Analytical Applications of UV-VIS Spectroscopy -(2-Pyridylazo)-2-naphthol(PA Po 8-Hydroxyquinoline(oxin Formaldoxime 1.10-Phenanthroline 2.2'-Dipyridyl N-Benzoyl-N-phenyIhydroxylamine Fig.9.Structural formulas of some complexing agents SbCl6 in acid solution(6N HCI)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
30 Analytical Applications of UV-VIS Spectroscopy ©J¥l~ N H II N @ 1-(2-Pyridylazo)-2-naphthol (PAN) ~ 0, H 8-Hydroxyquinoline (oxine) H-C=N-OH I H Formaldoxime 1,10-Phenanthroline 2,2' -Dipyridyl N-Benzoyl-N-phenylhydroxylamine HO /H-NH-@ s=c \N=N-@ Dithizone (Qiphenyl-!hlocarbazone) /H-NH-@ O=C \H-NH-@ Diphenylcarbazide /NH-NH-@ O=C \N=N-@ Diphenylcarbazone \ /2 HS C-N e-.! \ I§ C2H5 Qiethyl-Qi!hio~arbamidate (DDTC) S H2C-CH2 ~ C-N I I e -.! \ I§ H2C-CH2 Pyrrolidin-dithiocarbamidate Fig. 9. Structural formulas of some complexing agents SbCl6 in acid solution (6N HCI) at a ratio of 1: 1 and can be extracted with benzene [64-68]. Further examples are the ion associates of methyl violet with fluorotantalate [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 Element Reagen in nm 1otem-t Ref. anine R 48 6 &ydroyguone 6.6 36 Antimony 3 4106 85.0 056 Arsenic S5n9erOg1hiearbamidate 36.40 ine R Chromal blue G+ 0创第11锅 Bismuth 98 3 Xylenol orange 1,1'-dianthrimide Cadmium 4 Calcium ait t-i Nitroso-R salt 14 Copper um Fluorine Gallium 11131044 ylazo)-resorcinol 1411第幼11008处 创150 050000661061560 o-tolidine
Photometric Determination of a Single Substance 31 Table S. Summary of photometric determinations of elements. The references refer to the bibliography of detailed analytical procedures Element Reagent A in nm e 10-3 Ref. lmol- I cm-I Aluminium Aluminon 525 11.0 36 Eriochrome cyanine R 535 74.0 40 8-hydroxyquinoline 386 6.6 36 Salicylic acid 410 44 Antimony Silver diethyl dithiocarbamidate 510 18.2 40 Phenylfluorene 530 34.2 36 Rhodamine B 565 85.0 40 Pyrocatechol violet 555 45 Bromopyrogallol red 560 37.4 36 Arsenic Silver diethyl dithiocarbamidate 538 13.5 36,40 Determination as arsenic molybdenum blue complex Barium Dimethylsulfonazo DAL 670 5.3 36 Beryllium Acetylacetone 295 31.6 36 Erichrome cyanine R 512 13.5 36 Chromal blue G + 626 93.0 46 Cetyltrimethylammonium chloride Bismuth Dithizone 495 80.0 36 Sodium diethyl dithiocarbamidate 366 8.6 36 Xylenol orange 550 11.0 40 Boron Curcumin 555 146.0 36 Carminic acid 610 5.7 40 1,1' -dianthrimide 620 18.0 40 Cadmium Dithizone 520 65.0, 85 36,40 Pyridylazonaphthol 550 36 Calcium Glyoxal-bis (2-hydroxyanil) 520 16.31 36 8-hydroxyquinoline/n-butylamine 370 6.37 36 Cerium 8-hydroxyquinoline 505 6.0 40 Chlorine o-tolidine 440 28.0 40 Chromium Diphenylcarbazide 540 34.0 40 Cobalt 1-nitroso naphthol-2 420 34.0 36,40 2-nitroso naphthol-1 530 14.7 36 Nitroso-R salt 500 14.0 40 1-(2-pyridylazo) resorcinol 510 56.7 48,49 Copper Bathocuproine 479 14.2 36 Cuprizon 595 16.0 36,40 Sodium diethyl dithiocarbamidate 440 16.0 40 Diphenylcarbazide 495 158.8 50, 51 Fluorine Ce-chelate with alizarine-3-methyl- 617 13.7 36 amine-N,N-di-acetic acid La-chelate ditto 620 11.0 40 Gallium Xylenol orange 545 32.9 36 Germanium Phenylfluorene 510 87.0 40 Gold Rhodamine B 565 61.0 40 Pyridine-2-aldoxime 420 36 Hafnium Arsenazo (with Zr) 570 36 Indium Dithizone 510 69.0 40 4-(2-pyridylazo )-resorcinol 500 17.1 36 Xylenol orange 560 25.9 36 Iodine o-tolidine 425 20.0 40
32 Analytical Applications of UV-VIS Spectroscopy Table5(continued) Element Reagent A in nm e10 Ref. Imol-1 cm-1 550 10.3 IFon (UD) nanthroline 1 40 16 Iron (IID) 610 550 72.9 8-hydroxyquinoline in molten 360 91.0 Magnesium 380 Eriochrome black T Manganese carbamidate 0 1005 Mercury dithizone Molybdenum Chloranilic acid lic acid Nickel ium diethyl 35. Niobium Osmium -naphthylamine-4,6,8-trisulfonic 191005 0005503050 benzimidazole Palladium 2-nitroso-naphthol-(1) Phosphorus 366663636 Platinum Rhenium anic phase z-naphthol-(2) N.N-diphenyl thiourea Scandium Selenium 3,3 aine 2 henylenediamine nap Silicon as silico molybdenum blue 30.6 治0
32 Analytical Applications of UV-VIS Spectroscopy Table 5 (continued) Element ~eagent A in nm e 10- 3 Ref. lmol- I cm- I Iridium Pyridyl azonaphthol 550 10.3 36 Iron (II) 1,10-phenanthroline 512 11.1 36 Bathophenanthroline 533 22.4 36,40 2,2' -dipyridyl 522 8.7 36 Iron (III) Ferron (7-iodo-8-hydroxyquinoline- 610 5.7 36 5-sulfonic acid) Lanthanides Alizarin S (total determination) 530-550 36 Lead Dithizone 520 72.9 36,40 8-hydroxyquinoline in molten 360 91.0 47 naphthalene ICHCl3 Magnesium 8-hydroxyquinoline/n-butylarnine 380 5.6 36 Eriochrome black T 530 24.0 40 Manganese Formamidoxime 450 11.0 40 Diethyldithio carbamidate 500 4.0 36,40 Mercury Dithizone 485 68.0 36,40 Molybdenum 6,7 -dihydroxy-2,4-diphenyl 535 50.0 52 benzopyrilium chloride toluene-3,4-dithiol 670 23.0 40 Chloranilic acid 350 10.0 40 Quercetin 420 36.0 40 Thioglycolic acid 365 2.35 36 Nickel Dimethylglyoxime 450 16.0 36 Sodium diethyl dithiocarbamidate 325 35.0 40 Pyridylazonaphthol 560 61.0 53-55 Niobium 4-(pyridyl-2-azo)-resorcinol 550 38.0 40 Bromopyrogallol red 610 47.5 36 Osmium 1,5-diphenylcarbazide 560 140.0 40 1-naphthylarnine-4,6,8-trisulfonic 555 29.8 36 acid Mercapto-benzimidazole 550 10.5 36 Palladium 2,2'-furildioxime 380 22.5 36 2-nitroso-naphthol-(1) 370 22.3 36 Phosphorus as phosphorus molybdenum blue 725 16.3 36 (P03 -) as molybdato phosphoric acid 310 24.4 36 Platinum Dithizone 720 38.0 36 Rhenium 2,2'-furildioxime a) in aqueous phase 522 41.3 36,40 b) in organic phase 530 29.8 36 Rhodium 1-(pyridylazo )-naphthol-(2) 600 5.4 40 Ruthenium Nitroso-R salt 580 22.2 36 N,N'-diphenyl thiourea 650 0.23 40 Scandium Alizarin S 520 5.4 36,40 8-hydroxyquinoline 378 6.9 36 Selenium 3,3'-diarninobenzidine 420 9.9 36 a-phenylenediamine 355 17.8 36 2,3-diaminonaphthalene 377 23.8 36 Silicon as molybdato silicic acid 390 1.7 36 as silico molybdenum blue 691 or 36 730 Silver Dithizone 462 30.6 36,40 Strontium Arsenazo III 600 39
Photometric Determination of a Single Substance 33 Table5(continued) Element Reagent A in nm imol-cm Ref. Tantalum Pyrogallol 325 Tellurium 36 335 280 Thallium Brilliant green,see Table6 630 100.0 9 100.0 Thorium 545 10.2 ene Hematin Titanium N-De acid 3.5 l-bis-2-hydroxyani 9 00556056006656000 40 530 380 320 Vanadium N-benzoyl-N-phenylhydroxylamine boxydiphenyl- Yttrium chol violet -5-sulfo vlidenel-hydra- Zirconium 3 9,61 61 Arsenazo III 63 monomethylthionine [73].These ion associates with basic or acid dyes generally have very high extinction coefficients since several dye molecules can be r resent in the complex .On account of the demand for greater sen sitivit and the resulting ring of the detection limit into the nun rous in vestigatio ion spe ophotometry w have out in rec and 7 pro de umma h of the elements extracted in the form of ion associates with czenko [74]. basic or acid dyes
Photometric Determination of a Single Substance 33 Table 5 (continued) Element Reagent A. in nm e 10- 3 Ref. Imol- 1 cm- 1 Tantalum Pyrogallol 325 4.8 36 Tellurium Sodium diethyl dithiocarbamidate 430 3.7 36 Bismuth thiol 335 28.0 36 Thallium Brilliant green, see Table 6 630 100.0 40 Rhodamine 560 100.0 40 Dithizone 505 36 Thorium Thorin 545 10.2 36 Arsenazo 660 130.0 40 Tin Phenylfluorene 510 56.0 36,40 Pyridyl-3-fluorene 545 110.0 40 Hematin 590 76.0 36 Bromopyrogallol red 515 18.0 36 Titanium Pyrocatechol disulfonic acid 3,5 410 13.6 40 N-benzoyl-N-phenylhydroxylamine 380 6.7 36 Tungsten Dithi{)l 640 36 Uranium Glyoxal-bis-(2-hydroxyanil) 570 24.0 36,40 Pyridylazoresorcinol 530 38.7 36 1-(pyridyl-2-azo)-naphthol-2 560 20.0 40 2-(5-bromopyridyl-2-azo)-5-(di- 580 74.0 40 ethylamino )-phenol Vanadium N-benzoyl-N-phenylhydroxylamine 510 4.7 36,40 Pyridylazoresorcinol 550 36.0 36 Vanadox (2,2'-dicarboxydiphenyl- 610 23.0 40 amine) Yttrium Alizarin S 550 56 Pyrocatechol violet 665 25.9 57 Dicarboxy arsenazo III 645 79.6 58 Zinc Dithizone 538 95.0 36,40 Zincon[2-{ I a (2-hydroxy-5-sulfo- 625 24.0 40 phenylazo)-benzylidene I-hydrazinoJ-benzoic acid-monosodium salt] Zirconium Alizarin S 560 36 Pyrocatechol violet 650 32.6 59,61 Xylenol orange 535 12.8 40,61 600 75.0 62 Arsenazo III 665 120.0 63 monomethylthionine [73]. These ion associates with basic 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 sensitivity and the resulting lowering of the detection limit into the ppb region, numerous investigations of extraction spectrophotometry have been carried out in recent years. Thbles 6 and 7 provide a summary, compiled by Marczenko [74], of the elements extracted in the form of ion associates with basic or acid dyes
34 Analytical Applications of UV-VIS Spectroscopy Table6.Summary of selected extraction spectrophotometric methods of determination with basic dyes 7] Element Complex Dye Solvent Emax orptior Antimony odamine B R 0.89 Toluene/butanol 120x10 0.99 Bismuth Rhodamine B Boron BF ethane azole Chlorofor 67×10 6.20 Gallium Methylene blue /CH.Cl 7510 1.3 orobenzen Germanium 141×1031.94 ocatec Alizarin Rhodamine6G CCl/CHCl 290×1034.00 Gold Rhodamine B Benzene 97×100.49 AuCl hyl violet richloroethylene Indium 15100.92 Rhodamine B Benzene/diiso 110×1030.96 Mercury propylether 55×1030.27 Benzene/toluene 131×100.65 Phosphorus Hetero Malachite green Propylacetate 170×103 5.49 Crystal violet Propylacetate 270×1038.72 Rhenium 40×1030.21 Tantalum T en ene/toluene 91x1886 trichloroethylene Capri blue Tellurium Victoria blue 4R Benze e+nitro 18g×1889 Thallium Crystal violet Diisopropylether DE 114×1030.s6 trichloroethane Tin od ptanone ngsten 5x1887 Benzene+MIBK 103x103 0.43 Uranium Benzoic 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 be seen that,in some cases,very high extinction coefficients are actually ob- served which implies a high sensitivity of detection.For the evaluation of
34 Analytical Applications of UV-VIS Spectroscopy Table 6. Summary of selected extraction spectrophotometric methods of determination with basic dyes [74] Element Complex Dye Solvent s",ax Specific absorption a Antimony SbC~ Rhodamine B Benzene 97x 103 0.80 SbCl6 Brilliant green Toluene 103 x 103 0.85 SbC~ Butylrhodamine B Toluenelbutanol 120x 103 0.99 Bismuth Bil6 Rhodamine B Benzene 130 x 103 0.62 Boron BF4 Methylene blue Dichloroethane 65 x 103 6.01 BF4 Chromopyrazole II Chloroform 67x 103 6.20 Gallium GaCl4 Methylene blue Benzene/CzHzClz 75x 103 1.07 GaCl4 Rhodamine B o-dichlorobenzene 90x 103 1.29 Germanium Dinitro py- Brilliant green CCl4 141 x 103 1.94 rocatechol Alizarin Rhodamine 6 G CCI4/CHCI3 290 x 103 4.00 complexone Gold AuCl4 Rhodamine B Benzene 97x 103 0.49 AuCl4 Methyl violet Trichloroethylene 115x103 0.58 Indium InI4 Malachite green Benzene/hexane 106x 103 0.92 InBr4 Rhodamine B Benzene/ diiso 110x 103 0.96 propylether Mercury HgCl4 Crystal violet Toluene 55 x 103 0.27 HgCl4 Methyl green Benzene/toluene 131 x 103 0.65 Phosphorus Hetero- Malachite green Propylacetate 170x103 5.49 polys. Hetero- Crystal violet Propylacetate 270 x 103 8.72 polys. Rhenium Re04 Butylrhodamine B Benzene 40x 103 0.21 Re04 Nile blue Chlorobenzene + methanol Tantalum TaF6 Nitrochromopyrazole Benzene/toluene 83x 103 0.46 TaF6 Methylene blue Dichloroethane + 91 x 103 0.50 trichloroethylene TaF6 Capri blue Chloroform 107x 103 0.59 Tellurium TeBr6 Victoria blue 4R Benzene + nitro- 83 x 103 0.63 benzene Thallium TlCl4 Crystal violet Diisopropylether 102x 103 0.50 TlCl4 Brilliant green Diisopropylether 106x 103 0.52 TICl4 Methylene blue Dichloroethane + 114x 103 0.56 trichloroethane Tin SnC~ Crystal violet Heptanone 85x 103 0.72 Tungsten Dinitro py- Brilliant green Chloroform 132 x 103 0.72 rocatechol Benzene + MIBK 103 x 103 0.43 Uranium Benzoic acid Rhodamine B The solvents listed in Thbles 6 and 7 refer to the solvent used for extracting the ion associate. If the extinction coefficients of the ion associates in these tables are compared with the corresponding entries in Thble 5 it can be seen that, in some cases, very high extinction coefficients are actually observed which implies a high sensitivity of detection. For the evaluation of