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International Journal of Analytical and Bioanalytical Chemistry

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ISSN-2231-5012 Original Article Solvent extraction of Iron (III) with Tetra butyl ammonium bromide from aqueous acid solutions
A.V.L.N.S.H. Hariharan1, Ch. Sudhakar1, and B. Venkateswara Rao2
2

Department of Chemistry, GIT, GITAM University. Visakhapatnam 530 045, India. Department of Engineering Chemistry, Andhra University. Visakhapatnam 530 003, India. *Corresponding Author E-mail: ahharan@sifymail.com Received 14 July 2013; accepted 21 Augst 2013

Abstract Solvent extraction of iron (III) has been carried out with Tetra butyl ammonium bromide in chloroform from hydrochloric, sulphuric, nitric and perchloric acid media. Stripping of iron from the organic phase was done with 2M hydrochloric acid. The extractions were nearly quantitative with all the acid systems employed in the study. Based on the results obtained, estimation of iron in tannery samples has been attempted. 2013 Universal Research Publications. All rights reserved Key words: Extraction -iron (III) - Tetra butyl ammonium Bromide (TBAB) - Mineral acid tannery samples INTRODUCTION: Iron plays an important role in humans, animals, plants, and oceans. Its deficiency is anemia and is one of the worlds most common nutritional deficiency diseases whereas at higher concentrations it is toxic [1]. Extraction in trivalent form from aqueous hydrochloric [27] and sulphuric acid [8-9] solutions was carried using various amines. There are very few studies reported on its extraction from quaternary ammonium salts. In our earlier studies, we reported the extraction of iron with TBAI in chloroform from hydrochloric, sulphuric, nitric and perchloric acid solutions [10]. In this paper the investigations carried out on the extraction of Iron (III) with Tetra butyl ammonium Bromide (TBAB) in presence of mineral acids were presented. The method was extended for separation of Iron (III) in synthetic and tannery samples. EXPERIMENTAL: Equipment: An ELICO SL 191 UV-Visible Double beam Spectrophotometer with matched 10 mm corex glass cuvetts were used to determine iron content. Iron (III) stock solution was prepared by dissolving 482.25 g/mol of Ammonium iron (III) sulfate (E.Merck) in 500 ml of double distilled water. The solution was standardized volumetrically with potassium dichromate using diphenyl amine as the indicator. A diluted solution of iron (III) of appropriate concentration was prepared from the stock solution. A solution of 5.0X10-2 M TBAB in chloroform is used throughout the extraction. Procedure for Iron.(III) Extraction: 10ml solution containing iron (III) was added with appropriate concentration of mineral acid in a separating funnel..10 ml of 5X 10-2 M of TBAB dissolved in chloroform was added to it. The solution was thoroughly shaken for five minutes. After the separation of phases,. Iron (III) from the organic phase was stripped with 10 ml of 2M hydrochloric acid and was determined spectrophotometrically [11] at 480 nm as its colored complex with thiocyanate. The concentration of Iron (III) was computed from the calibration curve. RESULS AND DISCUSSION Variation of acidity The results obtained on the extraction of iron (III) from different mineral acids (HCl, H2SO4, HNO3 and HClO4) with 5.0X10-2 M TBAB in chloroform and are presented in Table-1. The variation of distribution ratio as a function of aqueous phase concentration of the acid (HCl, H2SO4, HNO3 and HClO4) solutions increased sharply with increasing concentration of the acid up to 7.0 M, 9.0 M, 10.0 M and 8.0 M acidity respectively is noticed. Composition of the Extracted species: Composition of the extracted species was determined using extraction isotherm method [12] and distribution ratio method [13]. In the extraction isotherm method the limiting ratio of the metal to TBAB was found unity with all the acid systems. Representative plot from hydrochloric acid solutions was presented in Fig-1. Effect of Reagent Concentration Iron (III) was extracted with 10 ml of the reagent

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International Journal of Analytical and Bioanalytical Chemistry 2013; 3(3): 78-81

concentration ranging from 1.0 X 10-2 M to 4.5 X 10-2 M with. The log-log plots of Kd Vs TBAB from various acid solutions gave straight lines. Maximum extraction (98.93%) in HCl media was noticed with 5.0 X 10-2M of the reagent. With hydrochloric, nitric acid, and perchloric solutions the log-log plot gave straight line of unit slope. On the other hand, the slope analysis of the distribution data in sulphuric acid solutions indicates that the solvation number is two. This indicates that the solvation number is two where as in other acid solutions the solvation number is unity. Representative plot and corresponding data from hydrochloric and nitric acid media respectively were provided in (Fig-2) and (Table-2) respectively.

acid (0.1 2.0 M). For all practical purposes 2 M hydrochloric acid was used as the stripping agent. Table 1: Extraction as a function of varying Acidity [Fe(III) ]= 1.0 x 10-3 M [TBAB] = 5.0 x 10-2 M
Molarity(M) 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 HCl %Extraction 91.77 93.92 94.99 97.13 97.86 98.21 98.93 98.93 ------H2SO4 %Extraction 92.49 93.20 93.56 94.65 95.71 96.42 97.13 97.86 98.20 ---HNO3 %Extraction 87.83 91.77 92.49 93.20 93.56 94.63 95.71 97.13 98.00 98.20 HClO4 %Extraction 91.77 93.20 93.56 94.60 94.99 95.70 96.42 97.13 -------

Table 2: Effect of TBAB on the extraction of Iron (HNO3 medium) [Fe(III) ]= 1.0 x 10-3 M [TBAB] = 5.0 x 10-2 M TBAB(g/lit) Log Kd 0.5084 1.0046 0.8094 1.3056 0.9063 1.4025 0.9855 1.4817 1.0525 1.5487 1.1104 1.6066 1.1616 1.6578 1.2074 1.7036 Table 3: Effect of various diluents on extraction [Fe(III)] = 1.0 x 10-3 M [TBAB] = 5.0 x 10-2 M (From HCl medium) Diluent Dielectric constant % extraction Benzene 2.28 90.2 CHCl3 4.81 99.3 CCl4 2.23 92.8 Cyclo hexane 2.0 81.3 n-Hexane 1.89 83.5 n-heptane 1.92 74.7 Nitrobenzene 34.82 69.2 Toulene 2.43 84.3 Xylene 2.56 87.5 Spectral studies: The individual Iron (III) extracted species were studied in U.V. region. The spectra from sulphuric acid media exhibits absorption peak at 305 nm. corresponds to the complex[14] [Fe(SO4)2]- . Existence of Fe(X) complexes (as mentioned below) were observed from other acid solutions [15]. TBABr TBA+ + BrBased on the spectral data obtained the following extracted species were identified. From sulphuric acid solutions: (TBA)2+ FeSO4-2. From Other acid solutions:(TBA)+ (FeCl4)- ; and Fe(X)2+, Fe(X)2+, Fe(X)3, Fe(X)4-, where X= Cl-,ClO4- and NO3-, Effect of Diverse ions: Iron (III) was extracted in presence of large number of diverse ions (Table 5). The tolerance limit was set as the amount of foreign ion causing 1.6 % error in recovery.

Effect of Diluent Several solvents with varying dielectric constants were tested as diluents (Table 3). Only with chloroform the extraction was quantitative. More than 80% efficiency was obtained with hexane, carbon tetrachloride, xylene, toluene, cyclo hexane and benzene. Nitrobenzene and n-heptane were found to be poor in extraction. Hence chloroform was preferred as diluent in all these studies. Effect of stripping agent: After extraction iron (III) was stripped with varying concentration of mineral acids as the tripping agents (Table 4). The stripping was quantitative only with hydrochloric

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International Journal of Analytical and Bioanalytical Chemistry 2013; 3(3): 78-81

When 55g of iron was taken in the presence of 330 g of anions they were tolerated in the ratio of 1:6. The 275 g of alkali metals with 50 g of iron (III) were tolerated in the ratio of 1:5 while the main group elements were tolerated in the ratio of 1:4 but transition metals were tolerated in

similar ratio of 1:2. However anions like phosphate and cations like vanadium(V), magnesium(II), aluminum(III), chromium(III), nickel(II), copper(II), molybdenum(VI) were not tolerated in any ratio (Table 5) to show interference.

Table 4: Separation of Iron (III) from a binary mixture (Fe = 55 g): [TBAB] = 5.0 x 10-2 M (From HCl medium) Foreign ions Li+, Na+, Cs+, Sr2+ Sb3+, Sn4+, Bi3+, As3+, Ti+, Ag+ Pd2+, Co2+, Pb2+ Zn2+, Mn2+, Cd2+ K+, Zr4+ Al3+, Mg2+, V5+, Cr3+, MoO42-, Ni2+ Br-, CH3COO-, PO43-, C2O42- and S2O32Table 5: Analysis of iron in synthetic samples and tannery effluents Sample iron(III) added (g/l) Synthetic samples 1 0.1 2 0.2 3 0.3 4 0.4 5 0.5 Tannery Effluent Samples : 1 (Inlet of ETP) 2 (Outlet of ETP) ETP = Effluent treatment plant S.D = Standard Deviation (Average of four determinations)

Amount tolerated (g) 275 220 165 110 55 0 0

Ratio 1:5 1:4 1:3 1:2 1:1 Interfere Interfere

Iron (III) found after recovery by extraction. S.D 0.097 0.022 0.186 0.011 0.288 0.014 0.390 0.014 0.495 0.018 0.245 0.90X10-3 0.006 0.0001

Analysis of iron in tannery effluents: Based on the results obtained, in the separation and determination of iron outlined earlier, an attempt was made for the estimation of iron from tannery effluents collected from a chrome tannery industry situated at Nellimarla, Vizianagram district, Andhra Pradesh, India. The pH of the collected samples (after washing with dilute sulphuric acid (1:1) rinsing and then washing with redistilled water) is adjusted to 2 with a 1.0 M sulphuric acid solution. Then the undisclosed impurities and the particulate matter in the sample solutions are removed by filtration through a Whatmann No. 42 filter paper and then through a fiber filter of porosity 50 m pores. An aliquot (100ml) of the filtered sample is taken and boiled till its volume is reduced to about 1/5 th of the initial volume (20ml) . As chromium (III) interferes in the proposed method of separation of iron (III). It is eliminated as the hexa valent complex (obtained by oxidation[16]using Ce(IV) as oxidizing agent (0.2 N solution of ammonium hexa nitrato cerate )) followed by extraction[17] with 10.0 ml of TBAB in toluene. The iron (III) content of the solution is quantitatively transferred to a 250 ml volumetric flask and made up to the mark. 10 ml of this solution is then extracted out by extraction in hydrochloric acid medium at pH 7.0 with 10 ml of 0.01 M TBAB in chloroform as per the procedure described earlier. A synthetic solution with a composition Fe (III ) = ( 0.1 0.5 ) g/l , Cr(III ) = 0.2 g/l , pH 7.0 is subjected to the same

procedure to test the validity of the method.(Table 5 ). It may be recalled that the recovery of iron (III) is (99.7 +0.3 %) both in the presence and in the absence of the impurities usually associated with tannery wastes. Hence the data in Table-5 on iron (III) recovery may be considered to be reliable. Conclusions: The proposed method is simple, rapid and selective. It does not take more than half an hour to extract and determine iron (III) content. The method is reproducible with relative standard derivation of 1.5%. The method has practical utility as iron(III) can be separated from manganese, lead, copper, cobalt, cadmium and zinc (under the experimental conditions) which are generally associated with it in alloys and minerals. Acknowledgements: Thanks are due to Dr. V. Muralidhara Rao, Retd. Professor, School of Chemistry, Andhra University, Visakhapatnam for his valuable suggestions. Thanks are also due to Principal, GIT and Management of GITAM University for providing necessary facilities. References 1. B. Ghadamali, A.C. Mansour and B. Zeinab ,Eurasian J. Anal. Chem.,.4,(3) (2009) 285-293. 2. M.S. Lee, K.J. Lee, Sepn. of Iron by extraction, Hydrometallurgy, 80 (2005) 163. 3. K. Staszak, R. Clerpiszewski and K. Prochaska, Polish J. Chem. Tech., Vol.1(1) (2011) 1-5.

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Source of support: Nil; Conflict of interest: None declared

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International Journal of Analytical and Bioanalytical Chemistry 2013; 3(3): 78-81