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ORGANIC REAGENTS FOR SPECTROPHOTOMETRY DETERMINATION OF ANIONS Y.K. Agrawal Chemistry Department, School of Sciences Gujarat University, Ahmedabad - 380 009, India CONTENTS Introduction 25 Summarizing Tables for Various Anions 26 Frequently Used Spectrophotometric Determinations of Common Anions .... 51 References 55 INTRODUCTION Organic reagents have a remarkable versatility for inorganic and organic analysis. The most important among the organic reagents are those which form 'chelates' with the metal ion. The chelating agents should possess two functional groups which may be either acidic, coordinating or a combination of both. The acidic character may be due to the presence of a hydroxy (-OH), mecapto (-SH), or imino (=NH) group, including forms such as enol I (HO C = CH -), oxime (=N-OH), acid nitro (=N-OH), sulphinic (-SO-OH), sulphonic (-S02 - OH) or their thio analogue. On the other hand, groups like carbonyl (>C=0), thio (>C=S), primary amino (-NH), secondary amino (-NH2) or tertiary amino (-NR'), nitrosyl (-NO), etc. coordinate by virtue of the lone pair of electrons on the N, S or Ο atoms. Systematical study of organic reagents containing the aforesaid groups for the development of analytical methods for anions is scanty. Generally the organic reagents have been used widely for anions by indirect methods, either forming ion pair complexes or adding to the metal complexes to make metal chelates, from which the anion concentration is determined. A large number of organic reagents have been used for the extraction spectrophotometric determination 25 Vol. XVI, No. 1, 1997 Organic Reagents for Spectrophotometric Determination of Anions of several anions. The use of organic reagents for the determination of various anions has been summarised in Tables 1-8/1- 254/. Some frequently used spectrophotometric methods for the most common anions are discussed in the subsequent paragraphs. SUMMARIZING TABLES FOR VARIOUS ANIONS In Tables 1-8, the following abbreviations are used: Ac20 Acetic anhydride EtOH Ethyl alcohol AcOH Acetic acid ex excitation wavelength BG Brilliant Green HDTMA hexadecyl trimethyl BPG Bromopyrogallol ammonium BuAc Butyl acetate IAA Isoamyl alcohol iBuAc Isobutylacetate MB Methylene Blue CA Chromotropic acid Me Methyl CAS Chrome Azurol S Me2CO Acetone CP Cetyl pyridinium MePh Toluene CPB Cetyl pyridinium bromide MG Malachite Green CPC Cetyl pyridinium chloride Μ IB Κ Methyl isobutyl ketone CTMA Cetyl trimethyl MTB Methyl Thymol Blue ammonium NaHMP Sodium hexametaphos- cv Crystal Violet phate D2EHP bis (2-ethyl hexyl) OAc" Acetate phosphate PAR 4,2-pyridylazoresorcinol DMF Dimethylformamide PhCl Chlorobenzene DMSO Dimethyl sulfoxide Phen 1,10.phenanthroline EBT Eriochrome Black Τ PV Pyrocatechol Violet ECAB Eriochrome Azurol Β SPACA 3 -(4-sulphophenylazo) ECR Eriochrome Cyanin R chromotropic acid EDTA Ethylenediaminetetracetic TBP Tri(n) butyl phosphate acid disodium salt TOA Trioctyl amine em emission wavelength TOMA Trioctyl methyl ETAc Ethyl acetate ammonium Et20 Diethyl ether XO Xylenol Orange 26 Y.K. Agrawal Reviews in Analytical Chemistry - s 9 o\ 1 <N c<-> Ό r- 1 ι—I 10,1 18,1 ence Refer e 1 1 I 1 I 1 I 1 I Interferenc s y ) ) ) ) ) ) 1 0 0 0 (Beer' 0 ppm , I 1 500 1400 6600 (0-16 2540 (0-3.0 Absorptivit r (0.1-6.0 (0.4-5.6 Law (0.03-0.16 l.mor'cm" Mola 6 3 0 3 7 ο <N «—« 5 <N o\ ΓΛ •q- Ι£Ο , ex-46 ex-31 ex-36 em-55 Ji em-38 em-50 t Ν C» ίΛ ο <5 Ο Ο Ο 00 00 Solven £ 1 £ ffi Iα £ Ο ffi iο v % s / d t·» rr <ri 00 (Ν Ο 3 1 pH 00 § «a § Κ Ο * § κ υ molarit - e - - e 4-4 + d aci e c d e m Zephiramin t t + aci d d c H aci aci Viole c c Reagen l c pyridiniu l Zephiramin + A 1,8-dihydroxynaphthalene^4 Organi Carmini Catecho Chromotropi C sulphoni Azomethine- Dibenzoylmethan diethylamino-phenylazo)-N 2,6-dihydrobenzoi methy 2-4-dihydroxybenzophenon 27 Vol. XVI, No. I, 1997 Organic Reagents for Spectrophotometric Deleiviination of Anions 00 VO £ 8 <N <N Γ·» (Ν X <U ΡΉ A 00 -<"! ο „ Λο; & < ο I A •w; *. - «Sο, A Ο υ ί* £ <5 <-.- α as co Ο . Ή| οδ a 8 2 >η I" Ο ο Ö ^if ^ >3 (Ν £ δ Ι "ο Ο 0Q sa Ι 1 1 J3 « υ Ο 'ο οί J3 Ü υ 1J :§ ζ& CO ν α «η I <4 s m+ <Ν I 28 Y.K. Agrawal Reviews in Analytical Chemistry 8 4 5 vo 0 VO νο r-l Cl rr •sr •tr 34,3 38-4 42-4 47,4 ' t*1 Ο ι 1 1 I 2 1 1 I ι I I ) ) ) ) ) ) 0 0 0 0 0 0 1 0 100 100 580 650 1100 1800 1060 (0.2-2 (0.2-10 (0-0.42 (0.2-1.0 (0.04-0.4 (2.1-12.6 ο ο ο VO ο ο c ο ο t- Γ- 9 r- <N (Ν U-l 1/-1 >/-) u-i Ε <Λ1 VO MS 1/-1 l TT r τ Ο Ο υ Ο ο l l CN Κ 00 00 ΐ X Κ 1Ν ο PhC PhC U Highe alcoho ν Χ Χ U c τ Τ c c VO1 1 ° α ° c m VI Ό vo «a ο «a 8 ä s I χ υ Χ U X + Acidi Acidi Acidi - 'i? - n - ο e e ferroi + e υ n R thionin thiazin diphenyl ε 4 + e + t-· + n l d l l e & Gree t e e Blu salicylat aci υ a c Gree m ο e Viole d 1,2,5,8-Tetrahydroxy-anthra Sodiu Victori H-resorcino H-resorcino H-resorcino Tetracyclin quinone-3-methyl-amine-N,N diaceti Iodin Methylen Re guanidin 29 Vol. XVI, No. I, 1997 Organic Reagents for Spectrophotometric Deteiviination of Anions - s 5 0 o\ ο TS vo r- 00 ON •sr «Λ m u-1 VL 1Λ ence 53-5 60-7 Refer V 4 " e 1 o <+N 1 I I 1 1 I Ο 1 I Ä " Ο ·»R S TT Interferenc A " 2 υ %Ζ ο + A" Ο 3 υ υ s y ) ) ) ) ) 0 1 0 (Beer' ppm I I I , 1 1 1090 1500 (1-10 Absorptivit (13-39 (0.5-10 r (0.06-0.8 Law l.mor'cm' «s W Mola υ ρ - t t Ο >Λ Ο Ο <N VO Ο Ο R- <N <0 <N VO <—ι WI vo VO VO VO VO VO viole Ji Viole Μ Bluish (%οε t tn J .TTAT/ Ο ο Ο Ο Ο Ο 8 # iα, sΟ Ν ? u CS <N ES 5K T Χ Κ s Κ i ) κ X Solven 2 + y / r» ON CS Ο Ο FI ι RR >N TT CI pH I s molarit e c e e e - + e + oxim ) e complexon S e m t d B n resaceto CP complexon Re l complexon e n n + n R Alizari (Paeonol Reagen complexon e c n n + x EC d + l Organi diphenylguanidin Bora Ce-Alizari Ce-Alizari diphenylguanidin Ce/La-Quinalizar complexon aci Alizari Alizari A Fe-4-Methy Fe-5,5'-Methylene-bissalicyli La-Alizari phenon 30 Y.K. Agrawal Reviews in Analytical Chemistry , 5 0 8 t—< fi 7 <N Μ Ov ο r- Ρ r- , 00 00 oo 3 οο 00 σν ON 76-8 86-9 74 61,69 1 *δ 0C0S 'ΰ δ CO I I I 1 1 ι 1 £ I • • I'd υ 00 Η« Λ ^TT A" CQ Cd <! ο ÖH OH 1 ) ) ) ) " ) ) ) ) ί s ) 0 0 0 VI 1 I 1 <N • 800 (0-4 fS 3000 (0.04 (0-0.5 (10-80 (5.160 (0.05-1 1.7x10 (0.2-2.0 (0.1-1.4 (0.07-0.3 (0.04-0.25 5 ο •Λ «ο ο v> 00 <N S r- ο VO ο 0<0S VοO r(Νo Ό vo •Λ Ί- VO 3 'ί- VI I ι vo 520-52 + Ο A Ο ο Ο Ο Ο Ο ο Ο Ο £ ι IA £ £ Κ £ κ χ SC £ • f Ι» 0 3 0 l l f> σι M 00 ON Ο •«r TT ι vi t—« 1 HC <Ν HC τΤ 1.2 2.9-3. 3.6-8. 2.2-2. e e d + a 1 aci + - g c e squarin l c S ί l c 4| "c ξ complexon S S e d "c pheny Ι d e t § •5 ) I l Π o Re complexon 1i Re 1 o n n c1 1 n 1 chlorid "ö O s A Ι < jt § 1,3-N-N'-bis-4-(4'-nitro diphenylanilin TOM Th-Alizari Th-Arsenaz La-Alizari Zr-Alizari Zr-Arsenaz Zr-chlorosulfopheno Zr-Thoron-C Zr-X Al(HI)-calcon-carboxyli benzene-diazo 1 31 Vol. XVI, No. 1, 1997 Organic Reagents for Spectropliotometric Detetviination of Anions - 5 s , , 1 4 m 9 Γ<Ί fS , r- 00 Ο o\ as 0\ ο\ 10 10 100 o 103 ence Refer 94 e 'rt Ο Ο ' f» I I 1 1 I I ι ο Interferenc ζ s y ) ) ) ) ) (Beer' 1 ppm , I I 1 ' 2 Absorptivit (0-136 r (0.34-68 (0.07-1.8 Law (0.034-1.02 .mor'cm' 1 Mola υ S a ο r- ο Ο 00 00 U-1 •Ί· 3 ο ο ο J i <Ν >n •Ί- τ ι/ι m t ΟΝ Ο Ο Ο ο Ο ΟΝ Οη Χ £ X u Χ Χ Χ χ Solven y - - ) 3 / ο 1 1 1 ι ι ι pH οό • ated HCO (satur molarit .3 ju Ο ίΜ 3 Χ t 1+ + i <Ν o Λ VIQ e δ '6Χ ί υ «S C/3 υ Ο < H Reagen Q I £ υ ο c χ + < + w w Ρ%Η Ο + + + Ο + + + Α + ο Ph +T U Ηrs Η * ,! ο I Organi Η U ο Ρ Η 32 Y.K.

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