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MMS210801 - 3 CREDITS

Electrochemistry

Department of Metallurgy and Materias Engineering
University of Indonesia
yunce@metal.ui.ac.id ivan@metal.ui.ac.id
Ir. Yunita Sadeli, Msc & Ahmad Ivan Karayan, ST, MEng
I:
A science studying the relationship between
chemical energy and electrical energy and the
rules of conversion of two energies.

II:
Electrochemistry is the study of solutions of
electrolytes and of phenomena occurring at
electrodes immersed in these solutions.
Definition of Electrochemistry
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Based on conduction and conductivity,
materials can be classified as:

Material Classification
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Conductor

Semiconductors

Insulator (dielectrics)

Conduction in Conductors
Electronic Conductor
Conduction in Conductor
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Depending on the type of charges involved
Ionic Conductor
Electronic Conduction
Found in all metals and in certain other
substances: carbon materials (graphite,
carbon black), oxides, and other inorganic
compounds (e.g. tungsten carbide)
Electronic Conduction
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The main topic of electrochemistry is
investigation of the properties of ionic
conductors and of electric circuits
containing ionic conductors, and
investigation of phenomena occurring
during passage of an electric current
through such circuits.
Ionic Conductors
Ionic Conductors
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Ionic Conductors
Also known as electrolytes.
Can be solid electrolytes (which is
naturally conductive) and other
substances which are not conducting but
produce ionic conduction after being
dissolved in water or other solvent (e.g.
electrolyte solution and weak electrolyte)
Ionic Conductor
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The crystallographic structure in solids with fixed positions for
atoms or ions restricts the free mobility of the ions. The ionic
conductivity observed in solid electrolytes is based on defects
and disorder in the crystallographic structure. One can
distinguish

(i) Crystal defectsdefects are formed during crystal growth.
(ii) Intrinsic disorderdefects are formed according to
temperature and partial pressure and can be described by
thermodynamics.
(iii) Extrinsic disorderdefects are formed by variation of the
composition of a mixed phase or doping.
(iv) Disorder in sub-lattices (quasi molten sub-lattices)these
types of materials are called super ionic conductors or fast ionic
conductors. The material develops a structure of conduction
channels within a network
Ionic Conductors
Ionic Conductance in Solids
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Intrinsic Disorder
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Yttria Stabilzed Zirconia in SOFC
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Electrolyte - A substance that conducts
electricity through the movement of ions.

Most electrolytes are solutions or molten salts, but
some electrolytes are solids and some of those
are crystalline solids. Different names are given
to such materials:
Solid Electrolyte
Fast Ion Conductor
Superionic Conductor
Solid Electrolytes
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So, what do electronic conductor of metal and solid
electrolyte have in common? And whats the difference
between them?
They exist in solid state
Metals
Conductivity Range = 10 S/cm < s < 10
5
S/cm
Electrons carry the current
Conductivity Increases linearly as temperature decreases (phonon scattering
decreases as T +)

Solid Electrolytes
Conductivity Range = 10
-3
S/cm < s < 10 S/cm
Ions carry the current
Conductivity decreases exponentially as temperature decreases (activated transport)
Electronic Conductor and Solid Electrolyte
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Application of Solid Electrolyte
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There are numerous practical applications, all based on electochemical
cells, where ionic conductivity is needed and it is
advantageous/necessary to use solids for all components.
Batteries
Fuel Cells
Gas Sensors



In such cells ionic conductors are needed for either the electrodes, the
electrolyte or both.
Electrolyte (Material needs to be an electrical insulator to
prevent short circuit)
Electrode (Mixed ionic and electronic conductivity is needed to
avoid open circuit)


Electrolyte
Anode
Cathode
Useful
Power
e
-

Solid Electrolyte - Defects
In order for an ion to move through a crystal it must hop from an
occupied site to a vacant site. Thus ionic conductivity can only
occur if defects are present. The two simplest types of point
defects are Schottky and Frenkel defects.
Schottky Defect
(i.e. NaCl)
Na
+
+ Cl
-
V
na
+ V
Cl

Frenkel Defect
(i.e. AgCl)
Ag
+
V
Ag
+ Ag
+
interstitial

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Ionic Conductors
The most common ionic conductors: aqueous
solution of acids, bases, and salts.
Ionic Conductor
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Acids, bases, and salts (i.e., electrolytes in the second sense of the
word) dissociate into ions when dissolved in water (or in other solvents).
This dissociation can be complete or partial.
The fraction of the original molecules that have dissociated is known as
the degree of dissociation, .
Substances that exhibit a low degree of dissociation in solution
are called weak electrolytes, whereas when the value of
comes close to unity we speak of strong electrolytes.

Ions in Electrolyte Solution
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Ionic halides - After melting, alkali halides consist exclusively of metal cations and
halide anions. These complexes are exclusively ionic. NaCl.
Ionic Melts
Ionic glasses - Glasses are amorphous substances consisting of a network former like
SiO2,B2O3, and P2O5, which have a strong tendency to form solid polymeric networks below
the glass temperature Tg instead of crystalline structures. In addition they usually contain a
network modifier like Li2O or Ag2O and can contain other oxides like Al2O3. The
conductivity is achieved by the addition of a doping salt, e.g., alkali halides. ionic
conducting glasses: 0.4 mole Ca(NO3)2 + 0.6 mole KNO3
Separation of the ions in an ionic crystal is also possible by thermal energy. At higher
temperatures the crystals melt which gives the ions a certain amount of free mobility.
While pure salts have relatively high melting temperatures, mixtures of different salts form
eutectic systems with considerably lower melting points.
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Ionic liquids - A new class of ionic melts. They consist of organic ions or a mixture of
organic and inorganic ions. An ionic liquid is a salt in which the ions are poorly coordinated,
which results in these solvents being liquid below 100C, or even at room temperature (room
temperature ionic liquids, RTIL's). At least one ion has a delocalized charge and one
component is organic, which prevents the formation of a stable crystal lattice.
They are liquid at temperatures between room temperature and 100 C.
They are inflammable and have high thermal stability.
Newly developed ionic liquids also have hydrophobic properties that allow handling in air.
They have a negligible vapor pressure.
Their large electrochemical potential window (Figure 1.6) allows electrochemical
processes that are not possible in aqueous electrolytes such as deposition of metals that
are not deposable in aqueous electrolytes.
Find an example of ionic liquid and give a concise description of it !!
Ionic Melts
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By mixing a polymer with a salt, one can form ionic-conducting
polymers. The polymer can react with the ionic components
partially dissociating the salt (polymer electrolytes)
Ionic Conductance in Polymers
An ionic-conducting polymer can also be prepared by mixing a
solution of an alkali salt in an organic solvent (gel forming
component/plasticizer) with a polymer, which forms a gel
polymer electrolyte.
The polymer itself can contain ionic groups in which case only
the counter ion is mobile and the polymer has ionic exchange
properties (ion exchangers).
The application of these materials in lithium batteries has led to
intensive interest in this class of materials.
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Some polymers with hetero-atoms
carrying free electron pairs have
solvating power to dissolve metal salts,
e.g., alkali halides. An example is LiClO4
dissolved in polyethylene oxide (PEO,
Figure 1.8). The polymer has a helix like
structure with oxygen atoms
coordinated to Li cations. The anions
stabilize the chain structure. The
polymer and the LiClO4 can form
different complexes. The polymer has
crystalline and amorphous regions. The
conductivity increases with an increase
in volume of the amorphous regions. A
reference point is the glass transition
temperature Tg (transition from
crystalline structure to amorphous
structure): the lower the glass
transition temperature, the higher the
conductivity at a given temperature.
Polymer Electrolytes
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The addition of gel-forming components
(plasticizers) to polymer electrolytes above)
produces gel like structures. Therefore, this
type of ion-conducting polymers can also be
described as gel polymer electrolytes.
Gel polymer electrolytes can also be
prepared, if a solution of a salt in an organic
solvent is added to a polymer matrix
(polyvinyl chloride, polyvinyl fluoride).
The solvent dissolves in the polymer matrix
and forms a gel like structure. The
conductivity as well as the current density
and rate of diffusion, etc., are determined
by the mobility of the solvated ions in the
polymer matrix.
The transport constants are again
proportional to the free volume in the
polymer.
Gel Polymer Electrolytes
Sulphur Lithium Ion Battery
Dye-Sensitized Solar Cell
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The representative substance of this type of polymer ionic conductors
is nafion.
This polymer consists of a porous perfluorated carbon matrix with
sulfonic acid groups. While the anion is fixed, the material shows high
cation conductivity and is of high chemical stability.
These materials are applied, for example, in membrane chlorine alkaline
electrolysis and in polymer electrolyte membrane (PEM) fuel cells.
Other types of fixed anions are carboxylic acid groups (weakly acid).
Examples for ion exchange polymer electrolytes with fixed cations and
anion conductivity are polymers with ternary amino groups (weakly
basic) or quaternary amino groups (strongly basic).
Ion Exchangers
Nafion is a copolymer of tetrafluoroethylene (Teflon) and perfluoro-3,6-dioxa-4-
methyl-7-octene-sulfonic acid. Like Teflon, Nafion is highly resistant to chemical
attack, but the presence of its exposed sulfonic acid groups confers unusual
properties. Sulfonic acid has a very high water-of-hydration, absorbing 13
molecules of water for every sulfonic acid group in the polymer. Consequently,
Nafion absorbs 22% by weight of water.
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Solids are mixed conductors that means electronic and ionic
charge carriers show mobility in the lattice. One speaks of
preferential ionic conductivity if the electronic transference
number is te < 0.01.
The electronic conductivity increases exponentially with the
temperature and, for oxides, depends on the partial pressure of
oxygen.
Materials with preferential ionic conductivity can be found only
in a certain temperature and pressure region.
Materials with comparable ionic as well as electronic
conductivity are called MIECs (mixed ionic electronic
conductors). These materials have become especially interesting
for applications. E.g Ce
0.8
Gd
0.2
O
1.9
.
Mixed Ionic and Electronic Conductance
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Faradays Law
Michael Faraday, a British chemist and physicist, studied the
decomposition of solutions of salts, acids and bases by electric current.
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Faradays Law
Faraday's law of electrolysis states that the
amount of any substance that is deposited or
dissolved in electrolysis is directly proportional to
the total passed electric charge.
It can be expressed as
m is the mass of the substance liberated at an electrode in grams
Q is the total electric charge passed through the substance
F = 96,485 C mol1 is the Faraday constant
M is the molar mass of the substance
z is the valency number of ions of the substance (electrons transferred per ion).
Note that M / z is the same as the equivalent weight of the substance altered..
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Coulometer
The silver coulometer and copper coulometer are
commonly used ones.

If one mole of silver, 107.870 g, is deposited on
the cathode of a silver coulometer, we will know
that the quantity of electricity passed through
the coulometer is 1 coulomb.
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In solids, current is carried by electrons
In solutions, current is carried by ions
The definition of transport number t is that current
carried by ion B divided by the sum of the current of all the
ions in solution, which is also called the transference
number of ion B.


c
n I Q
t
I I Q Q n
+ + +
+
+ + +
= = = =
+ + +
v
v v
Transport Numbers
a
n I Q
t
I I Q Q n

+ + +
= = = =
+ + +
v
v v
n
c
and n
a
are the amount of substance of positive ions
migrate out from anodic region and that of negative
ions migrate out from cathodic region respectively.
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Suppose the boundary moves a distant x
from AA to BB for the passage of Q
coulombs. All the ions, H
+
, passed
through the boundary AA.
The amount of substances transported is
then Q/F, of which t
+
Q/F are carried by
the positive ion. If the volume between
the boundaries AA and BB is V, and the
concentration of HCl is c, then
/ t Q F Vc
+
=
FVc
t
Q
+
=
Measurement of Transport Numbers by
Hittorf Method
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An electrolyte is a substance that
produces ions when dissolved in water
AB

A
+
+ B
-



The presence of these ions enhances
the electrical conductivity of the
solution

Electrolytes
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Strong electrolytes ionize completely
when dissolved in water
Addition of strong electrolyte leads to a
large increase in the electrical
conductivity of the solution
Examples: HNO
3
, HCl, NaOH and salts
produced by neutralization of a strong
acid and strong base
Strong Electrolytes
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Incomplete ionization when dissolved in
water
K
AB
(aq)
A
+
(aq)
+ B
-
(aq)


Addition of weak electrolyte in solution
leads to some increase in conductivity
Examples: weak acids and bases such as
CH
3
COOH

Weak and Non-Electrolytes
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Soluble in water but do not dissociate
Addition of non-electrolyte lead to no
increase in conductivity
Examples: ethanol (C
2
H
6
OH) and
Sucrose (C
12
H
22
O
11
)

Non-Elecrolytes
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Conductivity of Electrolyte Solution
NaCl
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Conductance and Conductivity
Conductance of a solution is the inverse of its resistance.
Resistance is measured in ohms, W. Conductance is expressed
as the reciprocal of ohms and is called the siemens, S (1S =
1W-1)

Resistance o l
A
where l is the distance between the electrodes and A is the
area of the electrodes
Resistance = l where is resistivity
A
l
A
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Conductance G in S


in equation is specific conductivity. In S m-1.

Molar conductivity (in S m2 mol-1)


where C is the molar concentration

1
G
R
=
s
A
G
l
k =
/
m
c k A =
Conductance and Conductivity
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Charge is carried in the solution by both
cations moving towards the cathode and
anions moving to the anode.
The molar conductivity is therefore a
combination of the molar conductivities of the
cation and anion:

m
= v
+

+
+ v
-

-

+
and
-
are respectively the ionic
conductivities of the cations and anions
v
+
and v
-
are the number of cations and anions
produced per mole of salt


Conductivity
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An alternating voltage is
applied sequentially to
attract and repel ions
from the
electrode/solution
interface. This allows
measurement of the
resistance of the
solution without
changing the nature of
the ions
Conductivity can be
determined if the cell
constant is known

Measurement of Conductivity
Electrode B
+
-
+
Half cycle 1
Half cycle 2
Half cycle 3
V
Time
Electrode A
V/Volts
-
-
+
+
+
+
+
+
-
-
-
-
- - -
- -
-
- - -
Electrode A
Electrode B
H.C.1
H.C.2
H.C.3
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Measurement of Conductivity
3 1
4
R R
R R
=
3 1
4
R R
R R
=
3
1 4
1 R
G
R R R
= =
cell
s
l
G G K
A
k = =
cell
s
l
K
A
=
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Concentration Dependence of
Molar Concentration
For strong electrolytes molar
conductivity decreases
slightly with increasing
concentration

For weak electrolytes, molar
conductivity is small at
moderate concentrations but
high at very low
concentrations. This is
because at low
concentrations the
proportion of dissociated
molecules is high.

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The conductivity and molar conductivity of
a saturated aqueous solution of silver
chloride are 3.4110
-4
Sm
-1
and
138.2610
-4
Sm
2
mol
-1
respectively at
25. The conductivity of the water used to
make the solution is 1.6010
-4
Sm
-1
at
the same temperature. Calculate the
solubility of silver chloride in water at 25
Exercise
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Model for SIngle Ion
Molar Conductivities
Z
+

-
+
V Volts; l metres
Electrical attraction
Viscous drag
The two forces acting on the ion are:
Electrical force = zeV
l
Viscous force = 6tavq
where v is the velocity and q is the viscosity
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The retarding force increases as the ion moves
faster. The ion in solution will reach as steady
velocity, then the forces of attraction and
repulsion balance each other
zeV = 6tavq
l
The molar conductivity of the ion is
o v o ze
(V/l) 6taq
conductivity should be larger for : small ions, highly
charged ions and solvents of low viscosity


Model for SIngle Ion
Molar Conductivities
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When considering the size of the ion the size of the hydration
sphere should be taken into account
Ions of same charge but smaller size will have higher electric
field at the surface, leading to a larger hydrations sphere and
thus larger effective size.
Potassium ion has higher conductivity in solution than
lithium ion but has a larger gas phase radii than lithium
Li
+
K
+

Hydration
Sphere
Model for SIngle Ion
Molar Conductivities
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H
+
and OH
-
ions are very small but they
have anomalously high conductivities,
this is because their conduction
mechanism is different to other ions

Other ions are pulled to the electrode
by coulombic attraction and move by
pushing aside solvent molecules
Ion Migration
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H
+
and OH
-
ions take advantage of the
hydrogen bonded nature of water. They can
induce re-organisation of hydrogen bonding to
affect rapid motion
Ion Migration
H + O - H | | | | | O - H | | | | | O - H | | | | | O - H
| | | |
H H H H
H - O - H | | | | | O - H | | | | | O - H | | | | | O H+
| | | |
H H H H
O - H | | | | | O | | | | | H - O | | | | | H O-
| | | |
H H H H
O- H -O | | | | | H - O | | | | | H - O
| | | |
H H H H
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Fro strong electrolytes, Kohlrausch observed that
Am decreased with concentration according to
the expression


m m
A c

= A A
Concentration Dependence of
Molar Concentration
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Kohlrausch discovered relations between the values of
for different electrolytes. For example







The difference in for pairs of salts having common ion is
always approximately constant.
2 -1
(KCl) 0.01499 S m mol
m

A =
2 -1
(LiCl) 0.01150 S m mol
m

A =
2 -1
3
(KNO ) 0.01450 S m mol
m

A =
2 -1
3
(LiNO ) 0.01101S m mol
m

A =
Law of the Independent Migration of Ions
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This behavior indicates that ions in an
extremely dilute solution migrate
independently. There is no interaction between
different ions. Therefore
2 -1
3 3
(KCl) (LiCl) (KNO ) (LiNO ) 0.00349 S m mol
m m m m

A A = A A =
2 -1
3 3
(KCl) (KNO ) (LiCl) (LiNO ) 0.00049 S m mol
m m m m

A A = A A =
, , m m m
v v

+ +
A = A + A
Law of the Independent Migration of Ions
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At 25
(NaAc) = 91.010-4 Sm2mol1
(HCl)=426.210-4 Sm2mol1
(NaCl)=126.510-4 Sm2mol1
What is the molar conductivity of HAc at
25?
Exercise
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