The Evaluation of Potentiostats: Electrochemical

Detection Devices
N. A. Abdul-Kadir1, S. Noi1 and F. K. Che Harun1,2
1
Faculty of Biosciences and Medical Engineering, Universiti Teknologi Malaysia,
81310 UTM Johor Bahru, Johor Bahru, Malaysia.
2
Faculty of Electrical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor Bahru, Malaysia.
[email protected]

Abstract—This study evaluated the performance of three chloride [25], glucose [26], hydrogen peroxide [27,28], e
types of potentiostats; EmStat, CheapStat and UTMStat. coli [15], bovine serum albumin [29], pH [30], potassium
EmStat is the smallest potentiostat available in the market. [30] and blood pressure [31].
CheapStat is an open-source potentiostat suitable for It is crucial to monitor the chemicals and biomarkers to
educational applications. In addition, UTMStat is the extension predict patients’ critical condition especially during surgical
of CheapStat, which was designed to overcome few weaknesses
of CheapStat such as the input controller/ switch and data
procedures and in intensive care units. Monitoring
storage handling of the cyclic voltammogram. The cyclic biomarkers could provide information of any abnormalities
voltammetry and amperometry measurements of ions which have occur in the metabolic pathways of patient.
ferrocyanide ([Fe(CN)6]4−) and chloride (Cl-) were carried out Hence, further understanding or earlier diagnosis could aid
for each potentiostat. EmStat potentiostat is not only able to clinician or physician.
detect but also to measure ferrocyanide and chloride ions. Therefore, this study is to compare the existing
However, CheapStat and UTMStat are only able to detect and instruments for electrochemical detection. The purpose is to
measure ferrocyanide ions. The experiment is unable to be use the selected electrochemical detection device to be
conducted due to limitation of waveform selection on both integrated with a biomedical device for designing a
devices. Nevertheless, CheapStat and UTMStat could provide a
continuous monitoring lab-on-chip (LOC) device later. LOC
reliable measurement to realize miniaturized lab-on-chip
applications as shown in this study. device is an integration of at least one laboratory function on
a single integrated circuit, such as a micropump and the
Index Terms—Amperometry; Chloride and Ferrocyanide reaction zone.
Ions; Cyclic Voltammogram; Potentiostat.
II. ELECTROCHEMICAL THEORY
I. INTRODUCTION
To introduce electrochemistry, the reversible
Potentiometric system has always been related to ferricyanide-ferrocyanide couple is commonly used in
electrochemical detection method [1]. The combination of educational tool [10]. The ferricyanide/ferrocyanide couple
electrochemical cell and a potentiostat circuit forms a is used as a standard to demonstrate cyclic voltammetry
potentiostatic system [2]. Potentiostat is a feedback control (CV). The ferricyanide/ferrocyanide couple requires no any
system [3] which adjusts the voltage across the WE - CE complications of proceeding or post chemical reactions but
pair to maintain the preset potential between the WE and RE able to illustrate nearly a reversible electrode reaction, as
of an electrochemical cell [4]. Multitude of research activity evidence by [4, 32-34].
has been focused on various potentiostat designs such as From Figure 1, as the potential is in forward scan and is
standard potentiostat [5-8], virtual potentiostat [9], CMOS sufficiently positive to oxidize ferrocyanide ions to
potentiostat [10-12] and BiCMOS potentiostat [13]. ferricyanide ions, the oxidation current is due to the
LabVIEW, a program development environment which electrode process given by Equation (1). The role of the
uses graphical programming language (language G) to electrode is an oxidant (electron acceptor) and the oxidation
program in block diagram form [14] which is developed by current increases to a peak is observed. The concentration of
National Instruments (NI) and could be used to develop a ferrocyanide ions at the electrode surface depletes and the
virtual potentiostat [9]. LabVIEW has been utilized in current then decreases.
monitoring system [15-19], converter life prediction system
[14], conversion technique simulator [20], data acquisition [Fe(CN)6] 4− → [Fe(CN)6] 3− + e− (1)
system [21, 22] and fully automated electromechanical
system [23] due to user friendly and rich of graphical As the potential is in reverse scan, the potential is still
interface. sufficiently positive to oxidize ferrocyanide ions to
The electrochemical detection method is utilized into the ferricyanide ions, therefore oxidation current continues.
continuous monitoring system due to its specificity, When the role of the electrode is a strong reductant,
inexpensive, user friendly and portability [24]. A lot of ferricyanide ions which has been formed will be reduced to
inventions of continuous monitoring to determine a patient’s ferrocyanide ions, the reduction current is due to the
internal condition of physiological systems, such as nervous electrode process given by Equation (2). The reduction
system, breathing system and blood circulation have been current increases to a peak and then decays as ferricyanide
developed. The system is for continuous monitoring of ions are consumed.

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III. POTENTIOSTAT DEVICES

[Fe(CN )6] 4− ← [Fe(CN )6] 3− + e− (2)
CV and amperometry techniques have always been related
In clinical diagnosis, monitoring of chloride ions is to potentiometric system. In this study, there are three types
essential because it is a major mineral nutrient in body fluids of potentiostats used: EmStat, CheapStat and UTMStat
and a prominent negatively charged ion of the blood [36], (modified CheapStat).
therefore when deficiency of chloride occurs, the blood
becomes overly alkaline or known as alkalosis which will A. Potentiostat - EmStat
results in a life-threatening condition. EmStat (Figure 3) - the smallest potentiostat [38]
developed by PalmSens which is controlled and powered by
USB and used with the PSTrace software (Figure 4).

Figure 1: CV for ferricyanide/ferrocyanide couple detection [35]

Figure 3: EmStat by PalmSens [38]

Figure 2 illustrates CV for chloride ions. As seen in the

green line, without the presence of chloride ions, only peak
B is observed. Peak B correlates to the one electron
oxidation of silver given by Equation (3).

Ag → Ag + e (3)

In the presence of chloride ions, two broad peaks (peaks A

and B) are observed. The reaction occurs at peak A given
by Equation (4). This is proven by observing the peak height
of peak A linearly proportional with the concentration of
chloride ions. Besides, when the height of peak A increases,
the height of peak B decreases. This is due to the reaction at
peak A has consumed some of the silver. Therefore, less
charge to be passed under peak B.

Ag + Cl− → AgCl + e− (4)

Figure 4: GUI of EmStat

B. Potentiostat – CheapStat
CheapStat (Figure 5) - an open-source potentiostat which
is developed by [10]. Same as EmStat, it is controlled and
powered by USB. The GUI (Figure 6) is a Java program
which receives results from the CheapStat device via USB.
CheapStat is a surface-mount device (SMD) which
employed surface-mount technology (SMT). The
development of CheapStat started by purchasing the
Figure 2: CV for chloride ions detection [37] electronic components from Element14, formerly Farnell,
and Mouser Electronics while the printed circuit board
(PCB) was printed by the PCB manufacturer based on the
Ferrocyanide ions detection does not require any
given parts list and schematic diagram in [10]. Then, the
complications of proceeding or post chemical reactions. It
electronic components were mounted onto the surface of
can be detected by using any screen printed electrode (SPE).
PCB and the fabricated device as in Figure 5.
As for chloride ions detection, the SPE used must have
silver WE [25, 37].

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 The Evaluation of Potentiostats: Electrochemical Detection Devices

Table 1
Output from CheapStat (Waveform Parameters)

Source code Output string

USART_PutChar(&USARTC0, CV); \01
USART_PutChar(&USARTC0, name[j]); CV\s#1\s\s\s\s\s
\s\s\s\s\s
USART_PutChar(&USARTC0, slope>>8); \13
USART_PutChar(&USARTC0, slope); \88
USART_PutChar(&USARTC0, start>>8); \FF
USART_PutChar(&USARTC0, start); \9C
USART_PutChar(&USARTC0, stop>>8); \00
USART_PutChar(&USARTC0, stop); d
Figure 5: The CheapStat, an inexpensive, “do-it-yourself” potentiostat [10] USART_PutChar(&USARTC0, scans>>8); \00
USART_PutChar(&USARTC0, scans); \01
USART_PutChar(&USARTC0, sample_rate>>8); \00
USART_PutChar(&USARTC0, sample_rate); \01
USART_PutChar(&USARTC0, curr_range); \01

Table 2
Output from CheapStat (Data Points)

Source code Output string

USART_PutChar(&USARTC0, i>>8); \01
USART_PutChar(&USARTC0, i); \EF
USART_PutChar(&USARTC0, current[j]>>8); 495 data points
USART_PutChar(&USARTC0, current[j]);
USART_PutChar(&USARTC0,CV); \01

Figure 6: GUI of CheapStat

C. Potentiostat - UTMStat
UTMStat - a LabVIEW based modified CheapStat was
developed due to few weaknesses of CheapStat such as the
waveform parameters have to be input by controlling the 4-
way switch and the cyclic voltammogram and the data
points for cyclic voltammogram have to be manually saved
onto the computer. Firstly, the input to CheapStat and the
output from CheapStat were studied.
In CheapStat source code (CheapStat_v2.c), the waveform
parameters are stored in a structure named profile. For
example, if selected waveform is CV with 5000 mV/s,
potential range from -100 mV to 100 mV, one time scan, Figure 7: Input from user
1 mV/sample and 0 – 10 µA current range are input by
controlling the 4-way switch.
In order to observe the output from CheapStat, it was In UTMStat, the ISR function in CheapStat_v2.c was
connected to PC via USB. LabVIEW example program modified to read the waveform parameters from LabVIEW.
(Basic Serial Write and Read.vi) was used to read the output Once all the data had been read, the data was processed in
from CheapStat. For example, if selected waveform is CV the main function in CheapStat_v2.c. After all waveform
with 5000 mV/s, potential range from -100 mV to 100 mV, parameters were stored, CV_test function was invoked.
one time scan, 1 mV/sample and 0 - 10 µA current range are UTMStat sent the output to LabVIEW program. Firstly,
input by controlling the 4-way switch; the output string is 27 bytes of data (Table 1) was discarded. The next data
shown in Table 1 and Table 2. The output is in word size obtained was the data point size and followed by current
data (16-bit), therefore MSB and LSB stand for most data points which needed in drawing the cyclic
significant bit and least significant bit respectively. voltammogram. Since the data was in word size data, the
In Table 1, part of the output is just the waveform total current data points which needed to be read was
parameters. The most important part is listed in Table 2. The multiplication of data point size by 2. Both files were saved
output string "\01\EF" shows that there are 495 data points automatically on the computer at the selected paths (Figure
which are needed in drawing the cyclic voltammogram. 7).
Integration with LabVIEW started by reading the waveform Therefore, by enhancing CheapStat, the waveform
parameters from the user through Figure 7. parameters can be input easily through the LabVIEW. The
cyclic voltammogram and the data point can be saved into
BMP (Figure 8) and CSV files automatically. Comparisons
among the three potentiostats: EmStat, CheapStat and
UTMStat are shown in Table 3.

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Table 4
Oxidation peak current at potential 0.25 V of various concentration of
potassium ferrocyanide in 1 M potassium nitrate using EmStat [24]

Concentration (mM) Current (µA)

10 15.22945
8 13.61254
6 9.72236
4 6.20588
2 3.10379

For amperometry measurement of various concentrations

range 2-10 mM, in 2 mM increments of potassium
ferrocyanide in 1 M potassium nitrate had been carried out
using EmStat and the result is shown in Figure 10. The
constant applied voltage of 0.25 V was chosen based on the
result in Figure 9 and the duration is 60 seconds. According
Figure 8: BMP file
to Levich theory, the current is directly proportional to the
concentration of the species; therefore 10 mM potassium
Table 3 ferrocyanide obtained the highest average current at
Comparisons of Potentiostats 3.46672 µA, as shown in Figure 10 and Table 5.

Specifications EmStat CheapStat UTMStat

Number of potential
15 6 6
waveforms
~100 nA to ~50 ~100 nA
Current range 1 nA to 10 mA
µA to ~50 µA
Potential range ± 3.000 V ± 1.600 V ± 1.600 V
Price ~RM 8800 ~RM 230 ~RM 230

IV. EVALUATION OF POTENTIOSTAT

The CV and amperometry measurements of ions

ferrocyanide ([Fe(CN)6]4-) and chloride (Cl-) were carried
out. The results from the EmStat, CheapStat and UTMStat
are as follow.

1. EmStat - Ferrocyanide & Chloride Ions Detections

Figure 10: Amperometry-based monitoring of potassium ferrocyanide in
A. Ferrocyanide Ions Detection 1 M potassium nitrate using EmStat.
The CV measurement of various concentrations range 2-
10 mM, in 2 mM increments of potassium ferrocyanide in 1
M potassium nitrate at a scan rate of 0.1 V/s had been
Table 5
carried out using EmStat and the result is shown in Figure 9. Average oxidation peak current at potential 0.25 V using EmStat
According to Levich theory, the peak current is directly
proportional to the concentration of the species; therefore 10 Concentration (mM) Average Current (µA)
mM potassium ferrocyanide achieved the highest oxidation 10 3.46672
8 2.78650
peak of 15.22945 µA at potential 0.25 V, as shown in Figure 6 2.20068
9 and Table 4. 4 1.04415
2 0.54273
0 0.03699

The CV measurement was extended by various

concentrations range 2-10 mM, in 2 mM increments of
potassium ferrocyanide in 0.1 M potassium nitrate at a scan
rate of 0.1 V/s had been carried out using EmStat and the
result is shown in Figure 11. According to Levich theory,
the peak current is directly proportional to the concentration
of the species; therefore 10 mM potassium ferrocyanide
achieved the highest oxidation peak of 10.18181 µA at
potential 0.32 V, as shown in Figure 11 and Table 6.

Figure 9: Background-subtracted cyclic voltammetry-based monitoring of

potassium ferrocyanide in 1 M potassium nitrate using EmStat [24]

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 The Evaluation of Potentiostats: Electrochemical Detection Devices

B. Chloride Ions Detection

The CV measurement of various concentrations range 10-
50 mM, in 10 mM increments of potassium chloride in 0.1
M potassium nitrate at a scan rate of 0.05 V/s had been
carried out using EmStat and the result is shown in Figure
13. To have a clear view of Figure 13, another cyclic
voltammogram of Figure 13 was recorded from +0.00 V to
+0.20 V (Figure 14). According to Levich theory, the peak
current is directly proportional to the concentration of the
species; therefore 50 mM potassium chloride achieved the
highest oxidation peak of 114.10837 µA at potential 0.13 V,
as shown in Figure 13, Figure 14 and Table 8.
Figure 11: Background-subtracted cyclic voltammetry-based monitoring of The formal potential of the redox couple of Ag/AgCl (4)
potassium ferrocyanide in 0.1 M potassium nitrate using EmStat was +0.32 V vs. NHE and the redox potential of chloride
ions was measured at -0.25 V [37]. In this study experiment,
the redox potential of chloride ions was achieved at +0.13
Table 6
V. The difference is due to the type of reference electrode
Oxidation peak current at potential 0.32 V of various concentration of
potassium ferrocyanide in 0.1 M potassium nitrate using EmStat used. [37] used Ag/Ag (10 mM) and NaNO3 (90 mM)
reference electrode while Ag/AgCl was used as the
Concentration (mM) Current (µA) reference electrode in this experiment. The potential of the
10 10.18181 redox pair of Ag/Ag+ (3) was +0.69 V vs. NHE but the
8 8.21473 potential of the redox pair of Ag/AgCl was +0.197 V vs.
6 6.39368
4 4.46598 NHE.
2 2.20702

The amperometry measurement was furthered by various

concentrations range 2-10 mM, in 2 mM increments of
potassium ferrocyanide in 0.1 M potassium nitrate had been
carried out using EmStat and the result is shown in Figure
12. The constant applied voltage of 0.32 V was chosen
based on the result in Figure 11 and the duration is 60
seconds. According to Levich theory, the current is directly
proportional to the concentration of the species; therefore 10
mM potassium ferrocyanide obtained the highest average
current at 2.98336 µA, as shown in Figure 12 and Table 7.

Figure 13: Cyclic voltammetry-based monitoring of potassium chloride in

0.1 M potassium nitrate using EmStat

Figure 12: Amperometry-based monitoring of potassium ferrocyanide in

0.1 M potassium nitrate using EmStat

Table 7
Average oxidation peak current at potential 0.32 V using EmStat

Concentration (mM) Current (µA)

10 2.98336
8 2.23123 Figure 14: Cyclic voltammetry-based monitoring of potassium chloride in
6 1.68447 0.1 M potassium nitrate using EmStat from +0.00 V to +0.20 V
4 1.15318
2 0.51247
0 0.01128

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Table 8 3. UTMStat - Ferrocyanide Ions Detection

Oxidation peak current at potential 0.13 V of various concentration of The CV measurement of various concentrations range 2-
potassium chloride in 0.1 M potassium nitrate using EmStat
10 mM, in 2 mM increments of potassium ferrocyanide at a
Concentration (mM) Current (µA) scan rate of 0.1 V/s was tested using UTMStat and the result
10 114.10837 is illustrated in Figure 16. According to Levich theory, the
8 88.16505 peak current is directly proportional to the concentration of
6 65.05255 the species; therefore the highest peak current at potential
4 39.54370
2 17.45438 0.25 V was obtained by 10 mM potassium ferrocyanide at
0 1.67044 0.43233 µA as shown in Figure 16 and Table 10.
In this study, the amperometry measurement of various
Theoretically, the electrode potentials were converted to concentrations range 2-10 mM, in 2 mM increments of
the NHE scale using Equation (5) [39]. By using (5) and the potassium ferrocyanide in 1 M potassium nitrate using
formal potential of the redox couple of Ag/AgCl (4) was UTMStat was not performed because the waveform selection is
+0.32 V vs. NHE [37], the formal redox potential of chloride not available in original CheapStat.
ions should have a theoretical potential at +0.123 V; which
was close to the experimentally measured at +0.13 V.

E(NHE) = E(Ag/AgCl) + 0.197 V (5)

2. CheapStat - Ferrocyanide Ions Detection

The CV measurement of various concentrations range 2-
10 mM, in 2 mM increments of potassium ferrocyanide at a
scan rate of 0.1 V/s was tested using Cheapstat and the
result is illustrated in Figure 15. According to Levich theory,
the peak current is directly proportional to the concentration
of the species; therefore the highest peak current at potential
0.25 V was achieved by 10 mM potassium ferrocyanide at
0.41033 µA as shown in Figure 15 and Table 9.

Figure 16: Background-subtracted cyclic voltammetry-based monitoring of

potassium ferrocyanide in 1 M potassium nitrate using UTMStat

Table 10
Oxidation peak current at potential 0.25 V using UTMStat

Concentration (mM) Current (µA)

10 0.43233
8 0.33133
6 0.22767
4 0.19467
2 0.09167

V. DISCUSSIONS
Figure 15: Amperometry-based monitoring of potassium ferrocyanide in
0.1 M potassium nitrate using EmStat The electrochemical detection of ferrocyanide ions is
compared among three potentiostats: EmStat from
PalmSens, CheapStat [10] and in house UTMStat.
Table 9 UTMStat is actually an extention of existing CheapStat
Oxidation peak current at potential 0.25 V using CheapStat integrated with LabVIEW program to overcome few
drawbacks of CheapStat such as the waveform parameters
Concentration (mM) Current (µA) have to be input by controlling the 4-way switch and the
10 0.41033 cyclic voltammogram and the potential- current pair data
8 0.32733 points have to be manually saved onto the computer.
6 0.27500 Therefore, by enhancing CheapStat, the waveform
4 0.16467
2 0.09033
parameters can be input easily through the LabVIEW.
Additionally, the CV and the potential-current pair data
points can be saved into BMP CSV files automatically at the
The amperometry measurement of various concentrations
desired folder path.
range 2-10 mM, in 2 mM increments of potassium
The CV measurement of various concentrations range 2-
ferrocyanide in 1 M potassium nitrate using CheapStat was
10 mM, in 2 mM increments of potassium ferrocyanide in 1
not carried out due the waveform selection was not available
M potassium nitrate at a scan rate of 0.1 V/s has been
in CheapStat.
carried out using EmStat. 10 mM potassium ferrocyanide
achieves the highest oxidation peak of 15.22945 µA at

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 The Evaluation of Potentiostats: Electrochemical Detection Devices

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