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Krystyna Jackowska, Paweł Krysiński
Applied Electrochemistry
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Krystyna Jackowska, Paweł Krysiński

Applied
Electrochemistry

Aspects in Material and Environmental Science

2nd Edition, expanded and amended

Authors
Prof. Krystyna Jackowska
Professor Emeritus
University of Warsaw
Faculty of Chemistry
Laboratory of Electrochemistry
Pasteur 1
02-093 Warsaw
Poland

Prof. Paweł Krysiński

University of Warsaw
Faculty of Chemistry
Laboratory of Electrochemistry
Pasteur 1
02-093 Warsaw
Poland

ISBN 978-3-11-116034-4
e-ISBN (PDF) 978-3-11-116098-6
e-ISBN (EPUB) 978-3-11-116344-4

Library of Congress Control Number: 2024933394

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Cover image: The template-assisted electrodeposited Pd nanowires. Courtesy of Dr.
Magdalena Tagowska, Faculty of Chemistry, University of Warsaw
Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck

www.degruyter.com
Preface
A multiplicity of definitions exists for applied electrochemistry as a discipline. The
most general, attempting to embrace all aspects, can be formulated as science that
aims at improving our life, taking advantage of the phenomena occurring at the inter-
faces between metallic or semiconducting electrodes and electrolyte solutions (so-
called electrodics) as well as those occurring in the bulk of the electrolyte solutions
(so-called ionics). Such improvement can come through the understanding of these
phenomena, with subsequent construction and design of new devices or systems that
can be used not only by industry (e.g., catalysis) but also in more personalized appli-
cations, such as batteries for smartphones, pacemakers, solar panels, and so on.
To facilitate understanding of these phenomena, Basic concepts part in this book
present first a brief thermodynamic background allowing the reader to understand
the electrified interfaces and electrolyte solution under equilibrium and steady-state
conditions. Then it continues with a basic introduction to the structure of interfaces,
followed by the charge transfer processes occurring at metal/electrolyte interface
from the point of view of equilibrium and nonequilibrium phenomena, defining the
so-called reversible and irreversible electrodes. The next part begins with an intro-
duction to the selected electrochemical methods applied in the analytical and material
chemistry that benefit from the essential knowledge gained in the previous chapters.
The next part of this book guides through the Electrochemistry in material sci-
ence – selected topics. It aims at describing in more detail how the electrochemistry
can be used in corrosion science, catalysis, deposition of new material on a conduct-
ing support, allowing to get insight into the mechanism of deposition and its kinetics.
This chapter will lead to the nanostructured materials of different dimensions, organi-
zation, and topologies. Then, a very broad area, extremely important nowadays for
our population, namely – the energy storage and conversion, will be set forth in order
to show how the electrochemistry can be applied to understand the working of batter-
ies and fuel cells, to stimulate and push forward their development and design, thus
improving their reliability and durability. This part will conclude with the applica-
tions of electrochemistry in biology and medicine, thereby improving the quality of
life of patients and providing information on the energetics of living organisms.
Finally, the last part, Photoelectrochemistry in material science – selected topics,
will guide the reader through the selected topics of photoelectrochemistry, where light
acts as a power source for electrical energy generation, photocatalysis, and photoelectro-
catalysis, including the nanoscale processes at the semiconductor nanoparticles.
The goal of this book is to show all graduate and PhD students that electrochemis-
try not only has many applications for understanding of various phenomena in nowa-
days life but also has many applications in practical devices and can also stimulate
new science-enabled technologies, nourishing leaps from bench-top to large-scale indus-
tries, providing also means for protecting our environment. Our book is based on lec-
tures given at the University of Warsaw, Faculty of Chemistry. It addresses advanced

https://doi.org/10.1515/9783111160986-202
VI Preface

students and PhD students of chemistry, physics, engineering, and related subjects and
also those scientists who want to get a solid background knowledge of this area.
We hope that this background will be useful to the interested reader, encouraging
him/her to take the next several steps into the attractive area of applied electrochem-
istry. Our aim is to guide him/her through the selected topics of contemporary life in
which electrochemistry progressively improves our knowledge and quality of life.

Acknowledgments: Krystyna Jackowska dedicates her part of this book to Polish

and valued Russian friends (Dr. R.V. Ivanova and Prof. M.N. Rodnikova from Moscow)
for their encouragement and support. Special thanks are due to Prof. Magdalena
Skompska and Prof. Marek Szklarczyk from Warsaw University, and to Prof. G.A.Tsir-
lina and Prof. O.A. Petrii from Moscow State University for some reviews and referen-
ces. She is also very grateful to her family for patience.
Paweł Krysiński highly acknowledges the understanding and forbearance of his
family, with special thanks due to his wife, Hanna, for her extreme patience, kindness,
support, and help.
The authors thank Dr. Magdalena Osial for her skills and time devoted for prepar-
ing all the graphics in this book. Without her work and willingness to share some of her
experimental data, this book will be largely delayed, to say nothing about its form.
The authors are also greatly indebted to the editorial staff of De Gruyter.
Preface to the 2nd edition
In the still growing awareness of the necessity of minimizing the deteriorating impact
on the environment by all fundamental activities of mankind, electrochemistry can
provide tools for environmental control, pollution avoidance, and destruction of pol-
lutants as well as clean energy conversion and storage. Moreover, the use of electrons
in electrochemical processes is considered a “green” model in its preventive mode
(electrosynthesis, hydrogen production, power storage, metal recovery/recycling) and
the control/remedial mode (wastewater treatment, air pollution control, destruction
of organic pollutants). In all these processes, the electron as a reagent frequently
leads to cleaner technology by simple avoidance of the use of hazardous chemicals
and allows for subsequent recovery, recycling, or at least pollution control.
Therefore, in this second edition of the Applied Electrochemistry textbook, we
added a brief review of current and emerging approaches utilizing electrochemistry
for a cleaner environment, the so-called “green” electrochemistry. This review is con-
tained in Part IV, entitled Electrochemistry in Environmental Science – selected
topics.
This part entails the utilization of electrochemistry to monitor the environment
for certain most commonly polluting gases (Chapter 13. Sensing the environment).
This chapter classifies and shows the applications of electrochemical sensors in moni-
toring the safety of life through the development of rapid, selective, and miniaturized
detection techniques that can trigger further remediation processes. As described in
Chapter 14 entitled Green fuel – hydrogen production. Environmental pollution,
and global warming, have triggered vast research for new, promising sources of
clean, “green” energy, such as hydrogen. One of the simplest methods for hydrogen
production is water electrolysis. Therefore, this chapter encompasses methods and
technologies currently used in water electrolysis, stressing out its thermodynamics,
efficiency, and energy losses. A brief description of a new method of water electrolysis
that is based on bioelectrochemical systems, such as microbial electrolysis, is also in-
cluded. Furthermore, this chapter presents an outline of solar energy utilization in
water electrolysis, including the semiconducting nanostructured systems and again,
thermodynamics and efficiency for such devices.
Then, we will describe the electrochemical processes and methods in the elimina-
tion of the most common pollutants (Chapter 15. Electrochemical and photocata-
lytic methods in pollutant removal). An outline is given to the electrochemistry in
the removal and recovery of heavy metals, followed by the removal of organic pollu-
tants via the electrochemical treatment. This chapter finally will summarize the appli-
cation of solar energy for a cleaner environment with a description of the processes
utilizing this renewable and sustainable source of natural energy in the removal and
degradation of some inorganic and organic pollutants.
To better understand all processes involved in the application of electrochemistry
for a greener environment, some modifications were also necessary to previous chap-

https://doi.org/10.1515/9783111160986-203
VIII Preface to the 2nd edition

ters, particularly to the Basic concepts part. And so, the Basic Concepts part, as be-
fore, consists of Chapter 1.1 Structure of interfaces, which introduces a brief ther-
modynamic background for understanding the electrified interfaces and electrolyte
solution under equilibrium and steady-state conditions. As in the first edition it con-
tinues with a basic introduction to the structure of interfaces, followed by the charge
transfer processes occurring at metal/electrolyte interface from the point of view of
equilibrium and non-equilibrium phenomena, defining the so-called “reversible” and
“irreversible” electrodes. However, the Basic concepts part in the current edition
was expanded to include Chapter 1.2 Structure of the bulk of electrolytes. Conduc-
tivity, followed by Chapter 1.3 Nonaqueous electrolytes, describing the structure of
the bulk of aqueous electrolytes, conductivity, as well as nonaqueous electrolytes, in-
cluding ionic liquids, molten salts, and solid electrolytes. Finally, Part I was amended
with a brief background to Membranes and membrane potentials (Chapter 1.4),
both under equilibrium conditions and non-equilibrium conditions, necessary for a
better understanding of the design of batteries and other storage devices.
We hope that this 2nd edition, completed with new information contained in the
additional chapters will be found interesting and useful, by giving the background
knowledge and directions in the applications of electrochemistry for cleaner, “greener”
and sustainable environment and quality of life.
Contents
Preface V

Preface to the 2nd edition VII

Part I: Basic concepts

1 Basic concepts 3
1.1 Structure of interfaces 3
1.1.1 Electrical double layer at interfaces: metal/electrolyte 7
1.1.2 Electrochemical potential – potentials at interfaces: internal, surface,
external potential 14
1.1.2.1 Metal–solution interface at equilibrium: Nernst equilibrium
potential 18
1.1.2.2 Electron work function 20
1.1.3 Charge transfer processes across the metal/electrolyte interface 21
1.1.3.1 Basic concepts of nonequilibrium thermodynamics 21
1.1.3.2 “Reversible” electrode processes 27
1.1.3.3 “Irreversible” electrode processes: basic concepts of electrochemical
kinetics 32
1.1.3.4 Briefly on Marcus, Hush, Levich, Dogonadze (MHLD) theory of
electrode processes 37
Bibliography 39
1.2 Structure of the bulk of electrolytes: conductivity 40
1.2.1 Interactions in aqueous electrolytes 40
1.2.1.1 Ion–solvent interaction; solvation 40
1.2.1.2 Ion–ion interactions 41
1.2.2 Conductivity of electrolytes 44
1.3 Nonaqueous electrolytes 48
1.3.1 Ionic liquids 48
1.3.2 Molten salts 50
1.3.3 Solid electrolytes 51
Bibliography 53
1.4 Membranes and membrane potentials 53
1.4.1 Equilibrium potentials 53
1.4.2 Nonequilibrium potentials 56
Bibliography 63
X Contents

2 Selected electrochemical methods applied in analytical chemistry

and material science 64
2.1 Transient methods 64
2.1.1 Capacitive current 65
2.1.2 Faradaic current 67
2.2 Electrochemical impedance spectroscopy 70
2.2.1 Data presentation 74
2.3 Electrochemical quartz crystal microbalance method 82
Bibliography 87

Part II: Electrochemistry in material science – selected topics

3 Corrosion 91
3.1 General remarks 91
3.2 Corrosion – what does it mean? Mechanism of corrosion 91
3.3 Characterization of corrosion: corrosion potential, corrosion
current 97
3.3.1 Stability of materials: potential/pH (Pourbaix) diagrams – the
thermodynamic aspect 98
3.3.2 Stability of materials: current–potential (Evans) diagrams – the kinetic
aspect 103
3.4 Evaluation of corrosion rate from electrochemical measurements 105
3.4.1 Linear scan voltammetry 106
3.4.2 Electrochemical impedance spectroscopy in corrosion 107
3.5 Localized corrosion: pits, crevices, intergranular corrosion – oxygen
reduction as accompanying cathodic reaction 109
3.6 Hydrogen evolution as accompanying reaction – role in corrosion:
embrittlement and cracking 111
3.7 Protection against corrosion 113
3.7.1 Electroplating 116
Bibliography 117

4 Electrocatalysis 118
4.1 General remarks 118
4.2 How to compare the activity of catalysts in electrochemical
reactions? 120
4.3 Electrocatalysts 122
4.3.1 Metals, alloys, and oxides 122
4.3.2 Carbon catalysts and supports 124
4.4 Catalyst activity 125
4.4.1 Electron work function effect 126
 Contents XI

4.4.2 Adsorption impact 126

4.4.3 Size effect 129
4.5 Electrocatalysts in hydrogen–oxygen fuel cells 131
4.5.1 Oxygen reduction reaction 132
4.5.2 Hydrogen evolution and oxidation reactions 135
Bibliography 136

5 Electrodeposition 138
5.1 General remarks 138
5.2 Electrocrystallization: nucleation and growth 139
5.2.1 Critical size of nuclei 141
5.2.2 Instantaneous and progressive nucleation 142
5.2.3 Analytical approach to experimental data 144
5.3 Deposit morphology 148
5.4 Practical aspects of electrodeposition 149
5.5 Electrodeposition of binary alloys and semiconductor compounds 152
Bibliography 156

6 Underpotential deposition (UPD) 157

6.1 General remarks 157
6.2 Experimental examples – UPD features 158
6.3 Underpotential deposits – catalytic properties 161
Bibliography 163

7 Electrochemical methods in the formation of nanostructures 164

7.1 General remarks 164
7.2 Template-assisted electrodeposition of nanostructures 165
7.2.1 Active template-assisted electrodeposition 165
7.2.2 Restrictive template-assisted deposition 166
7.2.2.1 Porous anodic alumina (PAA) matrices 167
7.2.2.2 Porous anodic titanium dioxide matrices 168
7.2.3 Concluding remarks 168
7.3 Applications of nanostructured materials 170
7.3.1 Catalysis 170
7.3.2 Batteries: supercapacitors 171
7.3.3 Photoelectrochemical devices: solar cells 171
7.3.4 Biological applications: nanozymes 171
Bibliogaphy 172
XII Contents

8 Electrochemistry in energy conversion and storage 175

8.1 Batteries 175
8.1.1 Electrochemical cell – fundamentals 175
8.1.2 Characteristics of batteries 179
8.1.3 Classification of batteries and examples 183
8.1.3.1 Primary batteries 183
8.1.3.2 Secondary batteries 184
8.1.3.3 Lithium batteries 186
8.1.3.4 Fuel cells 188
8.2 Supercapacitors 192
8.2.1 General remarks 192
8.2.2 Capacitor versus electrochemical cell/battery 193
8.2.3 Working characteristics of supercapacitors 198
Bibliography 200

9 Interfacing applied electrochemistry and biology 202

9.1 General remarks 202
9.2 Bioelectrocatalysis 203
9.3 Biosensors 208
9.4 Biofuel cells 212
9.4.1 Design and enzymes used in biofuel cells 214
9.4.1.1 Biocatalysts and design of biocathodes 214
9.4.1.2 Biocatalysts and design of bioanodes 216
9.4.2 Energy and power of the biofuel cells 217
Bibliography 221

Part III: Photoelectrochemistry in materials science – selected

topics

10 Semiconductors electrochemistry and photoelectrochemistry:

fundamentals 229
10.1 Basic characteristics of semiconductors 229
10.1.1 Semiconductor under illumination 232
10.1.2 Recombination 235
10.1.3 Carriers and electric field 236
10.2 Semiconductor–electrolyte interface 237
10.2.1 Model of semiconductor–electrolyte interface 237
10.2.2 Space charge layer 239
10.2.3 Polarization of semiconductor–electrolyte interface 242
10.3 Fundamentals of electrochemical reactions on the SC electrode 243
10.4 Photoeffects at/in semiconductor electrode in electrolyte 250
 Contents XIII

10.5 Influence of surface states 254

10.6 Corrosion, photocorrosion, and stability 258
Bibliography 262

11 Solar energy conversion in photoelectrochemical cells 264

11.1 General remarks 264
11.2 Efficiency and key parameters 265
11.3 Photoelectrochemical cells: classification – principle of operation 267
11.3.1 Liquid photovoltaic cells 267
11.3.2 Dye-sensitized solar cells 269
11.3.3 Quantum dot-sensitized solar cells 271
11.3.4 Photoelectrosynthetic cells 272
Bibliography 278

12 Semiconductor particles in photocatalysis 280

12.1 General remarks 280
12.2 Size effect and dimensionality 281
12.3 Photocatalytic degradation of organic/inorganic pollutants 284
Bibliography 288

Part IV: Electrochemistry in environmental science – selected

topics

13 Sensing the environment 291

13.1 General remarks 291
13.2 Electrochemical sensors 292
13.2.1 Amperometric sensors 293
13.2.2 Potentiometric sensors 302
13.2.3 Conductometric sensors 307
13.3 Future perspectives and challenges 310
Bibliography 312

14 Green fuel: hydrogen production 313

14.1 General remarks 313
14.2 Water electrolysis 314
14.2.1 Thermodynamics, energy losses, and efficiency 314
14.2.2 Methods and technologies 321
14.2.2.1 Alkaline water electrolysis (AWE) 322
14.2.2.2 Polymer electrolyte membrane electrolysis (PEM) 323
14.2.2.3 Solid oxide electrolysis (SOE) 325
14.2.2.4 Seawater electrolysis 326
XIV Contents

14.2.2.5 Microbial electrolysis (MEC) 329

14.3 Solar energy in photo water splitting 331
14.3.1 Thermodynamics, energy losses, and efficiency 333
14.3.2 Photoelectrolysis of water: trends 340
14.3.3 Photocatalysis of water: trends 345
References 350

15 Electrochemical and photocatalytic methods in pollutant

removal 352
15.1 General remarks 352
15.2 Removal and recovery of heavy metals: electrochemical
treatment 353
15.2.1 Electrodeposition and electrodialysis 354
15.2.2 Electrocoagulation and electroflotation 357
15.3 Degradation and removal of organic pollutants: electrochemical
treatment 361
15.3.1 Fenton and electro-Fenton oxidation 361
15.3.2 Anodic oxidation 363
15.4 Solar energy: pollutant degradation and removal 367
15.4.1 Inorganic pollutants 368
15.4.2 Organic pollutants 370
References 372

List of abbreviations 375

List of Symbols 379

Index 385
Part I: Basic concepts
1 Basic concepts

1.1 Structure of interfaces

To begin with, it is necessary to establish a solid foundation for all topics presented in
the following chapters. This foundation can be derived from the laws of thermody-
namics that provide tools not only for qualitative and quantitative description of sys-
tems and processes but also capabilities to predict their further development. There
are four state functions in thermodynamics, namely, the internal energy, U, enthalpy
H, entropy, S, Gibbs’ free energy, G (also called the thermodynamic potential), and the
Helmholtz’ free energy, F. Together with their parameters of state – V, p, T, ni, these
functions describe precisely the state of a given system or process. For the purpose of
this book, let us choose Gibbs’ free energy G (the thermodynamic potential) for subse-
quent chapters of this book. As mentioned earlier, this function is the state function,
meaning that its change depends only on the initial and final state of the system.
From the mathematical point of view such extremely small change can be written as
the total differential versus the state parameters of Gibbs’ free energy: G = G(p, t,
ni ). Thus,




∂G ∂G ∂G
dG = dp + dT + Σ dni (1:1)
∂p T, n ∂T p, n ∂ni p, T
i i

Subscripts next to parentheses show that the remained parameters of state are constant.
Thus, the meaning of this total differential is that we can sum partial differential of G
versus p, keeping T and ni constant, controlling the change dp, and so on, and then sum
all partial differentials to get the overall change of G, dG. As long as we do not assign the
physicochemical meanings of all three partial differentials in the above equation, it re-
mains purely mathematical. However, taking into account the laws of thermodynamics,
we can identify the meanings of these partial differentials, rewriting the above equation
as follows:

dG = Vdp − SdT + Σμi dni , (1:2)

where V is volume, S – entropy, and μi is the chemical potential of species “i” in the
system under consideration.
The detailed arguments behind this transformation is beyond the scope of this
book. Interested reader is directed to the textbooks on thermodynamics.
Now, let us identify the system that is used in electrochemistry – the electrode. Typi-
cally, an ideal conductor (semiconductor electrodes will be discussed in Section 10.2) and
its properties do not depend on the bulk (volume), but surface behavior, where all of the
excess charges originating, for example, from the external polarization, are localized. An
experimentally measurable parameter that can be initially used for an interface with
zero electric charge is the so-called surface or interface tension. The latter is more ap-

https://doi.org/10.1515/9783111160986-001
4 1 Basic concepts

propriate, because there are no free surfaces, but surfaces separating two phases
in contact. For our purposes, we will use the term “surface tension” throughout
the text. Quantitatively, a work δw, required to increase a surface area by δA, is
given by the following equation:

δw = γdA, (1:3)

Proportionality coefficient γ [ J/m = N/m] is called the surface tension (interfacial

2

tension)
Thermodynamics of such an interface can be described with the help of the change
of selected state function like Gibbs’ free energy, which will depend only on the initial
and final state. For an open, multicomponent system of a surface area A, we can write:

G = Gðp, T, ni , AÞ, (1:4)

and its total differential:





∂G ∂G ∂G ∂G
dG = dp + dT + Σ dni + dA (1:5)
∂p T, n , A ∂T p, n , A ∂ni p, T, A ∂A p, T, n
i i i

or

dG = Vdp − SdT + Σμi dni+γ dA (1:6)

Therefore, at constant p, T, ni, we can obtain the thermodynamic definition of surface

tension:

dG = γ dA (1:7)

Until now we have considered the total value of Gibbs’ free energy change (thermody-
namic potential change) of a system with the surface. Now let us turn to the descrip-
tion of the surface (interface) itself. In doing this we will use the so-called Gibbs
model, in which the ideal surface has no volume and the two phases separated by this
surface are at equilibrium. This is illustrated in Fig. 1.1.

interface σ

Fig. 1.1: The Gibbs model of two contacting phases A and

B at equilibrium, represented by two slabs of different
A B colors and separated by an ideal surface σ of Vσ = 0. See
text for details.

All these regions are at equilibrium, and so chemical potentials of any component “i”
that can distribute itself between these three regions are also at equilibrium:

μAi = μBi = μσi = μi (1:8)

 1.1 Structure of interfaces 5

This model formally assumes that the total internal energy of such a system can be
described by a sum of selected constituents: phase A, phase B, and their contact sur-
face σ:

Utot = UA + UB + U σ (1:9)

The total volume is due solely to a sum of volumes A and B, Vσ = 0, so

Vtot = VA + VB (1:10)

Moreover, any component ni of the system partitions itself between phase A, phase B,
and surface σ. All these regions are at equilibrium, and the equilibrium condition is
fulfilled also by the equilibrium of chemical potentials of species “i” in the system:

μAi = μBi = μσi = μi . (1:11)

With the help of some thermodynamic relations that are beyond the scope of this book,
we can finally write the expression for the Gibbs’ free energy change of the surface σ:

dGσ = −Sσ dT − Adγ + Σμi dni σ (1:12)

This equation describes the equilibrium change of Gibbs’ free energy of the interface
(surface) separating two phases, relating it to the change of parameters T, γ, and ni. Set-
ting T = const and dividing by A to obtain the specific values per unit surface, we finally
get after some rearrangement:

dγ = −Σ Γσi dμi (1:13)

or, in a more convenient form for the case of adsorbing species on a solid surface:

Γ = −ða=RT Þδγ=δa (1:14)

where Γ stands for the surface concentration of adsorbing species [mol/m2], and a is
the activity of this species in the solution, often replaced by its bulk concentration,
c [mol/dm3]. What we just derived is the quantitative relationship between the amount
of a substance accumulated at the surface with its activity (or concentration) in the
bulk of the solution. This equation, known as Gibbs’ adsorption isotherm, plays a cru-
cial role in, for example, separation techniques and catalysis.
Now, having all necessary instruments provided by the thermodynamics of the
uncharged systems, it is time to utilize the above knowledge for the systems, in
which the surface can be charged in a controlled manner – the electrodes [1–6].
Most if not all of the areas of applied electrochemistry contain electrode/electrodes as
an integral part of the systems, determining the systems’ properties, applications, and
performance. Thus, let us introduce here the new state parameter – charge, q. At con-
stant temperature, by virtue of the approach described earlier in this chapter, we can
write:
6 1 Basic concepts

σ
σ ∂Gσ
dG = − Adγ + Σμi dni + γ, ni (1:15)
∂q

The last term describes Gibbs’ free energy (work at const. T), required for bringing a
charge q from infinity into the system.1 As we should remember from physics classes,
this is the definition of the electrical potential E. Therefore,

dGσ = − Adγ + Σμi dni σ + Edq (1:16)

Because simultaneously the integral form for Gibbs’ surface free energy is

Gσ = Σμi ni σ + E × q (1:17)

and therefore

dGσ = Σμi dni σ + Σni σ dμi + Edq + qdE, (1:18)

we finally get the relationship between the changes of surface tension, concentration
changes in the bulk of a solution, surface concentration of species “i” and the surface
charge of a metal electrode, σ Me:

dγ = −σ Me dE − ΣΓi dμi (1:19)

Before we go deeper into the models describing the structure of the interface between
the metallic electrode and electrolyte, we should place these efforts in a broader pic-
ture. First, we should stress that the metal/solution interface should be considered as
model interface, easy to control experimentally (e.g., by controlling the polarization of
the electrode), and the theory derived from the investigations of such an interface
should be useful also for other types of interfaces, including the nanostructured interfa-
ces and biointerfaces. But why the interfaces should be charged, is this process a spon-
taneous one? Yes, it is spontaneous, except for the case of external polarization. The
reasons for the appearance of a charge on the interfaces can be summarized below:
– external polarization (electrodes);
– adsorption and orientation of solvent dipoles;
– ionic adsorption from the solution;
– dissociation of surface functional groups
Of course, all these effects can occur simultaneously.

Essentially, one can say that there are no uncharged interfaces. The consequences of this
charge will be manifested in chapters that follow. Here, we will present the model of
metal/solution interface that allows us to get insight into the structure of the interfacial

 Since our charged phase (metal electrode) behaves like an ideal conductor, this charge will be accu-
mulated on its surface.
 1.1 Structure of interfaces 7

region, but more important from the point of view of applications – its utilization in
the construction and design of modern power sources and electrode processes.

1.1.1 Electrical double layer at interfaces: metal/electrolyte

What is the electrical double layer (e.d.l.)? It is a region of molecular dimensions at the
interface between the two phases/substances, in which the electric field is created (e.g.,
by polarizing an electrode or by dissociation of surface groups). Of course, both phases in
contact have to contain charged species (electrons, ions, or polar molecules).
In the e.d.l., charges of opposite sign attract themselves and have the tendency to ac-
cumulate at the interface. Finite sizes and solvation result in the separation of these par-
ticles. Charges of the same sign repel themselves leading to an unequal distribution of
opposite charges with respect to the charges of the same sign within the interfacial re-
gion. Taken together, these interactions generate the electric field in the interfacial region,
regardless of the nature of two phases in contact (with the proviso discussed above).
In order to describe quantitatively the profiles of potential and the distribution of
charges in the interfacial region, we will take advantage of the relation introduced
above for the metal/solution interface (eq. 1.19). For the sake of simplicity, let us as-
sume that we do not change the electrolyte concentration nor its content so that dμi = 0.
Then, the above equation can be simplified to

dγ = −σ Me dE (1:20)

Let us now focus on the model electrified interface of ideally polarizable electrode/aque-
ous electrolyte solution. By an ideally polarizable electrode, we will understand an elec-
trode that within a given potential range can only accumulate charge (being polarized
or charged) with no redox reaction (electron transfer across the interface). Changing its
polarization by dE, we also change the interfacial tension by dγ, with proportionality co-
efficient being the charge σMe, introduced onto the electrode surface (ideal conductor) as
a result of its polarization. The negative sign tells us immediately that the interfacial ten-
sion decreases with an introduction of charge onto the surface. This is intuitively under-
standable, because the charges of the same sign on the surface repel each other with
Coulomb forces, thus decreasing the cohesion interactions between the surface atoms.
Furthermore, one can predict that at zero surface charge, the surface tension will be the
largest. Such interfacial behavior has its further consequences, for example, in the elec-
trocatalysis (Chapter 4), corrosion (Chapter 3), or in the underpotential deposition (Chap-
ter 6), and will be discussed in the appropriate chapters. Here, we will continue to
develop a model describing the interfacial property responsible for charge storage and
electrical power generation.
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