30___Analytcal Applications of UV.VIS Spectroscopy Oe & Ho” rene 12-Pyryiazo}-2-naphtol PAN) pom) \—6) © mone (Dpentecarbrone WF ON, os pw {O) 8-Hydroxyquinoline (oxine) J Nua —1i Ophenerbacce Formaldoxime aa <8 6 = Lf of tay Oty secant BOT) yo ' I ‘| N-BonzoylA-phonythycroxlamine Pyroiin-cthvocarbamidate ig-9. Structural formuls of some complexing agents SbCl, in acid solution (6N HCD at a ratio of 1:1 and can be extracted with benzene [64-68]. Further examples are the ion associates of methyl violet with fluorotan- talate [69], of dodecamolybdato phosphoric acid with safranin [70] or crystal violet [71] and of tetrafluoroborate with methylene blue [72] orPhotometric Determination of a Single Substance 31 Table. Summary of photometric determinations of elements. The references refer to the bibliography of detailed analytical procedures Element Reagent Ainnm 10-? Ref. mol" em Aluminium Aluminon 525 110 36 Eriochrome cyanine R 533140 0 S:hydroxyquinoline 386 66 36 Sallie acid 410 “4 ‘Antimony Sver diethyl dithiocarbamidate $10 182 0 Pheaylfluorene 53042 36 Rhodamine B 565850 0 Pyrocatechol violet 588 4“ Bromopyrogallol red 560374 36 ‘Arsenic Silver diethyl dithiocarbamidate 538 Bs 36, 40 Determination as arsenic ‘molybdenum biue complex acum Dimethylsulfonazo DAL 670 33 36 Berylium Acetylacetone 2s 316 36 Erichrome cyanine R siz 13s 36 Chromal blue G+ 625 (93.0 46 Cetytrimethylammonium chloride Bismath Dithizone 9s 800 36 Sodium diethyl dthioearbamidate 366 86 36 Xylenol orange 580110 0 Boron Curcumin 5831460 36 Carminic aid 610 37 40 1,1-dianthrimide 18.0 “0 cadmiuen ne 520 65.0,85 36,40 jazonaplthot 550 36 Calcium Giyoxal-bis @-hydroxyani) 5201631 36 Sthydroxyquinoline/a-butylamine 370 637 36 Cerium Shydroxyquinoline 50s 60 40 Chlorine o-olidine “80 «0 Chromium Diphenylearbazide 540 340 0 Cobalt {-nitroso naphthol mo 340 36, 40 2ritroso naphthol 1 330147 36 Nitroso-R salt 5040 40 12-pyridylazo) resorcinol S10 567 8,49 Copper Bathocuproine a 42 36 CCuprizon 395 16.0 36, 40 Sodium diethyl dithiocarbamidate 440 160 rn Diphenylarbazide 9S 1588 50, 51 Fluorine CCe-chelate with alizarineS-methyl- 617 7 36 amine-N,N-d-scetic acid Lachelate ditto oo 0 40 Gallium Xylenol orange ss 329 36 Germanium —__Phenylfluorene 50870 0 Gold Rhodamine B 5656.0 “0 Pynidine-2aldoume a 3 Hagnium ‘Arsenazo (with Zi) 570 36 Indium Dithizone 5106.0 40 4-€-pyridylazo)- resorcinol so mt 36 Xylenol orange 50 259 36 Iodine o-tolidine 2 (00 032__ Analytical Applications of UVVIS Spectroscopy Table S (continued) Bement Reagent Ain am Ret. ° mot”! em” Isigium Pyridyl azonaphthol 30103 36 Iron (1) 410-phenanthroline st 36 Bathophenanthroline se 36, 40 2,2-dipyridyl oo 87 36 Iron (11) Ferron (7-iodo-8-hydroxyguinoline- 610 37 36 S-sulfonic acid) Lanthanides _Alizarin $ (total determination) $3050 36 Lead Dithizone 5029 36, 40 Shydroxyquinoline in molten 360 91.0 a naphthalene /CHC, Magnesium ——-Shydroxyquinoline/n-butylamine 380 56 36 Eriochrome black T 530 ko 0 Manganese Formamidoxime 40 110 Po Diethyldithio carbamidate 300 40 36, 40 Mercury Dithizone 485 68.0 36,40 Molybdenum 6,7-lihydroxy-2,4-iphenyl 535 50.0 2 Denzopyrilium chloride toluene 3,¢-dthiol om 3.0 ‘0 ‘Chloranile aid 30100 0 Quercetin 2 360 0 Thioglyeotic acid 365 2.35 36 Nickel Dimethyleyoxime 40 16.0 36 Sodium diethyl dithiocarbamidate 325 35.0 0 Pyridylazonaphthol 560610 53-55 Niobium 4 (yridy|-2-a20} resorcinol 550380 «0 Bromopyrogalol red 60 ans 36 Osmium 1,5-diphenplearbazide 560 1400 0 Cnaphthylamine-46,8ciulfonie 385 29.8 36 acid Mercapto-benzimidazole 30 108 36 Palladium 2,2-furildioxime 30 0s 36 2'nitroso-naphthol{t) sm 3 38 Phosphorus as phosphorus molybdenum blue 725163, 36 @o) fs molybdato phosphoric acid 310248 36 Platinum Dithizone mo 380 36 Rhenium 2,2-furldioxime a) in aqueous phase sma 36, 40 yin organic phase 53098 36 Rhodium ‘-{pyridylazo}-naphthol(2) 600 S4 0 Ruthenium —_-Nitroso-R salt, sso 222 36 N,N'-iphenyl thiourea 650 023 0 Scandium Alizarin S 320 34 36, 40 Shydroxyquinotine 378 69 36 Selenium 3,3-diaminobenzidine ‘20 99 36 ‘o-phenylenediamine 355 78 36 2.3-diaminonaphthalene sn 88 6 Silicon ‘as molybdato silicic acid 390 19 36 as silico molybdenum blue 1 or 36 70 Silver Dithizone 42 306 36, 40 Strontium ‘Arsenazo TIL 600 33‘Titanium Tungsten Uranium Vanadium Yusium Zine Zieconiuen monomethyithionine [73]. These ion associates with bi Photometric Determination of a Single Substance Reagent Pyrogallol Sodium diethyl dithiocarbamidate Bismuth thiol Brillant green, see Table 6 Rhodamine Dithizone ‘Thorin ‘Arsenazo Phenyifluorene Pyridyl-3-fluorene Hematin Bromopyrogalol red Pyrocatechol disulfonie acid 3,5 ‘N-benzoyL-N-phenylhydronylamine Dithiol Gyoxal-bis-2-hydroxyani) Pyridyazoresoreinal ‘-(pyridy-2-az0)-naphthol-2 2-(-bromopytidyl-2az0}-5(a- ‘thylamino)-phenol ‘N-benzoyl-N-phenylhydroxylamine Pyridylazoresoreinol ‘Vanadox (2,2-dicarboxydiphenyl- amine) Alizarin S Pyrocatechol violet Dicarboxy arsenazo IIT Dithizone Zincon(2{\a(2-hydrony-S-sulfo- phenylazo)-benzylidene|-hydra- ing} benzole acid-monosodium salt) Alizarin S Pyrocatechol violet, Xylenol orange ‘Arsenazo IIL Ain am sis 410 380 370 530 560 380 310 550 610 560 650 535 600 665 210 240 337 200 740 ar 360 230 259 736 95.0 240 26 28 750 1200 3 36, 40 36 36 36 36 36, 40 36 36, 40 36 56 38 36, 40 36 59, 61 0,61 a or acid dyes generally have very high extinction coefficients since several dye molecules can be present in the complex. On account of the demand for greater sen- sitivity and the resulting lowering of the detection limit into the ppb region, numerous investigations of extraction spectrophotometry have been carried ‘out in recent years. Tables 6 and 7 provide a summary, compiled by Mar- czenko [74], of the elements extracted in the form of ion associates with basic or acid dyes.34_Analytical Applications of UV.VIS Spectroscopy ‘Table, Summary of selected extraction spectrophotometric methods of determination with basic dyes [74] Element Complex Dye Solvent fom Specific absorption ‘Antimony SbC ‘Rhodamine B= Benzene 97x10 0.80 Soc; Brillant green Toluene 10310" 0.85 SbCl, Butyrhodamine B_Toluene/butanol 12010? 0.99 Bismuth Bilg Rhodamine Benzene 13010? 042 Boron BF, Methylene blue Dichlooethane 68102 6.01 BF, Chromopyrazole It Chloroform 67x10" 6.20, Gallium — GaCly Methylene blue Benzene/C3H,Cl; 75X10" 1.07 GaCl, Rhodamine B——ovdichlorobenzene 90x10" 1.29, Germanium Dino py- Brant green CC, tsixi0? 1.98 rocatechol ‘Aliarin Rhodamine 6G CCL/CHCl 28010? 4.00, ‘complexone Gold AUC, Rhodamine Benzene srx10? 049 ‘AuCl, Methyl violet Trichloroethylene 115%102 0.58 Indium Inky Malachite green Benzene/herane 10610" 0.92 Int, ——-Rodamine B= Benzene/diso. 11010" 0.96, propyiether Mercury Hal, Crystal violet Toluene ssx10! 0.27 gC Methyl green Benzene/toluene 131x102 0.65 Phosphorus Hetero- Malachite green Propylacetate— 17010? 549 poly. Hetero. Crystal violet Propylacetate 270x108 8.72 polys Rhenium ReO, -—-Butylrhodamine Benzene 40x10? 0.21 ReO, Nile blue Chlorobenzene + methane! ‘Tantalum Taf, _Nttochromopyrazole Benzene/iuene 83% 102 0.46 Tar, Methylene blue —Dichlooethane+ 91x10" 0.50, twichloroethyene Tare Capri blue Chlorotorm 10730" 099 Tellurium TeBt, _—Wistoia blue 4R_—— Benzene nitro. BBX 10? 0463 benzene Thallium TIC Crystal violet Diksopropyleter 102x108 0.50 Tic, Brillant green _—_—Diisopropylether 106% 10? 0.32 Tic; Methylene blue —_—Dichloroethane-+ 114x10? 0.56 twchlorosthane Tin SaCl, Crystal violet ——“Heptanone 85x10) 0.72 Tungsten Dinito py- Brillant green Chloroform 132102 0.72 rocatechol Benzene+MIBK 10310" 0.43 Uranium —Benzoie acid Rhodamine B ‘The solvents listed in Tables 6 and 7 refer to the solvent used for extract- ing the ion associate, If the extinction coefficients of the ion associates in these tables are compared with the corresponding entries in Table 5 it can bescen that, in some cases, very high extinction coefficients are actually ob- served which implies a high sensitivity of detection. For the evaluation ofPhotometric Determination of a Single Substance 35 ‘Table. Extraction spectrophotomettic methods of determination with acid dyes; metals complexed with 1,10-phenanthroline [74] Dye Element Solvent feax Specific absorption Rose Bengal B Copper (II) Chloroform x18 0.99 thyl acetate TBxi0 1.23 Palladium Chloroform s0xi8 0.87 Zine Chloroform 51x10! 0.78 Cadmium Chloroform 64x10 0.37 Lead Chloroform 58x10) 028 Bovin Silver Nitrobenzene + 55x10) 051 chloroform + butanol soxi0 0.46 Lanthanides Toluene+ butanol 120x 10 Zine Chloroform i20x10 1.84 Lead Chloroform s10xi0 0.33, Erythrosin Lamhanides Toluene-+butanol 160 10 Lead Chloroform x10 031 Bromphenol blue Iron (I) Chloroform+amylol 59x10 1.06, Nitromethane mxie 1.47 Silver Chloroform Zine Chloroform 100% 108 1.53 Zine Chloroform 3Bx10 0.58 Cadmium —_Dichloroethane 31x18 028 Bromphenol red Iron (I) __Nitromethane s6x108 037 Zine Chloroform+amylol 32108 0.49 Bromeresol green Zine Chloroform 1x18 0.29 Methyl orange Iron (I) __ Chloroform 48x10 0.86 the sensitivity, the values of the specific absorption “a” are also given for each element calculated from Eq. (16). It has been found that some low-solubility ion associates of basic dyes with anion complexes cannot be extracted by means of organic solvents which have low dielectric constants, because they coagulate into flakes which collect at the phase boundary or adhere to the walls. The solvent and aqueous solution are separated by decanting or filtering and the precipitate is then dissolved (usually in acetone or alcohol). The complex. then dissociates and the procedure forms the basis of a new photometric tech- nique which is called flotation spectrophotometry. ‘The high extinction coefficients determined with this method depend on the dissociation of the low-solubility ion associate which dissociates upon dissolution, Subsequently, the absorbance of the dye transferred into solu- tion is measured in the solution. Since several dye molecules can be fixed ina complex and since the measured absorbance is related to the molecular weight of the complex, extremely high extinction coefficients are obtained per gram atom of the element to be determined. Whole-number multiples of the extinction coefficient of the dye in the same solvent are involved. For example, rhodium as RhCl; with SnCl, results in an ion associate in which