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Hindawi Publishing Corporation

International Journal of Analytical Chemistry
Volume 2012, Article ID 981758, 12 pages
doi:10.1155/2012/981758

Research Article
Spectrophotometric Determination of Iron(II) and Cobalt(II) by
Direct, Derivative, and Simultaneous Methods Using
2-Hydroxy-1-Naphthaldehyde-p-Hydroxybenzoichydrazone

V. S. Anusuya Devi1 and V. Krishna Reddy2
1 Department of Chemistry, S.E.A. College of Engineering and Technology, Bangalore 560049, India
2 Department of Chemistry, Sri Krishnadevaraya University, Anantapur 515003, India

Correspondence should be addressed to V. S. Anusuya Devi, anukmp@gmail.com

Received 5 September 2011; Revised 24 October 2011; Accepted 3 November 2011

Academic Editor: Ricardo Vessecchi

Copyright © 2012 V. S. A. Devi and V. K. Reddy. This is an open access article distributed under the Creative Commons
Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.

Optimized and validated spectrophotometric methods have been proposed for the determination of iron and cobalt individually
and simultaneously. 2-hydroxy-1-naphthaldehyde-p-hydroxybenzoichydrazone (HNAHBH) reacts with iron(II) and cobalt(II)
to form reddish-brown and yellow-coloured [Fe(II)-HNAHBH] and [Co(II)-HNAHBH] complexes, respectively. The maximum
absorbance of these complexes was found at 405 nm and 425 nm, respectively. For [Fe(II)-HNAHBH], Beer’s law is obeyed over the
concentration range of 0.055–1.373 μg mL−1 with a detection limit of 0.095 μg mL−1 and molar absorptivity ε, 5.6 × 104 L mol−1
cm−1 . [Co(II)-HNAHBH] complex obeys Beer’s law in 0.118–3.534 μg mL−1 range with a detection limit of 0.04 μg mL−1 and
molar absorptivity, ε of 2.3 × 104 L mol−1 cm−1 . Highly sensitive and selective first-, second- and third-order derivative methods
are described for the determination of iron and cobalt. A simultaneous second-order derivative spectrophotometric method is
proposed for the determination of these metals. All the proposed methods are successfully employed in the analysis of various
biological, water, and alloy samples for the determination of iron and cobalt content.

1. Introduction A good number of reviews have been made on the use of
large number of chromogenic reagents for the spectrophoto-
Iron and cobalt salts are widely used in industrial materials metric determination of iron and cobalt. Some of the recently
[1, 2], paint products [3], fertilizers, feeds, and disinfectants. proposed spectrophotometric methods for the determina-
They are important building components in biological tion of iron [8–15] and cobalt [16–22] are less sensitive and
systems [4]. Special cobalt-chromium-molybdenum alloys less selective. We are now proposing simple, sensitive and
are used for prosthetic parts such as hip and knee replace- selective direct and derivative spectrophotometric methods
ments [5]. Iron-cobalt alloys are used for dental prosthetics for the determination of iron(II) and cobalt(II) in various
[6]. There has been growing concern about the role of complex materials using 2-hydroxy-1-naphthaldehyde-p-
iron and cobalt in biochemical and environmental systems. hydroxybenzoichydrazone as chromogenic agent. We are also
Normally small amounts of iron and cobalt are essential for reporting a highly selective second-order derivative method
oxygen transport and enzymatic activation, respectively, in for the simultaneous determination of iron and cobalt in
all mammals. But excessive intake of iron causes siderosis and different samples.
damage to organs [7]. A high dosage of cobalt is very toxic
to plants and moderately toxic to mammals when injected 2. Experimental
intravenously. Hence, quantification of various biological
samples for iron and cobalt is very important to know their 2.1. Preparation of Reagents. 0.01 M iron(II) and cobalt(II)
influence on these systems. solutions were prepared by dissolving appropriate amounts

The system was operated at full power for 30 minutes. cooled. 1% solution filter paper no. Then. 50 mL of 5% hydrochloric acid was from different parts of Anantapur district. volume of alcohol.2.2. This was filtered through Whatman sample was dissolved in a mixture of 2 mL HCl and 10 mL filter paper.4. Pharmaceutical Samples. cooling. Kurnool. 5 mL con- in 100 mL of dimethylformamide (DMF). 25 mL standard flask with distilled water.306 g sample was taken into 100 mL Kjeldal flask. repeating HNO3 addition. The product showed melting point 272–274◦ C. The soil sample (5. Water Samples.6. India and added and heated close to boiling to leach the residue. After filtered using Whatman filter paper. Blood and Urine Samples.2 M 2. and the filtrate was diluted to 100 mL with . 40. A 2 mL of 1 M sulphuric acid and made up to the volume in a reddish brown coloured solid was obtained on cooling.0). India. Working solutions centrated HNO3 was added and gently heated. Buffer solutions of water.5.0 g) was weighed 0. 2. The product was filtered and dried.2. Preparation of Sample Solutions 30 minutes and then cooled. The solution was again heated to dense white fumes. of the normal adult and patient (male) were collected from mined from infrared and NMR spectral analysis. Then added 3 mL of 0. P. NH4 OH in the presence of 1-2 mL of 2. It was recrystallized from aqueous ethanol in the presence of norit. Other metal ion solutions were prepared from in 15 mL of distilled water and filtered through Whatman their nitrates or chlorides in distilled water.2. The filtrates were 2.5 g of the alloy dissolved in alcohol. The heating was continued for 2. The solution was further diluted as required.2 International Journal of Analytical Chemistry H C O H2 N NH C OH OH Reflux O −H2 O Parahydroxybenzoichydrazide 2-hydroxy-1-naphthaldehyde H C N NH C OH O 2-hydroxy-1-naphthaldehyde-p-hydroxybenzoichydrazone Scheme 1 of ferrous ammonium sulphate (Sd.5 g (pH 7. The contents were filtered and neutralized with dil. Different water samples were collected incipient dryness. The resulting solution was evaporated to a small acid and cobaltous nitrate (Qualigens) in 100 mL distilled volume.2 M CH3 COOH. pH 1–10 are prepared using appropriate mixtures of 1 M HCl–1 M CH3 COONa (pH 1–3. Alloy Steel Sample Solution. 0.01% tartrate solution. The solution was evaporated to dryness. The dried mass was again 2. Soil Samples. H2 SO4 and 1 mL of 70% HClO4 were added.2. 5 mL of 1 : 1 H2 O and H2 SO4 mixture was water. The filtrate was collected in a 100 mL of cetyltrimethylammonium bromide (CTAB). and 1 M NH4 OH and 1 M NH4 Cl employed in the preparation of the sample solution. The solution was transferred into into a 250 mL Teflon high-pressure microwave acid digestion a 10 mL volumetric flask and diluted to the volume with bomb and 50 mL aquaregia were added. Fine) in 2 M sulphuric HNO3 . 1 mL con. The bomb was distilled water. 1 × 10−2 M Government General Hospital. The digested material was evaporated to 2. A wet ash method was CH3 COONa (pH 3. the solution was removed and Scheme 1). 0.2. When the were prepared by diluting the stock solution with DMF (see initial brief reaction was over. HNAHBH was prepared by mixing equal of the sample was dissolved in a 1 : 1 mixture of nitric acid amounts of 2-hydroxy-1-naphthaldehyde in methanol and and perchloric acid.0).5–7. The ash was dissolved in amounts and refluxing for three hours on water bath. p-hydroxybenzoichydrazide in hot aqueous ethanol in equal and the residue was ashed at 300◦ C.1.0). Food and Biological Samples. sealed tightly and then positioned in the carousel of a microwave oven. Blood and urine samples The structure of the synthesized HNAHBH was deter.2. The residue was dissolved required. The stock solutions were diluted appropriately as added and evaporated to dryness. To this. 0.3.2.5–10.1–0. A known quantity of the quantitatively collected in a 250 mL volumetric flask and sample was taken in a beaker and dissolved in minimum diluted to the mark with distilled water. the residue was filtered and washed two times with a small volume of 5% hydrochloric acid. A. 50 mL of solution of the reagent was prepared by dissolving 0. a cationic volumetric flask and made upto the mark with distilled surfactant in distilled water is used.01 M nitric acid and evaporated to dryness. A 0.

55a Thiocyanate 870 Hf(IV) 36 Ni(II) <1. Variable amounts of Fe(II) were treated ∗ with suitable amounts of reagent.1. Table 2: Determination of iron in surface soil. Anantapur distrcct molar absorptivity.50a Bromide 1138 Cd(II) 45 In(III) 4.558 μg mL−1 pH = 5. Tolerance limit Tolerance limit Tolerance limit Foreign ion Foreign ion Foreign ion (μg mL−1 ) (μg mL−1 ) (μg mL−1 ) Sulphate 1440 Na(I) 1565 La(III) 18 Iodide 1303 Mg(II) 1460 Ag(I) 15 Phosphate 1424 Ca(II) 1440 Hg(II) 16 Thiosulphate 1424 K(I) 1300 U(VI) 6. Anantapur Studies on reagent (HNAHBH) concentration effect revealed Cotton cultivation soil.24 From the absorption spectra of [Fe(II)-HNAHBH] the Garladinne.0 was chosen (mg Kg−1 ) ± SD∗ for further studies. Sweet lemon cultivation soil.36 that a maximum of 15-fold excess reagent is required Singanamala.1.373 μg mL−1 . S3 44. Iron(II) and cobalt(II) react with HNAHBH forming reddish which strongly interfered. The colour of the masking agents. 1 cm path length quartz cell was used for UV-Vis spectra acquisition.60b Chloride 531 Ce(IV) 28 Zn(II) <1. All the anions and many cations were tolerable 3. complex [Fe(II) : HNAHBH] was determined as 2 : 3 by Job’s continuous variation method and the stability constant of the 2. 0. Results and Discussions in more than 100 fold excess.86 ± 0.80b Fluoride 285 Cr(VI) 27 Al(III) <1. to get maximum and stable absorbance for the complex. Anantapur district.60a Tartrate 1414 Ba(II) 1260 Mn(II) 4. Numerous cations and anions were with a combined glass electrode was used to measure pH of added individually to the experimental solution containing buffer solutions. Other analytical results tometer controlled by a computer and equipped with a are presented in Table 5.45a EDTA 124 Mo(VI) 22 Cu(II) <1.055–1.37 104 L mol−1 cm−1 . Apparatus. Amount of Fe(II) taken = 0. Hence pH 5.8 × 1018 .98 ± 0.558 μg mL−1 of iron and the influence was examined (Table 1). coefficient ε is calculated as 5. complex was calculated as 1. Direct Method of Determination of Iron(II). The composition of the the appropriate dilution of the stock solution. the validity of Beer’s law was tested by plotting the mea- sured absorbance values of the prepared solutions against concentration of Fe(II). The lower concentrations were prepared by over the range 0.5–5. A Perkin Elmer (LAMBDA25) spectropho. The tolerance limits of some ions were in the range of 5–50 folds.55a Thiourea 1140 Pd(II) 63 Th(IV) 3.6 × Paddycultivation soil S4 Garladinne. The absorp.45 intensity in the presence of 0.0. could be masked using appropriate brown and yellow coloured complexes. by Direct Spectrophotometric Method.1. Spectra were acquired between 350–600 nm 3.88 ± 0. A considerable increase in the colour Groundnut cultivation soil S1 40. and buffer and Average of five determinations. Some of the metal ions. complexes was stable for more than two days.48 ± 0. The applicability of tion spectrum of [Fe(II)-HNAHBH] shows maximum the developed direct method was evaluated by applying the .50a Citrate 115 Zr(IV) 19 Oxalate 95 Sr(II) 18 In the presence of a = 500 μg of tartrate.5. surfactant.2.1.International Journal of Analytical Chemistry 3 Table 1: Tolerance limits of foreign ions.1% CTAB was observed. S2 27. Determination of Iron in Surface Soil and Alloy Steels 3.50a Carbonate 900 W(VI) 37 Co(II) <1. The calibration curve was linear distilled water. 3. absorbance at 405 nm. Akuthotapalli.60a Nitrate 930 Bi(III) 42 Sn(II) <1. b = 400 μg of thiocyanate.3. ELICO model LI-120 pH-meter furnished by Direct Method. Anantapur district 20. Effect of Diverse Ions in the Determination of Iron (1 nm resolution). The preliminary investigations indi- Amount of iron cate that the absorbance of the complex is maximum and Sample Source of the sample stable in pH range of 4.

Hence Fe(II) was determined by measuring the Tolerance limit (in folds) derivative amplitudes at 427 nm for 1st order. 1. It can be observed from the table that large number of ions showed method for the analysis of some surface soil and alloy steel significantly high-tolerance limits in some of the derivative samples for their iron content. The amounts of Fe(II) in the samples 3.3.32 F) 34. and 4.06 Sn. solutions containing suitable amounts of iron were treated with known and required volume of HNAHBH at pH 5.89 Si. Different aliquots of sample methods.0–7.57 Sb. Known aliquots of the The absorbance of the resultant solutions was measured prepared food and biological sample solutions were treated at 405 nm. The first-order derivative spectra showed maximum derivative 3.2.351 Pb. Effect of Foreign Ions in Derivative Method of Determi- nation of Iron.04 Ca.13 4.2. Amount of iron (%) Alloy steel composition (%) Present Relative Certified value method ± SD∗ error (%) High tensile steel BY0110-1 (42. The food and biological samples were with suitable amounts of HNAHBH in buffer solutions of further analyzed by Atomic Absorbance Spectrophotometric pH 5.1% CTAB and made upto 10 mL with method. 0.024 As. The results were CTAB surfactant and diluted to the volume in 10 mL compared with the certified values and presented in Tables volumetric flasks. The second-order derivative HNAHBH] complex shows maximum absorbance at spectra gave one large trough at 421 nm and a large crust at 425 nm. which Ni(II) <1 interfere 5 10 showed serious interference in zero order method. recorded. and at 415 nm and 426 nm for 3rd Direct First Second Third order spectra. 19.46 ± 0.4 International Journal of Analytical Chemistry Table 3: Determination of iron in alloy steels.0 3. The influence of some of the cations. Determination of Iron in Food and Biological Samples and 0.1% CTAB and diluted to 10 mL with distilled water. by First Order Derivative Method. were computed from predetermined calibration plots and ent amounts of Fe(II) (0.2.14 Cu. 0. and 0.26 Zn.08 ∗ Average of five determinations.2.38 Si.53 Fe) 9.021 0.95 S.0 at 415 nm and a large trough at 426 nm with zero cross was chosen for further studies. [Co(II)- amplitude at 427 nm (Figure 1).98 Zn.18 ± 0. Differ. 0.022 0. Table 4: Tolerance limits of some cations in derivative methods. and 3rd order derivative spectra of the present method. and from the predetermined calibration plot.1.17 4.04 Cd.039 0.375 μg mL−1 . The first-order derivative spectra were 2 and 3. Maximum and stable absorbance of the complex 435 nm with zero cross at 428 nm (Figure 2). The calibration plots are linear in the range Th(IV) 5 10 16 20 0.13 Fe) YSBC19716 (34.2.53 9.26 4. 1.0. 2nd. 0.027–1. 1st.3. A large crust is achieved in the pH range of 5.0 along with 0.375 μg mL−1 ) were treated presented in Table 6. on the Cu(II) <1 5 12 10 derivative amplitudes was studied by the reported methods and the results obtained are shown in Table 4.29 Al.027–1. Determination of Iron(II) by Derivative Method. at 421 nm and Foreign ion 435 nm for 2nd order. 48. Determination of Iron(II). 0.15% of . and the amount of iron present was computed with suitable volumes of HNAHBH.2 Cd. method derivative derivative derivative Ag(I) 14 18 35 22 3.06 ± 0. and the derivative amplitudes were measured at analytical wave lengths. Direct Method of Determination of Cobalt(II).01 GSBD33001-94 (9. 0. The derivative amplitudes Hg(II) 11 20 40 30 measured at the analytical wavelengths as mentioned above U(VI) 11 12 25 18 for different derivative spectra were plotted against the Mn(II) 7 20 16 20 amount of Fe(II). (Figure 3). All the derivative methods are found to In(III) 7 28 48 34 be more sensitive with a wider Beer’s law range than the zero Au(III) 4 35 55 28 order method (Table 5) Sn(II) <1 8 15 22 Co(II) <1 interfere 7 15 3. Hence pH 6. 0. buffer solution. were recorded in the wavelength region 350–600 nm. and the results obtained were compared with those distilled water. A marginal increase in at 421 nm were observed for the third-derivative spectra the absorbance was observed in presence of 0. 9.

68 ± 0.45 15.89 1.093 0. Amount of iron(μg mL−1 ) ± SD (n = 4) Samples Found Recovered present AAS Added present AAS recovery Wheat 6.54 ± 0.04 ± 1.9999 0.28 ± 0.0012 — — — (μg cm−2 ) Angular coefficient (m) 0. Direct method First derivative Second derivative Third derivative Parameter 405 nm 427 nm 421 nm 435 nm 415 nm 426 nm Beer’s law range 0.50b In the presence of a = 700 μg of tartrate.027–1.75 22.31 1 Detection limit 0. 0.73 16.8 0.100c Thiourea 1140 Hf(IV) 72 Th(IV) 6.055–1.1 × 10−3 −0. Foreign ion Tolerance limit (μg mL−1 ) Foreign ion Tole limit (μg mL−1 ) Foreign ion Toler limit (μg mL−1 ) Tartrate 1707 Na(I) 1666 Au(III) 20 Phosphate 1425 Mg(II) 1530 Sr(II) 18 Sulphate 1440 Ca(II) 1426 Mo(VI) 15 Oxalate 1320 K(I) 1200 Tl(IV) 13 Bromide 1198 Ba(II) 1162 Pd(II) 11.3 0.373 0.15 ± 1.9999 0.15 11.18 6.068 0.86 ± 1.9997 0.5 10.27 21.376 0.50a Chloride 525 W(VI) 55 Cu(II) 2.3 Prostate gland 3.8 × 1018 — — — Table 6: Determination of iron in food and biological samples.80b Fluoride 285 Pb(II) 42 Zn(II) <1 EDTA 144 Hg(II) 40 Sn(II) <1 Citrate 115 Cr(VI) 26 In(III) <1.767 μg mL−1 .26 ± 0.11 0. 0.66 95.48 102 Tomato 11.95 104 Orange 18.18 ± 1.76 0.68 96 Banana 10.International Journal of Analytical Chemistry 5 Table 5: Analytical characteristics of [Fe(II)-HNAHBH].66 5 22.376 0.60a Thiosulphate 1120 Se(IV) 64 U(VI) 5.86 ± 1. pH = 6.28 2.6 Rice 14.96 ± 1.09 5 11.197 0.027–1.40 ± 1.12 ± 0.6 × 104 — — — (L mol−1 cm−1 ) Sandell’s sensitivity. b = 400 μg of oxalate and c = 500 μg of thiourea.006 0.46 11.027–1.0.04 ± 0.19 0.10 ± 40.68 9.25 16.5 17.14 5 17.376 (μg mL−1 ) Molar absorptivity.12 Table 7: Tolerance limits of foreign ions.2 × 10−4 0.25 17.46 ± 0.40 ± 0.376 0.96 ± 1.9999 RSD (%) 2.56 20.50a Ru(III) 21 V(V) <1.20 ± 0.10 97.0045 −0.12 ± 1.46 98.002 0.974 0.022 0.20 12.18 13.9999 0.98 ± 0.027–1.68 ± 0.914 (μg mL−1 ) Composition (M : L) 2:3 — — — Stability constant 1.08 6.38 ± 3.0047 −0.60a Bi(III) 21 Ga(III) <1.94 103 Benign (enlarged prostate gland 12.7 ± 40.60a Nitrate 930 Cd(II) 56 Mn(II) 5.027–1.9 × 10−3 Correlation coefficient 0.036 0.50a Carbonate 300 Zr(IV) 46 Ni(II) <1.072 0.4 ± 0.94 ± 0.376 0.26 ± 0.304 (μg mL−1 ) Determination limit.44 ± 0.9999 0.68 ± 0.1 0. 5. . amount of Co(II) taken = 1.065 0.085 Y-intercept (b) 0.12 5 14.18 6.1 × 10−3 0.85 0.18 5 19.0268 0.

14. and HNAHBH.24 ± 0. e = 0. Of the tested cations.022 (black soil.032 c Paralysis patient −2 d Urine 2. The tolerance limits of CTAB.020 0. Cobalt (μg mL−1 ) Sample source Sample Present AAS method ± SD method ± SD × 10 − 3 (n = 5) (n = 5) 4 Normal adult Blood 2. −8 Diverse ion Zero order Second derivative Third derivative 420 430 440 450 460 470 Wavelength (nm) Th(IV) 6 55 35 U(VI) 5 40 45 Figure 2: Second-order derivative spectra of [Fe(II)-HNAHBH].022 2 Anemia patient Blood 0. Tadipatri.20 ± 0. Beer’s law is Among anions.3.43 ± 0. d = 0. EDTA of suitable buffer. Effect of Foreign Ions in the Determination of Cobalt V(V) <1 15 20 by Direct Method.014 (male) Urine 0.92 ± 0. The stoichiometry of the complex which interfere seriously are masked with suitable anions.030 0.46 ± 0.030 17.027.68 ± 0. Mn(II) 5 60 20 Amount of Fe(II) μg mL−1 : a = 0.118–3.022 2. the calibration curve is found between 0. f = 0.124 μg mL−1 (Table 11).11.86 ± 0. f = 0. Cu(II) 2 80 45 Ni(II) <1 30 50 Zn(II) <1 45 20 was found to be 2 : 3 (Metal : Ligand) by Job’s method. c = 0. Cations of the present method. some of them did not with a detection limit of 0.12 ± 0.030 8. b = 0.) d Riverbed soil 0.22.44 ± 0.68 ± 0.65 ± 0. Wavelength (nm) Figure 1: First-order derivative spectra of [Fe(II)-HNAHBH].96 ± 0.055.48 ± 0. linearity of and citrate were tolerable in 144. In(III) <1 15 28 Ga(III) <1 20 35 3.48 ± 0. Table 9: Analysis of blood and urine samples for cobalt content. .1.04 μg mL−1 and determination interfere even when present in more than 500 fold excess.010 0.014 0 b d 2 A/dλ2 Blood 8.33.010 −4 Pulmonary patient e Urine 1.027.015 4.04 ± 0. The effect of various anions and cations normally associated with Co(II) on the absorbance of the experimental solution was studied.88.11.015 c S3 (Tungabhadra river. Amount of Fe(II) μg mL−1 : a = 0.024 (red soil Anantapur.06 Present Reference method method∗ [23] 0.6 International Journal of Analytical Chemistry Table 8: Determination of cobalt in surface soil samples.020 2. b = 0. The Sn(II) <1 25 18 stability constant is calculated as 7. 10-folds excess of HNAHBH is sufficient to get the tested foreign ions.075 f Sample and source Cobalt (μg mL−1 ) 0.and 150-fold excess.020 a (female) Urine 0. except EDTA and citrate. Molar absorptivity of the complex absorbance by ±2% were calculated and presented in Table 7.045 Agricultural land e S1 16. c = 0.020 2. all other tested tested taking the different amounts of Co(II) in presence ions were tolerable in more than 200-fold excess. which bring about a change in the maximum absorbance.042 122.65 ± 0.) dA/dλ Agricultural land 0.23 ± 0. d = 0.26 ± 0.018 −6 f −1 Table 10: Tolerance limit of foreign ions (μg mL ).026 23.33.015 industry.029 −0.88.025 Blood 4.03 S2 24.26 ± 0. surfactant.3 × 104 L mol−1 cm−1 .35 ± 0. limit 0.055. was calculated as 2.40±0.7 × 1019 . which shows the sensitivity many cations were tolerable between 10–80-folds.018 b a Kurnool) 0 Industrial soil S4 (electroplating 118. Anantapur) 410 420 430 440 450 460 470 ∗ Average of four determinations. 0.32 ± 0.38 ± 0.22.15 ± 0.534 μg mL−1 respectively.034 15. e = 0.

0 River water (Penna.0 1. In the for cobalt content by the proposed method.20 2.375 0.15 7.83 100.0 b c 4. Table 13: Determination of cobalt in pharmaceutical tablets.11. Suitable aliquots of the soil.0003 0.9 × 10−4 −0.2 410 420 430 440 450 industry.0197 3. Blood and wavelength region 350–600 nm against reagent blank.9 × 10−4 Correlation coefficient 0. and the derivative spectra were recorded in the 3.35 100.45 7.48 98. 449 nm.5 4.5 5. which indicate the acceptability of (cyanocobalamine.12 3.3 × 104 — — — — Sandell’s sensitivity.00 99.31 104.534 0.International Journal of Analytical Chemistry 7 Table 11: Analytical characteristics of [Co(II)-HNAHBH]. Determination of Cobalt in Surface Soil.999 0.0 6.0 0. Wavelength (nm) 3.8 0 a d 3 A/dλ3 supply.9999 0.6 −10 e Tadipatri.114 0. (μg mL−1 ) 0. taken in different ∗ Average of four determinations. c = 0.5 1. μg cm−2 0.37 1.055.4 −0.0 3.84 4.32 — 2.88. Amount of Fe(II) μg mL-1: a = 0. 443 nm.84 4.60 — 1.13 0. were treated with optimal amounts of reagent HNAHBH at pH 6. Tadipatri. and 456 nm.4. d = 0.15% CTAB.059–4.90 1.056–1.52 — 3.90 3. 15 mg) Basiton forte (cyanocobalamine. ×10−4 cobalt (μg mL−1 ) 10 Sample Recovery RSD Added Found (%) (%) 5 0. maximum amplitude was are presented in Tables 8 and 9.009 Y-intercept (b) 0.18 2. e = 0.2 × 10−4 −0.95 98.9999 0. 10 mL volumetric flasks.9999 0.027. The Urine Samples by Direct Method.7 Drain water (vanaspati 1.) 3. and biological zero crossings at 431 nm. 437 nm. .66 2. 1.124 0.0 −15 0.24 −2.22. and the results obtained were compared with Neurobion forte those of present method.65 Composition (M : L) 2:3 — — — Stability constant 7.380 0.712 0.712 0. and urine sample solutions were taken and analyzed and a crust at 443 nm with a zero cross at 437 nm.2 d −5 0.380 Molar absorptivity.059–1.2 × 10−5 −0.5 4.0002 0.21 Determination limit.0 3.093 0.5 3.6 Figure 3: Third-order derivative spectra of [Fe(II)-HNAHBH].059–4. b = 0.07 99.7 × 1019 — — — Table 12: Determination of cobalt in environmental water samples.67 the present method. and at 462 nm with further analyzed by a reference method [23]. Anantapur) 3.0 in presence of 0.712 μg mL−1 ) of Co(II). Direct method Second derivative Third derivative Parameter 425 nm 431 nm 443 nm 437 nm 449 nm Beer’s law range (μg mL−1 ) 0.06 0.04 0. and the results third-derivative spectra (Figure 5).18 0.9999 RSD (%) 1.5 5. Determination of Cobalt by Derivative Method.42 3.3.3 1. f = 0. 7.2.0 4.118–3.8 f 4.5 Tap water (municipality water 1.33. Variable 15 mg) amounts (0.5 8.003 — — — — Angular coefficient (m) 0. 7.80 98. second-derivative curves (Figure 4) gave a trough at 431 nm blood.04 0.39 0.42 7.63 3. (L mol−1 cm−1 ) 2.55 100. The soil solutions were observed at 424 nm. Sample (mg/tablet) Amount of cobalt (μg mL−1 ) Relative samples were analyzed by flame atomic absorption spec- Reported Found∗ error (%) trophotometer.059–4.6 Detection limit (μg mL−1 ) 0.34 1.

3) 0. Amount taken (μg mL−1 ) Amount found∗ (μg mL−1 ) Relative error (%) Fe(II) Co(II) Fe(II) Co(II) Fe(II) Co(II) 0. and d = 0.9 × 10−4 0.120 (103.33 3.44 0.33 1.334 (101. Simultaneous Second-Order Derivative Spectrophoto- Co(II) and calculating their recovery percentage.33 1.5) 3.33 2.8) −3.280 (96.81 1.6) 4. obtained with pharmaceutical samples were compared with The results obtained in the analysis of water samples by the those obtained by AAS method and presented in Table 13.59 0.9999 0.5.6) 2. All the parameters like 8 b detection limit.0 ∗ Average of four determinations.06 0.5) 0.3 × 10−6 0.60 −1.12 0.81 −3.60 −0.4 × 10−4 0. Metal ion determined Other metal present (μg mL−1 ) Wave length (nm) Slope Intercept Correlation coefficient Fe(II) Co(II) Fe(II) 436 3. and relative standard deviation values are presented in Table 11.4 × 10−4 2.6) −1.8) 4.8) 1.9) −0.4.18 0. −16 U(VI).118. proposed method are presented in Table 12 and the validity of the results was evaluated by adding known amounts of 3.8 International Journal of Analytical Chemistry Table 14: Linear regression analysis of the determination of Fe(II) and Co(II) in mixture by second derivative spectrophotometry. Iron and .328 (99.72 0.441 (100.44 0.59 0.3. Cu(II). Determination of Cobalt. The results metric Determination of Iron(II) and Cobalt(II).22 0.590 (100. Amount of Co(II) μg mL−1 : a = 0.059.59 0. The selectivity of the derivative −4 methods was evaluated by studying the effect of metal ions −8 closely associated with cobalt on its derivative amplitudes under experimental conditions.9998 Table 15: Simultaneous second-order derivative spectrophotometric determination of Fe(II) and Co(II).5 0. Determination of Cobalt in Water and Pharmaceu- tical Samples by Second-Order Derivative Method.586 (99. 4 a d 2 A/dλ2 0 3. b = 0.053 (96. The results show that the tolerance limits of Th(IV).21 −5. Ni(II).670 (98.3 0.4. 3. The results are presented in −12 Table 10. Effect of Foreign Ions. Suitable aliquots of water and pharmaceutical samples were taken and analysed for cobalt by second-order derivative method. Figure 4: Second-order derivative spectra of [Co(II)-HNAHBH].6 −2. c = 0.5 0.354. correlation coefficient.9) 1. Mn(II).86 −0. In(II).4) −0.33 4.4) 0. Zn(II).59 0.600 (101.2 × 10−3 1.21 −2.1) 3.592 (100.59 0.1) 0.33 0.6 0.332 (100.2) 0.9994 0.572 (98. The derivative amplitudes ×10−5 measured for different concentrations of Co(II) at appropri- ate wavelengths for 2nd and 3rd order derivative spectra were 16 d plotted against the amount of Co(II) which gave linear plots 12 c in the specified concentration regions.3) 1.9) 0.8 0.59 0. Sn(II).0 × 10−6 0.326 (89. 3.670 (98.542 (98.8 0.55 0.9 × 10−3 2.23 0.2.1.7) −1.45 −0.0 0. Ga(III) and V(V) which interfere seriously in zero order method −20 were greatly enhanced in the derivative methods indicating 410 420 430 440 450 460 470 480 the greater selectivity of derivative methods over the direct Wavelength (nm) method.5 0.120 (94.7 0.4 × 10−4 2.3) −1.589 3.4.586 (99.54 0.572 (98.236.9995 Co(II) 426 1.33 0.36 0.2 0.2) 0.230 (99.324 (98.336 (101.59 0.1) 0.

b = 0. b = Co(II) Figure 6: Second-order derivative spectra of (a) [Fe(II)-HNAHBH] and (b) [Co(II)-NAHBH].055. and buffer solution (pH 5.08 ± 0.38 25. 4.20 1. CTAB (1%. Amount of Fe(II) (μg mL−1 ): 0. the characterizations of these samples include the determination of their metal ion content. 7 Mo.06 2.52 (20 Cr.38 1.236. At 436 nm. tude (Figure 6). 4 mL) were added to each of these flasks and diluted to 3. of both the systems with reference to the reagent blank.53.12 ± 0. Amount of Co(II) μg mL−1 : a = 0. HNAHBH (1 × 10−2 M.354.35 49.5.98 ± 0.719. maximum derivative amplitude Calibration plots for the determination of Fe(II) and Co(II) was noticed for Fe(II) where there was no amplitude for were constructed by measuring the second-derivative ampli- Co(II).89 ± 1. and plotting . c = 0. 0.92 (Fe and Co) Sofcomag 49 51 49 52. steels. and environmental samples.18 0.118. 0.48 3. and selective second-order 3. We are now reporting a simple..33 1.15 39. respectively. Sample (composition) Amount (%) Relative error (%) Certified Found (n = 3) ± SD Fe(II) Co(II) Fe(II) Co(II) Fe(II) Co(II) Elgiloy-M 15 40 14. 1. Aliquots of solu- derivative spectrophotometric method for the simultaneous tions containing 0.05 Be) Rim alloy 68 12 69.86 12.18 ± 0.82 ± 0. Derivative Spectra .650 μg mL−1 of Fe(II) or 0. biological fluids.36 (Fe and Co) ×10−5 ×10−4 4 12 c a 3 8 b 2 4 a b 1 d 3 A/dλ3 0 d 2 A/dλ2 0 −4 −1 −8 −2 −3 −12 −4 −16 410 420 430 440 450 460 470 480 Wavelength (nm) 410 415 420 425 430 435 440 445 450 455 Wavelength Figure 5: Third-order derivative spectra of [Co(II)-HNAHBH]. This facilitates the determination of Fe(II) and tudes at zero crossing points of [Co(II)-HNAHBH] (436 nm) Co(II) simultaneously by measuring the second-derivative and [Fe(II)-HNAHBH] (426 nm).5. Determination of Fe(II) and Co(II). 10 mL calibrated volumetric flasks. respectively.3 mL).059.5.2. 0. The need for amplitudes of binary mixtures containing Fe(II) and Co(II)at the determination of iron and cobalt in environmental and 436 nm and 426 nm.5 showed sufficiently large derivative amplitude for determined by recording the second-order derivative spectra cobalt at 426 nm while the Fe(II) species exhibit zero ampli.39 ± 0. 3Mn) Sofcomag 25 75 25 73. biochemical materials has increased after reports on different roles of these metals in human health and diseases. 15 Ni. cobalt occur together in many real samples like alloy Co(II) (μg mL−1 ): 3.88 0. 2 Mn.5 mL).66 (17 Mo.15 C.055–1.28 ± 0.117– determination of Fe(II) and Co(II) using HNAHBH without 4. In most cases.International Journal of Analytical Chemistry 9 Table 16: Determination of iron and cobalt in alloy samples.11. and a = Fe(II) d = 0.1. sensitive. The 2nd order derivative spectra the mark with distilled water.86 1. The zero-crossing points recorded for [Fe(II)-HNAHBH] and [Co(II)-HNAHBH] at of [Fe(II)-HNAHBH] and [Co(II)-HNAHBH] species were pH 5.719 μg mL−1 of Co(II) were transferred into a series of the need to solve the simultaneous equations.

6–6. Co(II) Ni(II) Zn(II) Present Fe(II) 405 5 Aqueous 0. [31] and C2 O4 −2 2-Hydroxy-1-naphthaldehyde-p-hydroxybenzoic Sn(II).36 Co(II). Sn(II).7 7.0 Extraction 0–5.0 Aqueous 3. Zn(II).92 [16] Co(II) 2-Pyridine carboxalde hydeisonicotinyl-hydrazine 346 9 Aqueous 0.0 Extraction 0–10 1. EDTA Fe(II) Dyformyl hydrazine 470 7.6 hydrazone Al(III) Cu(II) method Co(II) Sodium isoamyl xanthate 400 4. Cu(II).37 5.10-Phenanthroline-tetraphenylborate 515 4.5–10 1. In(III).5 Extraction 0.05–1.2 — [27] Cu(II). Ni(II).24–37.0–9.10-Phenanthroline and picrate 510 2.5–4.2 — [33] Co(II) 2-Hydroxy-l-naphthalidene-salicyloylhydrazone 430 8.04 — [32] Co(II) Bis-4-phenyl-3-thiosemicarbazone 400 4 — 0.0–35 1. Fe(II) 1.5 9. H2 PO4 −2 .1 Au(III).87 — [10] Tl(I).0 2 — [30] tetraphenylborate Cu(II).0 Aqueous 0.6 4. Pb(II). λmax Beer’s law Metal ionReagent pH/medium Aqueous/extraction ε × 104 L mol−1 cm−1 Interference Reference (nm) μg mL−1 Fe(II) Thiocyanate-phenanthroline 520 — Aqueous 0–24 1.156 [28] Mo(VI).3 Many cations and anions [34] 2-Hydroxy-3-methoxy benzaldehyde Co(II) 390 6 Aqueous 0.6 13 EDTA.01–2.1–3. Zn(II).5–7.25 Aqueous 2.0–6. 2-[2-(3.5-Dibromopyridyl-azo]-5-dimethyl Fe(II) 615 2.7-Diphenyl-1. and [24] amino-benzoic acid Pd(II) Fe(II) 1. 10 Table 17: Comparision of the results with already reported methods.54 2.0 2.5 Extraction 0–2.0 Extraction 0–10 0.01–0. Fe(II) Thiocyanate-acetone 480 HClO4 Aqueous — 2. Cr(III).0–9. Co(II).1 NO2 − .12–3. Ag(I).0–7. Zn(II). Pt(III) [18] Co(II) 2-Hydroxy-1-naphthalidene salicyloyl hydrazone 430 8.5–9.25–13 0.0 6 [26] EDTA Fe(II) 1.0 Extraction 0.29 1.3-Diphenyl-4-carboethoxy pyrazole-5-one 525 3.0 Extraction 0.74 — [35] thiosemicarbazone 2-Hydroxy-1-naphthaldehyde-p-hydroxybenzoic Ni(II).6 × 103 — [22] Co(II) 2-(2-Quinolynylazo)-5-dimethylamino aniline 625 5.16 [22] Co(II) Pyridine-2-acetaldehyde salicyloyl hydrazone 415 1. W(VI).3 hydrazone and Ga(IIII) method International Journal of Analytical Chemistry . and Fe(II) 4-(2-Pyridylazo)resorcinol 505 6. Co(II).0–7.0 1.06–2.0–9.35 2. Present Co(II) 425 5 Aqueous 0.3 Aqueous 0.10-phenanthroline and Fe(II) 534 — Extraction 0–20. CN− [25] Ni(II).3–9. S2 O3 −2 .3258 — [29] 4.

Kennedy. I.International Journal of Analytical Chemistry 11 against the respective analyte concentrations. EDTA. 24. [31].4. 61–74. Loer. Disegi. L. and 0. Zhongyun.” in Ullmann’s Encyclopedia of Industrial Chemistry. Simultaneous Determination of Iron and Cobalt in Archives of Orthopaedic and Trauma Surgery. which indicate the operated by iron. vol. Cun. Metallurgical Analysis.” US Patent. pp. Nolte. [30]. 1999.” Fenxi Shiyanshi (Analytical reported spectrophotometric methods and presented in Laboratory). 66–68. and Martins et al. C. Wang et al. M. Biomedical Applications. Li-Xiang.7-trihydroxyl-6- 4. Balbo. Bi(III). Adolfsson. The methods proposed by J. K. The amounts of iron and cobalt in [8] Wu. determination of cobalt. no. Patil and Sawant [32]. Co(II) obeyed Beer’s law in the range 0. 2004. 1999. “Systemic effects of implanted prostheses made of cobalt-chromium alloys. [33]. Conclusions fluorone. 1991. some analytical applications. Andrade. 647–651. [22]. 2005. and the derivative amplitudes were measured at no. Tarafder and R. K. vol. 77–79. soils.5. were calculated from the measured derivative amplitudes Patent number: 5985987.589 μg mL−1 of Co(II). tometric determination of iron(III)-dimethyldithiocarbamate (ferbam) using 9-(4-carboxyphenyl)-2. Ling-Zhao Kong. Wildermuth. 63–71. You. Appropriate volumes of the alloy samples were treated with [7] J. Patil and Dhuley chemical Journal. the preset method is less sensitive than the methods were constructed for standards containing Co(II) alone and reported by Guzor and Jin [21] and Qiufen et al. M. and T. vol.055–1. 2. vol. pp. nitric oxide. Casto. 1. However they are less selective than the proposed method as pp. pp. W. “Cobalt and cobalt alloys. trophotometric method was employed for the simultaneous [6] J. 1996.3. “Molecular control of results obtained along with the recovery percentage and vertebrate iron metabolism: mRNA-based regulatory circuits relative errors are presented in Table 15. CN− . and M. Cr(III). 110. 24. The developed second-order derivative spec. 0. . The slopes. ASTM International Standards. 2004. 557–558. Fe(II) and they suffer interference from W(VI). Zhang et [12] F.” 3. “Spectropho- A comparison of the analytical results of the proposed tometric determination of micro amount of iron in oils with methods was made with those of some of the recently thiocyanate-phenanthroline-OP.5.. Nagabhushana et al. no. [26] are more sensitive than the present method. Tl(I). [28]. Ellis. Mo(VI). This allows the determination of Fe(II) and organic solvents where as the present methods are simple. 30. the samples were evaluated with the help of predetermined no. Fe(II) and Co(II) were mixed in different proportions and then treated with required amount of [1] E. [34]. The data in the above table reveals that the [11] P. “Spectropho- calibration plots and presented in Table 16. and iron oxidation in the iron(II)/thiocyanate/acetone system and Reddy et al. ASM tive amplitudes were measured at 436 nm and 426 nm.15% of CTAB and diluted to the volume in 10 mL Wiley-VCH. 2005. 8175–8182.” Micro- than those reported by Malik and Rao [27]. Michel.719 μg mL−1 at 436 nm and 426 nm. Kühn. the calibration graphs However. J. 2005. Martins. proposed method of determination of iron is more sensitive minerals. without the need for their prior separation. Saloranta. G. G. and C. and J. 16. 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M.” Proceed- usefulness of the proposed method for the simultaneous ings of the National Academy of Sciences of the United States of determination of Fe(II) and Co(II) in admixtures. 63. solutions containing Fe(II) alone and in the presence of Adinarayana Reddy et al. pp. Schulman. al. R. and Prabhulkar et al.650 μg mL−1 Pb(II). A. Guo. Alloy Samples. Campbell. T. pp. 2. inter. The derivative simultaneous determination of Fe(II) and Co(II) are well amplitudes measured at 436 nm and 426 nm were found to comparable with the reported methods. Hentze and L. volumetric flasks. L. Morales and Toral [25]. ranean) anemia with observations on the pathogenesis of the The second-derivative curves for the resultant solutions were siderosis AND fibrosis. and Li Wang. The second-order derivative spectra for [2] F. “Iron com- HNAHBH in the presence of buffer solution (pH 5.330 μg mL−1 of Fe(II). Similarly. Above all most be independent of the concentration of Co(II) and Fe(II). Reich. Co(II) in their mixtures without any significant error and nonextractive. Pd(II). F. no. [29]. vol. 2008. The [4] M. A. [5] R. F. Hg(II). Lourenco. no. 39–43. [10] Qi-Kai Zhang. pp. 30. 2000. no. no. C. The amounts of Fe(II) and Co(II) in the mixtures taken [3] M. the present method is more sensitive tively. pp. H. stream sediments and water samples. M. 3. H. C. using the respective predetermined calibration plots. A. Cobalt-Base Alloys for determination of iron and cobalt in some alloy samples. Friedrich et al. 3. vol. America. and correlation coefficients of the prepared calibration of many cations and anions. C. R. vol. of the reported methods involve extraction into spurious respectively.117–4. K. and R.” Eclética Quı́mica. Regarding the and 0. Silander. recorded. and reasonably accurate. Calibration plots were constructed for the standard than those reported by Malik et al [16]. “Generalized siderosis required amount of HNAHBH at pH 5. 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