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Department of Chemistry, Sri Krishnadevaraya University, Anantapuramu, A.P, India.
KEYWORDS: Iron (III), HMBAHBH, Triton X-100, surface soils, biological, food
materials and pharmaceutical samples, UV-Visible spectrophotometer.
INTRODUCTION
Iron is one of the most important and essential elements for living beings. It is abundantly
used both in industry and as a biological constituent. We can’t imagine advancement of
human civilization without the use of iron. From primitive man to the present civilized
human being iron has been employed as important component of tools, weapons, industrial
reactors, space crafts and as a main constituent of oxygen transporter in human beings.
Iron exists in many of its natural constituents as Fe (II) or Fe (III). Among these two
oxidation states Fe (III) compounds are more stable due to their half field d-orbital
configuration in their valence shell. Iron is an important constituent of several plant enzymes
like peroxidise, catalyse and cytochrome oxidase. Its function in photosynthesis and in
fixation of nitrogen is well understood.
Traister and Schitt[1] have reviewed the spectrophotometric methods proposed for the
determination of iron employing a variety of organic reagents. Most of the
spectrophotometric methods proposed for the determination of iron are based on the
[2-
formation of intensely coloured complexes between the metal ion and the selected reagent
7]
. Black[8] has stated that numerous methods have been employed to assess the available
states of iron in soils. The analytical results evaluated in some of the recently proposed
spectrophotometric methods for iron are reviewed and shows in Table 1
A various spectrophotometric methods are available for the determination of iron, every
method has its own limitations either in its sensitivity or selectivity or stringent experimental
conditions. Hence there is a need to propose simple sensitive and selective methods for the
determination of iron in various complex materials.
We are now proposing simple selective and sensitive direct spectrophotometric method for
the determination of iron (III) using 2-hydroxy-3-methoxy benzaldehyde-p-hydroxy
benzoichydrazone as an easily synthesizable, less carcinogenic and as a good analytical
chromogenic reagent for the determination of iron (III) in a variety of its complex materials.
EXPERIMENTAL
Apparatus
Model LI-120 Elico digital pH meter, manufactured by M/S Elico private limited,
Hyderabad, was used for measure the pH of different buffer solutions.
Synthesis of reagent
HMBAHBH was prepared by mixing equal amounts of 2-hydroxy-3-methoxy benzaldehyde
and p-hydroxy benzoichydrazide in hot ethanol was refluxing on water bath for two hours[9].
On cooling, light yellow coloured product was crystallized. The solid was filtered, washed
and dried. It was recrystallized from aqueous ethanol using norit. The recrystallized product,
2-hydroxy-3-methoxybenzaldehyde-p-hydroxybenzoichydrazone (HMBAHBH), showed a
melting point 208-210oC which is different from that of the reactants. The melting point
obtained has coinsided with the reported value indicating the formation of the hydrazone
whose structure is shown in scheme I.
Scheme-1
Table 1:Analytical characteristics of reported spectrophotometric methods for the determination of iron
pH/ Aqueous/ Beer’s law εx104
Reagent λmax Interference Ref
medium extraction μg ml-1 L mol-1cm-1
Di-2-pyridyl methanone-2-(5-nitro)- pyridyl
hydrazone 505 2-7.5 Extraction Up to 0.84 5.83 - 10
Ferron
465 - Extraction Up to 3.2 - - 11
3-hydroxy picolinic acid
400 5.5 Aqueous - 1.5 - 12
3-hydroxy-2-picolinamide
425 - Aqueous 0.2-0.5 2.24 - 13
2-hydroxy nicotinic acid
360 5.0 Aqueous - 4.88 - 14
Up to
5-methyl salicilaldehyde guanyl hydrazone 430 8.8 Aqueous 3.2 - 15
13ppm
Cyanese-301
613 - Extraction - 5.048 - 16
5-Chloro salicylic acid 510 - - 18.5-40.2 - - 17
Ti(I), Zn(II), Cr(III),
2-[2-(3,5-di bromo) pyridil azo]-5 dimethyl
615 2.0-7.0 Extraction 0-5.5 9.36 W(VI), Co(II), Cu(II), 18
amino benzoic acid
Ni(II) and Pb(II)
EDTA, CN-, Ni(II),
1,10 phenanthroline and picrate 510 2.0-9.0 Extraction 0.1-3.6 13 19
Cu(II) and Pb(II)
2,6 diacetyl pyridine Bis (benzoyl hydrazone) Ag(I), Bi(III),
and 2,6 Di acetyl pyridine bis(2-hydroxy W(IV),Co(II), Sn(II),
336 2.0-2.5 - - 2.77 20
benzoyl hydrazone) Ti(IV), Zr(IV), Fe(III)
and EDTA
4-(2-pyridyl azo) resorsinol
505 6.0-7.5 Extraction 0-2.0 6 EDTA 21
Contd…
30 minutes. The digested material was evaporated to incipient dryness. Then, 50ml of 5%
hydrochloric acid were added and heated close to boiling to leach the residue. After cooling,
the solution was filtered and the residue was washed two times with small volumes of 5%
hydrochloric acid. The filtrate was quantitatively collected in 250ml volumetric flask and
diluted to the mark with distilled water.
calibration curve was linear over the range of 0.14 – 4.19 µg mL-1(Figure 3). The
composition of the complex [Fe-HMBAHBH] was determined 1:2 by Job’s continuous
variation method and the stability constant of the complex was calculated as 1.02x1011
(Figure 4). Other analytical results are presented in Table 2.
1.0
b
0.8
Absorbance
0.6
0.4
0.2
a
0.0
360 380 400 420 440 460 480 500
Wavelength(nm)
0.8
0.6
Absorbance
0.4
0.2
0.0
0 1 2 3 4 5 6 7
pH
1.6
A390= 0.3580C -0.0091
1.4
1.2
Absorbance
1.0
0.8
0.6
0.4
0.2
0.0
0 1 2 3 4 5
-1
Amount of Fe(III) (µg mL )
Figure 3 Calibration plot [HMBAHBH] = 7.5 x 10-4 M, [CPC] = 0.05%, pH = 3.0, λmax
= 390 nm
0.55
0.50
0.45
0.40
0.35
Absorbance
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0.0 0.2 0.4 0.6 0.8 1.0
APPLICATIONS
The present method was employed for the determination of the amount of iron present in
some surface soil, biological, food and pharmaceutical samples. Sample solutions were
prepared by adopting the given erlier procedure. Different aliquots of sample solutions were
treated with known and required volume of HMBAHBH, surfactant and DMF at pH 3.0 with
distilled water. The absorbance of the resultant solutions was measured at 390nm and the
amount of iron present was computed from the predetermined calibration plot. The surface
soil samples, biological samples and food samples were further analyzed by atomic
absorption spectrophotometric method. The results of the proposed method were compared
with those obtained by AAS method and are represented in Table 4&5. The results relating to
the analysis of pharmaceutical samples were compared with the certified values and
presented in Table 6.
CONCLISIONS
The present direct spectrophotometric method is simple, fast, and sensitive for the
determination of Fe(III). The metal ion reacts with 2-hydrox-3-methoxy benzaldehyde-p-
hydroxy benzoichydrazone (HMBAHBH) forming brown coloured water soluble complex
[Fe(III)- HMBAHBH] in acidic pH condition. The brown colour was stable for more than 24
hours. However in the presence of cetyl perydinium chloride (CPC), a cationic surfactant, the
intensity of brown colour was increased and the colour was stable for more than 48 hours.
The absorption spectrum of [Fe(III)- HMBAHBH] complex showed maximum absorbance at
390nm. The reagent absorbance was negligible at this wavelength.
The complex system was found to obey Beer’s law in the range 0.14- 4.19 µg mL-1 with molar
absorptivity 1.87×104 Lmol-1cm-1, Sandell’s Sensitivity 2.9x10-3 µg cm-2. The analytical
parameters of the present method are: angular coefficient (m)=0.3580, Y-intercept (b)=
-0.0091 and correlation coefficient (r) 0.9997.
The stoichiometric studies on the brown coloured water soluble complex showed a 1:2
composition between the metal and the ligand. The formation constant of the complex was
calculated as 1.02x1011.
The results of the present method were compared with those of some of the reported
spectrophotometric methods and presented in Table 7. Analytical reagent 2-hydroxy-3-
methoxy benzaldehyde-p-hydroxy benzoichydrazone40 as a reagent is also used for the
spectrophotometric determination of Al(III), Ga(III), In(III),V(V), La(III) and Ya(III) were
summarized in Table 8.
Table 7:Comparison of the analytical results of the proposed method with already reported methods for iron
pH/ Aqueous/ Beer’s law εx104
Reagent λmax Interference Ref
medium extraction μg ml-1 L mol-1cm-1
3-hydroxy picolinic acid
400 5.5 Aqueous - 1.5 - 12
3-hydroxy-2-picolinamide
425 - Aqueous 0.2-0.5 0.224 - 13
EDTA, CN-, Ni(II),
1,10 phenanthroline and picrate 510 2.0-9.0 Extraction 0.1-3.6 13 19
Cu(II) and Pb(II)
1,10 phenanthroline tetra phenyl borate
515 4.25 Aqueous 2.24-37.29 1.2 - 22
Cu(II), Co(II), Zn(II),
1,3 diphenyl- 4- carboethoxy pyrazole -5- one 525 3.5-4.0 Aqueous 0.5-10 1.16 23
Mo(VI) and EDTA
Di formyl hydrazide
470 7.3-9.3 Aqueous 0.25-13 0.3258 - 24
Thio cynate phenanthroline
520 - Aqueous 0-24 1.87 - 26
NO2-, S2O32-H2PO42-
Thiocyanate acetone 480 HClO4 Aqueous - 2.1 27
and C2O42-
2,4 di hydoxy benzaldehyde Isonicotinyl {(E)-N1-
Co(II),V(V), Al(II)
(2,4 di hydroxy benzeledine) hydrazone 395 7.0 - 0.1-1.5 3.5 29
and Pb(II)
4-hydoxy 3,5-di methoxy benzaldehyde 4hydroxy
benzoyl hydrazone 380 1.0-6.0 Aqueous 0.279-2.79 1.71 - 30
ACKNOWLEDGEMENTS
The author (G.GOVINDU) thanks to Department of Chemistry S.K. University for providing
facilities to my research work. I express my sincere thanks to my Research Supervisor Prof.
V. Krishna Reddy for his valuable guidance. I express my sincere thanks to
Prof. P. Raveendra Reddy, who is giving valuable suggestions during my research.
DISCLOSURE OF INTEREST
The authors declare that they have no conflicts of interest concerning this article.
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