Organic Analytical Reagents for the Determination

of Inorganic Cations
Paris D. N. Svoronos and Thomas J. Bruno
The table entitled Organic Analytical Reagents for the
Determination of Inorganic Substances, by G. Ackermann, L.
Sommer, and D. Thorburn Burns, has been revamped and consid-
erably expanded for this edition. The many recent advancements
in this area have been surveyed, and in this table, specifically for
inorganic cations, we present the major tests, reagents, and some
guidance as to the expected result or method of observation. The
abbreviations used here are defined in the abbreviations table in
this section. In addition, for brevity, when a determination calls
for a spectrophotometric measurement at a particular wavelength,
for example at 500 nm, we denote this as: “spec λ = 500 nm.” No
wavelength is specified if it is variable, for example, with pH; here
we indicate: “spec determination.” When a determination calls
for spectrofluorimetric determination, the excitation and emis-
sion wavelengths are provided, thus: specf λex  = 303.5 nm, λem  =
353 nm. Note that a common surfactant used in many of these
tests is cetyltrimethyl ammonium bromide, abbreviated (CTAB).
Some of the procedures listed here require the use of hazardous
chemicals (carcinogens such as benzene, strong acids such as HF).
Appropriate precautions must be observed.
While a great deal of the information presented here is from the
recent literature, the reader is referred to several excellent reviews
and monographs for additional information (Refs. 1–9).
References
1. Marczenko, Z., Separation and Spectrophotometric Determination
of Elements, Ellis Horwood, Chichester, 1986.
2. Sandell, E. B., and Onishi, H., Photometric Determination of Traces
of Metals. General Aspects, Part I, 4th Edition, John Wiley and Sons,
New York, 1986.
3. Onishi, H., Photometric Determination of Traces of Metals. Part IIa:
Individual Metals, Aluminium to Lithium, 4th Edition, John Wiley
and Sons, New York, 1986.
4. Onishi, H., Photometric Determination of Traces of Metals. Part IIb:
Individual Metals, Magnesium to Zinc, 4th Edition, John Wiley and
Sons, New York, 1986.
5. Townshend, A., Burns, D. T., Guilbault, G. G., Lobinski, R.,
Marczenko, Z., Newman,  E., and Onishi, H., Dictionary of
Analytical Reagents, Chapman and Hall, London, 1993.
6. West, T. S., and Nürnberg, H. W., The Determination of Trace
Metals in Natural Waters, Blackwell, Oxford, 1988.
7. Savvin, S. B., Shtykov, S. N., and Mikhailova, A. V., Russ. Chem.
Rev. 75, 341, 2006.
8. Ueno, K., Imamura, T., and Cheng, K. L., Handbook of Organic
Analytical Reagents, CRC Press, Boca Raton, FL, 1992.
9. American Chemical Society, Reagent chemicals: specifications and
procedures: American Chemical Society specifications, official from
January 1, 2006, American Chemican Society, Washington, D.C.,
2006.

Determination Reagents Results

Aluminum Alizarin red S Red color develops; spectrophotometric determination preferred
Aluminon Lake pigment stabilized with CTAB
Chrome azurol S Spec λ = 500 nm, stabilized with CTAB
Chromazol KS Spec λ = 625 nm, stabilized with cetylpyridinium bromide
Eriochrome cyanine R (also known as mordant Red dye lake (pH = 6) stabilized with CTAB
blue 3) + CTAB
Eriochrome cyanine R (also known as mordant Spec determination by use of cationic surfactants
blue 3) + N,N-dodecyltrimethylammonium
bromide (DTAB)
8-Hydroxyquinoline Produces tris(8-hydroxyquinolinato) aluminum (Alq3), found in organic light
emitting diodes (OLEDs)
Bromopyrogallol red + cetyltrimethyl ammonium Spec λ = 627 nm
bromide
Bromopyrogallol red + nonylphenol Spec λ = 612 nm
tetradecaethylene glycol ether
Pyrocatechol violet Spec λ = 578 nm after separation of aluminum from the matrix materials by
chloroform extraction of its acetylacetone complex (pH = 6.5), from an
ammonium acetate-hydrogen peroxide medium
2,2′,3,4-Tetrahydroxy-3′,5′-disulfoazobenzene Spec determination of the binary system (pH = 5)
Antimony Brilliant green Isolated as the hexachloroantimonate (V) salt extracted by either toluene or
benzene
Bromopyrogallol red Used for the determination of antimony (III) with EDTA, cyanide or fluoride ions
as masking agents
Catechol violet Ternary complex stabilized with CTAB
Malachite green (basic green 4) Isolated as the hexachloantimonate (V) complex after benzene extraction
Phenyl fluorene Sensitive color reaction with antimony (III) by use of cationic surfactants
Potassium iodide Antimony (III)-iodide complex formation in the presence of ascorbic acid
Rhodamine B Ion pair or ion association extraction by use of toluene or benzene as solvents
Silver diethyldithiocarbamate Spec λ = 504 nm to avoid arsenic interference
Thiourea Determination by hydride generation inductively coupled plasma atomic emission
spectrometry after reduction of antimony (V) to antimony (III) by thiourea
Arsenic Michler’s ketone Spec λ = 640 nm trophotometric determination of trace arsenic (V) in water

8-82
Organic Analytical Reagents for the Determination of Inorganic Cations 8-83

Determination Reagents Results

Silver diethyldithiocarbamate Spec λ = 600 nm to avoid antimony interference
Thiourea Determination by hydride generation inductively coupled plasma atomic emission
spectrometry after reduction of arsenic (V) to arsenic (III) by thiourea
Barium Dimethylsulfonazo-III (DMSA-III) Spec λ = 662 nm of the chelate complex
Alizarin S red Red color used spectrophotometrically as a stain to determine the amount of
barium in bone
Beryllium Aluminon Lake pigment derivative
Ammonium bifluoride Derivative detected by fluorescence
Beryllon II A resin phase spectrophotometric method that detects a change in absorbance of
the resin phase immobilized with beryllon II
Beryllon III Determination achieved via third –derivative spectrophotometry and
decolorization of excess reagent
Chrome azurol S Spec determination with chrome azurol S in the presence of EDTA or CTAB
Eriochrome cyanine R + (CTAB) Spec λ = 590 nm of ternary complex
Sulfon black F Derivative has a long color-development time
Bismuth Amberlite XAD-7 Determination system implemented with (HG-ICP-AES) associated with flow
injection (FI)
Sodium azide Azidodimethylbismuthine precipitate formed by the reaction of the
corresponding bismuthine with sodium azide
Diethyldithiocarbamate Heterometric micro-determination of lead with sodium diethyldithiocarbamate
by use of a mixture of EDTA, cyanide and ammonium hydroxide (λ = 400 nm)
Dithizone Orange-red derivative that is extracted in carbon tetrachloride
Pyrocatechol violet Spec determination of bismuth (III) with pyrocatechol violet in the presence of
septonex CTAB
Quinolin-8-ol Determination system implemented with HG-ICP-AES associated with flow
injection (FI)
Thiourea Determination by HG-ICP-AES
Xylenol orange Derivative used for sol-gel thin films that serve as bismuth (III) sensors
Boron Azomethine H Spec determination
Carminic acid Spec determination
Curcumin Spec determination of rosocyanine and rubrocurcumin formed by the reaction
between borates and curcumin
Methylene blue Spec determination of complex formed between fluoroborate ions and methylene
blue after treatment with hydrofluoric and sulfuric acids and extraction with
ethylene chloride
Cadmium 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol Spec determination in the presence of cationic surfactant cetylpyridinium
(PAR) chloride
Cadion Determination by β-correction spectrophotometry with cadion and surfactant
Triton-X
Dithizone Determination of dithizonate derivative by the extraction – spectrophotometric
method
1-(2-Pyridylazo)-2-naphthol (PAN) Two-dimensional absorption spec determination of complex in aqueous micellar
solutions
4–(2-Pyridylazo)resorcinol Preconcentration by cloud point extraction of the complex; determination by ICP
optic emission spectrometry. Simultaneous spectrophotometric determination
of cadmium and mercury
Calcium Alizarin S Red dye used in staining bones for calcium determination
Chlorophosphonazo III Spec λ = 667.5 nm (pH = 2.2)
Eriochrome black T + EDTA Complexometric titration where the initially formed red calcium-eriochrome
black T color is replaced with the blue calcium-EDTA color at the end point
Glyoxal-bis(2-hydroxyanil) Spectrophotometric titration of the complex without preliminary extraction
Murexide Spec λ = 506 nm (pH = 11.3)
Phthalein purple High-performance chelation ion chromatography involving dye-coated resins
Cerium Butaperazine dimaleate propericiazine Spec determination of the colored complex in a phosphoric acid medium
Persulfate oxidation to cerium (IV) UV spec λ = 320 nm
Propericiazine Spec determination of the colored complex in a phosphoric acid medium
Propionyl promazine phosphate (PPP) Spec λ = 513 nm of the red-colored radical cation formed upon the reaction of
PPP with cerium(IV) in a phosphoric acid medium
N-Benzoyl-N-phenylhydroxylamine Spec titration of the cerium (IV) complex (pH = 8 to 10)
Sodium triphosphate Specf λex = 303.5 nm, λem = 353 nm of the cerium (III) complex
8-Hydroxyquinoline Spec determination of the metal-ligand complex
Chromium Alizarin S Lake pigment complex formation
1,5-Diphenylcarbazide Spec determination during sonication in carbonated aqueous solutions saturated
with CCl4 that produces chlorine radicals
8-84 Organic Analytical Reagents for the Determination of Inorganic Cations

Determination Reagents Results

3-(2-Pyridyl)-5,6 bis(5-(2 furyl disulfonic Indirect spec λ = 593 nm in aqueous samples with a chromogen ferene-TM
acid))-1,2,4-triazine disodium salt (ferene-TM)
4-(2-Pyridylazo)resorcinol (PAR) Spec determination of the ternary chromium-peroxo-par ternary complex
4-(2-Pyridylazo)resorcinol (PAR) + hydrogen Spec determination of the ternary chromo-peroxo-PAR mixture after ethyl
peroxide acetate extraction in 0.1 M sulfuric acid
4-(2-Pyridylazo)resorcinol (PAR) + Spec determination of the orange-red anionic complex formed in a heated acetate
xylometazolonium (XMH) chloride buffer medium (pH = 4.0 to 5.5) and extracted with the xylometazolonium
(XMH) chloride
Sulfanilic acid Spec λ = 360 nm on the catalytic effect of chromium (VI) in the oxidation of
sulfanilic acid by hydrogen peroxide with p-aminobenzoic acid as an activator
Cobalt 8-Hydroxyquinoline Spec determination of the metal-ligand complex
p-Nitroso-N,N-dimethylaniline Spec determination of the binary complex
Nitroso-R salt AAS by use of a continuous on-line precipitation-dissolution procedure
1-Nitroso-2-naphthol Spec determination by use of non-ionic surfactant Triton X-100
1-Nitroso-2-naphthol Spec Tween 80 micelar determination
1-Nitroso-2-naphthol AAS by use of a continuous on-line precipitation-dissolution procedure based on
1-nitroso-2-naphthol
2-Nitroso-1-naphthol Spec λ = 530 nm after isoamyl acetate extraction
1-(2-Pyridylazo)-2-naphthol + surfactants Spec λ = 620 nm of the cobalt complex in the presence of surfactants (Triton
X-100 combined with sodium dodecylbenzene sulfonate (DBS)) and trace of
ammonium persulfate (pH = 5.0)
4-(2-Pyridylazo)resorcinol (PAR) Spec determination of complex at both pH = 7.2 to 7.9 and in 1 M H2SO4
4-(2-Pyridylazo)resorcinol (PAR) + Ion-pair reversed-phase high-performance liquid chromatography of the complex
triethanolamine
Copper Bathocuproine disulfonic acid Spec λ = 470 nm to 550 nm of the Bathocuproine-disulfonic acid complex after
extraction with chloroform and methanol by use of (PLS2)
Dithizone Spec determination of the dithizone complex at pH = 2.3
Neocuproine Spec determination of the deep orange-red Cu(neocuproine)2+ complex color
Cuprizone Spec determination of the highly chromogenic copper (III) cuprizone complex
p-Nitroso-N,N-dimethylaniline Spec determination of the binary complex
1-Nitroso-2-naphthol Spec determination by use of non-ionic surfactant Triton X-100
4-(2-Pyridylazo)resorcinol Preconcentration of copper by cloud point extraction of the complex and
determination by ICP optic emission spectrometry
Europium 1-Nitroso-2-naphthol Spec Tween 80 micelar determination
ChromAsurol S Spec determination of the binary complex
4-(2-Pyridylazo)resorcinol (PAR) + tetra­decyl­ Spec λ = 510 nm of the ion-associate complex extracted with chloroform at
dimethyl­benzylammonium chloride (TDBA) pH = 9.7
Gallium Chrome azurol S + (CTAB) Spec λ = 640 nm of the ternary complex
Haematoxylin or its oxidized form + (CTAB) Spec determination of the ternary complex of indium with haematoxylin or its
oxidized form in the presence of cationic, anionic and non-ionic surfactants such
as (CTAB)
Pyrocatechol violet + diphenylguanidine Spec determination of the ternary complex
8-hydroxyquinoline Spec determination of the gallium complex
1-(2-Pyridylazo)-2-naphthol Spectrofluorimetric determination of Ga(III) with 1-(2-pyridylazo)-2-naphthol in
sodium dodecyl sulfate micellar medium
4-(2-Pyridylazo)resorcinol (PAR) Extraction and spec λ = 510 nm of gallium with 4-(2-pyridylazo)resorcinol
Rhodamine B Comparison of the determination of gallium by a rhodamine B
spectrophotometric method and by an AA method based on preliminary solvent
extraction
Xylenol orange + 8-hydroxyquinoline Spectrophotometric determination of the ternary complex
Germanium Brilliant Green + Molybdate Spec λ = 430 nm of the yellow germanomolybdic acid
Phenylfluorone Spec determination of the complex previously extracted with carbon tetrachloride
at pH = 3.1
Gold 5-(4-Diethylaminobenzylidene) rhodanine Immobilized 5-(4-dimethylamino-benzylidene) rhodanine serves as a stable solid
sorbent for trace amounts of gold (III) ions (pH = 2 to 4)
Di(methylheptyl)methyl phosphonate (DMHMP) Trace gold determination by on-line preconcentration with flow injection atomic
absorption spectrometry, by use of di(methylheptyl)methyl phosphonate
(DMHMP) as the immobilized phase loaded onto a macroporous resin
2-Mercaptobenzothiazole Radiochemical separation and determination of gold complex matrices employing
substoichiometric thermal neutron activation analysis
Molybdate + nile blue (NB) A spectrophotometric method based on the reaction of gold(III) with molybdate
and nile blue (NB) to form an ion-association complex in the presence of
poly(vinyl alcohol)
Rhodamine B Aqueous spec determination of gold with rhodamine B and surfactant
Organic Analytical Reagents for the Determination of Inorganic Cations 8-85

Determination Reagents Results

Hafnium Arsenazo III Spec determination of the arsenazo III complex in 10 M HCl or H2SO4
Indium Bromopyrogallol red Spec determination of indium after an ether extraction from hydrobromic acid,
and benzyl alcohol extraction of its complex with bromopyrogallol red (pH 9.0)
5-Bromine-salicylaldehyde salicyloylhydrazone Specf λex = 395 nm, λem = 461 nm of the indium: 5-Br-SASH chelate in a water–
(5-Br-SASH) ethanol (63%) medium (pH = 4.6)
Chrome azurol S Spec determination of the binary complex
Chrome azurol S + benzyldodecyl­dimethyl­ Spec determination of the mixed complex with chrome azurol S and (BDDMAB)
ammonium bromide (BDDMAB)
Chrome azurol S + (CTAB) Spec λ = 630 nm of the ternary complex after n-butyl acetate extraction from
hydrobromic acid
Chrome azurol S + cationic surfactants Spec determination by use of chrome azurol S and surfactants such as CTA, CP,
or zephiramine
Dithizone Spec determination of the binary complex
Haematoxylin or its oxidized form + (CTAB) Spec determination of the ternary complex of indium with haematoxylin or its
oxidized form in the presence of cationic, anionic and non-ionic surfactants such
as (CTAB)
8-Hydroxyquinoline Spec determination of the binary complex
Methylthymol blue + zepheramine Spec determination of the ternary complex
1-(2-Pyridylazo)-2-naphthol (PAN) Spec determination of the chelate complex after chloroform extraction (pH = 6)
4-(2-Pyridylazo)resorcinol Spec λ = 520 nm after indium extraction from the aqueous phase (pH 5.0 to 5.5)
into chloroform with N-p-chlorophenyl-2-furohydroxamic acid and formation of
the 4-(2-pyridylazo)resorcinol red chelate
Pyrocatechol violet Spec determination of the binary complex
Pyrocatechol violet + tridodecylammonium Spec determination of the ternary complex
bromide
Quinalizarin (1,2,5,8-tetrahydroxyanthraquinone) Spec λ = 565 nm of the binary 3:1 Quinalizarin:In(III) colored complex in
dimethylformamide-water solution
2,2′,3,4-Tetrahydroxy-3′,5′-disulfoazobenzene Spec determination of the binary system (pH = 5)
Xylenol orange Spec determination of the ternary complex
Iridium 1,5-Diphenylcarbazide Spec determination of the complex (pH = 5.0)
1-(2-Pyridylazo)-2-naphthol Spec λ = 550 nm of the red complex (pH = 5.1) after chloroform extraction
Iron Bathophenanthroline Determination of iron(II) in the presence of thousand-to-one ratio of iron(III) by
use of bathophenanthroline
Bathophenantroline-disulfonic acid Spec λ = 470 nm to 550 nm of the bathophenantroline-disulfonic acid complex
after extraction with chloroform and methanol
2,2′-Bipyridine Spec determination of the iron (II)-2,2’-bipyridine dark red complex
FerroZine Spec λ = 562 nm of iron (II)-ferrozine complex after all iron(III) has been reduced
by ascorbic acid
Hematoxylin + (CTAB) Spec of the ternary complex. Addition of CTAB shifts λmax from 630 nm to 640 nm
1-Nitroso-2-naphthol Spec determination by use of non-ionic surfactant Triton X-100
1-Nitroso-2-naphthol Spec determination Tween 80 micelar determination
1,10-Phenanthroline (o-Phen) Spec λ = 508 nm of the Fe(o-Phen)3+2 complex
1,10-Phenanthroline + bromothymol blue Spec determination of the Fe(o-Phen)3+2 complex in the presence of bromothymol
blue
Phenylfluorone Spec λ = 530 nm of the binary complex (pH = 9.0)
Phenylfluorone + Triton X Spec λ = 555 nm of the binary complex sensitized with Triton X-100 (pH = 9.0)
Lanthanum Ammonium purpurate Spec determination of lanthanum with ammonium purpurate as a chromogenic
reagent
Arsenazo III Spec determination of the lanthanum complexation with reagents of the arsenazo
III group on the solid phase of fibrous ion exchangers
Eriochrome cyanine R (ECR) Spec λ = 540 nm of the binary complex
N-Phenylbenzohydroxamic acid + xylenol orange Solvent extraction followed by the spec λ = 600 nm of the ternary complex
(pH = 8.8 to 9.5)
Lead Dithizone Orange-red derivative that is extracted in carbon tetrachloride
Sodium diethyldithiocarbamate Electrothermal AAS determination of the diethyldithiocarbamate derivative
extracted in carbon tetrachloride
Sodium diethyldithiocarbamate Heterometric micro-determination of lead diethyldithiocarbamate derivative
4-(2-Pyridylazo)resorcinol Spec λ = 520 nm of 4-(2-pyridylazo)-resorcinol:lead (1:1) complex in an
ammonia-ammonium chloride medium at pH = 10 after extracting the lead in
isobutyl methyl ketone
Lithium 1-(o-Arsenophenylazo)-2-naphthol-3, Spec λ = 480 nm of Thoron-lithium complex in an alkaline acetone medium is
6-disulfonate (Thoron) measured against the reagent as reference
Magnesium Chlorophosphonazo III Spec λ = 669 nm (pH = 7.0)
8-86 Organic Analytical Reagents for the Determination of Inorganic Cations

Determination Reagents Results

Eriochrome black T + EDTA Complexometric titration where the initially formed red magnesium-eriochrome
black T color is replaced with the blue magnesium-EDTA color at the end point
8-Hydroxyquinoline Volumetric, titrimetric, and colorimetric determination
8-Hydroxyquinoline + butylamine Spec λ = 380 nm of the complex after chloroform extraction
Titan yellow Spec determination of magnesium by titan yellow in biological fluids
Xylidyl blue Spec determination of magnesium in biological fluids
Manganese Formaldoxime Spec determination of the formaldoxime/ammonia complex (pH = 8.8 to 8.9)
1-(2-Pyridylazo)-2-naphthol (PAN) Preconcentration determination by use of (PAN) anchored SiO2 nanoparticles
Mercury Dithizone Spec λ = 500 nm of dithizone complex after chloroform extraction at pH = 0.3
Michler’s thioketone Spec λ = 560 nm of the binary complex in acetate buffer
4–(2-Pyridylazo)resorcinol Simultaneous spec determination of cadmium and mercury with 4-(2-pyridylazo)
resorcinol
Rhodamine 6G Photoelectrochemical determination of mercury (II) in aqueous solutions by use
of a rhodamine 6G derivative (RS) and polyaniline (PANI) coated optical probe
in a photoelectrochemical cell
Xylenol orange + amine buffer Spec λ = 590 nm of Hg(II)/xylenol orange complex display a sharp hyperchromic
effect in the presence of amine buffers (pH= 7.5)
Xylenol orange + citric acid-phosphate buffer Spec λ = 580 nm of Hg(II)/xylenol orange complex display a sharp hypochromic
effect upon substituting amine buffers with a citric acid-phosphate (pH = 7.5)
Molybdenum Bromopyrogallol red + cetylpyridium chloride Sequential injection analysis to the determination of CPC based on the sensitized
molybdenum-bromopyrogallol red reaction
Phenylfluorone Spec λ = 560 nm of molybdenum with phenylfluorone (pH of 1.5 to 3)
8-Hydroxyquinoline-5-sulfonic acid and Diffuse reflection spectrometry with 8-hydroxyquinoline-5-sulfonic acid and
phenylfluorone phenylfluorone after sorbing on a disk of an anion exchange fibrous material
Pyrocatechol violet Preconcentration (by use of basic anion exchanger AV-17-10P) and determination
via diffuse reflection spectroscopy. The colored surface compound to be
determined involves Mo(VI) sorption on the resin and subsequent treatment of
the concentrate obtained with pyrocatechol violet
Neodymium Semi-xylenol orange + cetylpyridinium chloride Fourth-order derivative spectrophotometric determination of the ternary complex
Neptunium Arsenazo III Spec after separation by use of thenoyltrifluoroacetone extraction method and
determination in 5M HNO3
Nickel 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol Spec λ = 520 nm and 560 nm of the red-violet complex in water-ethanol (pH = 5.5)
Dimethylglyoxime + ammonia Spec λ = 543 nm of the complex
Dimethylglyoxime, voltammetry Nickel voltammetric determination at a chemically modified electrode based on
dimethylglyoxime-containing carbon paste
2,2′-Furildioxime Spec λ = 438 nm after separation by adsorption of its α-furildioxime complex on
naphthalene
Hematoxylin Spec λ = 595 nm of the binary system (pH = 7.8 to 8.3)
Hematoxylin + (CTAB) Spec λ = 608 nm of the ternary system (pH = 7.4 to 8.1)
1-Nitroso-2-naphthol Spec Tween 80 micelar determination
p-Nitroso-N,N-dimethylaniline Spec determination of the binary complex
2-(2-Pyridylazo)-2-naphthol Derivative spectrophotometry λ= 569 nm determination of nickel complex in
Tween 80 micellar solutions
4-(2-Pyridylazo)resorcinol Preconcentration of nickel by cloud point extraction of the complex and
determination by ICP optic emission spectrometry
1-(2-Thiazolylazo)-2-naphthol (TAN) Flow-injection solid phase spectrophotometry by use of TAN immobilized on
C18-bonded silica (λ = 595 nm)
Xylenol orange Spec determination by mean centering of ratio kinetic profile (pH = 5.3)
Niobium N-Benzoyl-N-phenylhydroxylamine Separation and determination of the complex from a tartrate solution at pH > 2
Bromopyrogallol red Spec λ = 610 nm of complex extracted into isopentyl acetate containing
di-n-octylmethylamine
O-Hydroxyhydroquinonephthalein (Qnph) + Spec λ = 520 nm of the complex in strong acidic media
hexadecyltrimethylammonium chloride (HTAC)
4-(2-Pyridylazo)resorcinol + citrate Determination of the ternary complex by ion-interaction reversed-phase HPLC
on a C18 column with a 5 mM citrate buffer (pH = 6.5, λ = 540 nm)
Pyrocatechol violet Extraction and spec determination of niobium complex in the presence of
pyridine and trichloroacetic acid
Sulfochlorophenol S Spec determination of the complex after extraction into amyl alcohol
Xylenol orange Spec λ = 530 nm of chelate (pH = 5.0)
Osmium 1,5-Diphenylcarbazide Spec λ = 560 nm of the bluish-violet complex after extraction with isobutyl
methyl ketone
Thiourea Spec λ = 540 nm of the red-rose complex in acid medium
Palladium Ammonia + iodide Thermogravimetric determination of palladium as Pd(NH3)2I2
Organic Analytical Reagents for the Determination of Inorganic Cations 8-87

Determination Reagents Results

2,2-bis-[3-(2-Thiazolylazo)-4-4-hydroxyphenyl- Application of TAPHP immobilized on silica beads to determine the palladium
propane], (TAPHP) concentration in a trans-luminance configuration (pH = 2) by use of flow-
through spectrophotometric sensing phase
2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol Spec determination of the complex in a sulfuric acid medium in the presence of
ethanol
Dithizone Volumetric determination of palladium with dithizone in acid medium after
extraction of its dimethylglyoxime complex with chloroform; PAS determination
of the dithizone extraction solution into a thermally thin solid film
Dithiazone + iodide Spec determination of palladium with dithizone, by use of an iodide medium in
the presence of sulfite at pH = 3 to 5, to separate platinum
Dithizone + stannous chloride Extractive separation and spec determination of palladium in the presence of
stannous chloride to separate platinum
Isonitrosobenzoylacetone Radiochemical separation and determination of palladium in complex matrices
employing substoichiometric thermal NAA
2-Nitroso-1-naphthol Spec λ = 370 nm of the violet complex
4-(2-Pyridylazo)resorcinol Spec determination of complex at both pH = 7.2 to 7.9 and in 1 M H2SO4 
4-(2-Pyridylazo)resorcinol + diphenylguanidine Spec determination after extraction of the red Pd(II) chelate with 4-(2-pyridylazo)
resorcinol in the presence of N,N′-diphenylguanidine into n-butanol
Platinum N-Phenylbenzimidoylthiourea (PBITU) Flow injection analysis spec λ = 345 nm of the Pd:PBITU complex in (0.2 to 2.0)
M HCl in10% (vol/vol) ethanol solution
Dithizone + iodide Spec determination of platinum with Dithizone, by use of an iodide medium in
the presence of sulfite at pH = 3 to 5, to separate palladium
Dithizone + stannous chloride Extractive separation and spectrophotometric determination of platinum in the
presence of stannous chloride to separate palladium
2-Mercaptobenzothiazole Radiochemical separation and determination of platinum complex matrices
employing substoichiometric thermal NAA
Protactinium Arsenazo III Spec λ = 680 nm of the complex after extraction with 7 N H2SO4 and isoamyl
alcohol
EDTA + tannic acid Gravimetric analysis of the tannic acid precipitate (pH = 5.0)
Rhenium 2,2′-Furildioxime Spec λ = 532 nm of the complex
N,N-Diethyl-N′-benzoylthiourea Spec λ = 383 nm of the green complex in hydrochloric acid medium in the
presence of tin(II) chloride
Tin(II) Spectrophotometric titration for the determination of rhenium by use of tin(II) as
the titrant
Rhodium 1,5-Diphenylcarbazide Spec determination of the complex after isobutyl alcohol extraction (pH = 5.0)
p-Nitrosodimethylaniline Spec λ = 510 nm of the cherry-red binary complex (pH = 4.4)
1-(2-Pyridylazo)-2-naphthol Spec λ = 598 nm of the green complex (pH = 5.1) after chloroform extraction
Ruthenium 4-Benzylideneamino-3-mercapto-6-methyl-1,2,4- Spec λ = 620 nm
triazine (4H)-5-one
1,10-Phenanthroline Chemiluminescence determination of chlorpheniramine by use of tris(1,10-
phenanthroline)-ruthenium(II) peroxydisulfate system and sequential injection
analysis; Spec determination of the complex after reducing Ru (IV) to Ru(II)
Thiourea Spec λ = 640 nm of ruthenium complex in carbon supported Pt-Ru-Ge catalyst in
5 M HCl
1,4-Diphenylthiosemicarbazide Spec determination of the bright red complex
Scandium Alizarin red S Cathodic adsorptive stripping of the scandium-alizarin red S complex onto a
carbon paste electrode
Ammonium purpurate Spec determination of scandium with ammonium purpurate as a chromogenic
reagent
Chrome azurol S Spec determination of the binary complex
Xylenol orange Spec λ = 553 nm of the binary mixture
Selenium 3,3′-Diaminobenzidine Spec λ = 350 nm of the yellow complex (pH = 3.0)
2,3-Diaminonaphthaline Fluorometric determination of the binary complex in water
Thiourea Determination of selenium by hydride generation inductively coupled plasma
atomic emission spectrometry
Silver Dithizone Graphite-furnace atomic-absorption spectrophotometric determination of silver
on suspended dithizone particles from acidic sample solutions with ultrasonics
to facilitate the separation
Eosin + 1,10-phenanthroline Spec λ = 540 nm to 555 nm of the 1,10-phenanthroline (PHEN) and eosin
(2,4,5,7-tetrabromofluorescein) association complexes
Strontium Phthalein purple High-performance chelation ion chromatography involving dye-coated resins
Tantalum N-Benzoyl-N-phenylhydroxylamine Separation and determination of the complex from a tartrate solution at pH < 1.5
Crystal violet (CV) + N,N′-diphenylbenzamidine Spec λ = 600 nm of Ta(V)-F-CV+ cation complex with a benzene solution of
(DPBA) DPBA from sulfuric acid solution
8-88 Organic Analytical Reagents for the Determination of Inorganic Cations

Determination Reagents Results

O-Hydroxyhydroquinonephthalein (Qnph) + Spec λ = 510 nm of the complex in strong acidic media
hexadecyltrimethylammonium chloride (HTAC)
Malachite green Spec λ = 623 nm of the complex in HF after extraction with benzene or toluene
Methyl violet Spec determination of the complex
4-(2-Pyridylazo)resorcinol + citrate Determination of the ternary complex by ion-interaction reversed-phase HPLC
on a C18 column in 5 mM citrate buffer (pH = 6.5, λ = 540 nm)
Phenylfluorone Spectrophotometric determination from HF-HCl solution with methyl isobutyl
ketone
Victoria blue Spectrophotometric determination of the complex after benzene extraction
Tellurium Ammonium pyrrolidinedithiocarbamate Differential determination of tellurium(IV) and tellurium(VI) by AAS with a
carbon-tube atomizer
Bismuthiol II Spec λ = 330 mm of the yellow complex in acidic medium (pH = 3.5) after
chloroform extraction
Dithizone Differential determination of tellurium(IV) and tellurium(VI) by AAS with a
carbon-tube atomizer
Sodium diethyldithiocarbamate Differential determination of tellurium(IV) and tellurium(VI) by AAS with a
carbon-tube atomizer
Thiourea Determination of selenium by hydride generation inductively coupled plasma
atomic emission spectrometry
Thallium Brilliant green Spec determination of the binary complex after toluene extraction
Dithizone Spec λ = 505 mm of the complex after chloroform extraction from a citrate-
sulfite-cyanide medium at pH = 10.6
8-Hydroxyquinoline Spectrophotometric determination of the metal-ligand complex
Rhodamine B Fluorimetric determination of thallium (in silicate rocks) with rhodamine B after
separation by adsorption on a crown ether polymer
Rhodamine B hydroxide Spec λ = 565 nm via oxidation of rhodamine B hydrazide by thallium(I) in acidic
medium to give a pinkish violet radical cation
Thorium Arsenazo III Spec determination of the arsenazo III complex in 10 M HCl or H2SO4
Eriochrome cyanine R (ECR) Spec λ = 540 nm of the binary complex
Thoron Spectrophotometric determination of binary complex in tartaric acid
Xylenol orange Spec λ = 570 nm of the binary complex (pH = 4.0)
Xylenol orange + CTAB bromide Spec λ = 600 nm of the complex sensitized by CTMAB (pH = 2.5)
Tin Catechol violet + CTAB bromide Spectrophotometric determination of the green complex
Pyrocatechol violet (and + CTAB bromide) Spec λ = 660 nm of the complex (pH = 2.0)
Gallein Spectrophotometric determination of complex in acid medium
Phenylfluorone Spec determination of the complex (pH = 1) in 36% aqueous ethanol after a
preliminary solvent extraction of the tin as the iodide
Toluene-3,4-dithiol + dispersant Spec determination of the complex
Titanium Chromotropic acid Spec λ = 443 nm of the complex by use of a flow injection manifold
Diantipyrinylmethane Spec λ = 390 nm of the yellow complex
3-Hydroxy-2-methyl-1-(4-tolyl)-4-pyridone (HY) Spec λ = 355 nm of the ternary complex formed in perchloric acid and is
extracted by chloroform
Methylene blue-ascorbic acid redox reaction Spec λ = 665 nm of the titanium-methylene blue-ascorbic acid redox reaction
Tiron Spec λ= 420 nm of the yellow Tiron derivative (pH = 5.2 to 5.6)
Tungsten Cyanate Spectrophotometric determination of tungsten with thiocyanate after both
tungsten(VI) and molybdenum(VI) are extracted into chloroform as benzoin
α-oxime complexes
Pyrocatechol violet Determination of the 2:1 green complex in acid medium which is fixed on a
dextran-type anion-exchange resin (Sephadex QAEA-25) by first-derivative
solid-phase spectrophotometry (λ = 674 nm)
Tetraphenylarsonium chloride + thiocyanate Gravimetric determination of tungsten with tetraphenylarsonium chloride after
its extraction as thiocyanate (pH = 2 to 4)
Toluene-3,5-dithiol Spec λ = 630 nm of the toluene-3,4-dithiol derivative after extraction with isoamyl
acetate
Uranium Arsenazo III (1,8-dihydroxynaphthalene-3,6- Spec determination of the binary complex
disulfonic acid-2,7-bis[(azo-2)-phenylarsonic
acid])
2-(5-Bromo-2-pyridylazo)diethylaminophenol Spec λ = 578 nm of the complex (pH = 7.6)
Chlorophosphonazo III Spec λ = 673 nm of the complex after extraction into 3-methyl-1-butanol from
(1.5 to 3.0) M HCl
8-Hydroxyquinoline Spectrophotometric determination of the metal (UO2 (II))-ligand complex
2-(2-Pyridylazo)-5-diethylaminophenol (PADAP) Spec λ = 564 nm of the complex after extraction into methyl isobutyl ketone
(pH = 8.2)
Organic Analytical Reagents for the Determination of Inorganic Cations 8-89

Determination Reagents Results

1-(2-Pyridylazo)-2-naphthol (PAN) Spec λ = 560 nm of the deep red precipitate in ammoniacal solutions extracted
with chloroform
4-(2-Pyridylazo)-resorsinol (PAR) Spec λ = 530 nm of the intensely deep red complex after extraction into methyl
isobutyl ketone (pH = 8.0)
2-(2-Thiazolylazo)-p-cresol + surfactants Spec λ = 588 nm of the complex (pH = 6.5) with surfactants such as Triton X-100
or N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)
Vanadium Chrome azurol S Spectrophotometric determination of the binary complex
N-Benzoyl-N-phenylhydroxylamine Spec determination of the violet complex in acidic medium
3,5-Dinitrocatechol (DNC) + brilliant green Extraction-spectrophotometric determination of the system V(V)-
3,5-dinitrocatechol (DNC)-brilliant green chelate complex
8-Hydroxyquinoline (oxine) Extraction with n-butanol and spec λ = 390 nm of a ternary complex
(vanadium:oxine:n-butanol = 1:2:2)
8-Hydroxyquinoline-5-sulfonic acid and Diffuse reflection spectrometry with 8-hydroxyquinoline-5-sulfonic acid and
phenylfluorone phenylfluorone after sorbing on a disk of an anion exchange fibrous material
4-(2-Pyridylazo)resorcinol (PAR) Spec determination of the binary complex based on the extraction
tetraphenylphosphonium or tetraphenylarsonium chloride
Xylenol orange Spec λ = 490 nm of chelate (pH = 5.0)
Yttrium Alizarin red S Spec λ = 550 nm of the complex
Ammonium purpurate Spec determination of yttrium with ammonium purpurate as a chromogenic
reagent
Arsenazo III Spec λ = 660 nm of the blue colored complex after preliminary purification with
hydroxide and subsequent acidification
Eriochrome cyanine R (ECR) Spec λ = 540 nm of the binary complex
Pyrocatechol violet Spec λ = 665 nm of complex
Zinc 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol Spec determination by use of 2-(5-bromo-2-pyridylazo)-5-diethyl aminophenol in
the presence of cationic surfactant cetylpyridinium chloride
Carbonic anhydrase Enzymatic determination by use of carbonic anhydrase after removing zinc by
dialysis against dipicolinic acid
Dithizone Spec λ = 530 nm of binary complex after chloroform extraction
Eriochrome black T + EDTA Complexometric titration where the initially formed red zinc-eriochrome black T
color is replaced with the blue zinc-EDTA color at the end point (pH = 10)
7-(4-Nitrophenylazo)-8-hydroxyquinoline-5- Spec λ = 520 nm of the zinc derivative (pH = 9.2, borax buffer)
sulfonic acid (p-NIAZOXS)
Phenylglyoxal mono(2-pyridyl) hydrazone Spec λ = 464 nm to 470 nm of the yellow-orange complex (pH = 7.2 to 8.5) in 40%
(PGMPH) (v/v) ethanol
1-(2-Pyridylazo)-2-naphthol (PAN) Two-dimensional absorption spec determination of complex in aqueous micellar
solutions
1-(2-Pyridylazo)-2-naphthol (PAN) Preconcentration determination by use of 1-(2-pyridylazo)-2-naphthol (PAN)
anchored. SiO2 nanoparticles
4-(2-Pyridylazo)resorcinol Spec determination at pH = 7.0; preconcentration of zinc by cloud point
extraction of the complex and determination by ICP optic emission
spectrometry
1-(2-Thiazolylazo)-2-naphthol (TAN) Flow-injection solid phase spec λ = 595 nm with TAN immobilized on C18-
bonded silica
Xylenol orange Spec determination of 1:1 zinc-xylenol orange red-violet complex (pH= 5.8 to 6.2)
Xylenol orange Sequential injection analysis (SIA) based on the spec λ = 568 nm of zinc by use of
xylenol orange as a color reagent
Xylenol orange Spec determination by mean centering of ratio kinetic profile (pH = 5.3)
Xylenol orange + cetylpyridinium chloride Spec λ = 580 nm of the 1:2:4 ratio for the metal:ligand: surfactant ternary complex
(pH = 5.0 to 6.0)
Zirconium Alizarin red S Spec determination of the binary complex after phosphate extraction
Arsenazo III (1,8-dihydroxynaphthalene-3,6- Spec determination of the binary complex
disulfonic acid-2,7-bis[(azo-2)-phenylarsonic
acid])
N-p-Chlorophenylbenzohydroxamic acid (N-p-Cl- Spec λ = 420 nm and fluorimetric determination of the N-p-Cl-BHA greenish
BHA) + morin yellow complex after extraction with isoamyl alcohol from (0.2 to 0.5) N H2SO4
followed by morin addition; it is critical that the morin be very pure
Pyrocatechol violet Spec λ = 650 nm of the blue complex in sulfuric acid solution
Pyrocatechol violet + tri-n-octylphosphine oxide Spec λ = 655 nm of the blue complex after extraction with tri-n-octylphosphine
(TOPO) oxide (TOPO) in cyclohexane
Morin Fluorimetric determination of the complex after EDTA addition
Xylenol orange Flow injection spectrophotometric determination in sulfuric acid medium