Spectrophotometric Determination of Nickel and Cobalt: Methods and Reagents 9783111133119

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Ajay Kumar Goswami Spectrophotometric Determination of Nickel and Cobalt

Also of interest Spectrophotometric Determination of Copper and Iron. Reagents and Methods Ajay Kumar Goswami and Shilpa Agarwal,  ISBN ----, e-ISBN ----

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Ajay Kumar Goswami

Spectrophotometric Determination of Nickel and Cobalt Methods and Reagents

Authors Prof. Ajay Kumar Goswami 132, Road no 5, Subhash Nagar Udaipur 313001 Rajasthan India Email: [email protected]

ISBN 978-3-11-113311-9 e-ISBN (PDF) 978-3-11-113330-0 e-ISBN (EPUB) 978-3-11-113530-4 Library of Congress Control Number: 2023942144 Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the internet at http://dnb.dnb.de. © 2024 Walter de Gruyter GmbH, Berlin/Boston Cover image: Liliya Filakhtova/iStock/Getty Images Plus Typesetting: Integra Software Services Pvt. Ltd. Printing and binding: CPI books GmbH, Leck www.degruyter.com

Preface In continuation of my earlier books particularly determination methods for Copper and Iron the present book is next in this series. There are number of books on spectrophotometric methods but during my course of research and teaching I faced dearth of single source information on individual metals and to address this I am bringing this book for Nickel and Cobalt determination. I have tried to be as lucid and simple in presentation yet this is left to readers to make suggestions for still improving and removing deficiencies if at all.

https://doi.org/10.1515/9783111133300-202

Contents Preface

V

Introduction and basics of spectrophotometry

1

Chapter 1 Analytical reagents having N/O/S as donor atom and miscellaneous reagents 22 1.1 Dimethylglyoxime 22 1.2 2-(5-Bromo-2-pyridylazo)-5-dimethyl-aminoaniline (PADMA) 22 1.3 Triethylenetetramine 22 1.4 Tri isopropanolamine 23 1.5 Dimethylglyoxime using flotation 23 1.6 Dimethyloxime 23 1.7 4-(4-Chlorobenzene diazo)-amino-4ʹ-chloroazobenzene (CDACAB) 24 1.8 4-(5-Chloro-2-pyridyl)-azo-1,3-diaminobenzene (5-Cl-PADB) 24 1.9 Ammonium per sulfate dimethylglyoxime 24 1.10 Dimercaptophenols 25 1.11 2,2ʹ,4,4ʹ-Tetrahydroxybenzophenone (BP-2) 25 1.12 2,6-Dimethyl-morpholime dithiocarbamate (DM MDTC) 25 1.13 5-Methyl-2-acetylfuran-4-methyl-3-thiosemicarbazone (5-MAFMT) 25 1.14 2-(5-Bromo-2-oxoindolin-3-ylidene) hydrazine carbothioamide 26 1.15 bis-Thiosemicarbazone 26 1.16 Miscellaneous reagents 26 1.16.1 Murexide 26 1.16.2 MEDTA 26 1.16.3 Organic detector ferrozin 27 27 1.16.4 Methylene blue and H2O2 1.16.5 m-Acetylchlorophophanazo 27 1.16.6 Arsenazo-III 27 1.16.7 Chlorophosphanazo-III (CPA-III) 28 1.16.8 Auzarin Red S (ARS) 28 1.16.9 Eriochrome black T 28 1.16.10 Cefixime 28 1.16.11 Cyanidin 29 1.16.12 Arsenazo-III 29 1.16.13 p-Aminophenol on Amberlite–XAD 29 1.16.14 MESNA 30 References 30

VIII

Contents

Chapter 2 Analytical reagents having nitrogen and oxygen as donors 32 2.1 Imidazole derivative 32 2.2 [N-(O-hydroxybenzylidene) pyridine-2-amine] (NOHBPA) 32 2.3 N,Nʹ-bis(4-methoxysalicylidene) ethylenediamine 32 2.4 α-Furildioxime 33 2.5 4-(2-Pyridylazo)-resorcinol 33 2.6 1-(4-Methylphenyl)-3-(2-(trifluoromethyl) phenyl) triaz-1-ene-1-oxide 33 2.7 1-(2-Pyridylazo)-2-naphthol (PAN) 33 2.8 2-Hydroxy-1-naphthaldehyde thiosemicarbazone (HNT) 34 2.9 Para aminophenol (PAP) 34 2.10 [N-(O-methoxybenzaldehyde)-2-aminophenol] (NOMBAP) 34 2.11 3-Hydroxy-3m-tolyl-1-p-methoxyphenyltriazene 34 2.12 Schiff base 35 2.13 Nʹ-(2-hydroxybenzylidene)-3-(4-O-tolylpiperazin-1-yl) propanehydrazine (HTP) 35 2.14 Tween-80-PAN 35 2.15 Antipyrine azo orcinol (APAO) 36 2.16 5-Nitrosalicylaldehyde semicarbazone (NSS) 36 2.17 5-Bromo-2-hydroxy-3methoxybenzaldehyde-4 -hydroxybenzoichydrazone (5-BHMBHBH) 36 2.18 Antipyriyl azo-1-nitroso-2-naphthol 36 2.19 1-Nitroso-2-naphthol 37 2.20 2,4-Dimethoxybenzaldehyde iso nicotinoylhydrazone (DMBIH) 37 2.21 Salicylaldehyde isonicotinoyl-hydrazone (SAINH) 37 2.22 Schiff base 2-[(2-hydroxyphenylimino) methyl]-4-nitrophenol (HPIMNP) 37 2.23 Isocinchomeronic acid 38 2.24 3-(1-Benzhydrylazetidin-3-yl) 5-isopropyl 2-amino-1, 4-dihydro -6-methyl-4-(4-nitrophenyl) pyridine-3, 5-dicarboxylate 38 2.25 N,Nʹ bis (O-hydroxyacetophenone) ethylene diimine derivatives (HAPED) 38 2.26 Dimethylglyoxime 39 2.27 5-Bromo-2-hydroxyl-3-ethoxybenzaldehyde-4-hydroxy benzoichydrazone (5-BHMBHBH) 39 2.28 α-Oximino acetoacetanilide benzolyhydrazone (HINABH) 39 2.29 Antipyriyl azo-2,7-naphthalene-diol (1-APANDOL) 40 2.30 Pyridine-2, 3-dicarboxylic acid 40 2.31 2ʹ-Hydroxy-4ʹ-butoxychalconeoxime (HB CO) 40 2.32 Anthrone phenylhydrazone (APH) 40 2.33 Triazene-1-oxide derivatives 41

Contents

2.34 2.35 2.36 2.37 2.38 2.39 2.40 2.41 2.42 2.43 2.44

5-(4ʹ-Chlorophenylazo-6-hydroxypyridine-2,4-dione (CPAHPD) 41 o-Chlorophenylazo-bis-acetoxime 41 2-Hydroxy-1-naphthalenecarboxaldehyde phenylhydrazone 42 4-(2-Pyridylazo) resorcinol (PAR) 42 42 2-[2-(6-Chlorobenzothiazolyl] azo-resorcinol (6-CIBTAR = LH2) 2,2-Furildioxime 42 p-Chloro phenylazo-bis-acetoxime (p-CPABA) 43 Furildioxime in micellar solution 43 2,4-Dihydroxy-5-bromo butyro phenone oxime (DHBBO) 43 Diacetyl monoxime isonicotinoylhydrazone 43 Hydrazine carboxamide-2-(2-hydroxy-1-naphthalenyl) methylene] (HCHNM) 44 References 44

Chapter 3 Analytical reagents having N, S, O as donor atoms 47 3.1 NʹNʹ (1E, 1ʹʹE)-(propane-1,3-diylbis (sulfanediyl) bis(1-4-bromophenyl) ethan-2-yl-1-yilidene)) bis(2-hydroxybenzohydrazide) (BAPSSHZ) 47 3.2 4-Hydroxy-3-thiolbenzoic acid and diphenyl guanidine 47 3.3 3-Phenyl-2,4-thiazolidenedione 47 3.4 5-Bromo salicyledene-2-amino thiophenol 48 3.5 2-Amino-3-phenolazo-1-(4-sulfophenyl)-3-methyl-5-pyrozolone 48 3.6 Dithiophenols and diphenylguanidine 48 3.7 1-[(5-Benzyl-1,3-thiazol-2-yl) diazenyl] naphthalene-2-ol 48 3.8 1-2ʹ,4ʹ-Dinitroaminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2 -thiol (2ʹ,4ʹ-dinitro APTPT) 49 3.9 2-(Benzothiazolylazo) orcinol (BTAO) 49 3.10 5-(2-Benzothiazolyazo)-8-hydroxyquinolene (BTAHQ) 49 3.11 1-(2-Hydroxyphenyl) thiourea (HPTU) 50 3.12 2,6-Diacetylpyridine bis(4-phenyl-3-thiosemicarbazone) (2,6-DAPBPTSC) 50 3.13 3,4-Dihydroxy-5-methoxy benzaldehyde thiosemicarbazone (DHMBTSC) 50 3.14 Cinnamaldehyde thiasemicarbazone (CMTSC) 50 3.15 3-Hydroxy-3n-propyl-1-(4-sulphonamidophenyl) triazene 51 3.16 4-Hydroxybenzaldehyde thiosemi-carbazone (HBTS) 51 3.17 2,4-Dihydroxybenzaldehyde thiosemicarbazone (DHBATSC) 51 3.18 3-Hydroxy-3-isopropyl-1-(4-sulphonamidophenyl) triazene 51 3.19 2-Acetylpyridine thiosemicarbazone/semicarbazone (APT)/APS 52 3.20 2-Acetylpyridine-4-Methyl-3-thiosemicarbazone (APMT) 52

IX

X

3.21 3.22 3.23

Contents

p-Chloroacetophenon-4-(2ʹ-carboxy-5ʹ-sulphophenyl)-3 -thiosemicarbazone (p-CACST) 52 5-Bromosalicylaldehyde thiosemicarbazone (5-BSAT) 53 6-(Anthracen-2-yl)-2,3-dihydro-1,2,4-triazine-3-thione (ADTT) References 53

53

Chapter 4 Analytical reagents having N, O or S as donor atoms and miscellaneous reagents 56 4.1 2-(5-Cyano-2-pyridylazo)-2,4-diaminotoluene (5-CN-PADT) 56 4.1.1 Triethylenetetramine 56 4.1.2 Monotetrazolium 56 4.1.3 5-Chloro-2-(pyridyl)-1,3-diaminobenzene 57 4.1.4 5-Bromo-2-hydroxy-3-methoxy benzaldehyde-4 hydroxy benzoic hydrazone (5-BHMBHBH) 57 4.1.5 5-(5-Iodo-2-pyridylazo)-2,4-diaminotoluene (5-1-PADT) 57 4.1.6 4-(5-Chloro-2-pyridylazo)-1,3-phenylenediamine (5-Cl-PADAB) 57 4.1.7 Salicyl fluorone 58 4.2 Miscellaneous reagents 58 4.2.1 Wright stain 58 4.2.2 Murexide 58 4.2.3 Crown ether (DB-18-C6) 58 4.2.4 Orange G and m-cresol purple 59 4.2.5 Methylene blue (MB) 59 4.2.6 Esomeprazole 59 4.2.7 Nitroso-R-salt 60 4.2.8 Brilliant green 60 4.2.9 Chelating resin 60 4.2.10 Salen 60 4.2.11 Methylene blue 61 4.2.12 Nitroso-R-salt 61 4.2.13 Carmine 61 4.2.14 Alizarin Red-S 61 4.2.15 Picramazochrom 62 4.2.16 Phenosafranine and potassium periodate 62 4.2.17 Ninhydrin 62 4.2.18 Quercetin 62 4.2.19 Hydrophobic AZO dye 63 References 63

XI

Contents

Chapter 5 Analytical reagents having N–O as donor atoms 65 5.1 2-(5-Bromo-2-pyridylazo)-5-dimethyl-aminophenol (5-Br-PADAP) 5.2 N,Nʹ-bis(salicylidine)-ethylenediamine (salen) 65 5.3 1-(2-Pyridylazo)-2-naphthol 65 5.4 4-Nitro-o-phenylenediamine-salicylaldehyde 66 5.5 (1,5-Dimethyl-2-phenyl-4-[(2,3,4-trihydroxyphenyl) diazenyl) -1H-pyrazol-3 (2H)-one) (DPTPD) 66 5.6 2-{[(2-Mercurychlorid) 4-methyl phenylimino] methyl} phenol (K) 5.7 1-(2-Pyndylazo)-2-naphthol 66 5.8 2-Hydroxy-3-methoxybenzaldehydeisonicotinoyl hydrazone (HMBAINH) 67 5.9 Iodonitrotetrazolium chloride 67 5.10 2-(5-Bromo-2-pyridylazo)-5 [N-n-propyl-N-(3-sulfopropyl) amino] aniline 67 5.11 4-(Nitrophenyl azo imidazole) NPAI 67 5.12 1-(2-Pyridylazo)-2-naphthol 68 5.13 [2-(4-Methoxyphenyl) azo (4,5-diphenylimidazole)] (MPAI) 68 5.14 4-(2-Pyridylazo)-resorcinol 68 5.15 2-Aminoacetyle-3-hydroxy-2-naphthoic hydrazone 68 5.16 1-(2-Pyridylazo)-2-naphthol 69 5.17 3-[4-(Dimethylamino) cinnamoyl]-4-hydroxy-6-methyl-2H-pyran -2-one 69 5.18 2-(5-Nitro-4-methyl-2-pyridyl-azo)-5-dimethylaniline 69 5.19 1-Nitroso-2-naphthol in aq. sodium dodecyl sulfate (NNPh) 70 5.20 Res-acetophenolene guanylhydrazine (RAG) 70 5.21 2-Carboxy-5, methyl-3-nitrobenzaldoxime 70 5.22 Anthrone phenylhydrazone (APH) 70 5.23 4-[{(4-n-(3-O X O-1,2-Oxazolldin-4-yl) carboxymidoyl phenyl} methylidene) amino] 1-2-oxazolidin-3-one (OOCPMAO) 71 5.24 Nicotinohydroxamic acid (NHA) 71 5.25 2-Hydroxy-1-naphthalenecarboxaldehyde phenylhydrazone 71 5.26 Pyridylazoresorcinol 71 5.27 2-Hydroxy-4-butoxy-5-bromoacetophenone oxime (HBA) 72 5.28 1,2-Propanedime, 1-phenyl-1-(2-hydroxyl-5-bromo-benzidineazine) -2-oxime [PDPHBBAO] 72 5.29 2,4-Dihydroxy-5-bromo [2-methyl] propiophenone oxime [DHBMPO] 72 5.30 Hydrazine carboxamide-2-[(2-hydroxy-1-naphthalenyl) methylene] 5.31 2-Hydroxy-1-naphthaldehyde-p-hydroxy benzoichydrazone [HNAHBH] 73 References 73

65

66

72

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Contents

Chapter 6 Analytical reagents having N/S/O as donor atoms 76 6.1 6-Hexyl-4-(2-thiazolylazo) resorcinol (HTAR, HZL) 76 6.2 5-(4-Hydroxy benzylidine)-2,4-thiazolidindion 76 L-Cysteine 76 6.3 6.4 2,6-Dithiophenols in the presence of aminophenols 76 6.5 [4-Hydroxy-3] (2-hydroxyphenyl) methane [amino benzene sulphonica acid] (HPHMAB) 77 6.6 5-(2-Hydroxybenzylidene)-2,4-thiozolidindion 77 6.7 Ammonium pyrollidine dithiocarbamate 77 6.8 3-Phenyl-2,4-thiazolidinedione (Ph TAD) 77 6.9 Thiocyanate-cetyltrimethylammonium bromide 78 6.10 5-Bromosalicylaldehyde thiosemicarbazone (5-BSAT) 78 6.11 2,6-Dithiol-4-ethylphenol and phenanthroline (DTEP) 78 6.12 2,6-Dithiophenols in the presence of hydrophobic amines 79 6.13 3-(4-N-pyridine-2-yl benzene sulfonamide azo)-1-nitroso napthol 79 6.14 Dithiophenols and diphenylguanidine 79 6.15 5-Methylfuran-2-carbaxaldehyde thiosemicarbazone (5-MFAT) 79 6.16 2-(5-Bromo-2-oxoindolin-3-ylidene) hydrazinecarbothioamide (HBITSC) 80 6.17 (Nʹ,NʹʹE,Nʹ,NʹʹE)-Nʹ,Nʹʹ-(2,2ʹ (propane-1,3-diylbis(sulfanediyl) bis 1-(4-chlorophenyl) ethan-2-yl-l-ylidene) bis(z-hydroxybenzohydrazide) (CAPSH) 80 6.18 2-Hydroxy-3-methoxy benzaldehyde thiosemicarbazone (HMBATSC) 80 6.19 5-(2-Benzothiazolylazo)-8-hydroxyquinolene (BTAHQ) 81 6.20 3,4-Dihydroxy-5-methoxy benzaldehyde thiosemicarbazone (DHMBTSC) 81 6.21 2-Acetylfuran-4-methyl-3-thiosemicarbazone 2-AFMT 81 6.22 2,4-Dihydroxy benzaldehyde thiosemicarbazone (DHBATSC) 81 6.23 1-(2-Thiazolylazo)-2-naphthol (TAN) 82 6.24 Isatin-3-thiosemicarbazone (HITSC) 82 6.25 2,6-Pyridinedicarboxaldehyde thiosemicarbazone (PDTSC) 82 6.26 5-Nitro salicylaldehyde thiosemicarbazone (NSTS) 82 6.27 Mercapto acetic acid 83 6.28 (E)-N1-((1-Thiophen-2-yl) ethylidene) benzene-1,2-diamine 83 References 83

Contents

Chapter 7 Simultaneous spectrophotometric determination of Ni and cobalt 86 7.1 2,6-Dimethyl morpholine dithiocarbamate (DMMDTC) 86 7.2 5-(2ʹ-Carboxyphenyl) azo 8-hydroxyquinoline 86 7.3 2,6-Dimethyl-morpholinedithiocarbamate-K salt (DMMDTC) 87 7.4 1-(2-Pyridylazo) 2-naphthol 87 7.5 3-Hydroxy-5-(hydroxymethyl)-2-methyl-4-pyridine carboxyaldehyde -4-phenyl-3-thiosemicarbazone 87 7.6 Solid phase extraction and partial least squares approach 88 7.7 (2Z, 2ʹZ)-2,2ʹ-((4S, 5R)-4,5,6-trihydroxy hexane-1,2-diylidene bis (N-phenyl hydrazine carbothioamide) 88 7.8 1-(2-Pyridylazo)-2-naphthol in Triton X-100 88 7.9 Alizarin Red S 88 7.10 1-Nitroso-2-naphthol 89 7.11 Sodium diethyldithiocarbamate (Na-DDTC) 89 7.12 4-(5-Br-2-Pyridylazo)-1,3-diaminobenzene (5-Br-PADAB) 89 7.13 Ammonium purpurate (murexide) 90 7.14 Alizarin Red S 90 7.15 Diethanoldithiocarbamate (DEDC) 90 7.16 1-(2-Thiazolylazo)-2-naphthol 90 7.17 2-Aminocyclopentene-1-dithiocarboxylate 91 7.18 Partial least square method 91 7.19 Diphenylcarbazone 91 7.20 2-Hydroxy-3-methoxy benzaldehydethiosemicarbazone (HMBATSC) 91 7.21 1-(2-Pyrdylazo)-2-naphthol 92 7.22 2-Hydroxy-3-methoxy benzaldehydethiosemicarbazone (HMBATSC) 92 7.23 1-(2-Pyridylazo)-2-naphthol 92 7.24 1-(2-Pyridylazo)-2-naphthol 93 7.25 2-Amino-cyclopentene-1-dithio carboxylic acid (ACDA) 93 7.26 Nitroso-R-salt 93 7.27 1-(2-Pyridylazo)-2-naphthol (PAN) 93 7.28 2-(5-Bromo-2-pyridylazo)-5-dimethylaminophenol (5-Br-PADAP) 94 7.29 2-Carboxy-2ʹ-hydroxy-5ʹ-sulfo-formazyl benzene (Zincon) 94 7.30 2-Aminocyclo-1-pentene dithiocarboxylic acid (ACDA) 94 References 95 Index

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XIII

Introduction and basics of spectrophotometry Nickel, symbol Ni and atomic number 28, is a silvery or silvery-white metal having a golden tinge. It is a hard ductile metal showing significant reactivity in powdered form, but slow to react in larger pieces. Use of nickel as nickel-iron alloy goes back as 3,500 BCE, and it was first isolated and recognized as an element in 1751 by Alex Frendrik Cronstedt. An important source of nickel is the iron ore limonite having 1–2% nickel. Pen Handite and Garnierite are other ores. The major production sites of nickel are Sudbury region, Canada, New Caledonia in Pacific and Norilisk, Russia. Cobalt on the other hand is a chemical element found in the earth’s crust in chemically combined form. The element having atomic number 27 is a hard, lustrous silvergray metal produced by reductive smelting. It is primarily used in lithium-ion batteries, magnetic high strength alloys, glass, ceramics and varnishes.

Spectrophotometry: a versatile tool for transition metal determination Simple explanation of color in chemical compounds is that the compound absorbs, transmits or reflects light over an electromagnetic spectrum in visible region or wavelengths when light passes through any solution, for example, a part of it is absorbed. Spectrophotometry is a standard, economic method to measure light absorption or the concentration of the chemical in a solution. The technique is used in various fields like chemistry, biochemistry, physics, biology, metallurgy, alloys, metal-complex study or even pharmaceuticals. The instrument used is a photometer and spectrometer combined in one called spectrophotometer. Ultraviolet and visible spectroscopies show electronic transitions in molecules or atoms, which is measured using a spectrophotometer. Mostly compounds that absorb light in visible region are colored and those which absorb in UV region are colorless. Absorbance (A) and transmittance (T) are measured by spectrophotometer. The intensity of light (Io) is measure of photons per second. Reference is the blank samples without chemical compound (Analyte). Reference is containing everything that is included in a cuvette, except the analyte for which absorbance is being measured. Beer-Lambert law is the relationship between amount of light absorbed by the substance and its concentration. The mathematical equation can be represented as A = εCL where A is the absorbance of light of a specific wavelength, ε the molar extinction coefficient, C the molar concentration of the sample and L the the length of optical path of sample.

https://doi.org/10.1515/9783111133300-001

2

Introduction and basics of spectrophotometry

When a beam of light of intensity (Io) passes through solution a part or fraction of photons is absorbed and the existing beam has a lower intensity (I). The Lambert’s Law applies when x is the thickness of the solution and α is called absorption coefficient. The I/Io is known or defined as transmittance, and it is reverse of absorbance A = log10

Io I

The absorbance is a function of wavelength or frequency, and its variation gives, what is termed as absorption spectra. The combination of these two laws, the Beer’s law and the Lambert’ law form: A = ε. X. C. where X is the length of cuvette: log10

Io = εXC I

where ε is the molar absorptivity or extinction coefficient, X is the length of path and C the concentration of solution in mol cm−3. Normally UV and visible spectrophotometry use 10–390 nm for UV and 390–790 nm for the visible region as the wavelength. This wonderful law is the basic of any spectrophotometric determination.

Fundamental terms used in the book Since analytical chemistry is the fundamental branch of modern chemistry, analysis of constituent cannot be ignored. This has led to the development of numerous approaches and methods respective to the nature of sample. The branch has advantages and disadvantages which have been rectified in the journey of century. In 1894 Wilhelm Ostwald wrote “Analytical chemistry is art of recognizing different substances and determination of components of the system, what is present and how much is present.” We can understand that development of medical and health sciences or related branches like bio-chemistry and pharmaceutical chemistry to name a few could not have been possible sans analytical chemistry. Spectrophotometry is one of the most useful and applicable method for the trace determination of metals both micro or macro by quantitative measurement. The method was developed by T. S. West using UV-vis region of electromagnetic spectrum. It is used in clinical laboratories, industries, environmental laboratories and pharmaceutical industries as many substances can be selectively converted to colored products. The sensitivity of the method can reach pico gram level (10−12) which is comparable to the best available methods. As described above the determination is based on direct relation between color

Method

3

and electronic structure of the compound. The absorption of UV-vis light by such substance in question causes an electronic transition in molecule containing one or more chromophores. In general quantitative application of the method is based on the concept that the number of photons absorbed is directly proportional to the concentration of substance under investigation. A general outline of simple method and related terms has been described in brief to make user conversant with them while using the methods of the book.

Method Choice of wavelength The analysis importantly involves the selection of suitable wavelength of absorbance in a region where the molar absorptivity (ε) changes quickly with the wavelength. Since there is small inaccuracy in this region, the change in wavelength scale will result in big change in the apparent molar absorptivity. Thus, it is important to select a wavelength where absorbance is maximum and constant with small change in wavelength of a colored solution. It can be λmax or working wavelength.

Color development Any solution appears colored when it emits or absorbs a range of the radiation in the visible region. There is a close relation between the color of solution and the molecular structure of the constituents. So, the concentration can be measured by determining the extent of absorption of light at the appropriate wavelength of absorption of colored solution. In the spectrophotometric determination of transition metals, it is found that formation of metal complex is not always instantaneous in each case. However, it may take some time for developing maximum color instantly.

Deviation from Beer’s law Basic law which governs spectrophotometric determination is Beer’s law. It is expressed as a plot of absorbance against concentration and a straight line passing through origin is obtained. It covers a wide range of concentrations in the dissolved state. The presence of some small number of colorless electrolytes, not reacting chemically with the colored constituents, normally does not affect absorption. However, the presence of large amounts of such electrolytes may cause a shift of maximum absorption, possibly changing value of molar extinction coefficient. When the colored substances ionize, dissociate or associate in solution, the Beer’s law is not followed. Further, deviation is also observed when mono-

4

Introduction and basics of spectrophotometry

chromatic light is not used. So to say Beer’s law is the basis of quantitative application of UV-vis spectrophotometry.

Sensitivity of spectrophotometric method The sensitivity of spectrophotometric method is described in terms of molar absorptivity (ε, L/mol/cm) of the metal-ligand complex. It is important in the determination since it decides the suitability of the method for trace determination. It is expressed as ε=

A C.1

The sensitivity depends on the band width of monochromatic light radiation. A general criterion for describing sensitivity is Low sensitivity ε < 2 × 104 ðL= mol= cmÞ Moderate sensitivity ε = 2 − 6 × 104 ðL= mol= cmÞ High sensitivity ε > 6 × 104 ðL= mol= cmÞ Sensitivity is also described as specific absorptivity or Sandell’s sensitivity. It is mass of analyte per unit volume of the solution. Sandell’s sensitivity is concentration of the analyte (in µg/mL), which gives an absorbance of 0.001 in a cell path of length of 1 cm and is described as µg/cm2.

Interfering species or diverse ions Any method is more applicable when there is no interference of diverse ions or similar ions. The tolerance limits of interfering ions are established at those particular concentrations, where there is not more than ±2-0% of change in absorbance during determination of analyte in question.

Precision and accuracy Precision of any measurement is defined as reproducibility of the set of retrieved experimental data. Whereas accuracy denotes how close a given set of measurements are to their true value. There are three major factors which control accuracy and precision: instrumental errors, chemical variables and operator’s skills. Further concentration of analyte can also affect spectrophotometric measurement.

Analytical reagents

5

Stoichiometry of the complex The empirical formula of a complex can be determined from spectrophotometric data. Commonly used methods used for this are mole ratio method: Job’s method of continuous variation, Slope ratio method and Turner Anderson’s method.

Stability constant of complex Stability of the metal complex formed decides the selectivity of the spectrophotometric method. To understand the behavior of metal chelate in solution stability constants play an important role. The stabilities of any chelate are dependent on factors like size of the chelate ring, basic strength of chelating molecule and nature of donor atom.

The standard addition method An ideal calibration standard should approximate composition of the analyte in question with respect to both the concentration of analyte as well as other species in the sample so as to minimize the effects of various components in the absorbance measurement.

Analytical reagents An analytical reagent or even reagent is a substance or compound added to a system to cause a chemical reaction. These two terms are often used and are interchangeable. They are frequently used as color indicators in analytical chemistry. Common examples are dimethylglyoxime, Fehling’s solution, and α-nitroso β-naphthol. Turning to coordination chemistry and spectrophotometric reagents, both give a vast area in terms of method development as well as reagents. The branch called co-ordination chemistry has grown leaps and bounds during the last 50 years and has thus brought out significant development in the areas of medicinal chemistry, drug designing, pharmaceutics and even excellent synthetic routes and catalysts to name a few. The branches such as bioinorganic chemistry and metal-organic chemistry have found new dimensions to make human life safe and healthy. Earlier, the thrust of spectrophotometric determination was simply to analyze the metal complexes, stability and sensitivity or selectivity for particular reagent of late entire pharmacokinetics based on these parameters deeply help to understand the basic mechanism of action of a metal-based drugs. Thus, the aspect of spectrophotometry doing characterization task has fundamentally turned as a helping hand to drug design, catalyst synthesis and even kinetics of medicinally impor-

6

Introduction and basics of spectrophotometry

tant metal complexes. The spine of all these methods and aspects are analytical reagents. They play a key role in the determination of any important metal on the basis of chelating site of a reagent. There is literally a race for new reagents which are not only selective, sensitive yet future of important chemical sensors or biologically useful. The present introduction of such useful methods is an attempt to justify serious contribution offered by these reagents in the field of analysis. Old school classification of reagents used in inorganic analysis was broadly based on the donor atoms and included: 1. Reagents with oxygen as donor atom. 2. Reagents with N– as donor atom. 3. Reagents with S– as donor atom. 4. Reagents with N–O donors. 5. Reagents with N–S donors. 6. Reagents with N–S–O as donor atoms. 7. Miscellaneous reagents which may have combinations other than or including some A the above donor atoms. The present book will use these ligand or reagents based on donor sites to make reader more focused and to select easy to use methods of his choice. The chapters in each section, A as well as B and C, have been written on the basis of reagents used in the method as per above classification. At the end of this chapter, to facilitate the reader, lists of reagents for both nickel and cobalt have been compiled. Some useful parameters like λmax, pH, molar absorptivity Sandell’s sensitivity, medium of a reaction and detection limit of each method are also tabulated to give the monograph, a do it yourself (DIY) manual approach. The monograph is addressed to solve one source information problem for any analyst interested in nickel and cobalt determination using spectrophotometry. Not to mention, others who use spectrophotometric parameters for designing molecules particularly analytical reagents with biological significance would also be equally benefited. The monograph is a condensed information manual written on the basis of methods published during the last 10 years and is mostly being used by scientists and researchers in the field of pharmacy, chemistry, industry, medicinal chemists or even environmental monitoring agencies. Thus, the comprehensive monograph attempts to address all areas associated with the analysis of nickel and cobalt, two most important metals of transition–metal series. A list of different reagents used for spectrophotometric determination of nickel (Table 1) and cobalt (Table 2) is appended along with details of method for convenience of reader. However, table has some reagents repeated because of different method or conditions and this has increased number of reagents in the respectively list. The methods have been collected for the last 10 years (2013–2023) and are then the recent ones.

Table 1: List of spectrophotometric reagents for Ni determination. S. no. Analytical reagent name/structure

Absorptivity maximum (λmax)

Molar absorptivity (L/mol/cm)

Sandell’s sensitivity (ml/g/cm)

pH solvent

.

Azo dyes: (a) –ʹ-phenyl-ʹ-pyrazolyl azo) Schaffer acid (b) -(ʹ-phenyl-ʹ-pyrazolyl azo) resorcinol

 

. × −

.

– Universal buffer

.

Isonicotinic acid hydrazide and L-histidine

.

Diacetylglyoxime

.

-(-Carboxymethylphenyl-azo]-, -diphenylimidazole (-CMe PADI)

.

-(-Bromo--pyridylazo--dimethylaminoaniline



. × 

.

[N-(O-Hydroxy benzylidene) pyridine--amine] (NOHBPA)



.

N,Nʹ-Bis (-methoxysalicylidene) ethylenediamine



.

Triethylene tetramine and sodium dodecyl sulfate

.

-(-Pyridylazo)-resorcinol

.

α-Furildoxime

– µg/L

.

-(-Methylphenyl)--(-trifluoromethyl) phenyl) triaz--ene--oxide

. × − M

.

Nʹʹ Nʹʹʹʹ-((E, ʹʹE)-(Propane---diylbis (sulfanedyl)) bis  (-(-bromophenyl) ethan--yl--ylidene)) bis (-hydroxybenzohydrazide)

. × 

.

Michler’s thioketone

. × 

–. HACNaAC .–. A

,

. mg/ 



. µg/L

Analytical reagents

. µg/cm

–

. . (continued)

7

8

Table 1 (continued) S. no. Analytical reagent name/structure

Absorptivity maximum (λmax)

.

Dimethylglyoxime



.

N- benzylaminopurine

.

Murexide

.

-(-Pyridylazo)--haphthol (PAN)

.

-Thiobarbituric acid

.

-Hydroxy--naphlthaldehyde thiosemicarbazone

.

Chelating-azo-hydroxyl functionalized polystyrene

.

Dimercaptophenols and hydrophobic amines

–

.

-((-Bromophenyl) imino) methyl--((,-dimethyl pyridine--yl) diazenyl) phenol



.

Para-aminophenol (PAP)



.

[N-O-Methoxybenzaldehyde)--aminophenol] (NOMBAP)



,

. µg/cm

.–.

.

,ʹ,,ʹ-Tetrahydroxy benzophenone



. × 

. mg/L (dL)

.

.

Naphthol green-B



. × 

-Hydroxy--thiol-benzoic acid (HTBA) and diphenylguanidine

pH solvent

HCl: HNO : HO (::)



,



. × 

()

Sandell’s sensitivity (ml/g/cm)

. ×  µg  cm



– ng/cm

.–.

. mg/L (dL)



. × 

– −

. × 

µg/cm



.–.

Introduction and basics of spectrophotometry

.

Molar absorptivity (L/mol/cm)

.

-Hydroxy--m-tolyl--p-methoxyphenyltriazene



, d m/ mol/cm

.–.

.

-Phenyl-,-thiazolidinedione



. × 

.–.

–

.

CN ion

.

,-Methylenedioxy naphthaldehyde (naphtho [,-d] dioxole-carbaldehyde

.

α-Furildioxime

.

-Bromo salicylidene--aminothiophenol

.

Methyl-ethylene-diamine tetracetic acid (MEDTA)

.

-Amino--phenol azo -(-sulfophenyl)--methyl--pyrozolone (-(-((-hydroxy--nitrophenyl) diazenyl)--methyl--oxo--, -dihydro-H-pyrazol-l-yl) benzenesulfonic acid (-ANASP)

.

Dithiophenols and diphenylguanidine

.

DMG using cation exchanger Nʹ-(-hydroxybenzylidene)--(-O-tolylpiperazin--yl) propanehydrazide (HTP)

.

-p-Chloro thiocarbamido phenol -Propyl-(N-orthotoludine) quinazoline thiosemicarbazone

.

,-Dimethyl-morpholine dithiocarbamate (DMM DTC) + Triton X-

.

Triazine bearing & Pyrazolone group

.

DMG using triethylamine as extracting agent

.

. µg/cm

,

.

  

. × 

.

 

.–. ×  .–. µg/cm

.–. .–





. × 



. µg/cm



 µg/L



, µg/mL

. Analytical reagents

.



9

(continued)

10

Table 1 (continued) Absorptivity maximum (λmax)

Molar absorptivity (L/mol/cm)

Sandell’s sensitivity (ml/g/cm)

.



. × 

–





.

-(-Pyridylazo)--PAN-Tween- -[(-Benzyl-, -thiazol--yl) diazenyl] naphthalene--ol

. × 

pH solvent

. µg/L

.

. × − µg/cm

.

. µg/ mL

.



.

-[(-Antipyralaz)] orcinol (APAO)



. × 

.

-Methyl--acetylfuran--methyl--thiosemicarbazone(-MAFMIT)



. × 

.

Dithiocarbamate

.

Chrome azurol -hydrogenperoxide



.

-Nitrosalicylaldehyde Semicarbazone



. ×  

–. 

.

-(ʹ-ʹ-dinitro aminophenyl)-, , -trimethyl-, -dihydropyrimidine-thiol



. × 

. µg/cm

.

.

-(-Bromo--oxoindolin--ylidene) hydrazine carbothiomide



,

. ng/cm

.–.

.

-(Benzothiazolylazo) orcinol



. ng/mL

.

.

Methylene blue oxidized by HO



.

Benzenesulfonate, , ʹ-[-(-pyridinyl)-, , -triazine-, -diyl] bishydrogen sodium salt (::)



.

Acid Red  (AR ) + sodium dodecyl sulfate

.

-Bromo--hydroxy--methoxybenzaldehyde- hydroxybenzoic hydrazone (-BHMBHBH)

–

. × − µg/mL (DL) . . . µg/L



. ± . × 

 .

Introduction and basics of spectrophotometry

S. no. Analytical reagent name/structure

.

-(-Benzothiazolyl azo)--hydroxyquinolene [BTAHQ]

.

Antipyriyl azo--nitroso--naphthol (APAN)

.

Bis-thiosemicarbazone ligand

.

-Nitroso--naphthol

.

Methylene blue + HO

.

Salicylaldehyde isonicotinoylhydrazone (SAINH)

.

,-Dimethoxybenzaldehyde isonicotinoylhydrazone (DMBIH)

.

Schiff base -[(-hydroxyphenylimino) methyl] -nitrophenol [HPIMNP]

.

-(-Hydroxyphenyl) thiourea

 

. ng/L

.



. × 

 µg/L .



. × 



. × 







. ng/cm . µg/ mL

.

. µg/cm

. .

. × 



.

. µg/cm

.–.

.– ng/mL (DL) 

. × 

. × − µg/cm . µg/mL (DL)

.

.

,-Diacetyl pyridine bis (-phenyl--thiosemicarbazone)



.

Tri isopropanolamine



.

Pyridine ,  dicarboxylic acid

.

-(-Benzhydryl azetidin--yl) -CH Me -amino-, -dihydro--methyl --(-nitrophenyl) pyridine-, -dicarboxylate in phosphate buffer

.

-(-Hydroxy--nitro--methylphenyl-isoxazole (LI) -(-Hydroxyl--Me phenyl)--ph-isox azoline (L) and -phenyl--(hydroxyl--bromo--Me phenyl) -H-Pyrazole

.

,-Dihydroxy--methoxy benzaldehyde thiosemicarbazone in presence of Triton X-



. × 

. µg/ cm

–

.

Cinnamaldehyde thiosemicarbazone



. × 

. µg/cm

.

. ×  

. × 

.–. . µg/cm

.

Analytical reagents

.–.

(continued)

11

12

Table 1 (continued) Absorptivity maximum (λmax)

Molar absorptivity (L/mol/cm)

.



. × 

m-Acetylchloro phosphanazo

pH solvent

. 

,.

. µg/cm

.



. × 

. mg/cm

.–.

Arsenazo-III

 

. × 

. µg/mL (dL)

α-Oximinoaceto acetanilide benzoyl hydrazone (HINABH)



.

N,Nʹ Bis (O-hydroxyacetaphenone) ethylene diamine



.

Dimethylglyoxime

. ng/mL (dL)

.

-[-Hydroxy-phenylimino-ethyl]--methyl-pyrane-, -dion



.

-Bromo--hydroxyl--ethoxybenzaldehyde--hydroxy benzoic hydrazone

. . .

Sandell’s sensitivity (ml/g/cm)

Chlorophosphonazo-III

.–. 



. ×  

.

Antipyriyl azo-, –naphthalenediol



. × 

.

-Hydroxy--n-propyl--(-sulfonamido phenyl) triazene



,

. µg/mL

.

. ng/cm

.–.



.–.

.

Pyridine-,-dicarboxylic acid



. × 

.

-Hydroxybenzaldehyde thiosemicarbazone



. × 

.

ʹ-Hydroxy-ʹ-butoxy Chalcone oxime

.–.

.

,n-Dihydroxy benzaldehyde thiosemicarbazone

.

. µg/cm

–

Introduction and basics of spectrophotometry

S. no. Analytical reagent name/structure

.

-Hydroxy--isopropyl--(-sulfonamido phenyl) triazene



, dm/ mol/cm

. ng/cm

.–.

.

-Acetyl pyridinethiosemi carbazone/ Semicarbazone

 

. ×  . × 

. . µg/cm

Acidic and basic medium

.

Alizarin Red S (ARS)

. 



.

Ahthrone phenyl hydrazone (APH)

. 

. × 

. µg/cm



.

-Acetylpyridine--methyl--thiosemicarbazone



. × 

. µg/cm

.

.

Triazene--oxide derivative as optical sensor

. × − M (dL)

.

.

Eriochrome Black T. -(-hydroxy--naphthylazo)--nitro-naphthalene--sulfonate

.

Dimethylglyoxime



p-Chloroacetophenone--(ʹ-carboxy-ʹ-sulphophenyl-thiosemicarbazone



.

DMG, Picramin-epsilon, -quinolinazo-epsilon



.

-(ʹ-Chlorophenylazo--hydroxypyrimidine-, -dione

 



-Hydroxy--naphthalene-carboxaldehydrazone

.

DMG



.

p-Chlorobenzaldehyde--(ʹ-carboxy-ʹ-sulphophenyl)-thiosemicarbazone



. × 



.–. . µg/m

. × 

. ng/cm

, . × 

.–.



.

. ng/cm 

. × 

.



. µg/cm

.–.

Analytical reagents

o-Chlorophenylazo-bis-acetoxime

. –

.

.

. × 

(continued)

13

14

Table 1 (continued) Absorptivity maximum (λmax)

.

-(-Pyridylazo) resorcinol (PAR)

 

.

Cefixime

. .

Molar absorptivity (L/mol/cm)

Sandell’s sensitivity (ml/g/cm)



. × 

. µg/cm

-Bromosalicylaldehyde thiosemicarbazone



. × 

Cyanidin (-.  ,-pentahydroxy flavilium chloride)

.

. 

.

-(-Chlorobenzene diazo)-amino-ʹ-chloroazobenzene (CDACAB)



. × 

.

-[-(-Chlorobenzothiazolyl) azo] resorcinol



. × 

.

-(-Chloro--pyridyl)-azo-, -diaminobenzene



.

Arsenazo-III



.

-(Anthracen--yl)-, -dihydro-, , -trazine--thione

.

p-Amino phenol (PAP) on Amberlite XAD-

.

-(-Pyridylazo)-resorcinol

.

, -Furildioxime

.

p-Chlorophenylazo-bis-acetoxime (p-CPABA)

.

Furildioxime in micellar solution

.

Ammonium persulfate dimethylglyoxime

pH solvent

. .

.



. mol/L HCl

. × 

. Basic medium



–

–

Basic medium .

. µg/L  

– 

,

. ng/cm 

. × 



.–.

. ng/cm

.

. mg/g

NaOH

Introduction and basics of spectrophotometry

S. no. Analytical reagent name/structure

.

, -dihydroxy--bromobutyrophenone oxime (DHBBO)

.–.

.

Diacetyl monoxime isonicotinoyl hydrazone

Sodium acetate –acetic buffer

.

MESNA



.

Hydrazine carboxamide--[(-hydroxy--naphthalenyl) methylene]



.

Alzarin Red S + Triton X–



.

Cefixime



. ×  . × 

. × 

. 



. µg/cm

.

. µg/mL

Analytical reagents

15

16

Table 2: List of reagents for cobalt determination. λmax

Molar absorptivity

Sandell’s sensitivity/ determination/limit

pH solvent

.



. × 

.– ng/mL

.



-Hexyl--(-thiazylazo) resorcinol

.

-(-Cyano--pyridyl-azo)-, -diamino tolune (-CN-PADT)

 

. × 

.

N,Nʹ-bis (Salicylidene)-ethylenediamine (Salen)



. × 





.

-(-Hydroxy benzylidene)-,-thiazolidenedione

.

Wright stain

.

-(-Pyridylazo)--naphthol

.

-Nitro-o-phenylenediamine salicylaldehyde

.

Triethylenetetramine



. mol/L HSO . ng/cm

HSO

. × 

.–.



. × 

Weak acid . µg/L

. × 

. mg/L (DL)



 Alkaline Medium





.

,-Dimethyl--phenyl--((, , -trihydroxy phenyl) diazenyl)-H-pyrazole- ( H) one (DPTPD)



. × 

. µg/cm

.

.

-{[(-Mercurychlorid, -methylphenylimino] methyl} phenol



. L/mol/cm

. µg/cm

.



. × 



,

.

L-Cysteine

.

Murexide

.

,-Dithiophenols

.

Crown ether (DB--C)

.

.

-(-Pyridylazo)--naphthol



hydrochloride



.–. . × 

– . mg/L (DL)

Introduction and basics of spectrophotometry

S. no. Name of reagent

.

-Hydroxy- (-hydroxy phenyl) methane [amino benzene sulfonic acid (HPHMAB) 

. × 

.

-(-Hydroxybenzyledene)-,-thiazolidenedione



. × 

.

Ammonium pyrolidinedithio carbamate + sodium dodecyl sulfate (surfactant)

.

. × 

. ng/cm

.

-Phenyl-, -thiazolidinedioxe



. × 

. ng/cm

. mg/L (DL)

. .–.

−

.

Orange G and m-Cresol purple and (HO)

–

. × 

.

-Aminopyridine



,.

. µg/cm

.

Thiocyanate-cetyltrimethylammonium bromide



. × 

. µg/cm



–.

µg/mL (DL)

. µg/cm

. 

.

-Hydroxy--methoxy-benzaldehydeisonicotinoylhydrazone (HMBAINH)



. × 

.

-Bromosalicylaldehyde thiosemicarbazone (. BSAT)

 

. × 

.

Catalytic decolorization of methylene blue



. × 

. µg/L (DL)

.

Iodonitrotetrazolium chloride + SCN



. × 

. × − mg/cm 

.

-(-Bromo--pyridylazo)--[N-n-propyl-N-(-sulfopropyl) amino] aniline



.

-(-N-Pyridine--yl benzne sulfonamide azo)--nitroso naphthol



.

Dithiolphenol

– .–. ×  .–. ng/cm

.

-Methylfuran--carbaxaldehyde thiosemicarbazone



.

-(-Methoxyphenyl) azo (,-diphenyl imidazole (MPAI)



. × 

. µm (DL)

.

. × 

.–

. × − µg/cm

. × 



. µg/mL (DL)

. × 



. µg/cm

.–. .

Analytical reagents





– .–.

,-Dithiol--eithylphenol and phenanthroline

-(Nitrophenylazoimidazole)

.–. .

.

.

NH NHCl

. (continued)

17

18

Table 2 (continued) λmax

Molar absorptivity

Sandell’s sensitivity/ determination/limit

.

-(-Bromo--oxoindolin--ylidene) hydrazine carbothiomide and bromoisatinthiosemiemicarbazone



,.

. ng/cm

.

Nʹ,Nʹʹʹ, E Nʹ,Nʹʹʹ, E-Nʹ,Nʹʹʹ-(,ʹ-(Propane , -dylbis (sulfanediyl) bis (-chlorophenyl) ethan--yl –-ylidine) bis (-hydroxybenzohydrazide)



. × 

. µg/cm

.

-Bromo--hydroxy--methoxybenzaldehyde- hydroxybenzoichydrazene

 

. ×  ± . . ± . × 

.

-(-Pyridylazo)-resorcinol



. × 

.

-(-Iodo--pyridyl azo)-, -diaminotolune (-I-PADAT)



. × 

.

Polymethacrylate based sensor with immobilized -(-pyridylazo)--naphthol



.

-Aminoacetyl--hydroxy--naphthoic hydrazone



.

Esomeprazole



.

Nitroso-R-salt



.

-(-Pyridylazo)--naphthol

.

.

Ethambutol

  

.

-Hydroxy--methoxy benzaldehyde thiosemicarbazone (HMBATSC)



. .

.– buffer . mg/L



. × 



. × 

pH solvent

. µg/cm

. 

. µg/cm

. 

. .–.

. × 

. ng/cm

.

Introduction and basics of spectrophotometry

S. no. Name of reagent

.

-[-(Dimethyl amino) cinnamoyl] -hydroxy--methyl-H-Pyran-one + dimethylindocarbocyanin dye



.

-(-Nitro--methyl--pyridylazo)--dimethylaniline



. .–. 

. µg/L (DL)

.

Brilliant Green



. × 

.

-Nitroso--naphthol

.

. × 

.

Res-acetaphenone guanylhydrazone (RAG)

 

. ×  . × 

.

-(-Benzothiazolylazo)--hydroxyquinoline



. ×  

.

,-Dihydroxy--methoxy benzaldehyde thiosenicarbazone (Triton X-)



.

Chelating resin



.

SALEN + Triton X-



.

-Carboxy-, methyl--nitrobenzaldoxime



.

Methylene blue + HO



.

Nitroso R-salt



-Acetylfuran--methyl--thiosemicarbazone (-AFMT)



.

--Dihydroxy benzaldehyde thiosemicarbazone (DHBATSC)



.

Anthrone phenyl-hydrazone

.

-[({-[n-(-Oxo-, -oxazolidon--yl) carboximidoyl] phenyl} methylidene) amino]-  , -oxazolidon--one (OOCPMAO)

.

Isatin--thiosemicarbozone (HITSC)

.

Nicotinoyhydroxamic acid

.

 

. . ng/mL (DL) . mg/cm

. × 

. 

. .



,

. . × − g/L (DL) . µg/mL (DL) 

−

. × 

. × 

µg/cm



. .–. .

. × 





. µg/cm

. × 

. × − µg/cm

,.

. ng/cm 

. × 



.–. 

. µg/cm /. A

Analytical reagents

.

. ng/cm

.

19

(continued)

20

Table 2 (continued) λmax

.



Indigo-caramine

Molar absorptivity

pH solvent Basic Medium



. µg/cm

.

,-Pyridinedicarboxaldehyde thiosemicarbazone



. × 

.

-Hydroxy--naphthalene carboxaldehyde phenylhydrazone



. × 

.

-Nitrosalicylaldehyde thiosemicarbazone

.

-(-Pyridylazo) resorcinol

 

.

-hydroxy--butoxy--bromoacetophenone oxime





.

Mercaptoacetic acid



. × 



Na (CHCOO) acetic acid buffer

. µg/cm

. . .

. µg/cm .

.

,-Propanedione, -phenyl- (-hydroxy--bromo-benzilidine azine)--oxime [PDPHBBAO]



. × 

.

,-Dihydroxy--bromo [ʹ-methyl] propiophenone oxime



. × 

.

Sandell’s sensitivity/ determination/limit



. × 

Carmine



.

Alizarin Red S + Triton X-



. × 

.

Picramazochrom



. × 

.

Phenosafranine + Pot. Periodate

.

Ninhydrin



−

. × 

µg/cm

.

. µg/cm

.

. ng/mL (DL)

Alkaline

. µg/cm



. 

. × − g/mL 



. .

Introduction and basics of spectrophotometry

S. no. Name of reagent

.

(E)-N-(-Thiophen--yl (ethylidene) benzene-, -diamine



.

Hydrazine carboxamide--[(-hydroxy--naphthalenyl) methylene]

.

Quercetin



.

Alizarin Red S + Triton X–



.

-Hydroxy--naphthaldehyde-p-hydroxybenzoic hydrazone



 µg/l (DL) . × 

. µg/cm

 .

. × 

. 

. × 

. ng/mL

.

Hydrophobic Azo Dye -hexyl--(-thiazolylazo) resorcinol



.

Tiron + HO (catalytic effect of Co (II)



. µg/L (DL)

.

Salicyl fluorone



 µg/L

.

Ninhydrin



.

-Hydroxy--naphthaldehyde--hydroxy benzoic hydrazone



. × 

. µg/L

.

.

Analytical reagents

21

Chapter 1 Analytical reagents having N/O/S as donor atom and miscellaneous reagents 1.1 Dimethylglyoxime Biao et al. [1] have proposed a determination method for nickel using dimethylglyoxime in industrial electroplating waste water. The authors have used diacetylglyoxime for spectrophotometric determination successfully for waste water containing 1.0–15.0% nickel. The relative standard deviation reported for the method is 0.15–0.72% (RSD, n = 11) whereas recovery for standard addition is almost 105.17% to 93.53%. It is reported that it is comparable to EDTA complex titrimetric method and consistent with the proposed method. It has good reproducibility with accuracy and precision meeting other analytical requirements.

1.2 2-(5-Bromo-2-pyridylazo)-5-dimethyl-aminoaniline (PADMA) Huo et al. [2] have developed spectrophotometric method for trace determination of nickel using sodium dodecyl sulfate (SDS) as a surfactant and 5-Br-PADMA as a chromogenic agent at 5.0–6.5 and HAc-NaAc as buffer medium. It is reported that the mentioned reagent forms a stable orange complex with Ni (11) having maximum absorption of 574 nm. The reported molar absorption coefficient is 4.52 × 105 L (mol−1 cm−1). The method is reported to be fairly selective and is recommended for trace determination of nickel in samples of ores.

1.3 Triethylenetetramine Hoseinian et al. [3] have proposed a method for separation and spectrophotometric determination of Ni using triethylenetetramine (Trien) and sodium dodecylsulfate as an anionic surfactant via ion flotation. The report mentions the interaction of Trien at various pH and trien concentration. It is reported that at pH 9.7 a trien/Ni (II) with mole ratio of 2 and SDS/Ni (II) with mole ratio of 2 are most suitable conditions. Floatation results for nickel-zinc–SDS–trien solution exhibit higher nickel removal than zinc, which is said to be done to reverse order of removal in order of increasing crystal size lonic radius. It is further mentioned that at pH 9, removal of nickel ions reaches at 88.4.

https://doi.org/10.1515/9783111133300-002

1.6 Dimethyloxime

23

1.4 Tri isopropanolamine Guo [4] proposed a rapid spectrophotometric method for nickel determination in nickel-copper-plating bath. It is described that nickel reacts with the reagent to give a stable orange-yellow complex under strong alkaline pH condition. The reported maximum absorbance of this complex is 430 nm. Although the total absorbance of copper nickel alloy is reported at 680 nm, from which as per concentration of nickel, the absorbance is arrived by subtraction. A deviation of 1.0% is reported for nickel by the author. It is mentioned that the reported method is rapid, simple and superior compared to other available methods.

1.5 Dimethylglyoxime using flotation Hashemi-Moghaddam [5] has proposed a separation and preconcentration-based floatation method using dimethylglyoxime. The method uses floatation of nickel complex with dimethylglyoxime at the water-hexane interface. The quantitative floatation is done at pH 9–12, and after dissolving in 5 mL of 1 M HNO3, nickel can be spectrophotometrically determined. It is mentioned that method is simple and free from interference of all cations and anions with a wide linear range. Further the method is applied to a trace determination of nickel in well water and waste water of coating plants. The author mentions that accuracy of this method has been investigated with reference material alloys (NIST 864) as well as by spiking the samples with different quantities of Ni (II).

1.6 Dimethyloxime A method for the determination of nickel content in laterite nickel ore has been reported by Li et al. [6] with dimethyloxime spectrophotometry. It has been reported that nickel contents in laterite nickel ore can be determined by digesting it in acid and subsequently by dimethyloxime spectrophotometry. A sample is dissolved in HClHNO3-HF-mixed acids and further per chloric acid fumes are used to smoke. It has been described that in NaOH medium ammonium per sulfate is used as an oxidant. A red wine complex is formed with dimethyloxime which can be measured at 460 nm. The method was applied for the determination of nickel in nine different samples of laterite nickel ore and led to successful determination of nickel. The RSD reported is 1.10–3.78% with a recovery of 98.5–101.5%. The consistency of the method and the results has been compared with AAS, ICP-AES and sodium peroxide fusion DMG spectrophotometry as reported.

24

Chapter 1 Analytical reagents having N/O/S as donor atom and miscellaneous reagents

1.7 4-(4-Chlorobenzene diazo)-amino-4ʹ-chloroazobenzene (CDACAB) Wang et al. [7] have reported synthesis and spectrophotometric application of a new coloring agent CDACAB for the determination of nickel (ii). The method mentions that Ni (ii) forms in Na2 B4O7–NaOH buffer (pH 10.0) a stable red complex, in the presence of Triton X-100. The maximum absorbance at 583 nm is reported for determination and the apparent molar absorptivity ε1 = 1.58 × 105 L/mol/cm is reported in the Beer’s law range of 0–0.7 µg/mL. The reagent can be used for micro quantities of Ni in aluminum alloys. Consistency with certified values is also reported, with standard deviation of 1.6–2.5%.

1.8 4-(5-Chloro-2-pyridyl)-azo-1,3-diaminobenzene (5-Cl-PADB) Luo et al. [8] have proposed a spectrophotometric method for the determination of Ni (ii) in electroplating waste water using reaction with (5-Cl-PADB) as a reagent. In 2.0 mol/L HCl medium, the reagent reacts to give a stable complex with Ni (ii) in a mole ration of 2:1. The maximum absorbance at 565 nm is reported and 6.42 × 104 L/ mol cm of molar absorptivity is achieved. The reported Beer’s law concentration range is 0–1.0 mg/L of Ni (ii) with standard deviation of 98.5–101.8%. The results are comparable to catalytic spectrophotometric method as reported.

1.9 Ammonium per sulfate dimethylglyoxime Chu et al. [9] have reported a spectrophotometric method for the determination of Ni content in nickel laterite ores. The procedure described involves dissolving the sample in mixed acids of HCl, HNO3, HF and HClO4 in appropriate proportions. After complete dissolution the salt is again dissolved in 50% HNO3. Then Ni2+ is oxidized to Ni4+ using ammonium per sulfate in a NaOH medium. This Ni4+ reacts with dimethylglyoxime to give a red-wine complex which is measured using spectrophotometry. The reported Beer’s law range is 0–2.0 µg/mL with detection limit of 0.1 mg/g. The interference by other ions present in laterite ore is eliminated using potassium sodium tartarate and relative standard deviation reported are 0.75–1.69% with recovery for Ni as 95.4–102.7%. It is recommended as stable and reliable method for accurate and rapid determination of Ni in Ni laterite ores.

1.13 5-Methyl-2-acetylfuran-4-methyl-3-thiosemicarbazone (5-MAFMT)

25

1.10 Dimercaptophenols Kuliev et al. [10] have proposed a spectrophotometric determination method for heavy metals in soils using mercaptophenols as reagent. A method using dimercaptophenols (2,6-dimercaptophenol (DMP), 2,6-dimercapto-4-methylphenol (DMMP), 2,6dimercapto-4-ethylphenol (DMEP), 2,6-dimercapto-4-propylphenol (DMPP) and 2,6dimercapto-4-tertbutylphenol (DMBP) and hydrophobic amines is proposed. The reported optimum pH range is 3.0–8.1 and absorbance is 464–63 nm for Cu, Hg, V, Mn, Fe, Co and Ni. The method is reported to be successfully used for Ni determination in different soils in the detection range between 27 and 43 ng/cm3. Various soil samples like sod–podzoic sandy, sandy-loamy, sod–podzoic loamy, clayey, gray forest, black soils, chestnut and river soils are successfully used for determination as reported.

1.11 2,2ʹ,4,4ʹ-Tetrahydroxybenzophenone (BP-2) Liu et al. [11] have developed a trace determination method for Ni using above reagent and spectrophotometry. It is described that the reagent BP-2 reacts with Ni2+ in buffer solution of H3BO3–KCl–NaOH of pH 9.8 at 60 °C to yield a complex. The complex absorbs at 434 nm in the concentration range of 0.20–23.0 mg/L. The molar absorptivity reported is 2.025 × 104 L/mol/cm and detection limit of 0.17 mg/L. A RSD (n = 6) is 1.1% and recovery rates by standard addition method are 99.3–103% compared to AAs the relative error is 0.98% as mentioned.

1.12 2,6-Dimethyl-morpholime dithiocarbamate (DM MDTC) Topuz et al. [12] have reported preconcentration-based spectrophotometric determination of trace nickel using solid phase extraction with XAD-4N,Nʹ-bis-(salicylidene)cyclohexane diamine (XAD-4-SCHD) resin and ligand DMMDTC as complexing agent. The absorbance reported for Ni is 328 nm and detection limit of 7 µg/L is reported for Ni (ii). The method is comparable to ICPE-mass spectrometry.

1.13 5-Methyl-2-acetylfuran-4-methyl-3-thiosemicarbazone (5-MAFMT) Weldeabzgi et al. [13] have reported a method for spectrophotometric determination of Nickel (ii) in soil and standard alloy samples using 5-MAFMT as a reagent. It is described that at pH 9.5, the mentioned reagent forms a yellow-colored complex which is stable for 5 h. The absorbance for measurement is at 361 nm and the molar absorptivity is 1.2 × 103 µg/cm2. The detection limit is 0.0713 µg/mL with RSD of ≤1.0%. The

26

Chapter 1 Analytical reagents having N/O/S as donor atom and miscellaneous reagents

method is recommended to be rapid, simple, sensitive and without interference of usually associated ions with nickel. In alloy samples too, it is a suitable method with 98% recovery.

1.14 2-(5-Bromo-2-oxoindolin-3-ylidene) hydrazine carbothioamide Madan et al. [14] have reported an extraction method for spectrophotometric determination of nickel. It is mentioned that 2,(5-bromo-oxoindolin-3-ylidenehydrazine carbothioamide), [5-bromoisation thiosemicarbazone (HBITSC)] extracts nickel into n-amyl alcohol from aqueous solution at pH 7.2–8.8. This amyl alcoholic extract exhibits an intense peak at 510 nm (λmax). The Beer’s law concentration range reported is 1.06–6.0 µg/ mL. The molar extinction coefficient ε = 4,412 L/mol/cm, whereas Sandell’s sensitivity value is 13.3 ng/cm2. The complex is formed in 1:2 [Ni: HBITSC] ratio. The method could be successfully applied for the determination of Ni (ii) in alloy samples as reported.

1.15 bis-Thiosemicarbazone Rohani Moghadam et al. [15] have used a newly synthesized ligand (2z,2ʹz)-2,2ʹ-((4S, 5R)-4,5,6-trihydroxyhexane-1,2-diylidene) bis (N-phenylhydrazinecarbothioamide) for simultaneous determination of Cu2+, Ni2+, Co2+ and Fe3+ using chemometric method. Ni2+ is reported to form a 1:2 complex and a detection limit 4 µg/L is mentioned. The method has been successfully applied to simultaneous determination of elements in some food-stuffs.

1.16 Miscellaneous reagents 1.16.1 Murexide Elsherif et al. [16] have proposed spectrophotometric determination of nickel and cobalt using murexide as chelating agent. The nickel complex absorbs at 460 nm in 2.1 ratio. The formation constant reported for nickel complex is 1.21 × 1011. Molar absorptivity for the complex is 13,284 L/mol/cm as reported.

1.16.2 MEDTA Fernandez-Feal et al. [17] have published a simultaneous spectrophotometric determination method for Pb (11), Cu (11) and Ni (11) using methyl-ethylene-diamine tetracetic

1.16 Miscellaneous reagents

27

acid (MEDTA) as chelating agent. Ni (II) complex shows two peaks at 250 and 380 nm. In the samples containing three elements spectrum shows two peaks at 260 due to super position of the individual peaks of the cations, and at 250, 256 and 272 nm at 380 nm, characteristic of nickel. A normal or zero crossing method has been applied for each determination. It is recommended as a method for simultaneous determination.

1.16.3 Organic detector ferrozin Naser [18] has reported a new method for the determination of nickel using organic detector ferrozine. The nickel has been determined using azo reagent benzene sulforate, 4,4ʹ-[3-2-pyndinyl]-1,2,4-triazine-5-6-diyl] bis hyorogen sodium salt at λmax 562 nm. The optimum pH for determination is 7 ± 0.1, and mole ratio is 1:2 for the complex.

1.16.4 Methylene blue and H2O2 Hu [19] has proposed a spectrophotometric method for trace nickel in aluminum alloys using decoloration of methylene blue by oxidation with H2O2. It is mentioned that in Na3C6H5O7–NaOH buffer solution of pH 5.6, trace nickel has catalytic effect on decoloration of methylene blue by oxidation with H2O2. The content of nickel is linear to the degree of decoloration of methylene blue, which establishes a spectrophotometric determination method for trace determination of nickel in aluminum alloy. The detection limit 0.0118 µg/mL has been reported. The results of trace content of nickel are consistent with the certified values.

1.16.5 m-Acetylchlorophophanazo Zhau [20] has proposed a method for the determination of nickel (ii) using color reaction of nickel with m-acetylchlorophosphanazo. It is described that in pH 6.8 triacid, NaOH buffer medium nickel (11) and the reagent form a 1:3 blue complex. The triacid is composed of phosphoric acid, acetic acid and boric acid. It is described that the complex absorbs at 610 nm in the concentration range of 0.1–4.0 µg/mL where it can be determined. The molar extinction coefficient ε1 = 1.13 × 104 L/mol/cm is also reported and it is mentioned that method has been applied to nickel determination in Kelp.

1.16.6 Arsenazo-III Geng et al. [21] have reported the determination of nickel in tea using arsenazo-III as chelating agent. It is mentioned that arsenazo-III complexes with nickel and the com-

28

Chapter 1 Analytical reagents having N/O/S as donor atom and miscellaneous reagents

plex absorbs at 610 nm. The Beer’s law concentration range reported is 0.2–4.0 µg/mL. The extinction coefficient of the method is 1.76 × 104 L/mol/cm with detection limit of 0.093 µg/mL. The recovery of method is between 99.7 and 100.1% and it is successfully applied to determination of nickel in tea.

1.16.7 Chlorophosphanazo-III (CPA-III) Li et al. [22] have developed a method of spectrophotometric determination of nickel using CPA (III) as chelating agent. A successful determination of Ni (ii) determination in water samples uses pH 5.5 acetic acid–sodium acetate buffer and the complex (a blue colored) absorbs at 620 nm. The Beer’s law concentration range is 0.1–3.5 µg/mL, with molar absorptivity as 1.40 × 104 L/mol/cm with detection limit of 0.075 µg/mL.

1.16.8 Auzarin Red S (ARS) Rohilla et al. [23] have proposed a simultaneous determination method for zinc and nickel in micellar media using spectrophotometry with Alizarin Red S (ARS) as a chelating agent. The H-point standard addition method (HPSAM) has been used for simultaneous determination of Zn (11) and Ni (11) at trace levels. It is described that Ni (ii) forms a red complex with ARS at pH 7.0 which is soluble in Tinton X-100. A Beer’s law concentration range of 0.293–4.676 µg/mL is good for precise determination.

1.16.9 Eriochrome black T Siqinagaowa et al. [24] have reported a method for the determination of trace amount of nickel in drinks using Eriochrome black T as a chromogenic reagent. It is described that in a H2B4O7–KCl–NaOH buffer solution with pH 10.0 a complex of Ni and Erichrome black T is formed which is stable and has a λmax of 533 nm. Nickel can be determined in Beer’s law range within 1.2 mg/L. The reported molar absorptivity is 5.19 × 104 L/mol/cm. It is further mentioned that in drink samples the result of Ni content is consistent with AAs results.

1.16.10 Cefixime Azmi et al. [25] have reported method for the determination of nickel in synthetic mixture and water samples using cefixime as a complexing reagent. The reaction of cefixime with nickel yields a complex which has λmax = 332 nm. The Beer’s law concentration range reported is 0.447–4.019 µg/mL and has a molar absorptivity for the com-

1.16 Miscellaneous reagents

29

plex as 7.314 × 103 L/mol/cm. The reported Sandell’s sensitivity of 0.008 µg/cm2/0.001 absorbance limits is also mentioned. The application of the method has been validated as per International Conference on Harmonisation guideline. Further the results have been compared with those of AAS.

1.16.11 Cyanidin Okoye et al. [26] have developed and proposed the use of cyanidin (3, 31, 41, 5, 7 – pentahydroxyflavylium chloride) extracted from Hibiscus sabdariffa L. as a chromogenic reagent for simultaneous spectrophotometric determination of Pb, Hg, Cd, As and Ni in mixed aqueous mixture. The method describes complexation of Ni in the range 200–700 nm, in particular, at 401.0 nm, at pH 5. The Beer’s law range is 0.1–5.0 ppm as reported. The authors recommended this method as a simple, rapid, sensitive ecofriendly as well as economic method for simultaneous determination of trace heavy metals in particular for environmental and biological samples.

1.16.12 Arsenazo-III Liu et al. [27] report the determination of Ni (ii) in calcium magnesium phosphate by product ferrophosphorous using arsenazo-III as a chelating agent in HAC-NaAC buffer of pH 6.2. The reaction of Ni (ii) with the ligand yields a 1:3 blue complex which obeys Beer’s law in the concentration range of 0–1 µg/mL. The mentioned Ni arsenazo-III complex has a λmax at 620 nm. Thus, the method describes determination of Ni in NiP-Fe by product.

1.16.13 p-Aminophenol on Amberlite–XAD Yamini et al. [28] report a method for spectrophotometric determination of Ni (ii) using PAP as a chelating agent. It is said to be a sensitive, fairly selective spectrophotometric method by the authors. The ligand PAP reacts with Ni (ii) in basic medium to yield a blue complex having maximum absorbance at 445 nm. The complex is stable for several days. Amberlite-XAD-16, a polystylene divinyl–benzene resin, was synthesized and used for preconcentration of Ni (ii) in natural water and food. Method is suitable for the determination of Ni in various samples.

30

Chapter 1 Analytical reagents having N/O/S as donor atom and miscellaneous reagents

1.16.14 MESNA Lutfullah et al. [29] have reported the use of MESNA for determination of Ni (ii). It is mentioned that the method is sensitive as well as simple one for determination of trace amounts of Ni2+ MESNA (sodium 2-mercaptoethane sulfonate) is a detoxifying medicine for preventing hemorrhagic cystitis in patients having chemotherapy with high-dose cyclophosphamide or ifosfamide. The ligand at pH 8.2 forms a complex with Ni2+ absorbing at 410 nm (λmax). A 1.16–23.2 µg/mL of Beer’s law concentration range is suitable for determination and the ε = 8.23 × 103 L/mol/cm is reported. The method is successfully used for Ni (ii) determination in water samples as reported.

References [1]

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[14] Madan, P. U.; Barhate Vasant, D. Extractive spectrophotometric determination of nickel (11) using 2-(5-bromo-2-oxoindolin-3-ylidine) hydrazine carbothiomide as an analytical reagent. International Journal of Pharmaceutical Research Scholars. 2016, 5(1), 1–3. [15] Moghadam, M. R.; Jahromi, S. M. P.; Darehkordi, A. Simultaneous spectrophotometric determination of copper, cobalt, nickel and iron in food stuffs and vegetables with a new bis-thiosemi carbazone ligand using chemometric approaches. Food Chemistry. 2016, 192, 424–431. [16] Elsherif, K. M.; Nabbra, F. M.; Ewlad-Ahmad, A. M.; Huda Elkebbir, N. E. Spectrophotometric complex formation study of murexide with nickel and cobalt in aqueous solution. To Chemistry Journal. 2020, 5, 40–47. [17] Fernadez-Feal, M. C.; Castro-Romeo, J. M.; Fernandez-Solis, J. M. Simultaneous determination of Pb (11), Cu (11) and Ni (11) with MEDTA by ultraviolet and visible derivative spectrophotometry. Chemical Science International Journal. 2018, 22(4), CSIJ. 40983/1–CSIJ. 40983/8. DOI: 10.9734/CSJI/2018/ 40983. [18] Nasser, H. N. A new method for determination of Nickel ion (ii) using organic detector. Ferrozine Elixir International Journal. 2015, 88, 36270–36274. [19] Hu, X.-M.; Peng, Q.-L. Catalytic spectrophotometric method for determination of trace nickel in aluminum alloy based on decoloration of methylene blue by oxidation with hydrogen peroxide. Yejin Fenxi. 2014, 34(18), 54–57. [20] Zhai, Q.-Z. Color reaction of m-acetylchlorophosphonazo and nickel (ii). Journal of Chemical and Pharmaceutical Research. 2014, 6(3), 1195–1198. [21] Geng, A.-F.; Zhai, Q.-Z. Determination a nickel in tea with alsenazo-III by spectrophotometry. Journal of Chemical and Pharmaceutical Research. 2014, 6(1), 521–523. [22] Li, X.-D.; Zhai, Q.-Z. Spectrophotometric determination of nickel with chlorophosphanazo-III. Chemical Science Transactions. 2014, 3(3), 1023–1026. [23] Rohilla, R.; Gupta, U. H point standard addition method for simultaneous determination of zinc and nickel in micellar media. Chemical Science Transactions. 2012, 1(3), 582–589. [24] Gaowa, S.; Wang, L.-H.; Wang, N.; Chen, M.-Q.; Chen, G. Spectrophotometric determination of trace amount of nickel in drinks with eriochrome black T as chromogenic reagent. Lihua Jianyan, Huaxue Fence. 2013, 46(6), 735–737. [25] Azmi, S. N. H.; Bashir, I.; Khanbashi, R. S.; Hamhami, N. H.; Rahman, N. Utility of cefixime as a complexing reagent for the determination of Ni (ii) in synthetic mixture and water samples. Environmental Monitoring and Assessment. 2013, 185(6), 4647–4657. [26] Okoye, C. O. B.; Chukwuneke, A. M.; Ekere, N. R.; Ihedioha, J. N. Simultaneous ultraviolet-visible (UVVis) spectrophotometric quantitative determination of Pb, Hg, Cd, As and Ni ions in ions in aqueous solution using cyanides as a chromogenic reagent. International and Journal of Physical Sciences. 2013, 8(3), 98–102. [27] Liu, K.; Chen, B. Determination of Ni in calcium magnesium phosphate byproduct ferrophosphorous. Guangdong Huagong. 2012, 39(2), 189–153. [28] Yamini, P.; Kumar, K. V.; Kishore, R.; Govinda, K. V.; Venkateswarlu, P. Spectrophotometric method for the determination of nickel (ii) using PAP on Amberlite-XAD-16 in water and food samples. Analytical Chemistry an Indian Journal. 2012, 11(9), 305–310. [29] Khan, F.; Rahman, N.; Azmi, S. N. H. Utilization of MESNA as a complexing reagent and determination of Ni (ii) by spectroscopic methods. Advanced Science Letters. 2012, 10, 66–71.

Chapter 2 Analytical reagents having nitrogen and oxygen as donors 2.1 Imidazole derivative Taresh et al. [1] have used 2-[4- carboxymethyl-phenylazo]-4,5-diphenylimidazole (4CMe PADI) as a chromogenic reagent for the determination of nickel in water samples. The method includes adding ethanol (5 mL) to the cloud point layer before analysis. The maximum absorbance reported is 540 nm, and the limit of detection is 3.0705 ppm, with a sensitivity of 0.017 ppm. The reagent forms of 1:1 complex and other conditions have been studied for the system.

2.2 [N-(O-hydroxybenzylidene) pyridine-2-amine] (NOHBPA) Ritika et al. [2] have explored the use of NOHBPA as a chromogenic reagent for spectrophotometric determination of nickel (ii). It is mentioned that Ni (ii) forms a complex with the mentioned reagent which absorbs at 500 nm in pH 7.4–8.6 aqueous solution. The Beer’s law concentration range between 0.1 and 0.5 µg/mL is optimum for determination. The complex is reported to have molar absorptivity as 1,294 L/mol/ cm and 0.00435 µg/cm2 as Sandell’s sensitivity. It is recommended that Ni (ii) in alloy samples can be successfully determined using this method.

2.3 N,Nʹ-bis(4-methoxysalicylidene) ethylenediamine Tokay [3] has proposed a method for rapid spectrophotometric determination of nickel using N,Nʹ-bis (4-methoxysalicylidene) ethylene diamine as a chromogenic reagent. The method used in the determination of nickel in edible oil uses Ni-complex which absorbs at 396 nm. The method uses mixture of n-hexane and acetone in 1:4 v/v ratio as a solvent. The reported molar absorptivity is 6,540 L/mol/cm and detection limit is 0.24 and 0.82 µg/g. Beer’s law concentration range lies between 0.25 and 1.50 µg/L. The standard deviation value is 3.8%. It is used for nickel determination in nickel-spiked real samples having recovery between 96.0 and 104% as reported.

https://doi.org/10.1515/9783111133300-003

2.7 1-(2-Pyridylazo)-2-naphthol (PAN)

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2.4 α-Furildioxime Bahrami et al. [4] have developed a method for the determination of nickel based on experimental design optimization of supramolecular dispersive liquid-liquid micro extraction technique. The method uses solidification of the floating organic drop (SMDLLME SFOD), and combining it with spectrophotometry to determine nickel. The complex of nickel with α-furildioxime is extracted in an aqueous phase rich in macro molecules (Coacervate) made up of undecanol reverse micelles in water tetrahydrofuran mixtures. Beer’s law concentration range of 3–85 µg/L is reported and method has been successfully applied in water and vegetable samples as reported.

2.5 4-(2-Pyridylazo)-resorcinol Azeem et al. [5] have proposed simultaneous spectrophotometric determination method of binary elements nickel and cadmium. The preparation and pre-concentration of the metals was done using two polyurethane foam sorbents viz. cadion fundionalzed as well as untreated foam. These were separately packed in two minicolumns to facilitate online preconcentration/separation. Cadmium and nickel were separated/pre-concentrated on cadion foam minicolumn, subsequently eluted by HCl and mixed with a thiocyanate system. Nickel passed out to react with 4-(2-pyndyazo) resorcinol reagent. It was measured at 498 nm. The detection limit was 4.6 and 3.3 µg/L. The method as reported could be used for analysis of human urine and tap water as reported.

2.6 1-(4-Methylphenyl)-3-(2-(trifluoromethyl) phenyl) triaz-1-ene-1-oxide Rezaei et al. [6] have studied and reported synthesis crystal structure, theoretical study and use of above-mentioned reagent in extraction and spectrophotometric determination of nickel. The study reports the use of ligand for selective extraction of Ni2+ ions from natural water. In the Beer’s law range of 9.2 × 10−7–8.4 × 10−3 M, Ni could be determined in the limit of 6.0 × 10−7 M as reported. Further the determination does not have interference even in the presence of 100-times concentration of interfering ions.

2.7 1-(2-Pyridylazo)-2-naphthol (PAN) Roghieh et al. [7] have reported a spectrophotometric method for nickel determination in marine brown-green algae after preconcentration using surface-assisted dispersive liq-liq micro extraction (SADLLME). The report mentions that under optimum conditions, in the Beer’s law range of 0.1–100 µg/L, detection of 0.03 µg/L of Ni could

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Chapter 2 Analytical reagents having nitrogen and oxygen as donors

be achieved. The method thus has been used for Ni determination in marine brown algae from Chabahar Bay of Southeast Iran.

2.8 2-Hydroxy-1-naphthaldehyde thiosemicarbazone (HNT) Lokhande [8] has reported the use of HNT for the spectrophotometric determination of Nickel. It is reported that reagent forms a yellowish green-colored complex with Ni (ii), which is extractable quantitatively at pH 7 using ethylacetate. The extracted complex shows an intense peak at 430 nm. The Beer’s law concentration range is 10–100 µg of metal where it can be determined. A molar absorptivity value of 0.272 × 106 L/ mol/cm is reported with Sandell’s sensitivity value of 0.275 × 102 µg/cm2. The method thus has been successfully applied for the determination of Ni (ii).

2.9 Para aminophenol (PAP) Khudhair et al. [9] have reported a preconcentration-based determination method for nickel in urine samples using p-aminophenol as a reagent with Triton×-114 as non-ionic surfactant. In the method the Ni-PAP complex formed can be determined in the concentration range of 0.0625–1.25 mg/L at λmax 629 nm. The detection limit is 0.005 mg/L with a standard deviation of 1.07%.

2.10 [N-(O-methoxybenzaldehyde)-2-aminophenol] (NOMBAP) Makhijani et al. [10] have proposed the method of extractive spectrophotometric determination of nickel (ii) using NOMBAP as a chromogenic reagent. This is described that the reagent extracts 99.35% of Ni (ii) into chloroform from an aqueous solution of pH 7.5–8.7. This extracted complex has an intense peak at 490 nm in the Beer’s law concentration range of 0.1–4.0 µg/mL. The reported molar absorptivity of the system is 1,396 L/mol/cm, whereas Sandell’s sensitivity is 0.0435 µg/cm2. The study includes the interference of other ions and the method has been applied to determination of Ni (ii) in alloy samples.

2.11 3-Hydroxy-3m-tolyl-1-p-methoxyphenyltriazene Ochieng [11] has applied the above-mentioned reagent as chromogenic reagent for spectrophotometric determination of nickel (ii) in environmental samples. Ombaca Ochieng has proposed the application of 3-hydroxy-3 m-tolyl-1-p-methoxyphenyltriazene for Ni (ii) determination spectrophotometrically. It is mentioned that the reagent forms a yel-

2.14 Tween-80-PAN

35

low-colored complex in the ratio 1:2 (Ni: L) in pH range 8.0-8.3 which absorbs at 412 nm. It is described that method can be used for Ni (ii) determination in soil and plant as well as environmental samples successfully.

2.12 Schiff base Shoha [12] has reported synthesis and anti-microbial activities of cobalt (ii) and nickel (ii) Schiff base complexes using 3,4-methylenedioxynaphthaldehyde (naphtho [1, 2-d] [1, 3] dioxole-5-carbaldehye as reagent. The study reports Schiff base complexes of cobalt (ii) and nickel (ii) with the above reagent in methanol medium. After due characterization the ligand has been used to develop a sensitive and simple spectrophotometric determination of Ni (ii). It is mentioned that a 1:2 complex is formed which absorbs at 380 nm, the Beer’s law concentration is 8 ppm at pH 6.0 where molar absorptivity and Sandell’s sensitivity values are 0.80351 × 103 L/mol/cm and 0.00417 µg/cm2, respectively. It is mentioned that method has tolerance for other ions too.

2.13 Nʹ-(2-hydroxybenzylidene)-3-(4-O-tolylpiperazin-1-yl) propanehydrazine (HTP) Ravi Chandran et al. [13] have reported extraction-based spectrophotometric determination method for the determination of nickel in water, alloys and edible oil samples. At pH 9.0 the mentioned reagent reacts with Ni (ii) to give a 1:1 yellow complex, which is extracted in chloroform. This complex shows a λmax at 382 nm, and the Beer’s law concentration range of 1.17–12.91 µg/mL is reported for optimum determination. The values of molar absorptivity are 0.72 × 104 L/mol/cm and the Sandell’s sensitivity is 0.008 µg/cm2/0.001 absorbance unit. It is reported to be interference free with several ions and has been successfully applied to determine Ni (ii) in real samples of alloys and edible oils.

2.14 Tween-80-PAN Song [14] has reported a spectrophotometric determination method for Ni (11) determination in steel samples using Tween-80-PAN as a complexing agent. It is described that in NH3H2O–NH4Cl buffer solution a stable N (ii) – PAN complex is formed. The tween-80-1-(2-pyridylazo)-2-PAN complex absorbs at 568 nm. The molar absorptivity is 4.62 × 104 L/mol/cm in the Beer’s Law range of 0–15 µg/(25 mL) Ni (ii) solution. Further, it is mentioned as an accurate, simple yet selective method with satisfactory results.

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Chapter 2 Analytical reagents having nitrogen and oxygen as donors

2.15 Antipyrine azo orcinol (APAO) Mohammad et al. [15] have developed a spectrophotometric method for the determination of Ni (11) using APAO. The complex absorbs at 461 nm with molar absorptivity of 0.107 × 105 L/mol/cm. On the concentration range (Beer’s law) of 0.4–2.8 µg/mL of Ni (11), a 1:1 complex is formed. It is further mentioned that method can be successfully performed in the presence of many cations and anions in various samples.

2.16 5-Nitrosalicylaldehyde semicarbazone (NSS) Ram et al. [16] have developed a new reagent 5-nitrosalicylaldehyde semi-carbazone (NSS) for extractive spectrophotometric determination of Ni (ii). The mentioned reagent reacts with metal in the pH range of 4.0–4.4 to give a colored complex. The complex can be well extracted with ethyl acetate. The extraction has λmax at 420 nm in the concentration range of 1–6 µg/cm3. The reported molar absorptivity of the method is 2.5016 × 104 L/mol/cm and the Sandell’s sensitivity was 1.067 × 10−2 µg/cm2. The authors recommended method as suitable for Ni (ii) determination.

2.17 5-Bromo-2-hydroxy-3methoxybenzaldehyde-4hydroxybenzoichydrazone (5-BHMBHBH) Saritha et al. [17] have proposed a spectrophotometric method for simultaneous determination of aluminum (11) and nickel (11) using 5-BHMBHBH as a reagent. It is described that the reagent reacts at pH 6.0 giving a water soluble complex. Ni (ii) shows a maximum absorbance at 440. The molar absorptivity of Ni is 1.37 ± .002 × 104 lit mol−1 cm−1. The method developed is highly sensitive selective as well as precise for direct spectrophotometric determination of Ni (ii) and Al (ii) in alloy samples.

2.18 Antipyriyl azo-1-nitroso-2-naphthol Awad [18] has reported preparation, characterization and thermodynamic studies of complex of Ni (ii) using above reagent. The reagent has been used for spectrophotometric determination of Ni (ii), in trace amounts. It is described that Na (ii) forms a 2:1 complex with APANN, which has λmax at 469 nm. The authors report a Beer’s law concentration range between 0.1 and 1.8 µg/mL. The molar absorptivity εmax = 0.6 × 105 L/mol/cm. It is mentioned that this method was successfully applied to the synthetic mixtures and raw milk for nickel determination.

2.22 Schiff base 2-[(2-hydroxyphenylimino) methyl]-4-nitrophenol (HPIMNP)

37

2.19 1-Nitroso-2-naphthol Shar et al. [19] have developed a simple yet rapid method for spectrophotometric determination of nickel (ii) in trace quantities using 1-nitroso-2-naphthol as a chromogenic reagent. It is mentioned that use of miceller system replaces need for solvent extraction and increases sensitivity, selectivity and molar absorptivity too. The molar absorptivity is reported as 1.02 × 104 L/mol/cm and Sandell’s sensitivity as 5.7 ng/cm2 at λmax 471.6 nm. A 1:2 (Ni: [NNPh]2) complex is reported in the Beer’s law range of 0.25–4.0 µg/mL. The application of this method has been successfully done for alloy and real samples.

2.20 2,4-Dimethoxybenzaldehyde iso nicotinoylhydrazone (DMBIH) Viswanatha et al. [20] have published a direct and derivative spectrophotometric method for the determination of nickel (ii) using 2,4-dimethoxybenzaldehyde iso nicotinoylhydrazone (DMBIH) as a reagent. It is mentioned that these compounds are selective and sensitive analytical reagents. 2,4-Dimethoxybenzoldehyde iso nicotinoylhydrozone reacts with nickel (ii) in aqueous solution at pH 9.0 to yield a yellow-colored complex which absorbs at 410 nm. The reported molar absorptivity is 5.92 × 104 L/mol−1/cm−1, and Beer’s law is obeyed in 0.1467–1.760 µg/mL of Ni (ii). The method is applicable to Ni (ii) determination in alloy samples.

2.21 Salicylaldehyde isonicotinoyl-hydrazone (SAINH) Renuka et al. [21] have proposed a very simple non-extractive spectrophotometric method for nickel (ii) determination using SAINH as an analytical reagent. It is described that the reagent reacts in basic medium (pH 7.5, sodium acetate–acetic acid) forming a yellow complex with nickel (ii). The λmax of the stable complex is at 385 nm. The molar absorptivity reported is 1.81 × 104 L/mol/cm and Sandell’s sensitivity is 0.32 µg/cm2. In the Beer’s law range between 1.0 and 10.0 µg/mL the method is successfully applied. It is reported that the method has been applied to the determination of nickel in various reference materials such steels and alloys.

2.22 Schiff base 2-[(2-hydroxyphenylimino) methyl]-4-nitrophenol (HPIMNP) Mandhave et al. [22] have developed an extractive spectrophotometric method for the determination of nickel (II) using Schiff base 2-[(2-hydroxyphenylmino) methyl]-4nitrophenol as extractant. It is described that HPIMNP in the pH range 7.8–8.8 extracts

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Chapter 2 Analytical reagents having nitrogen and oxygen as donors

Ni (II) into n-Bu.alc. from an aqueous solution in the presence of 2 mL of 5 M ammonium chloride solution. The extract absorbs at 480 nm (λmax), in the Beer’s law concentration range 0.2–20.0 µg/mL. The reported molar absorptivity is 882.35 L/mol/cm and 0.67 µg/cm2 is the value of Sandell’s sensitivity as mentioned. The method has been tested for interference of various ions and could be applied to alloy samples successfully.

2.23 Isocinchomeronic acid Chauhan et al. [23] have proposed use, synthesis and characterization of isocinchomeronic acid (pyridine 2, 5 dicarboxylic acid) as a chromogenic reagent for spectrophotometric determination of nickel. It is reported that Ni forms a blue-colored complex with pyridine 2,5 dicarboxylic acid in pH 6.0–8.5. This complex absorbs at 620 nm and in the concentration range of 250–600 µg Beer’s law is obeyed. The reported value of molar absorptivity is ε = 2.1 × 102 L/mol/cm. The method is reportedly useful for synthetic samples.

2.24 3-(1-Benzhydrylazetidin-3-yl) 5-isopropyl 2-amino-1, 4-dihydro-6-methyl-4-(4-nitrophenyl) pyridine-3, 5-dicarboxylate Saranga Pani et al. [24] have used above reagent for simple, sensitive as well as selective extraction-based spectrophotometric method for Ni (ii) in water and alloy samples. It is described that reagent forms a blue-colored complex a pH 7.5. The colored complex absorbs at 445 nm, in the Beer’s law range 0.5–1.0 µg/mL. The reported molar absorptivity is 6.0 × 104 L/mol/cm and Sandell’s sensitivity is 1.02 µg/cm2.

2.25 N,Nʹ bis (O-hydroxyacetophenone) ethylene diimine derivatives (HAPED) Jayashree et al. [25] have proposed a simple and accurate spectrophotometric method for the determination of Ni (ii) using HAPED as analytical reagent. After synthesis and characterization of the reagent it was used for the determination of Ni (ii). It is described that the reagent reacts with nickel giving a light yellow complex, easily extractable into chloroform at pH 5.0. This extraction gives a λmax at 380 in the Beer’s law range of 1–10 µg/mL of nickel. The reported molar absorptivity is 1,715.97 L/mol/cm and Sandell’s sensitivity is 0.0344 µg/cm2. It has been further mentioned that the method

2.28 α-Oximino acetoacetanilide benzolyhydrazone (HINABH)

39

can be satisfactorily applied for the determination of Ni (ii) in pharmaceutical and alloy samples.

2.26 Dimethylglyoxime Ebrahimi et al. [26] have proposed the determination of nickel in food and well water samples by use of cold-induced aggregation micro extraction. It is described that nickel was extracted in the presence of dimethylglyoxime as chelating agent. Sodium hexaflurophosphate was added to the sample which contained small amounts of 1hexyl-3 methylimidazollum hexaflurophosphate [Hmim] [PF6] as extracting solvent for the Ni-dmg complex. Beer’s law concentration range as reported lies between 8.200 µg/mL and spectra were recorded in 300–900 nm range of absorbance. The technique could be applied to 0.47 ng/mL of detection limit.

2.27 5-Bromo-2-hydroxyl-3-ethoxybenzaldehyde-4-hydroxy benzoichydrazone (5-BHMBHBH) Saritha et al. [27] have developed a simple, sensitive and rapid method using direct spectrophotometry for Ni (II) determination. The reagent 5-BHMBHBH reacts with Ni (II) to give a green complex in a basic medium. The λmax shown by complex in pH range of 5.5–7.5 is 440 nm. In the Beer’s law concentration range 0.117 to 2.64 µg/mL the linearity is maintained. The report shows molar absorptivity value as 2.013 × 104 L/ mol/cm, whereas Sandell’s sensitivity value is 0.0029 mg/cm2. The proposed method can be used for the determination of Ni (II) in samples like alloy, drinking water, plant samples as well vegetable oil.

2.28 α-Oximino acetoacetanilide benzolyhydrazone (HINABH) Jagasia [28] has reported a method for sequential separation of Co (II), Ni (II) and Pb (II). The method is reportedly an accurate, sensitive and simple one. It is described that HINABH forms yellowish brown complex with Ni, which was extracted into isoamylalcohol, in the pH range 8.9–4.5. The colored complex absorbed at 420 nm in the Beer’s law range between 1 and 14 ppm. It is mentioned that the proposed method was applied for nickel determination in synthetic mixtures and alloys as well.

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Chapter 2 Analytical reagents having nitrogen and oxygen as donors

2.29 Antipyriyl azo-2,7-naphthalene-diol (1-APANDOL) Awad et al. [29] have developed a new spectrophotometric method for the determination of trace nickel (II) using 1-APANDOL as chromogen. It is said to be a rapid, simple and sensitive method. The complex has a λmax at 514 nm and has 1:2 stoichiometry. The reported molar absorptivity value is ε = 2.0 × 104 L/mol in the linear concentration range 0.1–2.0 µg/mL following Beer’s law. The authors report that study was performed for a number of interfering ions to check success of method in the presence of other ions. It is mentioned that method can be successfully applied without preconcentration or separation for Ni (II) determination in synthetic mixtures as well as tea samples.

2.30 Pyridine-2, 3-dicarboxylic acid Chauhan Jayprakash et al. [30] have developed a new spectrophotometric method for the determination of Ni (II) ion using pyridine-2,3-dicarboxylic acid as reagent. It is described that Ni (II) ions from a blue complex with the reagent in the ratio of 1:2 in pH range 4.0–5.5. The complex shows λmax at 620 nm in the Beer’s law concentration range between 200 and 500 µg of nickel. The reported molar absorptivity is found to be 1.10 × 102 L/mol/cm.

2.31 2ʹ-Hydroxy-4ʹ-butoxychalconeoxime (HB CO) Limbachiya et al. [31] have developed a method for studying Ni (II) chelate using HBCO as an analytical reagent. It is described that the reagent HBCO is a new analytical reagent for both gravimetric and spectrophotometric determination of Ni (II). It is reported that in the pH range 8.0–10.0, this reagent yields a light green complex with Ni (II). The absorbance range is between 300 and 800 nm but 500 nm was taken as λmax. In the Beer’s law range was obeyed and the reported molar absorptivity λmax × 500 is ε = 2.24 × 102 L/mol/cm with Sandell’s sensitivity value of 0.0473 µg/cm2. The authors have used this method for the determination of Ni (II) in German silver alloy.

2.32 Anthrone phenylhydrazone (APH) Veeranna et al. [32] have developed a simultaneous fourth-order derivative spectrophotometric determination of cobalt, nickel and copper using APH as reagent. It is described that the reagent gives yellow color with Co (II), Ni (II) and Cu (II) in alkaline medium. In a solution of pH 10.6 Ni (II) gives a peak between 426.3 and 625 nm. The reported molar

2.35 o-Chlorophenylazo-bis-acetoxime

41

absorptivity is 2.0 × 104 L/mol/cm and Sandell’s sensitivity is 0.005 µg/cm2 for Ni (II) complex. Further the results agree well with those obtained from APARI and AAS methods.

2.33 Triazene-1-oxide derivatives Alizadeh et al. [33] have developed an optical sensor of Ni2+ using triazene-1-oxide derivative immobilized on the triacetyl cellulose membrane. 1-p-Tolyl-3-(3-trifluromethylo) phenyl) triaz-1-ene-oxide has been used and immobilized. The spectrophotometric studies reveal that complex formation between the ligand and Ni2+ in acetonitrile solution has longer stability and larger stability constants for Ni2+ ion complex. Thus the new ligand was used as an ion ophore for developing a selective Ni2+ optical s sensor by immobilizing on transparent triacetyl cellulose tapes. In Beer’s law concentration range of 1.18 × 10−9 to 7.34 × 10−5 M at pH 5.7, the Ni2+ could be detected. The detection limit is 1.0 × 10−9 m as mentioned. The method successfully determines Ni2+ in the presence of several interfering ions.

2.34 5-(4ʹ-Chlorophenylazo-6-hydroxypyridine-2,4-dione (CPAHPD) Amina et al. [34] have studied solid phase extraction (SPE) and spectrophotometric determination method of Ni (II) determination using ligand CPAHPD. The study describes rapid reaction of nickel (II) with the CPAHPD reagent at pH 6.8 in the presence of cetylpyridiniumbromide. A red complex is formed in a 1:1 (Ni:CPAHPD) ratio enriched by SPE with a C18 membrane disk. The reported values of molar absorptivity and Sandell’s sensitivity are 3.11 × 105 L/mol/cm and 0.0189 ng/cm2, respectively. At 549 nm, Beer’s law is obeyed in the concentration range of 0.61–0.37 µg/mL. The method has been applied to nickel determination in water, food and biological as well as soil samples as mentioned.

2.35 o-Chlorophenylazo-bis-acetoxime Khanam et al. [35] have reported the use of o-chlorophenylazo-bis-acetoxime for spectrophotometric determination of Ni (II). It is reported that a 1:2 (Ni: R) ethanol soluble greenish yellow complex is formed with the reagent which absorbs at 370 nm in the pH range 7.3–7.9. Beer’s law concentration range is 0.117–0.939 ppm and molar absorptivity is ε = 2,451 L/mol/cm whereas Sandell’s sensitivity is 23.09 ng/cm2. It is further mentioned that Ni (II) can be determined using this method even in the presence of several fold concentration of different ions.

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Chapter 2 Analytical reagents having nitrogen and oxygen as donors

2.36 2-Hydroxy-1-naphthalenecarboxaldehyde phenylhydrazone Sonawane et al. [36] have brought forward an extractive spectrophotometric method for Ni (II) determination using 2-hydroxy-l-naphthalenecarboxaldehyde phenylhydrazone as a reagent. It is described that the reagent forms a colored complex at pH 8 which can be quantitatively extracted into n-butanol. The Beer’s law range is 1-12 ppm and λmax is 395 nm. The reported molar absorptivity is 1.736 × 104 L/mol/cm and Sandell’s sensitivity is 0.1613 µg/cm2. The method can be successfully applied to determination of Ni (II) in synthetic and commercial samples.

2.37 4-(2-Pyridylazo) resorcinol (PAR) Fang et al. [37] have studied and investigated simultaneous spectrophotometric determination of cobalt and nickel by PAR spectrophotometry. It is described that in the NaAC-HAC of pH 5 buffer nickel forms a stable colored complex with PAR, which absorbs at 568 nm. A dual wavelength linear regression method is used for simultaneous determination of cobalt and nickel.

2.38 2-[2-(6-Chlorobenzothiazolyl] azo-resorcinol (6-CIBTAR = LH2) Al-Adilee et al. [38] have brought forward the synthesis of a new reagent 2-[2-(6chlorobenzothiazolyl) azo]–resorcinol and used this for spectrophotometric determination of Ni (II) and Cu (II). A Ni (II)–CIBTAR complex is formed at pH 7.0, which is green colored and absorbs at 636 nm. The reported molar absorptivity is 0.3695 × 104 L/mol/cm. The Beer’s law range 1–20 µg/mL is described. Further a 1:2 complex is formed with the ligand as mentioned.

2.39 2,2-Furildioxime Rahana et al. [39] have developed a spectrophotometric method for trace determination of nickel in water samples using 2,2-furildioxime as a reagent. The method uses dispersive liq–liq micro extraction (DLLME) combined with uv-vis spectrophotometry applying 2,2-fluridioxime as a celating agent. A detection limit of 0.6 µg/L is reported and the method has been applied in various water samples.

2.43 Diacetyl monoxime isonicotinoylhydrazone

43

2.40 p-Chloro phenylazo-bis-acetoxime (p-CPABA) Khanam et al. [40] have explored analytical application of p-chlorophenylazo-bisacetoxime (p-CPABA) in the spectrophotometric determination of nickel (II). The method includes complex formation of Ni (II) with the reagent in the pH range 7.3–8.1. The complex absorbs at 375 nm, in the Beer’s law range 1.0–6.0 × 10−5 M. The molar absorptivity is 5.389 L/mol/cm and Sandell’s sensitivity is 10.89 ng/cm2.

2.41 Furildioxime in micellar solution Memon et al. [41] have proposed a simple, selective and fast flow injection-based spectrophotometric method for the determination of nickel using furildioxime as complexing agent. The described method includes employment of brij-35 as solubilizing agent to dissolve complex of Ni–furildioxime which is sparingly soluble complex. The pH is 9.00 and under optimum conditions Beer’s law range is 0.02–10 µg/mL. The complex absorbs at 480 nm, and the molar absorptivity is 6.0 × 103 L/mol/cm and Sandell’s sensitivity is 0.01 ng/cm2. The removal of cobalt interference is done using nitroso-R-saltmodified XAD-16. The method has been successfully applied to Ni determination in commercial cigarettes.

2.42 2,4-Dihydroxy-5-bromo butyro phenone oxime (DHBBO) Patel et al. [42] have developed a new spectrophotometric reagent for Ni (II) determination DHBBO. It is described that in pH range 7.0–10.0 this reagent gives light green ppt forming a 1:2 complex λmax of the complex was 560 nm and the molar absorptivity as 0.103 × 103 m/L/cm, whereas Sandell’s sensitivity as 0.057 µg/cm2 is reported by the authors. The reagent has been used for analysis of German silver.

2.43 Diacetyl monoxime isonicotinoylhydrazone Mallikarjune et al. [43] have reported a simultaneous determination method for nickel (II) and aluminum (III) using diacetyl monoxime iso nicolinoylhydrazone as analytical reagent. It is described that the reagent forms an intense yellow color in sodium acetate acetic buffer medium which absorbs at λmax 365 for Ni (II). A 1:1 complex is reported. The molar absorptivity reported is 2.08 × 104 L/mol/cm and Sandell’s sensitivity is 0.00282 µg/cm2. Beer’s law is valid in the concentration range 0.495–3.09 µg/mL, whereas detection limit for Ni is 0.0545 µg/mL as reported.

44

Chapter 2 Analytical reagents having nitrogen and oxygen as donors

2.44 Hydrazine carboxamide-2-(2-hydroxy-1-naphthalenyl) methylene] (HCHNM) Lokhande et al. [44] have used HC HNM as an extractive spectrophotometric reagent for determination of Ni (II). It is mentioned that Ni (II) forms a dark yellow-colored complex which can be extracted in n-butanol at pH 6.2. The complex extracted shows λmax at 395. The Beer’s law concentration range is 3–50 µg of Ni (II). The molar absorptivity value reported is 0.4785 × 105 L/mol/cm and Sandell’s sensitivity is 0.0585 µg/cm2. The application has been extended to commercial samples stated by the authors.

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Taresh, S. S.; Ali, S. M.; Radhi, S. S.; Mubarak, H. A. Cloud point extraction method for determination of nickel in different water samples using an imidazole derivative. Natural Volatiles and Essential Oils. 2021, 8(4), 1936–1952. [2] Ritika, M.; Dinesh, N.; Vasant, B. Role of [N-(O-hydroxybenzylidene) pyridine-2-amine] (NOHBPA) in extractive spectrophotometric determination of nickel (II). Research Journal of Chemistry and Environment. 2021, 25(4), 42–46. [3] Tokay, F. Development of uv-vis spectrophotometric method for rapid nickel determination in original oil matrix. Suleyman Demirel Universitesi Fen Bilimeri Enstitutsu Dergisi. 2017, 21(2), 332–337. [4] Bahrami, M.; Shabani, A. M. H.; Dadfarnia, S.; Moghadam, M. R. Experimental design optimization of supramolecular dispersive liquid–liquid micro extraction of nickel and its spectrophotometric determination. Journal of Analytical Chemistry. 2021, 76(4), 442–451. [5] Azeem, A.; Sami, M.; Hassan, A.; El-Nady, Y.; El-Shahat, M. F. Separation of nickel and cadmium from aqueous solutions of flow injection preconcentration onto cadion functionalized polyurethane foam. Micro Chemical Journal. 2021, 166, 106192. [6] Behrooz, R.; Faziollahi, M. Synthesis, crystal structure, theoretical study and application of 1-(4methyl-phenyl)-3-(2-trifluoromethyl) phenyl) triaz-1-ene-1-oxide in the extraction of Ni ions – Synthesis of a new triazene 1-oxide derivative, X-ray crystal structure and its theoretical studies. Journal of the Iranian Chemical Society. 2021, 18(7), 1581–1590. [7] Roghieh, G.; Mahmoud, N.; Sayyed, H. Spectrophotometric determination of copper and nickel in marine brown algae after preconcentration with surfactant assisted. Dispersive Liquid-Liquid Micro extraction. Iranian Journal of Chemistry & Chemical Engineering. 2020, 39(3), 117–126. [8] Pradnya, L. Solvent extraction and spectrophotometric determination of nickel (II) using 2-hydroxy -1-naphthaldehyde thiosemicarbazone (HNT) as an analytical reagent. International Journal of Trend in Scientific Research and Development. 2019, 3(3), IJTSRD 22964. DOI: 10.3/142/ijtsrd22964. [9] Khudhair, A. F.; Hassan, M. K.; Alessary, H. F.; Abbas, A. A simple preconcentration method for the determination of nickel (II) in urine samples using uv-vis spectrophotometry and flame atomic absorption spectrometry techniques. Indonesian Journal of Chemistry. 2019, 19(3), 639–649. [10] Makhijani, R.; Navale, D.; Barhate, V. Development of extractive spectrophotometric determination of nickel (II) using [N-O-methoxybenz as an aldehyde)-z-aminophenol] [NOMBAP] analytical reagent. International Journal of Scientific Research and Reviews. 2018, 7(4), 2144–2151. [11] Ochleng, O. Utility of 3-hydroxy-3-m-tolyl-1-p-methoxyphenyltriazene as chromogenic reagent for spectrophotometric determination of nickel (II) in environmental samples. IOSR Journal of Environmental Sciences, Toxicology and Food Technology. 2018, 12(6–2), 68–76.

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Shobha, B. Synthesis and antimicrobial activities of cobalt (II) and nickel (II) Schiff base complexes derived from 3, 4 methylenedioxy naphlhaldehyde (naphtho [1, 2-d] dioxole-5-carbaldehyde. International Journal of Pharmacy and Pharmaceutical Research. 2017, 10(1), 18–27. Ravichandran, C.; Benzil, D.; Ramachandraiah, C.; Chandrasekhar, K. B. Extraction spectrophotometric determination of nickel in water, alloys and edible oil samples. International Journal of Bioassays. 2015, 4(11), 4468–4472. Song, G. L. Determination of Ni (II) in steel samples by Tween-80-PAN Spectrophotometer. Dangdai Huagong. 2016, 45(1), 205–206, 209. Mohammad, J. H.; Sarhan, W. M.; Mohammad, W.; Muhl, A. Y.; Nadaa, S. Spectrophotometric determination of Fe (II) & Ni (II) as complexes with new derivative of antipyrine azo orcinol. Pharma Chemica. 2016, 8(19), 100–108. Ram, L. S.; Kalpana, P.; Irfan, M. R. Liquid-Liquid extraction and spectrophotometric determination of Ni (II) using 5-nitrosalicylaldehyde Semicarbazone (NSS) as an analytical reagent. International Journal of Research in Chemistry and Environment. 2016, 6(2), 28–30. Sarilha, B.; Reddy, T. S. Simultaneous spectrophotometric determination of aluminum (III) and nickel (II) using 5-BHMBHBH. World Journal of Pharmacy and Pharmaceutical Sciences. 2015, 4(8), 1741–1746. Awad, M. A. Preparation, characterization, analytical and thermodynamic studies of complex of Ni (II) with antipyriyl azo-1-nitrozo-2-naphthol. Chemical Science Transactions. 2015, 4(3), 654–662. Shar, G. A.; Gulafshan, S. A simple spectrophotometric determination of nickel (II) using 1-nitroso-2naphthol in anionic micellar solution. Asian Journal of Chemistry. 2015, 27(6), 2307–2310. Viswanath, C.; Devanna, N.; Chandrasekhar, K. B. Direct and derivative spectrophotometric determination of Ni (II) using 2, 4-dimethoxybenzaldehyde iso nicotinoylhydrazone (DMBIH). International Journal of Advances in Pharmacy, Biology and Chemistry. 2013, 2(2), 380–384. Renuka, M.; Saleembhasha, V.; Reddy, K. H. Non-extractive spectrophotometric determination of nickel in alloy samples using salicylaldehyde iso nicotinoylthydrazone. Journal of Applicable Chemistry (Lumami, India). 2015, 4(3), 918–924. Mandhare, D. B.; Barhate, V. D. Development of extractive spectrophotometric method for the determination of nickel (II) with Schiff base 2-[(2-hydroxyphenylimino) methyl) -4-nitrophenol. Journal of Chemical and Pharmaceutical Research. 2015, 7(4), 1069–1073. Chauhan, J. S.; Pandya Ajit, V. Synthesis, characterization and spectrophotometric determination of nickel ion by isocinchomeric acid. World Journal of Pharmaceutical Research. 2014, 3(2), 2527–2541. Saranga Pani, A.; Kumar, R. K.; Naidu, N. V. Determination of Ni (II) in water and alloy samples with 3-(1-benzhydrylazetidin-3-yl) 5-isopropyl 2-amino-1, 4-dihydro-6-methyl-4-(4-nitropheny) pyridine-3, 5-dicarboxylate using spectrophotometric method. International Journal of Advanced Research. 2014, 2(2), 691–699. Jayshree, S. P.; Ram, S. L.; Dharap, S. B.; Sonali, S. P. Liquid-Liqud extraction and spectrophotometric determination of Ni (II) with N,Nʹ bis (o-hydroxyacetophenone) ethylene demine derivatives as an analytical reagent. International Journal of Research in Chemistry and Environment. 2014, 4(2), 79–84. Ebrahimi, B.; Soleiman, B.; Moedi, S. E. Cold induced aggregation micro extraction techniques based on ionic liquid for preconcentration and determination of nickel in food samples. Journal of Brazillian Chemical Society. 2013, 24(11), 1832–1839. Saritha, B.; Reddy, T. S. Direct spectrophotometric determination of Ni (II) using 5-bromo-2-hydroxyl -3-ethoxybenzal dehyde-4-hydroxy benzoic hydrazone. Journal of Applied Chemistry. 2014, 7(3), 22–26. Jagasia, P. V. Sequential separation of cobalt, nickel and lead by using α-oximino aceto acetanilide benzoylhydrazone (HINABH). American Journal of Pharmtech Research. 2014, 4(1), Jagasia/1–Jagasia/7.

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[29] Awad, M. A.; Mohammad, H. J. Spectrophotometric determination of trace amount of nickel (II) in tea leaves samples by using antipyrilazo-2,7-naphthalenediol as new reagent. Chemical Science Transactions. 2014, 3(3), 1115–1123. [30] Chauhan Jayprakash, S.; Pandya Ajit, V. Synthesis, characterization and spectrophotometric determination of Ni (II) ion by pyridine-2,3-dicarboxylic acid. International Research Journal of Pharmaceutical & Applied Sciences. 2013, 3(5), 31–36. [31] Limbachiya, N. G.; Desai, K. K. 2ʹ-hydroxy-4ʹ-butoxychalcone oxime [HBCO] as an analytical reagent: Studies on Ni (II) chelate. International Journal of Chem Tech Research. 2013, 5(5), 2347–2350. [32] Veerama, V.; Rao, S.; Balraju, J. N. Simultaneous fourth order derivative spectrophotometric determination of cobalt, nickel and copper using anthrone phenylhydrazone (APH). Chemical Science Transactions. 2012, 1(2), 321–328. [33] Alizadeh, K.; Rezaei, B.; Khazaeli, E. A new triazene-1-oxide derivative, immobilized on the triacetyl cellulose membrane as an optical Ni2+ sensor. Sensors and Actuators, B: Chemical. 2014, 193, 267–272. [34] Amina, A.; Al-Attas, A. S. Study of the solid phase extraction and spectrophotometric determination of nickel using 5-(4ʹ-chlorophenylazo-6-hydroxypyrimidine-2-4-dione in environmental samples. Journal of Saudi Chemical Society. 2012, 16(4), 451–459. [35] Khanam, R.; Khan, S.; Dashora, R. Direct spectrophotometric determination of nickel (II) with o-chlorophenylazo-bis-acetoxime. Oriental Journal of Chemistry. 2013, 29(2), 603–608. [36] Sonawane, R. P.; Lokhande, R. S.; Chavan, U. M. Development of method for extractive spectrophotometric determination of Ni (II) with 2-hydroxy-1-naphthalene carboxaldehyde phenylhydrozone as an analytical reagent. International Journal of Chemical Sciences. 2013, 11(1), 598–604. [37] Fang, H.-W.; Kai, X.-M. Determination of cobalt and nickel by PAR spectrophotometry. Guangpu Shiyanshi. 2012, 29(3), 1915–1917. [38] Al-Adilee, K.; Azhar-Ghali; Hussein, A. Preparation and spectrophotometric study of reagent 2-[2-(6chloro benzothiazolyl) azo] -resorcinol as an analytical reagent for determination of nickel (II) and copper (II) ions. Journal of Chemistry and Chemical Engineering. 2012, 6(7), 651–657. [39] Rahmana, R.; Jojadeh, Z. C.; Jamali, M. R. Spectrophotometric determination of trace levels of nickel in water samples after dispersive liquid-liquid micro extraction using 2, 2-furildioxime as the complexing agent. Acta Chimica Slovenica. 2012, 59(3), 641–647. [40] Khanam, R.; Dashora, R.; Chauhan, R. S. Analytical application of p-chlorophenylazo-bis-acetoxime (p-CPABA) in the spectrophotometric determination of nickel (II). Oriental Journal of Chemistry. 2012, 28(2), 949–954. [41] Memon, N.; Memon, S.; Solangi Amber, R.; Soomro, R.; Rabel, S. Single channel flow injection spectrophotometric determination of nickel using Furildioxime in micellar solution. Scientific World Journal. 2012, 418047. DOI: 10.1100/2012/418047. [42] Patel, A. B.; Patel, N. K. B.; Desai, K. K. 2,4-Dihydroxy-5- bromobutyrophenone oxime [DHBBO] as an analytical reagent. Studies on Ni (II) chelate. International Journal of Chem Tech Research. 2012, 4(3), 1203–1206. [43] Mallikarjuna, P.; Mastanailh, T.; Venkata Narayana, B.; Praveen Varma, M.; Suryanarayana Rao, V. Simultaneous determination of Ni (II) and aluminum (III) using diacetyl monoxime iso nicotinoyl hydrazone second order derivative spectrophotometric technique. Research Journal of Pharmaceutical Biological and Chemical Sciences. 2012, 3(3), 1140–1149. [44] Lokhande, R. S.; Sonawana, R. P. Use of hydrazine carboxamide-2-[(2-hydroxyl-1-naphthalenyl) methylene] as analytical reagent for the extractive spectrophotometric determination of nickel (II). International Journal of Chemical Sciences. 2012, 10(1), 311–318.

Chapter 3 Analytical reagents having N, S, O as donor atoms 3.1 NʹNʹ (1E, 1ʹʹE)-(propane-1,3-diylbis (sulfanediyl) bis(1-4-bromophenyl) ethan-2-yl-1-yilidene)) bis(2-hydroxybenzohydrazide) (BAPSSHZ) Reddy [1] has suggested BAPSSHZ as a selective and sensitive reagent for Ni (II) at trace levels. The reagent has been successfully used for Ni (II) determination in environmental samples, medicinal plant materials and water samples using spectrophotometry. This is described that BAPSSHZ reacts with Ni (II) at pH 5.0 in DMF medium to give a yellow-colored complex. The complex shows λmax at 343 nm. The molar absorptivity reported is 7.21 × 104 L/mol/cm and Sandell’s sensitivity is 0.064 µg/cm2 as mentioned. Further it is reported that the system obeys Beer’s law in the range 2.34–23.71 µg/mL of Ni (II). It is advantageously reported that there is no interference of large number of anions and cations. The method thus is recommended for Ni (II) determination.

3.2 4-Hydroxy-3-thiolbenzoic acid and diphenyl guanidine Zalov et al. [2] have proposed extraction-spectrophotometric determination of Ni (II) using 4-hydroxy-3-thiolbenzoic acid-diphenyl guanidine as reagents. The two reagents in the pH range 4.2–5.8 complex with Ni (II) to give λmax at 510 nm and molar absorptivity ε = 3.35 × 104 L/mol/cm. The Beer–Bouger–Lambert law was valid in the concentration range of 0.5–12 µg/5 mL, whereas Sandell’s sensitivity is 5.34 × 10−3 µg/cm2, as reported.

3.3 3-Phenyl-2,4-thiazolidenedione Zalov et al. [3] have proposed a reagent 3-phenyl-2,4-thiazolidnedione for the spectrophotometric determination of nickel (II) after extraction. The extractants for the complex are dichloroethane, chloroform and carbon tetrachloride. It has been described that with single extraction 97.3% of nickel is recovered as a complex. Further the complex then is extracted with chloroform at pH 4.2–6.0, when the λmax of this complex is 492 nm. The mole ratio of the complex is Ni:L = 1:2. The molar absorptivity is 2.65 × 104 in the concentration range of 0.5–15 µg/mL. This method has also been applied to various samples of Ni (II) as reported.

https://doi.org/10.1515/9783111133300-004

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Chapter 3 Analytical reagents having N, S, O as donor atoms

3.4 5-Bromo salicyledene-2-amino thiophenol Patil [4] has developed a solvent extraction-based spectrophotometric method for the determination of Ni (II) using the above reagent. This is said to be a novel reagent for separation and extraction of Ni (II). It is described that the reagent 5-bromosalicylidene2-aminothiophenol forms a colored complex with Ni (II) which can be quantitatively extracted into n-butanol at pH 7.8. The concentration range 1–10 ppm obeys Beer’s law. The reported molar absorptivity is 7,428 L/mol/cm and Sandell’s sensitivity is 0.02083 µg/cm2. This method has been stated as a selective and sensitive method for the determination of nickel from various alloys, vegetable oil samples and synthetic mixtures as well.

3.5 2-Amino-3-phenolazo-1-(4-sulfophenyl)-3-methyl-5-pyrozolone Ali et al. [5] have reported a simple, sensitive yet rapid spectrophotometric method for the determination of trace quantities of Ni (II). The method involves the formation of a 1:2 complex between Ni and 4-((2-hydroxy-6-nitrophenyl) diazenyl)-3-methyl-5oxo-2,5 dihydro-1H-pyrazol-1-yl) benzene sulfonic acid (2-ANASP). The complex has a λmax at 516 nm in the linear concentration range of 0.25–4.0 µg/mL. The molar absorptivity is ε = 1.84 × 10 L/mol/cm. The method has been successfully applied to the analysis of diabetes blood and normal human blood as mentioned.

3.6 Dithiophenols and diphenylguanidine Kuliev et al. [6] have developed an extraction spectrophotometric method using ternary complex system. The ligand in the presence of diphenylguanide extracts Ni (II) quantitatively (99–99.4%) into chloroform in the pH range 4.7–7.7. The extract shows an intense peak at 515–542 (λmax). The Beer’s law concentration is 0.04–3/6 µg/cm3. The molar absorptivity for Ni (II)–DP–DPG system is 3.12–3.36 × 104 L/mol/cm. The method is successful in the determination of Ni (II) in sewage water, bottom sediments and plants.

3.7 1-[(5-Benzyl-1,3-thiazol-2-yl) diazenyl] naphthalene-2-ol Bazel et al. [7] have developed a new organic reagent 1-[(5-benzyl-1,3-thiazol-2-yl) diazenyl] naphthalene-2-ol for cloud point micro extraction and spectrophotometric determination of Ni (II). The optimum conditions for complexation are λmax = 605 nm in pH 5.5 and 10 min healing time for solution. The molar absorptivity is ε 610 = 1.56 × 144 L/mol/cm, whereas detection limit is 3.9 µg/L. The authors recommend cloud-point micro extraction as better than liquid-liquid micro extraction.

3.10 5-(2-Benzothiazolyazo)-8-hydroxyquinolene (BTAHQ)

49

3.8 1-2ʹ,4ʹ-Dinitroaminophenyl)-4,4,6-trimethyl-1,4dihydropyrimidine-2-thiol (2ʹ,4ʹ-dinitro APTPT) Kamble et al. [8] have reported synergistic extraction of Ni (II) using 2ʹ,4ʹ-dinitro APTPT with pyridine. Ni (II) reacts with the ligand to give a green-colored complex at pH 9.2. The colored complex can be measured at 660 nm. The Beer’s law concentration range is 5–50 µg/mL, and molar absorptivity and Sandell’s sensitivity reported are 1.64 × 103 dm3/mol/cm and 0.0585 µg/cm2, respectively, in the presence of pyridine and 7.4 × 102 dm3/mol/cm and 0.78 µg/cm2 in the absence of pyridine as reported by authors. It is further mentioned that the method has been successfully applied to the determination of Ni (II) in waste water effluents from foundry region and nickel plating industry of Kolhapur city, India. The results of the method have been confirmed by the method of AAS. The authors claim this method to be simpler than the conventional method which comprise of multiple steps.

3.9 2-(Benzothiazolylazo) orcinol (BTAO) El Sheikh et al. [9] have proposed an efficient cloud-point extraction-based method for preconcentration determination of nickel in water samples using spectrophotometry. The method is based on complex formation between Ni (II) and 2-(benzothiazolylazo) orcinol. The reagent BTAO reacts with Ni (II) to give a complex at pH 7.0, which is extracted using micelle-mediated extraction by non-ionic surfactant Trioton X-114 medium. The extraction phase was used for the determination of nickel at 558 nm. The Beer’s law range is 10–250 µg/mL and limit of detection is 2.0 ng/mL as mentioned. The method could be successfully applied to water samples with recovery from spiked samples to the tune of 95.85–78.50%.

3.10 5-(2-Benzothiazolyazo)-8-hydroxyquinolene (BTAHQ) Moalla et al. [10] have reported a rapid yet simple dispersive liquid-liquid micro extraction (IL-DLLME)-based method for spectrophotometric determination of Ni (II) using BTAHQ reagent. This is described that IL-DLLME procedure was performed by using microliters of ionic-liquid (RTIL) 1-hexyl-3-methylimidazoliumhexafluorophosphate [C6 mim] [PF6] as the extractant whereas methanol was a dispersive solvent. The complex absorbed at 682 nm and measured against a reagent blank. The detections limit reported is 9.8 ng/L with standard deviation as 1.47%. The method has been successfully applied for the determination of nickel in environmental samples.

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Chapter 3 Analytical reagents having N, S, O as donor atoms

3.11 1-(2-Hydroxyphenyl) thiourea (HPTU) Sunil et al. [11] have reported a sensitive simultaneous determination method for Cu (II) and nickel (II) using HPTU as an analytical reagent. The method involves enhancement of sensitivity of the method by pyridine as an activator, acetyl trimethylammonium bromide and sodium diodecyl sulfate as surfactants. The detection limits reported are 0.5–100 ng/mL for nickel. The method has been extended to the determination of nickel in plant samples too.

3.12 2,6-Diacetylpyridine bis(4-phenyl-3-thiosemicarbazone) (2,6-DAPBPTSC) Ramachandraiah et al. [12] have synthesized and applied 2,6-DAPBPTSC for sensitive and selective determination of nickel in medicinal leaves and soil samples. The reported method uses complex formation and extraction into ISO-amyl alcohol, with determination at 400 nm spectrophotometrically. The method is optimized at pH 4.0 in the Beer’s law range of 0.58–5.87 ppm. The reported value of molar absorptivity is 1.44 × 104 L/mol/cm and Sandell’s sensitivity as 4.076 × 10−3 µg/cm2. The detection limit of the method is 0.0053 µg/mL. This has been successfully applied to Ni (II) determination in medicinal leaves and soil samples as informed. The results obtained have been verified with those of AAS.

3.13 3,4-Dihydroxy-5-methoxy benzaldehyde thiosemicarbazone (DHMBTSC) Hymavathi et al. [13] have proposed a novel chromogenic reagent DHMPTSC for spectrophotometric determination of Ni (II). The reagent forms a yellow-colored complex with Ni (II) which absorbs at 385 nm. Validity of Beer’s law is in the concentration range 0.176–1.467 µg/mL. The method has molar absorptivity of 2.1 × 104 L/mol/cm for this complex and 1.232 µg/mL of Sandell’s sensitivity value. A 1:1 complex having stability constant value 3.08 × 106 is also reported. It is referred to as a rapid, sensitive and selective method for trace determination of Ni (II) in edible oil samples.

3.14 Cinnamaldehyde thiasemicarbazone (CMTSC) Using the above reagent as a chromogen Gopala et al. [14] have developed a simultaneous spectrophotometric determination method for Ni (II) and Co (II). The reagent CMTSC forms an intense yellow complex with Ni (II) in the presence of miceller medium Triton-X-100 (5%) at pH 9.0 λmax value of Ni (II) is 440 nm. The reported molar

3.18 3-Hydroxy-3-isopropyl-1-(4-sulphonamidophenyl) triazene

51

absorptivity is 4.77 × 104 L/mol/cm and 0.0012 µg/cm2 is the Sandell’s sensitivity value. However first-order derivative spectrophotometric determination for simultaneous determination of Ni (II) and Co (II) has been done at λmax 460 for Ni (II) and 420 nm for Co (II). The method has been reported for some alloy steels and soil samples.

3.15 3-Hydroxy-3n-propyl-1-(4-sulphonamidophenyl) triazene Rehana et al. [15] have reported the abovementioned reagent for spectrophotometric determination of Ni (II). It is described that at pH between 6.9 and 7.3 N(II) forms a complex with the reagent which absorbs at 400 nm. The molar absorptivity 6,743 dm3/ mol/cm and Sandell’s sensitivity of 8.61 ng/cm2 has been reported.

3.16 4-Hydroxybenzaldehyde thiosemi-carbazone (HBTS) Satheesh et al. [16] have synthesized and used 4-hydroxybenzaldehyde thiosemicarbazone for spectrophotometric determination of nickel at microgram level. The reagent HBTS reacts with Ni (II) in the pH range 5–6 (RT) giving a green complex in the ratio [Ni2+: HBTS: 1: 2]. The colored complex absorbs at 362 nm in the Beer’s law concentration range 0.117–1.117 µg/mL. The method is applicable even in the presence of several interfering ions and could be successfully extended to determination of nickel in water, waste water as well as alloy samples.

3.17 2,4-Dihydroxybenzaldehyde thiosemicarbazone (DHBATSC) Modawe et al. [17] have developed an H-point standard addition method for simultaneous spectrophotometric determination of Co (II) and Ni (II) using DHBATSC. At pH 7.0 and in Triton X-100 micellar medium the chromogenic reagent yields a colored complex with absorbance at the selected pair 463 and 500 nm, and it was monitored by standard addition of cobalt. In the concentration ratio of 5:1 to 1:5 (wt/wt), Co (II) and Ni (II) could be determined simultaneously. The proposed method was successfully used for the determination of cobalt and nickel in synthetic spiked mixtures as well as vitamin B12 samples.

3.18 3-Hydroxy-3-isopropyl-1-(4-sulphonamidophenyl) triazene Khanam et al. [18] have reported the use of above reagent in spectrophotometric determination of Ni (II). It is reported that the complex with the reagent absorbs at 395 nm in the pH range 6.7–7.3. The Beer’s law concentration range is 1 × 10−5 to 6 ×

52

Chapter 3 Analytical reagents having N, S, O as donor atoms

10−5 m for 1:2 complex. The molar absorptivity and Sandell’s sensitivity values are 7,076 dm3/mol/cm and 8.29 ng/cm2 as reported. The log β values found from two different methods are also reported as 9.46 and 9.43.

3.19 2-Acetylpyridine thiosemicarbazone/semicarbazone (APT)/APS Babu et al. [19] have reported a non-extractive spectrophotometric method for the determination of nickel (II) using APT and APS. The method involves reaction of Ni (II) with the reagents in acidic and basic medium (APT and APS). The Ni (II) complexes of APT and APS absorb at 375 and 350 nm, and complexes are 1:2 and 1:3 in ratio. The reported molar absorptivity for the two complexes is 1.6 × 104 and 2.8 × 104 L/mol/cm, whereas Sandell’s sensitivity is 0.0035 and 0.0210 µg/cm2. Further the two complexes, that is, APS-Ni and APT-Ni obey Beer’s law in concentration range between 0.09 and 094 (APS) and 0.47–4.7 (APT) complex, respectively. The method has been applied successfully to the determination of Ni (II) in water and environmental sample as mentioned by the authors.

3.20 2-Acetylpyridine-4-Methyl-3-thiosemicarbazone (APMT) Reddy et al. [20] have developed APMT as a new chromogenic reagent for spectrophotometric determination of Ni (II) based on extraction. It is described that the ligand reacts with Ni (II) to give in yellow-colored complex which can be extracted into n-hexanol from sodium acetate–acetic acid buffer of pH 6.0. The maximum absorbance of the complex is at 375 nm. The complex system follows Beer’s law in the concentration range 0.235–2.43 µg/mL with excellent linearity and coefficient of 0.999. The authors report molar absorptivity value of 2.16 × 104 L/mol/cm with Sandell’s sensitivity as 0.003 µg/cm2. The method is recommended as a sensitive and rapid spectrophotometric one even in the presence of several diverse ions. Applicability of this method has been mentioned for soil samples and alloy samples like CM 247 LC, 1N 718, BCS 233, 266, 253 and 251, which validate this method. Even the results obtained using this method is comparable to those obtained using AAS.

3.21 p-Chloroacetophenon-4-(2ʹ-carboxy-5ʹ-sulphophenyl)-3thiosemicarbazone (p-CACST) Patel et al. [21] have developed a method for spectrophotometric determination of Ni (II) in DMF using p-CACST as a reagent. At pH 7.0–8.5 the reagent gives a dark green complex absorbing at 315 nm. The reported molar absorptivity of this complex is

References

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11.278 × 103 L/mol/cm. It is mentioned that this reagent is selective and strong chelating one for the determination of nickel (II). The authors have reported 6.293 × 1011 as stability constant of the complex.

3.22 5-Bromosalicylaldehyde thiosemicarbazone (5-BSAT) Le Ngoc et al. [22] have reported a spectrophotometric determination method for nickel (II) using 5-BSAT; simultaneously with zinc (II) in waste water. The H-point standard addition method has been optimized and validated too. Ni (II) forms a complex with reagent which absorbs at 378 nm, and the Beer’s law is followed in the concentration range of 2.0 × 10−6 M to 6.0 × 10−6 M. The reported molar absorptivity value is ε = 0.92 × 104 L/mol/cm. The authors also recommend the method for the analysis of waste water samples.

3.23 6-(Anthracen-2-yl)-2,3-dihydro-1,2,4-triazine-3-thione (ADTT) Tehrani et al. [23] have synthesized and used ADTT as chromogenic reagent for derivative spectrophotometric determination of nickel (II) and copper (II). The metals have been determined by zero-crossing method in the second, third and fourth-order derivative spectra after derivatizing in basic medium. The Beer’s law range is 5–35 µg/mL and absorbances are 447 (first order), 400 nm (third order) and 385 (fourth order). The proposed method has been recommended as a simple and accurate one.

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[3]

[4]

[5]

Reddy, N. C. G. A rapid spectrophotometric determination of Ni (II) in medicinal plant materials and water samples using NʹʹNʹʹʹʹ-[1E, 1ʹʹE)-(propane-1,3-diylbis (sulfanediyl)) bis 1-4 bromophenyl) ethan-2yl-1-ylidene)) bis (2-hydroxybenzohydrazide) as a selective and sensitive analytical reagent. International Journal of Pharmaceutical Sciences and Research. 2021, 12(2), 838–844. Zalov, A. Z.; Kullev, K. A.; Shiralieva, S. M.; Askerova, Z. Q. Extraction spectrophotometric study on the complex formation in the Ni (II)-4-hydroxy-3-thiolbenzoic acid–diphenylguanidine system. Indo American Journal of Pharmaceutical Sciences. 2018, 5(12), 15681–15689. Zalov, A. Z.; Verdizadeh, N. A.; Aliyeva, K. R.; Abaskulieva, U. B.; Iskenderova, K. O.; Bakhshieva Ulviyya, S. H. 3-Phenyl-2,4-thiazo lindion as an analytical reagent for extraction–photometric determination of nickel (II). International Journal of Chemical Studies. 2018, 6(6), Pt. AM, 2258–2262. Patil, S. K. Solvent extraction and spectrophotometric determination of Ni (II) by using 5-bromo salicylidene-2-aminothiophenol as an analytical reagent. International Journal of Pharma and BioSciences. 2017, 8(3), 196–201. Ali, A. M.; Mohammad Hussain, J. Synthesis and solvatochromic studies of 2-amino-3-phenolazo 1-(4sulfophenyl)-3-methyl-5 pyrazolone and use it for the determination of trace amount of Nickel (II) in blood samples. International Journal of Bio-assays. 2016, 5(10), 4920–4926.

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Chapter 3 Analytical reagents having N, S, O as donor atoms

Kuliev, K. A.; Verdizade, N. A.; Mamedova, S. A. Extraction – Spectrophotometric study of ternary complexes of Co (III) and Ni (II) using dithiolphenols and diphenylguanidine. World Journal of Pharmacy and Pharmaceutical Sciences. 2017, 6(3), 60–76. Bazel, Y.; Tupys, A.; Ostapuk, Y.; Tymoshuk, O.; Matiychukvasyl. A green cloud point micro extraction method for spectrophotometric determination of Ni (II) ions with 1-[(5-benzyl-1,3-thiazol-2-yl) diazenyl] naphthalene-2-ol. Journal of Molecular Liquids. 2017, 2429, 471–477. Kamble, G. S.; Joshi, S. S.; Kolekar, A. N.; Zanje, S. B.; Kolelar, S. S.; Ghule, A. V.; Gaikwad Shashikant, H.; Anuse, M. A. A sensing behaviour synergistic liquid-liquid extraction and spectrophotometric determination of nickel (II) by using 1-(2ʹ-4ʹ-dinitro aminophenyl)-4,4,6-trimethyl-1,4dihydropyrimidine-2-thiol. Analysis of foundry and electroless nickel plating of waste water. Separation Science and Technology (Philadelphia, PA, USJ). 2017, 52(14), 2238–2251. El Sheikh, R.; Gouda Ayman, A.; Mostafa, A. H.; El Din, N. S. Development of efficient cloud point extraction method for preconcentration and spectrophotometric determination of nickel in water samples using 2-(benzothiazolyl-azo) orcinol. International Journal of Pharmacy and Pharmaceutical Sciences. 2015, 7(10), 176–184. Moalla, S. M. N.; Amin, A. S. An ionic liquid-based micro extraction method for highly selective and sensitive trace determination of nickel in environmental and biological samples. Analytical Methods. 2015, 7(24), 10229–10237. Sunil, A.; Rao, S., . J. First derivative spectrophotometric determination of copper (II) and nickel (II) simultaneously using 1-(2-hydroxyphenyl) thiourea. Journal of Analytical Chemistry. 2015, 70(2), 154–158. Ramachandraiah, C.; Admargyna, R. S.; Sreedevi, P.; Reddy, A. V. A new analytical reagent 2, 6diacetypyridine bis (4-phenyl-3-thiosemicarbazone) for the determination of Ni (II) in medicinal leaves and soil samples. Journal of Pharmacy and Chemistry. 2013, 7(3), 9–15. Hymavathi, M.; Viswanatha, C.; Devanna, N. A study on synthesis of novel chromognic organic reagent 3,4-dihydroxy-5-methoxy benzaldehyde thiosemicarbazone and spectrophotometric determination of nickel (II) in presence of triton X–100. Research Journal of Pharmaceutical, Biological and Chemical Sciences. 2014, 5(5), 625–630. Krishna, D. G.; Kethani, D. C. Simultaneous determination of Ni (II) and Co (II) using cinnamaldehyde thio-semicarbazone by first order derivative spectrophotometric technique. World Journal of Pharmaceutical Research. 2014, 3(Suppl. 5), 563–569. Khanam, R.; Saba, K.; Dashora, R. 3-Hydroxy-3-n-propyl-1-(4-sulphonamidophenyl) triazene: a new reagent for spectrophotometric determination of nickel (II). Oriental Journal of Chemistry. 2014, 30 (2), 837–841. Satheesh, K. P.; Rao, V. S. Spectrophotometric determination of Nickel and microgram level in environmental matrices using 4-hydroxybenzaldehyde thiosemicarbazone. Journal of the Indian Chemical Society. 2014, 91(5), 853–858. Modawe, N. M.; Eltayeb, M. A. Z. H-Point Standard addition method for simultaneous spectrophotometric determination of cobalt (II) and nickel (II). Advances in Analytical Chemistry. 2013, 3(1), 1–7. Khanam, R.; Saba, K.; Dashora, R.; Chauhan, R. S.; Goswami, A. K. Analytical application of 3-hydroxy -3-iso propyl-1-(4-sulphonamidophenyl) triazene in the spectrophotometric determination of nickel (II). International Journal of Pharmaceutical, Chemical and Biological Sciences. 2013, 3(3), 704–707. Babu, S. V.; Reddy, K. H. Non-extractive spectrophotometric determination of Ni (II) using 2acetylpyridine thio semicarbazone/semicarbazone in environmental samples and alloys. Journal of Indian Chemical Society. 2014, 91(2), 205–211. Reddy, D. N.; Reddy, K. V.; Tegene, B. M.; Reddy, V. K. Development of highly sensitive extractive spectrophotometric method for the determination of nickel (II) from environmental matrices using

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2-acetylpyridine-4-methyl-3-thiosemicarbazone. American Journal of Analytical Chemistry. 2012, 3(11), 719–726. [21] Patel, B. A.; Patel, N. C.; Malik, G. M. p-Chloroacetophenone-4-(2ʹ-carboxy-5ʹ-sulphophenyl)-3thiosemicarbazone as an extractive spectrophotometric reagent for nickel. International Journal of Chemistry (Mumbai, India). 2013, 2(2), 209–213. [22] Le Ngoc, T.; Levan, T.; Nguyen, X. C. Simultaneous spectrophotometric determination of Ni (II) and Zn (II) in waste water by H-point addition standard method using 5-bromosalicylaldehyde thiosemicarbazone. European Chemical Bulletin. 2013, 2(6), 311–314. [23] Tehrani, M. B.; Mir Kamali, S. M. S.; Souri, E.; Foroumadi, A. Derivative spectrophotometric method for simultaneous determination of nickel (II) and copper (II) using 6-(anthracen-2-yl)-2,3-dihydro1,2,4-triazine-3-thione. Asian Journal of Chemistry. 2012, 24(10), 4517–4221.

Chapter 4 Analytical reagents having N, O or S as donor atoms and miscellaneous reagents 4.1 2-(5-Cyano-2-pyridylazo)-2,4-diaminotoluene (5-CN-PADT) Han et al. [1] have developed a new method for spectrophotometric determination of Co (II) using 5-CN-PADT as a reagent. It has been described that in pH range 4.2–10.0, the reagent complexes with Co (II) to give a stable 2:1 species absorbing at 509 nm. Though in H2SO4 (2.4 mol/L) medium this can be changed to another species having two absorption peaks as 540 and 579 nm. The apparent molar absorptivity as reported is 1.36 × 105 L/mol/cm at 579 nm in the Beer’s law range 0–0.8 µg/mL. The method has been claimed to be a sensitive and selective one. The results are consistent with AAS as mentioned by the authors.

4.1.1 Triethylenetetramine Yingyao et al. [2] have proposed a method of determining cobalt in cadmium-cobalt alloy electroplating bath using triethylenetetramine reagent. It is described that Co2+ ions are oxidized to Co3+ by ammonium persulfate, which react with triethylenetetramine to give a stable red-orange complex under alkaline conditions. The contents of cobalt can be determined spectrophotometrically at λmax 490 nm. A 1.1% average deviation in determination is reported whereas recovery is from 98.3 to 102.5% as mentioned.

4.1.2 Monotetrazolium Divarova et al. [3] have studied extraction-based spectrophotometric study of Co (II)-4(2-thiazollyazo) resorcinol (TAR) with cations of monotetrazolium salts (TS). The method has been developed to find optimum conditions for Co (II). The studies include spectrophotometric determination of Co (II) using this system which follows Beer’s law. The authors recommend this method for the determination of trace Co (II) in alloys, medical and pharmaceutical samples.

4.1.3 5-Chloro-2-(pyridyl)-1,3-diaminobenzene Lu et al. [4] have proposed a method for the determination of cobalt in water using 5chloro-2-(pyridyl)-1,3-diaminobenzene as reagent. The method as reported improves https://doi.org/10.1515/9783111133300-005

4.1 2-(5-Cyano-2-pyridylazo)-2,4-diaminotoluene (5-CN-PADT)

57

samples preparation, preservation, eliminates interferences and enhances detection limit too. It is mentioned that a limit of 0.009 mg/L is raised to 4 × 0−4 mg/L using this method, with recovery of 96–101%, and the method can also be used for water, ground water, domestic sewage or even industrial waste water.

4.1.4 5-Bromo-2-hydroxy-3-methoxy benzaldehyde-4 hydroxy benzoic hydrazone (5-BHMBHBH) Saritha et al. [5] have developed a method for simultaneous determination of cobalt (II) and nickel (II) using the reagent 5-BHMBHBH as a chromogenic reagent. The abovementioned reagent gives a water-soluble yellow complex at pH 7.0 at 416 nm. This is mentioned that 416 and 440 nm were λmax used for the simultaneous determination of Co (II) and Ni (II). The molar absorptivity values at the two selected wave lengths are 2.025 ± 0.001 × 104 L/mol/cm (416 nm) and 1.845 ± 0.002 × 104 L/mol/ cm 440 nm, as mentioned by the authors. The method has been recommended as highly sensitive, selective, precise as well as rapid one for direct spectrophotometric method, extendable to alloys samples.

4.1.5 5-(5-Iodo-2-pyridylazo)-2,4-diaminotoluene (5-1-PADT) Han et al. [6] have developed a novel method for the simultaneous spectrophotometric determination of cobalt and palladium using 5-1-PADT. In stronger acidic medium of 0.6–2.4 mol/L HClO4, though Pd (II) reacted with 5-1-PADT, cobalt (II) could not. The reagent 5-I-PADT reacted with Co (II) at pH 36–10 buffer medium with strong peak at 580 and 583 nm. Thus based on the acidic chromogenic difference both of the ions could be determined simultaneous by dual wavelength overlapping spectrophotometry. Beer’s law range of Co (II) was 0–0.4 µg/mL, with molar absorptivity 2.17 × 105 L/ mol/cm, whereas the Sandell’s sensitivity also was 1.75 times higher than single wavelength method. Simultaneous determination of the two could be extended to samples of catalysts and ores too.

4.1.6 4-(5-Chloro-2-pyridylazo)-1,3-phenylenediamine (5-Cl-PADAB) Liu et al. [7] have developed a determination method for cobalt in five nickel substrates using reagent 4-(5-chloro-2-pyndylazo)-1, 3-phenylenediamine (5-Cl-PADAB). The determination involves optimum conditions for cobalt in pyrometalurgical nickelbased alloys such as samples preparation, optimal determination, wavelength and the

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quantity of chelating agent for color of complex. This is mentioned that the method is applicable for the determination of cobalt in pyrometallurgical samples.

4.1.7 Salicyl fluorone Chen et al. [8] have developed a sensitive method for the spectrophotometric determination of Co (II) using salicyl-fluorone as a reagent in the presence of cetylpyridinium bromide as solubilizer. It is described that reagent in basic medium reacts with Co (II) to give a complex having λmax at 540 nm. The Beer’s law range is 3–40 µg/L with a detection limit of 0.1 µg/L. The method can be successfully applied to trace Co (II) determination even in water samples.

4.2 Miscellaneous reagents 4.2.1 Wright stain Chen [9] has developed a novel spectrophotometric method for the determination of cobalt using decoloration of Wright stain by Co (II) in a weak acidic solution. The method is detailed and it is mentioned that the complex has λmax at 660 nm in the Beer’s range of 0.04–0.40 µg/mL of Co (II). The molar absorptivity is 1.26 × 105 L/mol/ cm. It is further mentioned that method is applicable to the determination of cobalt (II) in tea and results are comparable to the results of ICP-MS.

4.2.2 Murexide Elsherif et al. [10] have studied complex formation and the stoichiometry of murexide complexes with Co (II). It has been described that Co (II)-murexide complex absorbs at 480 nm with 2:1 (M:L) composition. The stability constants and molar absorptivity reported by the authors are 9.8 × 1011 and 18,235 L/mol/cm for the Co (II) complex.

4.2.3 Crown ether (DB-18-C6) Saoud et al. [11] have developed and used reagent crown ether (DB-18-C6) for simultaneous spectrophotometric determination of Co (II) and W (VI) in high speed steels. It is described that the ligand reacts with Co (II) to give yellowish [(DB-18-C6 NH4)]+2 [Co (SCN)4]2− and tungsten complex at overlapping λmax of 415 and 621.26 nm, respectively.

4.2 Miscellaneous reagents

59

The complex of Co (II) could be extracted at pH range 4–10, and Beer’s law range for Co (II) is 29.45–147.25 µg/mL. The reported value of molar absorptivity is 1.7 × 104 L/ mol/cm. It is further reported that this method can be successfully applied to simultaneous determination of Co (II) and W (VI) in HS2-9-1-8 type of high speed steel, which contains 2% W, 9% Mo, 1% V and 8% Co (II).

4.2.4 Orange G and m-cresol purple Chang et al. [12] have developed a spectrophotometric determination method for cobalt using catalytic kinetics based on oxidation of orange G and m-cresol purple by H2O2. The dual-wavelength dual-indicator-based method uses oxidation of Orange (OG) and m-cresol purple (m-CP), Co2+ as catalyst. The absorbance with and without catalytic system has been measured at 500 and 575 nm under the Beer’s law range of 0.004–0.04 µg/mL. However, the detection limit achieved is 3.0 × 10−5 µg/mL. The method can successfully determine Co (II) in vitamin B12 injections with recovery range of 95.8–102.8% as reported.

4.2.5 Methylene blue (MB) Chen et al. [13] have described sensitive spectrophotometric method for the determination of trace Co2+ in water. It is described that the method is based on acetate enhanced catalytic decolorization of methylene blue (MB) with Co2+ which is a catalyst and peroxymono sulfate is an oxidizing agent. The reported λmax is 664 nm in the linearity range from 0.20 to 7.0 µg/L. The molar absorptivity value is ε = 5.88 × 104 L/mol/ cm, where the detection limit is 0.10 µg/L. It is mentioned that method can be applied to Co2+ determination in practical samples.

4.2.6 Esomeprazole Rangnath et al. [14] have used esomeprazole as a new chromogenic reagent for the determination of Co (II). It is described that Co (II) forms a greenish yellow-colored complex which shows an absorbance maximum at 355 nm. At pH 8.0, the Beer’s law linearity range is 0.8–8.0 µg/mL. The molar absorptivity and Sandell’s sensitivity of this complex have been reported to be 4.56 × 104 L/mol/cm and 0.007526 µg/cm2, respectively. A 1:2 complex with stability constant value of 2.21 × 105 is also mentioned. The method has also been applied to alloy steel samples successfully.

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4.2.7 Nitroso-R-salt Qi et al. [15] have proposed a spectrophometric determination method for Co (II) using nitroso-R-salt as ligand. The traditional method using nitroso-R-salt has been improved to determine Co (II) in zinc sulfate solution. It is mentioned that Co (II) reacts with ligand to give a red complex, in acetic acid, sodium acetate buffer medium with pH 5.5–7.0. The absorption maximum is at 530 nm. Beer’s law range mentioned is between 0.1 and 5.0 µg/L.

4.2.8 Brilliant green Li et al. [16] have used complex formation of Co (II) – potassium thiocynate – light green system via new fading spectrophotometry for Co (II) determination. The method studies optimal condition of determination like acidity, quantity of KCNS, brilliant green, reaction condition such as temperatures as well as time. The λmax reported is 624 nm and the Beer’s law range is 0–0.30 µg/mL, molar absorptivity value is 2.2 × 105 L/mol/cm for detection limit 2.5 µg/L. Further the results obtained are consistent with those obtained using AAS.

4.2.9 Chelating resin Badawy et al. [17] have developed a method for the separation and determination of Co (II) using precipitation and chelating resin from mixed-waste mobile phone batteries, which have LICoO2 as active material. The method involves leaching with 4 M HCl, and ions removed selectively at 5.5 pH. Cobalt is then recovered by chelating resin. The method determines cobalt at λmax 510 nm. The resin used is polyamidoxime.

4.2.10 Salen Dhahir et al. [18] have developed a cloud-point extraction spectrophotometric method for the determination of copper, chromium and cobalt using salen as a chromogenic reagent. The authors have applied the method in environment samples like waste water of Rustimiyah city in Iraq and other sewage samples. It is described that salen in the presence of Triton X-100 complexes with cobalt to give λmax at 378 nm. The linearity of the system is 10–70 µg/L, with detection limit of 2.19 µg/L as mentioned.

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4.2.11 Methylene blue Gao et al. [19] have used catalytic spectrophotometric method for trace determination of Co (II) in tea. It has been described that in the medium of ammonia-ammonium fluoride and sodium dodecyl benzene sulfonate micelle, and Co (II) traces have a catalytic effect on reaction between MB and H2O2. It is mentioned that under optimum conditions Beer’s law is used in 4 µg/L–240 µg/L of Co (II). At 660 nm, the non-catalytic and catalytic systems have good absorbance difference. The detection limit of 2.55 × 10−6 g/L could be achieved and sensitivity is increased by two times than in the absence of dodecylbenzene sulfonic acid sodium micelle.

4.2.12 Nitroso-R-salt Mai et al. [20] have developed a method for cobalt determination in the purifying residue of zinc hydrometallurgy. It is mentioned that at pH 7.5, cobalt forms a stable complex with nitroso R-salt. This complex absorbs at 522 nm in the Beer’s law concentration range 0–50 µg/mL. The reported detection limit is 0.0274 µg/mL.

4.2.13 Carmine Zhai et al. [21] have proposed a new catalytic spectrophotometric method for the determination of trace cobalt (II) using caramine. The method is based on catalytic effect of Co (II) on the oxidative discoloration of caramine with H2O2 in 1.0 × 10−2 M NaOH. It has been mentioned that the Beer’s law concentration is 7.43 × 10−3–0.198 µg/mL for cobalt. Further, the apparent molar absorptivity is 1.94 × 105 4 mol/cm with detection limit of 6.23 ng/mL. The method as mentioned has been successfully applied to trace cobalt determination of vitamin B12 with satisfactorily results.

4.2.14 Alizarin Red-S Rohilla et al. [22] have developed a method for simultaneous determination of zinc (II) and cobalt (II) using first-order derivative spectrophotometry and Alizarin Red S (ARS) as chelating agent. It is described that the reagent forms a pink-colored complex with metal in pH range 7.0 and 1.0 (ARS in Triton X-100 micellar media). Further, the overlapping peaks of Zn (II)-ARS and Co (II)-ARS are found at λmax 535 and 548 nm, respectively. The first derivative spectra were determined by calculating the rate of change in absorbance as a function of wavelength. However, using this method the molar absorptivity and Sandell’s sensitivity of Co (II) complexes are 1.358 × 104 L/mol/

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Chapter 4 Analytical reagents having N, O or S as donor atoms and miscellaneous reagents

cm and 0.007 µg/cm2. This has been further applied to the determination of Co (II) in spiked water samples.

4.2.15 Picramazochrom Zhong et al. [23] have proposed a method for cobalt determination in copper alloys using picramazochrom as a complexing agent. The reagent in ammonium citrate-ammonia water solution at pH 10 reacts with cobalt to give a green complex which has a λmax at 650 nm. Beer’s law range, which this system functions, is 0–2.0 µg/L and molar absorptivity is reported as 2.62 × 104 L/mol/cm. The authors forward that this method has been applied to copper alloy, for cobalt, and results are consistent with the other methods.

4.2.16 Phenosafranine and potassium periodate Xie et al. [24] have developed a catalytic spectrophotometric method for trace determination of cobalt (II) using oxidation reaction of phenosafranine by potassium periodate. In the presence of nitrilotriacetic acid as an activator and HAC-NaAc buffer medium of pH 4.0 Co (II) can be determined in Beer’s law range of 0.010–1.20 µg/ 25 mL. The detection limit is 8.84 × 10−10 g/mL as mentioned.

4.2.17 Ninhydrin Mahmood et al. [25] have proposed a method for Co (II) determination using ninhydrin as a reagent. At pH 8.2 in sodium acetate buffer the reagent gives a violet complex which has λmax at 395 nm. The method can be extended to Co (II) determination in various samples as it is a selective, rapid and sensitive one.

4.2.18 Quercetin Yu et al. [26] have used quercetin (Qu) as a reagent for spectrophotometric determination of cobalt (II). It is mentioned that in HAC-NH4AC buffer, pH 4.7, Co (II) reacts with quercetin to give a complex which has λmax at 584 nm. The Beer’s law concentration range is 2.0 × 10−5 to 1.1 × 10−4 mol/L; with 1:2 composition, it has a stability constant value 2.7 × 107 L2/mol2 as mentioned.

References

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4.2.19 Hydrophobic AZO dye Gavazov et al. [27] have applied hydrophobic azo dye for a centrifuge-less cloud-point extraction spectrophotometric method for the determination of cobalt. The dye 6hyxyl-4-(2-thiazolylazo) resorcinol (HTAR, HZL) has been used for trace determination of cobalt. It is described that 1:2 (Co: HTAR) complex, [Co (III) (HL(-))] (o) is extracted and show λmax at 553 nm. Optimum conditions for centrifuge-less cloud-point extraction (CL–CPE) were worked out as 1 × 10−5 mol (L−1) of HTAR, 1.64% of Triton X-114, pH 7.8, with an incubation time of 20 min at 50 °C, with cooling time 30 min at −20 °C. Various parameters for detection are mentioned. The molar absorptivity is 2.63 × 105 L/mol/cm, with linear range 5.4–189 ng/mL and detection limit 1.64 ng/mL reported by the authors. The method has various advantages such as no use of organic solvent and is cheap, simple, environment friendly as well as convenient. The method has been successfully applied to the determination of cobalt in real samples like steel alloys, dental alloys, rain water and ampoules of vitamin B12.

References [1]

Han, Q.; Hao, T.-T.; Huo, Y.-Y.; Xiao-hui. Spectrophotometric determination of Co (II) with a new reagent 2-(5-cyano-2-pyridylazo)-2,4-diaminotoluene. Fenxi Kexue Xuebao. 2019, 35(2), 210–214. [2] Yingyao, N.; Chongwu, G. Spectrophotometric determination of cobalt chloride in potassiumchloride-cadmium-cobalt alloy electroplating bath. Diandu Yu Tushi. 2020, 39(2), 37–38. [3] Divarova, V. V.; Stojnova, K. T.; Racheva, P. V.; Lekova, V. D. Spectrophotometric study of the complex formation of anionic chelates of cobalt (II) with monotetrazolium cations. Journal of Applied Spectroscopy. 2017, 84(2), 231–236. [4] Haoyun, L.; Hua, L.; Hua, L. 5-Chloro-2-(pyridyl)-1,3-diaminobenzene spectrophotometric method for determination of cobalt in water. Zhongguo Huanjing Jiance. 2016, 32(1), 117–122. [5] Saritha, B.; Reddy, T. S. Simultaneous spectrophotometric determination of cobalt (II) and nickel (II) using 5-BHMBHBH. European Journal of Biomedical and Pharmaceutical Sciences. 2015, 2(5), 492– 499. [6] Han, Q.; Hao, T.-T.; Huo Yan, Z.; Yang, X.-H. Simultaneous determination of cobalt and palladium by 5-(5-iodo-2-pyridylazo)-2,4-diaminotoluene dual wavelength overlapping spectrophotometry. Yejin Fenxi. 2015, 35(3), 64–68. [7] Liu, X.; Shen, Y.-H.; Ge, H.-L.; Sun, B.-L.; Lu, N.-N. Determination of cobalt in Fire smelting nickel substrate material by 4-(5-chloro-2-pyridylazo)-1,3-phenylenediamine spectrophotometry. Yejin Fenxi. 2012, 32(12), 64–68. [8] Zhe, C.; Hua, L. A method of high sensitivity and in-situ determination of trace cobalt (II) in water samples with salicyl fluorone. Water Sciences and Technology. 2014, 70(7), 1182–1187. [9] Chen, J. Spectrophotometric determination of trace cobalt in Tea using Wright Strain. Guangdong Huagong. 2021, 48(20), 233–234. [10] Elsherif, K. M.; Nabbra, F.; Ewlad-Ahmed, A. M.; Huda Elkebbir, N. Spectrophotometric complex formation study of murexide with nickel and cobalt in aqueous solution. To Chemistry Journal. 2020, 5, 40–47.

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[26] [27]

Chapter 4 Analytical reagents having N, O or S as donor atoms and miscellaneous reagents

Soud, A.; Nee mes dour, S. H.; Nabieva, A.; Hamada, B.; Amrane, A.; Mohammad, N. Liquid liquid extraction and simultaneously spectrophotometric determination of Co (II) and W (VI) using crown ether (DB-18-(6) in aqueous media in high speed steel. International Journal of Environmental Analytical Chemistry. 2022, 102(8), 1814–1824. Chau, H.-M.; Du, J.-J.; Bai, L.; Zhao, W.-R. Catalytic kinetic spectrophotometric determination of trace cobalt based on oxidation of orange G and m-cresol purple by hydrogen peroxide. Fenxi Kexue Xuebao. 2015, 31(5), 734–736. Chen, M.; Dong, X.; Yao, L.; Song, Z.; Zhu, L. Sensitive spectrophotometric determination of trace level Co2+ in water based on acetate enhanced catalysis of Co2+. Microchemical Journal. 2019, 146, 327–331. Ranganath, B.; Basha, V. S.; Ravindranath, L. L.; Ramana, P. V. Simple selective and non-extractive spectrophotometric determination of Co (II) using esomeprazole. Research Journal of Pharmaceutical, Biological and Chemical Sciences. 2015, 6(3), 1108–1116. Qi, Y.-J.; Zhang, X.; Shen, Q.-F.; Zhang, Y.-P.; Xu, K.; Jiao, Z.-L. Determination of cobalt in zinc sulfate solution with nitroso-R-salt spectrophotometry. Kuangye (Beijing, China). 2014, 23(4), 97–100. Li, R.-Y.; Yin, Y.-Y.; Tao, M.-T. Determination of cobalt content in yeast by fading spectrophotometry with brilliant green. Zhongguoe, Tiaoweipin. 2014, 39(4), 112–115. Badawy, S. M.; Nayl, A. A.; El Khashab, R. A.; El-khateeb, M. A. Cobalt separation from water mobile phone batteries using selective precipitation and chelating resin. Journal of Material Cycles and Waste Management. 2014, 16(4), 739–746. Dhahir, S. A.; Bakir, S. R. Cloud point extraction spectrophotometric determination of copper, chromium and cobalt by Salen as reagent in waster water of Iraq. Asian Journal of Chemistry. 2014, 26(16), 5305–5310. Gao, Y.; Wang, X.-J. Catalytic spectrophotometric determination of trace cobalt (II) in tea. Shipin Yanjiu Yu Kalifa. 2013, 34(17), 77–79. Mai, Y.-Q.; Huang, H.; He, Y.; Zhuang, D.-L.; Wu-jie, F.; Zhang, Q.-W. Determination of Co (II) in the purifying residue of zinc hydrometallurgy by spectrophotometry with nitroso-R salt. Guangzhou Huangong. 2014, 42(6), 99–101, 107. Zhai, H.-Y.; Tan, X.-R.; Huang, C.-H.; Wang, B. Catalytic spectrophotometric method for determination of trace cobalt (II) with carmine. Fenxi Shiyanshi. 2012, 31(11), 21–23. Rohilla, R.; Gupta, U. Simultaneous determination of Zinc (II) and cobalt (II) by first order derivative spectrophotometry in Triton X-100 micellar media. Research Journal of Chemical Sciences. 2012, 2(11), 8–13. Zhong, G.; Huang, Q.; Tang, X. Spectrophotometric determination of cobalt in copper alloy with picramazochrom. Yejin Fenxi. 2012, 32(1), 68–70. Xie, J.-Y.; Lei, M.-J.; Zhang, Y.-H. Catalytic spectrophotometric determination of trace cobalt (II) based on phenosafranine by potassium periodate. Fenxi Kexue Xuebao. 2012, 28(1), 104–106. Mahmood, K.; Wattoo, F. H.; Wattoo, M. H. S.; Imran, M.; Muhammad Javaid, A.; Tirmizi, S. A.; Wadood, A. Spectrophotometric estimation of cobalt with ninhydrin. Saudi Journal of Biological Sciences. 2012, 19(2), 247–250. Yu, Y.; Guo, Y.; Hou, H. Study on the complex of cobalt (II)-quercetin by spectrophotometry. Gungpu Shiyanshi. 2012, 29(1), 191–194. Gavazov, K. B.; Racheva, P. V.; Milcheva, N. P.; Divarova, V. V.; Denitsa Dimitrova, K.; Saravanka, A. D.; Gene, F. Use of hydrophobic azo dye for the centrifuge-less cloud point extractionspectrophotometric determination of cobalt. Molecules (Basel, Switzerland) 2022, 27 (15), 4725. DOI10.3390/molecules27154725.

Chapter 5 Analytical reagents having N–O as donor atoms 5.1 2-(5-Bromo-2-pyridylazo)-5-dimethyl-aminophenol (5-Br-PADAP) Sonia et al. [1] have developed a derivative spectrophotometric method for the determination of cadmium and cobalt in environmental and standard samples. It has been described that in the presence of cationic surfactant cetylpyridinium chloride trace cobalt can be determined by complex formation with 5-Br-PADAP. At pH 9.5 λmax is 558 nm, with molar absorptivity as 1.26 × 105 L/mol/cm and Sandell’s sensitivity of 0.89 ng/cm2. The authors recommend this as a rapid, green, non-extractive procedure for simultaneous determination of Cd and Co (II).

5.2 N,Nʹ-bis(salicylidine)-ethylenediamine (salen) Ahmed et al. [2] have proposed a new spectrophotometric reagent salen for the determination of picotrace cobalt. In a slightly acidic medium (0.001–0.003 M H2SO4) salen gives a light orange chelate with cobalt (II). The λmax is at 459 nm. The reported values of molar absorptivity and Sandell’s sensitivity are 6.04 × 105 L/mol/cm and 5.0 µg/cm2. A 1:1 complex in Beer’s law range of 0.001–40 mg/L of Co (II) with the detection limit of 0.1 µg/L is mentioned. It is further mentioned that this method can be applied to several certified reference materials like steel, alloys bovine liver, human hair, drinking water, soils and sediments. Equally successfully, it could be used for Co (II) determination in human blood, urine and milk. The method is highly precise and accurate as reported.

5.3 1-(2-Pyridylazo)-2-naphthol Ezati et al. [3] have developed a continuous sample drop-flow-based micro extraction method for Co (II) determination using 1-(2-pyridylazo)-2-naphthol as a reagent. A new mode of liquid phase micro extraction method has been developed (CSDF-ME), which can determine cobalt in water samples. The enrichment factor is 167 for 20 mL samples with the detection limit of 1.3 µg/L. The method has been verified and recommended on the basis of synthetic samples spiked with known amounts of cobalt.

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5.4 4-Nitro-o-phenylenediamine-salicylaldehyde Xia-hong et al. [4] have developed a method for Co (II) using 4-nitro-o-phenylenediaminesalicylaldehyde (NADPS) as a complexing agent. The reagent reacts with cobalt at pH 9.60 in Na2 CO3-Na HCO3 buffer system to give 1:1 complex showing λmax at 530 nm. Beer’s law concentration range is 0.06–0.47 mg/L. The reported correlation coefficient is 0.996 with detection limit of 0.03 mg/L. However, molar absorptivity is 3.8 × 104 L/mol/cm. The method is verified with the results of AAS.

5.5 (1,5-Dimethyl-2-phenyl-4-[(2,3,4-trihydroxyphenyl) diazenyl)-1H-pyrazol-3 (2H)-one) (DPTPD) Essa et al. [5] have used DPTPD for spectrophotometric determination of cobalt (II) and Pb (II). The reagent absorbs at 381 nm. While Co2+ complex absorbs at 430 nm at pH 7.5, giving a purple reddish complex. The Beer’s law concentration range is 1–25 ppm. The reported molar absorptivity value is 1.02 × 104 L/mol/cm and Sandell’s sensitivity is 0.0725 µg/cm2 at 430 nm. The method has been applied to cobalt determination in filling samples too. It is mentioned that the reagent has antimicrobial and antioxidant properties too.

5.6 2-{[(2-Mercurychlorid) 4-methyl phenylimino] methyl} phenol (K) Aziz Fatima et al. [6] have developed a selective and sensitive reagent for the determination of cobalt. At pH 7.0 cobalt reacts with K to form a 1:1 complex with λmax at 389 nm. The molar absorptivity is 0.02 L/mol/cm and Sandell’s sensitivity is 0.013 µg/ cm2 as reported for cobalt, with the detection limit of 0.039 mg/L. The molar absorptivity is 0.02 L/mol/cm and Sandell’s sensitivity is 0.013 µg/cm2 as reported for cobalt, with the detection limit of 0.039 mg/L.

5.7 1-(2-Pyndylazo)-2-naphthol Chenz et al. [7] have proposed a detection method for cobalt using 1-(2-pyridylazo)-2naphthol and prepared a powder based on reaction of Co (II) and the reagent. The complex absorbs at 585 nm in the range of 0.05–0.07 µg/L. The limit of detection is 0.02 mg/L. The method has been consistent with the results obtained using ICP-AES.

5.11 4-(Nitrophenyl azo imidazole) NPAI

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5.8 2-Hydroxy-3-methoxybenzaldehydeisonicotinoyl hydrazone (HMBAINH) Devi et al. [8] have proposed a simple, sensitive and rapid spectrophotometric method for cobalt determination using HMBAINH as an analytical reagent. The reagent complexes with cobalt to give a yellow-colored complex in aqueous DMF at pH 6.0 in the presence of surfactant (1%) Triton X-100 in the pH range between 5.5 and 6.5. This complex has λmax at 415 nm. Further, the method is valid in the Beer’s law concentration range of 0.118–3.534 µg/cm2, where the molar absorptivity is 3.5 × 104 L/mol/cm and Sandell’s sensitivity is 0.00703 µg/cm2. Further, authors report first and secondderivative spectrophotometric methods for cobalt determination. It is mentioned that this method has been applied to environmental, medicinal as well as biological samples.

5.9 Iodonitrotetrazolium chloride Dospatliev et al. [9] have developed a new method for extraction spectrophotometric determination of Co (II) using iodonitrotetrazolium chloride as a chelating agent. The complex absorbs at 630 nm. The complex has ratio INT: [Co (SCN)4] [2:1]. The molar absorptivity is ε 630 = 0.6 × 103 dm3/mol/cm, whereas the Sandell’s sensitivity of this method is 9.8 × 10−2 mg/cm2. Beer’s law concentration range is between 6 and 125 mg of Co (II), and maximum extraction is at pH 2–7 as mentioned.

5.10 2-(5-Bromo-2-pyridylazo)-5 [N-n-propyl-N-(3-sulfopropyl) amino] aniline Rinda et al. [10] have developed a spectrophotometric determination method for cobalt (II) in horse urine using 2-(5-bromo-2-pyridylazo)-5N-n-propyl-N-3-sulfopropyl) amino] aniline as reagent. The method involves detection of cobalt based on complex formation between cobalt (II) and the reagent. It is mentioned that at pH 4.0, a complex is formed which absorbs at 602 nm in ratio of 1:2 (M: L). In the Beer’s law concentration range of 0–2.5 µm the detection limit is 0.044 µm. The method is successfully applied to the detection of cobalt in horse urine, since the cobalt abuse is an illegal dopant to improve horse performance in racing horses as reported.

5.11 4-(Nitrophenyl azo imidazole) NPAI Eassa [11] has proposed a spectrophotometric method for cobalt determination using NPAI as a chromogenic reagent. The method is described as a sensitive and selective

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one. The reagent forms a complex with cobalt absorbing at 556 nm. Molar absorptivity in the linear concentration range reported is 1.0162 × 104 L/mol/cm and the detection limit is 0.12 µg/mL. Suitable masking agents were used to remove interference of ions like Ni2+, Ag+ Cu2+ and Hg2+ as reported.

5.12 1-(2-Pyridylazo)-2-naphthol Gavrilenko et al. [12] have used polymethacrylate matrix with immobilized 1-(2pyridylazo)-2-naphthol for the determination of cobalt. The sensor is prepared by immobilizing PAN in an optically transparent polymethacrylate matrix. At pH 4 sensor reacts with cobalt solution and gives absorbance at 620 nm. The sensor detects in the range of 0.05–0.50 mg/L of cobalt and the detection limit is 0.04 mg/L. The authors claim the sensor capable of detecting cobalt in cyanocobalamin medical preparation and even potable water.

5.13 [2-(4-Methoxyphenyl) azo (4,5-diphenylimidazole)] (MPAI) Hussain et al. [13] have proposed the determination of Co (II) in formulation using MPAI as a chromogenic reagent. A stable red complex at pH 9 absorbs at 491 nm in the Beer’s law range of 3.00–50.0 µg/mL. The molar absorptivity and Sandell’s sensitivity are 0.2703 × 104 L/mol/cm and 0.0021 µg/cm2. The reported detection limit is 2.083 µg/mL.

5.14 4-(2-Pyridylazo)-resorcinol Wang [14] has proposed a method for the determination of cobalt in water using 4-(2pyridylazo)-resorcinol as a reagent. A purplish red complex is formed with Co (II) which absorbs at 430 nm. Beer’s law range is 0.02–1.60 mg/L and the method has been mentioned to be sensitive one.

5.15 2-Aminoacetyle-3-hydroxy-2-naphthoic hydrazone Venkateswarlu et al. [15] have used 2-aminoacetyl-3-hydroxy-2-naphthoic hydrazone as a chromogenic reagent for the determination of Co (II) by direct and derivative spectrophotometric method. It is described that the reagent forms a light pink-colored complex with Co (II) at pH 2.0, having λmax at 450 nm. The linear concentration range or Beer’s law range is 0.294–2.94 µg/mL. The reported molar absorptivity is 1.00 × 104 L/mol/cm and Sandell’s sensitivity is 0.00581 µg/cm2. The authors recommend this

5.18 2-(5-Nitro-4-methyl-2-pyridyl-azo)-5-dimethylaniline

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method as a selective sensitive and rapid method with encouraging results compared to certified values.

5.16 1-(2-Pyridylazo)-2-naphthol Shar et al. [16] reported cobalt (II) determination method using 1-(2-pyridylazo)-2naphthol in the presence of cationic aqueous solution of solution of cetyltrimethylammonium bromide surfactant. It is described as a simple and rapid method replacing the previously used method of solvent extraction. It is advantageous in reducing the cost, toxicity as well as improves sensitivity, selectivity and even molar absorptivity. The complex absorbs at 577.8 nm in the linear range of 0.12–6.0 µg/mL. The values of molar absorptivity and Sandell’s sensitivity are 1.89 × 104 L/mol/cm and 3.1 ng/cm2 for a 1:2 (Co: PAN) complex. The method has also been applied to samples of biological, pharmaceutical and water for Co (II) determination.

5.17 3-[4-(Dimethylamino) cinnamoyl]-4-hydroxy-6-methyl-2Hpyran-2-one Eleckova et al. [17] have proposed a new spectrophotometric method for the determination of cobalt using cinnamoyl derivative. The method uses reaction of Co (II) with 3-[4-(dimethylamino)-cinnamoyl]-4-hydroxy-6-methyl-2H-pyran-2-one (ligand) with dimethylindocarbocyanin dye. The reaction is followed by micro extraction of ion association formed by liquid-liquid dispersive method. Complex thus formed is detected by spectrophotometric method in pH 9.0, 0.14 mM dye toluene as solvent, 2.25 mM of ligand dispersive solvent acetonitrile, with CCl4 as auxillary solvent Beer’s law is obeyed in the concentration range of 0.06–0.42 mg/L of Co (II) at 558 nm. The authors mention that the method has been applied to the determination of cobalt in spiked samples as well as vitamin B12 samples.

5.18 2-(5-Nitro-4-methyl-2-pyridyl-azo)-5-dimethylaniline Hanau et al. [18] have reported a new chromogenic reagent 2-(5-nitro-4-methyl-2pyridylazo)-5-dimethylaniline for spectrophotometric determination of cobalt. This is described that in HAc-NaAc buffer solution of pH 4.0–7.0, the reagent reacts with Co (II) to give a violet red complex which has λmax at 568 nm. Based on this reaction cobalt (II) has been detected in trace quantities in minerals, if H2SO4 is used as medium the method achieves higher selectivity, precision and accuracy, as mentioned.

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5.19 1-Nitroso-2-naphthol in aq. sodium dodecyl sulfate (NNPh) Soomro et al. [19] have proposed a simple and rapid spectrophotometric method for tracing cobalt using NNPh as chromogenic reagent. In the presence of aqueous micellar surfactant 1.0% sodium doclecyl sulfate, NNPh reacts with Co (II) to give a greencolored cobalt complex. The complex absorbs at 436.2 nm in the linear range of 0.12–4.0 µg/ mL of Co (II). The molar absorptivity and Sandell’s sensitivity of this complex are 2.05 × 104 L/mol/cm and 3.49 ng/cm2, respectively, for 1:3 (Co: [NNPh)3] complex. The method has been successfully used for cobalt determination in alloys and pharmaceutical samples.

5.20 Res-acetophenolene guanylhydrazine (RAG) Divate et al. [20] have reported an effective, simple method for simultaneous determination of Co (II) and iron (III) using res-acetophenone guanyl hydrazone as a chromogenic reagent. Co (II)-RAG complex absorbs at 415 nm and 520 nm, with molar extinction coefficient Σ520 0.1230 × 104 L/mol/cm. The method as reported is used for Co (II) determination in synthetic samples as well as steel alloys.

5.21 2-Carboxy-5, methyl-3-nitrobenzaldoxime Mishra et al. [21] have proposed a quantitative extractive spectrophotometric method for cobalt determination using 2-carboxy-5, methyl-3-nitro benzaldoxime as chelating agent. From an aqueous solution of pH 7.0–8.5, M/10 sodium acetate, the ligand extracts 99.75% cobalt into carbontetrachloride. An intense peak at 454 nm is shown by this extract in the Beer’s law concentration range of 0.1–0.5 g/cm3. The molar absorptivity is found to be 14,850 dcm3/mol/cm. The method is applied to the simultaneous determination of Co (II), Ni (II) and Cu (II).

5.22 Anthrone phenylhydrazone (APH) Veeranna et al. [22] have used APH as a chromogenic reagent for simultaneous spectrophotometric determination of Co (II), Ni (II) and Cu (II). The method is based on fourth-derivative spectrophotometry. In a buffer of pH 10.0 λmax is observed between 426.3 and 625 nm for Co (II), Ni (II) and Cu (II). For Co (II) the molar absorptivity is 1.5 × 104 L/mol/cm and Sandell’s sensitivity is 0.0066 µg/cm2. The method can be applied for the determination of these metals in samples of grape leaves, sesame, laver, mung bean and in even alloy samples.

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5.23 4-[{(4-n-(3-O X O-1,2-Oxazolldin-4-yl) carboxymidoyl phenyl} methylidene) amino] 1-2-oxazolidin-3-one (OOCPMAO) Lokhande et al. [23] have developed an extractive spectrophotometric determination for Co (II) using OOCPMAO as a reagent. The reagent gives a colored complex with cobalt which is extracted in chloroform. This extracted complex absorbs at 425 nm between 1 and 10 ppm. The molar absorptivity of species was 4.9359 × 103 L/mol/cm and Sandell’s sensitivity was 8.391 × 10−5 µg/cm2. The method has been successfully applied to the cobalt determination in paints, varnishes super alloys as well as inks.

5.24 Nicotinohydroxamic acid (NHA) Muthuselvi [24] has developed a method for direct spectrophotometric determination of cobalt (II) using nicotinohydroxamic acid as an analytical reagent. In buffer medium of pH 9.2 Co (II) forms a pink-colored complex with NHA, which has λmax at 610 nm. The linear concentration range for the determination is 0.65–5.9 µg/mL. The molar absorptivity and Sandell’s sensitivity of the complex as reported are 7.038 × 104 L/mol/cm and 0.0065 µg/cm2, respectively. It has been recommended as a facile, sensitive and selective method by the authors.

5.25 2-Hydroxy-1-naphthalenecarboxaldehyde phenylhydrazone Sonawane et al. [25] have developed a spectrophotometric method for Co (II) determination using 2-hydroxy-1-naphthalene carboxaldehyde phenyl hydrazone as an extractive reagent. At pH 8.4, this reagent forms a colored complex with Co (II) which is quantitatively extracted into n-butanol. In the concentration range of 1–10 ppm the molar absorptivity is 2.380 × 104 L/mol/cm and Sandell’s sensitivity is 0.1176 µg/cm2. This has been applied to synthetic and commercial samples as a sensitive and selective method.

5.26 Pyridylazoresorcinol Fang et al. [26] have used 4-(2-pyridylazo) resorcinol (PAR) as a reagent for spectrophotometric determination of nickel and cobalt simultaneously. In pH 5 NaAC-HAC buffer, cobalt and nickel form stable complexes with this reagent. Two wavelengths 508 and 568 nm were selected for determination and a dual regression method was set up for simultaneously determining cobalt and nickel.

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5.27 2-Hydroxy-4-butoxy-5-bromoacetophenone oxime (HBA) Parmar et al. [27] have reported HBA as an analytical reagent for Co (II) determination. It is mentioned that reagent HBA forms a yellowish brown complex with Co (II), which absorbs at 640 nm. The Beer’s law range is 14.73–117.86 µg/mL at 640 nm in chloroform. The reported molar absorptivity is 312 L/mol/cm and Sandell’s sensitivity is 0.19 µg/cm2.

5.28 1,2-Propanedime, 1-phenyl-1-(2-hydroxyl-5-bromobenzidineazine)-2-oxime [PDPHBBAO] Lokhande et al. [28] have used PDPHBBAO for extractive spectrophotometric determination of Co (II). It is mentioned that at pH 9.0 the reagent forms a yellow-colored complex, extractable in chloroform. The λmax of the complex is at 430 nm in the Beer’s law range of 1–10 µg. The molar absorptivity and Sandell’s sensitivity values are 5.8470 × 103 L/mol/cm and 10.088 × 10−3 µg/cm2. The authors recommend this method as highly sensitive, selective, accurate and rapid method for synthetic mixtures, pharmaceutical samples, etc.

5.29 2,4-Dihydroxy-5-bromo [2-methyl] propiophenone oxime [DHBMPO] Patel et al. [29] have developed a spectrophotometric determination method for cobalt (II) using DHBMPO. At room temperature and pH 7.0, the reagent co-precipitates Co (II) which can be extracted in chloroform. The complex absorbs at 440 nm and in the Beer’s law range is