregnated graphite electrode ( 24 x 10-9~).4338Recent developments in this techniquehave been reviewed,439 and an analogue integrator for controlled-potentialcoulometry has been described.&OControlled-potential c o u h e t r y .421 H. E. Zittel and F. J. Miller, Analyt. Chem., 1965, 37, 200.422 W. R. Mountcastle, jun., Analyt.Chim. Acta, 1965, 32, 332.423 L. S. Marcoux, K. B. Prater, B. G. Prater, and R. N. Adams, And$. Chem.,424 G. Ciantelli and G. Raspi, Chimica e Industria, 1965, 47, 303.425 J. L. Roberts, jun., and D. T. Sawyer, J. Electroanalyt. Chenz., 1965, 9, 1.426 V. D. Bezuglyi and Yu. I. Beilis, Zhur. analit. Khim., 1965, 20, 1000.427 W. T. de Vries and E. van Drtlen, J . Electroanalyt. Chem., 1964, 8, 366.4as W. R. Matson, D. K. Roe, and D. E. Carritt, Andyt. Chem., 1965, 37, 1594.4 2 9 S. P. Perone and T. R. Mueller, Analyt. Chem., 1965, 37, 2.430 S. P. Perone and J. R. Birk, Analyt. Chem., 1905, 37, 9.431 W. L. Underkofler and I. Shah, Analyt. Chem., 1965, 37, 218.432 G. Gottesfeld and M. Ariel, J . Ekctroanalyt. Chem., 1965, 9, 112.433 E.N. Vinogradova and A. I. Kamenev, Zhur. analit. Khim., 1965, 20, 183.434 J. F. C. Tyler, Analyst, 1964, 89, 775.435 C. L. Newberry and G. D. Christian, J. Electroandyt. Chem., 1965, 9, 468.486 C. Macchi, J . Electroanalyt. Chem., 1965, 9, 290.m7 P. Emmott, Talanta, 1965, l2, 651.4s8 S. P. Perone and W. J. Kretlow, Analyt. Chem., 1965, 37, 968.43D V . A. Mirkin, Zauodskaya Lab., 1965, 81, 395.440 B. H6nin and R. Rosset, Bull. SOC. chim. Prance, 1964, 2250.1965, 37, 1446J . B . HEADRIDGE, T. B. PIERCE, D . M . W. ANDERSON 539Controlled-potential coulometry has been applied to the determination ofwater using Karl Fischer reagent. Iodide produced by the stoicheiometricreaction of water with Karl Fischer reagent is determined coulometrically.MlControlled-potential coulometry has also been used for the determination oftin in glass, brass, and ore concentrate^,"^^ of milligram amounts of plu-tonium(m) in sulphuric acid solution,443 and of millimolar amounts ofamericium(vr) ?4410.R,adiochemistry.-The first part of this section is devoted to theapplication of pre-produced radioactive isotopes to analysis, the second toactivation procedures. Only the direct applications of isotopes to analyticaldeterminations have been included; the uses of radiotracers to obtain dis-tribution or other data which may subsequently be used to devise analyticalmethods have not been considered.144Ce has been determined by isotope dilution invegetable material using 139Ce as diluting isotope, and the effects of chemicalyield and isotope ratio evaluated.445 85Sr additions have been recommendedas a means of making yield determinations for assay of sgSr and 90Sr,446 andthe use of substoicheiometry as a means of analysing radioactive preparationshas been outlined.**' The operation of substoicheiometric isotope dilutionon a continuous basis has also been proposed.44s Niobium has been deter-mined in the range 0-5-150 p.p.m.using g5Nb to assess the chemical yield,449and a new method for plotting results from radiometric exchange reactionshas been suggested.450 Determination of carbon-lithium bonds in lithium-terminated polymers has been carried out radiochemically by measuring theproduct of the reaction with tritiated alc0hols,45~ and the reaction of dichro-mate ions with silver according to the equationCk20,2- + 6Ag + 14H+-+6Ag+ + 2Crs+ + 7H,Ohas been applied to the measurement of dichromate ions in natural waters,measuring liberated 110mAg.452Absolute counting of radionuclides by a B-y coincidence method using aliquid scintillator as internal /3-detector has been discussed in detai1,453 anda reproducibility of s0.274 for counting 01- and p-emitters of an energygreater than 150 Kev has been claimed for a liquid scintillation methodbased on extrapolation of the integral spectrum t o zero energy.*" Several4a1G.A. Rechnitz and K. Srinivasan, 2. analyt. Chm., 1965, 210, 9.442 W. M. Wise and J. I?. Williams, Anal@. Chem., 1965, 37, 1292.443 G. C. Goode and J. Herrington, Analyt.Chim. Acta, 1965, 33, 413.444 G. Koehly, Analyt. Chim. Acta, 1965, 33, 418.446 L. A. Currie, G. M. France, and H. L. Steinberg, Internat. J . Appl. Radiation446 D. M. Keefer, L. F. Edmondson, and R. E. Isaacks, Health Physics, 1965, 11,447 J. RGiiEka, Coll. Czech. Chem. Comm., 1965, 30, 1808.448 J. Riiiii5ka and M. Williams, Talanta, 1965, 12, 967.449 J. Esson, Analyst, 1965, 90, 488.450 J. van R. Smit, Analyst, 1965, 90, 366.461 D. R. Campbell and W. C. Warner, AnaZyt. Chem., 1965, 37, 276.452 H. G. Richter and A. S. Gillespie, jun., Analyt. Chem., 1965, 37, 1146.453 G. Erdtmann and G. Herrmann, Internat. J. Appl. Radiation Isotopes, 1965,464 R. Vaninbroukx and A. Spernol, Internat. J . AppE. Radiation Isotopes, 1965,Isotope techniques.Isotopes, 1965, 16, 1.193.16, 301.16, 289540 ANALYTICAL CHEMISTRYmethods of counting blood samples by liquid scintillation have been coiii-pared,455 and a method for the liquid scintillation counting of l4C in aqueousdigests of whole tissues disc~ssed.~~6 A new method of colour quenchcorrection in liquid scintillation systems, using an isolated internal standard,has been pr0posed,4~7 liquid scintillation counting of emulsions has beencarried out to measure low-energy B-emitters in aqueous solution,458 andeight liquid scintillation systems have been evaluated for counting radio-iodine .459Many Papers have appeared on the subject ofactivation analysis during the year, and advances have been reviewed.460The y-ray photopeak yields have been determined experimentally for 118reactor thermal-neutron products,461 and the use of a single comparatorinstead of a number of standards, one for each element to be determined, hasbeen critically evaluated.462 A pulsed reactor system (peak flux 4.5 x 1016n/cm.2, pulse width at half maximum 15 m.sec.) has been shown to improvethe limits of detection of short-lived activities (ti < 50 ~ e c . ) , 4 ~ ~ the use offast neutron fluxes available in reactor cores has been assessed as a means ofdetermining 35 elements,464 and the relative importance of radioactive capture,inelastic neutron scattering, photoexcitation, and (n,2n) reactions comparedfor the production of a number of metastable isomers suitable for activationanalysis.465 X-Ray fluorescence and neutron activation results for zinc ingeochemical standards have been and other geochemical orcosmochemical determinations by neutron activation include bromine con-tent and isotopic content of bromine in stony meteorites,467 chlorine in stonymeteorites,468 40Ar content of iron meteorites,469 and ~candium,~70 c0pper,~71and rhenium and osmium 472 in a variety of matrices.30 trace elements have been determined simultaneously in cancerous andnon-cancerous human tissue by neutron activation,473 as also have strontiumActivation analysis.4 5 5 A.C. Houtman, Internat. J . Appl. Radiation Isotopes, 1965, 16, 65.456 R. Tye and J. D. Engel, Analyt. Chern., 1965, 37, 1225.4 b 7 H. H. Ross, Analyt. Chem., 1965, 37, 621.458 M. S.Patterson and R. C. Greene, Analyt. Chein., 1965, 37, 854.450 B. A. Rhodes, Analyt. Chem., 1965, 37, 995.460 F. Girardi, Talanta, 1965, 12, 1017; V. P. Guinn, Progress in Nuclear Energy,461 H. P. Yule, Analyt. Chem., 1965, 37, 129.462 F. Girardi, G. Guzzi, and J. Pauly, Analyt. Chem., 1965, 37, 1085.463 H. R. Lukens, jun., H. P. Yule, and V. P. Guinn, Nuclear Instruments and464 H. R. Yule, H;. R. Lukens, jun., and V. P. Guinn, Nuclear Instruments ajzd465 H. M. Kramer and W. H. Wahl, Nuclear Scieiace and Eizgineering, 1965, 22, 373.466 T. K. Ball and R. H. Filby, Geochiinica et Cosrnochinzica Acta, 1965, 29, 737.467 A. Wyttenbach, H. R. von Gunten, and W. Scherle, Geochimica et Cosmochinaiccr468 H. R. von Gunten, A. Wyttenbach, and W. Scherle, Geochimica et Cosmochimica460 R.E. Fisher, J . Geophysical Research, 1965, 70, 2445.47* H. Hamftguchi, T. Watanabe, N. Onuma, K. Tomura, and R. Kuroda, Analyt.471 J. R. Kline, Diss. A h . , 1965, 26, 582.472 J. W. Morgan, Analyt. Chim. Acta, 1965, 32, 8.473 K. Samsahl, D. Brune, and P. 0. Western, Internat. J . Appl. Radiation Isotopes,Series IX, vol. 4, part 2, p. 73.Methods, 1965, 33, 273.Methods, 1965, 33, 277.Acta, 1965, 29, 467.Acta, 1965, 29, 475.Chim. Acta, 1965, 33, 13.1965, 16, 273J . B . HEADRIDGE, T. B. PIERCE, D. BI. w. ANDERSOS 541in environmental media,474 and molybdenum in Neutron activationhas also been used to determine magnesium in needle-biopsy samples ofmuscle tissue, and the sensitivity of the method is estimated as 0.3 pg.476Non-destructive methods for the determination of copper 47 7 and silverand antimony 478 in bismuth have been gased on y-y coincidence measure-ments, sulphur and calcium have been measured non-destructively by photoneutron countingtp79 and a crystal with a thin beryllium window recom-mended for niobium determinati0ns.4~~17 elements have been assayed in polyethylene by y-spectrometry afterreactor irradiation,4*1 and the distribution of some elements in zone-refinedaluminium found by analysing drillings from the ingot by neutron activationSubstoicheiometric finishes to activation procedures have been proposedforGermanium counters have been used to permit easier calculation of y-lineintensities from spectra, recorded during activation and acompufer programme has been described based on the peak area methodwhich has been used for the routine determination of selected elements inmeteorites and separated meteoritic materials.488Work has continued to develop the applications of neutron generators ;analytical applications have been reviewed,489 the performance of a sealed-tube generator has been described,4B0 and the y-spectra of 37 elementsirradiated with 14 Mev neutrons have been publi~hed.4~1 An automatedsystem has been used to determine oxygen in chondrites, aehondrites, andgeochemical and oxygen has also been determined in ezesium ;493the effect of recoiling nuclei from activation of the atmosphere surroundingthe sample vial was found to be proportional to the surface area in contactwith air during the irradiation.Silicon 494 and rare earths 495 have beencopper and si1ver,4s4 c0pper,6~~ and474 P. J. Magno and F. E. Knowles, jun., AnaZyt. Chem., 1965, 37, 1113.476 W. B, Healy and L. C. Bate, Analyt. Chim. Acta, 1965, 33, 443.476 D. Brune and H. E. Sjoberg, AnaZyt. Clzim. Acta, 1965, 33, 570.477 J. I. Kim, A. Speecke, and J. Hoste, AnaZyt. Chim. Acta, 1965, 33, 123.478 J. I. Kim and J. Hoste, Analyt. Chim. Acta, 1965, 33, 449.478 S. Amiel and J. 0. Juliano, Analyt. Chem., 1965, 37, 343.480 A. A. Verbeek, Alzalyt. Chim. Acta, 1965, 33, 131.4s1H. Sorantin and P. Patek, 2. analyt. Chem., 1965, 211, 99.482 D. Gelli, R. Malvano, and G. B. Fasolo, Applied Materials Research, 1965, 4,107.48s J. Rb?;i5ka, A.Zeman, and I. Obrusnik, TaZanta, 1965, 12, 401.lls4N. Suzuki and K. Kudo, AnuZyt. Chim. Acta, 1965, 32, 456.485 M. Ki;iv&nek, F. Kukula, and J. Slune6ko, Tahnta, 1965, 12, 721.IE6 D. A. Beardsley, G. B. Briscoe, J. RbiMka, and 3%. Williams, Talanta, 1965,12, 829.487 S. G. Prussin, J. A. Harris, and J. M. Hollander, Analyt. Chem., 1965, 37, 1127;T. B. Pierce, P. F. Peck, W. M. Henry, and B. W. Hooton, Analyt. Chim, Acta, 1965,33, 586.488 S. C. Choy and R. A. Schmitt, Nature, 1965, 205, 758.48e J, E. Strain, Progress in Nuclear Energy, Series IX, vol. 4, part 3, p. 139.4e0 J. E. Bounden, P. D. Lomer, and J. D. L. H. Wood, Nuclear Instruments andlol Y. Kusaka, H. Tsuji, I. Fujii, H. Muto, and K. Miyoshi, Bull. Chsrn. 800.408 J, R. Vogt and W. D.Ehmann, Radiochina. Acta, 1965, 4, 24.498 0. U. Anders and D. W. Briden, Analyt. Chem, 1965, 37, 530.4 @ p J. R. Vogt and W. D. Ehniann, Qeochinaiea et Cosmochinzica Aeta, 1965, 29, 373.4,DS SL P. Menon and 35. Y . Cuypers, Analyt. Chem., 1965, 37, 1057.Methods, 1965, 33, 283.Japan, 1965, 38, 616542 ANALYTICAL CHEMISTRYdetermined after irradiation with 14 MeV neutrons, and a special study hasbeen made of the factors affecting precision of activation with 14 Mevneutrons.496Interest has been sustained in 3He activation; the scope of the techniquehas been reviewed497 and methods for carbon, oxygen, and fluorine dis-cussed.498 Surface analyses have been carried out with a-particles employinga 24Wm source and a silicon detector.499 Measurement of the 3-09 Mev y-lineemitted during the de-excitation of l3C formed by the reaction W(d,p)13Chaa been used as the basis of a method for the determination of carbon insteel.500 Reactions induced by secondary particles have also been applied toanalytical determinatiom.The sequence %i(n,cc)T, 1sO(t,n)18E” has beenused to determine surface oxygen on metals 501 and lithium in the presenceof alkali metals and magnesiurn,5O2 whilst recoil protons have been appliedto the measurement of the isotopic abundance of oxygen-1€L50311. MSSS Spectrometry.-Damoth504 has published a Review of recentadvances in time-of-flight mass spectrometry, and computer programmeshave been used to obtain the data, on ordered exact mass and abundance,praented in two important papers 505 on the interpretation of mass spectra.A number of interesting contributions dealt with aspects of instrumenta-tion.Cryosorption pumping is claimed to lead to a significant increasein the analytical performance of spark-source mass spectrometry, and asimplified vacuum lock for the direct insertion of mmples has been devised.607Brion 508 has described a windowless photo-ionisation source for high-resolu-tion work, and LincolnSOg has reported that flash-vapourisation massspectrometry offers advantages in the analysis of polymers and some in-organic compounds.Mass spectrometers were used in conjunction with other techniques in anumber of investigations, e.g., differential thermal analysis,510 gas evolutionanalysis ,511 and vacuum fusion analysis of metala.512 Fast -scanning, high-resolution mass spectrometers have been used 513 by several groups of inves-tigators €or the analysis of gas-chromatographic effluents.498 W.E. Mott and J. M. Orange, AnaZyt. Chem., 1965, 37, 1338.497 E. Ricci and R. L. Hahn, AnaZyt. CTiem., 1965, 37, 742.498 J. D. Mahony, Dks. Abs., 1966, 26, 663.40° J. H. Patterson, A. L. Turkevitch, and E. Franzgrote, J . Qwphyaical Research,boo T. B. Pierce, P. F. Peck, and W. M. Henry, Analyst, 1965, 90, 339.5 0 1 W. Leonhwdt, Andyt. Chim. Acta, 1966, 32, 355.602 G. W. Smith, D. J. Santelli, and H. Fiess, Analyt. Chim. Acta, 1965, 33, 1.Sos L. H. Hunt and W. W. Miller, Analyt. Chena., 1965, 37, 1269; D. C. Aumann604 D. C. Damoth, Adv. Analyt.Chem. Instrumn., 1965, 4, 371.605 D. D. Tunnicliff, P. A. Wadsworth, and D. 0. Schissler, Analyt. Chem., 1965,606 W. L. Harrington, R. K. Skogerboe, and G. H. Morrison, Anolyt. Chem., 1965,607 G. A. Junk and H. J. Svec, Anulyt. Chem., 1965, 37, 1629.608 C. E. Brion, Analyt. Chem., 1965, 37, 1706.60D K. A. Lincoln, AnaZyt. Chem., 1965, 37, 641.6loH. G. Langer, R. S. Gohlke, and D. H. Smith, AnaZyt. Chem., 1965, 37, 433.sllW. W. Wendlandt and T. M. Southern, Analyt. Chim. Acta, 1965, 32, 405.sl*R. J. Conzemius and H. J. Svec, Alzcrlyt. Chim. Acta, 1965, 33, 145.6x8 R. Ryhage, S. Wikstrom, and G. R. Waller, AnuZyt. Chem., 1965, 37, 435; J. T.Watson and K. Biemann, ibid., p. 844; C. Merritt, jun., I?. Issenberg, M. L. Bazhet,1965, 70, 1311.and H.J. Born, Internat. J . Appl. Radiation Isotopes, 1965, 16, 727.37, 643; D. D. Tunniclif!f and P. A. Wadsworth, ibid., p. 1082.37, 1480J . B . HEADRIDGE, T . B . PIERCE, D . M. W . ANDERSON 543McFadden et ~ 1 . 5 1 4 have published correlations and anomalies arisingfrom the mass spectra for 46 aliphatic thioesters and 17 lactones. Beckeyhas shown that, for mass-spectrometric analyses of solid natural products,the field ionisation method can be applied in addition to the electron impactmethod. Methyloximes have been used 516 as carbonyl derivatives for massspectrometry, and Russian workers 517 have continued their studies ofcarbohydrates. Sub-nanogram analyses of iodine have been achieved 518by using an ion-source that generates ions by sputtering, and methods havebeen developed 519 to determine 1 volume per million of helium in nitrogen,3 v.p,m.carbon dioxide in hydrogen, and 20 v.p.m. hydrogen in helium.12. Thermal Methods.-Fewer papers on thermal methods appearedin 1965 than in the previous year.Differential thermal analysis and its applications have been re~iewed,~~Oand the thermoanalytical properties of rubidium 521 and czesium 522 saltsreported. A micro-cell for differential thermal analysis 523 and an apparatusfor d.t.a. capable of working a t up to 1500" 524 have been described. Inconnexion with differential thermal analysis, a aample container has beendeveloped for measuring temperature and pressure changes up to 300 p.5.i.g.a t 500 * .525 Differential thermal analysis using high-frequency electricalfields has been applied to the study of curing reactions in rubbers andA technique named continuous flow enthalpimetry has been developedfor routine quantitative chemical analysis, on-line control of processes, andthe measurement of heats of reactions.527 The technique consists in passingtwo reacting solutions through a mixing vessel, the reagent solution beingin excess of the sample solution, and determining the concentration of theweaker sample solution as a result of the temperature change.13.Reaction-Rate Methods.-A simple computer circuit for automaticspectrophotometric analysis of binary mixtures by differential reaction rateahas been descrjbed.s28 Details have been published of a digital readoutpH-stat for obtaining quantitative results from reaction rate informationduring the initial stages of a rea~tion.6~~ The instrument has been employedfor the rapid determination of urea and glucose.B.N. Green, T. 0. Merron, and J. G. Murray, ibid., p. 1037; J. W. Amy, E, M. ChaihW. E. Baitinger, and F. W. McLafferty, ibid., p. 1265.614 W. H. McFadden, E. A. Day, and M. J. Diamond, Analyt. Chem., 1965, 37,89; W. H. McFadden, R. M. Seifert, and J. Urasserman, ibid., p. 560.616 H. D. Beckey, 2. analyt. Chem., 1965, 207, 99.616 H. M. Fales and T. Luukkainen, Analyt. Chem., 1965, 37, 955.617 N. K. Kochetkov, N. S. Vulfson, 0. S. Chizhov, and B. M. Zolotarev, Izvest.618 J. A. McHugh and J. C. Sheffield, dnalyt. Chem., 1965, 57, 1099.619 R. T. Parkinson and L.Toft, Analyst, 1965, 90, 220.s20A. Pande, Lab. Practice, 1965, 14, 566, 832, 938 and 1048.521 L. Erdey, G. Liptay, and S. Ghl, TaEunta, 1965, 12, 883.5 2 2 L. Erdey, G. Liptay, and S. Ghl, Talanta, 1965, 12, 257.623 S. Tanake, Bull. Chem. Soc. Japan, 1965, 38, 795.624 M. M. Hopkins, Rev. Sci. Imtr., 1964, 35, 1658.626 D. J. David, Anulyt. Chem., 1965, 37, 82.626 S. A. Wald and C. C. Winding, Analyt. Chern., 1965, 37, 1622.587 P. T. Priestley, W. S. Sebborn, and R. F. W. Selman, Andy&, 1965, 90, 689.629 H. V. Malmstadt and E. H. Piepmeier, Analyt. Chem., 1965, 37, 34.Akud. Nauk S.S.S.R., Ser. Khim., 1965, 776.D. Pinkel and H. B. Mark, jun., Tulunta, 1966, 12, 491544 AXALYTICAL CHEMISTRYAn automatic spectrophotometric method has been developed for thedetermination of galactose in blood and plasma.530 The method is based onthe action of galactose oxidase on galactose with the production of hydrogenperoxide.The rate of formation of the coloured product formed by reactionof the hydrogen peroxide with o-dianisidine in the presence of peroxidaseis related to the galactose concentration.Very small quantities of cholinesterase have been determined by a reac-tion-rate method based on the hydrolysis by cholinesterase of non-fluorescentresorufin butyrate and indoxylacetate to the fluorescent resorufin and in-doxy1 respectively.531 A reaction-rate method based on fluorescent resorufinhas also been described for measuring the activity of various dehydrogenases,namely lactic acid, alcohol, maleic acid, glutamic acid, glucose-6-phosphate,L- cc-glycerophosphate, and glycerol dehydrogenase~.~~~Ultratrace amounts ( 10-6~-10-10~) of metal ions have been determinedusing co-ordination chain reactions.The rate of the exchange reaction isdependent on the concentration of a free ligand, and the addition of traceamounts of metal ion alters this free ligand concentration.53314. Miscellaneous.-The r6le of the analyst in the pharmaceuticalindustry has been discussed.5aDangers associated with the unguarded use of ‘‘ high purity ” spectro-graphically analysed standards have been stressed.535 Eichholz et al. haveexamined the adsorption of ions on to glass and plastic surfaces from diluteaqueous solutions. It was concluded that, for most elements, the totaladsorption on glassware is so low that it can probably be neglected in themajority of radiochemical and trace analyses.536andrhenium,538 on methods for the detection and quantitative determination ofpesti~ides,5~~ on problems of sampling and sample preparationYu0 and onthe analytical properties and applications of chelating resins.541 Reviewshave also appeared on the quantitative analysis of solid mixtures by diffusereflectance measurement~~~4~ on the principles and analytical applications ofthe Faraday effect , magnetic rotatory dispersion and magnetic circulardichr0ism,~4~ on the applications of radio-frequency methods in analytical~hernistry,5~~ on the electrochemistry of cation-sensitive glass electrodes,545Reviews have been published on the determination of630 C.S. Frings and H. L. Pardue, Analyt. Chem., 1964, 36, 2477.531 G. G. Guilbault and D. N. Kramer, Analyt. Chem., 1965, 37, 120.632 G. G. Guilbault and D. N. Kramer, Analyt. Chem., 1965, 37, 1219.633 D. W. Margerum and R. K. Steinhaus, AnaZyt. Chem., 1965, 37, 222.634 D. C. Garratt, Proc. Soc. Analyt. Chern., 1965, 2, 55.635 S. S. Yamamura, Analyt. Chem., 1964, 36, 2515.536 G. G. Eichholz, A. E. Nagel, and R. B. Hughes, AnaZyt. Chenz., 1965, 31,637 Yu. G. Eremin, L. A. Lavrova, V. V. Raevskaya, and P. N. Romanov, Zat+ocEskya53BV. M. Tarayan and S. V. Vartanyan, Zavodskaya Lab., 1964, 30, 1301.63e I. K. Isitovich, Zhur. analit. Khim., 1965, 20, 875.& a o H. Sporbeck, 2. analyt. Chem., 1965, 209, 60.541 G.Schmuckler, Talanta, 1965, 12, 281.642 W. P. Doyle and F. Forbes, Analyt. C h h . Acta, 1965, 33, 108.543 J. G. Dawber, Analyst, 1964, 89, 755.544 M. F. C. Ladd and W. H. Lee, Talanta, 1965, 12, 941.5 4 5 G. Eisenman, Adv. Analyt. Chern. Instrument., 1965, 4, 213.863.Lab., 1964, 30, 1427J . B. HEADRIDGE, T . B. PIERCE, D . M. W. ANDERSON 545on phase-solubility techniq~es,~4~ on the analytical applications of differen-tial dialysis,5*7 and on recent developments in kinetic methods of analysis.548It is reported that hydrofluoric acid alone is the most effective reagentfor decomposing the minerals of silicate rocks. Many are decomposed byheating on the water-bath, while most others are decomposed at the highertemperatures available with a Teflon-lined b0mb.54~ The decomposition ofrocks, refractory silicates, and minerals is rapid and complete, if the materialis fused with a mixture of lithium fluoride and boric acid at about 800-8.50"in a platinum crucible.550A computer programme has been devised for identifying crystallinephases by powder diffra~tion.~~l Gleit 552 has developed a high-frequencyelectrodeless discharge system for ashing organic matter, and a condensat'ionpressure analyser has been described for the continuous determination ofuranium hexafluoride in a gaseous plant stream.553 The deuterium oxidecontent of water has been rapidly determined using a vapour-pressureosmometer.554 Chemical microscopy has been applied to the analysis ofurinary calculi.555Edge and Fowles have reported that titanium(Iv), vanadium( v), molyb-denum(vr), and iron(m) are quantitatively reduced to the 3 + , 2 + , 3 + ,and 2+ states respectively with sodium-lead alloy in acid solution.Thereducing action of the alloy is similar to that of zinc amalgam.556Cerium(rv), permanganate, and iron(ri1) in the micromolar concentrationrange have been determined by chemical stripping analysis where silver isoxidised from a rotating platinum electrode. From a plot of electrodepotential versus time, the time required to oxidise a known amount of silveris determined. This time is inversely proportional to the concentration ofoxidant in the s0lution.~57An automatic method for supplying the result in three minutes has beenapplied to the determination of phosphorus in copper. The metal is dis-solved by constant-current anodic oxidation and the phosphate determinedphotometrically with molybdovanadate reagent. The method should beapplicable to the analysis of other elements in other metal~.5~*Direct measurement of the e.m.f. of a concentration cell, with the elec-trodes consisting of thin silver rods submerged in a suspension of the cor-responding silver halide in dilute acid, has been employed for the satisfactorydetermination of small amounts of halide ions in solution. The method wasapplied to the determination of chlorine in organochlorine compounds after546 T. Higuchi and K. A. Connors, A h . Analyt. Chem. Instrument., 1965, 4, 117.547 L. C. Graig, Adv. Analyt. Chem. Instrument, 1965, 4, 35.518 K. B. Yatsimirskii, V. K. Povlova, and V. I. Skuratov, Zacodskaya Lab., 1965,549 F. 5. Langmyhr and S. Sveen, Analyt. Chim. Acta, 1965, 32, 1.550 V. S. Biskupsky, Analyt. Chim. Acta, 1965, 33, 333.551 L. K. Frevel, Analyt. Chem., 1966, 37, 471.552 C. E. Gleit, Analyt. Chem., 1965, 37, 314.553 W. S. Pappas and C. W. Weber, Analyt. Chem., 1965, 37, 407.554 E. Lazzarini, Nature, 1964, 204, 875.555 D. E. Laskowski, Analyt. Chern., 1965, 87, 1399.556 R. A. Edge and G. W. A. Fowles, Analyt. Chim. Acta, 1965, 32, 191.s57 S. Bruckenstein and J. W. Bixler, Analyt. Chem., 1965, 37, 786.658 8. Barabas and 6. G. Lea, Analyt. Chem., 1965, 37, 1132.31, 525546 ANALYTICAL CHEMISTRYoxygen-flask comb~stion.~~g Potentiometric measurements using a cationicsensitive glass electrode have been used to determine the concentration ofammonium ion in a trishydroxymethylaminomethane buffer at pH 7.0.The method was applied for determining urease activity from the amount ofammonium ion formed within a given period of time by the action of theenzyme on urea.56o A sensitive Clark-type electrode for use with samples assmall as 0.3 ml. has been constructed for measurement of oxygen concentra-tion in solutions.5G1A technique of spot electrolysis has been proposed for the determinationof 5-20 nanoequivalents of oxidisible or reducible ions. A spot of material,produced on an inert electrode by evaporation from aqueous solution, isbrought into contact with a supporting electrolyte and immediately elec-trolysed. The resulting current is a function of the quantity of electroactivematerial in the sp0t.5~~A new electroanalytical technique, phase angle titration, has been des-cribed. When a constant alternating current is applied between two plati-num electrodes immersed in a reversible redox system, the relative phaseangle between current and voltage varies as the concentration of the reduciblespecies changes on titration with an oxidising agent. A large change inphase angle occurs at the end-point of the titration. The precisions of titra-tions are excellent even for O~OO1~-solutions.~~~Reviews have been published on the determination of oxygen in metalsand inorganic compounds by reduction fusion in an inert gas atmo~phere,5~4and on the determination of gases in metals by vacuum fusion, by fusion inan atmosphere of inert carrier gas, and by isotopic ex~hange.5~6 The ther-modynamic principles of determining gases in metals by the vacuum fusionmethod have been examined, and equations derived to find the optimumconditions for applying this techniq~e.5~6 Lemm has described a fa& methodfor the determination of nitrogen in steel by carrier-gas extraction,s67 and avacuum melting instrument for the rapid and accurate determination ofoxygen, hydrogen, and nitrogen in metals without separation of the gaseshas been constructed.56* The Zaidel isotopic balancing spectroscopicmethod has been applied to the determination of hydrogen in uranium metal.The relative error was 3-7% for hydrogen contents between 0.5 and 5p . ~ . m . 5 ~ ~ Carbon in sodium in the range 3-12 p.p.m. has been determinedby removing the sodium by distillation at 600°, converting the carbon in theresidue into carbon dioxide by combustion in an excess of oxygen, andmeasuring the carbon dioxide manornetri~ally.~7~650 J. Roburn, Analyst, 1965, 90, 467.560 S. A. Katz, Analyt. Chem., 1964, 36, 2500.s 6 1 J. S. Kahn, AnaEyt. Biochem., 1964, 9, 389.562 D. H. Evans, Analyt. Chem., 1965, 37, 1520.5133 U. H. Narayanan, G. Dorairaj, and Y. M. Iyer, J . Electroandyt. Chem., 1964,564 A. M. Vasserman and Z. M. Turovtseva, Zhur. analit. Khim., 1964, 19, 1377.565Yu. A. Karpov and G. G. Glavin, Zavodskaya Lab., 1965, 81, 139.s66 L. L. Kunin, Zhur. analit. Khim., 1965, 20, 822.567 H. Lemm, 2. analyt. Chem., 1965, 209, 114.s68T. Kraus, 2. analyt. Chern., 1965, 209, 206.560 H. Kawaguchi, Japan Analyst, 1965, 14, 138.570 J. A. J. Walker and E. D. France, Analyst, 1965, 90, 228.8, 472