3.

ELECTROCHEMISTRY- REVISION NOTE (AJC)

➢ Electrochemistry deals with relationship between electrical energy and chemical energy and their inter-conversion.
➢ Electrochemical cell is a device in which chemical energy is converted into electrical energy

• The electrode at which oxidation occurs is called anode and at which reduction occurs is
called cathode.
• Salt bridge - It is inverted U like tube containing saturated solution of some electrolyte like
KCl, KNO3, NH4NO3 with agar-agar jelly or gelatine and connects the anode and cathode in an
electrochemical cell.

Functions of salt bridge:-

→ It allows the flow of current by completing the inner circuit.
→ It maintains electrical neutrality in both the half cells.
Cell representation:
A cell with the following chemical reaction:

may be represented as

EMF of the cell: - It is defined as the potential difference between the two terminals of the cell when either no or very little
current is drawn from it. Ecell = ECathode– Eanode
Standard Hydrogen electrode (SHE) OR Normal Hydrogen Electrode (NHE)

➢ H2(g) 2H+ +2e

if SHE acts as anode
➢ 2H+ +2e H2(g)
if SHE acts as cathode
• Presentation of the cell having SHE and a copper electrode:
• This is a half cell having zero electrode potential.
• Electrode potential of any element is determined in relative term of it.
Nernst equation:
This equation is used to measure the electrode potential of any half cell at any concentration with respect to SHE.

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)

Relationship between equilibrium constant and standard electrode potential

Relationship between standard Gibbs free energy and standard electrode ΔG° = -n F E0
Relationship between standard Gibbs free energy and equilibrium constant ΔG° = -2.303RT ×log Kc

Metallic or electronic conductance: It isdue to flow of electrons.

Electrolyte or ionic conductance:–It is due to the movement of ions when an electrolyte decomposes in a
solvent.
Metallic conductance depend upon
i) The nature & structure of metal.
ii) The no. of valence electrons per atom.
iii) Temperature (decreases with increasing temperature.)
Ionic Conductivity depends upon-
i) The nature of electrolyte & solvent.
ii) size of ion & solvation.
iii) concentration of electrolyte.
iv) temperature (increases with increasing temperature.)
Molar conductivity
the conductance property of a solution containing one mole of the electrolyte
Λm = K / C

K is specific conductivity and c is the concentration in mole per litre. The unit of molar conductivity is S⋅m2⋅mol-1.

limiting molar conductivity - The molar conductivity of a solution at infinite dilution is known as limiting molar
conductivity. In other words, When the concentration of the electrolyte approaches zero, the molar conductivity is
known as limiting molar conductivity.

Change in conductivity with concentration – conductivity decreases with decrease in concentration or increase
in dilution for both strong and weak electrolytes. Reason - number of ions per unit volume that carry current
decreases on dilution.

Change in molar conductivity with concentration – molar conductivity increases with decrease in concentration
or increase in dilution.

• For strong electrolyte – slow increase in molar conductivity with decrease in concentration. Reason – inter ionic
attraction is decreasing and mobility is increasing during dilution. Explained using Debye Huckel Onsagar
equation

slope = -K , intercept = Λ0m

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)

• For weak electrolyte – steeply increase in molar conductivity with decrease in concentration. Reason – degree
of dissociation of weak electrolyte increase with increase in dilution. Λ0m will no be obtained by extrapolating the
graph.

Λ0m is calculated using Kohlrausch’s law.

KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS: It states that limiting molar conductivity of an
electrolyte can be represented as the sum of the individual contributions of the anion and cation of the
electrolyte.

if Λ0m Na+ and Λ0m Cl are limiting molar conductivity of the sodium and chloride ions respectively, then the limiting molar

conductivity for sodium chloride is given by the equation:

Applications of Kohlrausch law: This law is used to measure the limiting molar conductivity ,

degree of dissociation and dissociation constant of weak electrolytes

Electrolytic cell - In this cell electric energy is used to carry non spontaneous chemical reaction. An electrochemical
cell works as electrolytic cell if external voltage supplied is more than the emf of the cell.
FARADAY’S LAWS OF ELECTROLYSIS
(i) First Law: The amount of chemical reaction occurs at any electrode during electrolysis proportional to the quantity
of electricity passed through the electrolyte.
M = Zit (M=Mass of substance obtained at electrode, i = current in Ampere, t= time in seconds)
(ii) Second Law: The amounts of different substances liberated by the same quantity of electricity passing through
the electrolytic solution are proportional to their chemical equivalent weights.

PRODUCTS OF ELECTROLYSIS
➢ Molten NaCl – NaCl → Na+ + Cl-
Anode reaction: Cl- → ½ Cl2 + 1e
Cathode reaction: Na+ + 1e → Na
➢ Aqueous NaCl solution – NaCl (aq) → Na+(aq)+ Cl- (aq) (products = H2,Cl2,NaOH)
Anode reaction : Cl- → ½ Cl2 + 1e
Cathode reaction: H2O + 1e → ½ H2 + OH-
➢ Sulphuric acid: cathode reaction: 2H+ + 2e → H2
Anode reaction: 2H2O → O2 + 4H+ + 4e ( normal case)
2SO42- → S2O82- + 2e (when con. Of H2SO4 is higher)
BATTERIES: Any battery or cell that we use as a source of electrical energy is basically a galvanic cell.

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)
1. Primary batteries In the primary batteries, the reaction occurs only once and after use over a period of time battery
becomes dead and cannot be reused
eg : Dry cell or Leclanche cell: Ecell = 1.5V
Anode – zinc container, cathode – carbon rod surrounded by MnO2 and carbon, electrolyte – moist paste of
NH4Cl and ZnCl2

Eg : Mercury or Button cell: Ecell = 1.35V

Anode- zinc amalgam, cathode – paste of HgO & carbon, electrolyte – paste of KOH & ZnO

T
2. Secondary Batteries: A secondary cell after use can be recharged by passing current through it in the
opposite direction so that it can be used again.
Eg: Lead Storage Cell: anode- lead, cathode – lead packed with PbO2, electrolyte – 38% H2SO4

overall cell reaction consisting of cathode and anode reactions is:

Eg: Nickel Cadmium cell: longer life span but expensive

➢ Fuel Cell : fuel cell are galvanic cell that convert energy of combustion of fuel directly in to electrical
energy. Fuel used are hydrogen, methane , methanol. Its efficiency is about 70%. Pollution free. Used in
Appollo space program.
H2 and O2 bubbled through porous carbon electrode into concentrated aqueous NaOH solution.

CORROSION: the phenomenon of degradation of upper layer of metal in presence of oxygen, moisture
and atmospheric gases etc. e.g rusting of Iron

Prevention of Corrosion
1. Barrier protection through coating of paints or electroplating.
2. By the use of anti-rust solutions (bis phenol).

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)

3. By cathodic protection in which a metal is protected from corrosion by connecting it to another metal that is more
easily oxidized.

1. When electric current is passed through a cell having an electrolyte, the positive ions move towards the cathode and the
negative ions towards the anode. If the cathode is pulled out of the solution what happens?
ANS) The positive and negative ions will start moving randomly
2. If the half-cell reaction A+e−→A−has a large negative reduction potential? ANS) A−is readily oxidized
3. The specific conductance of a 0.1N KCl solution at 23oC is 0.012 ohm−1cm−1. The resistance of cell containing the solution
at the same temperature was found to be 55 ohm. The cell constant will be?
ANS) k= (1/R) × cell constant, cell constant = k × R = 0.012 × 55 = 0.66 cm-1
4. At 25°C specific conductivity of a normal solution of KCl is 0.002765 mho. The resistance of cell is 400 ohms. The cell
constant is?
5. Ag+(aq) + e– → Ag(s) E° = + 0.80 V, Fe2+(aq)+ + 2e– → Fe(s) E° = – 0.44 V, What is emf of Fe(s) + 2Ag+(aq) → Fe2+(aq) + 2Ag(s)
ANS) Ecell = Ecathode – Eanode = 0.80 - (-0.44) = 1.24 V

6. What is the expression for ‘Ka’ in terms of Λ° and Λ, where ‘C’ is molarity. ANS)
7. A new galvanic cell of E0v more than E°V of Daniel cell is connected to Daniel cell in a manner that new cell gives electrons
to cathode, what will happen?
ANS) Daniel cell will work as electrolytic cell where Zn will be deposit on zinc rod and copper will dissolve from copper rod
8. A silver cup is plated with silver by passing 965 coulombs of electricity, the amount of silver deposited is?
ANS) W= (EAg × Q )/ 96500 = (107.87 × 965) / 96500 = 1.0787g
9. Following reactions occur at cathode during the electrolysis of aqueous sodium chloride solution:
Na+(aq) + e-1 ——-> Na E° = – 2.71 V
H+(aq) + e-1 ——–> ½ H2 E° = 0.00 V
On the basis of their standard reduction electrode potential (E°) values, which reaction is feasible at the cathode and why?
ANS) reaction with high potential is preferred at cathode during electrolysis. so, H+(aq) + e-1 → ½ H2will be occurring at cathode.
10. Blocks of magnesium are straped to the steel hubs of ocean going ships. Why ?
ANS) magnesium provides cathodic protection and prevent rusting or corrosion thus prevent the action of water and salt.
11. Why does the cell potential of mercury cell remain constant throughout its life?
ANS) The mercury has a constant cell potential throughout its useful life because the ions of mercury cell are not involved in the
overall cell reaction. It gives 1.5V constant potential throughout the lifespan. The life time of any cell is dependent on the ions
present in that cell.
12. Write two advantages of fuel cell.
ANS) High Efficiency, Good reliability, Noise- offers a much more silent and smooth alternative to conventional energy production,
greatly reduces CO2 and harmful pollutant emissions, fuel cells are significantly lighter and more compact
13. Can you store copper sulphate solutions in a zinc pot?

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)
ANS) No, Zn is highly reactive than Cu. So, it can displace Cu from its solution. Zn + CuSO4 → ZnSO4 + Cu
14. Why button cell is used in voltage sensitive devices? ANS) because they are reliable and have high output to mass ratio.
15. Out of Zn and Sn which one protects iron from corrosion better even after cracks and why?
ANS) Zn undergoes oxidation in preference to iron. Thus, Zn is called sacrificial anode. But in case of tin, when the coating is
worn away partially tin cannot prevent iron from rusting.
16. Two half cell reactions of an electrochemical cell are given below :
MnO–4(aq) + 8H+(aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = + 1.51 V , Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Construct the redox equation from the two halfcell reactions and predict if this reaction favours formation of reactants or product
ANS) Anode reaction ( oxidation) - Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Cathode reaction (reduction) - MnO–4(aq) + 8H+(aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = + 1.51 V
E0cell = E0cathode – E0anode = 1.51 – 0.15 = 1.36 V, positive value therefore reaction is product favoured.(forward reaction)
17. Express the relation among the cell constant, the resistance of the solution in the cell and the conductivity of the solution.
How is the conductivity of a solution related to its molar conductivity?
ANS) conductance G = 1/R ,Conductivity k= G× G* = 1/R ×G* , Cell constant G* = Rk , Molar conductivity Λm= Kv = 1000k/ C
18. Given that the standard electrode potentials (E°) of metals are : K+/K = -2.93 V, Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34 V,
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V, Fe2+/Fe = -0.44 V. Arrange these metals in increasing order of their reducing power?
ANS) lower the electrode potential, the stronger is the reducing agent. Ag<Cu<Fe<Cr<Mg<K
19. Determine the values of equilibrium constant (Kc) and ΔG° for the following reaction :
Ni(s) + 2Ag+(aq) → Ni2+ (aq) + 2Ag(s),E° = 1.05 V(1F = 96500 C mol-1)
ANS) ΔG° = -n F E0 = - 2 × 96500 × 1.05 = 202600J
ΔG° = -2.303RT ×log Kc = 202600 = -2.303 × 8.314 × 298 × logKc → Kc = 3.16×10-36
20. A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is 95% dissociated at this dilution at 298 K. Calculate the electrode
potential.[ E°Zn2+ /Zn = – 0.76 V]

ANS) → E = E0 – (0.0591/n) × log (1/[Zn2+]) → E = -0.76 –( 0.0591/2 ) × log (1/[Zn2+])

2+
[Zn ]= 0.1 × (95/100) = 0.095M
E = -0.76 – (0.0591/2) × log (1/0.095) = -0.76 – (0.0591/2 ) × 1.0223 = -0.7902V
21. How many grams of bromine can be produced by the electrolysis of molten magnesium bromide with a current of 3.2A
for 50 minutes? (Mg=12;Br=80amu)
ANS) w= (E I t) / 96500 →
22. Write the cell reactions which occurs in lead storage battery when the battery is on charging mode.
ANS) During charging reverse reaction to normal cell reaction occur , 2PbSO4 + 2H2O → Pb + PbO2 + 2H2SO4
23. Aluminium metal cannot be produced by the electrolysis of aqueous solution of aluminium salt. Why?
ANS) Discharge potential of Al is higher than that of H2. Thus, the aqueous solution containing Al3+ and H+ ions, when electrolysed,
the H+ ions are discharged at cathode and H2 gas is evolved.
24. Conductivity of 2.5 X 10-4M methanoic acid is 5.25 X 10-5 S cm-1 Calculate its molar conductivity and degree of
dissociation. Given: Λ0(H+) = 349.5 S cm2 mol-1 and Λ0(HCOO–) = 50.5 S cm2
ANS) Molar conductivity Λm= 1000k/C = (1000 × 5.25×10-5) / 2.5×10-4 = 210 S cm2 mol-1
Limiting molar conductivity Λ0m(CHCOOH) = Λ0(H+) + Λ0(HCOO-) =349.5 +50.5 = 400 S cm2 mol-1
Degree of dissociation α = Λm/ Λ0m = 210/400 = 0.52 = 52%
25. Calculate E°cell and ΔG° for the following reaction at 25 °C: A2+(aq) + B+(aq) → A3+(aq) + B(s) Given Kc=1010, 1F=96500 C
ANS) : ΔG° = -2.303RT log Kc = -2.303 × 8.314 × 298 log 1010 = -17139.11J
ΔG° = - n F E0 = -17139.11= - 1 × 96500 × E0 → E0 = 0.178 V
26. Calculate emf of the following cell at 25 °C: Fe| Fe2+(0.001 M) II H+(1 M) | H2(g) (1 bar) | Pt(s),
E°(Fe2+|Fe) = -0.44V, E°(H+|H2) = 0.00 V

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)

ANS): Fe(s) + 2H+(aq) → Fe+2(aq) + H2(g)

Nernst equation Ecell = E0cell – (0.0591/n) × log [oxidised]/[reduced]
There are two electron are transfering so that n=2
E0cell= E0cathode – E0anode → E0cell= 0−(−0.44)V = +0.44V
Ecell= 0.44− (0.0591/2) × log [Fe2+] / [H+]2 = 0.44 – (0.0591/2) log (0.001/12)
Ecell= 0.44 – (0.0591/2) log(10−3) = 0.44 – (0.0591/2) (−3) = 0.44 + 0.089 =0.53V
27. A copper silver cell is setup the copper ion concentrations in it is 0.01M. The concentration of silver ion is not known. The cell
potential measured 0.422V Determine the concentration of silver ion in the cell. Given E0Ag+/Ag = 0.80V and E0Cu2+/Cu = +0.34V
ANS) Reduction potential of Ag is higher than Cu. So, Cu is anode and Ag is cathode. Cu + 2Ag+ → Cu2+ + 2Ag
E = E0(cathode – anode) – (0.0591/2) log [Cu2+]/[Ag+]2 → 0.422 = (0.80 -0.34 ) – (0.0591/2) log 0.1/[Ag+]2 → log 0.1/[Ag+]2 = 1.288
[Ag+] = 7.1 × 10-2 M
28. The conductivity of 10-3mol /L acetic acid at 250C is 4.1 x 10 -5 S cm-1. Calculate its degree of dissociation, if λom for acetic
acid at 250C is 390.5 S cm2 mol-1 ANS) Molar conductivity Λm= 1000k/C Degree of dissociation α = Λm/ Λ0m
29. Solutions of two electrolytes ‘A’ and ‘B’ are diluted. The limiting molar conductivity of ‘B’ increases 1.5 times while that
of ‘A’ increases 25times.Which of the two is a strong electrolyte? Justify your answer.
ANS) B is stronger electrolyte than A. In B number of ions remain the same on dilution. But only interionic attraction decreased.
That is why molar conductivity increased only 1.5 times. While in weak electrolyte A on dilution number of constituent ions
increases. So, drastic increase in molar conductivity.
30. The conductivity of 0.20 mol L-1 solution of KCl is 2.48 X 10-2 S cm-1. Calculate its molar conductivity and degree of
dissociation Given Λ0m (K+) = 73.5 S cm2 mol-1 and Λ0m (Cl-) = 76.5 S cm2 mol-1
31. The conductivity of 0.1 mol L-1 solution of NaCl is 1.06 X 10-2 S cm-1. Calculate its molar conductivity and degree of
dissociation. Given Λ0m (Na+) = 50.1 S cm2mol-1 and Λ0m (C1-) = 76.5 S cm2 mol-1
32. Resistance of a conductivity cell filled with 0.1 mol L-1 KCl solution is 100 Ω. If the resistance of the same cell when filled
with 0.02 mol L-1 KCl solution is 520 Ω, calculate the conductivity and molar conductivity of 0.02 mol/ L KCl solution. The
conductivity of 0.1 mol L 1.29 X 10-2 S cm-1

ANS)

33. Calculate the potential of hydrogen electrode in contact with a solution whose Ph is 10?

ANS) pH=10, we known that pH= −log[H+] ⇒ [H+]= 10−10M

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 3. ELECTROCHEMISTRY- REVISION NOTE (AJC)
for hydrogen electrode : Ecell = E0− (0.0591/1) × log([H2]/[H+]

(no of electron included =1) E=0

Ecell = −(0.0591/1) × log(1/10−10) → Ecell=−0.591V

34. How many coulombs are required for the oxidation of 1 mol of H2O to O2
ANS) Oxidation of H2O to O2 is:
2H2O→4H++O2+4e−
Oxidation of 2 moles of water requires 96500×4 C
∴ oxidation of 1 mole of water requires =(96500×4)/ 2=1.93×105 C
35. Name the cell used in hearing aids and watches? ANS) Mercury cell
36. How much charge in terms of Faraday is required to reduce one mol of MnO4 – to Mn2+ ?
ANS) 8H++5e−+MnO4−→Mn2++4H2O , 5 mole e−= 5 Faraday.
37. i) Predict the nature of electrolytes A and B.
(ii) What happens on extrapolation of Λm to concentration approaching zero for electrolytes A and B?