Electronic & electrolytic conductors

Galvanic (Voltaic cell) Electrolytic cell

Chemical to electrical Electrical to chemical

Galvanic Cell - Daniel Cell
Galvanic cell – Daniel cell

https://youtu.be/xDITrdbajAs
 Representation of galvanic cell.

• Anode Representation:
Zn│Zn2+ (1M) or Zn ; Zn2+ (1M)
Zn │ ZnSO4 (1M) or Zn ; ZnSO4 (1M)

• Cathode Representation:
Cu2+ (1M) │ Cu or Cu2+ (1M) ;Cu
Cu2+ (1M) ; Cu or CuSO4(1M) │ Cu

• Cell Representation:
Zn │ ZnSO4 (1M)║ CuSO4(1M) │Cu
 Anode vs Cathode in Galvanic cell

Anode:
• Electrode at which oxidation occurs
• is where electrons are produced
• has a negative sign

Cathode:
* Electrode at which reduction occurs
• is where electrons are consumed
• has a positive sign

Oxdn. Is Losing Electrons, Rdn. Is Gaining Electrons

Electrolytic Cell

external circuit

internal circuit
Electrolytic cell

https://youtu.be/HQ9Fhd7P_HA 9
 Comparison between Galvanic and
Electrolytic Cell
Galvanic Cell Electrolytic Cell

• Cell reaction is spontaneous • Cell reaction is non spontaneous

• Converts Chemical Energy to •
Electrical Energy
• Anode is negative terminal and •
cathode is positive terminal
• Have two electrodes and two •
electrolytes
• Used as portable source of
electric energy.
• Salt bridge is used
• Eg: Daniel Cell
Converts Electrical Energy into
Chemical Energy
Anode is positive terminal and
cathode is negative terminal
Have two electrodes and single
electrolyte
• Used in Electrolysis apparatus.
• Salt bridge is not used
• Eg : Electroplating.
 Comparison…….contd..
•Similarities:

•Involves oxidation at anode & reduction at cathode

• oxidation & reduction in the separate regions

•Electrons flow from anode to cathode in the external

circuit

•Reactions occur on electrode surface only

Porous diaphragm Salt bridge 12
 Liquid Junction Potential (LJP)
With Porous disc
• Difference between the
electric potentials
developed in the two
solutions across their
interface .
• Ej = Ø soln, R − Ø soln,L
Eg: Contact between:
✓ Two different electrolytes
(ZnSO4/ CuSO4).
✓ Same electrolytes of
different concentrations.
 Salt Bridge - Elimination of LJP
A device that permits electrical contact between two solutions,
while preventing direct reaction between the reactants/mixing.

Cell: Zn/Zn2+(0.01M) // Cu2+(0.1M)/Cu

 Functions of SB
▪ It maintains electrical neutrality in the two half cells
▪ It provides electrical contact between the two electrolyte solutions
of a cell
▪ It minimizes LJP in galvanic cells containing two dissimilar
solutions in contact

salts used in salt

bridge: potassium nitrate,
potassium chloride, ammonium
nitrate etc.
 Origin of single electrode potential

Zinc ions moves into Copper ions gets deposited as

solution leaving copper leaving behind free
behind electrons negatively charged sulfate ions in
making it electron rich solution makes the electrode
electron poor
• The potential of single electrode is the difference of
potential between a metal and the solution of its salt. i.e
the tendency of an electrode to lose or gain electrons
when in contact with its own ions in the solution

• In a cell, the electrode with lower electrode potential

has less tendency to undergo reduction and acts as
anode.
• The electrode with higher electrode potential has higher
tendency to undergo reduction and acts as cathode. 17
 Measurement of electrode potential
• It is impossible to determine the absolute half cell potential.
• We can only measure the difference in potential between two
electrodes potentiometrically, by combining them to form a
complete cell.

Platinum

SHE

https://www.google.com/search?q=measuring+single+electrode+potential+of+zinc+electrode+when+copuled+with+SHE&rlz=1C1CHBF_enIN922IN922&source=lnms&tbm=isc
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Measurement of electrode potential
Zn electrode

Ecell = Ecathode- Eanode

Cu electrode
Standard electrode potential: E0 is the electrode potential
when electrode is in contact with a solution of unit concentration at
298 K involving pure solids and liquids
 Emf of a cell
The difference of potential, which causes a current to flow from
the electrode of higher potential to one of lower potential.
Ecell = Ecathode- Eanode

ECell 3 factors:

*The nature/composition of the electrodes

*Temperature E α T
*Conc. of the electrolyte solns E α C.

Ecell is always +ve

ΔG = - nFE
Standard emf of a cell(Eo cell) is defined as the emf of a cell when the
reactants & products of the cell reaction are at unit concentration or
unit activity, at 298 K and at 1 atmospheric pressure.

The emf cannot be measured accurately using ordinary voltmeter

• part of the cell current is drawn to deflect the needle

• part of the emf is used to overcome the internal resistance of the
cell

Measured emf < Actual emf of cell

The potentiometric measurement of emf of a cell:
Poggendorff’s compensation method
S
Rh
C
+ -

The emf of the cell Ex is D D’

proportional to the length AD A

B

Ex

Ex α AD J

The emf of the standard cell Es is Es

proportional to the length AD1

Es α AD1 AB- Potentiometric wire
ES- Standard cell
Ex ═ AD
Ex- unknown cell
Es AD1
G- Galvanometer
Ex = AD x Es J- Sliding contact.
AD1 C-Rh – adjustable resistance
S- Storage battery
25
 Energetics of Cell Reactions
• Net electrical work performed by the cell reaction of a galvanic cell:
W = QE ------ (1)
Q is the quantity of electrical charge in coulombs produced by the reaction and
E is the emf of the cell in volts
• Charge on 1 mole of electrons = F Coulombs (96,500 )
• When ‘n’ moles of electrons are involved in the cell reaction, the total charge on
‘n’ moles of electrons = nF coulombs
Q = nF
Substituting for Q , W = nFE
• The cell does net work at the expense of the decrease in free energy change
(ΔG) accompanying the cell reaction
i.e., Net electrical work = Decrease in free energy

ΔG = - nFE
Energetics of Cell Reactions

Ratio is temperature coefficient

 Nernst Equation
An expression of a quantitative relationship between electrode
potential/cell potential and concentration of the electrolyte species
in an electro-chemical reaction
Mn+ (aq) + ne- M(s)
vant Hoff reaction isotherm: R = 8.314J/mol/K T in kelvin, F = 96500 C

G = Go + RT ln K RT 1
E = E − 2.303
o
log n+
[M] nF [M ]
G = Go + RT ln
[Mn+ ]
ΔG =-nFE At T = 298K,
[M]
− nFE = − nFE o + RT ln
[Mn+ ] E = Eo −
0.0592 1
log n+
RT 1 n [M ]
E = Eo − ln n+
nF [M ] 0.0592
E = Eo + log [Mn+ ]
n
 Nernst Equation
.From Nernst equation,
If concentration of solution (Mn+) and temperature is increased, the
electrode potential increases and vice versa.

 RT Conc of species at Cathode 

E cell = E cell + 2.303 nF log Conc of species at anode 
0

 
For Daniel cell

RT Cu 2+
Ecell = E𝑐0 − 𝐸𝐴0 + 2.303 log
nF Zn 2+
 Significance of the Nernst equation
• To calculate the potential of a cell that operates under non-standard
conditions.

• To measure the equilibrium constant for a reaction, when the overall

cell potential for the reaction is zero
At equilibrium the overall cell potential for the reaction is zero. i.e. E=0
Nernst equation,
E=E° - (RT/nF)lnKc
0 = Eo - RT/nF lnKc
Eo = RT/nF lnKc
RTlnKc = nFE°
Kc = e nFE° / RT
 Calomel electrode
• Consists of a tube, in the
bottom of which is a layer
of mercury, over which is
placed a paste of mercury
and mercurous chloride.
• Remaining portion of the
cell is filled with a solution
of normal/decinormal/
saturated solution of KCl.
• A platinum wire sealed at its
end fixed into the main tube
dipping into the mercury
layer for electrical contact.
 Calomel electrode
• Representation: Hg; Hg2Cl2 / KCl
2Hg → Hg22+ + 2e- Hg22+ + 2Cl- → Hg2Cl2
As anode: 2Hg + 2Cl- → Hg2Cl2 + 2e-
As Cathode: Hg2Cl2 + 2e- → 2Hg + 2 Cl-
0.0592 [product]
E = Eo − log
n [Reactant]
E= Eo - 0.0591 log [Cl-]2 at 298 K
2

Nernst equation E= Eo - 0.0591 log [Cl-] at 298 K

Its electrode potential depends on the concentration of KCl.

Conc. of Cl- Electrode potential
0.1M 0.3335 V
1.0 M 0.2810 V
Saturated 0.2422/2444 V
 Calomel electrode
To determine the EMF of a cell and pH of a solution.

Pt|H2|H+(X) ||KCl|Hg2Cl2|Hg

Ecell= 0.2422-(- 0.0592pH)

pH = (Ecell – 0.2422) / 0.0592

 Calomel electrode
Advantages
• It is very simple to construct.
• It can be used for a long time without much attention.
• Electrode potential is stable over a long period.
• It has low temperature coefficient of emf.
• It is less prone to contamination.

Disadvantages
• Calomel electrodes should not be used above 50oC .
• Calomel electrode should be used with proper precaution as
mercury compounds are toxic.
 Ion Selective Electrode

• The electrode which is sensitive to a specific ion present in an

electrolyte whose potential depends upon the activity of specific
ion in the electrolyte is called ion selective electrode.
Combined
glass electrode
 Glass electrode

Electrical contact
Glass Membrane
Protective sleeve

Ag/AgCl wire

HCl, 0.1 mol dm-3(Reference solution of dilute HCl)

Thin walled glass

membrane Inner Outer
Solution of
unknown pH E2 E1
C2 C1

H+ + Na+ ↔ Na+ + H+
(soln.) (glass) (soln.) (glass)
Schematic diagram of the
structure of glass, which consist of an irregular
network of SiO4 tetrahedra connected through
Oxygen atoms.

Cations are coordinated to the oxygen atoms.

SiO2 gel layers on

glass surface

Internal solution External solution

0.1 mm glass membrane

With exchangeable Na+
 Electrode Potential of glass electrode.

The overall potential of the glass electrode is given by:

Eg = Eb + Eref. + Easy.

It has three components:

➢ The boundary potential Eb,
➢ Internal reference electrode potential Eref.

➢ Asymmetric potential Easy

• Eb = E1 – E2

= (RT/nF) ln C1 – (RT/nF) ln C2
= L + (RT/nF) ln C1 where L is - 0.0592 log C2
Eb depends upon [H+]

Eg = Eb + EAg/AgCl + Easy

= L + (RT/nF) ln C1 + EAg/AgCl + Easy.

= Eog + (RT/nF) ln C1
= Eog + 0.0592 log [H+]

Eg = Eog – 0.0592 pH
 Application of glass electrode

Determination of pH:

Cell: SCE │Test solution ║ GE

E cell = Eg – Ecal.

E cell = Eog – 0.0591 pH – 0.2422

pH = Eog -Ecell – Ecal. / 0.0591

 Disadvantages of glass electrode
▪ The bulb is very fragile and has to be used with great care.

▪ In the presence of alkali ions, glass surface becomes responsive to

both hydrogen and alkali ions. Measured pH values are low.

▪ In highly acidic solutions measured pH values are high.

▪ When not in use, the electrode should be stored in an aqueous

solution.

▪ Ordinary potentiometers can not be used to measure the potential

of glass electrode

▪ The commercial version is moderately expensive

▪ Standardization is to be carried out frequently

 Q-1
KCl solution is used to make salt bridge because
• KCl is highly soluble in water
• To increase liquid junction potential
• Mobilities of K+ and Cl- are nearly the same
• Mobility of K+ is greater than Cl-

Which of the following statements is incorrect?

• An external power supply is needed in an electrolytic cell.
• In a galvanic cell difference between the electrode potentials of two
electrodes is responsible for the flow of electrons between the two half
cells.
• The electrode with a higher standard electrode potential will undergo
reduction with respect to other electrode.
• In a galvanic cell, the passage of a current through the electrolytes drives a
redox reaction.

Which of the following factors will not affect appreciably the emf of the cell?
• 1. Nature of the electrode
• 2. Concentration of the electrolyte
• 3. Temperature
• 4. Liquid junction potential 46
 Q-2
The EMF of the following cell is found to be 0.20 V at 298 K,
Cd(s)/Cd2+(aq)(?)// Ni2+ (aq) (2.0 M)/Ni (s)
What is the molar concentration of Cd2+ ions in solution?
• 1. 4.00 M
• 2. 0.040 M
• 3. 0.400 M
• 4. 0.004 M

Ans: 
E = E 0
- 2 . 303
RT
log
P  − 1.692 = [logx - log2 
 cell R 

cell
nF

 x  − 1.692 + 0.3010 = [logx

 0 . 20 = 0.15 - 0 . 0591 / 2 log
 2
− 1.391 = [logx 

0 .05 = - 0. 0591 / 2 log
x 
 2
 X = 0.04 M 
0.1 = - 0.0591 [logx - log2  47
 Q-2
If E1, E2 and E3 are the emf values of the following three galvanic cells
respectively
Mg|Mg2+(0.02 M)||Cu2+(0.2 M)|Cu
Mg|Mg2+(0.2 M)||Cu2+(0.2 M)|Cu
Mg|Mg2+(0.1 M)||Cu2+(0.2 M)|Cu
Which one of the following is true?
• E3>E2>E1
• E1>E3>E2

E = [2.71] - 0.0295 log
0.2
• E1>E2>E3  2 0.2

• E2>E3>E1
 RT  P  
E 2 = 2.71
 E cell = E 0
- 2.303 log
   
=
0.1
 
cell
E
 3 [2.71] - 0.0295 log
0.2
nF R

 0.02
E
 1 = [0.34 - (-2.37)] - 0.0591/2 log
   E 3 = 2.71 - 0.0295 log (-0.3010)
 0.2 
E1 = 2.71 - 0.0295 log (-1) E1 = 2.71 + 0.0295 E 3 = 2.7188
E1 = 2.7395
 Q-2
Which among the following combinations of electrodes in 1M concentration of itꞌs
salt solution at 298K produce maximum emf?
(Given Eo of Fe3+ = 0.77 V, Cu2+ = 0.34 V, Sn2+ = -0.14 V and Mg2+ = -2.37 V)
1. Fe3+ and Sn2+ E = 0.77 - (- 0.14) = 0.91
2. Cu2+ and Mg2+ E = 0.34 - (- 2.37) = 2.71
3. Fe3+ and Mg2+ E = 0.77 - (- 2.37) = 3.14
4. Cu2+ and Sn2+ E = 0.34 - (- 0.14) = 0.48

A standard cell has a

1) 0.0V potential at 298K
2) Negligible temp. coeff. Of emf
3) 1.0V potential at 298K
49
4) high temp. coeff. Of emf
 Q-2
What is EoNi2+/Ni at 298 K if the emf of Zn(s)/Zn2+(1M)││Ni2+(1M)/Ni(s) is 0.51V and
Zn(s)/Zn2+(1M)││SCE is 1.002V (ESCE = 0.2422V).
1. 0.7568
2. -1.2698
3. 1.2442
4. -0.2498


0.51 = [E0Ni - (-0.7598)] - 0.0591/2 log
1
 1

E0Ni = 0.51 - 0.7598 = - 0.2498 V
E0Zn = 0.51 - 0.7598 = - 0.2498 V E cell = E calomel - E Zn 
1.002 = 0.2422 - E Zn 
E Zn = 0.7598
 Q-2
The standard free energy change in joules of the following cell at 300 K.
Cu(s) / Cu2+(0.1M)║Ag+(0.25M) / Ag(s); Eocell = 0.46 V
1. -88,780
2. -44,390
3. 88,780
4. 44,390

ΔG° = -nFE°

= -2×96500×0.46 = -88,780 J

51
 Q-2
Saturated calomel electrode is called as a secondary reference electrode because
1. Its potential depends on the concentration of KCl used
2. Its potential is fixed as zero volt
3. Its potential is constant and measured with respect to primary reference
electrode
4. Mercurous chloride decompose above 50° C

Calomel electrode is an example of

1. Redox electrode
2. Metal insoluble salt electrode
3. Ion selective electrode
4. Gas electrode 52
 Q-2
Calculate the free energy of Cu electrode with Cu2+ concentration 0.015 M.
1. -44816 J
E = E° - 0.0591/2 log1/[Cu2+)
2. -55217 J
= 0.34-0.0591/2 log 1/0.015 = 0.2861 V
3. -65620 J
4. -65260 J ΔG = -nFE = -2×96500×0.2861
= -55217 J

The emf of a cell, Pt | H2 | H+ (x) || KC l |Hg2Cl2 | Hg is 0.83V at 298K.

Then the pH of the unknown solution is
1) 8.9
2) 9.9 pH = (Ecell – 0.2422)/0.0592
3) 4.11 = (0.83-0.2422)/0.0592
4) 5.02 = 9.9
53
 Q-3

1.Calculate the standard emf in volts for a cell containing Sn2+ / Sn and Br2 / Br -
electrodes.
[ Eo ( Sn2+ / Sn) = − 0.14 V, Eo ( Br2 / Br -) = 1.08 V]

Ans: Eocell = Eocathode − Eo anode

Because reduction potential of Eo ( Br2 / Br-) is higher, it is cathodic
Eocell = Eo ( Br2 / Br -) - Eo ( Sn2+ / Sn)
= 1.08 – (− 0.14)
= 1.22 V

54
2.Using the electrochemical series, calculate the emf in volts for the
cell Fe(s) | Fe2+(0.1 M) || Cd2+(0.2 M) | Cd at 298 K. Write the
cell reactions.

Ans: From the series we have;

Eo Cd2+/Cd = − 0.40 V ; Eo Fe2+/Fe = − 0.44 V
At anode Fe →Fe2+ + 2 e−
At Cathode Cd2+ + 2 e− → Cd
Net reaction: Fe + Cd2+→ Fe2+ + Cd
EMF of the cell at 298 K is given by
Eocell = Eocathode − Eo anode
= − 0.40 − (− 0.44)
= 0.04 V
Ecell = Eocell − (0.0591 / n) log [ Fe2+ ] / [Cd2+]
= 0.04 −( 0.0591/ 2 ) log [0.1] / [0.2]
55
= 0.0488 V
3. Find the molar concentration of Cd2+ ions in the given electrochemical cell.
Zn / Zn2+ (0.1 M) // Cd2+(M)/ Cd
Given Eo Zn2+/Zn = − 0.76 V; Eo Cd2+/Cd = − 0.40 V ; and Ecell = 0.3305 V at
298 K
Ans: Cell representation
Zn│Zn2+(1M)││Ag+(10M)│Ag
Cell reaction:
Zn + 2Ag+ → Zn2+ + 2Ag
Eocell = Eocathode − Eo anode
= 0.80 − ( −0.76) = 1.56 V
Ecell = E°cell − (0.0592/ 2) log [1]/[10]2
= 1.56 – (0.0591 /2) log [1] / [10]2
= 1.6192 V

56
4.Write the cell reactions and calculate the EMF in volts for the following cell at
298K.
Mg/ Mg2+ (0.001M) // Cu2+ ( 0.0001M) / Cu .
Given Eo Cu2+/Cu = 0.34 V and Eo Mg2+/Mg = − 2.37V
Ans: At anode Mg → Mg2+ + 2 e−

At cathode Cu2+ + 2 e− → Cu

Net reaction Mg + Cu2+ → Mg 2+ + Cu

Ecell = Eocell − (0.0591/n ) log [ Mg2+]/ [Cu2+]

Eocell = Eocathode − Eo anode

= 0.34 – [ −2.37]
= 2.71V

Ecell = 2.71 – (0.0591 /2) log [0.001]/ [0.0001]

= 2.6805 V 57
5. Emf of Weston Cadmium cell is 1.0183 V at 293 K and 1.0181 V at 298 K.
Calculate

∆G, ΔH and ΔS of the cell reaction at 298 K.

∆G = - n FE
n = 2 for the cell reaction;
F = 96,500 C E= 1.0181 V at 298 K
∆G = -2 x 96,500 x 1.0181 J = -196.5 KJ
∆H = nF [ T (δE /δT)P – E]
(δE/δT)p = 1.0181 – 1.0183 / 298-293 = -0.0002 / 5
= - 0.00004VK-1
T = 298 K
∆H = 2 x 96,500 { [298 x (-0.00004)] – 1.0181}
= -198. 8 KJ
ΔS = nF(δE / δT) P
= 2 x 96,500 x (0-00004) = -7.72JK-1 58