J Solution Chem (2010) 39: 959966 DOI 10.

1007/s10953-010-9557-2

Automated Conductometry Measurements of Simple Electrolytes and Micellar Solutions Using a Voltage Divider Technique
Arash Daghighi Kiumars Ghowsi Mohammad Reza Nilforoushan

Received: 12 November 2009 / Accepted: 3 February 2010 / Published online: 11 July 2010 Springer Science+Business Media, LLC 2010

Abstract A new automated technique was developed for online monitoring of the conductance of a conductive type of cell. Shining metal electrodes were used for the conductometry measurements and the frequency of the input signal was swept from a few hertz to 1 MHz. A theoretical model was developed based on the voltage dividing technique. The model was in good agreement with the experimental results. Conductances of simple electrolytes such as HCl and micellar solutions were compared. Solutions of HCl with concentrations as low as 45 molL1 were investigated. Critical micellar concentrations of two types of micelles, SDS and CPC, were also measured. It was shown that this voltage divider circuit can be used for automated online conductometric titrations. Keywords Conductometry Oscillometry Micellar solution Electrolytes Titration 1 Introduction Oscillometric measurements have been used to characterize some structural properties of solutions [1]. A detailed theoretical and experimental investigation of the Debye-Falkenhagen effect was made with a network analyzer using a capacitor cell [2]. In this type of cell, the solution to be analyzed is placed between external, parallel metal sheet electrodes. Because the solution is insulated from the metal plates by the walls of the container, the measurements and characterization methods can only be performed at high frequencies. For these purposes, electrodeless cells were used for the high frequency titrations [3, 4].

A. Daghighi ( ) Department of Electrical Engineering, Faculty of Engineering, Shahrekord University, Shahrekord, Iran e-mail: daghighi_a@eng.sku.ac.ir K. Ghowsi Department of Chemistry, Islamic Azad University Majlesi Branch, Isfahan, Iran e-mail: k_ghowsi@yahoo.com M.R. Nilforoushan Department of Materials Science, Shahrekord University, Shahrekord, Iran e-mail: m_r_nilforoushan@yahoo.com

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In a previous work, conductive-type cells were studied in which the electrodes are in contact with the electrolytes [5]. Using a network analyzer, the conductometry of a conductivetype cell was measured over the tens of MHz frequency range. In another work, shining (polished) metal plates were used to study the conductometry of micellar solutions by incorporating a LCR meter [6]. The present work is a further study of the conductive type of cell, where low to high frequencies have been investigated. In the present experiments, for the rst time, shining platinum metal electrodes were used for a conductometric investigation in the 1 Hz to 1 MHz range for electrolyte solutions as well as micellar solutions. Although the use of an additional layer of black coating on platinum electrodes absorbs gases generated at the electrodes surface during the measurements [7], their use suffers from the following drawbacks: (1) electrode deterioration, and (2) a complicated mechanism is needed for understanding the conductance measurement. Shining metal plates, on the other hand, have a very low rate of electrode wear. Additionally, the surface gases that normally result from conductometry measurements are not produced when high frequencies are used because of the high rate of change of the input signal. Consequently, shining metal plates are a good candidate for automated on-line conductometry measurements at high frequencies. In order to accurately measure the conductance as a function of frequency, a Wheatstone bridge is usually used [3]. However, the Wheatstone bridge needs to be balanced at each measurement point. In this work, by applying a theoretical model to the measurements, a voltage dividing technique is developed. Using this method, automated conductometry measurements were carried out for electrolyte concentrations as low as 45 molL1 . The conductometry of a conductive type cell was studied over a signal frequency range from a few hertz to 1 MHz. The equivalent model for the conductive type cell and an equation for the conductometry are explained in Sect. 2, the experimental procedure and the measurement setup are presented in Sect. 3 followed by a discussion of the measurement results in Sect. 4, and the conclusions are reported in Sect. 5.

2 Theory An equivalent circuit for cells of the conductive type is given in Fig. 1. The capacitance (C1 ) is due to the double-layer capacitance and the induction (L) is mainly due to the wirings. The parasitic capacitor that forms between the parallel plate electrodes is modeled by C0 . The dielectric for this capacitor is the solution in the cell. The voltage-dividing resistor is denoted by R2 , while R1 is the resistance of the solution. Typical values of the double-layer capacitance (C1 ) are several orders of magnitude larger than the solution capacitance (C0 ). Thus, the impedance of the parasitic capacitor (C0 ) was ignored. The ratio of the output
Fig. 1 Circuit model of the voltage divider

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Fig. 2 Amplitude and phase response versus frequency

potential to the input potential, for the model circuit shown in Fig. 1, is computed as: H (j ) = R2 R1 + R2 +
1 j C1

+ j L

(1)

where is the angular frequency of the input voltage source. After the necessary transformations, the amplitude and the phase angle are obtained: |H (j )| =
2 R2 (R1 + R2 )2 + ( L 1
1 2

1 )2 C1

H (j ) = tan

1 C1

(2)

R1 + R2

Graphs of Eq. 2, showing changes as the frequency is varied from 1 Hz to 10 MHz, are plotted in a semilog scale in Fig. 2. Typical values of R1 = 2 k , R2 = 1 k , C1 = 1 F and L = 1 mH were chosen. The peak occurs at the resonant frequency fr , which is dened as: fr = 1 2 L C1 (3)

For the above typical values, the resonant frequency is computed to be fr = 5 kHz. As seen from the graph of |H (j )| in Fig. 2, a at region is observed in the vicinity of the resonant frequency. At the peak, where resonance occurs, the reactance of the inductor (L) and capacitor (C1 ) cancel each other. The graph of phase angle versus frequency in Fig. 2 further shows capacitive and inductive dominant regions at low and high frequencies, respectively. Near the resonant frequency, the circuit shows a zero phase shift between the input and output ports. In the vicinity of this region, the circuit behavior can be modeled as a resistive network. Thus, |H (j )| can be further simplied as: |H (j )| = R2 R1 + R2 (4)

962 Fig. 3 Amplitude response versus frequency as the solution resistance increases

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where r = 2fr . Using Eq. 4, the solution resistance (R1 ), or alternatively, the conductance of the solution (gsolution ), can be written as: gsolution = 1 |H (j r )| R2 1 |H (j r )| (5)

Therefore, by measuring the ratio of amplitudes of the output voltage (Vo ) to the input voltage (Vi ) at the resonant frequency, the conductance of the solution can be computed using Eq. 5. By increasing the concentration of an electrolyte solution the conductance increases, and consequently the peak amplitude increases in Fig. 2. In order to further investigate the impact of the parasitic solution capacitance (C0 ) on the frequency response of the cell, the circuit of Fig. 1 was simulated with a typical capacitor value of 1 nF (C0 = 1 nF). Figure 3 shows the results obtained for three different values of the solution resistance. As suggested by Eq. 4, the y-axis was scaled by the proportionality factor (1 + R1 /R2 ). Thus, all three curves have identical values at the resonant frequency. However, as depicted in Fig. 3, with increasing solution resistance (R1 ) a high frequency overshoot shows up in the output characteristics. This is an indication of signal bypassing through the parasitic solution capacitance (C0 ), rather than a series connection to the solution resistance (R1 ) and the double-layer capacitance (C1 ). On the other hand, the at region in the vicinity of the resonant frequency is unchanged compared with Fig. 2. Therefore, as the value of the solution resistance varies, the value of |H (j )|(1 + R1 /R2 ) is constant at the resonant frequency. This veries Eq. 4 and, consequently, Eq. 5 can be used as a method of measuring the conductometry of a solution.

3 Experimental Procedure In a previous work, the high frequency conductometry of capacitive cells was studied [2]. However, in the present work, the frequency response is studied over a large frequency range, from a few hertz to 1 MHz, using a conductive-type cell. In conventional conductometry, a Wheatstone bridge is usually used to measure the conductance of a solution. In the presently proposed technique, a voltage divider is used rather than a Wheatstone bridge. As a result, automated on-line conductometry can be carried out.

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3.1 Instrument As a signal source, a function generator was used that could supply sine wave signals with frequencies ranging from a few Hz to 1 MHz. Signal amplitudes were measured using a conventional two-channel oscilloscope. The function generator output was connected to channel A while the voltage across the voltage-dividing resistor was measured through channel B. The measurement bandwidth for the combination of oscilloscope and probes was chosen to be well above the operating frequency of the whole circuit. Non-porous shining platinum metal electrodes were used with a surface area of 1 cm2 . A 50 mL pipette was employed for the titrations. Experiments were done at 25 C. 3.2 Chemicals Sodium hydroxide pellets were used for preparing sodium hydroxide solutions. Analytical grade hydrochloric acid was employed for preparing three concentrations of hydrochloric acid: 38% HCl (12 molL1 ), 12 mmolL1 HCl, and 1.2 mmolL1 HCl. The sodium salt of dodecyl sulfate (SDS) and 1-cetylpyridinium chloride monohydrate (CPC) were used to prepare micellar solutions. Merck was the supplier of these chemicals. 3.3 Procedure The apparatus was assembled as a voltage dividing circuit. A l k resistor was connected in series to the conductive cell. This resistor and the electrolytic cell together were considered as a voltage divider. Sine wave signals were applied across both the resistor and the electrolytic cell. The frequency of the function generator was varied from a few Hz to 1 MHz. An oscilloscope was used to measure the voltage across the l k resistor connected to channel B. The function generator output was connected to channel A. The ratio was computed of the signal amplitude on channel B to the signal on channel A. If the current is low, as in the case for pure water, the measured potential across the l k resistor is low. On the other hand, for more concentrated solutions, the current is high and, consequently, the measured potential across the resistor is high. For conductance measurements, several solutions with different concentrations were prepared and the amplitude response (|H (j )|) was computed. The best t curves to the measured data points, in a least-square sense, were obtained and the resonant frequency was identied. Thus, the amplitudes at the resonant frequency (|H (j r )|) and the corresponding solution conductances (gsolution ) were calculated. Note that the double layer capacitance is composed of an inner Helmholtz, an outer Helmholtz, and a diffuse layer capacitor in series. The dominant capacitors are the inner Helmholtz and outer Helmholtz plane capacitors, which are independent of concentration [8]. As a result, the resonant frequency is considered to be independent of the solution concentrations used in our experiments.

4 Results and Discussion Figure 4 depicts the conductance versus frequency for water and hydrochloric acid at various concentrations. Semilog plots are used. There is very good agreement between the theoretical Fig. 2 and the experimental Fig. 4 for 38% HCl (12 molL1 ) and 12 mmolL1 HCl solutions. Three regions are observed, an increasing region due to the impedance of the double-layer capacitor, a at region due to the conductance of the solution, and a decreasing

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Fig. 4 Conductance of 10 Hz to 1 MHz of 38% HCl (12 molL1 ), 12 mmolL1 HCl, and 1.2 mmolL1 HCl Fig. 5 Conductance of HCl solutions versus concentration

region that represents impedance due to the inductance of the wiring. The signal bypasses the solution parasitic capacitor (C0 ) of the dilute solution, and starts to appear as an overshoot in the conductance graph for 1.2 mmolL1 HCl, which is similar to the conductance of water in Fig. 4. Figure 5 depicts the conductances of HCl solutions at various concentrations. A semilog plot is used for this description. Conductances initially increase linearly with concentration, but then a at region appears. The range of HCl concentrations in Fig. 5 is from 45 molL1 to 12 molL1 . This suggests that the sensitivity of this technique is high enough to allow concentrations as low as 45 molL1 HCl to be studied. The conductometry of micellar solutions was previously reported using a conductivity probe [9]. In order to investigate the functionality of our technique, the conductometry of micellar solutions was studied. Figure 6 shows the results from measurements of conductance versus concentration for SDS and CPC solutions. In both graphs, two regions are observed with different conductance behavior. The rst region is that having a larger slope and the second region is the part with a smaller slope. The region with the smaller slope is due

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Fig. 6 Conductance of CPC and SDS solutions versus concentration

Fig. 7 Titration of 0.1 molL1 NaOH with 0.1 molL1 HCl

to formation of micelles. The intersection point between the smaller slope and larger slope regions, for both SDS and CPC solutions, is the critical micellar concentration (CMC). In order to determine the CMCs for both SDS and CPC solutions, least-squares analyses were used [10, 11]. Using this method, straight lines were passed through the last three data points in the conductivity diagrams for SDS and CPC solutions. Different straight lines were also passed through the rst ve data points. The pair of equations obtained for these straight lines, separately for SDS and CPC solutions, were solved simultaneously and the intersection points were calculated. The coordinates of the intersection points are Xp1 = 2.4, Yp1 = 18.2 and Xp2 = 1.84, Yp2 = 20.03 for CPC and SDS solutions, respectively. For simplicity, the variable X was dened as the logarithm of the concentration. Thus, the critical micellar concentration (CMC) for CPC solutions is computed to be 4 mmolL1 whereas that for the SDS solutions is 14.5 mmolL1 . In addition to measuring conductance by this technique, this conductive type of cell, combined with a voltage divider, can be used for titrations. Figure 7 shows the results of titration of 0.1 molL1 NaOH with 0.1 molL1 HCl. As can be seen, this titration curve

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is V-shaped. The minimum of the curve and its corresponding coordinate on the x-axis is the equivalent point.

5 Conclusion A new technique was developed for routine conductometry studies of simple electrolytes and micellar solutions. Good agreement was observed between the experimental measurements and the theoretical model. It was shown that this technique could be used for computerized conductometric titrations. The automated technique proposed in this article constitutes an efcient method for detailed studies of the conductances of simple electrolytes and micellar solutions.

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