ISSN 1023 1935, Russian Journal of Electrochemistry, 2012, Vol. 48, No. 9, pp. 936940. Pleiades Publishing, Ltd.

., 2012. Original Russian Text F.I. Danilov, A.A. Kityk, V.S. Protsenko, 2012, published in Elektrokhimiya, 2012, Vol. 48, No. 9, pp. 10261030.

SHORT COMMUNICATIONS

Parameters of the Double Electric Layer and n Butanol Adsorption on Lead in Methanesulfonate Solutions
F. I. Danilovz, A. A. Kityk, and V. S. Protsenko
Ukrainian State University of Chemical Technology, Dnepropetrovsk, Ukraine
Received June 16, 2011

AbstractA differential capacity measurement showed that the zero charge potential of a lead electrode in a sodium methanesulfonate solution was 0.69 V. Like sulfate anions, methanesulfonate anions had low spe cific adsorbability on lead. The adsorption of n butanol from a methanesulfonate electrolyte on a lead elec trode was approximated by the Frumkin isotherm equation. The parameters of n butanol adsorption in a methanesulfonate solution were close to those reported for fluoride and sulfate solutions in the literature. Keywords: adsorption, n butanol, lead, double electric layer, differential capacity, electrocapillary curves DOI: 10.1134/S1023193512050059

INTRODUCTION Methanesulfonic acid (MSA) was characterized by many researchers as a promising component of various electrochemical systems [110]. In recent years, an astounding number of its applications have been found due to the appearance of new large scale industrial synthesis methods and hence objects of application. Methanesulfonic acid is known to be a strong electro lyte, the equivalent conductivity of its aqueous solu tions being higher than that of sulfuric acid solutions [11]. In addition, nearly all MSA salts are well soluble in water and concentrated aqueous solutions of the majority of metal salts can thus be created without using chelates, which generally hinder waste disposal. It is also important that methanesulfonic acid is eco logically safe, degrading in a natural way into carbon dioxide and the products further involved in the sulfur cycle in nature [12]. The above mentioned appealing properties of MSA occasionally dictate its choice as a component for metal electropolishing and electrodeposition baths. Many aspects of the electrochemical behavior of metals in methanesulfonic acid solutions, for exam ple, the parameters of the double electric layer (DEL) and adsorption phenomena in aqueous solutions of CH3SO3Na (NaMS), have not yet been studied. This substantially hinders the prediction and rationaliza tion of experimental data on the effects of surfactants on the electroreduction kinetics of metal ions. The goal of this study was to characterize the adsorption of MS anions on lead and their effects on the adsorption of aliphatic alcohols and to determine the zero charge potential of the Pb electrode in a methanesulfonate solution.
z

The choice of lead for a working electrode was dic tated by its widest ideal polarizability range compared with the corresponding range of other solid electrodes and the large number of publications on the adsorp tion on Pb [1318], making it possible to compare our experimental data with the literature data and verify them. EXPERIMENTAL The differential capacity of DEL was measured with a Galvanostat Reference 3000 (Gamry) poten tiostat at 500 Hz. The experiments were performed in a three electrode cell thermostatted at 25C, in which the electrode compartments were separated by a porous glass diaphragm. The working electrode was a platinum disc sealed into glass with a 10 m lead coating and a PD 2 quality addition deposited on it electrochemically from an electrolyte with the following composition (g/L): Pb(CH3SO3)2134 and CH3SO3H100. Lead elec trodeposition was conducted at i = 2 A/dm2 and t = 25C [19, 20]. Before each experiment, the electrode with a freshly deposited lead coating was placed for a few sec onds into a 1 : 3 acetic acid solution until luster appeared. Then it was thoroughly washed with a bidis tillate water and subjected to cathode polarization in a sulfuric acid solution 0.05 M at i = 2 A/dm2, where upon it was washed once again with the bidistillate water and immediately placed in the working solution. All these procedures afford a well reproducible surface of the lead electrode. n Butanol was distilled. Sodium sulfate and methane sulfonate were twice recrystallized. All solutions were prepared from twice distilled water. The solutions

Corresponding author: fdanilov@optima.com.ua (F.I. Danilov).

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PARAMETERS OF THE DOUBLE ELECTRIC LAYER AND n BUTANOL ADSORPTION C, F/cm2 40 30 1 20 2 10 0 0.4 3 Eq = 0 = 0.69 V 0.8 1.2 1.6 E, V 20 0.4 0.8 1.2 1.6 E, V 30 0.5 1.0 3 1.5 0 20 3 1 2 20 1 2 2.0 E, V 10 (a) q, C/cm2 40 (b) , mN/m 0 (c)

937

Fig. 1. (a) Differential capacity curves (dashed line: experimental data, solid line: theoretical data); (b) charge densities; and (c) electrocapillary curves of a lead electrode in (1) 0.1, (2) 0.01, and (3) 0.001 M NaMS solutions.

were deaerated by blowing them down with electro lytic hydrogen. The potentials were measured relative to a silver chloride electrode and recalculated into the scale of the standard hydrogen electrode. RESULTS AND DISCUSSION Figure 1a presents the differential capacity curves (dashed lines) recorded in sodium methanesulfonate solutions with different concentrations. As the solu tion became more dilute, the , curves acquired a minimum, which became deeper at lower concentra tions. The minimum is generally attributed to an increase in the diffuse character of the double electric layer at low charges on the electrode. In our experi ments, the potential corresponding to the minimum capacity did not change for methanesulfonate solu tions with different concentrations (0.69 0.02 V). The integration of the capacity curves [21] gave the dependences of the charge density on the potential (Fig. 1b). Further integration of the latter gave electro capillary curves (Fig. 1c). The shape of the , dependences suggests that methanesulfonate anions did not exhibit a significant specific adsorbability on a lead electrode. The experimental data were checked for corre spondence with the principles of Grahams theory in order to verify that the minimum potential corre sponded to the zero charge potential Eq = 0 of the lead electrode [22]. According to Grahams theory, in the absence of pronounced specific adsorption, DEL can be modeled by two capacitors connected in series to the capacities 1 and 2, where 1 is the capacity of a dense layer, and 2 is the capacity of a diffuse layer. The
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electrode capacity and the quantities 1 and 2 are related by the equation

1= 1 + 1. (1) C C1 C2 The capacity of the diffuse layer for an aqueous solu tion of 1,1 valence electrolyte at 25 is recorded as
C2 = 19.5 138c + q ,
2

(2)

where is the molar concentration of the electrolyte, and q is the density of the surface charge. Using (1) to analyze the results for solid electrodes with a surface which cannot be regarded as ideally smooth, it should be taken into account that all quan tities in (1) are related to the true surface unit [23]. Therefore, we introduce the coefficient f in (1). The equation takes the form

1 = 1 + 1 . (3) C fC1 fC 2 The experimental capacities of DEL for the elec trolyte with the highest concentration allow us to obtain the 1 values, calculate the theoretical , curves by (1)(3), and compare them with the experimental values. According to Fig. 1a, the differ ences between the theoretical and experimental differ ential capacity curves are insignificant. The depen dences of the experimental values of 1/ on the calcu lated values of 1/2 are linear (Fig. 2), their slopes f being close to unity, which suggests that the electrode was satisfactorily prepared before the experiments. The data presented confirm that Grahams theory is useful for describing our results and make it possible to regard the minimum capacity potential (0.69 V) as a zero charge potential of the lead electrode. Table 1 compares the q = 0 values of lead reported for various solutions in the literature with the zero charge potential obtained in this study.
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938 1/C, F1 cm2 0.18

DANILOV et al. C, F/cm2 40

0.12

30 (Eq = 0 = 0.67 V) 20 2 1 (Eq = 0 = 0.69 V) 10

0.06

f = 1.20 (3) f = 1.19 (2) f = 1.02 (1)

0.04

0.08

0.12 0.16 1/C2, F1 cm2

0.2

0.6

1.0

1.4

1.8 E, V

Fig. 2. Dependences of 1/ on 1/2 of a lead electrode in methanesulfonate solutions obtained at potentials of (1) 0.69, (2) 0.75, and (3) 0.8 V.

Fig. 3. Differential capacity curves of a lead electrode in sodium (1) methanesulfonate and (2) sulfate solutions.

As is known, the specific adsorbability is least expressed for F , HF2, BF4, PF6, and several doubly 2 charged anions such as SO 2 and CO3 [27]. The q = 0 4 value of lead in a methanesulfonate solution is slightly lower negative than that of the fluoride and sulfate solutions, but higher positive than that of the solution containing specifically adsorbed iodide ions. Since the absence of the q = 0 dependence on the concentration of the methanesulfonate solution points to negligible specific adsorption of MS anions, we assumed that the observed shift of the zero charge potential to the nega tive region compared with the literature values was due to the difference in the nature of the electrodes used. To verify this hypothesis, we compared the capacity curves obtained on our working electrode in methane
Table 1. Zero charge potentials of a lead electrodes Solution 0.001 M NaF 0.001 M HCl 0.1 M NaBr 0.1 M NaI 0.0005 M Na2SO4 0.001 M NaMS Eq = 0, V (s.h.e.) 0.56 0.69 0.63 0.76 0.59 0.69 Refs. [24] [25] [13] [13] [26] This work

sulfonate and sulfate solutions (Fig. 3). It appeared that q = 0 in these electrolytes almost coincided. Tak ing into account that the sulfate electrolyte is nonsym metric, we can conclude that though methane sulfonate ions have a slightly higher adsorbability on lead than SO 2 ions, this cannot be the reason for the 4 discrepancies between our data and the data of [26]. The observed shift of q = 0 can be explained by the fact that the working electrode used in this study was a galvanic lead coating, which, unlike fused lead, evi dently has a pronounced texture characterized by def inite crystal faces coming out to the surface and differ ing in the corresponding zero charge potentials. The differential capacity curves (Fig. 4a) of the lead electrode in the methanesulfonate solution in the presence of n butanol have a classical shape. The anode peaks of alcohol desorption were not measured because of the electrochemical dissolution of lead at these potentials. Note that the desorption peaks of n butanol on the lead electrode are largely diffuse compared with those of mercury because of the non homogeneous and textured structure of the electrode surface. The above described preparation of an elec trode, however, allowed us to obtain a roughness factor close to unity and peaks with a satisfactory shape. The coverages at = m were determined for dif ferent concentrations of n butanol using the model of two parallel capcitors [28]
I Cd = Cd,0 (1 ) + Cd,

(4)

where d is the differential capacity in an alcohol solu I tion, d,0 is the capacity at = 0, and C d is the capacity for 1.
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PARAMETERS OF THE DOUBLE ELECTRIC LAYER AND n BUTANOL ADSORPTION C, F/cm2 40 (a) ln(/(1 )c) 3.1 6 30 1 2 20 2.9 3 5 4 3.0 (b)

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10

2.8

0.6

1.0

1.4

1.8 0.4 E, V

0,5

0,6

0,7

Fig. 4. (a) Differential capacity curves of a Pb electrode in (1) 0.1 M NaMS containing n butanol at concentrations of (2) 0.05, (3) 0.06, (4) 0.07, (5) 0.08, and (6) 0.1 M; (b) dependence of ln(/(1 )c) on during the adsorption of n butanol on a lead electrode.

According to Fig. 4b, the adsorption of n butanol under the given experimental conditions is satisfacto rily described by the Frumkin isotherm equation [29]:

CONCLUSIONS The zero charge potential of a lead electrode in a methanesulfonate solution and the parameters of n butanol adsorption in a methanesulfonate medium were determined by the differential capacity method. The results of our study indicate that MS anions exhibit weak specific adsorbability on a Pb electrode. The parameters calculated for the solution being stud ied proved close to the literature data for sulfate solu tions. ACKNOWLEDGMENTS We are grateful to the Ministry of Education and Science and the Ministry of Youth and Sports of Ukraine (project 0109U001259) for the financial sup port of this study. REFERENCES
1. Smirnov, M.I., Tyutina, K.M., and Popov, A.N., Elek trokhimiya, 1995, vol. 31, p. 543 [Smirnov, M.I., Tyutina, K.M., and Popov, A.N., Russ. J. Electrochem., 1995, vol. 31, p. 438]. 2. Chernyshova, I.S., Maksimenko, S.A., and Kudryav tsev, V.N., Galvanotekh. Obrab. Poverkhn., 1996, vol. 4, p. 12. 3. Chen, C.S., Wan, C.C., and Wang, Y.Y., Trans. Inst. Met. Finish., 1998, vol. 76, p. 86. 4. Wang, H. and Pritzker, M., Electrochim. Acta, 2008, vol. 53, p. 2430.
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ln

(1 ) c

= ln B + 2a,

(5)

where is the adsorption equilibrium constant and is the attraction constant. A comparison of the obtained adsorption parame ters for n butanol with the literature data (Table 2) showed that the adsorption parameters calculated for the methanesulfonate solution were close to those reported in [15] for the sulfate solution, which again confirms that the anions under study have low adsorb ability.
Table 2. Parameters of n butanol adsorption on a lead elec trode for different supporting solutions Solution 0.1 M NaMS a 1.1 CI, F/cm2 5.45 4.90 EN, V 0.22 0.24 B0, M1 10.3 10.0

0.05 M Na2SO4 1.2

Notes: Our data are given for the methanesulfonate solution; the data of [15], for the sulfate solution.

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