Electrochemistry

89

4. ELECTROCHEMISTRY

Electrochemistry is that part of chemistry which studies the interaction

between matter and electric field. It consists in two parts: ionic electrochemistry
and electrodic chemistry.
Ionic electrochemistry studies the appearance of the ions in solution, the
interactions between them or with other particles, the transport phenomena of ions:
diffusion, migration, conduction.
Electrodic electrochemistry studies what happened at the interface solid
solution: electrical double layer, electrode potential, galvanic cells, heterogenous
redox reactions, chemical sources of energy, corrosion and protection methods
against corrosion.
Electrochemical processes are important to be studied since electronics
deals with semiconductors, galvanic cells, electrochemical depositions on circuits
etc. This study includes the understanding of the main electrode processes, the
current distribution and reaction phenomena.

4.1. Electrolyte solutions. Electrolytic dissociation

Electrical electrolytes can be divided into:

1st degree electric conductors electronic conductors: metals,

semiconductors, alloys;

2nd degree electric conductors ionic conductors: electrolytes

as solutions or melted electrolytes.

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GENERAL CHEMISTRY

In the case of electronic conductors the main charge carrier are electrons
and passing an electric current does not lead to chemical modifications in the
material structure.
By definition, electrolytes are chemical species which dissolved in certain
solvents or melted down are able to generate ions. When an electric field is applied
to an electrolyte, the electric current flows, because ions in that particular
environment migrate to the oppositely charged electrodes in contrast to an
electronic conductor where the unique carriers are the electrons.
Electrolytes may be divided into true electrolytes and potential
electrolytes.
A true electrolyte has an ionic structure and forms in solid state ionic
lattice (ions are maintained in fixed positions). By solvating in water, the
electrostatic bonds are broken and free ions appear in solution.
Examples: NaCl, KCl, Al2(SO4)3, CuSO4, NiSO4, ZnSO4
H2 O

NaCl

Na+ + Cl-

H2 O

AgNO3

Ag+ + NO 3-

A potential electrolyte is a polar covalent molecule. The ions are

generated by reaction with the solvent.
Examples: HCl + H2O
NH3 + H2O

H3 O+
NH4+ + HO-

The process that may occur when a chemical compound is dissolved in a

solvent breaking up into two or more ions forming an ionic conducting solution is
called electrolytic dissociation. This process takes place before the action of
electric field and it is independent on it.
The equilibrium constant which characterizes the electrolytic dissociation
is called dissociation constant Kd.
Types of dissociations:
a) Dissociation of strong acids
H2SO4

2H+ + SO42-

Electrochemistry

91

Kd =

cH2 + cSO 2
4

cH 2 SO4

= Ka ;

[177]

The dissociation constant Ka is called the acidity constant

b) Dissociation of bases
Cu2+ + 2HO-

Cu(OH)2
Kd =

2
cHO
c
Cu 2+

cCu ( OH ) 2

= Kb ;

[178]

The dissociation constant Kb is called the basicity constant

c) Salt dissociation
Ni2+ + SO42-

NiSO4

Kd =

cNi2+ cSO2

[179]

cNiSO4

Not all the dissolved molecules are always dissociated. The ratio of
dissociated molecules at equilibrium and the total number of molecules in solution
is called degree of dissociation, .

dissociated molecules
100, %
dissolved molecules

[180]

The electrolytes with < 5 % are weak electrolytes (solutions of 0.1 n or

more diluted). The electrolytes with 5% < < 50 % are medium electrolytes and
the electrolytes with > 50 % are strong electrolytes. It is possible to have
electrolytes in which all molecules dissociate ( = 100 %).
Some electrolytes dissociate in several steps. Each step may have different
degree of dissociation:
H3PO4 + H2O
-

H2PO4 + H2O
2-

HPO4 + H2O
takes place in special conditions.

H3O+ + H2PO4+

H3O + HPO4
+

H3O + PO4

3-

2-

big
small
very small , the reaction

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GENERAL CHEMISTRY

d) Dissociation of weak electrolytes

Weak electrolytes could be:
-

organic acids CH3COOH, HCN

inorganic weak acids H2S, H2SO3

weak bases Al(OH)3, NH4OH

Let us consider the dissociation of a weak acid:

H + + A-

HA

Kd =

c H + c A

[181]

cHA

The number of dissociated molecules is equal to the molar

concentration of A- and H+ ions c A = c H + .
The number of dissolved molecules is equal to the initial molar
0
concentration of the acid cHA

cA
c

0
HA

cH +
0
cHA

[182]

At equilibrium:
0
0
0
(1 )
cHA = cHA
cHA
= cHA

[183]

Kd =

0
0
cHA
cHA
0
cHA
(1 )

[184]

Kd =

0
2cHA
(1 )

[185]

Equation [185] represents the Ostwalds Law or Law of dilution

If the dissociation constant Kd for a weak acids is known then it is
possible to calculate the degree of dissociation for some of their concentration:

0
K d K d2 + 4cHA
Kd
0
2cHA

or knowing Kd and one can calculate the concentration:

[186]

Electrochemistry
0
cHA
=

93

K d (1 )

[187]

e) Water dissociation
Pure water is a weak electrolyte and exhibits a very low electrical
conductivity.
H2 O

Kd =

H+ + HO-

c H + c HO
c H 2O

cH + cHO = K d cH 2O

[188]
[189]

The product of hydrogen ions (H+) concentration and hydroxide ions

(HO-) concentrations takes a constant value at a given temperature. It is called

ionic product of water, Kw.

K w = cH + cHO = 1014 (at 22C)

[190]

In pure water cH + = cHO = 107 iong/L.

One defines:

pH which is the decimal logarithms of the hydrogen ions

concentration, taken with (-) sign,:
pH = log cH +
[191]
The solutions with 0 < pH < 7 are acid solutions ( cH + > cHO ), the
solutions with pH = 7 are neutral solutions ( cH + = cHO ) and the solutions with
7 < pH < 14 ( cH + < cHO ) are basic solutions.
f) Dissociation of strong electrolytes
The strong electrolytes have the dissociation degree close to 1. To this
category belong all the salts, strong acids (HCl, H2SO4), strong bases (NaOH,
KOH).

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GENERAL CHEMISTRY

4.2. Electrical conductivity of the electrolytes

Electrical conductivity represents the substance property to conduct
electric charge (charge mobility). For all conductors the Ohm laws says: E = RI,
where E represents the applied voltage, R is the ohmic resistance, I is the current
intensity.

1st degree electric conductors

For the 1st degree electric conductors the ohmic resistance is R =

l
s

where

is the conductor resistivity, l is the conductor length and s is the section of the
conductor. The inverse of ohmic resistance is called electrical conductance, G. The
inverse value of the conductor resistivity is called conductivity or specific
conductivity, .
1
= G [-1] or [S] (Siemens)
R

[192]

[193]

2nd degree electric conductors

Conductivity, , is the conduction capacity of a volume of 1 cm3 of
electrolyte solution when subjected to an electric field equal to 1 V/cm. The
conductivity of the electrolytes is tens or hundred times smaller than the
conductivity of metals. At the same time the electrical conductivity of some weak
electrolytes as water or alcohols is a several orders of magnitude bigger than those
of dielectrics.
It is important to know the electrical conductivity in order to reduce the
electrical

energy

conductivity).

consumption

(using

electrolytes

with

higher

electric

Electrochemistry

95

Equivalent conductivity, , represents the conductivity of a volume of

electrolyte which contains ions of one equivalent gram dissociated substance. The
ions are located between the electrodes of a conducting cell while the distance
between the electrodes is 1 cm.
=

1000
c

[194]

where c is the concentration expressed in ion g/L.

The equivalent conductivity depends on concentration, degree dissociation
and charge mobility.

Kohlrausch's Square Root Law: For strong electrolytes sufficiently

diluted, the molar conductivity c of an electrolyte with concentration c is a linear
function of the its square

c . If 0 represents the molar conductivity at infinite

dilution and A represents a constant which is function on the valence of the salt
then:

c = 0 c

[195]

For weak electrolytes:

c
0

Kd =

[196]

2c
(Ostwald Law)
1

Kd =

2c c
0 ( 0 c )

[197]

Kohlrausch's Law on the independence of migrating ions: The molar

conductivity of an electrolyte equals the sum of the molar conductivities of the
cations and the anions; being the number of anions or cations:

= ++ +

[198]

It results that in electrolytes the contribution of each ion to the equivalent

conductivity is the same, and does not matter the chemical compound.

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GENERAL CHEMISTRY

4.3. Electrical charged interfaces

Interface represents a surface contact between two phases. Usually it is
thin and defined as a monoatomic layer.
Interphase represents a region with modified properties with respect to
those inside the phase. It is a region of at least two molecular diameters. Interphase
is a region between two phases. In this region the properties are not the same as in
each phase. The properties of this interphase region influenced and even dominate
the electrochemical reactions of the charge transfer.
Air
Interface

Interphase
Solution

Figure 24. Schematic representation of the interface and interphase

If the two phases contain charged particles (ions or electrons) than, as a

consequence of the rearrangements of these particles in the interphase region, the
interface is charged: the two phases are charged with equal, but opposite sign,
charges. The interphase region is electrically neutral.
In this way a double electric layer, similarly to a condensator, is formed. This
layer is characterized by a variation of electrical potential, as shown in figure 25.
Processes which influences the formation of a double layer:
-

agglomeration of the electrons at the metal surface as a consequence

of the fact that in this region the electrons could arrive to the exterior at
a distance larger than atomic ray. Negative charges of the metal attract
the positive ions from the solution or orient the dipoles;

Electrochemistry

97

specific adsorption of some ionic species of the solution at the

interface followed by the electrostatic attraction of the ions of opposite
sign from the solution;

oriented dipole adsorption at the interface;

transfer of the electrical charged particles through the interface

metal/own ions solution system M/Mz+.

Electrical
Potential
Phase I

Phase II

+
+
+
+

Distance

a)

b)

Figure 25 Schematic representation of the double electric layer (a) and the variation of
electrical potential at the double layer

4.3.1. Internal Potential, External Potential, Surface Potential

Electrode represents a system formed from different phases charged
electrically and being in contact.

Electrode potential is the difference in electrical potential of metal and

solution phases.
A phase conducting electric current is characterized by an internal

potential or Galvani potential, .

The internal potential is the electrostatic potential of one point within the
phase compared to the potential of one point which is placed at infinite in the

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GENERAL CHEMISTRY

uncharged vacuum. The internal potential is the work necessary to bring the
elementary charge from the infinity to inside the phase.
The internal potential has two distinct components. One is the Volta

potential, which is determined by the long range coulombic forces near the
electrode, and the surface potential, which is determined by the short range
effects of adsorbed ions and oriented water molecules:

=+

[199]

The Volta potential can be measured directly while the surface potential
cannot. Thus the Galvani potential can be only measured relative to a reference
electrode.

4.3.2. Equilibrium Electrode Potential

In order to establish the equilibrium conditions in electrochemical systems
M/Mz+ Gugenhein (1929) introduced the electrochemical potential i :

i = i + ziFI

[200]

where i represents the component; i represents the chemical potential, zi

the valence and i the equilibrium potential of the phase of ith component. F is the
Faraday constant; F = 96500 C/mol.

a) System M/Electrolyte solution

At equilibrium the electrochemical potential of the cations from solution
(s) is equal to the electrochemical potential of the cations from metal (m).

M =M M

z+

[201]

Si + zFS = Mi + zFM

[202]

z+

The equilibrium potential is:

= M S
=
But

1
(Si Mi)
zF

[203]
[204]

Electrochemistry

99

I = i0 +RT ln ai

[205]
th

where ai is the activity of the i ions. The activity represents the deviation
of the behaviour of electrolyte from the ideal solution, behaviour characterized by a
total dissociation.

i0 is the standard chemical potential.

=

RT aiS
1
ln
(Si0 Mi0) +
zF aiM
zF

[206]

For the metal (pure component) aiM =1

= 0 +

RT
ln aiS
zF

[207]

Equation [207] is called Nernst equation

is the electrode equilibrium potential

In this equation:

0 is the standard electrode potential electrode

equilibrium at p = 1 atm, t = 25 C and aiS = 1
R is the universal gas constant (J/mol K)
F is the Faraday constant
z is the number of electrons involved in given
electrochemical process.
b) Redox equilibrium
Ox + ze-

Red

Mz+ + ze-

= 0 +

RT
ln aM
zF

(Cu2+ +2e-

Cu)
[208]

z+

Or

Cu

2+

/ Cu

= 0Cu

2+

/ Cu

RT
ln aCu
zF

2+

[209]

By generalization:

Cu

2+

/ Cu

= 0Cu

2+

/ Cu

RT aox
ln
zF ared

[210]

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GENERAL CHEMISTRY

4.3.3. Types of electrodes

Reversible electrodes are divided in three types: 1st type electrodes, 2nd
type electrodes and 3rd type electrodes according to the metal and electrolyte
nature.

a) 1st type electrode

a1) The electrode Metal Ion (metal is introduced in its solution)
Mz+ +ze- (heterogenous reaction)

RT
ln aM z +
zF

M z+ / M = 0M z+ / M +

[211]

Examples: Cu/CuSO4, Zn/ZnSO4, Ni/NiSO4, Ag/AgNO3

a2) Gas electrode consists in an inert metal (platinum) immersed in a
solution which contains a gas dissolved (i.e. H2, O2 Cl2) at a given partial pressure
and ion of this gas (H+, HO-, Cl-) at a given concentration. The gas is partially
adsorbed on the platinum surface and establishes with its ions from solution a
chemical equilibrium. The Nernst expression for the electrode potential is given by:

= 0 +

RT aox
ln
zF ared

[212]

a21) Hydrogen electrode: (Pt) H2/H+ or (Pt) H2/HCl is characterized

by the following reactions:
H2(aq)

2H

H+ / H = H+ / H
0

or

2
RT aH +
+
ln
2 F pH 2

[213]

RT aH +
ln 1 / 2
F
pH 2

[214]

H + / H = 0H + / H +
2

2H+(aq) +2e-

By convention for standard conditions ( pH2 = 1atm, t = 25 C) and

aH + = 1 0H + / H = 0
2

Electrochemistry

101

H+ / H =

RT aH +
ln 1 / 2
F
pH 2

[215]

H + / H = 0.059 pH (for aH + 1; t = 25 C and pH2 = 1atm)

2

a22) Oxygen electrode: (Pt) O2/HO- or (Pt) O2/NaOH is formed

from oxygen introduced under pressure in an electrolyte which contains hydroxide
ions, HO-, (i.e. NaOH) and a platinum bare:
O2 + 2H2O + 4e-

2 / HO

= 0O
= O

2 / HO

2 / HO

2 / HO

4HO-

pO
RT
ln 4 2
4 F aHO

[216]

pO1/24
RT
+
ln
F
aHO

[217]

For pO2 = 1 atm and t = 25 C

2 / HO

= 0O

2 / HO

+ 0.059 lg aHO

a23) Chlorine electrode (Pt) Cl2/Cl-:

Cl2 + 2e-

2Cl-

Cl / Cl = 0Cl- / Cl +
2

RT pCl2
ln
2 F aC2l

[218]

b) 2nd type electrodes have the general form:

M/MX, XSuch types of electrodes consist of a metal (Ag, Hg) in direct contact
with an insoluble salt (or hardly soluble) of the above mentioned metal (AgCl,
Hg2Cl2). The whole system being immersed into a solution containing a soluble salt
of the anionic species involved (KCl).
The best known examples are the calomel electrode Hg/Hg2Cl2, KCl
and silver chloride electrode Ag/AgCl, KCl.
For the silver chloride electrode equilibrium reactions at the interface
are:

102

GENERAL CHEMISTRY

Ag+ + e-

Ag
Ag+ + Cl-

: Ag + Cl-

AgCl
AgCl + e-

The electrode potential for this 2nd type of electrode could be obtained
starting from the potential expression for a 1st degree electrode, considering for
instance the silver chloride electrode as 1st degree electrode: Ag/Ag+. The silver
ions activity is deduced from the product of solubility of AgCl:
PS = a Ag + aCl

a Ag + =

[219]

PS
aCl

[220]

Ag / AgCl , KCl = 0Ag / Ag + +

Ag / AgCl , KCl = 0Ag / Ag + +

c)

RT
ln a Ag +
F

P
RT
ln S
F
aCl

[221]
[222]

Redox electrodes consist in an inert metal immersed in a solution

which contains two substances able to pass from one in another by electronic
transfer. This electronic transfer is realized through the inert metal.
Examples:
Pt/Fe2+, Fe3+; Pt/Sn4+, Sn2+.
For the electrode Pt/Fe2+, Fe3+ the electrode reaction is:
Fe3+ +e-

Fe2+

and the electrode potential is:

Fe3+ / Fe2+ = 0Fe3+ / Fe2+ +

RT aFe3+
ln
F
aFe2+

Depending on the nature of ion which involved in the charge transfer

through the double electric layer there are:

Reversible electrodes with respect to the cation (ex. 1st type

electrodes);

Electrochemistry

103

Reversible electrodes with respect to the anion (ex. 2nd type of

electrodes);

Redox electrodes having only electronic transfer to the double

layer.

4.4. Electrochemical cells

4.4.1 Definition. Redox reactions. Electromotive force. Electrode
Potential measurement.
An electrochemical (galvanic) cell is a device used for creating an

electromotive force (voltage) and the electrical current from chemical energy of
the oxido reduction reactions.
The electrochemical cells are sources of direct current generated by the

redox reactions which take place spontaneously. The word redox summarized the
electrochemical reactions (reduction and oxidation)
The reverse process is the electrolysis, in which the chemical reaction takes
place due to the passing of the electric current.
Table 2 Comparison between electrochemical (galvanic) cells and electrolytic cells
Electrochemical cells

Electrolytic cells

Transform chemical energy in

electrical energy

Transform

electrical energy in

chemical energy

Oxidation reaction takes place

Oxidation reaction takes place at

at the anode which is symbolised

the anode which is symbolised by

by negative sign (-)

positive sign (+)

Reduction reaction takes place

at

the

cathode

which

symbolised by positive sign (+)

is

Reduction reaction takes place at

the cathode which is symbolised
by negative sign (-)

104

GENERAL CHEMISTRY

Any oxidation reaction takes always place in tandem with a reduction

reaction. By oxidation a substance looses electrons while by reduction a substance
gains electrons. The number of lost electrons is always equal to the number of
gained electrons. Per total, the process is neutral from the electrical point of view.
Example:
Zn2+ + 2e- oxidation reaction which takes place at the anode

Zn
Cu2+ + 2e-

Cu reduction reaction which takes place at the cathode

: Zn + Cu2+

Zn2+ + Cu the redox process (overall reaction)

A galvanic cell consists in:

two compartments or two half cells, each composed of an electrode

dipped in a solution of electrolyte. These half cells are designed to
contain the oxidation and reduction half reactions;

a porous barrier (salt bridge) preventing the spontaneous mixing of the

aqueous solution in each compartment, but allowing the migration of
ions in both directions in order to maintain electrical neutrality;

The two half-cells are also connected externally. In this way, electrons
provided by the oxidation reaction are forced to travel via an external circuit to the
site of the reduction reaction.
A galvanic cell is symbolized in the following way:
() M1/electrolyte1, aM

z+
1

// electrolyte2, aM

z+
2

/ M2 (+)

The fact that the reaction occurs spontaneously once these half cells are
connected indicates that there is a difference in potential energy between them.
This difference in potential energy is called electromotive force, emf, and is
measured in Volts.
Conventionally, the electromotive force is the difference between the
equilibrium potential of the positive electrode and the equilibrium potential of the
negative electrode.
E = e+ - e-

[223]

Electrochemistry

105

The electrode potential is determined by using commonly a reference

electrode. An electrochemical cell with a common reference electrode and the
electrode with unknown electrode potential is formed and the emf is measured.
Knowing the electrode potential of the reference electrode one can determins the
electrode potential for the metal.
Common reference electrode:

Hydrogen electrode ( 0H + / H = 0 V)

Mercury chloride (calomel) electrode ( 0cal = 0.242 V)

4.4.2. The Volta electrochemical series

Alessandro Volta arranged the metals in a series after their ability to form
ions in solution taking hydrogen as reference. In this way the electrochemical
series were obtained taking advantage of the fact that the metals are also arranged
in order of their standard electrode potentials (redox potentials). The most negative

values are placed on the left side of the electrochemical series, and the most
positive on the right side, respectively:
Li Mg Al Zn Fe Ni H Cu ... Ag ... Au
(-3.01) (-2.38) (-1.66) (-0.76) (-0.44) (-0.23) (0.00) (+0.34) (+0.79) (+1.42) , V

The electrochemical potential series has a special importance. After its

position in this series one can predict the chemical behaviour of metal in different
media (acid, basic or neutral).
Every metal replaces in its solutions the metals located on its right in the
electrochemical potential series.
Example: Al + CuSO4

Al2(SO4)3+Cu

The metals which are on the left side of hydrogen replace it in water and in
diluted acidic solutions while the metals placed on the right side do not.
Example 2Na + 2H2O

2NaOH + H2

106

GENERAL CHEMISTRY

Generally the metals placed on the left side of hydrogen are oxidized
relatively easy, react with acids and sometimes with water generating stable
combinations.
Theoretically the replacement of the hydrogen from water at pH = 7 by the
metals is a spontaneous reaction with release of hydrogen for the metals with
electrode potential less than 0.414 V.

= H0

/ H2

/ H2

RT aH
ln 1 / 2 ; H0
F
pH
+

/ H2

= 0, pH = 1atm
2

/ H2

=0,059 ( 7) = 0,414 V

The more a metal is on the left, the more active it is, and the more difficult
is to reduce it. This means its ionization capacity is larger.
The metals situated on the right side of the hydrogen, called also noble
metals, present a reduced chemical activity. They oxidize with difficulty and they
have a big tendency to pass from ions state in atomic state.
Example Cu2+ + 2e-

Cu

The electrochemical potential series reveal also that the electrochemical

potential depends on chemical nature of the metal and on its valence.
Example: 0Cu

2+

/ Cu

= + 0.344 V; 0Cu

/ Cu

= 0.521 V

4.4.3. Reversible and irreversible galvanic cells

a) Reversible galvanic cell Daniel Jacobi cell has the following
structure:
() Zn/ZnSO4//CuSO4/Cu (+)
With the following half reactions:
Anode ()

oxidation reaction: Zn

Cathode (+)

reduction reaction: Cu2+ + 2e-

Zn2+ + 2e-

: Zn + Cu2+
or Zn + CuSO4

Cu
Zn2+ + Cu
ZnSO4 + Cu

Electrochemistry

107

If to this device we apply a larger voltage, with opposite sign than emf then
we will transform the electrochemical cell into an electrolytic cell. In such cell the
reverse reactions will take place:
-

copper will be dissolved in CuSO4 solution

Cu

Cu2+ + 2e-

zinc will be deposed on Zn electrode

Zn2+ + 2e-

Zn

Conditions for a reverse cell:

-

when the circuit is open, no chemical reaction will occur;

cell reaction which takes place when a little bit higher external voltage
with respect to emf is applied should be the reverse of that which
appears when the cell produce voltage;

during the function the current should be not very high and the emf
should be constant.
b) Irreversible galvanic cell Volta cell has the following structure:
() Zn/H2SO4/Cu (+)

with the following half reactions:

Anode ()

oxidation reaction: Zn

Cathode (+)

reduction reaction: 2H+ + 2e-

Zn2+ + 2eH2

: Zn + 2 H+
or Zn + H2SO4

Zn2+ + H2
ZnSO4 + H2

It can be easily observed that the current will have the direction from
anode to cathode.
If we apply an external voltage, a little bit higher then emf and with
opposite sign the copper electrode will be dissolved (Cu
the hydrogen will be reduced on the zinc electrode (2H+ + 2ethe reverse reactions are not produced.
An electrochemical cell is irreversible if:

Cu2+ + 2e-) and

H2 ). So

108

GENERAL CHEMISTRY

there are chemical transformations even when the cell does not
produce current in open circuit;

the half reactions which occurs when the electrochemical cell is

transformed in electrolytic cell is not the reverse of that taking place
when the cell produces the current;

Electromotive force is decreasing quickly when cell produces current.

4.5. Applications of electrochemistry in electronics

Driven by the electronics industry, electrochemical technology has rapidly
evolved, finding increasing applications in microelectronics, batteries, sensors,
materials science, industrial fabrication, corrosion, microbiology, neurobiology and
medicine.
Semiconductors are probably the most used materials in electronics.
Electrochemical processes in semiconductors are practiced today in the fabrication
of microelectronics products. Electrochemical technology has been an integral part
of major advances in semiconductor technology of the 20th century. While, the
microelectronics industry is rapidly reaching maturity, its explosive start and
sustained growth has been partly enabled by the use of scalable electrochemical
processes.
Prior to the invention of the transistor and the birth of the semiconductor
industry, the field of electrochemistry was already very advanced with respect to
both theoretical understanding and industrial applications. Most semiconductors
materials for opto-electronic applications must be in the form of single crystals
with exceptional crystalline perfection and purity. Some semiconductors in
polycrystalline film or bulk form have also been found useful in a few applications,
the most important being low cost solar cells. This latter application has stimulated
much of the recent work on the electrolytic deposition of semiconductors materials.

Electrochemistry

109

Traditional macroscopic electrochemistry started 200 years ago, presenting

technological connection to energy technology and electrolysis. In the last 10
years, electrochemical nanotechnology has been favored and it is, in fact, a field for
fundamental science. As a link between these different fields, micro
electrochemistry

is

fast

growing

part

of

electrochemistry,

forming

interdisciplinary bridges to science and medicine. Figure 26 shows the

interdisciplinary character of electrochemical microsystems. These systems include
and develop the fundamental knowledge of electrochemistry, but in difference to
fundamental science.

Figure 26 Electrochemical microsystem technologies to five special topics of fundamentals,

galvanics, systems, analysis and biology. Many special subjects are located in between,
because they belong to various topics (J.W. Schultze)

System means a combination of two or more parts or devices. A single

microelectrode is essential for an electrochemical microsystem, but it represents
only a part of it. Due to the large applications, electrochemical technologies include
electrochemical processes.

When we talk about electrochemical system in

electronics, the scale ranges to micro domain. Micro limits the systems and
processes to the range below 1 mm in all three dimensions: x, y, z. This yields a

110

GENERAL CHEMISTRY

clear difference to the well known field of thin film technology which limits only
the vertical dimension (z). For example, the miniaturization to ultra microelectrode
of nm dimensions is in progress with common technologies.

Microgalvanics The technologies of microgalvanics are now well

established. Electrochemical Microsystems started in electronics with the invention
of the printed circuit board in the mm-range, but the dimensions were continuously
decreased due to the requirements of electronics. The dominating technology is
now lithography. The number of interconnections increased, and they had to be
miniaturized. While galvanic processes are applied in the nm-range for micro and
nano electronics, packaging in m dimensions is still a limiting factor.
Simultaneously, the development of the new processes opened up the
electrochemical mass production of micro mechanic and opto-electronic tools,
which now enhance the development of micro reactors for chemical synthesis,
mixers and other tools.

Microelectrodes and microcells

During the last year, large progress were unregistered in the process of
miniaturization of electrodes, that was not done without some problems coming from
mechanism of electrode production, sensitivity and insulation or leakage currents.
Microelectrodes successfully found their appliance in electroanalysis and studies of
nucleation and growth. Even in biological research, pH sensitive electrodes in glass
technology have been applied. The resolution measured by the tip is in atomic
dimensions, while the exposed electrode surface remains in the m range.
Another interesting direction in electrochemistry applied in the field of
electronics was the developing of small instrumentation market and software
intended for military and consumer applications. The only big time product
remains the pH-meter. To predict the future it is enough to take a look to
telecommunications, including the integration of video with computers, worldwide
wireless communications, advanced software development tools, and further
miniaturization of hardware by great integration of digital and analogue modules.
Even now we can use processor-based instrumentation to carry out an array of

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111

electrochemical techniques on a given sample. One of the most productive aspects

of this approach is the fact that multiple users can employ an electrochemical
workstation without interfering with each other.

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GENERAL CHEMISTRY