1 s2.0 S0360319904004434 Main PDF

International Journal of Hydrogen Energy 30 (2005) 1423 1436
www.elsevier.com/locate/ijhydene
The phase-shift method for determining Langmuir and Temkin

adsorption isotherms of over-potentially deposited hydrogen for the
cathodic H2 evolution reaction at the poly-Pt/H2 SO4 aqueous
electrolyte interface
Jang H. Chuna, , Sang K. Jeona , Nam Y. Kima , Jin Y. Chunb
a Department of Electronic Engineering, Kwangwoon University, Seoul 139-701, South Korea
b School of Chemical Engineering, Seoul National University, Seoul 151-744, South Korea
Received 15 July 2004

Available online 22 January 2005
Abstract
A linear relationship between the behavior ( vs. E) of the phase shift (0 90 ) for the optimum intermediate
frequency and that ( vs. E) of the fractional surface coverage (1 0) of over-potentially deposited hydrogen (OPD H) for
the cathodic H2 evolution reaction (HER), i.e., the phase-shift method, at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface
has been veried using cyclic voltammetric, differential pulse voltammetric, and ac impedance techniques. The phase-shift
method for determining the suitable adsorption isotherm (Langmuir, Frumkin, Temkin) of OPD H for the cathodic HER at the
interface also has been proposed. At the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, the Langmuir adsorption isotherm
( vs. E) of OPD H, the equilibrium constant (K =1.3104 ) for OPD H and the standard free energy (G0ads =22.2 kJ/mol)
of OPD H are determined using the phase-shift method. At the same interface, the Temkin adsorption isotherm ( vs. E) of
OPD H, the equilibrium constant (1.3 103 K 1.3 105 with , i.e., 0 1) for OPD H, and the standard free
energy (16.5 G0 27.9 kJ/mol with , i.e., 0 1) of OPD H are also determined using the phase-shift method. At the
intermediate values of , i.e., 0.2 < < 0.8, the Langmuir and Temkin adsorption isotherms of OPD H for the cathodic HER
at the interface are converted to each other. The equilibrium constant (K0 ) for the Temkin adsorption isotherm ( vs. E) is
ca. 10 times greater than that (K) for the corresponding Langmuir adsorption isotherm ( vs. E). The interaction parameter
(g) for the Temkin adsorption isotherm ( vs. E) is ca. 4.6 greater than that (g) for the corresponding Langmuir adsorption
isotherm ( vs. E). These numbers (10 times and 4.6) can be taken as constant conversion factors between the corresponding
adsorption isotherms (Temkin, Langmuir, Frumkin). The Temkin adsorption isotherm corresponding to the Langmuir or the
Frumkin adsorption isotherm, and vice versa, can be effectively converted using the constant conversion factors. Both the
phase-shift method and constant conversion factors can be effectively used as a new electrochemical method to determine the
suitable adsorption isotherms (Langmuir, Frumkin, Temkin) of H for the cathodic HER in electrochemical systems.
2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Phase-shift method; Langmuir, Frumkin, and Temkin adsorption isotherms; Constant conversion factors; Hydrogen adsorption;
Pt electrode
1. Introduction
Corresponding author. Tel.: +82 2 940 5116;
fax: +82 2 942 0107.

E-mail address: jhchun@daisy.kwangwoon.ac.kr (J.H. Chun).
For clean environment and energy, the cathodic H2 evolution reaction (HER) at noble and transition-metal/aqueous
0360-3199/$30.00 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2004.12.005
1424
J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436
electrolyte interfaces has been extensively studied in electrochemistry and electrochemical hydrogen technologies.
Many experimental methods have been used to study the adsorption sites and processes of under-potentially deposited
hydrogen (UPD H) and over-potentially deposited hydrogen
(OPD H) for the cathodic HER at these interfaces [120].
It is well known that UPD H and OPD H occupy different
surface adsorption sites and act as two distinguishable electroadsorbed H species, while only OPD H can contribute to
the cathodic HER [4,68,1420]. However, the kinetics and
mechanism of the cathodic HER have been studied mainly
using steady-state polarization experiments. Thus, there is
not much reliable kinetic and thermodynamic data, i.e., the
equilibrium constant and standard free energy relating to
the adsorption sites and process of the OPD H, at these
interfaces.
At interfaces, it is preferable to consider the adsorption
isotherm (Langmuir, Frumkin, Temkin) for H (UPD H,
OPD H) rather than an equation of the electrode kinetics
and thermodynamics for H (UPD H, OPD H), because
the adsorption isotherm (Langmuir, Frumkin, Temkin) can
be associated more directly with the atomic mechanism
of H (UPD H, OPD H) adsorption. A link between the
microscopic system of adsorption sites and processes on
atoms and the macroscopic system of electrode kinetics and
thermodynamics at interfaces has been extensively studied
in chemistry, physical electrochemistry, surface science,
etc. [21]. The adsorption isotherms (Langmuir, Frumkin,
Temkin) are effective for characterizing the relation, transition, and criterion between UPD H and OPD H for the
cathodic HER at interfaces. Thus, there is a technological
need for a fast, simple, and reliable technique to determine the suitable adsorption isotherm (Langmuir, Frumkin,
Temkin) of H (UPD H, OPD H) for the cathodic HER
at interfaces.
For the cathodic HER in electrochemical systems, the
currentpotential relationship is determined completely by
the electrode potential (E) dependence of the fractional surface coverage () of H. Thus, one can interpret that the
electrode kinetic parameters for H will depend on the corresponding adsorption isotherm ( vs. E) of H, which relates
the surface concentration of H to the bulk concentration of
H and to the electrode potential (E). At limited values of ,
i.e., 0 and 1, the distinction between the adsorption isotherms (Langmuir, Frumkin, Temkin) of H is almost
impossible. At low and high values of , e.g., < 0.2 and
0.8 < , the distinction between the adsorption isotherms
(Langmuir, Frumkin, Temkin) of H is difcult. At intermediate values of , e.g., 0.2 < < 0.8, the distinction between
the adsorption isotherms (Langmuir, Frumkin, Temkin) of
H is easy. It is related to the rate of change of vs. E, i.e.,
/E or d/dE, which is maximized at 0.5 and minimized at 0 and 1. However, a linear relationship between
the behavior ( vs. E) of the phase shift (0 90 )
for the optimum intermediate frequency and that ( vs. E)
of the fractional surface coverage (1 0) of intermedi-
ates at interfaces has not been suggested to provide the link

between the adsorption sites and processes of H (UPD H,
OPD H) and the adsorption isotherms (Langmuir, Frumkin,
Temkin) of H (UPD H, OPD H) for the cathodic HER at
interfaces.
Recently, we have experimentally found that the
phase-shift method1 can be effectively used to determine the Langmuir or the Frumkin adsorption isotherms
of UPD H and OPD H for the cathodic HER at noble and transition-metal (Pt, Ir, Pd, Au, Re, Rh, PtRh
alloy, Ni)/aqueous electrolyte interfaces [2234]. This
method is an effective way to study the H adsorption
sites and processes for the cathodic HER, the relation, transition, and criterion between UPD H and OPD
H, the electrode kinetics and thermodynamics at these
interfaces.
We consider the determination of the suitable adsorption isotherm (Langmuir, Frumkin, Temkin) of H (UPD
H, OPD H) for the cathodic HER at these interfaces
as follows. First, we determine the Langmuir adsorption isotherm and then nd the interaction parameter (g)
for the Frumkin adsorption isotherm based on the relevant experimental results, e.g., the fractional surface
coverage for the electrode potential, the phase-shift prole for the optimum intermediate frequency, etc. Finally,
the applicability of the Temkin adsorption isotherm at
these interfaces can be considered. It appears that the
phase-shift method is effective for determining the suitable adsorption isotherm (Langmuir, Frumkin, Temkin)
of H (UPD H, OPD H) for the cathodic HER at these
interfaces.
In this paper, we represent the phase-shift method
for determining the Langmuir and Temkin adsorption
isotherms of OPD H for the cathodic HER at a polycrystalline platinum (poly-Pt)/0.5 M H2 SO4 aqueous
electrolyte interface. This method is useful for estimating the electrode kinetic and thermodynamic parameters of OPD H for the cathodic HER at the interface.
This method is also useful to facilitate selection of the
optimal cathodic HER materials for yielding electrochemical systems of maximum performance. This paper is intended to supplement the previously published
papers [24,25].
1 A linear relationship between the behavior ( vs. E) of

the phase shift (0 90 ) for the optimum intermediate
frequency and that ( vs. E) of the fractional surface coverage (1 0) of H (UPD H, OPD H) at noble and transitionmetal/aqueous electrolyte interfaces has been veried using cyclic
voltammetric, linear sweep voltammetric or differential pulse
voltammetric, and electrochemical impedance spectroscopic techniques. The behavior ( vs. E) of the fractional surface coverage
(1 0) of intermediates is well known as the electrochemical
adsorption isotherm (Langmuir, Frumkin, Temkin).
2. Experimental
Taking into account the H+ concentration and effects

of the diffuse double layer and pH [35], an acidic aqueous electrolyte was prepared from H2 SO4 (Sigma Aldrich,
reagent grade) with puried water (resistivity: > 18 M cm)
obtained from a Millipore system. The 0.5 M H2 SO4 aqueous electrolyte was deaerated with 99.999% puried nitrogen gas for 20 min before the experiments.
A standard three-electrode conguration was employed
using a saturated calomel electrode (SCE) reference
electrode and a poly-Pt wire (Johnson Matthey, purity:
99.9985%, 1 mm diameter, estimated surface area: ca.
1.01 cm2 ) working electrode. It appears that Pt is suitable
for verifying the adsorption isotherm (Langmuir, Frumkin,
Temkin) of H (UPD H, OPD H) for the cathodic HER using
the phase-shift method. The poly-Pt working electrode was
prepared by ame cleaning and then quenched and cooled
in Millipore Milli-Q water and in air, sequentially. A Pt wire
(Johnson Matthey, purity: 99.95%, 1.5 mm diameter) was
used as counter electrode. Taking into account the OPD H
and its large current distribution, the working and counter
electrodes were separated by ca. 4 cm in the same compartment of a Pyrex cell using Teon holders [36]. At the steady
state, by comparing the 15th cyclic voltammogram with the
20th cyclic voltammogram shown in Fig. 1, one can interpret that the contamination from anodic produced species
for the cathodic HER is negligible. For ac impedance experiments, negative dc potentials are sequentially applied to
the interface. Note that this conguration is effective for the
cathodic HER rather than general electrochemical reactions.
2.2. Measurements
A cyclic voltammetric (CV) method was used to observe
the UPD H peak, which is useful for verifying the adsorption isotherm (Langmuir, Frumkin, Temkin) of UPD H or
OPD H at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The CV experiments were conducted at a scan rate
of 200 mV/s and a scan potential of 0.241 to 1.0 V vs. SCE
for the poly-Pt electrode. This high scan rate (> 100 mV/s)
was used to conrm the state of the poly-Pt working electrode at the commencement of the cyclic scan.
After the CV experiments, a differential pulse voltammetric (DPV) method was used to study the Tafel slopes at
the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The
DPV experiments were conducted at a scan rate of 1 mV/s,
pulse height of 25 mV, pulse width of 50 ms, step/drop time
of 2 s, reversible potential of ca. 0.694 V vs. SCE, and scan
potential of 0 to 0.65 V vs. SCE. This slow scan rate
(< 10 mV/s) was used to obtain the steady-state Tafel plots.
An ac impedance method was used to study the relation
between the phase-shift prole for the optimum intermediate frequency and the corresponding adsorption isotherm
0.4
Current Density (i ) / mA cm-2
2.1. Preparations
1425
0.2
0.0
-0.2
A
-0.4
0.0
0.4
0.8
Potential (E ) / V vs. RHE
15th scan
20th scan
1.2
Fig. 1. Typical cyclic voltammogram at the poly-Pt/0.5 M H2 SO4

aqueous electrolyte interface. Scan potential: 01.241 V vs. RHE.
Scan rate: 200 mV/s. Number of scans: 20. Region: (A) Hydrogen
adsorption process, i.e., hydrogen reduction reaction, (B) hydrogen
desorption process, i.e., hydrogen oxidation reaction, (C) oxygen
adsorption process, i.e., oxygen oxidation reaction, and (D) oxygen
desorption process, i.e., oxygen reduction reaction.
(Langmuir, Frumkin, Temkin) of H (UPD H, OPD H) at

the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The
ac impedance experiments were conducted at a single sine
wave, scan frequency of 104 5 Hz, ac amplitude of 5 mV,
and dc potential of 0 to 0.42 V vs. SCE for the poly-Pt
electrode.
The CV and DPV experiments were performed using an
EG&G PAR Model 273A potentiostat controlled with the
PAR Model 270 software package. The ac impedance experiments were performed using the same apparatus in conjunction with a Schlumberger SI 1255 HF Frequency Response
Analyzer controlled with the PAR Model 398 software package. To obtain comparable and reproducible results, all measurements were carried out using the same preparations,
procedures, and conditions at room temperature. The international sign convention is used, i.e., cathodic currents and
lagged phase shifts or angles are taken as negative. To clarify the hydrogen adsorption in the different aqueous electrolytes, all potentials are given in the reversible hydrogen
electrode (RHE) scale.
3. Results and discussion

3.1. UPD H peak
Fig. 1 shows a typical cyclic voltammogram of the steady
state at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The UPD H peaks, i.e., the hydrogen adsorption
peaks, due to the reduction of hydrogen occur at ca. 0.06
and 0.20 V vs. RHE. The hydrogen desorption peaks due to
the oxidation of hydrogen occur at ca. 0.08 and 0.22 V vs.
Overpotential () / V vs. RHE
1426
-0.85
-0.80
(b)
-0.75
(a)
-0.70
-0.5
0.0
0.5
1.0
Current Density (log i ) / mA
1.5
2.0
cm-2
Overpotential () / V vs. RHE
Fig. 2. Tafel plot at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

interface. (a) Slope: 31 mV/decade and (b) slope: 122 mV/decade.
The Tafel plot is based on the technique of current impulse vs.
potential step.
-0.85
(b)
-0.80
(a)
-0.75
-0.70
-0.5
0.0
0.5
1.0
Current Density ( log i ) / mA
1.5
2.0
cm-2
Fig. 3. Tafel plot at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

interface. (a) Slope: 31 mV/decade and (b) slope: 122 mV/decade.
The Tafel plot is based on the technique of current step vs. potential
step.
RHE. These peaks imply that the oxidation and reduction of

hydrogen at the interface are reversible. The UPD H peaks
and the corresponding potentials (E) are useful for verifying the adsorption isotherm (Langmuir, Frumkin, Temkin)
of UPD H or OPD H for the cathodic HER at the interface.
However, it is well known that only OPD H can contribute
to the cathodic HER.
sured against the standard reference electrode.2 The negative overpotential, < 0, implies the cathodic HER at the
interface. It is well known that Tafel plots depend on the
technique of pretreatment.
The Tafel slopes shown in Figs. 2(a) or 3(a) and 2(b) or
3(b) are 31 and 122 mV/decade, respectively. These results
are similar to the typical Tafel slopes at noble metal (Pt, Ir,
Rh) electrode interfaces [1,38,27,31,37]. It is well known
that the Tafel slopes due to the rate-determining steps of the
proton discharge reaction and the electrochemical desorption are 30 and 120 mV/decade, respectively. Considering
the sequential reaction for the cathodic HER, one can interpret that the proton discharge reaction corresponding to
the Tafel slopes of 31 mV/decade shown in Figs. 2(a) and
3(a) is the rate-determining step for the cathodic HER at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. At high
current densities, as shown in Figs. 2(b) and 3(b), the Tafel
slopes are usually ca. 120 mV/decade. Also, considering the
high values of the fractional surface coverage () of OPD H
for the cathodic HER, i.e., 1 (refer to Fig. 9), one can
interpret that the electrochemical desorption corresponding
to the Tafel slopes of 122 mV/decade shown in Figs. 2(b)
and 3(b) is the rate-determining step for the cathodic HER
at the interface.
Comparing Figs. 2 and 3 with Fig. 1 shows that the Tafel
slopes of Figs. 2 and 3 are plotted beyond the UPD H regions. This implies that the Tafel slopes shown in Figs. 2(a)
and 3(a) are attributed to the OPD H for the cathodic HER
at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.
From Figs. 2(a) and 3(a), one can understand that the range
of for the rate-determining step of the proton discharge reaction is ca. 0.694 to 0.780 V vs. RHE. The range of ,
ca. 0.694 to 0.780 V vs. RHE, corresponding to the Tafel
slopes shown in Figs. 2(a) and 3(a) is necessary for verifying the proton discharge reaction of the adsorption isotherm
(Langmuir, Frumkin, Temkin) of OPD H for the cathodic
HER at the interface. This is discussed in more detail later.
3.3. Phase-shift prole for the optimum intermediate
frequency
The equivalent circuit for the cathodic HER is usually expressed as shown in Fig. 4(a) [38,39]. Taking into account
the various factors, e.g., the relaxation time effect, the surface diffusion process, the specic adsorption effect, etc.,
which are inevitable under the ac impedance experiment
[40,41], we dene the equivalent circuit elements shown in
Fig. 4(a). RS is the electrolyte resistance, RF is the equivalent resistance due to the adsorption process of OPD H and
3.2. Tafel slopes

Figs. 2 and 3 show Tafel plots at the poly-Pt/0.5 M H2 SO4
aqueous electrolyte interface. In Figs. 2 and 3, the overpotential () is dened as = E Er , where E is the electrode
potential and Er is the reversible potential at the equilibrium. Note that E is the actual electrode potential as mea-
2 In practice, E is not a xed value during the experimenr
tal measurements. Therefore, E in the RHE scale is usually used

in most experimental data, e.g., cyclic voltammograms, electrochemical impedance spectroscopies, electrochemical adsorption
isotherms, etc. Note that in the RHE scale is frequently used in
Tafel plots.
RP
RF
CP
RS
CD
(a)
(b)
RS
RF
CP
Fig. 4. (a) Equivalent circuit for the cathodic HER at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface and (b) simplied equivalent circuit for the intermediate frequencies at the
interface.
its relaxation time effect at the interface, RP is the equivalent resistance due to the recombination reaction, CP is the
equivalent capacitance due to the adsorption process of OPD
H and its relaxation time effect at the interface, and CD is
the double-layer capacitance.
The two equivalent circuit elements, RF and CP , are the
equivalent resistance and capacitance associated with the
faradaic resistance (R ) and the adsorption pseudocapacitance (C ) of OPD H, respectively. Under the ac impedance
experiment, RF is smaller than R due to the surface diffusion process and the relaxation times of the previously
adsorbed hydrogen (OPD H), i.e., the increase of H+ on
the electrode surface. However, CP is greater than C due
to the surface diffusion process and the relaxation times
of the previously adsorbed hydrogen (OPD H), i.e., the increase of H+ on the electrode surface. Because a resistance
is inversely proportional to the concentration of charged
species, but a capacitance is proportional to the concentration charged species, the surface diffusion process and the
relaxation time effects of RF and CP can be compensated
together at the interface (refer to Eq. (2) and Table 1).
Note that both RF and CP cannot exist unless charge is
transferred across the interface. This implies that the behavior of RF and CP depends strongly on that of R and C
or , i.e., the proton discharge reaction of OPD H for the
cathodic HER. Therefore, the adsorption process of OPD H
corresponding to the combination of RF and CP can be correctly expressed in terms of the phase delay, i.e., the lagged
phase shift (). This aspect was not well interpreted in
our previously published papers [22,23]. The experimental results and discussions presented there are unchanged.
1427
However, it is well known that the fractional surface coverage () of H and the phase shift () depend on the applied
electrode potential (E) at the interface.
The frequency responses of the equivalent circuit shown
in Fig. 4(a) are essential for studying the relationship between the behavior ( vs. E) of the phase shift (0
90 ) for the optimum intermediate frequency and that
( vs. E) of the fractional surface coverage (1 0) of
OPD H for the cathodic HER at the interface. At low frequencies, the equivalent circuit for all frequencies shown in
Fig. 4(a) can be expressed as a series circuit of RS , RF , and
RP . At high frequencies, the equivalent circuit for all frequencies shown in Fig. 4(a) can be expressed as a series circuit of RS and CD . At intermediate frequencies, the equivalent circuit for all frequencies shown in Fig. 4(a) can be
simplied as the series circuit of RS , RF , and CP shown in
Fig. 4(b). For a wide range of , i.e., except for low values,
CP is much greater than CD . In practice, CP includes CD .
In addition, RP is much greater than both RF and |1/CP |
for intermediate frequencies. Therefore, RP and CD can be
eliminated from the equivalent circuit for the cathodic HER
shown in Fig. 4(a). This implies that the simplied equivalent circuit for the intermediate frequencies shown in Fig.
4(b) can be applied to the poly-Pt/0.5 M H2 SO4 aqueous
electrolyte interface regardless of H2 evolution. However,
the simplied equivalent circuit shown in Fig. 4(b) is not for
the change of the cathodic HER itself, but only the intermediate frequency response. The behavior of RF and CP depends strongly on that of R and C or . In other words, it
is valid for studying the adsorption sites and process of OPD
H at the interface. The frequency responses of the equivalent
circuit shown in Fig. 4(a) are described elsewhere [38,39].
The impedance (Z) of the equivalent circuit for the intermediate frequencies shown in Fig. 4(b) and the corresponding phase shift () are given by
Z = (RS + RF ) j/CP ,
(1)
= tan1 [1/(RS + RF )CP ],
(2)
RF R , RF > RS , CP > CD , and CP C

(for a wide range of ),
(3)
where j is an operator and is equal to the square root of 1,

i.e., j2 = 1, (=2f ) is the angular frequency, R is the
faradaic resistance for the proton discharge reaction of OPD
H and depends on of OPD H, and C is the adsorption
pseudocapacitance for the adsorption process of OPD H and
also depends on of OPD H.
The minus sign in Eq. (2) implies a lagged phase. In practice, for a wide range of , RS and CD can be neglected
compared to RF and CP at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. From Eq. (2), the lagged phase
shift () depends strongly on RF and CP , i.e., R and
C or . This implies that also depends markedly on
the adsorption process of OPD H, i.e., , at the interface.
However, CP should not be confused with C , which has a
1428
Table 1
Measured values of the equivalent circuit elements for the optimum intermediate frequency (ca. 5 Hz) and the estimated fractional surface
coverage () at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface
E (V vs. RHE)
RS + RF ( cm2 )
CP a (F cm2 )
b (deg)
(deg)
c
0.061
0.041
0.021
0.001
0.019
0.039
0.059
0.079
0.099
0.119
0.139
0.159
2.241
2.700
11.484
16.887
7.299
2.756
1.673
1.444
1.422
1.414
1.418
1.479
433
431
511
1147
4925
23,050
90,050
249,703
478,811
681,387
899,505
1,123,762
88.25
87.91
79.56
58.69
41.54
26.63
11.94
5.05
2.68
1.89
1.43
1.10
88.3
87.9
79.6
58.7
41.5
26.6
11.9
5.0
2.7
1.9
1.4
1.1
0
0.005
0.100
0.339
0.537
0.708
0.876
0.955
0.982
0.991
0.997
1
800
20
600
15
10
400
(b)
(a)
200
-0.2
Equivalent Resistance (RF ) / cm2
maximum value at = 0.5 and can be neglected at

0 and 1 [3841]. Also, it should be understood that the
simplied equivalent circuit shown in Fig. 4(b) is not for the
change of the cathodic HER itself but only the intermediate
frequency response. Consequently, the simplied equivalent
circuit for the intermediate frequencies shown in Fig. 4(b)
is valid for determining the suitable adsorption isotherm
(Langmuir, Frumkin, Temkin) of OPD H for the cathodic
HER at the interface.
Figs. 5(a) and (b) show the proles of the measured RF
and CP vs. E for the optimum intermediate frequency (ca.
5 Hz) at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, respectively. As previously described, Fig. 5(a) shows
that RF is smaller than R , because the left side of the prole (RF vs. E) is lower than the right side of the prole. This
is attributed to the superposition of the adsorption process,
the surface diffusion process, the relaxation time effect of
RF , and the nature of a resistance, which is inversely proportional to the concentration of charged species. However,
as described, Fig. 5(b) shows that CP is greater than C ,
because the prole (CP vs. E) increases from the right side
to the left side, i.e., towards more negative potentials. Similarly, this is attributed to the superposition of the adsorption
process, the surface diffusion process, the relaxation time
effect of CP , and the nature of a capacitance, which is proportional to the concentration of charged species.
Note that the equivalent resistance prole (RF vs. E)
shown in Fig. 5(a) has a peak. But, the equivalent capacitance prole (CP vs. E) shown in Fig. 5(b) has no peak. As
described, this is attributed to the reciprocal nature between
the resistance and the capacitance at the interface. This also
implies that the H+ at the interface increases consistently
with increase of the electrode potential (E) or the fractional
surface coverage (). However, Fig. 5(b) shows that CP
).
Equivalent Capacitance (CP ) / mF cm-2
P practically includes CD (CP ?CD except for low values of

b Calculated using R , R , C , and Eq. (2).
S
F
P
c Estimated using the measured phase shift ().
aC
-0.1
0.0
0.1
Fig. 5. Proles of the measured equivalent circuit elements (RF ,

CP ) vs. E for the optimum intermediate frequency (ca. 5 Hz) at
the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. Single sine
wave; scan frequency: 104 5 Hz; ac amplitude: 5 mV; dc potential;
0.081 to 0.179 V vs. RHE. (a) Equivalent resistance prole (RF
vs. E) and (b) equivalent capacitance prole (CP vs. E).
increases rapidly beyond the peak potential (ca. 0.016 V

vs. RHE) of the equivalent resistance prole (RF vs. E). It
is understood that C has a maximum value at the peak potential, i.e., =0.5, due to the adsorption process of OPD H.
The determination of the optimum intermediate frequency
100
(a)
(b)
80
60
- Phase Shift ( ) / deg
- Phase Shift ( ) / deg
1429
(c)
40
(d)
20
(e)
(f)
(g)
0
20
40
60
80
2
3
Frequency ( log f ) / Hz
Fig. 6. Comparison of the phase-shift curves ( vs. log f ) at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. Vertical solid
line: ca. 5 Hz; single sine wave; scan frequency: 104 5 Hz; ac
amplitude: 5 mV; dc potential: (a) 0.061 V, (b) 0.021 V, (c) 0.001 V,
(d) 0.019 V, (e) 0.039 V, (f) 0.059 V, and (g) 0.139 V vs.
RHE.
is discussed in more detail later. Consequently, one can interpret that the surface diffusion process and the relaxation
time effects of RF and CP are unique features for analyzing the adsorption sites and process of OPD H at the polyPt/0.5 M H2 SO4 aqueous electrolyte interface. The surface
diffusion process and the relaxation time effects of RF and
CP are compensated together at the interface (refer to Eq.
(2) and Table 1). The various effects on the adsorption process of OPD H are negligible at the interface.
Fig. 5 and Eq. (2) show that the real surface area problem
of the poly-Pt electrode is not important for studying the
phase-shift prole for the optimum intermediate frequency.
The real surface area effects of RF and CP are completely
compensated together. Also, the adsorption sites and process
of OPD H at the interface can be expressed in terms of the
lagged phase shift (). In practice, RF is greater than RS
for a wide range of (refer to Fig. 5 and Table 1), and
so described in Eq. (2) can be substantially determined
by the series circuit of RF and CP . In other words,
is substantially characterized by the adsorption sites and
process of OPD H, i.e., . This implies that the behavior (
vs. E) of the phase shift (0 90 ) for the optimum
intermediate frequency can be linearly related to that ( vs.
E) of the fractional surface coverage (1 0) of OPD H,
i.e., the suitable adsorption isotherm ( vs. E) of OPD H,
at the interface. This is discussed in more detail later.
Fig. 6 compares the phase-shift curves ( vs. log f ) for
the different electrode potentials (E) at the poly-Pt/0.5 M
H2 SO4 aqueous electrolyte interface. In this gure, and
vs. log f are markedly different at intermediate frequencies due to the combination of RF and CP , i.e., the adsorption process of OPD H, at the interface. The intermediate
-0.4
-0.2
0.0
0.2
Potential ( E ) / V vs. RHE
0.4
Fig. 7. Phase-shift prole ( vs. E) for the optimum intermediate frequency (ca. 5 Hz) at the poly-Pt/0.5 M H2 SO4 aqueous
electrolyte interface.
frequency, i.e., a vertical solid line (ca. 5 Hz) on the phaseshift curves ( vs. log f ) shown in Fig. 6, can be set as the
optimum intermediate frequency for the phase-shift prole
( vs. E). Note that the optimum intermediate frequency
(ca. 5 Hz) indicates a maximum lagged phase shift on the
phase-shift curve ( vs. log f ) shown in Fig. 6(a).
At a maximum lagged phase shift for the optimum intermediate frequency, it appears that the adsorption process
of OPD H and the various effects at the interface are minimized. In other words, of the OPD H can be set to zero,
as shown in Table 1. Therefore, from Eq. (2) and Fig. 6,
has a maximum value of 90 , as shown in Fig. 6(a). At a
minimum lagged phase shift for the optimum intermediate
frequency, it appears that the adsorption process of OPD H
and the various effects at the interface are maximized or almost saturated. In other words, of the OPD H can be set to
unity, as shown in Table 1. Therefore, from Eq. (2) and Fig.
6, has a minimum value of 0 , as shown in Fig. 6(g).
Also, by comparing the calculated phase shift () with the
measured phase shift () shown in Table 1, one can interpret that the discussions on the simplied equivalent circuit
for the optimum intermediate frequency shown in Fig. 4(b)
and derived Eqs. (1)(3) are valid. The determination of the
optimum intermediate frequency for the phase-shift prole
( vs. E) is described elsewhere [2234].
Finally, the electrode potential (E) and the corresponding
phase shift (0 90 ) for the optimum intermediate frequency (ca. 5 Hz) at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface can be plotted as the phase-shift
prole ( vs. E) for the optimum intermediate frequency
(ca. 5 Hz) shown in Fig. 7. The same shape of vs. E
can also be obtained around the optimum intermediate frequency (ca. 5 Hz), e.g., 10 and 20 Hz, as shown in Fig. 8.
Fig. 8 also shows that the determination of the optimum intermediate frequency for the phase-shift prole ( vs. E)
1430
1.0
5 Hz
10 Hz
20 Hz
20
40
60
80
Fractional Surface Coverage ()
- Phase Shift () / deg
experimental data
fitted data
0.8
0.6
0.4
0.2
0.0
-0.4
-0.2
0.0
0.2
0.4
Fig. 8. Comparison of the phase-shift proles ( vs. E) for three

different intermediate frequencies (ca. 5, 10, and 20 Hz) at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.
corresponding to the suitable adsorption isotherm ( vs. E)

of OPD H at the interface is reasonable.
Table 1 shows that both ()/E or d()/dE and
/E or d/dE are maximized at 0.5 and minimized
at 0 and 1. It is a unique feature of the adsorption
isotherms (Langmuir, Frumkin, Temkin) of intermediates
for sequential reactions in electrochemical systems. As discussed, it implies that the relaxation time effects of RF and
CP , and the surface diffusion process do not conict with
analysis of the adsorption sites and process of OPD H at the
interface. In other words, described in Eq. (2) depends
strongly on R and C , i.e., . Consequently, it appears
that the shape of the phase-shift prole ( vs. E) for the
optimum intermediate frequency can be linearly related to
the form of the suitable adsorption isotherm ( vs. E) of
OPD H at the interface. The various effects on the adsorption isotherm (Langmuir, Frumkin, Temkin) of OPD H for
the cathodic HER are negligible at the interface.
3.4. Langmuir adsorption isotherm of OPD H
The Langmuir adsorption isotherm assumes that the electrode surface is homogeneous and that the lateral interaction effect is negligible. However, oxide layer formations,
different single-crystal face substrates, and different phase
substrates are serious considerations for the Langmuir adsorption process of OPD H, and these should be considered
inhomogeneous. In this case, the Frumkin or the Temkin
adsorption process of OPD H should be applied to the interface. This is discussed in more detail later.
The derivation of the practical form of the electrochemical adsorption isotherms (Langmuir, Frumkin, Temkin)
is described elsewhere [4245]. The Langmuir adsorption
isotherm ( vs. E) of OPD H for the cathodic HER at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface can be
-0.4
-0.2
0.0
0.2
0.4
Fig. 9. Comparison of the experimental and tted data for the

Langmuir adsorption isotherm ( vs. E) of OPD H for the cathodic
HER at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface;
K = 1.3 104 .
expressed as
[/(1 )] = KC +
H [exp(EF /RT )],
(4)
where is the fractional surface coverage of OPD H, K is

+
the equilibrium constant for OPD H, CH
is the H+ concentration in the bulk electrolyte, E is the electrode potential, F
is the Faraday constant, R is the gas constant, and T is the
absolute temperature. In Eq. (4), as previously described,
E is not the overpotential () but the actual electrode potential as measured against the standard reference electrode.
Therefore, Eq. (4) can be expressed in terms of as follows
[43,44]:
[/(1 )] = KC +
H [exp(F /RT )],
(5)
where (=E Er ) is the overpotential and Er is the reversible potential at the equilibrium.
For the poly-Pt/0.5 M H2 SO4 aqueous electrolyte (pH
0.46) interface, the tted data, i.e., the numerically calculated Langmuir adsorption isotherm ( vs. E) for K = 1.3
104 using Eq. (4), are shown in Fig. 9. As expected, the
Langmuir adsorption isotherm ( vs. E) shown in Fig. 9
can be linearly related to the phase-shift prole ( vs. E)
for the optimum intermediate frequency (ca. 5 Hz) shown
in Fig. 7. From Figs. 7 and 9, one infers that the Langmuir
adsorption isotherm for K = 1.3 104 is applicable to the
formation of OPD H at the interface. This also implies that
the applicability of the Frumkin adsorption isotherm ( vs.
E) of OPD H for the cathodic HER at the interface is trivial
(refer to Fig. 12). Figs. 10(a)(c) show the three numerically
calculated Langmuir adsorption isotherms corresponding to
K = 1.3 102 , 1.3 104 , and 1.3 106 , respectively.
The Langmuir adsorption isotherm shown in Fig. 9 is
attributed to OPD H for the cathodic HER. As discussed,
the Langmuir adsorption isotherm due to UPD H has not
1.0
1.0
0.8
0.6
(c)
(b)
(a)
0.4
0.2
0.0
1431
-0.4
-0.2
0.0
0.2
0.4

Fig. 10. Comparison of three numerically calculated Langmuir adsorption isotherms ( vs. E) of OPD H for the cathodic HER
at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface: (a)
K = 1.3 102 , (b) K = 1.3 104 , and (c) K = 1.3 106 .
been observed at the cathodic potential range. It is understood that the adsorption sites of UPD H on the poly-Pt
electrode surface are almost masked due to the high H+
concentration in 0.5 M H2 SO4 aqueous electrolyte and/or
anionic adsorption effects under the steady-state conditions
[19,20,2325,30,31,46]. Note that the Langmuir adsorption
isotherm of OPD H shown in Fig. 9 or 10(b) is located
beyond the UPD H peaks (ca. 0.06 and 0.20 V vs. RHE)
on the cyclic voltammogram shown in Fig. 1. This implies
that the Langmuir adsorption isotherm of OPD H is located
beyond that of UPD H, which cannot be obtained at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The
Langmuir adsorption isotherms ( vs. E) of UPD H and
transitions between UPD H and OPD H regions at noble
metal (Pt, Ir)/alkaline aqueous electrolyte interfaces are
described elsewhere [2325,30,31].
As discussed, the shape of the phase-shift prole (
vs. E) for the optimum intermediate frequency (ca. 5 Hz)
shown in Fig. 7 is the exact form of the Langmuir adsorption
isotherm ( vs. E) of OPD H shown in Fig. 9. Therefore,
one can interpret that the various assumptions and effects,
e.g., the simplied equivalent circuit for the optimum intermediate frequency, the relaxation time effect, the surface
diffusion process, the compensation effects, the lateral interaction effect, the homogeneous surface, etc., are well supplemented for the Langmuir adsorption isotherm of OPD H
at the interface. It especially appears that the assumption of
a linear relationship between the phase-shift prole ( vs.
E) for the optimum intermediate frequency and the Langmuir adsorption isotherm ( vs. E) of OPD H is valid.
Fig. 11 compares three different ranges of , which are estimated using the measured phase shift () shown in Table
1 and through the previously described procedures, for the
Langmuir adsorption isotherm of OPD H, K = 1.3 104 ,
( 0.0 < <1.0 )
0.8
( 0.1 < < 0.9 )

( 0.2 < < 0.8 )
0.6
0.4
0.2
0.0
-0.4
-0.2
0.0
0.2
0.4

Fig. 11. Comparison of three different ranges of for the Langmuir
adsorption isotherm ( vs. E) of OPD H for the cathodic HER at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface; K=1.3104 .
at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.

In contrast to the different values of K shown in Fig. 10,
different ranges of are not of serious concern for determining the Langmuir adsorption isotherm of OPD H corresponding to K (=1.3 104 ), as shown in Fig. 11. For
a wide range of , except for low values, CP and RF are
much greater than CD and RS , respectively. Therefore, the
phase-shift prole ( vs. E) for the optimum intermediate frequency (ca. 5 Hz) can be linearly related to the
Langmuir adsorption isotherm ( vs. E) of OPD H at the interface. In addition, both C and R have maximum values
at = 0.5 and minimum values at 0 and 1. This implies
that the rates of change, i.e., ()/E or d()/dE and
/E or d/dE, are maximized at 0.5 and minimized
at 0 and 1, as described in Table 1. This also implies
that the linear portion of the phase-shift prole ( vs. E)
for the optimum intermediate frequency (ca. 5 Hz) shown
in Fig. 7 can be related to that of the Langmuir adsorption
isotherm ( vs. E) of OPD H shown in Fig. 9 through the
previously described procedures, as shown in Figs. 10 and
11. In other words, the Langmuir adsorption isotherm ( vs.
E) of OPD H shown in Fig. 9 can be denitively determined
by the superposition of the linear portion of the phase-shift
prole ( vs. E) for the optimum intermediate frequency
shown in Fig. 7. However, there are unique features of the
Langmuir adsorption isotherm and process at the interface.
Consequently, it appears that the behavior ( vs. E) of
the phase shift (0 90 ) for the optimum intermediate frequency can be linearly related to that ( vs. E) of
the fractional surface coverage (1 0) of OPD H at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.
As shown in Figs. 10 and 11, the Langmuir adsorption
isotherm of OPD H described in Eq. (4) is denitively determined by the value of K, which is dened by the ratio (kf /kr ) between the rate constant (kf ) of the forward
reaction, i.e., the hydrogen adsorption reaction, and the rate

constant (kr ) of the reverse reaction, i.e., the hydrogen desorption reaction, in the proton discharge reaction [4245].
Thus, by comparing Fig. 9 with Figs. 2 and 3, one can conrm the validity of the Langmuir adsorption isotherm of the
OPD H for the cathodic HER at the interface. In other words,
the range of , ca. 0.694 to 0.780 V vs. RHE, shown in
Figs. 2 and 3 corresponds to the range of , ca. 0.3490.927,
shown in Fig. 9. Note that 0.0 V vs. RHE on the potential
(E) scale shown in Fig. 9 is equivalent to 0.694 V vs.
RHE on the overpotential () scale shown in Figs. 2 and 3.
The range of , ca. 0.3490.927, which corresponds to the
portion of the rate-determining step of the proton discharge
reaction on the Langmuir adsorption isotherm plot, is sufciently large to verify the mechanism of OPD H for the cathodic HER at the interface. Thus, the Langmuir adsorption
isotherm of OPD H for the cathodic HER shown in Fig. 9 is
valid. At limited values of , i.e., 1, it is well known that
the rate-determining step of the cathodic HER is determined
by the electrochemical desorption or the recombination reaction. However, it should be understood that the proton discharge reaction corresponding to the Langmuir adsorption
isotherm of OPD H proceeds continuously at the interface
regardless of H2 evolution. The nature of the Langmuir adsorption isotherm of OPD H is not the rate-determining step,
but the proton discharge reaction itself. Finally, considering the high negative values of and the rate-determining
step of the proton discharge reaction corresponding to the
range of , one can conclude that the Langmuir adsorption
isotherm of OPD H for the cathodic HER shown in Fig. 9 is
acceptable at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte
interface.
3.5. Frumkin and Temkin adsorption isotherms of OPD H
Considering an inhomogeneous Pt/0.5 M H2 SO4 aqueous
electrolyte interface, the Frumkin or the Temkin adsorption
isotherm should be applied to the interface. The practical
form of the electrochemical Frumkin adsorption isotherm (
vs. E) of OPD H can be expressed as follows [4245]:
+
[/(1 )] exp(g) = K0 CH
[exp(EF /RT )],
(6)
g r/RT ,
(7)
K = K0 exp(g),
(8)
where g is the interaction parameter for the Frumkin

adsorption isotherm, K0 is the equilibrium constant for
OPD H at g = 0, K is the equilibrium constant for OPD H,
and r is the rate of change of the standard free energy of
OPD H with , i.e., 0 1.
Figs. 12(a)(c) show the three numerically calculated
Frumkin adsorption isotherms ( vs. E) of OPD H corresponding to g = 0, 5, and 10 for K0 = 1.3 104 at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, respectively. As g increases, changes more slowly with E. In
1.0
1432
( 0.0 < <1.0 )

( 0.1 < < 0.9 )
0.8
( 0.2 < < 0.8 )
0.6
(c) (b) (a)
Langmuir
Frumkin
0.4
0.2
0.0
-0.4
-0.2
0.0
0.2
0.4
Fig. 12. Comparison of the experimentally determined Langmuir

adsorption isotherm ( vs. E) for K = 1.3 104 and three numerically calculated Frumkin adsorption isotherms ( vs. E) for
K0 = 1.3 104 at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte
interface: (a) g = 0, i.e., Langmuir adsorption isotherm, (b) g = 5,
and (c) g = 10 for K0 = 1.3 104 (OPD H).
Fig. 12, g = 0 shown in Fig. 12(a) corresponding to the

Langmuir adsorption isotherm for K = 1.3 104 . By comparing the Frumkin adsorption isotherms with the Langmuir
adsorption isotherm shown in Fig. 12, one can interpret that
the applicability of the Frumkin adsorption isotherms is unreasonable at the interface. The phase-shift method for determining the Frumkin adsorption isotherms of OPD H for
the cathodic HER at metal (Pd, Ni)/aqueous electrolyte interfaces is described elsewhere [22,26].
At intermediate values of , [/(1 )] changes little
with compared to the changing of exp(g) in Eq. (6).
Under the approximate conditions, the Temkin adsorption
isotherm can be simply derived from the Frumkin adsorption
isotherm described in Eq. (6). The practical form of the
electrochemical Temkin adsorption isotherm ( vs. E) of
OPD H can be expressed as follows:
+
exp(g) = K0 CH
[exp(EF /RT )].
(9)
Fig. 13 compares the experimentally determined Langmuir adsorption isotherm ( vs. E) for K = 1.3 104
and the three numerically calculated Temkin adsorption isotherms ( vs. E) for K0 = 8.1 102 at the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. Figs.
13(a)(c) show the three numerically calculated Temkin
adsorption isotherms corresponding to g = 0, 12, and 15,
respectively, at the same potential range for the Langmuir
adsorption isotherm. Under the Temkin adsorption conditions, as shown in Figs. 13(b) and (c), changes linearly
and more slowly with E than it does under the Langmuir
adsorption conditions. By comparing the Temkin adsorption
isotherms with the Langmuir adsorption isotherm shown
in Fig. 13, one can interpret that the applicability of the
1.0
( 0.0 < <1.0 )
0.8
( 0.1 < < 0.9 )

( 0.2 < < 0.8 )
Langmuir
Temkin
0.6
(c)
(b) (a)
0.4
0.2
0.0
-0.4
-0.2
0.0
0.2
0.4

adsorption isotherm ( vs. E) for K = 1.3 104 and three numerically calculated Temkin adsorption isotherms ( vs. E) for
interface: (a) g = 0, (b) g = 12, and (c) g = 15 for K0 = 8.1 102
(OPD H).
1.0
( 0.0 < <1.0 )
( 0.1 < < 0.9 )
0.8
( 0.2 < < 0.8 )

Langmuir
0.6
(c) (b) (a)
Temkin
0.4
0.2
0.0
-0.4
-0.2
0.0
0.2
0.4

adsorption isotherm ( vs. E) for K = 1.3 104 and three numerically calculated Temkin adsorption isotherms ( vs. E) for
interface: (a) g = 0, (b) g = 4.6, and (c) g = 10 for K0 = 1.3 103
(OPD H).
1433
Eq. (8), the range of K is 1.3 103 K 1.3 105

with , i.e., 0 1. Taking into account the determination
of the suitable adsorption isotherm (Langmuir, Frumkin,
Temkin) of OPD H for the cathodic HER at the interface
and the behavior of the Temkin adsorption isotherms shown
in Figs. 13 and 14, the validity of the Temkin adsorption isotherm at the interface is unclear even though the
range of K is acceptable. However, it should be noted that
Fig. 14(b) shows an overlapped region between the Langmuir and Temkin adsorption isotherms ( vs. E) of OPD H
at the range of , ca. 0.2 < < 0.8. At 0.2 < < 0.8, using
Eq. (8), the range of K is 5.2 104 > K > 3.3 105
with . At = 0.5, it especially appears that the equilibrium constant (K = 1.3 104 ) for the Temkin adsorption
isotherm is the same as that (K = 1.3 104 ) for the corresponding Langmuir adsorption isotherm. It is attributed
to a maximum value of R and C vs. E at = 0.5, which
cannot be measured at the interface, and a maximum rate
of change of and vs. E for the optimum intermediate
frequency at 0.5 (refer to Table 1). The equilibrium
constants (K) for OPD H corresponding to the adsorption
isotherms (Langmuir, Temkin, Frumkin) of OPD H and
are summarized in Table 2. Consequently, one can interpret
that the Langmuir and Temkin adsorption isotherms ( vs.
E) of OPD H for the cathodic HER are converted to each
other even though the adsorption conditions are different
from each other. Correspondingly, one can interpret that
the Frumkin and Temkin adsorption isotherms ( vs. E) of
OPD H for the cathodic HER are converted to each other.
Note that the equilibrium constant (K0 ) for the Temkin
adsorption isotherms ( vs. E) is ca. 10 times greater
than that (K) for the corresponding Langmuir adsorption
isotherm ( vs. E). Similarly, note that the interaction parameter (g) for the Temkin adsorption isotherm ( vs. E)
is ca. 4.6 greater than that (g) for the corresponding Langmuir adsorption isotherm ( vs. E). These numbers (10
times and 4.6) can be taken as constant conversion factors
between the corresponding adsorption isotherms (Temkin,
Langmuir, Frumkin) [47]. This implies that the Temkin
adsorption isotherm corresponding to the Langmuir or the
Frumkin adsorption isotherms, and vice versa, can be effectively converted using the constant conversion factors. This
aspect was not well interpreted in our previously published
papers[2234].
3.6. Standard free energy of OPD H
Temkin adsorption isotherms is also unreasonable at the

interface.
Fig. 14 also compares the experimentally determined
Langmuir adsorption isotherm ( vs. E) for K = 1.3 104
and the three numerically calculated Temkin adsorption
isotherms ( vs. E) for K0 =1.3103 at the poly-Pt/0.5 M
H2 SO4 aqueous electrolyte interface. Figs. 14(a)(c) also
show the three numerically calculated Temkin adsorption
isotherms corresponding to g = 0, 4.6, and 10, respectively.
For g = 4.6 and K0 = 1.3 103 shown in Fig. 14(b), using
The standard free energy of OPD H is given by the difference between the standard molar Gibbs free energy of
OPD H and that of a number of water molecules on the
adsorption sites of the poly-Pt electrode surface. Under the
Langmuir adsorption conditions, the relation between the
equilibrium constant (K) for OPD H and the standard free
energy (G0ads ) of OPD H is given [42] as follows:
2.3RT log K = G0ads .
(10)
1434
Table 2
Comparison of the equilibrium constants (K) for OPD H corresponding to the adsorption isotherms (Langmuir, Temkin, Frumkin) of OPD
H and fractional surface coverages () at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface
Adsorption isotherm
Langmuir (g = 0)
Temkin (g = 4.6)
Frumkin
K
01
0.2 < < 0.8
= 0.5
1.3 104
1.3 103 K 1.3 105
1.3 104
5.2 104 > K > 3.3 105
1.3 104
1.3 104
The denition of G0ads is described elsewhere [48,49]. At

the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, using Eq. (10), G0ads is 22.2 kJ/mol for K = 1.3 104
(OPD H). As expected, in contrast to the exothermic reaction, G0ads < 0, in the UPD H region, an endothermic
reaction, G0ads > 0, occurs in the OPD H region of the
poly-Pt electrode interface. This implies that the OPD H
on the adsorption sites of the poly-Pt electrode surface requires 22.2 kJ/mol to remove the appropriate number of water molecules.
Under the Temkin adsorption conditions, the relation between the equilibrium constant (K) for OPD H and the standard free energy (G0 ) of OPD H is given as [42]
2.3RT log K = G0 .
(11)
As expected, in contrast to the Langmuir adsorption

isotherm, both K and G0 depend strongly on . At the
poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, using Eqs. (8) and (11), G0 is 16.5 G0 27.9 kJ/mol
for 1.3 103 K 1.3 105 (OPD H) with , i.e.,
0 1. Similarly, using Eqs. (8) and (11), G0 is
18.7 < G0 < 25.6 kJ/mol for 5.2104 > K > 3.3105
(OPD H) with , i.e., 0.2 < < 0.8.
3.7. Complementary statement
A linear relationship between the phase-shift proles for
the optimum intermediate frequencies and the corresponding Langmuir and Temkin adsorption isotherms of OPD H
at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface
was proposed based on purely empirical relationships. The
behavior ( vs. E) of the phase shift (0 90 )
for the optimum intermediate frequency can be linearly related to that ( vs. E) of the fractional surface coverage
(1 0) of the OPD H at the interface. This implies that
the phase-shift method experimentally provides the link between the microscopic system of the adsorption sites and
process of OPD H on the atoms and the macroscopic system of the electrode kinetics and thermodynamics for OPD
H at the interface.
The Langmuir and Temkin adsorption isotherms ( vs. E)
of OPD H at the poly-Pt electrode interface can be practically determined using the phase-shift curves ( vs. log f )
and the phase-shift prole ( vs. E) for the optimum intermediate frequency. It appears that the phase-shift method
is a simple and efcient tool for determining the electrode
kinetic and thermodynamic data (, K, K0 , g, G0ads , G0 )
relating to the adsorption sites and processes of H (UPD
H, OPD H) for the cathodic HER at the interface. Note
that the other tedious procedures described in this paper are
only used to verify the validity of the phase-shift method.
However, at rst glance, it seems that there is no linear relationship between the phase-shift proles ( vs. E) for
the optimum intermediate frequencies and the adsorption
isotherms ( vs. E) of H (UPD H, OPD H) for the cathodic
HER at the interfaces [5053]. At present, the various effects on the adsorption sites and processes of H (UPD H,
OPD H) for the cathodic HER have not been combined into
a single equation for the linear relationship. Therefore, it
seems difcult to obtain a relationship based on theoretical
derivations or numerical calculations.
4. Conclusions
The phase-shift method for determining the suitable adsorption isotherm (Langmuir, Frumkin, Temkin) of H (UPD
H, OPD H) for the cathodic HER in electrochemical systems
is proposed. The simplied equivalent circuit for the optimum intermediate frequency and the corresponding phaseshift equation are well tted to the poly-Pt/0.5 M H2 SO4
aqueous electrolyte interface. The phase-shift method experimentally veries that the behavior ( vs. E) of the
phase shift (0 90 ) for the optimum intermediate
frequency can be linearly related to that ( vs. E) of the fractional surface coverage (1 0) of OPD H, i.e., the Langmuir and Temkin adsorption isotherms ( vs. E) of OPD H,
at the interface. At the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, the Langmuir adsorption isotherm ( vs.
E) of OPD H, the equilibrium constant (K =1.3104 ) for
OPD H and the standard free energy (G0ads = 22.2 kJ/mol)
of OPD H are determined using the phase-shift method. At
the same interface, the Temkin adsorption isotherm ( vs. E)
of OPD H, the equilibrium constant (1.3103 K 1.3
105 with , i.e., 0 1) for OPD H, and the standard free
energy (16.5 G0 27.9 kJ/mol with , i.e., 0 1) of
OPD H are also determined using the phase-shift method.
At the intermediate values of , i.e., 0.2 < < 0.8, the Langmuir and Temkin adsorption isotherms of OPD H for the
cathodic HER at the interface are converted to each other.
The equilibrium constant (K0 ) for the Temkin adsorption
isotherm ( vs. E) is ca. 10 times greater than that (K)
for the corresponding Langmuir adsorption isotherm ( vs.
E). The interaction parameter (g) for the Temkin adsorption isotherm ( vs. E) is ca. 4.6 greater than that (g) for
the corresponding Langmuir adsorption isotherm ( vs. E).
These numbers (10 times and 4.6) can be taken as constant conversion factors between the corresponding adsorption isotherms (Temkin, Langmuir, Frumkin). The Temkin
adsorption isotherm corresponding to the Langmuir or the
Frumkin adsorption isotherm, and vice versa, can be effectively converted using the constant conversion factors.
The phase-shift method experimentally provides the link between the microscopic system of the adsorption sites and
process of OPD H on the atoms and the macroscopic system of the electrode kinetics and thermodynamics for OPD
H at the interface. Both the phase-shift method and constant conversion factors can be effectively used as a new
electrochemical method to determine adsorption isotherms
(Langmuir, Frumkin, Temkin) of intermediates for sequential reactions in electrochemical systems.
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
Acknowledgements
[17]
The authors thank Professor G. Jerkiewicz (Department

of Chemistry, Queens University, Canada) and Reviewers
for their valuable suggestions and encouragements on the
phase-shift method. This work has been performed through
the Support Project of University Information Technology
Research Center (ITRC) supported by the Ministry of Information & Communication of Korea.
[18]
[19]
[20]
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International Journal of Hydrogen Energy 30 (2005) 1423 1436

The phase-shift method for determining Langmuir and Temkin

Received 15 July 2004

fax: +82 2 942 0107.

ates at interfaces has not been suggested to provide the link

1 A linear relationship between the behavior ( vs. E) of

Taking into account the H+ concentration and effects

Fig. 1. Typical cyclic voltammogram at the poly-Pt/0.5 M H2 SO4

(Langmuir, Frumkin, Temkin) of H (UPD H, OPD H) at

3. Results and discussion

Overpotential () / V vs. RHE

Current Density (log i ) / mA

Overpotential () / V vs. RHE

Fig. 2. Tafel plot at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

Current Density ( log i ) / mA

Fig. 3. Tafel plot at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

RHE. These peaks imply that the oxidation and reduction of

3.2. Tafel slopes

2 In practice, E is not a xed value during the experimenr

tal measurements. Therefore, E in the RHE scale is usually used

Fig. 4. (a) Equivalent circuit for the cathodic HER at the

= tan1 [1/(RS + RF )CP ],

RF R , RF > RS , CP > CD , and CP C

where j is an operator and is equal to the square root of 1,

Equivalent Resistance (RF ) / cm2

maximum value at = 0.5 and can be neglected at

Equivalent Capacitance (CP ) / mF cm-2

P practically includes CD (CP ?CD except for low values of

Fig. 5. Proles of the measured equivalent circuit elements (RF ,

increases rapidly beyond the peak potential (ca. 0.016 V

- Phase Shift ( ) / deg

- Phase Shift ( ) / deg

Fig. 6. Comparison of the phase-shift curves ( vs. log f ) at the

Fractional Surface Coverage ()

- Phase Shift () / deg

Fig. 8. Comparison of the phase-shift proles ( vs. E) for three

corresponding to the suitable adsorption isotherm ( vs. E)

Fig. 9. Comparison of the experimental and tted data for the

where is the fractional surface coverage of OPD H, K is

Fractional Surface Coverage ()

Potential (E ) / V vs. RHE

( 0.0 < <1.0 )

( 0.1 < < 0.9 )

Potential (E ) / V vs. RHE

at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.

reaction, i.e., the hydrogen adsorption reaction, and the rate

where g is the interaction parameter for the Frumkin

( 0.0 < <1.0 )

( 0.2 < < 0.8 )

(c) (b) (a)

Fig. 12. Comparison of the experimentally determined Langmuir

Fig. 12, g = 0 shown in Fig. 12(a) corresponding to the

Fractional Surface Coverage ()

( 0.1 < < 0.9 )

Potential (E ) / V vs. RHE

Fractional Surface Coverage ()

( 0.2 < < 0.8 )

= tan1 [1/(RS + RF )CP ],