Electrochemical Cell / Galvanic Cell / Voltaic cell L 1

It is a device which converts free energy of a chemical reaction into electrical energy. -ΔG = nFE
It is also called Galvanic cell or voltaic cell.
Electrochemical cell usually consists of two electrodes immersed in one or more suitable electrolyte and the
electrodes are connected externally.
Chemical reaction occurs in the cell. Oxidation at one electrode and the electrons given out are consumed for
reduction at other electrode.
The electrode at which oxidation occurs is anode. The electrode at which reduction occurs is cathode.
Flow of electrons is from anode to cathode, therefore flow of electricity is from cathode to anode.
Example of electrochemical cell is Daniel Cell,
It consists of Zn rod dipped in ZnSO4 solution and a Cu rod dipped in CuSO4 solution.

Zn metal has a greater tendency for oxidation than copper. Therefore oxidation takes at zinc compartment. Zn 
Zn2+ + 2e . Zinc act as anode. Zn2+ goes to the solution leaving behind the 2e on the Zn rod. Hence zinc rod
achieves a negative charge.
Cu2+ has a greater tendency for reduction than Zn2+, therefore Cu2+ accepts electrons and get reduced and
deposited on copper metal. Cu2+ + 2e  Cu. Cu acts as cathode.
The flow of electrons through externally connected wire from zinc to copper and therefore flow of electricity is
from Cu to Zn.

Functions of Salt Bridge:

Consider the oxidation of Zn metal. Zn  Zn2+ + 2e . Zn2+ ions are added to ZnSO4 leaving behind the 2e on the Zn
rod. Therefore excess of positive charge develops in oxidation half cell.
In the reduction half cell due to consumption of Cu2+ from CuSO4, excess negative charge develops.
This charge build up process oppose the current flow. Therefore a path has to be provided to maintain electrical
neutrality in each compartment. A porous partition or slat bridge can be used for this purpose.
Salt bridge is an inverted U tube. Containing salts like KCl or NH 4NO3 in agar-agar or gelatine. The ions of K+ and Cl-
have equal mobility. The excess positive charge developed in ZnSO4 solution is neutralized by negative ions from
salt bride. Similarly excess charge developed in CuSO4 is neutralised by positive ions from salt bridge.
Thus the salt bridge completes the circuit.
Salt bridge also prevents the diffusion of interfering ions from one compartment to another. For example in the
Daniel cell the diffusion of Cu2+ ions to Zn compartment has to be prevented as it get deposited over Zn metal.
Representation of electrochemical cell, (L2)
Anode components on left hand side. Cathode components on right hand side. All phase interfaces are separated
by a single line. A salt bridge by double line.
Example Daniel cell Zn/Zn2+//Cu2+/Cu.

various types of electrodes with suitable examples

a. Metal-metal ion electrode: A metal rod dipped in a solution of its own ion.
Example Zn rod dipped in ZnSO4 solution, Zn2+/Zn.
Copper rod dipped in CuSO4, Cu2+/Cu.
The electrode potential depends on logarithm of concentration of Mn+ ions.

b. Metal-metal insoluble salt electrode: A metal in contact with its own sparingly soluble salt dipped in a
solution containing a common anion.
Example calomel electrode Cl-/Hg2Cl2(aq)/Hg(aq)
Silver-silver chloride electrode Cl-/AgCl(s)/Ag(s)
The electrode potential depends on logarithms of concentration of common anion.

c. Gas electrode: Gases continuously bubbled through the solution of their ions. The gases are non-
conductors of electricity; therefore an inert metal like Pt, Au etc is employed for establishing electrical
contact.
Example Oxygen electrode OH-(aq)/O2(g)/Pt
Hydrogen electrode H+(aq)/H2(g)/Pt
Chlorine electrode Cl-(aq)/Cl2(g)/Pt
Electrode potential depends on the logarithm of concentration of ions and the pressure at which gas is
bubbled.

d. Redox electrodes: A metal in contact with a redox system.

Example Pt/Fe3+/Fe2+
Pt/Ce4+/Ce3+
Here the electrode potential depends on the logarithm of concentration of ionic species involved in redox
system.

e. Ion selective electrode: Sensing part is an ion specific membrane. The membrane can be a glass membrane
or ion exchange resin. These are sensitive to specific ions like H +, Na+, Ag+ etc. Example H+ ion selective
glass electrode.
Single electrode potential: Origin of Single electrode potential - Helmholtz double layer
A metal can be imagined as - metal ions embedded in a pool of valence electrons.
When a metal rod is dipped in its own salt solution, two possibilities,
Oxidation: M  Mn+ + ne. The positive ions in the metal go into the solution leaving behind the electrons on the
metal. Hence metal acquires a negative charge. As oxidation continues more and more negative charge
accumulate on the metal surface.
Reduction: Mn+ + ne  M. The positive Mn+ from the solution enters to the metal. Hence metal acquires a positive
charge. As reduction continues more and more positive charge accumulates on the metal surface.
Due to oxidation or reduction a charge density is created at the electrode surface, which attracts ions of opposite
charge from the electrolyte. The charge held on the electrode surface is balanced by the redistribution of ions
close to the electrode surface.
A simplified model to imagine this situation is Helmholtz electrical double layer. A layer of positive and negative
charge remains close to each other, one on the electrode surface and other on the electrode-electrolyte
interphase.

A difference in potential is consequently developed between the metal and solution. This potential difference is
called single electrode potential. The electrode potential of a metal is the measure of tendency of metallic
electrode to loose or gain electrons, when it is in contact with its own salt.
Its magnitude depends on 1. Nature of the metal. 2. Concentration of ions. 3. Temperature.
If the concentration is 1M and temperature is 298 K (25 ⁰C) then it is called standard electrode potential.
Tendency of electrode for oxidation (loose electrons) is oxidation potential E oxd and tendency for reduction (gain
electrons) is reduction potential Ered. Ered = - Eoxd
Generally the standard electrode potential refers to reduction potential.

It is impossible to measure the absolute value of electrode potential, because neither

oxidation nor reduction takes place independently (both occurs conjointly. Therefore
one can only measure the cell potential. That is, relative value of emf with respect to
a reference electrode can only be obtained.
Reference electrode And its applications
It should have a stable and well defined electrode potential at a particular temperature.
One application of reference electrode is to evaluate the potential of other electrodes.
Use of reference electrodes
1. Electrode potential of other electrodes can be evaluated.
2. PH of a solution can be determined.
Examples of reference electrodes
1. Standard Hydrogen electrode (H+ (1M)/H2 (1 atm)/ Pt). It is a primary reference electrode. Its electrode
potential value is arbitrarily assigned as zero.
2. Calomel Electrode (Cl- (x M)/Hg2Cl2/ Hg). It is a secondary reference electrodes
3. Glass electrodes (Pt/H+(0.1 M)/glass). It is internal reference electrode used for pH measurements.

Standard Hydrogen Electrode Construction and its working

Standard Hydrogen Electrode (SHE) or Normal Hydrogen Electrode (NHE) is the primary reference electrode. Its
electrode potential is arbitrarily fixed as zero.
SHE is an example of gas electrode.
It consists of an inert platinum rod dipped in 1M HCl solution. H2 gas is bubbled at 1 atm pressure at 298 K
temperature. Pt/ H2(g)(1 atm) /H+(aq)(1M).

It can act as anode or cathode depending on the potential of the electrode to which it connected. Thus SHE is a
reversible electrode.

If the potential of the coupled electrode is less than zero, then SHE acts as cathode. Reduction takes place at SHE.
H+ + e  ½ H2 .
If the potential of the coupled electrode is greater than zero, then SHE acts as anode. Oxidation takes place at SHE.
½ H2  H+ + e

Limitations of SHE
1. SHE is difficult to construct. Bubbling H2 gas at 1 atm around Pt through the solution is difficult.
Maintaining activity of H+ at unity is difficult.
2. Pt metal has high adsorption and catalytical activity. Hydrogen on Pt surface is reduction catalyst. A
number of organic substances are reduced. Inorganic ions like Fe3+, MnO4- etc reduce to their lower
valence state. Cations of Ag, Cu, Cd, Pb will get reduce and deposit on Pt metal. Substance like arsenic and
sulphides also interfere.
Measurement of single/Std. electrode potential of Zinc electrode Using SHE as reference
electrode
It is impossible to know the absolute value of electrode potential because neither oxidation nor reduction takes
place independently. It is measured relative to a reference electrode.
The reference electrode taken is standard hydrogen electrode SHE (also called normal hydrogen electrode NHE).
The electrode potential of SHE is arbitrarily assigned a value of zero. All other electrode potential values are
expressed relative to this value.
In order to measure standard electrode potential of Zn (Zn metal dipped in 1M ZnSO4 at 25 ⁰C)
Zn/Zn2+ metal-metal ion electrode is coupled with SHE through a salt bridge.

The direction of flow of current further indicates on which electrode oxidation or reduction takes place with
respect to SHE (one can use analogue voltmeter to find out the direction of current flow).
Here Zn is oxidised, therefore Zn is anode.

Zn| Zn2+|| H+(aq)(1M)|H2(g)(1 atm)|Pt.

The emf of the cell must be measured without drawing current from the cell. Analogue voltmeter cannot be used
but digital voltmeter can be used. In digital voltmeter the measurement of potential is based on using field effect
transistor, which draws no current from the cell during emf measurement.
The digital voltmeter reading directly gives the cell emf.
E⁰cell = E⁰cathode - E⁰anode
SHE is cathode therefore, E⁰cell = E⁰SHE - E⁰Zn2+/Zn
ie E⁰cell = 0 - E⁰Zn2+/Zn
E⁰Zn2+/Zn = - E⁰cell
The emf of cell is found to be 0.76 V (ie oxidation potential is 0.76 V). Therefore reduction potential is -0.76 V.
Measurement of single electrode potential of Copper electrode Using SHE as reference
electrode
It is impossible to know the absolute value of electrode potential because neither oxidation nor reduction takes
place independently. One can only measure the cell emf. Ie, It is measured relative to a reference electrode.

Construct a cell. One half cell is Cu/Cu2+

Other half cell is SHE Pt/H2(1 atm)/H+ (1 M)
Direction of Flow of Current can be obtained by connecting an analogue voltmeter. (Cu to SHE). Therefore SHE is
anode and Cu is cathode

Cell Rep: Pt/H2(1 atm)/H+ (1 M) || Cu2+/ Cu

The digital voltmeter reading directly gives the cell emf.

E⁰cell = E⁰cathode - E⁰anode
= E⁰Cu(2+)/Cu - E⁰SHE = E⁰Cu(2+)/Cu – 0 = E⁰Cu(2+)/Cu

E⁰Cu(2+)/Cu = E⁰cell
Electrochemical series and its applications L3
The arrangement of various metals and non-metals (top to bottom) in order of increasing value of
standard reduction potential is called electrochemical series (activity series).
Applications
1. Relative oxidizing and reducing powers of various substances.

2. Calculation of EMF of cell.

E⁰cell = E⁰cathode - E⁰anode The electrode with higher electrode potential act as cathode
while that with lower electrode potential act as anode.

3. Predicting Feasibility of a redox reaction.

A reaction is feasible when E⁰cathode > E⁰anode . Consider the reverse of Daniel cell reaction,

4. Predicting the capability of Metal to liberate hydrogen gas from acid.

Q Zinc reacts with dilute H2SO4 to give hydrogen but silver does not. Explain
given that
E0Ag+/Ag = + 0.080V
E0 Zn2+/Zn = - 0.76V.
Soln:

All metals with negative reduction potential can liberate hydrogen gas from acid solutions.

Since zinc has negative reduction potential and is placed above hydrogen in electrochemical series, it
liberates hydrogen. But silver has positive reduction potential and is placed below hydrogen in emf series.
So, Ag does not liberate hydrogen.

5. Predict displacement Reaction.

Any metal with lower reduction potential displace a metal with higher reduction potential from it
compound.

Q. Can we use a nickel spatula to stir a solution of copper sulphate? Given that
E0 Ni2+/Ni= + 0.0025
E0 Cu2+/Cu= + 0.34V
Soln:
Reduction potential of Ni is less than Cu. Nickel will be anode and undergo oxidation. Nickel will go into
solution as Ni2+ and Cu2+ will be reduced to Cu. Thus Ni spatula cannot be used to stir a solution of
CuSO4.

Q. What would happen if the protective tin coating over an iron bucket is broken in some places ?
given that
E Sn /Sn > E
0 + 0
Fe2+/Fe
Soln:
Since E
0
Fe2+/Fe 0
< E
Sn+/Sn
Iron will act as anode therefore undergoes oxidation. Iron will corrode faster as the reduction potential of
Fe is lower than that of tin.
Q. What would happen if the protective Zinc coating over an iron bucket is broken in some places?
given that
E0Zn(2+)/Zn < E0 Fe(2+)/Fe
Soln:
Since E0Zn(2+)/Zn < E0 Fe(2+)/Fe
Zinc will act as anode therefore undergoes oxidation. Iron will be cathodic. Zinc will sacrificially
protect iron.
Q. A Zinc wire is dipped in silver nitrate solution taken in beaker A and a silver wire is dipped in zinc sulphate
solution taken in beaker B. Predict in which beaker the ions present will get reduced? Given that standard
reduction potential of zinc and silver are -0.76 and 0.8 V respectively.
Soln:

In Beaker A
E0Zn(2+)/Zn < E0 Ag+/Ag . A metal having low reduction potential is immersed into
a solution of metal having higher reduction potential. Displacement
reaction takes place. Therefore Zinc act as anode, and undergo oxidation.
Ag+ will get reduced. Ions in beaker A will get reduced.
In Beaker B
E0 Ag+/Ag > E0Zn(2+)/Zn Therefore, No displacement reaction.

Q. Predict whether, to any significant extent, O2(g) will oxidize Cl-(aq) to Cl2(g) in acidic
solution. Given that O2 + 4H+ + 4e → 2H2O Eo = +1.23 V

Cl2 + 2e → 2Cl- Eo = +1.36 V

Soln,
O2(g) has to oxidize Cl-(aq) to Cl2(g) in acidic solution, then Cl-/Cl2 electrode has to
be anode and O2/H+(aq) electrode should be cathode.

= -0.13 Not feasible

Q. Predict whether, to any significant extent, I2(s) will displace Br- (aq) to produce Br2(l).
Given that, Br2 + 2e → 2Br- Eo = 1.07 V
I2 + 2e → 2I- Eo = 0.54 V
Soln,
I2(S) has to oxidize Br-(aq) to Br2(l), then Br-/Br2 electrode has to be anode and I-/I2
electrode should be cathode.

= -0.53 Not feasible,

Q. Give the electrochemical mechanism of etching of copper using FeCl3. Give the reactions and
explain.
Given E0Cu2+/Cu=0.34V and E0Fe3+/Fe2+ 0.77
Soln
E0Cu2+/Cu=0.34V < E0Fe3+/Fe2+= 0.77
Anode Cathode
Cu → Cu2+ + 2 e (oxidation)
2Fe3+ + 2 e → 2Fe2+ (reduction)
Cu + 2Fe3+ → 2Fe2+ + Cu2+

Electrochemical mechanism of etching of copper using FeCl3 is, Cu + 2FeCl3 → 2FeCl3 + CuCl2.

Q Metal 'X' reacts slowly with steam. There is no visible change observed when it is placed
in FeSO4. Suggest the position of metal X in the activity series.

Soln

X + Fe2+ → No displacement reaction E0X > E0Fe(2+)/Fe

X + H2O → Xn+ + n/2 H2 E0X < E0H(+)/H2

Therefore position is Fe2+ + 2e → Fe

Xn+ + ne → X

H+ + e → 1/2 H2

Q The Co3+ ion is unstable in aqueous solution, Why?

Given that Co3+ + e → Co2+ (E0= 1.82 v) and O2 + 4H+ + 4e → 2H2O (E0= 1.23 v)

Soln

E0Co3+/ Co2+ > E0 O2/H+/H2O

Cathode Anode

Reduction happens at Cobalt ion compartment and oxidation happens at water

compartment.

Co3+ + e → Co2+ (the Co3+ ion is unstable in aqueous solution)

Home Works

Q1. The Cu+ is unstable in aqueous solution why?

Q2. Choose the feasible reaction from the following:

a) Cu + NiCl2 → CuCl2 + Ni, b) Ni + CuCl2 → NiCl2+ Cu; Given: E0 Ni2+/Ni=0.25V and
E0Cu2+/Cu=0.34V
Q3. Three iron sheets have been coated separately with three metals A, B, C whose standard electrode
potentials are given below :

A B C Iron

E°value – 0.46 V – 0.66 V – 0.20 V – 0.44 V

Identify in which rusting will take place faster when coating is damaged.

Q4. In Redox titration using KMnO4 as oxidizing agent, dil HCl and HNO3 cannot be used to provide acidic
medium, whereas dilute H2SO4 can be used. Give reason
Given that,
MnO4- + 8H+ + 5e → Mn2+ + 4H2O
Cl2 + 2e → 2Cl-
S2O82- + 2e → 2SO42-
Fe3+ + 1 e → Fe2+

Q5. In Redox titration using K2Cr2O7 (Potassium Dichromate) as oxidizing agent, both dil HCl and dilute
H2SO4 can be used. Give reason
Cr2O72- + 14H+ + 6e → 2Cr3+ + 7H2O
Cl2 + 2e → 2Cl-
S2O82- + 2e → 2SO42-
Fe3+ + 1 e → Fe2+

Q6. Silver tarnish is mainly silver sulphide, Ag2S

Ag2S + 2e → 2Ag + S2- E° = -0.691 V

A tarnished silver spoon is placed in contact with a commercially available metal product in a glass-
baking dish. Boiling water, to which some baking soda (salt bridge) has been added, is poured into the
dish, and the metal product and spoon are completely covered. Within a short time, the spontaneous
removal of tarnish from the spoon begins. Is this commercially available metal product Al or Cu? Explain
by writing out the oxidation half reaction and solve for the overall spontaneous E°cell value.

Given that Al3+ + 3e → Al E0 = -1.68 V and Cu2+ + 2e → Cu E0 = 0.34 V

(a) What possible metal or metals are in the product other than aluminium?
(b) What is the probable reaction that occurs?
(c) What do you suppose is the function of the baking soda NaHCO3.
(d) An advertisement for the product appears to make two claims: (1) No chemicals are involved,
and (2) the product will never need to be replaced. How valid are these claims? Explain.
Nernst Equation Derivations L4
Nernst equation allows one to predict cell voltages (emf) when the conditions are not standard.

R is universal gas constant (8.314 J K-1 mol-1 )

F is Faraday (96500 C) = Charge Carried by 1 mole of electrons
T is temperature in Kelvin scale.
n is number of electrons involved in electrode process.
Activity is effective concentrations (in dilute solutions activity is molar concentration)

The voltage difference between electrodes of an electrochemical cell is called cell voltage (or emf) –
At standard conditions we call it standard emf –
The emf associated with any redox reaction can be calculated,

For a spontaneous reaction both E and Eo should be positive.

Electrical energy produced per mole = quantity of charge in one mole multiplied with EMF
For the general reaction Mn+ + ne  M
Electrical energy produced per mole = n F E
23 -19
F is faraday, which is charge carried by one mole of electrons = 6.023 x 10 x 1.6 x 10 C = 96500 C.
In a reversible electrochemical cell electrical energy is produced at the expense of decrease in free energy. Then,

Under standard conditions,

The decrease in free energy ΔG associated with an equilibrium reaction is given by,

R is universal gas constant (8.314 J K-1 mol-1 )

T is temperature in Kelvin scale.

Q is the reaction quotient =

Activity is effective concentrations (in dilute solutions activity is molar concentration)

Substituting equation 1 and 2 in 3, we get

Rearranging it,

In dilute solutions activities can be replaced by molar concentrations

In general for single electrode reduction reaction, Mn+ + ne  M
[ ]
[ ][ ]
[e] and [M] ie concentration of pure solid both are taken as unity.
Then

[ ]
At 25 ⁰C the equation becomes

[ ]
This is the Nernst Equation for single electrode at 25 ⁰C.

In general for the reaction aA + bB  cC + dD

[ ] [ ]
[ ] [ ]
At 25 ⁰C the equation becomes
[ ] [ ]
[ ] [ ]
This is the Nernst Equation for the cell reaction.

Derivation of Nernst equation for Daniel cell

Zn + Cu2+  Zn2+ + Cu
Nernst Eqn:

[ ]
[ ]
Effect of temperature on emf in Daniel Cell
Consider the Daniel cell,
[ ]
[ ]
Case 1: [Zn2+] = [Cu2+], then E = Eo and emf of the cell is independent of temperature.
Case 2: [Zn2+] > [Cu2+], then E = Eo – Tx, ie always E < Eo and emf of the cell is decreases as temperature is
increased.
Case 2: [Zn2+] < [Cu2+], then E = Eo + Tx, ie always E > Eo and emf of the cell is increases as temperature is
increased.
Derive Nernst Equation Hydrogen electrode and Discuss the effect of pH on emf.

+
Hydrogen Gas Electrode reduction reaction, H + e  ½ H2
Nernst Eqn

[ ]
[ ]
and E0 = 0 (SHE)

Then
At 25 ⁰C the equation becomes

[ ]
This is the Nernst Equation for Hydrogen electrode at 25 ⁰C.

That is [ ]
is
At 0 pH E = = 0.0 V
At 7 pH E = = - 0.413 V
At 14 pH E = = - 0.826 V
Q… Why metals like Aluminium can liberate hydrogen gas from both acids and bases whereas metals like
Fe can liberate hydrogen only from acids. E0Al3+/Al=-1.66V and E0Fe2+/Fe =-0.44 V

Soln,
+
Hydrogen Gas Electrode reduction reaction, H + e  ½ H2
Nernst Eqn

[ ] 0
[ ]
and E = 0 (SHE)

is
At 0 pH E = = 0.0 V & E0Al3+/Al=-1.66V . Electrode Potential of Aluminium is lower.
Aluminium is anodic and Hydrogen is cathodic, therefore oxidation happens at Aluminium Al → Al3+ + 3e and H+
+ e → 1/2 H2
At 14 pH E = = - 0.826 V & E0Al3+/Al=-1.66V. Here also, Electrode Potential of Aluminium is
lower. Aluminium is anodic and Hydrogen is cathodic, therefore oxidation happens at Aluminium Al → Al3+ + 3e
and H+ + e → 1/2 H2

At 0 pH E = = 0.0 V & E0Fe2+/Fe =-0.44 V. Electrode Potential of Iron is lower. Iron is anodic
and Hydrogen is cathodic, therefore oxidation happens at Iron Fe → Fe2+ + 2e and H+ + e → 1/2 H2
At 14 pH E = = - 0.826 V & E0Fe2+/Fe =-0.44 V. Here in this case, Electrode Potential of Iron
is greater. Iron becomes cathode and Hydrogen become anode, therefore Hydrogen gas is not liberated in this
case.
Derive Nernst Equation for Chlorine gas electrode at 1 atm Pressure
2-
The reduction reaction of chlorine gas electrode Cl2 + 2e  Cl
Nernst Eqn:
SEE THE DIFFERENCE
IN THE REDUCTION
That is
REACTION OF
[ ]
HYDROGEN AND
CHLORINE
[ ]

[ ]

Nernst Equation Applications

1. It allows one to predict the cell voltage when the conditions are not
standard.
2. To find the concentration of one of the ionic species in the cell if the
concentrations of other ionic species are known.
3. It can be used to find the number of electrons involved in the redox
process.
4. PH of a solution can be obtained, PH = -log [H+]. Make this solution a
hydrogen electrode, couple this half cell with any reference electrode
and apply Nernst equation.
5. To find the equilibrium constant of a reaction.
At equilibrium ΔG = 0 and Q = Kc (equilibrium constant) (a cell at which
overall reaction at equilibrium can do no work and the cell potential is
zero) Then Ecell = 0.
Nernst Eqn becomes,

This implies

6. To study the effect of electrolyte concentration of single electrode

potential.
[ ]
This is the Nernst Equation for single electrode at
25 ⁰C.
For one electron process for a 10 fold change in concentration emf changes by 59 milli-Volts
For two electron process for a 10 fold change in concentration emf changes by 29.5 milli-Volts
---------------------------------------------------------------------------------------------------------------------------------------------
Q1. A voltaic cell is created under standard conditions with the cell notation
Cu(s) | Cu2+(aq) || Ag+(aq) | Ag(s).
If water is added to the Cu2+ cell, how will the voltage be affected?
Soln: Since Cu is listed first in the cell notation, it is the anode, meaning that
Cu(s) is oxidized to form Cu2+. Since Cu2+ is a product in the reaction, decreasing
its concentration will increase the cell potential.
Ag+ is get reduced to Ag

Nernst Eqn

log term becomes –ive then emf of cell

Q2. How much charge is required to reduce 1 mole of Al3+ to Al ?

Soln:
The reduction reaction is
Al3+ + 3e- → Al
Thus, 3 mole of electrons are needed to reduce 1 mole of Al3+
Q = 3 × F = 3 × 96500 = 289500 coulomb

Q3. Why is the equilibrium constant K, related to only E°cell and not Ecell ?

Soln: This is because Ecell is zero at equilibrium.

═══════════════════════════════════
Q4. (a) How will the value of Ecell change in an electrochemical cell involving the following reaction
of the concentration of Ag+ (aq) is increased ?

(b) What will be e. m. f. when the cell reaches equilibrium :

Mg (s) + 2 Ag+ (aq) ——> Mg2+ (aq) + Ag (s)

0.059 Mg2 
Soln: (a) Ecell = E°cell – log 2
2  Ag 

As the concentration of [Ag+] ion increases, Ecell increases.

(b) e.m.f. = 0

═══════════════════════════════════
Q5. What is source of energy in a galvanic cell? Give the relationship between
electrical energy and chemical energy?
Soln:
The decrease in free energy of a redox reaction is converted into electrical energy.

═══════════════════════════════════
Q6. Find the concentration condition at which the cell EMF of the following cell
will be independent of temperature. Al(s)| Al3+||Fe2+|Fe(s) .
Ans:

The concentration condition at which the cell emf becomes independent of

temperature is logarithmic term should vanish to zero. i.e when
═══════════════════════════════════
Q7. The potential of a hydrogen electrode set up at 25 oC in a aqueous solution is
-0.295 V. Calculate pH?
Soln: No reference electrode, therefore apply Nernst Equation.
H+ + e → ½ H2

[Here E0 = 0 for SHE and n =1 ]

pH = = 5

Q8. The emf of the cell Pt, H2 (1 atm) | HClaq || SCE is 0.4195 V at 25 oC. Calculate
the pH of the HCl solution? ESCE = 0.2422 V.

Soln: Here reference electrode is saturated calomel electrode SCE

pH = = 3

Q9. The emf of the cell when a hydrogen gas electrode set up in an acid solution of
unknown strength coupled with a SHE is 0.0295 V at 25 oC . Calculate the pH of the
HCl solution?

Soln: Here reference electrode is standard hydrogen electrode SHE

pH = = 0.5

═══════════════════════════════════
Q10. Represent the cell corresponding to the cell reaction,

and calculate emf at 25oC. Given

Eo = 0.46 V.

Soln: Apply Nernst Eqn

[ ]

n = 2
[ ] [ ]
[ ]

Then = 0.46 V

Q11. Calculate the concentration of chloride ion in the following electrode at 25 oC.

Pt, Cl2(1 atm) |Cl- (aq.)

Given that the standard potential is 1.36 V and its electrode potential is 1.46 V

Soln: Apply Nernst Eqn by writing reduction reaction

½ Cl2 + e → Cl- here n =1

[ ]

= =

Then = 0.02 M
Q12. Calculate the equilibrium constant of a Daniel cell reaction, given that the
standard potential is 1.1 V.

Soln: For any cell at equilibrium the cell potential becomes zero. Daniel cell is
Zn2+ | Zn || Cu2+ | Cu . Here n = 2

here n =2

Then = 1.67 1037

Q13. Calculate the amount of electrical energy available from a dry cell of emf 1.5 V,
which consumes 10 g of Zinc. (atomic weight of Zn is 65.5).

Soln: Decrease in free energy is converted into electrical energy G = -nFE

Then electrical energy per mole = nFE

Zn2+ + 2 e → Zn [ n = 2, E = 1.5V, F = 96500 C]

[Per mole = 65.5 g of Zn]

Electrical Energy for 65.5 g Zn = 2 96500 1.5 = 289500 J
Electrical Energy for 10 g Zn = 289500 J 10/65.5 = 44198 J

Q14. A zinc rod is kept in 0.02 M ZnSO4 solution at 25 oC. if and the
ZnSO4 undergo 90% dissociation, calculate the potential of this electrode at this
temperature?

Soln
Zn2+ + 2e → Zn

= Molar concentrations x dissociation fraction 0.02 x 90/100 = 0.018 M

R = 8.314 JK-1 mol-1. F = 96500 C . T = 25 0C = 273 + 25 = 298 K . n=2

= -0.76 – 0.051
 = 0.811 V

Q15. Find the potential of hydrogen electrode at 25 0C for a solution of pH =0 and pH

=14.
Soln
H+ + e → ½ H2

At pH = 0
At pH = 14

Q16. At 25 oC the standard emf of a cell having reaction involving two electron charge is
found to be 0.295 V. Calculate the equilibrium constant of the reaction.
Soln
At equilibrium E = 0 V
log K = n / 0.0591 = (2 X 0.295) / 0.0591 = 10
K = antilog (10) = 1010.
Q17. Calculate the emf of the cell Cd|CdSO4(0.01 M)||CuSO4(0.5)|Cu, if

Soln

Cd|CdSO4(0.01 M)||CuSO4(0.5)|Cu Product is CdSO4 and reactant is CuSO4. [n=2] (SO42-)

= 0.38 + 0.049 = 0.429 V

Q18. A hydrogen electrode set up in acid solution of pH 4.9 and is coupled with SHE.
Predict the emf of the cell.
pH =
4.9 =
Ie = 0.2891 V
Q19. Find the cell potential of a galvanic cell based on the following reduction half-reactions at 25
°C. Where [Cd2+] = 0.020 M and [Pb2+] = 0.200 M.
Cd2+ + 2 e- → Cd E0 = -0.403 V
Pb2+ + 2 e- → Pb E0 = -0.126 V

Soln

. Therefore Cd is anode (oxidation) and Pb is cathode(reduction).

Cd → Cd2+ + 2 e- E0 = -0.403 V
Pb2+ + 2 e- → Pb E0 = -0.126 V

Cd + Pb2+ → Pb + Cd2+
Then
-
= -0.126 - 0.403 = 0.277 V

= 0.3065 V

Q22. The standard cell potential for the reaction

Fe + Zn = Zn + Fe2+
2+

is -0.353 V. If a piece of iron is placed in a 1 M Zn2+ solution, what is the

equilibrium concentration of Fe2+?
Soln
0
At equlibrum emf becomes Zero. n = 2 E = -0.353

= 1.08 e-12.
1.08 e-12 and [Zn2+]= 1 M Therefore [Fe2+] = 1.08 e-12 .
Limitations of SHE
SHE is difficult to construct (Maintaining unit fugacity and unit activity is difficult)
Pt/H2 is a reduction catalyst will catalyse unwanted reduction reaction.
Platinum gets easily poisoned by the impurities present in the gas and HCl.
Calomel electrode: Its Construction and its working
Due to limitations of SHE, secondary reference electrodes are needed. The potential of secondary
reference electrodes are calibrated using SHE.
Calomel Electrode is an example of metal-metal insoluble salt electrode.
Composition : Mercury is the metal. Mercurous chloride (Hg2Cl2, calomel) is the insoluble salt. Soluble
salt with common anion is KCl. Electrical contact is made using Pt wire.
Electrode representation: Cl-(aq) / Hg2Cl2 /Hg
Construction: It is made up of glass tube. Mercury is kept at the bottom. Over which a paste of Hg +
Hg2Cl2 kept. A solution of KCl is placed over calomel. A platinum wire is used to make electrical contact.
The side tube is used to make contact with other electrodes through a salt bridge.

It is a reversible electrode. It can act as cathode or anode depending on the potential of the electrode to
which it is coupled. If the potential of coupled electrode is greater than calomel electrode, calomel
electrode undergoes oxidation (Anode). If the potential of coupled electrode is less than calomel
electrode, calomel electrode undergoes reduction (Cathode).
The electrode reaction (reduction),
Hg2Cl2 + 2e  2Hg(l) + 2Cl-(aq).
The potential of the electrode is given by,

([ ] ) ([ ])

The potential of Calomel electrode depends on the concentration of Chloride (KCl) solution. Ie the
Calomel electrode is reversible with respect to chloride ion. If the KCl is saturated then we call it
saturated calomel electrode (SCE), If 1N KCl is used then it is Normal calomel electrode (NCE) and if 0.1 N
KCl is used then it is deci-normal calomel electrode. Electrode potential decreases in the order 0.1N > 1 N
> saturated KCl.
Calomel electrode is convenient to handle and it can be constructed easily.
It cannot be used above 50 ⁰C due to instability of Hg2Cl2 and mercury is poisonous.
Glass electrode and its working
Is an example of ion selective electrode.
This electrode is a doped glass membrane. It is made of low melting glass. It is having electrical
conductivity. The composition of Na2O is slightly more than ordinary soda glass.
It is selective to specific ions. H+ ion selective glass rod is commonly used for pH measurements. There
are specialized glass electrodes to find concentrations of Li +, NH4+, Na+ etc.
Construction:
Assembly consists of a long glass tube with a thin glass bulb at the bottom. It is filled with 0.1 M HCl.
Electrical contact is made using Pt wire or Ag-AgCl wire, which is kept inside glass tube. HCl in the glass
tube furnishes a constant H+ ion concentration.

Representation of electrode
Ag/AgCl(S), HCl (0.1 M)/Glass
Pt/ HCl (0.1 M)/Glass
When two solutions of different pH values are separated by a thin glass membrane there
develops a potential difference between the two surfaces of the membrane. The potential difference is
proportional to difference in pH value and the nature of glass electrode.
For a particular type of glass the potential difference varies with H + ion concentrations.
Nernst equation for the glass electrode immersed in a solution of unknown pH,

( )
[ ]

Advantages:
1. It is simple to construct
2. Easy to use
3. Equilibrium is attained rapidly
4. Results are accurate
5. It is not easily poisoned.
6. Can be used in turbid, coloured and colloidal solutions.
Limitations:
1. It can only be used in a solution whose pH is between 0 and 10. Above pH 10 the glass electrode
become sensitive to Na+ ions. This systematic alkaline error affects the measurements.
2. Requirement of electron tube voltmeter for emf measurements. (due to high resistance of glass
electrode)
Energy producing cells / battery:
Primary Cells: These are cells which cannot be recharged. Once the cell is completely discharged it
becomes dead. Example (Weston-Cadmium Cell and Lechlanche Cell or Dry Cell).

Secondary Cells (accumulator or storage cell): These cells can be recharged by forcing an
electric current through it in opposite direction, this will regenerate the original reactant. Example
(Lithium-ion battery, Lead-storage battery and nickel-cadmium battery).

Fuel Cell (Flow battery): A fuel cell is a device that directly generates electricity from the
chemical reaction between a fuel and an oxidant (not by combustion reaction). The device has two
electrodes, an electrolyte and a catalyst which speeds the reaction. Example H2-O2 fuel cell.

Battery
A Galvanic cell or a number of identical cells connected in series. It is a source of direct current. When
the cells of same type are connected in series the emf gets added.
Note:
When batteries are connected in series, the voltage increases.
When batteries are connected in parallel, the voltage remains the same, but the
current that can flow in the circuit increases

Lithium +ion Battery (Li+ ion Battery)

Is a rechargeable battery. Commercialized by Sony Corporation.

Li+ moves between anode(negative electrode) and cathode (positive electrode)

during charging and discharging.

Advantages of Lithium: More negative value of electrode potential (reduction

potential) than other metals. Li+ + e  Li (Eo = -3.05 V), Which leads to much higher open
circuit voltages.
Lithium has the lowest atomic mass than any other metal. Therefore, high specific
energy in terms of volume and mass.

Electrode material Graphite carbon and Lithium metal oxide (Lithium cobalt oxide
(LiCoO2) or Lithium cobalt mixed oxide (LiOCo2O3).LiMn2O4, LiNiO2 or LiFePO4 etc.

Electrolyte: is a combination of Lithium salts (like LiPF6, LiBF4 or LiClO4) and an

organic solvent (like ether).

Charging (Device act electrolytic cell): During charging the electrical energy is
converted into chemical energy. Anode is Lithium cobalt oxide and cathode is Graphite
electrode (CG)
At anode

Few Lithium ions get removed from the crystal lattice. Electrical neutrality is
maintained in the crystal lattice by oxidation of Co3+ to Co4+.
At Cathode
The lithium ion produced at the anode get migrated through the electrolyte and get
reduced to lithium atom at the graphite electrode.
 Li atoms are inserted between the layers of C-atoms (Lithiated Graphite). No lithium
metal as such is deposited.

Discharging (Device act electrochemical cell): During discharging the chemical

energy is converted into electrical energy. Anode is Graphite electrode (C G) and cathode is
Lithium cobalt oxide.
At anode

At Cathode

Applications
Used to power electronic devices like mobile phone, laptop etc.
Note: A combination of 18650 cells give 3000 mAh
Potentiometric Titrations
Analytical Application of Nernst Equation is Potentiometric Titrations.
 Titrations based on monitoring EMF
 Construct an Electrochemical Cell
Reference Electrode|| Analyte Solution| Indicator Electrode
Analyte solution should be electro active (Capable to donate or accept electron to or from an
electrode.
Reference Electrode should be a reversible electrode. The Potential E ref should not change with
changes in analyte concentrations. Example: Saturated Calomel Electrode (Hg|Hg 2Cl2|Cl(aq)(sat)
Indicator Electrode should develop a potential when dipped in analyte solution. The potential E ind
should respond to the changes in concentration of analyte solution. Selection of indicator electrode
is based on the titrations.
For Acid – Base titrations a change of pH value occurs. An electrode whose electrode potential
depends of pH can be used as indicator electrode. Example: Hydrogen Electrode E = -0.059pH or
Glass electrode E = EoG – 0.059 pH.
For Redox titrations any inert metal electrode can be used as an indicator electrode. For example
when Pt metal comes in contact with Fe2+/Fe3+ redox couple it develops a potential.

End point determination.

(1) Plot a direct graph : EMF vs Volume of Titrant added
There is sudden jump of emf at the end point.

(2) Plot a first derivative graph : ΔEMF vs Volume(average) of Titrant added.

Rate of change of emf is maximum at the end point.

(3) Plot a second derivative graph : Δ2EMF vs Volume(average) of Titrant added.

Second derivative passes through zero at the end point.

Example of a Potentiometric Redox Titrations
Fe3+ + e → Fe 2+

Ce4+ + e → Ce 3+

< Fe2+ can be oxidized to Fe3+ by Ce4+

Consider the titration of Fe2+ with standard solution of Ce4+ monitored potentiometrically with Platinum
Indicator electrode and Saturated Calomel Reference electrode.
Fe 2+ + Ce4+ → Fe3+ + Ce 3+

Before the equivalence point there will be un-reacted Fe2+. Ce4+ added is completely consumed to produce
Fe3+ and Ce3+ . [Ce4+] = 0 Here the platinum electrode is in contact with Fe2+/Fe3+ redox couple. The Emf
value changes logarithmically with respect to changes in concentration ratios of [Fe2+] and [Fe3+].

After the equivalence point there will be no Fe2+, only Fe3+ , Ce3+ and Ce4+ in the solution. So the Pt metals
comes in contact with Ce3+/Ce4+ redox couple. The Emf value changes logarithmically with respect to
changes in concentration ratios of [Ce3+] and [Ce4+].

The Emf values of Pt in Fe2+/Fe3+ couple is much different from Emf values of Pt in Ce3+/Ce4+ redox couple
at the end point there is jump in cell potential.

Procedure:

Take a known volume of Fe2+ solution in a beaker. Make it a cell by inserting a Pt electrode in it.
Connect the half cell to a reference electrode via a salt bridge.
Slowly add Ce4+ titrant to the Fe2+ solution and measure EMF.

Plot a graph EMF Vs Volume of titrant added. At the end point there is a sudden jump in emf.

Advantages of Potentiometric titrations

No visualization indicator is required.

It can be used when the solution has colour or turbidity
Can be easily automated.
End point is obtained graphically.
Potentiometric Acid Base titration (Important)

During acid-base titration pH value changes.

Take a known volume of acid

solution in beaker and make it a
cell by inserting a reference
electrode (saturated calomel
electrode) and pH sensitive electrode (glass
electrode).

Pt/H+(0.1M)/Glass/Test solution//Cl-/Hg2Cl2/Hg

Slowly add base from a burette and stir well. Measure

the emf against the volume of titrant added.

Since emf and pH are directly related. We will get a

similar graph. At the end point there is a sudden jump of emf.

FUEL CELL
FUEL CELL
A fuel cell is a device that directly generates electricity from a chemical reaction between a fuel and an
oxidant (not a combustion reaction).
The device has two electrodes, an electrolyte and a catalyst to speed up the reaction.
It differs from ordinary electrochemical cell in the sense that here the reactant are supplied from
outside, but in the case of galvanic cell the reactants are integral part of cell.
Example H2-O2 fuel cell. Fuel is H2 and oxidant is O2. Hydrogen and oxygen combine to form water a
needed and harmless by-product.
Electrolyte

- Alkaline solution (KOH)

- Molten Carbonate Electrolyte
- Phosphoric acid electrolyte
- Proton Exchange membrane
Etc

At anode (for alkaline electrolyte)

2H2 + 4 OH-  4H2O + 4e E0 = -0.828 V
The electrons flow through the external circuit.
At Cathode
O2 + 2H2O + 4 e  4OH- E0 = 0.401 V
Net Reaction
2H2 + O2  2H2O

Advantages
1. Has high efficiency
2. No pollution (free of noise, no vibration and by-product is water). Quiet and clean
3. It can supply energy continuously as long as reactants are fed.
4. The concentration remains unchanged.
5. It is simple and easy to operate.
Disadvantages
1. Gaseous fuels are difficult to handle
2. The electrolytes are corrosive
3. The fuels used should be extremely pure
4. Difficulty in getting a suitable catalyst.
Use:
As an auxiliary energy source in space vehicles and submarines etc.
Possible power source for automobiles.