INTRODUCTION TO

ELECTROCHEMISTRY
ELECTRODE POTENTIAL
ELECTROCHEMICAL CELL

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 Electrode potential
The potential difference that develops
between a metal and its ions.
Consider a metal M immersed in a solution
containing ion Mn+.
Two reactions may take place
i) Atoms of metal M losses electrons:
M(s) Mn+ + ne (oxidation)
ii)Ions Mn+ from the solution gain electrons
• Mn+ + ne M (s) ( reduction)
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• The two equations will take place until a
dynamic equilibrium is reached.
• M(s) Mn+ + ne

A potential difference that develops between

the surface of the negatively charged metal
and the positively charged solution is called
the electrode potential of metal M.

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Suppose a piece of magnesium is immersed in a beaker containing Mg2+
There will be some tendency for the magnesium atoms to shed electrons
and go into solution as magnesium ions. The electrons will be left behind on
the magnesium

Mg(s) Mg2+ + 2e

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• In a very short time, there will be a build-
up of electrons on the magnesium metal
strip.

• The newly formed mg2+ ions and the mg2+

already in the solution will form a layer of
positive ions and they tend to stay close to
the magnesium metal strip because they
are attracted to the negative charge on the
piece of metal.

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Some of the mg2+ will be attracted enough that they will reclaim
their electrons and stick back on to the piece of metal
Mg2+ + 2e Mg(s)

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• After sometime a dynamic equilibrium will be
established when the rate at which the mg
atom change into ions equals the rate of the
ions changing back to metal atoms.
Mg(s) Mg2+ + 2e
When this happens there exist a potential
difference and it is called the electrode
potential of magnesim.

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• Electrode potentials also exist between
aqueous ions :
Fe2+ (aq) Fe3+(aq) + e
MnO4- + 8H+ + 5e Mn2+ + 2H2O

In these cases an inert electrode (e.g

platinum) is used to provide surface where
the equilibrium can take place.

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 . Standard Electrode Potential- Eo
• The electrode potential of an electrode system
measured at standard conditions:

-concentration of the aqueous ions must be 1 M

- temperature is at 25 oC or 298 K
- pressure is fixed at 1 atm
- Platinum is used as the inert electrode for system which
does not involve solid metal.

The electrode potential measured under these

conditions is called the standard electrode potentials
and given symbol EO

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 Reference electrode
• The absolute value of an electrode potential
cannot be measured unless the electrode is
connected to a reference electrode
• A reference electrode is an electrode whose
potential remains constant and against which
other potentials can be measured. The
electrode is used to facilitate measurement of
electrode potential of other electrodes

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 Standard Hydrogen Electrode (SHE)-
• H2 gas at pressure 1 atm is bubbled over the
surface of a platinum electrode which is
immersed in an acid solution ( H+) of 1 M.
• Reactions taking place on the surface of
platinum
• H2 (g) 2H+ (aq) + 2e
The standard electrode potential of hydrogen
is assigned as Eo = 0.00 V

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• The standard hydrogen electrode
The standard hydrogen electrode looks like this:

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 Standard electrode potential
series
The standard electrode potential series-

A series obtained when all the electrode system

(half-cells) are arranged in order of increasing
standard electrode potentials values
(from the most negative to the most positive)

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 In the series:
• All ions are aqueous ions.
• The half-cell reactions are written in
reduction and the value is for the reduction
reaction.
• Sometimes called reduction potentials.
• The magnitude of the standard electrode
potential does not depend on the
stoichiometric equation

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Part of Standard Electrod potential series

Reaction at Interface Half-cell Potential (Eo)

Al3+ + 3e-  Al -1.706 V

Zn2+ + 2e-  Zn -0.763 V
Easily reduced, Better Oxidizing Agent

Cr3+ + 3e-  Cr -0.744

Easily oxidized, Better Reducing Agent

Fe2+ + 2e-  Fe -0.409V
Cd2+ + 2e-  Cd -0.401 V
Ni2+ + 2e-  Ni -0.230 V
Pb2+ + 2e-  Pb -0.126 V
2H+ + 2e-  H2 0.00 V
AgCl + e-  Ag + Cl- +0.223 V
Hg2Cl2 + 2e-  2Hg + 2Cl- +0.268 V

Cu2+ + 2e-  Cu +0.340 V

Ag+ + e-  Ag +0.799 V
Au+ + e-  Au +1.680 V 15
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 Electrochemical cell.
• An electrochemical cell consists of two
conductors called electrodes, each immersed
in an electrolyte solution and being
connected by a salt bridge.

An electrochemical cell can be constructed by

combining two half-cells of different Eө value
and are connected to each other by a salt
bridge

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 The half-cell with the more positive electrode
potential (E0 value) will be the cathode. ( right
electrode)
The half-cell with more negative electrode
potential is the anode.(left electrode)

At cathode : Reduction occurs

At anode : Oxidation occurs

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Electrochemical Cell:
Basic Set-up:
a) Two electrodes
b) electrolytes solution
c) external connection between electrodes (wire)
d) internal connection via contact with a common solution or by different
solutions connected by a salt bridge.

salt bridge – acts to isolate two halves of electrochemical cell while allowing migration
of ions and current flow.
- usually consists of a tube filled with potassium chloride
- separate species to prevent direct chemical reactions

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Flow of current (charge) in cell:
a) electrons (e-) within wires between two electrodes
b) ions within solution of each ½ cell (anions & cations) and through salt
bridge
c) electrochemical reactions at electrode
electrons

Cl- K+

Zn2+ Cu2+
SO42- SO42-

At Cu electrode: Cu2+ + 2e- Cu(s)  reduction – CATHODE

At Zn electrode: Zn(s) Zn2+ + 2e-  oxidation- ANODE

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 Cell potential IUPAC Sign
Convention
• The IUPAC sign convention is a short-hand
representative for the electrochemical cell.
• The cathode is written on the right –hand
side, while the anode on the left-hand side.

Sometimes referred to as
IUPAC symbol
Cell notation

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22
Cell notation involving metal
Zn(s)| Zn2+(x M) || Cu2+(y M) | Cu(s)

Cell notation involving ions

Pt| Cl-(1 M),Cl2 (g) || Fe3+(1M),Fe2+(1M)| pt

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 Effect of concentration
• In measuring standard electrode potential
(Eo), the concentration of any aqueous
species must be 1 M.

• Will the value of E be affected if the

concentration is not 1 M?

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Effect of concentration
The Nerst Equation gives – the relationship
between electrode potential and concentration
of the aqueous ions.
Referring a reaction:
aA + bB cC + dD
The reaction quotient,
Q = [C]c[D]d or [ product ]
[A]a[B]b [reactant]

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 Nerst equation

E = Eo - RT ln [ product ]
nF [reactant]
where Eo is at 1 M, E≠1 M

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Substituting ( eqn 1)
T= 298 K ( room temperature)
R= gas constant, F= faraday constant
converting ln to log10
E = Eo - 0.059 log [ product ]
n [reactant]

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• E = Eo – 0.059 log [reduced species]
n [oxidized species]

(concentration of solid, gas is not included in

the Nerst Equation)

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• Example1 :
Calculate the electrode potential for the following
half- cell system: Ag/Ag+ (0.5 M)

Ag+ + e Ag (s) Eo = + 0.80 V

E = Eo - 0.059 log 1
1 [Ag+]

E = 0.80 - 0.059 log 1 = 0.78 V

1 0.5 M

at [Ag+] =1 M, E = 0.80 V but when [Ag+] =0.5 M

E = 0.78 V
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• Example: calculate the electrode potential
for the following half- cell system.
Fe 3+(0.8 M)/Fe2+(0.4 M)

• Fe3+ + e Fe2+ Eo = + 0.77 V

• E = Eo - 0.059 log [Fe2+]
• 1 [Fe3+]
• E = 0.77 – 0.059 log 0.4 M
• 1 0.8 M
• E = 0.79
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MnO4- + 8H+ + 5e Mn2+ + 2H2O
[MnO4-]= 0.5 M, [Mn2+ ] = 0.8 M pH =0.22
Eo = 1.52 V

E = Eo - 0.059 log [ Mn2+]

5 [MnO4-][H+]8

1.52 – 0.059 log (0.8) = 1.50 V

5 (0.5)(0.6)8
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 Calculating Ecell
Given the following cell notation:
Zn(s) | Zn2+(1.8M) || Cu2+(0.2 M)| Cu (s)
• Write the equation for reactions at the
anode, cathode and the overall reaction.
• Calculate electrode potential for the cell.

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Step 1: Writing the overall equation

Anode(oxidation): Zn(s) Zn2+ + 2e

Cathode (reduction):Cu2+ + 2e Cu(s)

Overall: Zn(s) + Cu2+ Zn2+ + Cu(s)

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Step 2 : calculate Eo for the cell
Eocell = Eo cathode – Eo anode
= Eocu - Eozn
= 0.34 – (-0.76) = +1.10

Step 3: Apply nerst equation to the overall eqn

Zn(s) + Cu2+ Zn2+ + Cu(s)

• E = Eo cell – 0.059 log [Zn2+]

2 [Cu2+] 34
E = 1.10 V – 0.059 log (1.8)
2 (0.2)
= 1.02 V

At standard condition; Electrode potential

of the cell measures + 1.10 V but when
the concentrations of the aqueous ions
changes the electrode potential changes
to +1.02 V

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A half-cell containing 0.0835 M Cr3+ and 0.119 M
Cr2+ is connected to another half-cell containing
0.0361 M V3+ and 0.0904 M V2+
i) Write the overall equation for the cell reaction
ii) Determine the cell potential
iii) Write the cell notation
iv) Draw a complete cell diagram
v) Determine the potential at equivalent point.
Given : Eo Cr3+/Cr2+ = -0.407V
• Eo V3+/V2+ = -0.225 V

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 i) Cr2+ + V3+ →V2+ + Cr3+
ii) -0.20 V
iii) Pt / Cr2+ (0.119 M), Cr3+ (0.0835 M) // V2+
(0.0904 M), V3+ ( 0.0361M)/ Pt

V
v

pt

pt

Cr3t V2t(0.0904M )
( 0.0835 M) Cr2t ( 0.119 M) V3t(0.0361M )

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 At Equivalent point
Eeq = Ecr 3+ /cr2+ = Ev /v
3t 2+

1) Eeq= E0 cr /cr = – 0.0592log [Cr2+]

3t 2+

1 [Cr2+]
2) Eeq=E0 v /v – 0.0592 log [V2+]
3+ 2+

1 [V3+]

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 Electrode potential at equivalent point

• equation (1) + (2) = (3)

2E = Eocr3+ /cr2+ + Eo v2+ /v2 - 0.5292 log [Cr2+][V2+]

[Cr3+] [V3+]

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From the overall reaction:
Cr2+ + V3+ → V2+ + Cr3+

Eeq = Ecr
3+ /cr2+ = Ev /v
3t 2+

[Cr2+] = [V3+] [Cr3+] = [V2+]

•

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Substitute in 3
• 2E = Eocr +cr + Eov t/v – 0.0592 log[Cr2+][Cr+3]
3 3+ 3 2t

1 [Cr3+] [Cr 2+]

2E = Eocr
3+ /cr 2t + Eov /v3t 2t

• Eeq = E0cr 3+ /cr 2+ + E0v /v 3t 2t

2
• Eeq = -0.0407V + -0.225 V =- 0.133 V
• 2

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• Nerst equation for gaseous system:
• At standard condition pressure of any
gases must be 1 atm.
In cases whereby the pressure is not 1
atm, nerst equation is applied:
example : For half cell
pt| O2(1.12 atm), H+(0.0794 M)
equation : 4H+ (aq) + O2(g) 2H2O (l)
E = E0 – 0.0592 log 1
n [H+]4 ρO2