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Coulometric generation of hydrogen ions by oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
R.P. Mihajlovic a,*, V.M. Joksimovic b, Lj.V. Mihajlovic a
a

Department of Chemistry, Faculty of Science, University of Kragujevac, Radoja Domanovic a 12, PO Box 60, 34000 Kragujevac, Serbia and Montenegro b Institute of Mining, Belgrade-Zemun, Serbia and Montenegro Received 27 December 2002; received in revised form 31 March 2003; accepted 11 April 2003

Abstract Mercury(II)-chloride reacts with anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone in a precise stoichiometry ratio (1:2), and weakly ionized compounds of mercury with ketones are formed and equivalent quantity of HCl is released. The application of a mercury anode for the quantitative generation of H ' ions in 0.25 M sodium perchlorate in anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone has been investigated. Current/potentials curves for the solvents, titrated bases, indicator and mercury showed that in these solvents mercury is oxidized at potentials much more negative than those for the titrated bases and other components present in the solution. The protons generated in this way have been used for the titration of some organic bases, with either visual or potentiometric end-point detection. The oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone and the reaction of mercury ions with these solvents have been found to proceed with 100% current efficiency. # 2003 Elsevier Science B.V. All rights reserved.
Keywords: Coulometric titration; Hydrogen ion electrogeneration; Mercury oxidation; Ketones

1. Introduction Methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone (dipolar aprotic solvents) have a

* Corresponding author. Tel.: '/381-34-33-5039; fax: '/38134-33-5040. E-mail address: randjel@knez.uis.kg.ac.yu (R.P. Mihajlovic ).

small autoprotolysis constant, relatively high permittivity and dipole moment as well as a pronounced differentiating effect, relative to many electrolytes; on account of these properties they are suitable as solvents for the determination of weak organic acids and bases, either individually or in mixtures [1 /10]. A solution of perchloric acid in methyl ethyl ketone [1,2] or dioxan [7] has been used as the

0039-9140/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0039-9140(03)00270-4

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titrant in the titration of weak organic bases in ketones, with visual or potentiometric end-point detection. Streuli et al. [8] titrated an organic acid by generating hydroxide ions in acetone containing 1% of water, tetraethylammonium bromide and sodium perchlorate; Fritz and Grainner used a lower concentration of water (0.2%) [9]. Christian [10] titrated weak organic bases in acetone containing 10% of water and a high concentration of lithium perchlorate (3 M). Marinenko [11] proved that the direct coulometric titration of bases with H ' ions generated by the oxidation of water at a platinum anode is not feasible, since the bases are also oxidized, which results in a negative error of several percent. To prevent the oxidation of bases at the platinum anode in aqueous solvents, Hoyle et al. generated the H ' ions separately from the test solution (externally generated titrant), but the results obtained in the titration of 4-aminopyridine were still low by 2 /6%. These authors considered that this might have been due to the formation of ( peroxydisulfate anions (S2O2 8 ) when sodium sulfate was used as the background electrolyte or peroxydiperchlorate (Cl2O8) when sodium perchlorate was used [12]. To prevent both the oxidation of the bases to be titrated and the formation of peroxydiperchlorate or peroxydisulfate anions, these authors used sodium hydrazine sulfate as the depolarizer in the generation of H' from water [12] and later, they used this technique in the most accurate electrochemical determination of the Faraday constant yet reported [13]. The application of hydrazine sulfate as a depolarizer is limited to aqueous solutions, since this compound behaves as a base in non-aqueous solvents. Hence, the coulometric generation of acids (H ', D ', CH3CO ' ions) in non-aqueous solvents requires the presence of an anode depolarizer, the oxidation potential of which is more negative than that of the base to be titrated or of other species present in the solution. To avoid the preparation of standard perchloric acid solution for the titration of bases in nonaqueous solvent and to control the titration process automatically, in our previous papers we

showed that the coulometric titrations of bases in non-aqueous solvent could be carried out with H' generated by anodic oxidation of phenols, esters of gallic acid, ascorbic acid, 2,3,4-trihydroxy benzoic acid, hydrogen dissolved in palladium, and of mercury in acetic acid /acetic anhydride and acetone, as well as with D ' ions generated by the anodic oxidation of deuterium dissolved in palladium [14 /28]. In this paper, we investigated the possibility of application of HgCl2 as a primary standard in the determination of weak bases in anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, as well as the possibility of the quantitative production of H ' ions in these solvents by the electrolytic oxidation of mercury.

2. Experimental 2.1. Reagent All the chemicals used were of analytical reagent grade (Merck and Fluka). Methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone were purified as described by Kreshkov et al. [29]. The liquid organic bases were dried before use over fused potassium hydroxide and then distilled under reduced pressure. Their purity was checked by titration with protons generated by the oxidation of hydrogen dissolved in palladium [20]. The supporting electrolyte was 0.25 M sodium perchlorate in methyl ethyl ketone or methyl isobutyl ketone, or 0.4 M sodium perchlorate in cyclohexanone. The titration end-point was detected by means of a 0.1% solution of Methyl Red in ketones, or potentiometrically. The volumes of the bases were measured by means of a microburette with a PTFE tip; for the visual end-point detection 1.00 ml of the investigated bases were measured, whereas for potentiometric end-point detection 2.00 /3.00 ml of the bases were used. Methanolic potassium hydroxide was prepared according to Kreshkov [29]. Tetra-n -butylammonium hydroxide (laboratory-reagent grade) 0.1 M solution in toluene /

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methanol (3:1 v/v) was standardized against an aqueous solution of potassium hydrogen phthalate with phenolphthaleine as an indicator. The solution of sodium methylate was prepared according to Kreshkov [29]. 2.2. Apparatus The apparatus for the coulometric titration of bases with visual end-point detection has been described previously [26]. The anode and cathode compartments were separated by a sintered glass G-4 disk. The cathode was a platinum spiral of 25 mm2 area, and the anode was pure liquid mercury with a surface area of 1 cm2. The current source was a voltage/current stabilizer (Vinc a, Belgrade). The current in the generator circuit was measured with a precise milliammeter (Iskra, Kranj). The apparatus for coulometric /potentiometric titration was previously described [26]. The indicator electrode was an H2/Pd-wire spiral electrode and the reference electrode was a modified calomel electrode containing methanolic potassium chloride solution. The potential changes during the titration were followed with a Radiometer pHM28 pH-meter. The apparatus for the potentiometric titration of the acid obtained in the reaction of HgCl2 with anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone was a one-compartment cell containing a laboratory-made H2/Pd indicating electrode and a modified saturated calomel reference electrode. 2.3. Procedures 2.3.1. Determination of the concentration of the acid obtained by the reaction of HgCl2 with anhydrous ketones 2.00 ml of the HgCl2 solution of known concentration (0.01 /0.4 M) in the corresponding ketone was weighed into the titration vessel, 20.0 ml of anhydrous solvent and a drop of Thymol Blue indicator were added. The H2/Pd indicator electrode and the modified saturated calomel electrode were immersed and the solution of base (sodium methylate or tetrabutylammonium hy-

droxide) was added from a burette. The potential of the solution was measured after each addition of titrant. The titration end-point was determined by the second derivative method. 2.4. Coulometric generation of hydrogen ions 2.4.1. Photometric end-point detection With enough mercury in the anode compartment just to cover the bottom, the anode and cathode compartments were filled to the same level with 0.25 M sodium perchlorate solution in anhydrous solvent (methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone). A drop of the indicator solution is added to the anolyte, the current is switched on, and the supporting electrolyte is titrated with proton generated by oxidation of mercury until the indicator changed color. Known amount of the base to be investigated was added and, after simultaneously switching on the current and the chronometer, the electrolysis was continued until the same color change was obtained. Another sample of the base was then added and titrated in the same way. Thus several samples can thus be analyzed using the same supporting electrolyte solution. The current efficiency can be determined from the coulometric titration of a known amount of base. 2.4.2. Potentiometric end-point detection The supporting electrolyte was placed in the cathode compartment of the electrolysis vessel and a platinum spiral was immersed in it. Mercury was poured into the anode compartment to cover the bottom, and previously titrated supporting electrolyte and a known quantity of to be investigated base were added. The indicator (H2/Pd electrode) and reference electrode (a modified calomel electrode) were immersed into the anolyte and connected to a pH-meter. The current was switched on and hydrogen ions were generated discontinuously, the potential being measured after each pulse, with small generating pulses in the vicinity of the equivalence point. The titration end-point was determined by the second derivative and the Gran methods. A new aliquot of base solution was then added to the anolyte and the solution was

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titrated in the same way. Three or four samples could be titrated in the same supporting electrolyte. When the Gran method was applied, the generation of H ' ions continued even after the endpoint had been reached.

be expressed by the following equations: 2CH3 CH2 COCH3 ' HgCl2 0 (CH3 CH2 COCH2 )2 Hg ' 2HCl 2CH3 CH(CH3 )CH2 COCH3 ' HgCl2 0 (CH3 CH(CH3 )CH2 COCH2 )2 Hg ' 2HCl (2)

3. Results and discussion (3) 3.1. HgCl2 as acidimetric standard in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Morton and Penner [30] established that mercury (II) nitrate react with the ketones according to the following scheme: Hg(NO3 )2 ' CH3 COCH3 0 CH3 COCH2 HgNO3 ' HNO3 (1) 4 In order to check whether Eqs. (2) and (3) and Eq. 4 are correctly formulated, the released HCl was titrated with sodium methylate or tetrabutylammonium hydroxide by applying visual (Thymol Blue) and potentiometric determination (application of H2/Pd-modified saturated calomel electrode couple) of the end-point. In the potentiometric determination of the end-point, the indicator was added to the investigated solution in order to determine whether the indicator color change corresponded to the potential jump at the endpoint. Typical potentiometric titration curves of the released acid with sodium methylate in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone as solvents are shown in Fig. 1. As it can be seen, the potential jump at the end-point of the titration is very large. The indicator color change was very sharp. The relation (expressed in moles) between the weighed amount of HgCl2 and the used volume of sodium methylate or TBAH is shown in Table 1. One mole mercury(II) chloride reacts with 2 mol of solvent and 2 mol of acid are released. Thus it may be concluded that mercury(II) chloride can be applied in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone as a primary standard for the titration of bases in these solvents. These authors considered that the replacement of hydrogen in ketones is most easily carried out on the carbon atom in the a-position to the carbonyl group of acetone. In methyl ethyl ketone both primary and secondary atoms are exchanged in the a-position. The same authors established that the mercury is bound to carbon, not to oxygen in these compounds, which was confirmed by IR spectroscopy. Somewhat later, Montequi et al. [31] used a solution of HgCl2 in acetone as the standardized solution for the titration of weak organic bases. However, acetone shows the tendency towards polymerization [33] in the presence of strong acids and strong bases and that is why standard solution of strong acid and strong bases in acetone are not applied in the titration of acids and bases, respectively. Since methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are very good solvents for acid /base determinations (large relative acid scale, small autoprotolysis constant, pronounced differentiating effect, high permittivity), we investigated the possibility to apply the solution of HgCl2 in MEK, MIBK and cyclohexanone as an primary acidimetric standard in the determination of weak bases. The reactions of mercury(II) chloride with methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone can

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Fig. 1. Potentiometric titration curves of the acid (HCl) obtained by the reaction of mercury with (a) methyl ethyl ketone, (b) methyl isobutyl ketone and (c) cyclohexanone.

3.2. Coulometric generation of hydrogen ions by oxidation of mercury in methyl ethyl ketone and methyl isobutyl ketone In our previous papers [26], it was shown that mercury is quantitatively oxidized to Hg2' or ' Hg2 ions in acetone which released H ' ions in 2 the reaction with the solvent. Since methyl ethyl ketone and methyl isobutyl ketone are very good solvents for the coulometric determination of weak organic bases either individually or in mixtures [19,20], it was considered of interest to investigate possibility of applying Hg as an anodic depolarizer to the coulometric generation of hydrogen ions by the oxidation of mercury in these solvents. The current /potential curves for Hg in 0.25 M sodium perchlorate solution in MEK (Fig. 2) show that the oxidation potentials of Hg are much more negative than those of the titrated base, the indicator and the supporting electrolyte. Similar current /potential curves were obtained for MIBK as well. The current /potential curves were recorded under the same experimental condition as those applied in the coulometric titration. Small

amounts of water (0.05%) affect neither the curves nor the results obtained. In order to establish whether the oxidation of mercury and the reaction of its ions with MEK and MIBK are quantitative, triethylamine, triethanolamine, N ,N ,N ?,N ?-tetramethylethylenediamine, aa?-bipyridine and ethanolamine in MEK and quinoline-8-ol, ethanolamine, quinoline and triethylamine in MIBK were titrated with visual (Methyl Red as indicator) and potentiometric (by using a H2/Pd or calomel reference electrode and a glass or H2/Pd indicator electrode) end-point detection. The Gran method or the second derivative method was applied in the potentiometric determination of the end-point titration. Since the reaction of mercury ions with MEK and MIBK gives rise to the formation of slightly ionized compounds, which are very soluble in MEK and MIBK, the change of indicator color at the titration end-point is very sharp and the results obtained are very reproducible: 2CH3 CH2 COCH3 ' Hg2' 0 (CH3 CH2 COCH2 )2 Hg ' 2H' (5)

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Table 1 Stoichiometric relation of mercury(II) chloride and ketones Mecury(II) chloride (mol l ( 1) Solvent Titrant Relation in moles Potentiometric end-point 0.00988 0.02531 0.05192 0.1022 0.2596 0.00988 0.02531 0.05192 0.1022 0.2596 0.01133 0.03275 0.07616 0.1015 0.2293 0.01133 0.03275 0.07616 0.1015 0.2293 0.01524 0.02331 0.04052 0.07572 0.1229 0.3789 0.01524 0.02331 0.04052 0.07572 0.1229 0.3789
a b c

Photometric end-point 1:2.00 1:1.99 1:2.01 1:1.98 1:2.00 1:1.99 1:1.98 1:2.00 1:1.99 1:2.01 1:1.99 1:2.00 1:1.99 1:2.01 1:2.01 1:1.99 1:1.99 1:2.00 1:2.01 1:2.00 1:1.99 1:2.01 1:2.03 1:1.98 1:1.98 1:2.00 1:2.01 1:2.03 1:2.00 1:1.98 1:2.02 1:2.00

MEKa MEK MEK MEK MEK MEK MEK MEK MEK MEK MIBKb MIBK MIBK MIBK MIBK MIBK MIBK MIBK MIBK MIBK Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone

Na-methylate Na-methylate Na-methylate Na-methylate Na-methylate TBAHc TBAHc TBAHc TBAHc TBAHc Na-methylate Na-methylate Na-methylate Na-methylate Na-methylate TBAH TBAH TBAH TBAH TBAH Na-methylate Na-methylate Na-methylate Na-methylate Na-methylate Na-methylate TBAH TBAH TBAH TBAH TBAH TBAH

1:1.99 1:1.99 1:1.99 1:2.00 1:1.99 1:1.98 1:2.00 1:1.98 1:1.99 1:2.00 1:2.00 1:1.99 1:1.99 1:2.00 1:2.01 1:1.99 1.1.98 1:2.00 1:1.99 1:2.01 1:1.98 1:1.99 1:1.99 1:2.00 1:2.03 1:2.03 1:1.99 1:1.98 1:1.99 1:2.00 1:2.03 1:2.02

Methyl ethyl ketone. Methyl isobutyl ketone. Tetrabutylammonium hydroxide.

or
' 2CH3 CH2 COCH3 ' Hg2 2

0 Hg2 (CH3 CH2 COCH2 )2 ' 2H'

(6)

MIBK (Eq. (3)) reacts in a similar way when equivalent amount of H ' ions (HClO4) is re' leased. (Hg can be oxidized to Hg2' or to Hg2 2 , 2' because the standard reduction potentials of H2 / 2Hg and Hg2'/Hg are very close).

The results obtained in the determination of some organic bases with either photometric or potentiometric end-point detection are given in Table 2. In the potentiometric titration with the H2/Pd indicator electrode, the potential was established in less than 0.5 min, whereas in the vicinity of the TEP in about 1 min. Fig. 4 shows the titration curves for triethanolamine in MEK (curve 1), and for aa?-bipyridine in MIBK (curve 2). The titration curves show that the potential jump at the equivalence end-point is greater that

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Fig. 2. Change of the anode potential (vs. SCE) with current density in 0.25 M sodium perchlorate solution in anhydrous methyl ethyl ketone: (1) methyl ethyl ketone; (2) Methyl Red; (3) ethanolamine; (4) mercury.

Fig. 3. Change of the anode potential (vs. SCE) with current density in 0.25 M sodium perchlorate solution in anhydrous cyclohexanone: (1) mercury; (2) pyridine; (3) Methyl Red; solvent.

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Table 2 Coulometric titration of bases with the H ' ions generated by the oxidation of mercury with photometric end-point detection or potentiometric end-point detection Solvent Photometric end-point Methyl ethyl ketoneb Methyl ethyl ketone Methyl ethyl ketone Methyl ethyl ketone Methyl ethyl ketone Methyl isobutyl ketonec Methyl isobutyl ketone Methyl isobutyl ketone Methyl isobutyl ketone Cyclohexanoned Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Potentiometric end-point Methyl ethyl ketoneb Methyl ethyl ketone Methyl ethyl ketone Methyl ethyl ketone Methyl ethyl ketone Methyl ethyl ketone Methyl ethyl ketone Methyl isobutyl ketonec Methyl isobutyl ketone Methyl isobutyl ketone Methyl isobutyl ketone Cyclohexanoned Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone
a b c d

Titrated base

n a Taken (mg)

Current efficiency (%)

Triethylamine Triethanolamine N ,N ,N ?,N ?-tetrame-thylethylenediamine aa?-Bipyridine Ethanolamine Quinoline-8-ol aa?-Bipyridine Quinoline Triethylamine aa?-Bipyridine Morpholine Pyridine Piperidine Triethanolamine Triethylamine Triethanolamine N ,N ,N ?,N ?-tetrame-thylethylenediamine aa?-Bipyridine Ethanolamine aa?-Bipyridine Ethanolamine Quinoline-8-ol aa?-Bipyridine Quinoline Triethylamine aa?-Bipyridine Morpholine Pyridine Piperidine Triethanolamine

5 6 6 5 6 6 5 5 6 6 5 6 6 6 6 5 6 6 6 5 6 6 5 5 5 6 5 5 6 6

1.569 2.222 1.925 1.780 3.170 2.035 0.882 2.236 1.847 2.912 2.359 2.829 1.880 1.810 6.276 8.888 5.180 7.120 12.680 1.780 3.170 8.138 3.528 8.942 7.389 11.646 9.437 11.307 7.520 7.241

100.09/0.4 100.09/0.3 99.99/0.4 99.99/0.3 100.09/0.4 99.99/0.1 99.99/0.3 100.09/0.3 100.09/0.3 100.09/0.3 100.09/0.4 99.99/0.3 99.99/0.4 100.09/0.3 100.09/0.4 100.09/0.4 99.99/0.3 99.39/0.8 100.09/0.6 99.99/0.3 100.09/0.4 99.99/0.1 99.09/0.3 100.39/0.3 99.89/0.2 99.99/0.3 100.09/0.1 99.89/0.1 99.99/0.1 99.99/0.1

Number of titration. I 0/15 mA. I 0/4 mA. I 0/9 mA.

250 mV. In the titrations of very weak bases in these solvents the potential jump was not less that 60 mV. Both the photometric and potentiometric titration gave good reproducibility (Table 2). From the result shown in Table 2 it can be seen that the current efficiency is 100% and the generated hydrogen ions can be applied for the coulometric determination of bases in these solvents.

3.3. Coulometric generation of hydrogen ions by oxidation of mercury in cyclohexanone In our previous papers, it was shown that cyclohexanone is a very good solvent for acid / base and electrochemical investigations [20,32]. Since it reacts with mercury ions in a precise stoichiometric relation (Eq. 4), our aim was to investigate the possibility of the quantitative gen-

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Fig. 4. Titration curves obtained in the coulometric titration of triethanolamine in anhydrous MEK (1), aa?-bipyridine in methyl isobutyl ketone (2) and triethanolamine in cyclohexanone (3) with protons generation by mercury oxidation.

eration of H ' ions by the electrochemical oxidation of mercury in this solvent as well. In this ' solvent Hg can be oxidized to Hg2' or to Hg2 2 , as well. The current-potential curves for Hg in 0.25 M sodium perchlorate solution (Fig. 3) in this solvent showed that the oxidation potentials of Hg were much more negative than those of the titrated base, the indicator (Methyl Red) and cyclohexanone. In order to establish whether the oxidation of mercury and the reaction of its ions with cyclohexanone are quantitative, aa?-bipyridine, morpholine, pyridine, piperidine, triethanolamine and triethylamine were titrated with visual (Methyl Red as indicator) and potentiometric (by using a H2/Pd or calomel reference electrode and a glass or H2/Pd indicator electrode) end-point detection (Fig. 4, curve 3). As in MEK and MIBK, the reaction of mercury ions with cyclohexanone gives rise to the formation of slightly ionized compounds which are very soluble in cyclohexanone (Eq. 4), the change of indicator color at the titration end-point is very

sharp, the potential during titration and at endpoint is very stable and established quickly and the current efficiency is 100%.

4. Conclusion Mercury(II) chloride react with anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone in a precise stoichiometric relation (1:2). The oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone and the reaction of mercury ions with these solvents have been found to proceed with 100% current efficiency.

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