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CHAPTER-1
Section ( i ) : Introduction
Organic analytical reagents are the carbon compounds capable of reacting
quantitatively with metal ions or the inorganic anions, resulting in the formation of a
precipitate, an insoluble complex or a stable colour. Based on this type of reactivity,
the reagents are widely used in gravimetry and colorimetry. In either case, it is
observed that the chelating properties of the organic compounds play a significant
role. However, a good number of methods based on the formation of coloured
products (soluble or insoluble) through redox–reactions rather than the complex
formation reactions have been reported. But the complex forming methods still
occupy predominant place in chemical analysis. The complex forming reagents are
required to possess the functional groups capable of coordinating with the metal ion
concerned to form stable and coloured metal complexes.
Even though one cannot predict easily which organic compound is suitable for
the analysis of a particular metal ion, some guidelines could be worked out on the
basis of available data in the literature. It is observed that an organic compound is
required to possess acidic or basic groups besides the group containing coordinating
atoms to function as organic reagents. Some of the acidic or basic groups are listed in
Table 1.1.
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Table 1.1: Some acidic or basic groups
Carboxyl
Sulfonic
Sulfinic
Arsonic
Oximic
Nitro (primary)
Nitro (secondary)
Enolic
Phenolic (alcoholic) C OH
Thiophenolic
Thioenolic
Sulfonamidic
Acid-imide –CO–NH–CH2
Basic groups that are
derivatives of ammonia
–NH2, –NHR, –NR1R
2 and cyclic allyl bound
nitrogen atoms
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The atomic groups involved in the coordination shall contain oxygen, nitrogen
or sulphur as coordinating atoms. Presence of other atoms or groups in the compound
exerts a fundamental effect on the usefulness or otherwise of the organic compound as
an analytical reagent. Organic compounds are easily convertable into compounds of
desired structural features through condensation or substitution reactions. It is found
that compounds containing -OH, -SH and -NO serve as good organic reagents. Some
typical examples are given in Table 1.2.
A careful analysis of the different reports made in the literature on the use of
organic compounds as inorganic analytical reagents suggest that, certain groups are
specific for specific metals or groups of metals. These are presented in Table 1.3.
The facts mentioned above indicates that the presence of a coordinating group
(>C=N–) together with the acidic groupings (–OH, –SH) seems to favour the
reactivity of the compounds with metals such as copper, cobalt, nickel, vanadium,
molybdenum, uranium, thorium, ruthenium, palladium and zirconium etc. Among the
compounds possessing these characteristics, hydrazones or azomethines are
characterized by the presence of atomic group (>C=N–N<) seems to offer
advantageous over others. A large number of such hydrazones find application as
spectrophotometric analytical reagents.
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Table 1.2 : Compounds containing –NO, –OH, –SH groups
Reagent Complex
1-nitroso-2-napthol-3,6-disodium
sulfonate
o-nitrosophenol
Ammonium salt of
nitrosophenylhydroxylamine
N
NO
OH(NH4)
4–chloro–1,2–dimercaptobenzene
Thionalid
Thioglycolic anilide
4-Hydroxybenzothiazole
(M =1/2 Cu, Ni, Zn etc)
Pyrogallol
Bismuth pyrogallate
Mercaptobenzothiazole
Methoxy salicylaldoxime
CH
OCu/2
NOCH3
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Reagent Complex
Dihydroxy anthraquinone
Rhodizonic acid
Sodium rhodizonate
Sodium rhodizonate
7-Iodo-8-hydroxyquinoline-sulfonic
acid
Blue coloured ferric complex
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Table 1.3 : Groups of specific formulas
Metal (or) Groups of metals Specific groups
Germanium [=C(OH)–CO–]
Thallium [–CO–CH2–CO–]
Zirconium [–CHOH–COOH]
Copper
Nickel and Palladium
Vanadium, Molybdenum and
Uranium
Aluminium, Ruthenium and
Molybdenum
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Important components of environment are air, water and soil. Water is an
essential commodity for human survival and industrial development. Effective
management of water resources and control of pollution are becoming increasingly
important for sustainable development and human welfare. Water is elixir of life. But
polluted / and contaminated water is the culprit for occurrence of dreadful diseases in
humans and animals. Inorganic pollutants especially mercury, cadmium, lead, copper,
chromium and nickel discharged from industries get into human food chain, enter the
human body and disturb biochemical processes leading to fatal diseases such as
Mina–Mata, Ouch–Ouch, cirrhosis of liver, skin cancer etc.
The determination of toxic metal ions in water and edible (food) materials is
an interesting research activity of inorganic–analytical chemist. The results obtained
from such research activities are very useful to decide the degree of water pollution
and food contamination. When the pollutants are found above permissible levels in
water, measures may be taken to control water pollution. Thus analytical data has
immense value in the control of water pollution, detection of diseases and in
providing public awareness.
Inorganic analytical chemistry has made a spectacular progress mainly due to
the following reasons. The first was due to advances in the design and development of
sophisticated analytical instruments permitting analysis at microgram concentration
while second reason was that the synthesis of novel organic ligands permitting the
quantitative analysis by complexation of metals with organic ligands at trace
concentration. Although a large number of organic reagents were synthesized and
characterized, unfortunately very few of them were used for the quantitative analysis
of heavy metal ions, especially mercury, lead, cadmium. Several methods involve
extraction step.
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Determination of microgram amounts of metals in biological and
environmental samples using sensitive organic reagents has been an important and
interesting research activity in University colleges having minimum facilities. UV–
Visible double beam spectrophotometer is one of the analytical instruments available
in the laboratories of university colleges. The success of spectrophotometric method
largely depends in the selection of new reagent synthesized in a research programme.
Chromogenic reagents containing aromatic groups, however, give intense colour with
metal ions possibly due to complex formation. In general, metal complexes of ligands
show intense colour due to metal to ligand charge transfer transition (MLCT).
The use of organic reagents in the inorganic analytical chemistry was known
during the last three decades. The colour forming reagents are called chromogenic
reagents. This field of work took great strides towards identification and
determination of metals at extremely low concentration. As a matter of fact entire
qualitative analysis schemes were based on the use of chromogenic ligands for the
detection of cations. The large number of metal ions were determined with plethora of
organic ligands. Such ligands consisted of β–diketone, oximes, naphthols,
azonaphthols, dithizone, diethyldithiocarbamates, dithiols, semicarbazones,
thiosemicarbazones, hydrazones which contained donor atoms such as oxygen,
nitrogen or sulphur. These reagents are not only used in qualitative analysis but also
in quantitative methods. Thus, the quantitative analysis of metals has been
predominated by spectrophotometric methods using chromogenic regents.
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Sources of Inorganic pollutants and their toxicity
A wide variety of inorganic pollutants have been identified in the environment
consequent to urbanization, industrialization and new technological developments.
The sources of heavy metals (Hg, Pb, Cd, As, Cu) are mainly aquatic releases from
industrial operations, atmospheric releases from fossil fuel burning, domestic sewage
discharges and land run off. These elements exhibit varying environmental behaviour
and toxicity to aquatic organisms and man.
Heavy metals in general cause only local pollution problems. Environmental
importance of these metals should be assessed in terms of the degree of toxicity and
the extent of exploitation of the metal, its applications and the ease of mobilization of
metal into the air, water and soil.
A. Mercury
Mercury occurs in the environment as metallic Hg and as HgS. Annual
production of the World is estimated to be about 10,000 tons. About 50 percent of it is
estimated to be lost to the environment1.
The principal sources of Hg pollution/contamination are mentioned here.
1. Chlor–alkali plants : Hg cells are used in the manufacture of chlorine and caustic
soda. A plant producing 100 tons of chlorine per day may release 4000 – 8000 Kgs of
Hg per year in the waste effluents. The products of chlor–alkali industry are bleaching
powder and sodium hydroxide. These are also found to be sources of long term Hg
pollution.
2. Mercury Catalysts : HgCl2 is used as catalyst in the manufacture of vinylchloride
plastics and acetaldehyde. Effluents from such plants contribute Hg to aquatic
environment1.
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3. Electrical Industry
fluorescent tubes, circuit breakers etc
4. Paints : Hg compounds are used in antifouling paints
5. Pulp and Paper industry
the waste water effluents.
6. Fungicides : Phenyl mercury acetate and ethyl mercuric chlori
fungicides, finally they enter water due to agricultural run
7. The use of mercury in research
cause water pollution.
8. Fossil fuel burning and cement manufacture cause emission of mercury into
atmosphere.
Aquatic food appears to be major source of human intake of Hg
major incident involving Hg poisoning from this source was reported from Minamata
Bay, Japan. Malfunctioning of central nervous systems
disease was caused by eating of contaminated fish
mercury as a result of water discharges from an acetaldehyde plant
Mercury combines with sulfhydryl groups of enzymes and are toxic to all
cells. Even trace quantities (0
marine phytoplankton.
Electrical Industry : Hg is used in the production of batteries,
circuit breakers etc., all which are finally discarded as waste
: Hg compounds are used in antifouling paints.
ndustry : Hg is used to prevent formation of slime and is lost to
.
: Phenyl mercury acetate and ethyl mercuric chloride have been used as
finally they enter water due to agricultural run–off.
The use of mercury in research, jewellery, moulding processes, pharmaceuticals
Fossil fuel burning and cement manufacture cause emission of mercury into
Aquatic food appears to be major source of human intake of Hg
major incident involving Hg poisoning from this source was reported from Minamata
Malfunctioning of central nervous systems, now known as Minamata
disease was caused by eating of contaminated fish2–4
, that accumulated methyl
as a result of water discharges from an acetaldehyde plant.
Mercury combines with sulfhydryl groups of enzymes and are toxic to all
Even trace quantities (0.001 ppm) of organomercurals reduces photosynthesis in
10
street lamps,
all which are finally discarded as waste.
: Hg is used to prevent formation of slime and is lost to
de have been used as
pharmaceuticals
Fossil fuel burning and cement manufacture cause emission of mercury into
Aquatic food appears to be major source of human intake of Hg. The first
major incident involving Hg poisoning from this source was reported from Minamata
now known as Minamata
that accumulated methyl
Mercury combines with sulfhydryl groups of enzymes and are toxic to all
001 ppm) of organomercurals reduces photosynthesis in
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B. Copper
Copper mining and metallurgical operations contribute to contamination of
aquatic environments. Copper salts are used as algicides and fungicides. Bordeaux
mixture (a formulation of copper sulphate and calcium carbonate) is still used as
fungicides. Copper is used as antifouling paints for protection of ships. Most of the
paints contain about 100 – 200 g of CuO per litre of paint.
Microgram quantities of copper cause significant reduction in the growth of
green algae. The toxicity of copper to aquatic organism vary with the chemical
species present in water. The main dissolved species of Cu in aquatic environments
are Cu(OH)+, Cu
2+, CuCO3.
Copper is an essential element. It is an important constituent of proteins and
enzymes. It is essential for mammals in the synthesis of hemoglobin. Excessive
accumulation of copper in liver, kidney and brain causes Wilsons' disease. It leads to
failure of liver, malfunction of kidney and various neurological abnormalities.
Wilson’s disease is due to genetic disorder but not due to pollution of water with
copper. This disease causes abnormalities in normal copper metabolism.
C. Lead
Lead poisoning is a medical condition caused by increased levels of the metal
in the body. Lead interferes with a variety of biological processes and is toxic to
many organs and tissues including the bones, intestines, kidneys and reproductive and
nervous system. It particularly causes permanent learning and behaviour disorders.
Its symptoms includes abdominal pain, confusion, headache, aneamia and in severe
cases, coma and death.
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Lead can be found in products kohl, an ancient cosmetic product from the
Middle East, South Asia. Tetra Ethyl Lead (TEL) is a gasoline additive and is still
used in fuels such as aviation fuel. TEL can enter the body through the skin.
Tetra Ethyl Lead (TEL)
Sources of Lead are industrial discharges, use of leaded petrol, forest fuel
burning and sewage sludge.
D. Nickel
Metallic nickel has carcinogenic properties because it can slowly dissolve in
the body and release ionic nickel, an active genotoxic and carcinogenic form of
nickel. The following nickel compounds are known as carcinogens.
Metallic nickel Ni
Nickel monoxide NiO
Nickel hydroxide Ni(OH)2
Nickel acetate Ni(C2H3O2)2
Nickel chloride NiCl2
Nickel carbonyl Ni(CO)4
E. Palladium
Palladium is regarded as less toxic, being poorly absorbed by the body when
ingested. It may cause skin, eye (or) respiratory tract irritation and may cause skin
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sensitization. PdCl2 is toxic if swallowed, inhaled as it is absorbed through the skin.
Tetrammine palladium hydrogen carbonate (TPDHC) causes bone nervous, liver and
kidney damage in laboratory animals.
Hydrazones as spectrophotometric reagents
The present review deals with spectrophotometric determination of
mercury(II), lead(II), copper(II) and nickel(II) using hydrazones.
Hydrazones are azomethines characterized by the presence of the triatomic
grouping >C=N–N<. They are distinguished from other members of this class
(imines, oximes etc.) by the presence of the two interlinked nitrogen atoms. The
hydrazone group occurs in organic compounds of the types.
Where
R and R = H, Alk, Ar, RCO, Ht (Heterocyclic group)
Y = H, Alk, Ar, Ht, RCO
X and X' = H, Alk, Ar, Ht, Hal, OR”‘ SR, CN, SO2R NO2, NHNR” R”‘
N=NR, COOR” R'“
The general name hydrazone is used for all compounds having structure (I).
The compounds of type (II) are termed “azines”.
Nomenclature
Hydrazones are usually named after the carbonyl compounds from which they
are derived. Thus benzaldehyde and phenylhydrazine give benzaldehyde
phenylhydrazone. The name originally used was benzylidene phenylhydrazine. Some
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authors have revoked to this system, which is, however, cumbersome when applied to
more complex hydrazone. Bis (hydrazones) of α–diketones are widely called
“osazones”. The nomenclature widely used in the literature is not in accordance with
IUPAC rules.
Preparation
Hydrazones, in general, are prepared by refluxing the stoichiometric amounts
of the appropriate hydrazine and aldehyde or ketone dissolved in a suitable solvent.
The compound usually crystallized out on cooling. Detailed account of their
preparation are given in a review5. Many hydrazones are now commercially available.
Non – analytical applications
Many of the physiologically active hydrazones find application6 in the
treatment of several diseases such as tuberculosis, leprosy and mental disorder. On the
other hand aroylhydrazones (III) are reported to possess tuberculostatic7'8 activity.
This is attributed to the formation of stable chelates with transition metals present in
the cells.
R–CH=N–NH–CO–R'
(III)
Thus many vital enzymatic reactions catalysed by these transition metals
cannot take place9–11
in presence of hydrazones. Hydrazones also act as herbicides,
insecticides, nematocides, rodenticides and plant growth regulators. They show
spasmolytic activity by potensive action and activity against leukaemia, sarcomas and
other malignant neoplasms. Hydrazones are used as plasticizers and stabilizers for
polymers and as polymerization initiators, antioxidants etc. They act as intermediates
in preparative chemistry. Hydrazones of 2–methyl phthalasone12
are effective
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sterilants for houseflies. 3–N–Methyl–N–(4–chloro–l–phthalazinyl) and 3–N–
Methyl–N– (4–oxo– 1–phthalazinyl) hydrazones possess anthelmintic activity13
. The
metal chelates of some hydrazones are useful in industry as dyes for wool, nylon,
rubber etc. and as photometric materials14
.
Analytical Applications
Jain and Singh15
reviewed critically the applications of hydrazones as
analytical reagents. The formation of hydrazones is extensively used in the detection,
determination and isolation of compounds containing the carbonyl group. Photometric
methods for determining aldehydes and ketones are based on their reaction with 2,4–
dinitrophenylhydrazine to form the corresponding hydrazones16–17
.
Hydrozones gives a blue colour with traces of copper and is used for
determination of copper in paper pulp products18
, human serum19
, steel20,21
plants22,23
non–ferrous metals and alloys24,25,
and in cadmium sulphide26
. Analytical properties
of hydrazones for the spectrophotometric determination of metal ions are summarized
in Table 1.4.
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Table - 1.4
A list of hydrazones employed in the spectrophotometric determination of metal
ions
Name of the Hydrazone Metal ions λmax (nm) pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
1 2 3 4 5 6 7 8
Pyridine-2-aldehyde-2-pyridyl-
hydrazone(PAPH)
Pd (II)
Zn(II) Cd(II)
Mn(II)
Fe(III)
,Ni(II)
Pd 560
Fe 405
Basic
ethanol
and water
Acidic
-
Pd 10 – 100
1:1
-
Pyridine-2-aldehyde-2-quinolyl
hydrazone(PAQH)
Pd(II)
Pd(III)
Co(II)
Ni(II)
594
589
519
492
1.5-2.3
8.0
High
1.2 x 104
3 x 104 Co(II)
5.1 x 104 Ni(II)
0.2 – 2.0
0.1 – 1.0
1:1 Sea water
Quinoline-2-aldehyde-2-quinolyl
Hydrazone(QAQH)
Cu(II)
Cu(II)
536
540
-
-
4.7x104
5.8x104
- - Sea water
Quinoline-2-aldehyde-2-pyridyl-
hydrazone(QAPH)
Zn(II)
Cd(II)
Pd(II)
Cu(II)
Ni(II)
512
524
512
517
615
9.0 Borate
5.8 x 104
6.2x104
5.1 x 104
4.1 x 104
1.6 x 104
- - -
Phenanthridine-6-carbosaldehyde-2-
pyridylhydrazone(PDAPH)
Zn(II)
Cd(II)
Pd(II)
Cu(II)
Ni(II)
522
530
525
525
625
9.0 Borate
7.1 x 104
5.3 x 104
7.0 x 104
7.3 x 104
7.8 x 104
- - -
Phenanthridine-2-quinolyl-
hydrazone(PDAQH)
Cd(II)
Pd(II)
536,
530,
640
9.0 Borate
6.6 x 104
15.7 x 104
1.2 x 104
- - -
Benzoylpyridine-2-pyridyl-
hydrazone(BPDH)
Fe(II)
Co(II)
Cu(II),Ni(II)
and Zn(II)
- - -
Fe 0.3
Co 0.2
Ni 0.13 Cu
0.14 Zn 0-13
- -
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
2,2'-Dipyridyl-2-hydrazone(DPPH)
Cu(II)
Zn(II)
V(V) and
Pd(II)
- - - - -
Co(II) 480 3-11 3.2 x 104 0.15-2.0 1:2
Fe(II)
Fe(III)
538 1.5-3.5
-
1.5 x 104
-
0.7-2.8
-
1:3
–
Phenyl pyruvic acid-2-pyridyl-
hydrazone(PPAPH)
Cu(II)
420
-
-
-
1:2
-
Benzoyl salicylalhydrazone (BSH) Pd(II) -
385
395
4.9-9.0
4.5-6.5
1.2-2.3
-
1.55 x 104
7.18 x 104
-
1:1
1:1
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Pyridine-2-aldehyde-1-thio-
napthylhydrazone(PATNH)
Cu(II)
480
1M Hcl
6.35x103
-
1:2
-
Furfural-2-benzothiazolyl-
hydrazone(FBTH)
Ag(I)
Co(II)
Zn(II)
989
408
415
6.5-9.2
9.9-11.2
5.6-9.6
2.6 x 104
5.1 x 104
4.4 x 104
- -
1:2
Water
Hydroxy benzaldehyde
isonicotinoylhydrazone (or) 1-
isonicotinoyl-2-salicylidene-hydrazine
(INSH)
Al(III)
Ga(III)
In(III)
Tl(III)
Ni(II),Zn(II),
Mn(II),Cd(II)
375
390
380
-
380
420
5.0
12.7 x 103
3.4 x 104
3.3 x 104
-
1.5 x 104
2.5 x 104
0.5-3.5
0.2-1.6
0.3-2.5
-
1:1
1:2
1:1
1:1
-
-
Hydroxy benzaldehyde benzoyl-
hydrazone (BBH)
Zn(II) and
Mn(II)
380
400 - 1.35 x 10
4 - - -
Hydroxy benzaldehyde
isonicotinoylhydrazone
V(V)
In acidic 50%
ethanol
medium
Name of the Hydrazone Metal ions λmax
(nm) pH/ medium
ε
L mol-1
cm-1
Deter-mination
range (µg/ml) M:L Applications
-Methyl-2-pyridyl)glyoxal-
dihydrazone
Pd(II)
Co(II)
420 4.8-11.2 8.7 x 103 1:1
Saturated brain, Cu(II),
alkalis and milk
Methyl picolinaldehyde-hydrazone (6-
PAH)
Pd(II)
Cu(II)
425
-
- 7.0 x 103
-
1.0-7.0
-
-
Pyridylhydrazone Fe(II) 486 - 0.5-5.0 - -
Bipyridylglyoxal dihydrazone Fe(II) - - - - - -
Diacetyl dihydrazone Fe(II) - - - -
Phenyl-2-pyridyl ketone hydrazone Fe(II) - - - - -
Benzil-bis-2-pyridylhydrazone
Zn(II),
Fe(II)
Co(II) - 4.5-6.5 - - - -
Pyridyl-2-pyridylhydrazone
Zn(II),
Fe(II),Co(II),
Ni(II) - - - 0.2-2.5 - -
Pyridyl-bis-pyridylhydrazone
Zn(II)
Fe(II)
Co(II) - 3.2 x 104 - - -
Benzil mono-(2-pyridyl)hydrazone Co(II)
535 Ethanolic 2.7 x 104
- - Steel and alloy samples
(4-Hydroxy benzoylhydrazone) of
glyoxal, methyl glyoxal and
dimethylglyoxal
Ca(II),
Cd(II),
La(III),
Bi(III) - - - 0.0-5.0 1:1 -
Resorcylaldehyde acetyl-hydrazone
Fe(III),
U(VI)
Ti(IV),
Co(II), iron - - - - - -
18
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Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Salicylaldehydehydrazone
Pd(II)
Os(VIII)
Cu(II) Fe(III)
Co(II)
445
430
440
510
450
4-5
6.2-7.0
7.5-8.7
3.0-5.0
6.2-7.0
5.3 x 103
3.2 x 103
7.8 x 103
4.1 x 103
7.9 x 103
Up to 21
19.7
5.6
3.6
5.8 ppm
1:2
1:1
1:1
1:3
1:2 -
p-Nitro and 2, 4-dinitrophenyl-
hydrazone of 4-methylpentane-2,3-
dione-2-oxime
Co(II)
Ammonical
medium 1:2
-
Gossypol isonicotinoylhydrazone UO2(II) 440 3 3-12 1:2 -
Bis(Phenylhydrazone) of oxamide Fe(III) - - - - - -
Ethyl diketobutyrate 2-hydroxy
phenylhydrazone
Cr(III) 565 8-9
- -
-
Benzil di-2-pyridylhydrazone
Co(II)
Fe(II)
497
430
531
635
-
4.9 x 103
5.4 x 103
4.6 x 103
5.8 x 103 -
2:1
-
2,2'-Pyridil mono-2-pyridyl-
hydrazone Fe(II) 621 - 1.30 x 104
- 2:1
-
2,2'-Pyridyl di-2-pyridylhydrazone
Fe(II)
Co(II)
595
466
480
452
- 8.30 x 103
2.03 x 104
2.54 x 104
3.20 x 104
-
3:1
-
2,2'-Dipyridyl-2-pyrimidyl-
hydrazone Co(II) 460 2.5-11.5 2.95 x 104 1:2 Alloys
Pyridine-2-aldehyde-2'-pyridyl-
hydrazone Mn(II) - - 5.71 x 10
4 - - -
19
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19
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Benzamidazone Mn(II) - - 1.36 x 104 - 1:1 -
2,2'-Dipyridyl-2-quinolyl-
hydrazone(DPQH) V(V)
550
580
3.7-5.9
5.0-13.0
2.28 x 104
1.25 x 104
Up to
2.29
1:1
-
Benzothiozole-2-aldehyde-2-
quinolylhydrazone
Pd(II)
- 8.3-12.6 7.5 x 10
4 0.09-0.75
- -
2,2'-Dipyridyl ketone-2-pyrimidyl-
hydrazone(DDPMH) Fe(II) 540 1.5-2.5 1.15x10
4 Up to 5.0
- In alloys
2-Methyl isonicotinic salicylal-
hydrazone Ti(IV) 425 1.0-2.5 - 1:2
-
Picolinaldehyde-p-nitrophenyl-
hydrazone Pd(II) 480 - 9.5 x 10
3 3.0-9.0
- -
Di-2-pyridyl glyoxal-2-quinolyl-
hydrazone Fe(III) - 6.0-10.5 3.2 x 10
4 Up to 2.0
- -
5-Chloro-2-thiophenaldehyde-2'-
benzothiazolylhydrazone Co(II)
- 7.2-9.1 7.46 x 10
4 0-180
- -
2,2'-Dipyridyl-2-pyrimidyl hydrazone Co(II) -
2.5-6.5 M
HCIO3 3.13 x 104 ≤ 2.1
- -
2,2'-Bipyridyl glyoxal-2,quinolyl-
hydrazone Co(II)
- 4.0-8.0 3.2 x 10
4 0.24-1.92
- -
Salicylaldehydehydrazone Pd(II)
Os(VIII)
425
430
3.5-5.0 9.
5-10.0
5.3 x 103
3.2 x 103
Up to 21
Up to
19.7
1:2
1:1 -
2-Pyridylaldehyde-2-pyridyl-
hydrazone Fe(III) - 9.0
- 2.0-16.0 -
-
Bis-acetyl mono-(2-pyridyl)-
hydrazone Co(II) - -
- 0.5-3.5
-
20
Page 20
20
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
2-Pyridine carboxaldehyde-2-
pyridylhydrazone Co(II) - 6 - - - -
2,2'-Dipyridyl-2'pyridyl-hydrazone Co(II) 480
500
3-11
strong acid 4.2 x 104 >1 ppb
Sea water
brine
2,2'-Dipyridyl-2-quinolyl-hydrazone Pd(II)
570
604
-
0.2-0.9 M HCl
1.75 x 104
2.21 x 104
- 1:1 -
Fe(II)
645
566
475
3.4-4.5
1.3 x 104
3.11 x 104
3.61 x 104 -
1:2
-
Co(III) 528 2.5M(H2SO4) 4.18 x 104 1:2 -
Zn(II) 510 7.6-9.1 8.21 x 104 1:2 -
Di(2-Pyridyl) ketone-2-furan
carbothiohydrazone
Re(VII)
Ni(II)
Co(II)
Fe(II)
546
470
478
505
725
-
3.5-4.2
3.0-4.0
3.0-4.0
2.0-4.0
1.51 x 104
1.64 x 109
1.12 x 104
2.25 x 104
0.80 x 104
1.08 x 104
0.7-14
0.4-8.0
0.2-12.0
1.2-23.6
0.8-16.0
1:2
1:1
1:2
1:2
1:2 -
Diphenyl glyoxal bis(2-
hydroxybenzoyl) hydrazone
Ti(IV) 500 0.1 N H2SO4 1.5 x 104 0.5-2.5 1:3
-
2-Furaldehyde-2,pyridylhydrazone Pd(II) 430 8.0-8.5 - 0.5-2.5 -
2,2'-Dipyridyl-2-guinolyl hydrazone Fe(III) - 3.4-4.5 3.4 x 104 Up to 1.4 -
Pyridine-2-acetaldehyde salicyl-
hydrazone
Fe(III) - CHCl3 - 2.7-16.0
-
Pyridoxal salicylalhydrazone Ti(IV) 450 0.9-2.5 0.39 x 104 0-10.0 1:1
Pyridoxal-3-hydroxy-2-naphthayl-
hydrazone
Ti(IV) 430 2.7 - 0.5-7.0 - -
21
Page 21
21
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Pyridoxal nicotinoylhydrazone Ti(IV) 410 2.1-2.3 0.69 x 104 - 1:1 -
Pyridoxal-2-pyridylhydrazone V(V) 430 1.7-1.9 1.0 x 104 - - -
2-Thiophenoldehyde-2-quinolyl-
hydrazone
V(V) 425 HCl 1:1 - - - -
2-Aceto-1-naphthol-N-
salicylhydrazone
Mn(II) - - - - - -
2,2'-Dipyridyl ketonehydrazone Pd(II)
500 13.4
80% ethanol
0.5-4.0
2,2'-Dipyridyl benzothiazolyl-
hydrazone
Fe(III) - 4.5-8.4 3.41 x 10
4 0.1-1.6 - -
2-Pyridyl-3'sulphophenyl methanone-
2-pyrimidylhydrazone Fe(III) - 7.3-10.0 4.75 x 10
4 0.04-1.2 - -
Di(2-Pyridyl)methylene-2-furoyl-
hydrazone Fe(III) - 9.6 8.4 x 103 1.0-6.0 - -
3-Bromo-2-hydraoxy-5-methyl
acetophenonehydrazone Co(II) - 2.0-6.0 - 0.62-6.22 - -
3-(Picolinoyl)benzene sulphuric acid-
2-hydroxy benzoylhydrazone V(V) - - - - - -
2,2'-Dipyridyl-ketone-2-quinolyl-
hydrazine V(V) - Acidic - Up to 1.5 1:1 -
1,2-Cyclohexane dione(bis benzoyl)
hydrazone Ti(IV) 477 1.75-3.0 1 x 10
4 1.7-3.00 1:2 -
N-Cyanoacyl acetaldehyde-
hydrazone
Mo(VI)
V(V)
790
410 -
-
0.77 x 104
-22-49.0 1:1
1:1 -
Resacetophenone isonicotinoyl-
hydrazone Mo(VI) - - - - - -
22
Page 22
22
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
3,4-dihydroxy benzaldehyde gunyl-
hydrazone Mo(VI) - - - - - -
2-Hydroxy-1-naphthaldehyde
guonylhydrazone V(V) 405 0.77 x 104 0.7-8.2 1:1 -
Anthranilic acid resocylalde-
hydrazone V(V) 410 4.5 1.35 x 10
4 - - -
2,6-Diacetylpyridine bis(benzoyl-
hydrazone) V(V) 335 2.6-4.0 2.74 x 10
4 - - Fe(II)
2,6-Diacetyl pyridine bis(2-hydroxy
benzoylhydrazone) V(V) 336 2.6-3.5 2.77 x 10
4 - - -
Thiazole-2-carboxaldehyde-2-
guinolylhydrazone Pd(II) 588 C6H6 1.93 x 104 - - -
2-Pyridyl-3' -sulfophenyl methanone-
2-(5-nitro)pyridyl-hydrazone Co(II) - - 5.69 x 10
4 0.05-1.0 - -
2(-3'-Sulfobenzoyl)pyridine
benzoylhydrazone Co(II) 1.5 M HClO4 2.17 x 10
4 - - -
Salicylaldehyde isonicotinoyl-
hydrazine Mo(VI) 430 0.65 - 0.4-12.0 - -
3,5-dichloro-salicylaldehyde-2-
benzothiozolyl hydrazine Mn(II) 460 3.0-4.8 - Up to 60 - -
2(3'-sulfobenzoyl)pyridine
benzoylhydrazone Fe(III) 7.0-11.0 - Up to 4.0 -
Resacetophenone oxime salicylic acid
hydrazone V(V) 450 Acetic acid 6 x 10
3 0.5-4.0 - Steels
2,4-Dihydroxy benzophenone
benzoylhydrazone Ce(IV) 400 8.0-10.5 2.0 x 104 0.3-7.0 1:1 -
23
Page 23
23
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Di-2-pyridylketone-2-pyridyl-
hydrazone V(V) 545 1.4 x 10
4
Bis(thiophene-2-aldehyde)-
thiocarbohydrazone
Ru(III)
Ir(III)
540
380
0.3-0.7
5.6-6.6
1.6 x104
2.2 x 104
0.7-3.5
1.2-4.2 3:1 Synthetic mixture
2-Hydroxy-1-acetonaphthone
salicylic acid hydrazone(HANSH)
V(IV)
V(V)
U(VI)
Zr(VI)
Th(IV)
Mo(VI)
410
410
310
402
400
350
4.0
5.0
8.0
1.0
6.0 CH3COOH
1.22 x 104
1.4 x 104
0.78 x 104
2.6 x 102
1.1 x 104
5.4 x 103
0.5-5.0
0.5-5.0
0.6-3.0
18-180
46-460
10-100
1:2
1:2
1:2
1:2
1:2
1:2
-
2,4-Dihydroxy acetophenone
benzoylhydrazone
Mn(II)
V(V)
450
380
8.0-11.0
3.0-3.5
1.0 x 104
1.3 x 104
0.3-7.0
0.3-5.0 1:1
Steels, alloys plant
samples
Ortho hydroxy acetophenone
isonicotinoylhydrazone
V(IV)
Ti(IV)
390
380 Acidic 4.0
1.0 x 104
2.0 x 104
1.0-30.6
1.2-14.4
1:1
1:2 Steels
Fe(III) 380 5 2.8 x 104 0.14-0.38 2:3 Cement
2,4-Dihydroxy benzophenone
benzoichydrazone
V(V)
Mn(II)
390
455 9.0-9.5
2.0 x 104
2.5 x 104
1:1
1:1 -
2,4-Dihydroxybenzaldehyde
isonicotinoylhydrazone Ti(IV) 430 1-7 1.35 x 104 0.09-2.5 1:2
Nickelbase high
temp. alloy and steel
samples
24
Page 24
24
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Di-furfuralthiocabohydrazone
Rh(II)
Pd(II)
Os(VI)
Ir(III)
377
330
377
380
5.6-6.7
4.0-6.0 5.9.6.7
5.5-6.2
6.1 x 104
4.48 x 104
3.62 x 104
4.15 x 104
0.48-2.4
0.34-1.44
1.0-4.2
0.93-3.23
-
-
5-Chloro salicylaldehyde guanyl-
hydrazone Pd(II) 400 7.5-90 0.7129 x 10
4 1:2 -
2-hydroxyacetophenone benzoyl-
hydrazone(HABH) V(V) 375
CH3COOH
0.0-0.5M 8.93 x 103 0.0-3.5
2,4-Dihydroxy benzaldehyde
isonicotinoylhydrazone Mo(VI) 445 1.0-3.0 1 x 10
4 0.30-6.14 1:2
Steel, nickel based
high temp. alloys.
V(V) 440 2.0 15 x 104 0.1-2.0 1:1
Steel samples lead
samples and grape
Fe(III) 400 3.0 1.75 x 104 0.08 - 1.9 1:1
Banana fruit, Human
blood, Cu-Ni alloy
NTPC
2'-Hydroxyacetophenone benzoyl-
hydrazone V(II) 465 Acetic acid 1.05 x 10
4 0.0-1.5 1:2
Synthetic, alloy and
steel and
reverberotary flue
dust
2,5-Dihydroxy acetophenone
benzoichydrazone V(V)
400
405
5.0
5.5
1.1 x 104
1.05 x 104
0.3-3.0
0.25-2.5
- Steel, plant sample
Resacetophenone isonicotinoyl-
hydrazone Mn(II) 465 9.4 0.8 x 10
4 Up to 4.4 - Leaf sample of grape
Aceto acetanilide salicylalhydrazone V(V) 400 Acedic 4.38 x 103 - -- -
Isonitrosoacetyl acetone
benzoylhydrazone Ni(II) 390 – 400 10.0 1.13 x 104 0.09 – 3.0 -- --
25
Page 25
25
Name of the Hydrazone Metal ions λmax (nm) pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Benzoyl α-monoxime isonicotinoyl
hydrazone (BMIH)
Cd(II)
Ni(II)
Cu(II)Pb(II)
398
405
364
346
8.5
10.5
8.5
8.5
1.45 x 104
1.18 x 104
2.5 x 104
1.19 x 104
0.12-2.82
0.41-13.3
0.45-4.5
1.01-5.08
- -
Di-acetylmoxime isonicotinoyl
hydrazone (DMIH)
Cd(II)
366
374
346
346
8.15
10.5
9.0
8.5
1.7 x 104
1.24 104
2.0x 104
1.12x 104
- - -
Di-acetylmoxime benzoyl hydrazone
(DMBH)
Cd(II)
362
372
348
346
9.0
10.5
9.5
9.0
2.1 x 104
1.25 104
1.6 x 104
1.36 x 104
- - -
2-hydroxy naphthaldehyde benzoic
hydrazone OHNABH)
V(V)
Fe(II)
Co(II)
430
410
.410
465
455
3.0
5.0
5.0
5.0
5.0
1.6 x 104
2.27 104
2.24 x 104
3.7 x 104
3.18 x 104
- - -
2,4-dyhydroxy benzaldehyde
isonicotinoyl hydrazone (DHBINH)
Fe(II)
Al(II)
Zn(II)_
- - - - - -
2-hydroxy 1-naphthaldehyde
isonicotinoyl hydrazone (OHNAINH)
Al(II)
Zr(IV)
Pd(II)
Ti(II)
425
455
490
410
4.5
2.0
10.0
4.0
3.01 x 104
1.69 x 104
3.82 x 104
1.54 x 104
- - -
Diacetyl monoxime isonicotinoyl
hydrazone (DMIH)
Fe(III)
Fe(II)
Co(II)
366
360
334
4.5-5.5
6.0-7.0
6.0-7.0
1.3 x 104
1.25 x 104
1.25 x 104
0.11-2.4
0.22-2.29
0.23-2.35
- -
26
Page 26
26
Name of the Hydrazone Metal ions λmax nm pH/ medium ε
L mol-1
cm-1
Deter-
mination
range
(µg/ml)
M:L Applications
Di-acetylmoxime benzoyl hydrazone
(DMBH)
Fe(III)
Fe(II)
368
360
5.0-5.5
6.0-6.5
1.16 x 104
1.25 x 104 0.11-2.40
0.11-2.24 - -
2,4-dihydroxy acetophenone isonicotinoyl
hydrazone (RPINH)
Ti(IV)
Pd(II)
Zr(IV)
V(II)
Ru(III)
490
420
415
410
415
1.0-2.0
5.0
1.5
4.0
3.0
1 x 104
1.4 x 104
1.7 x 104
0.89 x 104
10.3 x 104
0.47-3.35
0.53-6.3
0.23-3.19
0.25-3.05
0.02-0.39
- -
2,4-dyhydroxy benzaldehyde isonicotinoyl
hydrazone (DHBINH)
Mo(VI)
Th(IV)
Zr(IV)
-
-
410
-
-
1.5
-
-
1.8 x 104
-
-
0.40-4.0
-
-
1 : 2
-
2-amino acetophenone isonicotinoyl
hydrazone (AAINH)
Au(III)
Pd(II)
V(V)
Co(II)
440
4.0
3.50 x 104
0.40-5.0
2 : 1 -
2,4-dyhydroxy benzaldehyde isonicotinoyl
hydrazone (DHBINH)
Mo(VI)
Th(IV) - - - - - -
2-hydroxy naphthaldehyde benzoyl hydrazone
(OHNABH)
V(V)
465
443
5.0
-
0.0 – 2.5
0.0 – 4.5
-
2,4-dyhydroxy benzaldehyde isonicotinoyl
hydrazone (DHBINH)
Zn(II)
390 6.8 3.5 x 104 0.1 – 1.5
-
Diacetyl monoxime 4-hydroxy benzoyl
hydrazone (DMHBH)
Sn(II)
430 - 3.2 x 104 0.25-2.76 -
-
di-2-pyridyl ketone salicylal hydrazone Zn(II) - - - - - -
2,4-dyhydroxy benzaldehyde isonicotinoyl
hydrazone (DHBINH)
Fe(III)
Co(III)
Ti(II)
Ni(II)
400
400
405
490
6.0
3.0
5.5
1 – 3
4.0 x 104
1.7 x 104
3.20 x 104
-
0.06-1.17
0.07-2.20
0.06-1.5
0.19-6.0
1 :1
1 :1
1 :1
-
-
2-amino acetophenone isonicotinoyl
hydrazone (AAINH)
Pd(II) 500 4.0 3.0 x 104 0.30-3.0 1 : 2
-
27
Page 27
27
Objectives of the present work
1. To synthesise and characterize new reagents viz. salicylaldehyde acetoyl
hydrazone (SAAH), 2,4–Dihydroxyacetophenone acetoylhydrazone (DAAH),
salicylaldehyde isonicotinoylhydrazone (SAINH) and pyridoxal thio
semicarbazone (PDT).
2. To investigate physico–chemical and analytical properties of these new
reagents (i.e., SAAH, DAAH, SAINH and PDT).
3. To develop spectrophotometric methods for the determination of Hg(II),
Pb(II), Cu(II) and Pd(II) using above reagents.
4. To employ developed methods for the determination of metal ions in different
alloys and water samples.
Page 28
28
REFERENCES
1. Goldberg, E.D., The health of Oceans, the UNESCO press, Paris, (1976) pp.
172.
2. World Health Organisation (1972). Health hazards of Human environment,
WHO, Geneva (1972).
3. Higgins, I.J. and Burns, R.G.(1975). The Chemists and Microbiology of
Pollution, Academic Press, New York, PP.248.
4. Schroeder, H.A. et al. (1973), “Relation of trace metals to human health
effects”: In: Chemical analysis of the environment and other Modern
Techniques (Ed. Sut. Ahuja et al) Plenum Press, New York.
5. Brown, E.V., Caglioti, L., Paolucci, G. and Sucrow, W., Hydrazones and
Hydrazones, In: Methodicum chemicum, C-N compounds, F. Zymalkowski, 6
(1975) 73, Academic Press, New York.
6. Kitaev, Yu. P., Buzykin, B.I. and Troepol’skays, T.V., Russain Chem. Rev.,
(1970) 441.
7. Buu-Hoi, Ng. Ph., Xuong, Ng.D., Ham, Ng. N., Binson, F. and Roger, R., J.
Chem. Soc., (1953) 1358.
8. Ma, T.S. and Tien, T.M., Antibiot. Chemother (Washington), 3(1953) 491.
9. Albert, Q., Nature, 153 (1953) 370.
10. Price, J.M., Federation Proc., 20 (1961) 223.
11. Price, J.M., Brown, R.R. and Larson, F.C., J. Clin. Invest., 36 (1957) 1600.
12. Buzykin, B.I., Bystrykh, N.N., Bulgakova, A.P. and Kitaev, Yu.P., Otkrytitya,
Lzobret, Prom Obraztsy, Tovarnye Znaki, 54 (1977) 69: Chem. Abstr., 88
(1978) 132034r.
Page 29
29
13. Molodykh, Zh.V., Buzykin, B.I., Rystrykh, N.N., and Kitaev, Yu. P., Khim.
Form Zh. 11 (1977) 37: Chem. Abstr., 88 (1978) 989280y.
14. Lueda, H., Chem. Abstr., 105 (1986) 32929.
15. Jain, P. and Singh, R.P., Talanta, 29 (1982) 77.
16. Budesinksy, B., Chem. Listry, 54 (1960) 916.
17. Terentev, V.A. and Andreeva, R.K., Zh. Analait. Khim., 23 (1968) 1089.
18. Wetlesen, C.V. and Gran, G., Svensk. Papperstid, 55 (952) 212.
19. Peterson, R.E. and Bollier, M.E., Anal. Chem., 27 (1955) 651.
20. Haywood, L.J.A. and Sutcliffe, P., Analyst, 81 (1956) 651.
21. Capelle, R., Chim. Anal. (Paris), 42 (1960) 69.
22. Somers, E. and Garraway, J.L., Chem. Ind. (London), 42 (1957) 69.
23. Middleton, K.R., Analyst, 90 (1965) 234.
24. Saichiro, O., Kunihiko, W. and Yukichi, Y., Bunseki Kaugaku, 14 (1965) 339.
25. A Brown, G. and Rohde, Anal. Chem., 38 (1966) 911.
25a. Saichiro, O., kunihiko, W. and Yukichi, Y., Bunseki Kaugaku, 15 (1966) 924.
26. Frontly, F.C., Anal. Chim. Acta, 47 (1969) 511.
27. Bell, C.F. and Rose, D.R., Talanta, 12 (1965) 696.
28. Heit, M.L., and Rayan, D.E., Anal. Chim. Acta, 32 (1965) 448.
29. Heit, M.L., Ph.D. Thesis, Dalhousie University (1965).
30. Heit, M.L. and Ryan, D.E., Presented at the 48th
Annual Conference of the
C.I.C., Montreal, Canada (1965).
Page 30
30
31. Heit, M.L. and Ryan, D.E., Anal. Chim. Acta, 34 (1966) 3407.
32. Jensen, R.E. and Pflaum, R.T., Anal. Chim. Acta, 37 (1967) 397.
33. Singhal, S.P. and Ryan, D.E., Anal. Chim. Acta, 37 (1967) 91.
34. Afghan, B.K. and Ryan, D.E., Anal. Chim. Acta, 41 (1968) 167.
35. Jensen, R.E, Bergman.N.C. and Helvig.R.J .,Anal. Chem .,40, (1968),624.
36. Sims.G.G. and Ryan .D.E .,Anal. Chim. Acta,48, (1969),139.
37. Abraham.J, Winpe.M and Ryan. D.E .,Anal.Chim.Acta 48, (1969),431.
38. Zatka, V., Abraham, J., Holzbecher, J. and ryan, D.E., presented at the joint
Conference of C.I.C. and American Chem. Soc., Toronota, Canada May
(1970) 24.
39. Zatka, V., Abraham, J., Holzbecher, J. and ryan, D.E., Anal. Chim. Acta, 54
(1971) 65.
40. Going, J.E., Doctoral Dissertation, University of Lowa (1968).
41. Going, J.E, and Pflaum, R.T., Anal.Chem., 42,(1970),1098.
42. Going.J.E, Benge.D. and Daigneault. G.(unpublishedwork).
43. Alexaki, H. Tzlavaniden, Doctoral Thesis, University of Thessaloniki (1972).
44. Vasilikiotis, GS., Kovimtzis, Th, Apostolopoulou, C. and Voulgaropulos, A.,
Anal. Chim. Acta, 70 (1974) 319.
45. Alexaki-Tzivanidou, M., Anal. Chim. Acta, 75 (197) 231.
46. Chiswell, B. and Lions, F., Anstral. J. Chem., 22 (1969) 71.
47. Bell, C.F. and Rose, D.R., Inorg. Chem., 7 (1968) 325.
48. Bruce, St. L., Cooper, M.K. and McGrath, B.G., J. Chem. Soc. D. (1970) 69.
Page 31
31
49. Katyal, M., Kushwala, V. and Singh, R.P., presented at the 60th
session of the
Indian Science Congress, Chandigrah, India, (Jan. 1973) 3.
50. Katyal,. M, Kundra .S.K, Goel D.P. and Singh R.P ., J. Indian chem..Soc.,51,
(1974) 576.
51. Rastogi, K.K., Dua, S.K., Praksh, S. and R.P., Analysis, (1973-1974) 661.
52. Rastogi, D.K., Dua, S.K., Praksh, S. and R.P., Analysis, Acta. Chim. Sci.
Hung., 87 (1975) 63.
53. Ryan.D.E, and Katyal.M ., Anal. Letters,2,(1969), 515.
54. Jensen.K.A and Pedersen.G ., Acta.Chim. Scand .,15,(1961),1097.
55. Odashima.T. and Ishii. H .,Anal. Chim. Acta,83,(1976), 431.
56. Vasilikiotis, G.S. and Tossidis, J.A., Micro Chem. J., 14 (1969) 380.
57. Vasilikiotis, G.S., Kouimitzis, Th. A., and Vasiliades, V.C., Micro Chem. J.,
20 (1975) 173.
58. Vasilikiotis, G.S., Dissertation, University of Thessaloniki (1968).
59. Vasilikiotis, G.S., Papavasillious, O.Ch. and Kouimtzis, Th.A., Chimica
Chronica, Proc. IVth Conf. Greek Chemists, Athens, (1970) 107.
60. Vasilikiotis, G.S. and Kouimtzis, Micro Chem. J., 18 (1973) 85.
61. Vasilikiotis, G.S., Kouimitzis, Th. A., and Vasiliades, V.C., Micro Chem. J.,
20 (1975) 173.
62. Zommer, S., Rocznici. Chem., 47 (1973) 425.
63. Valcarcel, M. and Pino, F., Analyst, 98 (1973) 246.
64. Valcarcel, M. and Pino, F., Inform. Quim. Anal. (Madrid), 26 (1972) 116.
Page 32
32
65. Valcarcel, M. and Pino, F., Talanta, 20 (1973) 224.
66. Constate, E.G. An. Quim., 67 (1971) 607.
67. Graciani, E., Ph.D. Thesis, University of Seville (1969).
68. Schilt, A.A., Wu, J.F. and Case, F.H., Talanta, 22 (1975) 915.
69. Pflaum, R.T. and Tucker, E.C., Anal. Chem., 43 (1971) 458.
70. Pinkus, G., Chem. Ber., 31 (1898) 31.
71. Lever, M., Anal. Chim. Acta, 65 (1975) 311.
72. Urner, Z., Collection Czech. Chem. Commun., 33 (1968) 1078.
73. Ray, H.L., Ph.D. Thesis, Delhi University (1973).
74. Anaddi, V.D., Deshmukh, G.S. and Kumar, M.B., J. Prakt. Chem., 22 (1993)
98.
75. Asamov, K.A., Talipov, Sh. T. and Dzhiyanbaeve, R.Kh., Dokl. Akad. Nauk
UZSSR 6 (1963) 32, (Ref. Zh. Khim. 19, GDE, 1964, (4) Abstr. No. 4G, 16;
anal. ABSTR., 12 (1965) 99.
76. Koshkin, N.V., Zh. Analit. Khim., 20 (1965) 534.
77. Mittsel, Yu. A. and Vasilev, A.V., Zh. Analit. Khim., 29 (1974) 596.
78. Quddus, M.A. and Bell, C.F., Anal. Chim. Acta, 42 (1968) 503.
79. Pelova, R. and Toleva Nauchri, Tr., A., Plodiviski Univ., 12 (1974) 29; Chem.
Abstr., 83 (1975) 85826k.
80. Singh, R.B., Kulshrestha, H., Garg, B.S., and Singh, R.P., Current Science,
India, 48(3) (1979) 109.
81. Singh, R.B., Garg, B.S. and Singh, R.P., Ind. J. Chem., 17A (3) (1979) 318.
Page 33
33
82. Dogorev, A.V., Zh. Analit. Khim., 28 (1973) 99.
83. Carillo, J. and Guzman, M., An. Quim., 75 (1979) 550.
84. Kulshreshtha, H., Garg, B.S. and Singh, R.P., J. Chim. Chem. Soc., (Taipei) 26
(1979) 271.
85. Odashima, T. and Ishii, H., Bunseki Kagaku, 26 (1977) 844.
86. Singh, R.B., Pramila Jain, Garg, B.S. and Singh, R.P., Anal. Chim. ACta, 104
(1979) 191.
87. Godyoki, L.E. and Pundle, R.E., Acta. Cryst., 6 (1953) 487.
88. (Mrs.) Hemlata Ray, Garg, B.S., and Singh, R.P., J. Indian Chem. Soc., LVI
(1979) 975, 976.
89. Gimmez Plaza, J. and Bocanegrs Garcces, J.M., Bol. Soc. Quim. Perm. 46
(1980) 278.
90. Asvero A.G and Rodriguez.M.M .,Analyst, 105,(1980),562.
91. Gimenez, P.J. andGarces, J.J., Afinidad, 37 (1980) 243.
92. Kouimtzis, Th. A., Apostolopoulou, C. and Staphilakis, J., Anal. Chimica
Acta, 113 (1980) 185.
93. Makoto Otomo, Anal. Chimica Acta, 116 (1980) 161.
94. Kettrup, A., Seshadri, T. and Takabi, F., Anal. Chim. Acta, 115 (1980) 383.
95. Silva, M. and Valcarcel, M., Microchem. J., 25 (1980) 117.
96. Hernadez Lopez, M. and Garcia Sanchez, F., An. Quim., 77 (1981) 112.
97. Makoto, O., Seiichiro, A. and Hirexuki, N., Microchem. J., 26 (1981) 228
Page 34
34
98. Garcia-Vorgas, M., Bautiste-Rodriguez, J.M., Avila Novas, S. and Coy,-Yll,
R., Microhem. J., 27 (1982) 519.
99. Gallego, M., Valcarcel, M. and Vargas, M., Micro Chim. Acta, 1 (1983) 289.
100. Gutierrer, M.C., Genez-hens, A. and Valcarcel, M., Mikrochim Acta, 3 (1984)
17.
101. Cejas, M.A., Gomez-Hens, A. and Valcarcel, M., Quim. Anal., 3 (1984) 164.
102. Rubio, S., Hens-Gonez, A. and Valcarcel, M., anal. Quim. Ser. B., 19 (1983)
72.
103. Gimenez Plaza, J. and Boschojeda. C., Rev. Soc. Quim., 27 (1983) 159.
104. Khattab.M.A, Enany.G.El. and Soliman M.E ., PaK.J.Sci.Ind. Res .,27,(1984),
81.
105. Grases, F., Garcia-Sanchez, F. and Valcarcelm M., Afinidad, 39 (1982) 30.
106. Singh, R.B., Odashima, T. and Ishii, H., Analyst, 108 (1983) 1120.
107. Aita, T., Odashima, T. and Ishii, H., Analyst, 109 (1984) 1239.
108. Garcia de Torres, A., Cano Pavon, J.M. and Castaneda, F., Microchim. Acta,
111 (1984) 375.
109. Keemti, L., Malhotra and Sita Rani, J. Indian Chem. Soc., 60 (1983) 308.
110. Garcia-Vergas. M., milla. M ., Antesuera. I., and Perez Busstamante,. J.A.,
Anal. Chim.Acta,171, (1985), 313.
111. Ogawa, Hatesuki, Doi, Kumio, and Otomo, Makotom Analyst, 110 (1985)
1009.
112. Garcia-Vargas, M . Frevilla, S. and Milla, M., Talanta, 33 (1986) 209.
113. Kbill, M.A. et al., J. Clin. Chem. Soc., 32 (1986) 183.
Page 35
35
114. Sreenivasulu Reddy, T., et al., J. Indian Inst. Sci., 66 (1986) 39.
115. Kavlent, E., Mikrochim. Acta, 4 (1986) 27.
116. Salnas, F., Berzas Nevada, J.J. and Expinose, A., Proc. Indian Acad. Sci., 97
(1986) 153.
117. Dudarev, V.I., Dolgarer, A.V. and Valkov, A.N., Zh. Anal. Khim., 41 (1986)
289.
118. Sasaki, Yoshihiro, Bull. Inst. Chem. Res. Kyoto Univ., 64 (1986) 140.
119. Nakagawa, T., Doi, K. and Otomo, M., Analyst, 110 (1985) 387.
120. Odashima, T., Kikuchi, T., Ohtani, W. and Ishii, H., Analyst, 111 (1986)
1383.
121. Nakanishi, T. and Otomo, M., Microchem. J., 35 (1987) 328.
122. Kavlentis, E., Anal. Lett., 21 (1988) 107.
123. Kumagai, Testsu et al., Kemkyu Hokoku Himeji Kogyo Daigaku, 42A (1989)
8.
124. Nakanishi, T. and Otomo, M., Microchem. J., 36 (1987) 128.
125. charulatha, T., M. Phil. Dissertation, S.K. University, Anantapur (1990).
126. Kesava Rao, C., Krishna Reddy, V. and Sreenivasulu Reddy, T., Indian
Council of Chemist, 10th
Annual Conferenc Abstract, Oct. 28-30, (1991).
127. Kuroda. R., Kurasaki. M., and Hayashibe. Y., Talanta., 77 (19900 619.
128. Sinha S.h., and Sawanth. A.D., Indian.J.Chem., 30A, (1991),641.
129. Chaudhury, S.Pac. and Shome, S.C., J. Ind. Chem. Soc., 68(7) (1991) 432.
Page 36
36
130. Ramamaurthy, P.S., Ph.D. Thesis, J.N.T. University, Hyderabad, A.P., India,
(1991).
131. Kesava Rao, C., Krishna Reddy, V. and Sreenivasulu Reddy, T., Symposium
on Recent Trends in Instrumental methods and Analysis UGC/CSIR Meets,
Abstract, Roorkee, India, (March 1992) 24.
132. Sathyanarayana K., M.Phil. Disseration, S.K. University, Anantapur (1992).
133. Krishna Reddy, V., Thippaiah, J., Kesava Rao, C., Raveendra Reddy, P. and
Sreenivasulu Reddy, T., J. Indian Chem. Soc., 76 (1999) 275.
134. Kesava Rao, C., Ph.D. Thesis, Sri Krishnadevaraya University, Anantapur,
India (1993).
135. Babaiah, O., Kesava Rao, C., Sreenivasulu Reddy, T. and Krishna Reddy, V.,
Talanta, 43 (1996) 551.
136. Chandhuri, A. et al., J, Indian Chem. Soc., 73(10) (1996) 549.
137. Kawakkar, S.G. and Ramachandra, V., Nimbalkar ., J. Indian Chem. Soc.,
74(1) (1977) 69.
138. Agni Hotri, N., Dass, R. and Metha, J.R., J. Indian Chem. Soc., 75(8) (1998)
486.
139. Babaiah, O., Ph.D. Thesis, Sri Krishnadevaraya University, Anantapur, A.P.,
India (1997).
140. Agni Hotri, N., Dass, R. and Metha, J.R., J. Indian Chem. Soc., 76 (1999) 165.
141. Kudapali, Y.S., M.Phil. Dissertation, S.K. University, Anantapur (1996).
142. Venkata Narayana Reddy, B., M.Phil. Disseration, S.K. University, Anantapur
(1997).
Page 37
37
143. Khader, A.M.A. and Shalini Proceedings of 19th
Indian Council of Chemists
Annual Conference held at Kvempu University, Shimoga, Karnataka (2000),
16.
144. Pardhi S. Karnik, Swati A., Mayank and Dave O.P. Proceedings (Abstracts) of
20th
Indian Council of Chemists Annual Conference held at Mysore
University, (2001), 232.
145. Ramesh M., Chandrasekhar K.B. and Hussain Reddy. Indian J. Chem. 39(A)
(2000) 1337.
146. Ramesh M., Chandrasekhar K.B. and Hussain Reddy., Res. J.Chem. and
Environ. 82(A), (2004), 12.
147. Chandrasekhar K.B. and Hussain Reddy K., Indian . J. Chem. Soc., 78 (2001)
340.
148. Chandrasekhar K.B. and Hussain Reddy K., , 18, 2 (2001) 1.
149. Chandrasekhar K.B. Ph.D. Thesis, Sri Krishnadevaraya University, Anantapur
(A.P.) India (1999).
150. Mutta Reddy S. Ph.D. Thesis, Sri Krishnadevaraya University, Anantapur
(A.P.) India (1999).
151. Satyanarayana K. Ph.D. Thesis, Sri Krishnadevaraya University, Anantapur
(A.P.) India (2000).
152. Chennaiah A. Ph.D. Thesis, Sri Krishnadevaraya University, Anantapur (A.P.)
India (2002).
153. Devanna N., Jayaveera K.N. and Chandrasekhar K.B., Asian J. of Chem. 16
(3-4) (2004) 1889.
154. Venkata Narayana Reddy, B., Ph. D. Thesis, S.K. University, Anantapur
(A.P.) (2006).
155. Basaiah B., Raveendra Reddy P., Krishna Reddy V. and Srinivasulu Reddy T.,
Indian. Journal of Chem. 32A (1999).
156. Shivaramaiah S., Raveendra Reddy P. and Srinivasulu Reddy T., J. Radio
analytical and nuclear chemistry. 245(2) (2000) 367.
Page 38
38
157. Shivaramaiah S., Raveendra Reddy P., Krishna Reddy V. and Srinivasulu
Reddy T., Ind. J. of Chem. 42A (2003) 109 – 111.
158. Gangadharappa M., Raveendra Reddy P., Krishna Reddy V. and Srinivasulu
Reddy T., J. Indian Chem. Soc. 81 (2004) 525 – 527.
159. Gangadharappa M., Ph. D. Thesis, S.K. University, Anantapur (A.P.) India
(2005).
160. Babaiah O., Raveendra Reddy P., Krishna Reddy V. and Srinivasulu Reddy T.
,Ind. J. Chem. 38A (1999) 1035.
161. Krishna Reddy V., Mutta Reddy S., Raveendra Reddy P. and Srinivasulu
Reddy T., J. Ind. Chem. Soc. Vol. 79 (2002) pp. 71 – 74.
162. Sivaramaiah S. and Raveendra Reddy P. , Journal of Analytical Chemistry, 60
(2005) 9.
163. Anitha Vergheese and Khadar A.M.A. ,Acta Chem. Slov. 53 (2006) 374 – 380.
164. Ivanise Gaubeur., Madalena C da Cunha Areias., Incia Helena, S. Avila Terra
maria Encarnacion V. and Suârez-Iha Spectroscopy letters 35(3) (2002) 455 –
465.
165. Babaiah O., Satyanarayana K., Raveendra Reddy P., Krishna Reddy K. and
Srinivasulu Reddy T. Dept. of Chemistry Sri Krishnadevaraya University,
Anantapur (A.P.) Ind. J. of Indian Chemists Soc, Vol. 83, (March 2006) pp.
259 – 262.
166. Babaiah O., Satyanarayana K., Raveendra Reddy P., Krishna Reddy V. and
Srinivasulu Reddy T. , J. Ind. Chem. Soc, Vol. 82 (2005) pp. 269 – 271.
167. Sivaramaiah M. and Raveendra Reddy P. Sri Krishnadevaraya University,
Anantapur (A.P.) India. J. Ind. Chem. Soc, Vol. 84 (July 2007) pp. 706 – 708.
168. Gangadharappa M. and Raveendra Reddy P., J. Ind. Chem. Soc. Vol. 83 (Nov-
2006) pp. 130 – 1134.
169. Babaiah O., Raveendra Reddy P., Krishna Reddy V. and Srinivasulu Reddy T.
J. Ind. Chem. Soc, Vol. 81 (August-2004) pp. 670 – 673.
