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International Journal of Analytical and Bioanalytical chemistry

Universal Research Publications. All rights reserved

Original Article

Studies on the Extraction of Chromium (VI) by tetra butyl ammonium bromide

A.V.L.N.S.H.HARIHARAN*, D.MURALIKRISHNA *Department of Chemistry, GIT, GITAM University,Visakhapatnam 530 045, India. Received 24 February 2011; accepted 02 March 2011 Available online 09 March 2011 Email: ahharan@rediffmail.com Abstract The extraction and recovery of hexavalent chromium from hydrochloric and sulphuric acid solutions with tetra butyl ammonium bromide in toluene has been studied. The study comprised the effect on metal extraction with change of acidity, concentration of the metal ion, extractant, etc.. The extracted chromium (VI) species was stripped using 0.1 N NaOH solution from the organic phase. The extractions were found quantitative in both the acid solutions. The extracted species were identified .The method was successfully employed to recover chromium from steel samples. 2011 Universal Research Publications. All rights reserved Key words: Extraction - Chromium (VI) - Tri butyl ammonium bromide-Mineral acid 1.1. INTRODUCTION Several workers [1-8] reported the extraction of metals by quaternary ammonium salts as well as tertiary amines including chromium. Very few studies appeared in literature on the extraction of chromium (VI) by quaternary ammonium salts especially in different acid media [9]. We report in the present communication the results obtained on the extraction of Chromium (VI) by Tetra butyl ammonium bromide (TBAB) from hydrochloric and sulphuric acid solutions have been discussed. 1.1. 2. EXPERIMENTAL A 0.5 M stock solution of TBAB (Aldrich Chemicals Molecular. weight. 332.38) in toluene was prepared and diluted appropriately to get the required concentration. Chromic acid (E.Merck) was used for preparing Chromium (VI) stock solution (0.5M) used as such without any further purification. All other chemicals used were of AnalaR grade or samples purified according to the standard methods. Double distilled water was used throughout. 1.1.3. Extraction of Chromium (VI): An aliquot (20ml) of chromic acid and mineral acid was equilibrated with an equal volume of TBAB in toluene (0.05M) pre-equilibrated with 0.1M mineral acid. The chromium (VI) concentrations in the aqueous phase before and after extraction was estimated spectrophotometrically [10] by measuring the absorption of Cr (VI) DPC complex at 540nm, using Shimadzu UV-Visible Spectrophotometer type UV-260. The equilibrium chromium (VI) concentration in the organic phase was determined by taking the difference in the initial chromium (VI) concentration and the equilibrium chromium (VI) concentration in the aqueous phase.

International Journal of Analytical and Bioanalytical chemistry 2011, 1 (1), 9-12

1.2.1. RESULTS AND DISCUSSION As described in the experimental procedure 20 ml of chromic acid with appropriate mineral acid has been subjected to extraction for different intervals of time period that is 1, 2,3,4,5 mins. It is observed that maximum extraction has been achieved with 5 minis shaking time. Hence same time period was maintained throughout the study.

Fig.2. Extractant Variation (HCl Medium) The individual chromium (VI) species can be identified on the U.V. region [13-15]. The absorption spectra of chromium (VI) in the organic phase obtained by extraction from different acid media exhibit absorption bands at 245, 285 and 355 nm. A comparison of the ratio of the molar extinctions () at 285 nm and 355 nm a function of acid molarity is taken as a criterion for identifying the species.. The peak ratios are constant ie., unity and two from hydrochloric & sulphuric acid systems respectively, confirming the presence of a single species (Table-1). This is in conformity with the observation of Rao and Sastri [16] using Aliquat-336 as extractant. Table 1 Spectral data of chromium (VI) by TBAB [Cr (VI)] = 0.0005M, [TBAB] = 0.025 M Acid (M) HCl H2SO4 1.2.2. Composition of the extracted species: The composition of the extracted species with all the acid systems was determined by the extraction isotherm method [11] and distribution ratio method [12]. In the extraction isotherm method the limiting ratio of the metal to TBAB was found to be unity irrespective of the acid used in the study. The log-log plots of Kd vs TBAB from various acid solutions gave straight lines. With hydrochloric acid solutions the log-log plot gave straight line of unit slope (Fig-2). On the other hand, the slope analysis of the distribution data in sulphuric acid solutions indicates that the solvation number is two. 0.25 0.50 1.25 0.1 0.5 Molar Extinction (E) at 285nm 355nm 1195 1085 1120 1095 1265 1180 1990 975 1985 995 (
285 /

Fig.1. Variation of acidity (M) The results obtained on the variation of distribution ratio as a function of aqueous phase concentration of mineral acid (HCl and H2SO4) is as follows. In the case of hydrochloric acid solutions the extraction of chromium (VI) by TBAB in chloroform as a function of acidity, the distribution ratio (Kd) decreased with increasing the concentration of the acid up to 0.5 M and remained constant up to 0.80 M acidity respectively followed by a gradual fall up to 2.0 M, beyond which chromium (VI) under goes reduction to chromium (III) (Fig.1). Similar trend is noticed in sulphuric acid solutions. The extractions are nearly quantitative from both the acid solutions.

355 )

1.10 1.02 10.7 2.04 1.99

Based on the result obtained, the observed chromium: TBAB molar ratio of two from all the acid solutions (by distribution ratio method) could be explained as arising from the extraction of chromium (VI) by the following solvation mechanism. From Hydrochloric acid solutions: TBAB+ + CrO3Cl - (aq) 2(TBAB ) + + Cr2O7-2 TBA HCrO3 Cl(TBA)2 Cr2O7 org

(aq)

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Table 2 Selective Recovery of chromium (VI) in the presence of other ions Sample 1. 2. 3. 4. 27 g Cr + 10 mg Cu, Co, Ni + 1.0 M H2 So4 54 g Cr + 10 mg Cu, Co, Ni + 1.0 M H2 So4 54 g Cr + 30 mg Cu, Co, Ni + 1.0 M H2 So4 54 g Cr + 10 mg V + 1.0 M H2 So4 TBAH Cr2O7 org (TBA)2 Cr2O7 org Result 27,26,26,27,28,25,26 53,54,54,55,53,54,55 54,53,54,54,53,55,53 54,54,54,53,53,53,55 Standard Deviation 0.90 0.75 0.70 0.70

TBAB H + HCr2O7- (aq) From sulphuric acid solutions: 2(TBAB ) +(org) + Cr2O7-2 +(aq)

The decrease in the distribution ratio at higher acidities (>2.0M) can be explained as due to the greater extractability of the mineral acid over the chromium (VI) species.

Table 3 EFFECTS OF DIVERSE IONS [Cr (VI] =54 mg; [TBAB] =0.05 M; [HCl] =0.25 M Foreign Tolerance Foreign Tolerance ion Cd Zn
2+

limit 280 190 962 922 964 980 247 974 939 972 978 188

ion Ni2+ Al3+ Mn2+ VO3CH3COOClO3Ascorbate

322-

limit 194 287 102 112 980 882 962 987 968 725 742 194

Sn2+
2+

Bi2+ Pd Sr
2+

UO22+
2+

Sb3+ Ru Th
3+ 4+

Malonate2Seo2 S2O3

Ce4+ Fe3+

PO43Ni2+

1.2. 3. Choice of stripping agent: The extracted chromium (VI) from the organic phase (TBAB) has been tried with 10 ml reagents of various concentrations (0.01 0.1 M) of HCl, HNO3, NaCl, NaNO3 and NaOH solutions. It was observed that HCl, NaCl, and NaNO3, are extremely poor stripping agents for chromium (VI). On the other hand, 1.0 M NaOH alone is a good stripping agent. However in no case NaOH strips out all the chromium (VI) in a single extraction. It was observed that 99.8% chromium (VI) could be recovered from organic phase by making contact three times with equal volumes of 0 .1M NaOH. It is thus possible, to extract chromium (VI) in the presenceof large number of cations and anions. The average

recovery of chromium (VI) was 99.8 + 0.2 %. The relative standard deviation and relative error calculated from ten repeated determinations with 54mg of Cr (VI) were found to be 1.02 % and 0.8 % respectively. The separation of chromium (VI) is possible in the presence of more than one foreign ion in the mixtures with an error of not more than 1.78 %. 1.2. 4 Analysis of chromium in alloys The accuracy of the method of extraction for recovery of chromium has been tested by analyzing synthetic samples and chrome alloys. It is done by extracting chromium from synthetic samples (composition Cr = 0.20 0.40 g/lt. About 0.5 gm of a chrome alloy (Type 303, 410 &

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Table 4 Estimation of Chromium in synthetic samples and chrome alloys .

Sample Synthetic sample 1 2 3 4 5 Stainless steel alloy type 302 303 410 416 0.20 0.25 0.30 0.35 0.40 0.198 0.243 0.296 0.348 0.397 99.0 97.2 98.67 99.43 99.25 Chromium (VI) added (g/l) Chromium found after extraction (g/l) % recovery

18.0 20.0 11.0 14.0

17.90 19.30 10.78 13.92

99.4 96.5 98.0 99.43

-416) was dissolved in 10ml aquaregia .The solution was evaporated and extracted with 20ml of dil. hydrochloric acid solution .to dryness. The resulting solution was made up to 100ml.An aliquot (10ml) of the filtered solution was taken. The interference due to Ni (II) & Mn (II) were removed by precipitating them as complex .Then precipitate was filtered and quantitatively washed for complete recovery of chromium. It was made up to 100ml. 10.0 ml of the solution was extracted with an equal volume of 0.05M TBAB in toluene followed by stripping with 0.1M NaOH and estimated the chromium content as Cr(VI) DPC complex as per the procedure described earlier. The results are presented in Table -4. CONCLUSIONS The developed method was applied to the extraction separation and determination of chromium in as well as synthetic samples. The average recovery % of chromium was found to be 98.7% each determination requires a minimum amount of 10 minutes time. 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

2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

(2002) 681 686. A.V. Padaraukas and L.G.Kalauskiene, Talanta, 40(6), (1993) 827-830. S.Kalidhasan and N.Rajesh, Journal of Hazardous Materials, 170 (2-3) (2009), 1079 -1085. M.Goldoni A.Caglieri D .Poli and M. Vttoria, Anal.Chim Acta 5629 (2), (2005), 229. P.Venkateswaran and K.Palanivelu, Separation and Purification Technology, 40 (2004) 279 284. S.L. Lo and S.F Shiue, Wat. Res., 32 (1) (1998) 174178. J. Noro, K. Maruyama, and Yu Komatsu, Anal. Sci., 17 (2001).11333. D.K,Mandal B.Bhattacharya and R.D, Bas. Sepn & Purifn. Tech., 40 (2004) 177. M Noroozifar, and Motlagh, K Anal. Sci., 19 (2003) 705-707. A.I.Vogel., A Text book of quantitative Inorganic Analysis 3rd Edition, 1962, P.311, Longman, London E Hesford and H.A.C.Mckay.. Trans Faraday Soc., 54 (1958) 573. K. B. Oldham Educ.Chem. 2 (1965) 7. W G Davis and J E Prue Trans.Faraday Soc. 1(1955) 45. Neuss J D and Reiman W J.Amer.Chem.Soc. 56 (1934) 2238. J Y Tong and E .L King J. Amer.Chem.Soc. 81 (1955) 1045. V.M Rao and M.N.Sastri., Talanta 27 (1980) 771.

Yoshifumi Akama, and Ahat Sali, Talanta, 57 (4)

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

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International Journal of Analytical and Bioanalytical chemistry 2011, 1 (1), 9-12