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Mass Transport Processes in the Electro-Oxidation of Organic Compounds for

Wastewater Treatment

Article in ECS Transactions · January 2012

DOI: 10.1149/1.3684789

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 ECS Transactions, 41 (17) 27-33 (2012)
10.1149/1.3684789 © The Electrochemical Society

Mass Transport Processes in the Electro-oxidation of Organic Compounds for

Wastewater Treatment

Q. Nia, D. W. Kirka, S. J. Thorpeb

a
Department of Chemical Engineering and Applied Chemistry, University of Toronto,
Toronto, Ontario M5S 3E5, Canada
b
Department of Materials Science and Engineering, University of Toronto,
Toronto, Ontario M5S 3E4, Canada

The mass transport of species, including diffusion, convection and

migration, involved in the electro-oxidation of oxalic acid was
investigated. A rotating-disk electrode technique was used as a tool
to investigate the influence of convection. The effect of pH and
potential on the degradation rate of oxalic acid was also
investigated by measuring oxalic acid oxidation over the pH range
0 to 7 and potential 1.6 to 2.4 vs. Ag/AgCl. The results showed
that higher degradation rates were achieved by increasing the
convection, using higher pH and E. The results also showed that
the local pH at the electrode surface had a significant impact on
electrolysis in a neutral non-buffered solution.

Introduction

Anodic oxidation can be used to degrade organic compounds in municipal wastewater, as

an alternative method to conventional microbial degradation (1). The advantages of this
approach include fast treatment, complete mineralization of the organics and the
amenability to the various plant size and power sources. Therefore it is a technically
viable solution to the worldwide problem of water pollution.

The major challenge facing this technology is the high energy requirement. The
energy consumption arises from the voltage needed to drive the reactions and the charge
needed to decompose the organics. The voltage is determined by the thermodynamic of
the reactions and the polarization in the electrode kinetics. The charge requirement is
determined by the required amount of organics to be degraded and the current efficiency.
This study focuses on improving the current efficiency in the electro-oxidation of the
organic compounds for wastewater treatment.

In previous work, square-wave current pulsing was adopted to replace constant-

current electrolysis, as an approach to enhance the current efficiency (2). The results
showed that under the conditions mimicking the plant operation, the degradation of the
organic compounds was controlled by mass transport of the organic compounds towards
the anode, and the current efficiency was not significantly improved by pulse electrolysis.
Therefore in the current stage, enhancing the mass transport was considered as the key to
better current efficiency.

Mass Transport Limit

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 ECS Transactions, 41 (17) 27-33 (2012)

The mass transport of solute is composed of diffusion, migration and convection.

Diffusion is due to the random movement of solutes down a concentration gradient.
Convection is related to the motion of the bulk electrolyte. Migration is due to the
movement of the charged species under the influence of an electric field in the electrolyte.

Diffusion and convection can be studied by the rotating-disk electrode technique,

which is one of the few systems involving controlled hydrodynamics that has an
analytical solution (3). In this method, a circular piece of electrode is allowed to spin
about its center at a controlled angular velocity (ω). The limiting current density (ilim) of
an electrochemical reaction is related to the square-root of ω by the number of electrons
involved (n), the Faraday constant (F), diffusivity of the solute (D) and the kinematic
viscosity of the solution (ν) in equation [1].

ilim = 0.62 nFD ν –1/6 ω1/2 [1]

Migration affects charged organic species. The actual municipal wastewater may
contain many ionic compounds such as phenols, carboxylic acids and amines. In this
study, oxalic acid (H2C2O4) was used as a model organic compound because it can be
singly or doubly charged depending on the pH. Figure 1 shows the theoretical distribution
of these species at equilibrium, based on its dissociation constants (pKa1=1.25,
pKa2=3.81). With increasing pH, more of the oxalic acid will carry negative charge and
be attracted towards the anode surface. Therefore the overall transport rate will increase.

Figure 1. Percentage of the ionized species of oxalic acid (H2A) with pH.

Migration rates are controlled by the electrode potential, as the electric field within
the electrolyte is the driving force of ionic drifting. This is described by the Nernst-
Planck equation [2]. The first term relates the migration current to the electric field (E),
with C being the concentration, whereas the second term describes the current due to
diffusion. The equation shows that the migration transport of the anion is a linear
function of the electric field (4).

ilim = (z2F2DC / RT) E – zFD (dC/dx) [2]

In the present study, the effect of mass transport by convection and migration was
studied. The convection and migration was studied by rotating-disk electrode technique,
and the migration was studied by investigating the effect of pH and potential in the
electrolysis cell. Oxalic acid was used as a model organic compound for the degradation.

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 ECS Transactions, 41 (17) 27-33 (2012)

Experimental Methods

Rotating-disk Electrode (RDE)

The rotating disk electrode experiment was conducted to observe the effect of
convection and diffusion on the reaction kinetics. The tests were conducted with an
EG&G PARC 616 RDE equipment. The anode was the antimony-doped tin oxide
(Ti/SnO2-Sb2O5) composite material, selected and developed in previous studies (2). It
was made as a 1.0cm2 round disk and was rotated at 10~100 rpm during electrolysis. At
these rotation speeds the average linear surface flow rate would be between 1 and 10
cm/s. The electrolyte contained 0.1M Na2SO4 and 0.02M H2C2O4. The counter electrode
was a nickel mesh located facing the anode. Linear Scan Voltammetry was performed
using an Iviumstat® between 1.0~2.0V vs. Ag/AgCl, at a scan rate of 1mV/s.

Degradation of Oxalic Acid Under Different pH and Voltages

The effect of pH and voltage on the electro-oxidation of oxalic acid was studied in an
undivided electrolysis cell. A piece of Ti/SnO2-Sb2O5 anode (Area: 34.7cm2) was used as
the working electrode. The counter electrode was a nickel mesh of the same dimensions
and located parallel to the anode at a 2cm spacing. The anode voltage was recorded
against the Ag/AgCl (4M KCl filling) reference electrode. During the electrolysis, the
solution was stirred by a magnetic bar at a constant stir rate.

The cell contained 300ml of electrolyte, which contained 0.01M oxalic acid as the
model organic compound to oxidize. The acidity was adjusted by different combinations
of sulfuric acid, sodium sulfate and sodium hydroxide. The composition is listed in table I.

TABLE I. The composition of the electrolyte

pH Oxalic Acid (mol/L) Supporting Electrolyte
0 0.01 0.5M H2SO4
0.7 0.01 0.1M H2SO4
3 0.01 0.1M Na2SO4, 0.01M NaOH
7 0.01 0.1M Na2SO4, pH adjusted to 7 by adding NaOH

Electrolysis was conducted under galvanostatic conditions. The current was selected
at nine levels from 25mA to 300mA, which correspond to current densities between 0.72
and 8.65 mA/cm2. For all the experiments, a total charge of 100mAh was supplied. After
electrolysis, the concentration of oxalic acid remaining in the cell was determined from
titration with KMnO4. The effective current of degradation was calculated from the
difference between the initial (Ci) and final concentrations (Cf). Since each mole of oxalic
acid requires 2 moles of charge to undergo complete degradation, the calculation follows
equation [3].

IEffective = (Ci – Cf) × Volume × 2F [3]

Results

Diffusion and Convection

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 ECS Transactions, 41 (17) 27-33 (2012)

Figure 2. The voltammetry curve of the rotating disk electrode at different rotation rates

The results from linear scan voltammetry are summarized in Figure 2. All the curves
have a shoulder starting at ~1.4V, indicating the onset of oxalic acid degradation. At 1.7V,
a secondary reaction occurs, which is likely the oxygen evolution reaction under charge-
transfer control. To obtain the limiting current for the electro-oxidation of oxalic acid, the
current due to oxygen evolution was subtracted from these voltammetry curves. Then the
limiting current values are plotted in Figure 3.

Figure 3. The limiting current of oxalic acid degradation plotted against ω1/2.

The limiting current was proportional to the square-root of the rotation speed, which
indicates the oxidation of oxalic acid was a mass transport-limited process. Increasing the
rotation rate increases the convection, therefore increasing the reaction rate. Also, using
equation [1] with n=2 (because each oxalic acid needs two units of charge to oxidize),
and the viscosity as that of pure water ν = 9.6 × 10-7 m2/s, the diffusion coefficient of
oxalic acid was estimated to be about 0.43 × 10-5 cm2/s. This value was close to those
reported in the literature with RDE (5) or other methods (6, 7).

Migration

The migration effect was studied by the electro-oxidation of the oxalic acid under
different potentials (E) and pH. The effective current is plotted against the measured half-
cell potential under different pH conditions in Figure 4.

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 ECS Transactions, 41 (17) 27-33 (2012)

Figure 4. Effective current at various pH and E levels

As seen in Figure 4, the electro-oxidation current for oxalic acid was found to
increase almost linearly with the applied voltage. This can be explained by the Nernst-
Planck equation if the potential is assumed to have a linear relation with the electric field
in the solution. In addition, the higher voltage results in more oxygen gas evolution on
the anode, which can promote convection and increase the transport rate. Figure 4 also
shows that the effective current increased with increasing pH, which is probably due to
the effect of pH on the anion population. The pH=7 trend is an exception, as the anodic
voltage was exceptionally high. This was later found to be caused by the local pH at the
anode surface.

Effect of Local pH

Follow-up experiments were conducted to investigate the interesting behaviour at

pH=7 in Figure 4. The effect was postulated to be caused by the local pH environment
adjacent to the electrodes, so potentiometric titration was performed to test the hypothesis.
The titration was performed in 300ml of electrolyte containing 0.01mol/L H2C2O4 and
0.1mol/L H2SO4. A constant current of 1.4mA/cm2 was applied while 2mol/L NaOH
solution was slowly added to the solution. During the addition of NaOH, the anode and
cathode potentials as well as the solution pH was measured and are plotted in Figure 5.

Figure 5. The titration curves of pH (solid line), anode potential (dashed line) and cathode
potential (dotted line) against the Ag/AgCl reference electrode.

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 ECS Transactions, 41 (17) 27-33 (2012)

The titration curves revealed important information about the pH near the electrode
surfaces. The Nernst equation states that for the reaction involving hydrogen ions, the
equilibrium potential is a linear function of pH. Therefore a sharp change of pH at the
titration endpoint will result in a sharp change in the electrode potential at the same time.
However, Figure 5 shows that the endpoint in pH did not occur at the same VNaOH as the
endpoint of either the anode or cathode potentials. Instead, the anode endpoint appeared
later than the pH, and cathode endpoint appeared earlier. This indicates that the local
environment at the anode was more acidic than the bulk. Indeed the anodic oxidation of
water and oxalic acid produces hydrogen ions which can decrease the pH near the anode.
Consequently the anode equilibrium potential is increased by low pH. This polarization
by pH would be most significant in the non-buffered solution near pH=7, because the
potential is most sensitive to the small changes in the concentrations of H+. This is
consistent with the abnormally high anodic voltages observed at pH=7 curve in Figure 4.
The opposite applies to the cathodic potential, which tends to be more negative.

The local pH leads to the polarization and consequently extra voltage required during
the electrolysis. In Figure 5, the required voltage is highest between pH 5 and 10, which
is about 0.5V higher than in the acidic or basic solutions. Therefore, in electrolysis of
non-buffered solution, neutral pH’s should be avoided if saving energy is desired.

Conclusions and Future Work

The present work investigated the mass-transport limit in the electro-oxidation of the
organic compounds. It was found to be improved by better convection, higher pH and
higher voltage. In studying the pH effect, the local acidity near the electrode surface was
found to shift the voltage, especial in a neutral solution without the addition of a buffer.
This could have significant impact in the operations in the electrochemical plants for
wastewater treatment.

Future work will address the role of electrode materials. The catalysis and stability of
the Ti/SnO2-Sb2O5 anode materials will be studied, in order to find methods to improve
the energy efficiency in the electrochemical treatment of municipal wastewater.

Acknowledgement

This project is supported by University of Toronto, in collaboration with Xogen

Technologies Inc. The funding support was provided by Sustainable Development
Technology Canada (SDTC) and University of Toronto Fellowship.

References

1. G. Chen, Sep. Purif. Tech., 38, 11 (2004)

2. Q. Ni, D. W. Kirk and S. J. Thorpe, ECS Trans., 28 (29) 33 (2010)
3. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and
Applications, 2nd ed., p. 339, Jon Wiley & Sons, New York (2001)
4. J. O’M. Bockris and A.K.N. Reddy, Modern Electrochemistry 1: Ionics, 2nd ed.,
p. 474, Kluwer Academic Publishers, New York (2002)
5. I. G. Casella Electrochim. Act., 44, 3353 (1999)

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terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 41 (17) 27-33 (2012)

6. P. Vany´sek, Ionic Conductivity and Diffusion at Infinite Dilution, in CRC

Handbook of Chemistry and Physics, 92nd Ed., W. M. Haynes, Editor, CRC
Press/Taylor and Francis, Boca Raton, FL (2011).
7. M. Ciszkowska, Z. Stojek, and J. G. Osteryoung, J. Electroanal. Chem., 398, 49
(1995)

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