Z. Anal. Chem.

282, 197-200 (1976) - 9 by Springer-Verlag 1976

Polarographic Determination of Molybdenum after Extraction of its N-Benzoyl-N-phenylhydroxylamine Complex

S. K. Bhowal and F. Umland Anorganisch-chemisches Institut der Universit/it, Gievenbecker Weg 9, D-4400 Mfinster Received January 9, t 976

Polarographische Bestimmung yon Molybdiin nach Extraktion seines N-Benzoyl-N-phenylhydroxylamin-Komplexes.

Eine spezifische und empfindliche Methode zur gleichstrompolarographischen Bestimmung yon Molybd/in wird beschrieben. Der Molybdgnkomplex von N-Benzoyl-N-phenylhydroxylamin wird in Chloroform extrahiert. Nach Zugabe wfil3riger Perchlorsfiure und methanolischer Lithiumchloridl6sung kann man eine gut definierte polarographische Stufe erhalten. Der Einflul3 verschiedener S/iuren, L6sungsmittel und Leitsalze wurde untersucht. Der Grenzstrom nimmt von 5 x 10 -6 bis 1 x 10-4 M Molybdfin linear zu. Diese Methode eignet sich zur Bestimmung von Molybd/in in Gegenwart yon fast allen Metallen und einigen Komplexierungsmitteln. Ein Beispiel ftir die Bestimmung kleiner Mengen Molybd~in in Stahl wird angeftihrt.

Summary. A sensitive and specific method for the DC-polarographic determination of molybdenum has been
described. The molybdenum complex of N-benzoyl-N-phenylhydroxylamine can be extracted into chloroform and subjected to polarography after mixing with aqueous perchloric acid and methanolic lithium chloride. Effects of different acids, solvents and supporting electrolytes on the system have been studied. The current increases linearly from 5 x 10 -6 to 1 x 10 .4 M molybdenum and the metal can be determined in presence of almost all the other metal ions and a number of complexing agents. Application of the method is made to the determination of small amounts of molybdenum in steel. Best. von Molybdfin; Polarographie, Gleichstrom; Extraktion, Mo-BPHA-Komplex.

1. Introduction
N-Benzoyl-N-phenylhydroxylamine (BPHA) has found wide application as an analytical reagent [5]. The polarographic reduction behaviour of a number of metal-BPHA complexes has been studied by Pyatnitskii and Ruzhanskaya [7], and they have reported that the complexes after extraction into i-amyl alcohol or m-xylene allow direct polarographic measurement in the organic phase. But this observation has not yet been reasonably utilised for analytical purposes. Only recently (after the present work was undertaken) titanium has been determined polarographically in presence of BPHA in water-ethanol mixture [2]. In the present paper a sensitive and specific method is described for the DC-polarographic determination of molybdenum after extraction of its BPHA-complex into chloroform. The chloroform extract of the complex~can be directly subjected to polarography after mixing with appropriate portions of aqueous perchloric acid and methanolic lithium

chloride. In this ternary solvent mixture microgram amounts of molybdenum can be determined without interference from almost all the other metal ions and most of the known complexing agents and the method can be successfully applied to determine low concentrations of molybdenum in steel samples. The halfwave potentials (Etlz) of some other metal-BPHA complexes which are extracted under the same condition as molybdenum have also been reported herein.

2. Experimental
2.1. Apparatus DC and pulse polarograms were recorded in a Tacussel PRG5 polarograph with a three electrode system, having a dropping mercury electrode, a saturated calomel referenceelectrode and a platinum counter electrode. The capillary used had the following characteristics: t = 8.94s; m = 0.784mgs -1 at 45 cm. All measurements in DC-polarography were done at a controlled drop time of 0.8 s/drop. The derivative pulse

198 polarograms were recorded with a controlled drop time of 1 s/drop and with 20 mV pulse amplitude.

Z. Anal. Chem., Band 282 (1976) observed by the present authors that when the MoB P H A complex is extracted into chloroform and subjected to polarography after adding methanolic LiC1 as the supporting electrolyte according to the method described in [7], two waves appear. The E1/2 of a very ill-defined first wave is difficult to assign by DC-polarography and even by pulse polarography. The second wave is slighty better defined with E1/2 at - 7 9 5 inV. For i-amyl alcohol and m-xylene values of Ell2 = - 8 3 0 and - 9 8 0 mV, respectively, have been reported [7]. We h a v e further observed that molybdenum(VI) can be completely extracted into chloroform from 1 M HC1 solutions and the extract when mixed with definite portions of aqueous perchloric acid and methanolic LiC1 furnishes a homogeneous solution where a well-defined reduction wave suitable for the determination of the element can be obtained. The composition of the solution was 4 ml of chloroform extract, 5 ml of aqueous perchloric acid and 16ml of 0.1 M LiC1 in methanol (total volume 25 ml). The number of waves and their E~/2 values depend on the acid concentration in the aqueous phase (Table 1). The more sensitive second wave, where the current remains constant from 0.75 to 0.1 M perchloric acid and the El/2 lies at - 4 6 0 mV at 18~ or at - 4 2 5 mV at 23~ was utilised for analytical purpose. B P H A does not furnish any reduction wave under the specified condition (Fig. 1). All measurements for analytical purpose were made with the solvent composition mentioned above and with 0.5 M perchloric acid in the aqueous phase. In pulse polarography this wave appears as a single broad peak (Fig. 1). The height of this wave depends on the mercury height, drop time and temperature. Rise of temperature shifts the Ell2 values to the positive direction with an increase in the current which shows that the reduction process is irreversible and the current is not adsorption-controlled. The slope of the curve obtained by plotting log h against log i was found to be 0.76, a value lying between diffusion-controlled and adsorption-c0ntrolled currents [4]. The value of ~ according to Tomeg [9] was calculated to be 0.56 for an one-electron reduction. The temperature coefficient of the current was found to be 2.8 ~ per degree and the energy of activation was determined to be 8 kcal/mole. These two data, however, point towards a kinetically controlled current. But this can be ruled out because of the dependence of the wave height on the mercury pressure, and therefore, the reduction is probably diffusion-controlled. Johnson and Robinson [3] reported that the enhanced current observed in the reduction of molybdate in acid medium in presence of nitrate ion is due to the catalytic reduction of nitrate by molybdenum(III). In our system, introduction of

2.2. Reagents The molybdenum(VI) solution was prepared by dissolving (NH4)6Mo~O24 94 H20 (Merck p.a.) in water and was standardised by atomic absorption spectrometry [1]. The solutions of niobium, titanium and rhenium were prepared from the respective pure metals and all other metal solutions were prepared from their salts of analytical purity. A 1.0 ~ (or 2.0 ~ whenever required) chloroformic solution of BPHA (Merck p.a.) was used. A 0.1 M LiC1 solution in methanol was used as the supporting electrolyte. 70 ~ Perchloric acid (Riedel-de Haen p.a.) was diluted to required strengths and used. The organic solvents, acids and other chemicals of analytical purity were used without further purification.

2.3. Procedure

2.3.1. Determination of Molybdenum when Present Alone (A ).

A definite volume of the standard solution of molybdenum was taken in a 50 ml separatory funnel and was diluted to 5 ml with water. The solution was adjusted to 1 M in HCI with 6 M HC1 solution and was extracted with 2 ml of 1 BHPA solution in chloroform for 5 min. The layers were allowed to separate and the chloroform layer was transferred to a 25 ml calibrated flask. The aqueous layer was further washed with 2 ml of chloroform and the washing was combined with the main extract. To the combined extract were added 5 ml of 0.5 M HC104 and the volume was made up with 0.1 M methanolic LiC1 solution. After thorough mixing the homogeneous solution was taken in a polarographic cell, deaerated for 10 min with nitrogen and the polarogram was recorded from - 100 mV to - 800 mV.

2.3.2. Determination of Molybdenum in Steel (B). About 1 g of the steel sample was accurately weighed out and treated with 15 ml of conc. HC1 and 5 ml of conc. H N O 3 in a 400 ml beaker. The mixture was carefully heated under cover on a hot plate and nearly evaporated to dryness. The mass was cooled, treated with 5 ml of conc. HC1, and again evaporated almost to dryness. The cooled mass was taken up with 6 ml of conc. HC1 and 15 ml of water, heated for a short time, cooled and filtered into a 100 ml calibrated flask. The filter paper was thoroughly washed with water and the flask was made up to volume. 5 ml of this solution were transferred to a separatory funnel, 100 mg of ascorbic acid were added and the funnel was shaken to dissolve the acid. The molybdenum was immediately extracted and determined as described above. 3. Results and Discussion
3.1. Polarographic Behaviour of the M o - B P H A Complex Molybdenum(VI) is precipitated by B P H A from acid solutions as a 1:2 complex [8] and the complex can be extracted into chloroform. Chloroform is found to be a better extractant than i-amyl alcohol or m-xylene for the M o - B P H A complex. It has been

S. K. Bhowal and F. Umland: Polarographic Determination of Molybdenum nitrate ion increased the current by about 50 % which indicates the generation of molybdenum(III) in the system. Thus, in all probability the M o ( V I ) - B P H A complex is finally reduced to molybdenum(III). H o w ever, the mechanism of the reduction could not be fully interpreted as it was not possible to determine, coulometrically, the number electrons involved in the reduction. 3.2. Solvent Mixture and Supporting Electrolyte It was observed that up to 7 ml of the chloroform extract when mixed with 5 ml of aqueous phase and the volume made upto 25 ml with methanolic LiC1 produced a perfectly homogeneous solution. H o w ever, the o p t i m u m volume of the chloroform phase was found to be 4 m l and in presence of more chloroform the wave was of a distorted shape. A 0.i M LiC1 solution in methanol was found to be the most satisfactory supporting electrolyte. Ethanolic solution of LiC1 did not yield well-defined waves and no reduction wave was obtained with LiC1 solution in ethylene glycol. Methanolic solution of 0.1 M LiCIO~ was also investigated as the supporting electrolyte. With this solution the number of waves obtained were the same as in the case of LiC1 but the second wave was not so well-defined and was actually a mixture of two waves, which was indicated by pulse polarography. 3.3. Effect of Different Acids Sulphuric, hydrochloric and perchloric acid solutions of different concentrations were investigated as the aqueous phase. With all the acids the nature and number of waves depended on their concentrations. Sulphuric acid yielded no well-defined wave suitable for analytical application. F r o m 0.5 to 0.25 M hydrochloric acid concentrations, the well-defined second wave had El~2 at - 4 2 5 mV, but the current was found to change sensitively with change of acid concentration, whereas, the current remained constant from 0.75 to 0.1 M perchloric acid concentrations. Moreover, the current was higher in the case of perchloric acid. So 5 ml ofO.5 M perchloric acid were used in all analytical measurements. 3.4. Analytical Application The current was found to increase linearly from 5 x 10 .6 to 1 x 10 .4 M m o l y b d e n u m concentrations and 2 ml of 1% B P H A solution were sufficient to extract the said concentrations of the element into chloroform. Use of more B P H A (upto 2 ml of 2 % solution was examined) had no effect on the current
i I/zA for curves 1end 2 0fl~,A for curve 3 0,4,~A for curve 4 /

199

!
f 2
1

/~ //~

-2

E --~,.+50 Fig. 1. Polarograms of the Mo-BPHA complex. Concentration of molybdenum --- 2 x 10 -4 M. 1 DC-Polarogram without and 2 with ascorbic acid; 3 Pulse polarogram; 4 DC-Polarogram of the BPHA reagent

-~60

-360

-~60

-7o0 -860m~

Table 1. Dependence of Ei/2 and current on perchloric acid concentration at 18~ Concentration of molybdenum = 2x 10-4 M Perchloric acid concentration, M

E1/2 of first wave, mV

- 5 - 35 -75

Ell2 of second wave, mV

- 370 -425 -438 -460 -487 - 512

Current gA 2.38 2.60 2.70 2.70 2.70 2.70

0.75 O.5 0.25 0.1

which was stable for 24 h. At 23 ~C the wave concerned had E1/2 at - 4 2 5 mV.

3.4.1. Effect of Diverse Ions and Complexing Agents.

The effects of diverse ions and complexing agents were investigated after mixing definite amounts of the respective metal ion or complexing agent solutions with m o l y b d e n u m and extracting and determining in the same way as described in Procedure A. The reduction behaviour of other metal complexes with BPHA, which are extracted under the same condition as molybdenum, were studied according to the Procedure A. Table 2 records the resulis obtained. However, it would not probably be out of point to mention specially the effect of ascorbic acid towards the system. No difference was observed between the waves of m o l y b d e n u m obtained in absence and in presence of a large excess of ascorbic acid. The current also remained the same (Fig. 1). Molybdenum(VI) is known to become reduced by ascorbic acid a n d so it m a y be concluded that the reduced molybdenum(VI) is reoxidised and complexed by B P H A and due to the removal of the hexavalent m o l y b d e n u m

200 Table 2. E1/z values of some metal complexes with BPHA and the tolerance limits of diverse ions and complexing agents Metal ion o r complexing agent

Z. Anal. Chem., Band 282 (1976) nickel, cobalt, manganese, chromium, uranium, cadm i u m and lead are not at all extracted with B P H A in chloroform under the same condition as m o l y b d e n u m and so they are not likely to interfere with the determination of molybdenum. In fact m o l y b d e n u m has been successfully determined in presence of some of these elements in steel.

E1/2, mV

Tolerance ratio of the diverse ions to molybdenum. (Masking agents used are given in parentheses) 12 (NH4F) 500 (Ascorbic acid) 40 (Ascorbic acid) 100 (Ascorbic acid) 100 Interferes 35 (NH, F) 5 (Tartaric acid) 10 (Tartaric acid) 25 2500 3000 2000 1000 750 (Saturated solution) 10 000

Ti(IV) Fe(III) V(V) Ce(IV) Hg(II) Sn(II) Zr(IV) W(VI) Nb(V) Re(VII) Tartaric acid Oxalic acid Citric acid Ascorbic acid EDTA Fluoride
a

- 550, - 725 No wave - 425", - 862 No wave No wave - 170, - 475 No wave -800 -665 No wave

3.4.2. Determination of Molybdenum in Steel. A

steel sample containing manganese (0.6~), chrom i u m (1.01 ~o), nickel (0.16~), copper (0.11~o) and m o l y b d e n u m (0.25 ~o) was analysed by Procedure B. The average value of m o l y b d e n u m was found to be 0.223 ~ . Out of ten measurements the average value of the current was 0.743 gA with a standard deviation of 0.0155 gA and a relative standard deviation of

+2.5%.
Acknowledgement. One of the authors (S.K.B.) wishes to express his heartiest thanks to the authorities of Alexander von Humboldt-Stiftung, West Germany, for awarding him a senior fellowship and to the authorities of Jadavpur University, Calcutta, India, for granting him a study leave.

The wave was very insensitive and difficult to assign.

complex in the organic layer, the reaction proceeds quantitatively in the same way as it was observed in the case of vanadium [6]. The only difference is that the reoxidation of m o l y b d e n u m is immediate. This observation has made the determination of m o l y b d e n u m specific by hindering the coextraction of vanadium, cerium and iron. Though cerium(IV) and iron(III) produce no waves, they disturb by the production of high current even at 0 V, probably due to reduction in the positive potential range. In the presence of zirconium, niobium and tungsten, molybdenum was extracted with 2 ml 2 ~ B P H A (instead of 1 ~ ) solution in chloroform. Metals like copper,

References
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