Design and Modeling of Electrochemical Sensor

for Determining ION Concentration

S. Jeya Bharathi S. Hosimin Thilagar, V. Jayasurya
Department of EEE Department of EEE Department of EEE
College of Engineering College of Engineering College of Engineering
Anna University, Chennai Anna University, Chennai Anna University, Chennai

Abstract—This paper presents design and modeling of from a start potential and when it reaches a required value,
electrochemical sensor for determining ion concentration in then it is swept back to the original potential value [1].
the solution considered. The proposed system consists of The redox potentials-oxidation and reduction potentials of
three planar electrodes namely working electrode, counter analyte species considered are located from the Cyclic
electrode and reference electrode on Polyester substrate. The
voltammetry graphs. By increasing the value of the
sensor is designed to ensure maximum peak current for
applied voltage on different geometries of working electrode. scanrate, its effect can be seen on the anodic and cathodic
This paper presents simulation results of cyclic voltammetry peaks of the voltammogram.
plots and concentration profiles of designed planar The process of fabricating and testing multiple
electrodes using COMSOL Multiphysics, a commercial iterations of these devices is time-consuming and
Finite Element Analysis Package. The total current is plotted expensive. Finite element analysis software packages,
at the working electrode by sweeping the scan rate of such as COMSOL, Coventor Ware, and ANSYS, have
voltammogram for different geometries of the electrode. The been used to optimize the design of electrodes of
simulation is carried out using Electro-analysis physics in electrochemical sensorprior to fabrication. In this work,
COMSOL.
results of COMSOL simulations of working electrode
Keywords—Electrochemical sensor,ion concentration, using five different designs of electrolytic cell are done.
cyclic voltammetry. The purpose of this is to detect the geometry that produces
better peak current for determining the concentration of
I. INTRODUCTION ion.
Electrochemical sensors are becoming vital and an
integral part in our day today life. Many of the II. DESIGN CONSIDERATION
applications are biochemical and biomedical. The most The transport of species to and from bulk solution
well-known, and the most impactful, electrochemical occurs by diffusion, convection, and migration. Diffusion
sensor is the self-monitoring blood glucose meter used to occurs due to a concentration gradient, migration is due to
assist in controlling diabetes. The other applications of electric field effects and convection is because of
electrochemical sensors include gas sensors, such as those externally applied forces. In this proposed work, the
used in homes to detect CO, heavy metal sensors for diffusion-controlled movement is only considered. The
water quality analysis, alcohol sensors and also for observed current depends on the kinetics and transport by
measuring motor oil degradation. The electrochemical diffusion of the electro active species that are given by
sensors have also been applied in areas such as Fick‘s laws.
Biological/Chemical Warfare, Food Monitoring, Medical Fick‘s first law of diffusion gives the relation of
Diagnostics, Manufacturing Automotive, Environmental diffusion fluxto the concentration gradient considering
Monitoring. steady state conditions [2]. The solutes move from a
The analytical techniques are used to measure the region of high concentration to a region of low
potential, charge or current which is directly proportional concentration across a concentration gradient. This is
to the ion concentration. The sensing mechanisms are given by
𝜕𝐶
based on various electrochemical detection methods, such J = -D ---------- (1)
𝜕𝑥
as amperometry, voltammetry, coulometry. In
J- Diffusion flux, D- Diffusion coefficient, 𝑥-position,
voltammetry, a varying potential is applied to a working
𝑐-concentration.
electrode and corresponding current is measured resulting
Fick‘s second law of diffusion gives the concentration
from the reaction of analyzed species at the working
change with time as proportional to the second derivative
electrode. In Amperometry, a fixed potential is applied to
of concentration. This is given by
the working electrode and therebycurrent is measured due 𝜕𝐶 𝜕2𝐶
to oxidation or reduction reactions. =D 2 ---------- (2)
𝜕𝑡 𝜕𝑥
The cyclic voltammetry is used to study the behavior Considering the reversible reaction
of analyte or ion under consideration.In this cyclic 𝑂 + 𝑛𝑒 − ⇋ 𝑅
voltammetry experiment the potential is varied between The solution resistance is assumed to be zero. Initially
the reference electrode and working electrode which the solution contains only species O, with the electrode
increases in a linear manner with time(scan rate(V/s)). held at a potential 𝐸𝑖,where no electrode reaction occurs.
The current is measured between the working and Now, the cyclic voltammetry is carried out with the
counter electrode resulting that is plotted as current (i) vs. following boundary conditions.
potential (V).In cyclic voltammetry the voltage is swept

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 At time t=0, there is no concentration gradienti.e.,
the concentration near the electrode called Surface
Concentration is equal to the concentration of the
bulk solution 𝐶𝑜 ∗ . Bulk concentration is where the
solution molecules are influenced only by other
solution molecules [2].
𝐴𝑡 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑥 = 0 𝐶𝑂 = 𝐶𝑜 ∗ 𝐶𝑅 = 0
𝐴𝑡 𝑏𝑢𝑘 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑥 = ∞ 𝐶𝑂 = 𝐶𝑜 ∗ 𝐶𝑅 = 0
 At time t>0, n mole of reactantis oxidized, and nmole
of product is reduced. This is given by mass Fig. 1 Three electrode arrangement of electrolytic cell [2]
conservation properties. Therefore, the net flux must
be Zero.
𝜕𝐶 (𝑥,𝑡) 𝜕𝐶 (𝑥,𝑡)
𝐷𝑂 [ 𝑂 ] + 𝐷𝑅 [ 𝑅 ] = 0 --------- (3)
𝜕𝑥 𝜕𝑥
where 𝐷𝑂 and 𝐷𝑅 are the diffusion coefficients of
oxidizing and reducing species.
 In Cyclic Voltammetry, the potential is reversed after a
time𝜆. An applied potential looks like an isosceles
Fig. 2 Circular and square shaped geometry of WE
triangle.
0<𝑡 ≤ 𝜆 𝐸 = 𝐸𝑖 – 𝑣𝑡
B. Geometries of working electrode
𝑡>𝜆 𝐸 = 𝐸𝑖 − 𝑣 𝜆 + 𝑣(𝑡 − 𝜆)
Therefore, the product of Reduction reaction
occurred in forward scan can be probed again during
the oxidation reaction in the reverse scan.
 Rewriting eq. (3) in Nernstian form we get the final
boundary condition
𝐶𝑂 0,𝑡 𝑛𝐹
= 𝑒𝑥𝑝 [(𝐸 − 𝐸 0 )] ---------- (4)
𝐶𝑅 0,𝑡 𝑅𝑇
Fig. 3 Circular toothed and circular slotted geometry of WE
 Considering all these conditions the Peak current
equation is given by
3 1 1
𝐼𝑷 = −2.69 ∗ 105 𝑛 2 𝐴𝐶𝐷 2 𝑣 2 ---------- (5)
n - number of electrons transferred/molecule,
𝐷- diffusion coefficient, 𝐴 - electrode surface area,
𝐶 - concentration, 𝑣-scan rate

TABLE I LIST OF PARAMETERS USED

Parameter Unit Description Fig. 4 14WSeD
Circular sharp edged and star geometry of WE
V 10-3 to 10-2[V/s] Voltammetric scan rate
c_bulk 1[mmol/L] Reactant bulk concentration
DA 1e-9[m2/s] Reactant diffusion coefficient
DB 1e-9[m2/s] Product diffusion coefficient
Cdl 0.2[F/m2] Double layer capacitance
T 298.15[K] Temperature
E_vertex1 -0.4[V] Start potential
E_vertex2 0.4[V] Switching potential
Fig. 5 Circular zigzag and Fibonacci geometry of WE
The Electrochemistry module of COMSOL 5.3,
Multiphysics simulation tool is used for modelling and TABLE II VARIATION OF GEOMETRICAL SHAPE OF WORKING
simulation of working electrodes of electrochemical ELECTRODE
sensor. Here the proposed design is a planar electrode of Shape Area(mm2)
Circle 5.855
different geometry. And so, the gradients are present on Rectangle 5.855
and near the electrode vicinity. Therefore, the design Circular toothed 5.855
simulation is carried out in two dimensions. The Circular slotted 5.855
parameters used for the simulation is shown in Table I. Circular sharp edged 5.858
Star 5.853
Fibonacci 5.559
III. ELECTRODE CONFIGURATIONS
Zig Zag 5.846
A. Electrolytic cell
The sensing structure in figure 1 consists of typical
The Table II lists the various shapes of working
electrochemical sensor that consists of a working
electrode design considered for simulation. The various
electrode-WEon which the electrochemical reaction takes
geometry of working electrode is also shown in figures
place, a reference electrode that provides standard
2,3,4,5.
potential and counter electrode that passes all the current
needed to balance the current observed at the working
electrode [2].

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IV. SIMULATION RESULTS AND DISCUSSION OF WORKING
ELECTRODE DESIGNS
a) Concentration profiles of different geometries
From equation (5), it is seen that the peak current not only
depends on the concentration but also on electrode surface
area and scan rate. The influence of different electrode
geometry on the output current is mainly focused and
analyzed by keeping the above parameters such as
concentration, electrode surface area, and scan rate to be
constant. After many trials, the scan rate is chosen in the
range of 0.01 to 0.001 V/s. These lower scan rates
produced currents even in milliamperes. It is also found
that higher scan rates resulted in adsorption of species that
produced a modified cyclic voltammogram graph.

Fig. 8 SP of circular sharp edged(top), star (bottom) shaped

geometry of WE

Fig. 6 SP of circular(top), square(bottom) shaped geometry of WE

Fig. 9 SP of circular zigzag(top), fibonocci (bottom) shaped geometry of

WE

The above figures 6,7,8,9 shows the surface plot(SP)

of concentration profiles of the various geometries
considered. It is known that electrochemical reaction
occurs on the electrode surface and so the concentration
decreases as it moves to the bulk solution boundary. And
this can be evidently seen on the concentration profiles of
various geometry of working electrode shown above. So,
it‘s found that to try simulation of different geometries
with edges, corners, narrow edges with same area.
b) CV graphs of different geometries
Figures 11, 12, 13, 14 shows the two-dimensional
graphical plot of cyclic voltammetry for the different
geometries considered. The cyclic voltammetry graphs
Fig. 7 SP of circular toothed(top), circular slotted (bottom) shaped can be used to know the behavior of cathodic and anodic
geometry of WE reactions. From these graphs the peak voltage occurs on

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the same line for varying scan rate. Figure 10 gives the
different scan rate for each cyclic voltammetry plots

Fig. 10 Legends for the cyclic voltammetry graphs plotted

Fig. 13 Graphical plot of circular sharp edged(top), and star (bottom)

geometry of WE

Fig. 11 Graphical plot of circle (top) and rectangle (bottom) geometry of

WE

Fig.14 Graphical plot of Zigzag (top) and Fibonacci (bottom) geometry

of WE

TABLE III PEAK CURRENT VALUE FOR VAR\YING

GEOMETRY
Name of the Area Perimeter i Peak
Rank
Geometry (mm2) (mm) (mA)
Fibonacci 5.559 58.9 93 1
ZigZag 5.846 46.1 75 2
Star 5.853 23.49 37 3
Circular sharp edged 5.858 22.36 35.4 4
Fig. 12 Graphical plot of circular slotted (top) and circular toothed Circular toothed 5.855 16.35 29.3 5
(bottom) geometry of WE Circular slotted 5.855 13.51 26 6
Rectangle 5.855 9.684 16.4 7
Circle 5.855 8.58 14.7 8

The Fibonacci geometry of WE delivers the highest

peak current. From concentration profile figures 6,7,8,9,it
is observed that the reaction is higher atthe electrode

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boundary than in the surface. This is because the bulk shown that geometry with higher perimeter produced
solution reaches the boundary first and hence higher better current than other geometries with lesser perimeter
boundary (i.e., perimeter) gives more reaction and hence value. Therefore, perimeter of electrode geometry has
higher current. So, the perimeter of different geometries is significance on the peak current of electroanalytical cell.
also calculated and tabulated in TABLE III. From the Thus, geometry is optimized by keeping the area nearly a
Table, it is seen that for same area the geometry with constant and the scan rate to be varying. The peak current
higher perimeter gives the better peak current i.e., peak value is maximum for Fibonacci geometry and the value
current output is directly influenced by perimeter of is found to be 93mA. This geometry can be used to
working electrode. fabricate the proposed Electrochemical sensor and can be
studied further for determining the ion concentration.

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