CYF102A 2electro

Lecture No.
2
Electrochemistry
At the end of this lecture, students will be able to:
• Explain thermodynamic relation of free energy and potential
• Derive Nernst equation for single electrode potential
• Illustrate the construction of an electrochemical cell
1
Faculty of Science and Humanities © Ramaiah University of Applied Sciences
Electrochemistry
• Thermodynamic Relation: Nernst Equation
• Single electrode potential can be expressed in the form of Nernst

equation
• Nernst equation is a thermodynamic equation, which relates the

change in free energy (∆G) and cell potential (E) with concentration
(Mn+)
2
Nernst Equation
• Consider a reversible redox reaction

of the electrode, Mn+ + ne  M
• Reaction constant K is related to the free energy by Vant- Hoff’s

isotherm as,
• ∆G = ∆G o + RT ln K where K is reaction constant = [ M ] (1)

[M n ]
3
Nernst Equation
• Maximum work derived from this reaction is equal to the decrease
in the free energy change
Wmax = - ∆G (2)
• Considering the work done as electrical energy,

Wmax = Electrical energy
= No. of coulombs x Energy available per coulomb
= nF x E (3)
∆G = -nEF (from equations 2 and 3)
∆Go = -nEoF
4
Nernst Equation
• Where, ∆Go is the standard free energy change and Eo is the standard
electrode potential
• Substituting the values for ∆G, ∆Go and K in equation (1),
[M ]
 nFE  nFE  RT ln
0
(4)
[M n ]
• Dividing equation (4) by – nF,

RT [M ]
EE  0
ln (5)
nF [ M n  ]
5
Nernst Equation
and ( [M] =1 )
RT
EE 0
ln[ M n  ] (6)
nF
• where, R is called gas constant = 8.314 JK-1mol-1 , T is standard

temperature = 298 K, F is the Faraday constant = 96,500 Coulomb
mol-1 and n is the number of electrons.
• Substituting the above constants converting the natural log into

log10 in equation (7), we get,
0.0591
E  E0  log[ M n  ]
n
6
Nernst Equation
For the following reversible reaction,
aA + bB  cC + dD
Nernst equation for cell potential is given by
RT [ A]a [ B ]b
EE  ln 0
nF [ B]b [ D]d
RT [Re ac tan ts ] Where R= 8.314 JK−1mol−1 , T=298K,

E  E0  ln F=96485.3 C mol-1, n- number of
nF [Pr oducts ]
electrons
at 25C
0.0591 [Re ac tan ts]
E  Ecell 
0
log 10
n [Pr oducts ]
0.0591 [CathodeSpe cies ]

E  Ecell 
0
log 10
n [ AnodeSpeci es ]
7
Electrode Potential and Cells
• How cells are made?
• Cells are made up of two electrodes, one being Anode (negative
electrode) and the other being Cathode (positive electrode)
• Ex: Cu2+/Zn2+
8
• Cell Representations, Notations and Conventions:
• Representation of Daniel Cell : Coupling Zn half cell and Cu half cell
through a salt bridge
Zn (s) / Zn2+(1M) // Cu2+(1M) / Cu (s)
Notations:
• Single vertical line indicates the phase boundary between the
metal and the solution of its own ions
• Double vertical lines represent the salt bridge
• Direction of the arrow indicates the direction of flow of the
electrons in the external circuit
9
• Conventions
• Electrode where oxidation takes place is called anode (negative
electrode) and is written on the left side of the salt bridge
• Electrode where reduction takes place is called cathode (positive
electrode) and is written on the right side of the salt bridge
• Anode is written as metal first and then electrolyte
• Anode half cell is written as Zn / Zn2+ (1M)
• Cathode is written as electrolyte first and then metal. The cathode
half cell is written as Cu2+ (1M) / Cu
10
• Cell reaction is spontaneous then emf of the cell has positive sign or if
electrons move from left to right in an external circuit then emf of a cell
has positive sign
. If the cell reaction is non-spontaneous then emf of the cell has negative
sign or if electrons move from right to left in an external circuit then emf
of a cell has negative sign
• Electrode potential is always referred to as reduction potential and is
represented as EMn+/M and oxidation potential is represented as E M /Mn+
• Ecell can be calculated using
• Ecell = Ecathode - Eanode
11
How electrode potentials are measured?
• Electrode potentials are measured by combining the electrode with
a reference electrode such as standard hydrogen electrode, calomel
or Ag-AgCl electrode
Ex: Zn2+/SHE
Ecell = - 0.76V
12
• RHS is the standard hydrogen electrode, and
• LHS is the electrode the potential of which is being defined
• By convention: ECell = ECathode − EAnode
• For the cell with the standard hydrogen electrode (potential of 0 by
convention)
• ECell = ERight − Eleft = ESHE – EZn2+= 0- 0.76 = -0.76V
13
• Reference electrodes can act both as anode and cathode depending on
the other electrode coupled
ECell = ERight − Eleft = ECu2+ − ESHE= 0.34 - 0 = 0.34V
14
Galvanic Cell:
Representation:
Zn/Zn2+//Cu2+/Cu
anode cathode
oxidation reduction
spontaneous
redox reaction
15
• Liquid Junction Potential: Difference between the electric
potentials developed in the two solutions across their interface
Ej = Ø soln, R - Ø soln,L
• Contact between two different electrolytes (ZnSO4/ CuSO4)
• Contact between same electrolyte of different concentrations

(0.1M HCl /1.0 M HCl)
• Liquid junction potential can be reduced by joining the electrolyte

compartments through a salt bridge
16
• Role of salt bridge?

• Provides electrolytic contact between the two electrolyte solutions
of a cell
• Avoids or at least reduces (to about 1 to 2 mV) junction potential in
galvanic cells containing two electrolyte solutions in contact
How a cell works?
17
• Definition of Electro Motive Force [EMF]: Difference of potential,
which causes a current to flow from the electrode of higher
potential to one of lower potential
• EMF is denoted by E and measured in volts or energy supplied per
unit charge is called EMF
Ecell = Ecathode- Eanode
18
Factors affecting electrode potential
• The factors affecting the magnitude of electrode potential are:
 Nature of metal or electrode
 The concentration of metal ions in solution
 Temperature
• The value of electrode potential developed on an electrode also

depends on:
 The concentration of ions in solution
 The temperature of the system
 Chemical nature of the metal or nonmetal
 A number of electrons transferred in the half cell reactions.
 It does not depend on the electrode.
19
Quiz
1. If a silver strip were immersed in an aqueous solution containing Cu2+
ions, what would you expect to happen?
(a) Copper would be deposited on the silver strip (b) No reaction would
occur (c) Cu2+ ions would be reduced. (d) Ag would be oxidized.
2. Consider the galvanic cell Zn (s) + Cu2+ (aq) → Cu (s) + Zn2+ (aq)
When the cell is running spontaneously, which choice has
only true statements?
(a) The copper electrode loses mass and the zinc electrode is the
cathode (b) The copper electrode gains mass and the copper
electrode is the cathode (c) The zinc electrode gains mass and the
zinc electrode is the anode. (d) The zinc electrode loses mass and the
zinc electrode is the cathode.
.
20
Quiz
3. Which of the following statements is FALSE?
(a) Oxidation and reduction half-reactions occur at electrodes in
electrochemical cells.
(b) All electrochemical reactions involve the transfer of electrons.
(c) Reduction occurs at the cathode.
(d) Oxidation occurs at the anode.
(e) All voltaic (galvanic) cells involve the use of electricity to initiate
nonspontaneous chemical reactions
4. On the basis of electrode potential values, suggest which of the
following reactions would take place (Note: check electrochemical
series)
21
Summary
• Thermodynamic relation of free energy and potential - Nernst

equation
• Construction of cells: Anode, cathode, salt bridge
• Representation of a cell
• Notations, signs and conventions for cells
Eg: Zn | ZnSO4 (1M) || CuSO4 (1M) | Cu
22

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Lecture No.

• Explain thermodynamic relation of free energy and potential

• Derive Nernst equation for single electrode potential

• Illustrate the construction of an electrochemical cell

• Thermodynamic Relation: Nernst Equation

• Single electrode potential can be expressed in the form of Nernst

• Nernst equation is a thermodynamic equation, which relates the

• Consider a reversible redox reaction

• Reaction constant K is related to the free energy by Vant- Hoff’s

• ∆G = ∆G o + RT ln K where K is reaction constant = [ M ] (1)

• Considering the work done as electrical energy,

• Substituting the values for ∆G, ∆Go and K in equation (1),

• Dividing equation (4) by – nF,

• where, R is called gas constant = 8.314 JK-1mol-1 , T is standard

• Substituting the above constants converting the natural log into

RT [Re ac tan ts ] Where R= 8.314 JK−1mol−1 , T=298K,

0.0591 [CathodeSpe cies ]

ECell = ERight − Eleft = ECu2+ − ESHE= 0.34 - 0 = 0.34V

• Contact between two different electrolytes (ZnSO4/ CuSO4)

• Contact between same electrolyte of different concentrations

• Liquid junction potential can be reduced by joining the electrolyte

• Role of salt bridge?

How a cell works?

• The value of electrode potential developed on an electrode also

• Thermodynamic relation of free energy and potential - Nernst

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