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Electrochemistry

Chapter 21

Electrochemistry and Redox
Oxidation-reduction: “Redox”
Electrochemistry:
study of the interchange between chemical
change and electrical work
Electrochemical cells:
systems utilizing a redox reaction to produce
or use electrical energy

Redox Review
Redox reactions: electron transfer processes
Oxidation:
Reduction:

loss of 1 or more egain of 1 or more e-

Oxidation numbers:imaginary charges
(Balancing redox reactions)

Oxidation Numbers (O.N.)
1.Pure element

O.N. is zero

2.Monatomic ion O.N. is charge
3.Neutral compound: sum of O.N. is zero
Polyatomic ion: sum of O.N. is ion’s charge
*Negative O.N. generally assigned to more
electronegative element

Redox Review
Redox reactions: electron transfer processes
Oxidation:
Reduction:

loss of 1 or more egain of 1 or more e-

Oxidation numbers:imaginary charges
(Balancing redox reactions)

Oxidation Numbers (O.N.)
1.Pure element

O.N. is zero

2.Monatomic ion O.N. is charge
3.Neutral compound: sum of O.N. is zero
Polyatomic ion: sum of O.N. is ion’s charge
*Negative O.N. generally assigned to more
electronegative element

Oxidation Numbers (O.N.)
4.Hydrogen
assigned +1
(metal hydrides, -1)
5.Oxygen
assigned -2
(peroxides, -1; OF2, +2)
6.Fluorine
always -1

Oxidation-reduction
Oxidation is loss of eO.N. increases (more positive)
Reduction is gain of eO.N. decreases (more negative)
Oxidation involves loss OIL
Reduction involves gain RIG

Redox
Oxidation is loss of ecauses reduction
“reducing agent”
Reduction is gain of ecauses oxidation
“oxidizing agent”

Oxidation Numbers (O.N.)
4.Hydrogen
assigned +1
(metal hydrides, -1)
5.Oxygen
assigned -2
(peroxides, -1; OF2, +2)
6.Fluorine
always -1

Oxidation-reduction
Oxidation is loss of eO.N. increases (more positive)
Reduction is gain of eO.N. decreases (more negative)
Oxidation involves loss OIL
Reduction involves gain RIG

Redox
Oxidation is loss of ecauses reduction
“reducing agent”
Reduction is gain of ecauses oxidation
“oxidizing agent”

Balancing Redox Reactions
1.

Write separate equations (half-reactions) for
oxidation and reduction

2.

For each half-reaction
a. Balance elements involved in e- transfer
b. Balance number e- lost and gained

3.To balance emultiply each half-reaction by whole numbers

Balancing Redox Reactions: Acidic
4.Add half-reactions/cancel like terms (e -)
5. Acidic conditions:
Balance oxygen using H2O
Balance hydrogen using H+
Basic conditions:
Balance oxygen using OHBalance hydrogen using H2O
6.Check that all atoms and charges balance

Examples
Acidic conditions:
MnO 4(aq)

2
Fe (aq)

acid



2
 Mn (aq)

3
Fe (aq)

Basic conditions:

Ag (s) 


CN (aq)

 O 2(g) 


 Ag(CN) 2(aq)

base



Types of cells
Voltaic (galvanic) cells:
a spontaneous reaction generates electrical energy

Electrolytic cells:
absorb free energy from an electrical source to
drive a nonspontaneous reaction

Common Components
Electrodes:
conduct electricity between cell and
surroundings
Electrolyte:
mixture of ions involved in reaction or
carrying charge
Salt bridge:
completes circuit (provides charge balance)

Electrodes
Anode:
Oxidation occurs at the anode
Cathode:
Reduction occurs at the cathode
Active electrodes: participate in redox
Inactive:
sites of ox. and red.

Voltaic (Galvanic) Cells

A device in which chemical energy
is changed to electrical energy.
Uses a spontaneous reaction.

17_360

e–

e–

e–

e–
Porous disk

Oxidation
e–

(a)

Reducing
agent

Anode

Reduction
Oxidizing
agent

(b)

e–

Cathode

When the circuit is completed by inserting the key in
the circuit, it is observed that electric current flows
through external circuit as indicated by the ammeter.
The following observations are made:

Therefore, the current flows from copper to zinc
N.B. The flow of electric current is taken opposite to
the flows of electrons

There observation can be explained as:
During the reaction, zinc is oxidized to Zn 2+ ions
which go into the solution. Therefore,
the zinc rod gradually loses its weight. The electrons
released at the zinc electrode move towards the other
electrode through outer circuit. Here, these are
accepted by Cu2+ ions of CuSO4 solution which are
reduced to copper.

The zinc electrode where electrons are released or
oxidation occurs s called anode while the copper
electrode where electrons are accepted or reduction
occurs is called cathode.

The two containers involving oxidation and reduction
half reactions are called half cells. The zinc rod
dipping into a ZnSO4 solution is oxidation half cell
and the copper electrode dipping into a CuSO 4
solution is reduction half cell

N.B. The galvanic cells which consists of the zinc rod dipping
into a ZnSO4 solution and the copper electrode dipping
into a CuSO4 solution is Daniell cell.
Its formula is:
Salt bridge and its function. It’s usually an inverted U-tube
filled with concentrated solution of inert electrolyte. The
essential requirements of electrolyte are:
a) The mobility of the anion and cation of the electrolyte
should be almost same.
b) The ions of the electrolyte are not involved in
electrochemical change.
c) The ions do not react chemically with the species of the
cell.

Generally, salts like KCl, KNO3, etc. are used. The seturated
solutions of these electrolytes are prepared in agar agar
jelly or gelatin. The jelly keeps the electrolyte in semisolid phase and thus prevents mixing.
The important functions of the salt bridge are:
a) Salt bridge completes the electrical circuit.
b) Salt bridge maintains electrical neutrality of two half cell
solution.
The accumulation of charges in the two half cells
(accumulation of extra positive charge in the solution
around the anode according to the realizing of Zn2+ in
excess and accumulation of extra negative charge in the
solution around the catode due to excess of SO42- ) is
prevented by using salt bridge, which provides a passage
for the flow of the charge in the internal circuit.

REPRESENTATION OF AN ELECTROCHEMICAL CELL

An electrochemical cells or galvanic cell consists of two
electrodes: anode and cathode. The electrolyte solution
containing these electrodes are called half cells.
The following conventions are used in representing an
electrochemical cell:
1. A galvanic cell is represented by writing the anode (where
oxidation occurs) on the left hand side and cathode (where
reduction occurs) on the right hand side.
2. The anode of the cell is represented by writing metal or
solid phase first and then the electrolyte (or the cation of
the electrolyte) while the cathode is represented by
writing the electrolyte first and then metal or solid phase.
3. The salt bridge which separates the two half cells is
indicated by two vertical lines.

Electrode Potential and E.M.F. of a galvanic cell
Electrode Potential
The flow of electric current in an electrochemical cell
indicates that a potential difference exists between two
electrodes.

If the metal has relatively high tendency to get oxidised, its
atom will lose electrons readily and form Cu2+ ions, which
go into the solution. The electrons lost on the electrode
would be accumulated on the metal electrode and the
electrode acquires a slight negative charge with respect to
the solution. Some of the Cu2+ ions from the solution will
take up electrons and become Cu atoms. After some time, an
equilibrium will be established as:

When such an equilibrium is attained, it results in separation
of charges (negative on the electrode with respect to the
solution).

Forming the double layer

Zn

1- metal
2 - solution

Similarly, if the metal ions have relatively greater
tendency to get reduced, they will take electrons
from the electrode. As a result, a net positive
charge will be developed on the electrode with
respect to the solution. This will also result into
separation of charges (positive on the electrode
with respect to the solution).
Due to separation of charges between the electrode
and the solution, an electrical potential is set up
between metal electrode and its solution.
The electrical potential difference set up between the
metal and its solution is known as electrode
potential.

The mechanism of the double layer forming
For example of the copper electrode is dipped into CuSO4
solution.
The chemical potential of copper’s ions in the metal and
in the solution is not equal. The chemical potential of
copper’s ions in the metal at the given temperature is
stable value, the chemical potential of copper’s ions in
the solution depends on the solution’s concentration.
If the at the given concentration of solution the chemical
potential of copper’s ions in the solution is greater than
the chemical potential of these ions in the metal . Then
at the dipping of the metal in the solution some quantity
of Cu2+ ions are hydrated and transferred on the metal
according to that positive charge forming on the metal’s
surface. Sulfate’s anions are attracted to metal’s surface,
they courses the negative charge. These processes cause
the double electrical layer and related with it the

Forming the double layer
Cu

+
-

+
+
+
+
+
+

-

(-)
- - - --CuSO4

The electrode potential may be of two types:
1. Oxidation potential:
The tendency of an electrolyte to lose electrons
or to get oxidised

2. Reduction potential. The tendency of an
electrode to gain electrons or to get reduced.

E.M.F. or Cell Potential of a Cell
The difference between the electrode potentials of the two
electrodes constituting an electrochemical cell is known as
electromotive force (e.m.f.) or cell potential of a cell. This
acts as a driving force for the cell reaction. The potential
difference is expressed in volts.

Therefore, the cell potential or e.m.f. arises from the difference
in the tendencies of the two ions to get reduced.
It is equal to the reduction potential for the substance that
actually undergoes reduction minus the reduction
potential of the substance that undergoes oxidation.

Thus, e.m.f. of a cell may be defined as the potential
difference between two electrodes of the cell when either no
or negligible current is allowed to flow in the circuit.

Standard electrode potential
Since a half cell in an electrochemical cell can work only in
combination with the other half cell and does not work
independently, it is not possible to determine the absolute
electrode potential of an electrode. We can, therefore, find
only the relative electrode potential.
This difficulty can be solved by selecting one of the electrodes
as a reference electrode and arbitrarily fixing the potential
of this electrode as zero. For this purpose, reversible
hydrogen electrode has been universally accepted as a
reference electrode. It is called standard hydrogen
electrode (S.H.E) or normal hydrogen electrode (N.H.E.)

Similarly, if the metal ions have relatively greater
tendency to get reduced, they will take electrons
from the electrode. As a result, a net positive
charge will be developed on the electrode with
respect to the solution. This will also result into
separation of charges (positive on the electrode
with respect to the solution).
Due to separation of charges between the electrode
and the solution, an electrical potential is set up
between metal electrode and its solution.
The electrical potential difference set up between the
metal and its solution is known as electrode
potential.

The mechanism of the double layer forming
For example of the copper electrode is dipped into CuSO4
solution.
The chemical potential of copper’s ions in the metal and
in the solution is not equal. The chemical potential of
copper’s ions in the metal at the given temperature is
stable value, the chemical potential of copper’s ions in
the solution depends on the solution’s concentration.
If the at the given concentration of solution the chemical
potential of copper’s ions in the solution is greater than
the chemical potential of these ions in the metal . Then
at the dipping of the metal in the solution some quantity
of Cu2+ ions are hydrated and transferred on the metal
according to that positive charge forming on the metal’s
surface. Sulfate’s anions are attracted to metal’s surface,
they courses the negative charge. These processes cause
the double electrical layer and related with it the

Forming the double layer
Cu

+
-

+
+
+
+
+
+

-

(-)
- - - --CuSO4

The electrode potential may be of two types:
1. Oxidation potential:
The tendency of an electrode to lose electrons or
to get oxidised

2. Reduction potential. The tendency of an
electrode to gain electrons or to get reduced.

E.M.F. or Cell Potential of a Cell
The difference between the electrode potentials of the two
electrodes constituting an electrochemical cell is known as
electromotive force (e.m.f.) or cell potential of a cell. This
acts as a driving force for the cell reaction. The potential
difference is expressed in volts.

Therefore, the cell potential or e.m.f. arises from the difference
in the tendencies of the two ions to get reduced.
It is equal to the reduction potential for the substance that
actually undergoes reduction minus the reduction
potential of the substance that undergoes oxidation.

Thus, e.m.f. of a cell may be defined as the potential
difference between two electrodes of the cell when either no
or negligible current is allowed to flow in the circuit.

Standard electrode potential
Since a half cell in an electrochemical cell can work only in
combination with the other half cell and does not work
independently, it is not possible to determine the absolute
electrode potential of an electrode. We can, therefore, find
only the relative electrode potential.
This difficulty can be solved by selecting one of the electrodes
as a reference electrode and arbitrarily fixing the potential
of this electrode as zero. For this purpose, reversible
hydrogen electrode has been universally accepted as a
reference electrode. It is called standard hydrogen
electrode (S.H.E) or normal hydrogen electrode (N.H.E.)

Standard electrode potential
Since a half cell in an electrochemical cell can work only in
combination with the other half cell and does not work
independently, it is not possible to determine the absolute
electrode potential of an electrode. We can, therefore, find
only the relative electrode potential.
This difficulty can be solved by selecting one of the electrodes
as a reference electrode and arbitrarily fixing the potential
of this electrode as zero. For this purpose, reversible
hydrogen electrode has been universally accepted as a
reference electrode. It is called standard hydrogen
electrode (S.H.E) or normal hydrogen electrode (N.H.E.)

Standard hydrogen electrode. It consists of platinum
wire sealed in a glass tube and has a platinum foil
attached to it. The foil is coated with finely divided
platinum and acts as platinum electrode. It is dipped
into an acid solution containing H + ions in 1 M
concentration (1M HCl). Pure hydrogen gas at 1
atmospheric pressure is constantly bubbled into
solution at constant temperature of 298K. The
surface of the foil acts as a site for the reaction.

Electrochemistry

Standard Potentials

• In a voltaic cell, current is produced when electrons flow externally
through the circuit from the anode to the cathode because of a difference
in potential energy between two electrodes in the electrochemical cell
• The flow of electrons in an electrochemical cell depends on
1.
2.
3.
4.

The identity of the reacting substances,
The difference in the potential
energy
The concentrations of the reacting
species, and
The temperature of the system

• The potential of the cell under standard conditions
(1 M soln, 1 atm for gases, or a pure solids, or
liquid) at 25ºC is called the standard cell
potential, Eºcell. • All Eº values are independent of
the stoichiometric coefficients for the half-reactions.

Electrochemistry
Constructing a Cell Diagram
• Because voltaic cells are cumbersome to describe in words, a
line notation called a cell diagram has been developed
• In a cell diagram
– the identity of the electrodes and the chemical contents of the
compartments are indicated by their chemical formulas, with the anode
written on the far left and the cathode on the far right;
– phase boundaries are shown by single vertical lines;
– the salt bridge, which has two phase boundaries, is shown by a double
vertical line;
Here’s a cell diagram for Zn/Cu cell:

Zn(s)| Zn2+(aq, 1M) || Cu2+(aq, 1 M) | Cu(s)
Anode

Salt Bridge

Cathode

The Zinc-Copper Cell

Cell components for the Zn-Cu cell are:
1. A metallic Cu strip immersed in 1.0 M copper (II) sulfate.
2. A metallic Zn strip immersed in 1.0 M zinc (II) sulfate.
3. A wire and a salt bridge to complete circuit
The cell’s initial voltage is 1.100 volts

Electrochemistry

Calculating Standard Cell Potentials

• The standard cell potential for a redox reaction, Eºcell, is a measure of the
tendency of the reactants in their standard states to form the products in
their standard states—it is a measure of the driving force for the reaction
(voltage)
• The standard cell potential is the reduction potential of the reductive
half-reaction minus the reduction potential of the oxidative halfreaction (Eºcell = Eºcathode – Eºanode).
• Calculations for the standard potential for the Zn/Cu cell represented by
the cell diagram:
Zn(s) | Zn2+(aq, 1 M) || Cu2+(aq, 1M) | Cu(s)
Cathode: Cu2+(aq) + 2e–  Cu(s)
Anode:

Zn(s)  Zn2+(aq, 1M) + 2e–

Eºcathode =

0.34 V

Eºanode = + 0.76 V

Overall: Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
Eºcell = Eºcathode – Eºanode =

1.10 V

The Copper - Silver Cell
Cell components:

1.A Cu strip immersed in 1.0 M copper (II) sulfate.
2.A Ag strip immersed in 1.0 M silver (I) nitrate.
3.A wire and a salt bridge to complete the circuit.

The initial cell voltage is 0.46 volts.

The Copper - Silver Cell
• Calculations for the standard potential for the Zn/Cu cell
represented by the cell diagram:
Cu(s) | Cu2+(aq, 1 M) || Ag+(aq, 1M) | Ag(s)
Cathode: 2Ag+(aq) + 2e–  2Ag(s)
Eºcathode = 0.80 V
Anode:
Cu(s)  Cu2+(aq, 1M) + 2e– Eºanode = – 0.34 V
Overall: 2Ag(s)+Cu2+(aq)  2Ag+(aq)+Cu(s)
Eºcell = Eºcathode – Eºanode = 0.46 V

• Compare the Zn-Cu cell to the Cu-Ag cell
– The Cu electrode is the cathode in the Zn-Cu cell.
– The Cu electrode is the anode in the Cu-Ag cell.

• Whether a particular electrode behaves as an anode or as a
cathode depends on what the other electrode of the cell is.

Electrochemistry
• These experimental facts demonstrate that Cu2+ is a stronger oxidizing agent
than Zn2+.

– In other words Cu2+ oxidizes metallic Zn to Zn2+.
• Similarly, Ag+ is is a stronger oxidizing agent than Cu2+.

– Because Ag+ oxidizes metallic Cu to Cu 2+.
• If we arrange these species in order of increasing strengths, we see that:

Electrochemistry
• To measure relative electrode potentials, we must establish an
arbitrary standard.
• That standard is the Standard Hydrogen Electrode (SHE).
– The SHE is assigned an arbitrary voltage of 0.000000… V
• The potential of a half-reaction measured against the SHE under
standard conditions is called the standard electrode potential for that
half-reaction.

Standard hydrogen electrode (SHE)
— consists of a strip of platinum wire
in contact with an aqueous solution
containing 1 M H+, which is in
equilibrium with H2 gas at a pressure
of 1 atm at the Pt-solution interface

The Zinc-SHE Cell
• Calculations for the standard potential for the Zn/Cu cell
represented by the cell diagram:
Zn(s) | Zn2+(aq, 1 M) || H+(aq, 1M) | H2(g)
Cathode: 2H+(aq) + 2e–  H2(g)
Eºcathode = 0.00 V
Anode:
Zn(s)  Zn2+(aq, 1M) + 2e– Eºanode = + 0.76 V
Overall: Zn(s)+ H+(aq)  H2(g) + Zn(s)
Eºcell = 0.76 V
Eºcell = Eºcathode – Eºanode = 0.00 – (–.76) = 0.76 V

• The cathode is the Standard Hydrogen Electrode.
– In other words Zn reduces H+ to H2.

• The anode is Zn metal.
– Zn metal is oxidized to Zn2+ ions.

The Copper-SHE Cell

The cell components are:
1. A Cu strip immersed in 1.0 M copper (II) sulfate.
2. The other electrode is a Standard Hydrogen Electrode.
3. A wire and a salt bridge to complete the circuit.
The initial cell voltage is 0.34 volts.

The Copper-SHE Cell
• Calculations for the standard potential for the Zn/Cu cell
represented by the cell diagram:
Cu(s) | Cu2+(aq, 1 M) || H+(aq, 1M) | H2(g)
Cathode: 2H+(aq) + 2e–  H2(g)
Eºcathode = 0.00 V
Anode:
Cu(s)  Cu2+(aq, 1M) + 2e– Eºanode = + 0.34 V
Overall: Cu(s)+ 2H2+(aq)  H2(g) + Cu(s)
Eºcell = 0.34 V
Eºcell = Eºcathode – Eºanode = 0.00 – (–.34) = 0.34 V

• In this cell the SHE is the anode
– The Cu2+ ions oxidize H2 to H+.

• The Cu is the cathode.
– The Cu2+ ions are reduced to Cu metal.

It may be noted that it is not always convenient to use
standard hydrogen electrode as reference electrode
because of experimental difficulties in its
preparation and use.

N.B. The standard electrode potentials given in the
following table are measured in their standard states
when the concentration of the electrolyte solutions are
fixed as 1M and temperature is 298 K.

Application of the Electrochemical
(electromotive) series:
1. Relative strengths of oxidising and reducing
agents.
The substances which have lower reduction potentials
are stronger reducing agents while have higher
reduction potentials are stronger oxidations agent.
2. Calculation of the E.M.F. of the cell.
E0cell = E0(cathode) - E0(anode)

3. Predicting feasibility of the reaction.
In general, a red-ox reaction is feasible only if the
species to release electrons must have lower
reduction potential as compared to the species
which is to accept electrolytes.
4. To predict whether a metal can liberate
hydrogen from acid or not.
In general, only those metals can liberate hydrogen
from the acid which have negative values of
reduction potentials , - E0 values.

Uses of Standard Electrode Potentials
• Use standard electrode potentials to predict whether an electrochemical
reaction at standard state conditions will occur spontaneously.
• In solution, will aqueous dichromate ions, Cr2O72-, oxidize aqueous I- ions
to aqueous iodine, I2, or will aqueous I- ions oxidize aqueous Cr3+ to
aqueous dichromate ions, Cr2O72-?
• Steps for obtaining the equation for the spontaneous reaction.
1.
Choose the appropriate half-reactions from a table of standard
reduction potentials.
2.
Write the equation for the half-reaction with the more positive E 0
value first, along with its E0 value.
3.
Write the equation for the other half-reaction as an oxidation with
its oxidation potential, i.e. reverse the tabulated reduction halfreaction and change the sign of the tabulated E 0.
4.
Balance the electron transfer.
5.
Add the reduction and oxidation half-reactions and their potentials.
This produces the equation for the reaction for which E 0cell is
positive, which indicates that the forward reaction is
spontaneous. Remember potentials are work functions and are not

The Effect of Concentration on Cell Potential:
The Nernst Equation
• Standard electrode potentials, those compiled in appendices, are determined at
thermodynamic standard conditions.
• Reminder of standard conditions.

Figure 21.11A

The relation between Ecell and log Q for the zinccopper cell.

If the reaction starts with [Zn2+] < [Cu2+] (Q < 1), Ecell is higher than the
standard cell potential.
As the reaction proceeds, [Zn2+] decreases and [Cu2+] increases, so
Ecell drops. Eventually the system reaches equilibrium and the cell can
no longer do work.

21-73

Thermodynamic calculations
Free Energy and Cell Potential
0

wmax  G   nFE
n:
F:

number of moles of eFaraday’s constant
96485 C
mol of e-

0

G0, E0, and K
0

G   RTlnK   nFE

RT
so E 
lnK
nF
0

At equilibrium: G0 = 0 and K = Q
At 298 K:

0.0592
E 
logK
n
0

0

Nernst Equation
Under nonstandard conditions
0

G  G  RTlnQ
0

 nFE   nFE  RTlnQ

E cell

RT
E 
lnQ
nF

298K
E cell

0.0592
E 
lnQ
n

0

0

Dependence of electrode and cell potentials on
concentration: Nernst equation
The electrode potentials depend on the concentration of the
electrolyte solutions.

or

E  E0 

0.059
log [ Mn  (aq) ]
n

Nerst equation
ЕOx / Re d  Е

0
Ox / Re d

RT

ln a
nF

RT
2.3
 0.059, that
F

ЕOx / Re d  Е

0
Ox / Re d

0.059

lg a
n

In general, for an electrochemical cell reaction:
ne 

aA  bB    cC  dD
The Nerst equation may be written as:

The value of a, b, c, d and n are obtained from the balanced
cell reactions.
N.B. It must be remembered that while writing the Nerst
equation for the overall cell reaction, the log term is the
same as the expression for the equilibrium constant for the
reaction. However, some books use the expression in the
reverse form as the expression for the equilibrium constant
but, sign after E0 is changed.

Equilibrium constant from Nernst equation
The e.m.f. of the cell may be used to calculate the
equilibrium constant for the cell reaction. At
equilibrium, the electrode potentials of the two
electrodes become equal so that e.m.f. of the cell is
zero. Consider the following redox reaction:

Significance of Kc. The value of Kc gives the extent of
the cell reaction. If the value of Kc is large, the reaction
proceeds to large extent.

Electrochemical cell and free energy
In electrochemical cells, the chemical energy is
converted into electrical energy. The cell potential is
related to free energy change. In an electrochemical
cell, the system does work by transferring electrical
energy through an electric circuit.

Where
is the standard free energy for the reaction.
Significance. The above equation helps us to predict the
feasibility of the cell reaction. For a cell reaction to be
spontaneous,
must be negative. This means that E must
be positive for a spontaneous cell reaction.

The gas-ion electrode (Standard hydrogen electrode)
Hydrogen electrode that works at the following conditions:
aH = 1, p = 101,3 kPa, T = 250C = 298K is called standard.
H+

Electrochemical potential of this electrode depends on
the hydrogen ions concentration. However the
standard potential of this electrode equals o and the
valency of hydrogen equals 1 (n=1) Nernst equation
is:
Ecell = 0,059 log [H+] = - 0,059 pH
Measuring of pH to use potentiometric method of the
determination of hydrogen ions concentration.
This method is based on the measuring of e.m.f of
the cell which consists of the reduction electrode
(calomel) and the electrode which has dependence
on the hydrogen ions concentration (gas-ion
electrode, glass electrode, quinonhydrone electrode

2. In the metal-insoluble salt-anion electrode, а metal is in
contact with one of its insoluble salts and also with а
solution containing the anion of the salt.

0.059
E E 
log a A z
n
0

An example is the so-called silver - silver chloride electrode,
written as а cathode as:
Cl-(aq)  AgCl(s)  Ag(s)
for which the cathode half-reaction is:
AgCl (s) + е-  Ag(s) + Cl- (aq)

EAg,AgCl | Cl- = E0Ag+/AgCl - 0.059 lg aClE0Ag+/AgCl = 0,2224

Silver - silver chloride electrode

Ag, is covered by the layer of nonsoluble AgCl
КCl solution

KCl, AgCl | Ag

Calomel electrode consists of the mercury and
calomel past that is dipped in potassium chloride
solution. It is often used as a reference electrode to
determine the standard electrode potential ( more
often than hydrogen electrode). Its scheme is:
Cl-|Hg2Cl2, Hg
The half reaction is:
Hg2Cl2 + 2e  2Hg + 2ClEcell = E0 - 0.059 lg aClAs a rule to use the calomel electrodes that contain
0,1 M, 1 M and saturated solution of potassium
chloride. Their standard potential at 298K equal;
0,337; 0,2801; 0,2412 V.

3. An inert oxidation-reduction electrode
It consists of а strip, wire, or rod of an inert materiel (Pl, Au,
Ir…) in contact with а solution, which contains ions of а
substance is two different oxidation states (oxidation and
reduction form). The difference between general metal
electrode and ox-red electrode is that ox/red electrode does
not take place in ox-red reaction which exist in solution but is
the electrons conductor. For example: Pt| Sn2+, Sn4+ or Pt| Fe2+,
Fe3+
a
0.059
E  E0 
log Red
n
a Ox
Ox +ze → Red
There are two types of ox-red electrodes:
1.Simple: Fe2+, Fe3+ | Pt Fe3+ + e → Fe2+
a Fe 2
0.059
0
E E 
log
n
a Fe3

Scheme of ox-red electrode
(the third reference electrode)
Pt

Fe3+ , Fe2+ | Pt
Fe3+ + e = Fe2+

FeCl3 + FeCl2
E Fe3 / Fe2  E

0
Fe3 / Fe 2

 0.059 lg

aFe3
aFe2

2. Complex ox-red electrode there is changing the charge and
the composition of the ions
Mn2+, MnO4-, H+ | Pt MnO4- + 8H++5e→Mn2++4H2O
Example is quinonhydrone electrode.
It is prepared by the platinum strip or wire which is contained
in the glass tube. The electrode is dipped in the solution
with unknown pH that is needed to determine and to add
some quinonhydrone’s crystalls in this solution.
Quinonhydrone is a crystalline product which consists of
quinone (benzoquinone) С6Н4О2 and hydroquinone
C6H4(OH)2. It is less solubility in water and decomposes
into quinone and hydroquinone in the solution. In the
saturated solution equal molar mixture of quinone and
hydroquinone is formed.

Quinonhydrone electrode
(the third reference electrode)
С6Н4О2, С6Н4(ОН)2, H+ | Pt
С6Н4О2 + 2Н+ + 2е = С6Н4(ОН)2

Ecell

aC6 H 4 (OH ) 2
0.059
E 
lg
2 
2
аC6 H 4O2  а Н
0

Including that the activity of
quinone and hydroquinone is equal
in the seturated solution, we have

Ecell  E  0.059 lg aH 
0

Quinonhydrone

The scheme of quinonhydrone cell
with one electrolyte
Pt, Н2 | quinhydr, H+ | KCl | KCl,Hg2Cl2| Hg

Ecell = E quinhydr - Ecalomel

The glass electrode for pH measurements. The cell consists of
a glass indicator electrode and а saturated calomel reference
electrode, both immersed in the solution whose pH is to be
determined. The indicator electrode consists of а thin, рНsensitive glass membrane sealed onto one end of а heavywalled glass or plastic tube. А small volume of dilute
hydrochloric acid saturated with silver chloride is contained in
the tube (in some electrodes this solution is а buffer containing
chloride ion). A silver wire in this solution forms а silver/silver
chloride reference electrode, which is connected to one of the
terminals of а potential-measuring device. The calomel
electrode is connected to the other terminal.
Show that the system contains two reference electrodes: (1) the
external – calomel electrode and (2) the internal silver/silver
chloride electrode. Although the internal reference electrode is
part of the glass electrode, it is not the pH-sensing element.
Instead, it is the thin glass membrane at the tip of the electrode
that responds to pH.

The make the cell with glass and calomel electrodes
and measuring its e.m.f can be determined pH of
solution.

E glass  const  0.059 lg a Na 
glass electrode’s constant which is depended on the
electrode nature. The constant is fined according to the
graph which is plotted between the Ecell and pH
ordinates.

Combination pH electrode (ref + ind)

Fig. 23-3 (p.666) Glass pH electrode

The mechanism of the diffusion
potential
HCl 1 н

H+
ClEcell

u Kt   u An 0.059 a1

lg
u Kt   u An n
a2

where a1 > a2

HCl 0.1 н
-

+
+
+
+
+
+
+
+
+

The scheme of concentrated cell
_

+

(+)

Ag | AgNO3 || AgNO3 | Ag(-)
C

1

>

C

2

Ecell = E2 Ag+/Ag – E1 Ag+/Ag =
= 0.059 lg (a2 / a1)
NO3AgNO3, C2

AgNO3, C1

The electric circuit with transfer and without it
The electric circuit without transfer is when the
electrodes are dipped in one solution.
Examples: Pt|H2|HCl|AgCl, Ag – hydrogen-silversilver chloride electrode;
Pb | PbSO4 || H2SO4(aq) | PbO2 | Pb – the lead storage
battery
The electric circuit with transfer is when the
electrodes are dipped in different solution which
contact with each other.
Examples: Zn|ZnSO4||CuSO4|Cu – Daniell cell
Pt|H2|HCl||KCl|Hg2Cl2,Hg – hydrogen-calomel cell

Concentration Cells
. . . a cell in which both compartments
have the same components but at
different concentrations

17_366

e–
e–
Ag

e–
Porous
disk

0.1 M Ag +

0.1 M NO 3
Anode

e–
Ag

1 M Ag +

1 M NO 3
Cathode

17_369

Reference solution of
dilute hydrochloric acid

Silver wire coated with
silver chloride

Thin-walled membrane

Concentration Cell
Cell potential depends on concentration.
Concentration Cell is a cell in which both
compartments have the same components
but at different concentrations.
The difference in concentration is the only
factor that produces a cell potential and
the voltages are typically small.

Figure 17.9 A Concentration Cell That Contains a Sliver Electrode and Aqueous Silver Nitrate in Both Compartments

Concentration Cells
A concentration cell exploits the effect of concentration
changes on cell potential.
The cell has the same half-reaction in both cell
compartments, but with different concentrations of
electrolyte:
Cu(s) → Cu2+(aq; 0.10 M) + 2e[anode; oxidation]
Cu2+(aq; 1.0 M) → Cu(s)
[cathode; reduction]
Cu2+(aq; 1.0 M) → Cu2+(aq; 0.10 M)

As long as the concentrations of the solutions are
different, the cell potential is > 0 and the cell can do work.

21-

Figure 21.12 A concentration cell based on the Cu/Cu2+ half-reaction.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Oxidation half-reaction
Cu(s) → Cu2+(aq, 0.1 M) + 2eReduction half-reaction
Cu2+(aq, 1.0 M) + 2e- → Cu(s)
Overall (cell) reaction
Cu2+(aq,1.0 M) → Cu2+(aq, 0.1 M)

21-

Ecell > 0 as long as the half-cell
concentrations are different.
The cell is no longer able to do work
once the concentrations are equal.

Sample Problem 21.7

Calculating the Potential of a Concentration
Cell

PROBLEM: A concentration cell consists of two Ag/Ag+ half-cells. In
half-cell A, the electrolyte is 0.0100 M AgNO3; in half-cell
B, it is 4.0x10-4 M AgNO3. What is the cell potential at
298.15 K?
PLAN: The standard half-cell potentials are identical, so E°cell is
zero, and we find Ecell from the Nernst equation. Half-cell A
has a higher [Ag+], so Ag+ ions are reduced and plate out on
electrode A, which is therefore the cathode. In half-cell B, Ag
atoms of the electrode are oxidized and Ag+ ions enter the
solution. Electrode B is thus the anode. As for all voltaic cells,
the cathode is positive and the anode is negative.

21-

Sample Problem 21.7
SOLUTION: The [Ag+] decreases in half-cell A and increases in halfcell B, so the spontaneous reaction is:
Ag+(aq; 0.010 M) [half-cell A] → Ag+(aq; 4.0x10-4 M) [half-cell B]
Ecell = E°cell = 0.0 V -

21-

+
0.0592 V log [Ag ]dil
[Ag+]conc
1

4.0x10-4
0.0592 log
0.010

= 0.0828 V

Figure 21.13

Laboratory measurement of pH.

The operation of a pH meter illustrates an important application of
concentration cells. The glass electrode monitors the [H +] of the
solution relative to its own fixed internal [H+].

An older style of pH meter
includes two electrodes.

21-

Modern pH meters use a
combination electrode.

Table 21.3 Some Ions Measured with Ion-Specific Electrodes

21-

Species Detected

Typical Sample

NH3/NH4+

Industrial wastewater, seawater

CO2/HCO3-

Blood, groundwater

F-

Drinking water, urine, soil, industrial
stack gases

Br-

Grain, plant tissue

I-

Milk, pharmaceuticals

NO3-

Soil, fertilizer, drinking water

K+

Blood serum, soil, wine

H+

Laboratory solutions, soil, natural
waters

Electrochemistry
Commercial Galvanic Cells
• Galvanic cells can be self-contained and portable and can
be used as batteries and fuel cells
1. A battery (storage cell) is a galvanic cell (or a series of galvanic
cells) that contains all the reactants needed to produce electricity.
2. A fuel cell is a galvanic cell that requires a constant external
supply of one or more reactants in order to generate electricity.

Electrochemistry
• Two basic kinds of batteries
1. Disposable, or primary, batteries in which the electrode reactions are
effectively irreversible and which cannot be recharged
2. Rechargeable, or secondary, batteries, which form an insoluble product
that adheres to the electrodes; can be recharged by applying an electrical
potential in the reverse direction, which temporarily converts a
rechargeable battery from a galvanic cell to an electrolytic cell

• Major difference between batteries and galvanic cells is that
commercial batteries use solids or pastes rather than solutions as
reactants to maximize the electrical output per unit mass

The Dry Cell



One example of a dry cell is flashlight and radio batteries.
The cell’s container is made of zinc which acts as an electrode.
A graphite rod is in the center of the cell which acts as the
other electrode.
The space between the electrodes is filled with a mixture of:
1. ammonium chloride, NH4Cl
2. manganese (IV) oxide, MnO2
3. zinc chloride, ZnCl2
4. and a porous inactive solid.

Secondary Voltaic Cells

• Secondary cells are reversible, rechargeable.
• The electrodes in a secondary cell can be regenerated by the
addition of electricity.
– These cells can be switched from voltaic to electrolytic cells.
• One example of a secondary voltaic cell is the lead storage or car
battery.

The Lead Storage Battery
• In the lead storage battery the electrodes are two sets of lead alloy
grids (plates).
• Holes in one of the grids are filled with lead (IV) oxide, PbO2.
• The other holes are filled with spongy lead.
• The electrolyte is dilute sulfuric acid.

The Lead Storage Battery
• Provides the starting power in automobiles and boats; can be discharged and
recharged many times
• The Lead Acid Storage Battery is an example of a very successful recylcing
program.
• The anodes in each cell of this rechargeable battery are plates or grids of lead
containing spongy lead metal, while the cathodes are similar grids containing
powdered lead dioxide, PbO2
• The electrolyte is an aqueous solution of
sulfuric acid
• The value of Eº for such a cell is 2 V;
connecting three cells in series produces
a 6-V battery, and a typical 12-V car
battery contains six of these cells
connected in series.

The Lead Storage Battery
• Diagram of the lead storage battery.

Batteries
• Lithium-iodine battery
– Water-free battery
– Consists of two cells separated by a
metallic nickel mesh that collects
charge from the anodes
– The anode is lithium metal, and the
cathode is a solid complex of 2
– Electrolyte is a layer of solid Li that
allows Li+ ions to diffuse from the
cathode to the anode
– Highly reliable and long-lived
– Used in cardiac pacemakers, medical
implants, smoke alarms, and in
computers
– Disposable

The Nickel-Cadmium (Nicad) Cell
• Nicad batteries are the rechargeable cells used in calculators,
cameras, watches, etc.
• A water-based cell with a cadmium anode and a
highly oxidized nickel cathode
• This design maximizes the surface area of the
electrodes and minimizes the distance between
them, which gives the battery both a high
discharge current and a high capacity
• Lightweight, rechargeable, and high capacity
but tend to lose capacity quickly and do not
store well; also presents disposal problems
because of the toxicity of cadmium

Fuel Cells
• A galvanic cell that requires an external supply of reactants
because the products of the reaction are continuously removed
• Does not store electrical energy but allows electrical energy to
be extracted directly from a chemical reaction
• Have reliability problems and are costly
• Used in space vehicles

Hydrogen is oxidized at the anode.
Oxygen is reduced at the cathode.

Electrochemical Processes in Batteries
A battery consists of self-contained voltaic cells arranged
in series, so their individual voltages are added.
A primary battery cannot be recharged. The battery is
“dead” when the cell reaction has reached equilibrium.
A secondary battery is rechargeable. Once it has run
down, electrical energy is supplied to reverse the cell
reaction and form more reactant.

21-

Figure 21.15

Anode (oxidation):

Alkaline battery.

Zn(s) + 2OH-(aq) → ZnO(s) + H2O(l) + 2e-

Cathode (reduction): MnO2(s) + 2H2O(l) + 2e- → Mn(OH)2(s) + 2OH-(aq)
Overall (cell) reaction:
Zn(s) + MnO2(s) + H2O(l) → ZnO(s) + Mn(OH)2(s) Ecell = 1.5 V

21-

Figure 21.16

Silver button battery.

Anode (oxidation):

Zn(s) + 2OH-(aq) → ZnO(s) + H2O(l) + 2e-

Cathode (reduction): Ag2O(s) + H2O(l) + 2e- → 2Ag(s) + 2OH-(aq)
Overall (cell) reaction:

Zn(s) + Ag2O(s) → ZnO(s) + 2Ag(s)

Ecell = 1.6 V
The mercury battery uses HgO as the oxidizing agent instead of
Ag2O and has cell potential of 1.3 V.

21-

Figure 21.17

Lithium battery.
The primary lithium battery is widely used
in watches, implanted medical devices,
and remote-control devices.

Anode (oxidation):
3.5Li(s) → 3.5Li+ + 3.5eCathode (reduction):
AgV2O5.5 + 3.5Li- + 3.5e- → Li3.5V2O5.5
Overall (cell) reaction:
AgV2O5.5 + 3.5Li(s) → Li3.5V2O5.5

21-

Figure 21.18

Lead-acid battery.

The lead-acid car battery is a secondary battery and is rechargeable.

21-

The reactions in a lead-acid battery:
The cell generates electrical energy when it discharges as a voltaic cell.
Anode (oxidation):

Pb(s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2e-

Cathode (reduction):
PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e- → PbSO4(s) + 2H2O(l)
Overall (cell) reaction (discharge):
PbO2(s) + Pb(s) + H2SO4(aq) → 2PbSO4(s) + 2H2O(l) Ecell = 2.1 V
Overall (cell) reaction (recharge):
2PbSO4(s) + 2H2O(l) → PbO2(s) + Pb(s) + H2SO4(aq)

21-

Figure 21.19

Nickel-metal hydride battery

Anode (oxidation):
Cathode (reduction):

MH(s) + OH-(aq) → M(s) + H2O(l) + eNiO(OH)(s) + H2O(l) + e- → Ni(OH)2(s) + OH-(aq)

Overall (cell) reaction:
MH(s) + NiO(OH)(s) → M(s) + Ni(OH)2(s) Ecell = 1.4 V

21-

Figure 21.20

Lithium-ion battery.

Anode (oxidation):
LixC6(s) → xLi+ + xe- + C6(s)
Cathode (reduction):
Li1-xMn2O4(s) + xLi+ + xe- → LiMn2O4(s)
Overall (cell) reaction:
LixC6(s) + Li1-xMn2O4(s) → LiMn2O4(s)
Ecell = 3.7 V

The secondary (rechargeable) lithium-ion battery is used to power laptop
computers, cell phones, and camcorders.

21-

Fuel Cells
In a fuel cell, also called a flow cell, reactants enter the
cell and products leave, generating electricity through
controlled combustion.
Reaction rates are lower in fuel cells than in other
batteries, so an electrocatalyst is used to decrease
the activation energy.

21-

Figure 21.21

Hydrogen fuel cell.

Anode (oxidation):

2H2(g) → 4H+(aq) + 4e-

Cathode (reduction): O2(g) + 4H+(aq) + 4e- → 2H2O(g)
Overall (cell) reaction:

21-

2H2(g) + O2(g) → 2H2O(g) Ecell = 1.2 V