UNIT: 3:- ELECTROCHEMISTRY (9 MARKS)

TOPIC :ELECTROCHEMICAL CELLS NERNST EQUATION,EQUILLIBRIUM CONSTANT,& GIBBS ENERGY

1. ELECTROCHEMISTRY: Electrochemistry is the study of production of electricity from energy released
during spontaneous chemical reactions and the use of electrical energy to bring about non-spontaneous
chemical transformations.
2. Electrochemical cell: A device in which chemical energy of the redox reaction is converted into electrical
energy. e.g., Daniel cell or Galvanic cell in which a zinc rod is placed in a solution of ZnSO 4 in the left
container and a bar of copper metal is immersed in a solution of CuSO4 in the right container. The two
metals which act as electrodes are connected by a metallic wire through a voltmeter and the two solutions
are joined by a salt bridge.
Reaction at Anode (Oxidation half reaction): Zn(s) → Zn2+ + 2e–
Reaction at Cathode(Reduction half reaction): Cu2+ + 2e– → Cu(s)
Overall cell reaction: Zn(s) + Cu2+ → Zn2+ + Cu(s),
The cell can be represented as: Zn(s)| Zn2+ (aq)|| Cu2+ (aq)| Cu(s)
Tip to remember: LOAN which means LEFT OXIDATION ANODE NEGATIVE

It converts the chemical energy liberated during the redox reaction to

electrical energy and has an electrical potential equal to 1.1 V . when
concentration of Zn2+ and Cu2+ ions is unity. Such a device is called a galvanic
or a voltaic cell.
3. GALVANIC CELL is an electrochemical cell that converts the chemical
energy of a spontaneous redox reaction into electrical energy. In this
device the Gibbs energy of the spontaneous redox reaction is
converted into electrical work which may be used for running a motor
or other electrical gadgets like heater, fan, geyser, etc.
4. Salt Bridge and Its Functions: It consists of a glass U-tube containing semi-solid paste of either KCl,
KNO3 or NH4Cl (inert electrolytes) in gelatin or agar-agar jelly. It helps in flow of ions by completing the
circuit and maintains electrical neutrality.
Electrode potential and standard Cell potential ( Ecell) Electromotive
electrode potential (E and E°) force(emf)
Electrode potential-A potential Difference between the Cell potential when
difference which develops between electrode potentials (reduction no current is drawn
the electrode and the electrolyte. potentials) of the cathode and through the cell
Standard Electrode potential - anode. (Measured in Volts)
Electrode potential When Since anode is put on left and
concentrations of all the species cathode on right so,
involved in a half-cell is unity. Ecell = Eright – Eleft
Eo cell = Eo cathode - Eo anode
Ecell = Ereduction – EOxidation
5. REVERSIBILITY OF DANIEL
CELL:
6. Measurement of electrode potential: Potential of individual half-cell can not be measured but we can
measure the difference between the two half-cell potentials that gives the e.m.f of the cell by using SHE
(Standard Hydrogen electrode).
7. STANDARD HYDROGEN ELECTRODE (SHE) :It consists of a platinum wire sealed in a glass tube, The wire
is coated with finely divided platinum black. Platinum black catalyze the reaction 2H+ (aq) + 2e- → H2(ag)
Pure hydrogen gas at 1 atmosphere pressure is bubbled through HCl solution containing H+ ions at 1.0M
concentration continuously over platinum black electrode. The temperature is 298K. It is assigned a
value of zero for it electrode potential and is used as reference electrode.
Example: (i) When SHE is couples with Zn, Pt(s) | H2(g, 1bar) || Zn2+(aq, 1M) | Zn(s)
EMF of the above cell = 0.76 V so E° of Zn /Zn+2 electrode =0.76V
(ii) When SHE is couples with Cu, Pt(s) | H2(g, 1bar) || Cu2+(aq, 1M) | Cu(s)
EMF of the above cell = 0.34 V so E° of Cu /Cu+2 electrode =0.32V
8. NERNST’S EQUATION : It is a relationship that relates electrode potential and concentration of metal

ion.
2.303RT
At T = 298 K substituting R=8.314 F= 96500 C, [ = 0.059 ]
F
[Products]n
Where Q =Reaction Quotient, Quotient Q=
[Reactan ts]n
,n=number of electrons
Examples:

Nerst equation for Daniel cell (Zn – Cu cell) : Zn(s)| Zn2+(aq)|| Cu2+(aq) | Cu(s)
•
• Nerst equation for Ni – Ag cell :

•
• Nerst equation for Mg – Cr cell : Mg/Mg+2// Cr+3 /Cr
3
2.303RT log Mg
+2 
E =E
0
−  
cell Cell  2
6F Cr+3 

9. Electrochemical cell and Gibbs free energy :

10. Relation between E0cell and Equilibrium constant

Kc : At equilibrium Q = Kc and Ecell = 0

2.303RT E cell   nF E cell
Ecell = Ecell − log KC , c = =
 nF

QUESTIONS BASED ON NERNST EQUATION, EQUILLIBRIUM CONSTANT,& GIBBS ENERGY

1. Define Electrochemical cell.What happens when applied external opposite potential becomes
greater than Eocell of electrochemical cell.
2. Explain the working of the galvanic cell by taking an example.
3. Explain the function of the salt bridge.
4. Write the Nernst equation and emf of the following cells at 298K:
a) Mg(s)/Mg2+(0.001M)//Cu2+(0.0001)/Cu(s); EoCu2+/Cu = +0.34V, EoMg2+/Mg = -2.36
b) Fe(s)/Fe2+(0.001M)//H+(1M)/H2(g)/Pt(s) EoFe2+/Fe= -0.44 V
c) Zn/Zn2+(0.1M)//Cd2+(0.01)/Cd; EoZn2+/Zn = -0.76V , EoCd2+/Cd = -0.40V
d) Cu/Cu2+(2M)//Ag+(0.05M)/Ag ; EoCu2+/Cu = +0.34V , EoAg+/Ag = + 0.80V
e) Mg(s)/Mg2+(10-3M)//Cu2+(10-4M)/Cu(s); EoCu2+/Cu = +0.34V, EoMg2+/Mg = -2.36
f) Zn/Zn2+(2M)//Cu2+(0.5M)/Cu; EoZn2+/Zn = -0.76V , EoCu2+/Cu = 0.34V
g) Sn/Sn2+(0.050M)//H+(0.020M)/H2(g)/Pt(s) EoSn2+/Sn= - 0.14V
h) Sn/Sn2+(0.04M)//H+(0.02M)/H2(g)/Pt(s) EoSn2+/Sn= - 0.14V
i) Pt(s)/Br2(l)/Br-(0.010)// H+(0.030M)/H2(g)/Pt(s)
5. Calculate the emf of the cell at 25oC for the following :
a) Mg(s) + 2Ag+(0.0001M)→ Mg+2(0.130M) + 2Ag(s). if Eocell =3.17V.
b) Ni(s) + 2Ag+ (0.002M)→ Ni+2(0.160M) + 2Ag(s),Given Eocell =1.05 V
c) 2Cr(s) + 3Fe2+(0.1M) → 2Cr3+(0.01M) + 3Fe(s) EoCr3+/Cr= - 0.74V , EoFe2+/fe= - 0.44V
6. The emf of the cell Zn/Zn2+(0.1M)//Cd2+(M1)/Cd has been found to be 0.3035 V at 298K.Calculate
the value of M1. EoZn2+/Zn = -0.76V, EoCd2+/Cd = - 0.40V.
7. Calculate the potential for half cell containing .10M K2Cr2O7(aq),0.20MCr3+(aq) and 1.0x 10-4 H+ (aq)
,The half cell reaction is Cr2O72-(aq) + 14 H+ (aq) + 6e-→ 2Cr3+(aq) + 7H2O(l) and the Standard cell
potential E0cell = 1.33V
8. How would you determine the standard electrode potential of the system Mg2+|Mg?
9. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
10. A Zinc rod is dipped in 0.1M solution of ZnSO4.The salt is 95% dissociated at this dilution at
298K.Calculate the electrode potential.
11. Using the Eo values of X & Y predict which is better for coating the surface of iron to prevent rust
and why? EoFe2+/Fe = -0.44V, EoX2+/x = -2.36V, EoY2+/Y = -0.14V
12. Calculate the emf of the cell . The following chemical reaction is occurring in an electrochemical cell.
Mg(s) +2Ag+ (0.0001 M)→ Mg2+(0.10M) + 2 Ag(s) The electrode values are Mg2+ / Mg = – 2. 36 V Ag+
/ Ag = 0.81 V. For this cell calculate / write (a) (i) E0 value for the electrode 2 Ag+ / Ag (ii) Standard
cell potential E0cell. (b) Cell potential (E)cell (c) (i) Symbolic representation of the above cell. (ii) Will
the above cell reaction be spontaneous?
13. A voltaic cell is constructed at 25oC with the following half cell Ag+(0.001M)/Ag and Cu+2 (0.01M)/Cu
what would be the voltage of this cell? Given EoAg+/Ag = + 0.80V, EoCu2+/Cu = +0.34V).
14. A Copper –silver is set up.The copper ion concentration in its is 0.10M.The concentration of silver is
not known.The cell potential measured 0.422V.Determine the concentration of silver ion in the cell.
EoAg+/Ag = + 0.80V, EoCu2+/Cu = +0.34V).
15. One half cell in a voltaic cell is constructed from a silver wire dipped in silver nitrate solution of
unknown concentration .The other half cell consists of a zinc electrode in a 0.10M solution of Zinc
nitrate .A voltage of 1.48V is measured for this cell.Use this information to calculate the
concentration of silver nitrate solution.( EoZn2+/Zn = -0.763V, EoAg+/Ag = + 0.80V)
16. A voltaic cell is set up at 250C With the following half cells :Al(s)/Al3+(0.001M) and Ni2+(0.50)/Ni(s)
,Write the equation for the cell reaction that occurs when the cell generates an electric current and
determine the cell potential (givenEoNi2+/Ni = -0.25V, Eo Al3+/Al(=-1.66V)
17. Calculate ΔrG0 & value of equilibrium constant for the following :
a) Mg(s)/Mg2+//Cu2+/Cu(s); EoCu2+/Cu = +0.34V, EoMg2+/Mg = -2.36
b) Zn(s) + Cu2+  Zn2+ + Cu EoCu2+/Cu = +0.34V, EoZn2+/Zn = -0.76V
c) Cu (s) + 2Ag+  Cu +2+ 2Ag(s) EoCu2+/Cu = +0.34V, EoAg+/Ag = + 0.80V
d) 2Fe3+ + 2I- → 2Fe2+ + I2 has Eocell =0.236 V
e) Fe2+(aq) + Ag+ → Fe3+(aq) + Ag(s),EoAg+/Ag = + 0.80V, EoFe3+/ Fe2+ = +0.77V
f) 2Cr(s) + 3Cd2+ → 2Cr3+ + 3Cd(s) EoCr3+/Cr= - 0.74V , EoCd2+/Cd= - 0.40V
18. Calculate the equilibrium constant for the reaction Calculate the equilibrium constant for the
reaction In the button cell widely used in watches and devices the following reaction takes place:
Zn (s)+ Ag2O(s) + H2O(l)→ Zn2+(aq) + 2 Ag(s) + 2OH- (aq) Determine ΔrG0 &E0 for the reaction.
EoZn2+/Zn = -0.76V, EoAg+/Ag = + 0.80V
19. Calculate emf and ΔG for the following cell : Mg(s)/Mg2+(0.001M)//Cu2+(0.0001M)/Cu(s); EoCu2+/Cu =
+0.34V, EoMg2+/Mg = -2.37V
20. Calculate ΔrG0 for the reaction at 250C :Au(s) +Ca+2 (1 M)→ Au3+(1M) + Ca (s) , Eo Ca2+/ Ca=–2.87 V,
EoAu3+ / Au=+1.50V. Predict whether the reaction will be spontaneous or not at 25 0C which of the
above two half cells will act as an oxidizing agent and which one will be a reducing agent?
21. Depict the galvanic cell in which the reaction:Zn+Ag +→Zn2++2Ag takes place. Further show:(a)Which
of the electrode is negatively charged?(b)The carriers of the current in the cell. (c)Individual reaction
at each electrode.
22. Two half cell reactions of an electrochemical cell are given below:
(i)MnO4- + 8 H+ + 5 e- →Mn2+ + 4 H2O Eo =+1.51V (ii)Sn2+ → Sn4++ 2e- Eo = +0.15V. Construct the
redox reaction from the two half cell reaction and predict if the reaction favours formation of
reactants or product shown in the reaction
23. Given the standard electrode potentials,:K+/K = –2.93V, Ag+/Ag = 0.80V, Hg2+/Hg = 0.79V Mg2+/Mg =
–2.37 V, Cr3+/Cr = – 0.74V.Arrange these metals in their increasing order of reducing power
24. Tarnished silver contains Ag2S. Can this tarnish be removed by placing tarnished silver ware in an
aluminium pan containing an inert electrolytic solution such as NaCl. The standard electrode
potential for half reaction : Al3+ + 3e → Al is -1.66 and Ag2S + 2e → 2Ag+ + S-2 is -0.71
25. The electrochemical cell given alongside converts the chemical energy released during the redox
reaction to electrical energy:
It gives an electrical potential of when concentration and ions is unity. State the
direction of flow of current and also specify whether zinc and copper are deposited or dissolved at
their respective electrodes when:
(i) an external opposite potential of less than 1.1 V is applied.
(ii) an external potential of is applied.
(iii) an external potential of greater than is applied.
TOPIC : CONDUCTIVITY, MOLAR CONDUCTIVITY, CELL CONSTANT, KOHLRAUSCH LAW AND ITS APPLICATION.
1. Electrical (Metallic) and Electrolytic Conductance

S.No. Metallic Conductance Electrolytic Conductance

Movement of electrons is responsible for Movement of ions is responsible for

conduction. conduction.

ii Does not involve transfer of matter. Matter moves in the form of ions.
Increases with increase in
Decreases with increase in temperature as
temperature due to decrease in inter
(iii) kernels start vibrating which produce
ionic attraction or increase in
hindrance in the flow of electrons.
dissociation.

• Electrical conductance through metals is called metallic or electronic conductance and is due to
the movement of electrons. The electronic conductance depends on (i) the nature and structure
of the metal (ii) the number of valence electrons per atom (iii) temperature (it decreases with
increase of temperature)
• Electrolytic or ionic conductance:The conductance of electricity by ions present in thesolutions is
called electrolytic or ionic conductance. The conductivity of electrolytic (ionic) solutions depends
on: (i) the nature of the electrolyte added (ii) size of the ions produced and their salvation (iii) the
nature of the solvent and its viscosity (iv) concentration of the electrolyte (v) temperature (it
increases with the increase of temperature).
2. Measurement of Conductance: The resistance of electrolytic solution is determined by Wheatstone
bridge method having variable resistance (R1), fix resistance (R3 andR4) and unknown resistance(R2 =
R) of electrolyte solution. A null point detected by P detector such that,

The reciprocal of gives the conductance (G)of the solution as,

l/A = G* ( called as cell constant ). The cell constant is usually determined by measuring the resistance of the
cell containing a solution whose conductivity is already known. It depends on the distance between the
electrodes and their area of cross-section.

3. Resistance: The electrical resistance is represented by the symbol ‘R’ and it is measured in ohm (Ω). The
electrical resistance of any object is directly proportional to its length, l, and inversely proportional to
l l
its area of cross section, A. R or R =  ( ) Where  is the constant which depends upon the
A A

nature of conductor. It is called specific resistance or resistivity. Unit is ohm-cm

4. The resistivity for a substance is its resistance when it is one metre long and its area of cross section is
one m2.
5. Conductance : The ease with which carried flows through conductor is called its conductance. It is
1
reciprocal of the resistance G = .The SI unit of conductance is siemens, represented by the symbol
R

‘S’ and is equal to ohm–1 ( −1 ) (also known as mho) .

6. Specific Conductance or Conductivity : of any conductor is the reciprocal of specific resistance and is
denoted by  (Greek work Kappa) .The SI units of conductivity are Sm–1 but quite often, κ is expressed in
S cm–1. Conductivity of a material in S m–1 is its conductance when it is 1 m long and its area of cross
1
section is 1 m2. It may be noted that 1 S cm–1 = 100 S m–1.  =   = 1 l   = GG* The
  RA
quantity l/A is called cell constant denoted by the symbol, G*. It depends on the distance between the
electrodes and their area of cross-section and has the dimension of length–1 and can be calculated if we
l
know l and A. (G*(cell constant) = ) The conductivity of a solution at any given concentration is the
A

conductance of one unit volume of solution kept between two platinum electrodes with unit area of
cross section and at a distance of unit length.
7. Superconductivity: Certain materials called superconductors by definition have zero resistivity or
infinite conductivity. Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were
known to behave as superconductors, but nowadays a number of ceramic materials and mixed oxides
are also known to show superconductivity at temperatures as high as 150 K.
8. Molar Conductivity : It is defined as the conducting power of all the ions produced by one gram mol of

an electrolyte in a solution.  m = In the above equation, if κ is expressed in Sm–1 and the
C

concentration, c in mol m–3 then the units of Λm are in Sm2mol–1

 (Sm -1)
 m (Sm 2 mol-1 ) =
1000(Lm −3 )  Molarity(molL−1 )

If we use Scm–1 as the units for κ and molcm–3, the units of concentration, then the units for Λm
are Scm2 mol–1.
 (Scm-1) 1000(Lcm−3 )
 m (Scm2mol-1 ) =
Molarity(molL−1 )

9. Limiting molar conductivity :When concentration approaches zero, the molar conductivity is known as
limiting molar conductivity and is represented by the symbol 0
10. Conductivity of a solution decrease with dilution because on dilution the number of ions per unit
volume decreases.so the conductivity decreases
11. Variation of molar conductivity with dilution (concentration is decreased) :
Debye–Huckel Onsager equation: Λm = Λ°m– AC1/2,
Plot of Λm against C1/2is a straight line with intercept equal to Λ°m and slope equal to ‘– A’. Thus, Λm
decreases linearly with , when C = 0, Λm = Λ°m and Λ°m can be determined experimentally.

Here, Λ°m = Molar conductivity at infinite dilution (Limiting molar conductivity) Λm = Molar
conductivity at V-dilution, A = Constant which depends upon nature of solvent and temperature, C =
Concentration
12. The increase in conductivity of strong and weak electrolyte upon dilution is due to different reasons:

a) FOR STRONG ELECTROLYTES molar conductivity increases slowly with dilution because in
strong electrolytes the dissociation of the electrolyte in to ions is almost complete however
interionic forces are quite strong. Upon dilution ionic attractions are reduced. This leads to
increase in ionic mobility thus molar conductivity increases with dilution(or decrease in
concentration). There is only a small increase in conductance with dilution

b) FOR WEAK ELECTROLYTES molar conductivity increases Steeply (fast) with dilution because in
weak electrolytes the dissociation of electrolyte into ions is comparatively less.Dilution helps in
dissociation of electrolyte .As a result more ions are formed and corresponding value of
conductivity also increases . There is a very large increase in conductance with dilution
especially near infinite dilution as number of ions increases.

13. Kohlrausch’s Law : The law 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.

(i)  NaCl =  (Na + ) +   (Cl− )

(ii)  CaCl 2 =  (Ca 2+ ) + 2  (Cl− ) (iii)  Al2 (SO4)3 = 2 (Al3+ ) + 3(SO4 )2−

(iv) =  0CH COONa +  0 HCl −  0 NaCl

0
CH3COOH 3

(v)  =  0 NH40Cl +  −  0 NaCl

0
NH4OH NaOH
 14. Application of Kohlrausch’s Law
1. Calculation of limiting molar conductivity of weak electrolyte

2. Calculation of degree of dissociation : Degree of Dissociation is ratio of molar conductivity at a

c
specific concentration ‘C’ to limiting molar conductivity. It is denoted by   = m
0m
2 2
c c
3. Calculation of dissociation constant Ka = =  
(1 − )  ( − )
QUESTIONS BASED ON CONDUCTIVITY MOLAR CONDUCTIVITY, CELL CONSTANT, KOHLRAUSCH LAW AND ITS
APPLICATION
1. Define conductivity,molar conductivity &. limiting molar conductivity.
2. Distinguish between Electrical conductance & Electrolytic (ionic conductance)
3. 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.
4. The resistance of 0.01M NaCl solution at 25oC is 200ohm.The cell constant of the conductivity cell is
unity .calculate the molar conductivity of the solution.
5. The conductivity of 0.20M solution of KCl at 298 K is 0.0248SCm-1.Calculate its molar conductivity.
6. The Molar conductivity of a 1.5M solution of an electrolyte is found to be 138.9 SCm2 mol-1 .
Calculate the conductivity of this solution.
7. The resistance of conductivity cell containing 0.001M KCl at 298K is 1500 ohm. What is cell constant
if conductivity of 0.001M KCl at 298K is 0.146X 10-3Scm-1.
8. When a certain conductance cell was filled with 0.1M KCl solution it has resistance of 85 ohm at
25oC.When the same cell was filled with an aqueous solution of 0.052M of unknown electrolyte the
resistance was 96 ohm. Calculate the molar conductivity of electrolyte. The conductivity of 0.1 M
solution of KCl is 1.29 x 10-2Scm-1.
9. Resistance of conductivity cell filled with 0.1molL-1 KCl solution is 100 ohm. If the resistance of the
same cell when filled with 0.02molL-1 KCl solution is 520 ohm. Calculate the conductivity & molar
conductivity of 0.02molL-1 KCl solution. The conductivity of 0.1 molL-1 solution of KCl is 1.29Sm-1.
10. The electrical resistance of a column of 0.05 molL-1 NaOH solution of diameter 1 cm and length 50
cm is 5.55 X 103 ohm. Calculate its resistivity, conductivity & molar conductivity.
11. State Kohlrausch law and its application. Limiting molar conductivity of NaCl, HCl and NaAc are
126.4, 425.9 &91 SCm2 mol-1.Calculate Limiting molar conductivity of HAc.
12. Define the term degree of dissociation.Write an expression that relates the molar conductivity of a
weak electrolyte to its degree of dissociation.
13. Calculate the degree of dissociation of acetic at 298K,given that Λm(CH3COOH)=11.7 SCm2 mol-1 ,
Λ0m(CH3COO-)=40.9 SCm2 mol-1 , Λ0 m(H+)=349.1 SCm2 mol-1
14. Conductivity of 0.00241M acetic acid is 7.896 X 10-6 S cm-1. Calculate its molar conductivity. If Λ0 for
acetic acid is 390.5 S cm2 mol-1. What is its dissociation constant?
15. Conductivity of 0.001028 M acetic acid is 4.95 X 10-5 S cm-1. Calculate its molar conductivity. If Λ0 for
acetic acid is 390.5 S cm2 mol-1. What is its dissociation constant?
16. The molar Conductivity of 0.025 molL-1 methanoic acid is 46.1 S cm2 mol-1. Calculate its degree of
dissociation & dissociation constant. If λ0(H+) is 349.6 S cm2 mol-1 and λ0(HCOO-) = 54.6 S cm2 mol-1.
17. How do you account for molar conductivity of strong and weak electrolyte with concentration? Plot
the graphs also.
18. Why on dilution the Λm of CH3COOH increases drastically, while that of CH3COONa increases
gradually?
19. Solutions of two electrolytes ‘A’ and ‘B’ are diluted. The Λm of ‘B’ increases 1.5 times while that of A
increases 25 times. Which of the two is a strong electrolyte? Justify your answer.
20. In an aqueous solution how does specific conductivity of electrolytes change with addition of water?
 21. Out of HCl and NaCl, which do you expect will have greater value for Λm and why?
22. Why does the conductivity of a solution decrease with dilution?

TOPIC :FARADAY’S LAWS OF ELECTROLYSIS

1. First Law: The amount of substance deposited or liberated at the electrode during electrolysis is directly
proportional to quantity of electricity passed through the electrolyte. If w g of the substance gets
deposit on passing Q coulomb of electricity wαQ or w=ZQ or w=ZIt, where w=amount of substance
deposited ,I is current in ampere and t is time in second Z= electrochemical equivalent
Eq.Wt Eq.WtxIxt mol.WtxIxt
Z= therefore w = w=
96500 96500 nx96500

2. Second Law:When same quantity of electricity is passed through different electrolytes, the amount of
different substances librated at the electrode is directly proportional to their chemical equivalent
weights(E).(Atomic Mass of Metal ÷ Number of electrons required to reduce the cation) w1 = E1
w2 E2
3. Quantity of electricity carried by n moles of electrons=nF(1F = 96500 coulombs)

QUESTIONS BASED ON FARADAY’S LAWS OF ELECTROLYSIS

1. State Faradays law of electrolysis.
2. How much charge is required for following reduction: (i) 1 mol of Al3+ to Al (ii) 1 mol of Cu2+ to Cu
(iii) 1 mol of MnO4- to Mn2+?
3. How much electricity in terms of Faraday is required to produce (i)20g of Ca from molten CaCl2 (ii) 40g
of Al from molten AlCl3
4. How much electricity in terms of Coulomb is required for the oxidation of (i) 1 mol of H2O to O2 (ii) 1
mol of FeO to Fe2O3
5. How much electricity in terms of Coulomb is required to reduce 1 mol of Cr2O72- to Cr3+.
6. A current of 1.50 A was passed through an electrolytic cell containing AgNO 3 solution with inert
electrodes.the Weight of silver deposited was 1.50g.How long did the current flow? (Molar mass of
Ag = 108gmol-1)
7. A solution of Ni (NO3)2 is electrolysed between platinum electrodes using a current of 5
amperes for 20 minutes. What mass of Ni is deposited at the cathode?
8. A solution of CuSO4 is electrolysed using a current of 1.5 amperes for 10 minutes. What mass of Cu is
deposited at the cathode?
9. Calculate the time to deposit 1.27g of copper at the cathode when a current of 2A was passed
through the solution of CuSO4. (Molar mass of Cu = 63.5gmol-1)
10. How many moles of mercury will be produced by electrolyzing 10M Hg(NO3)2 solution with a
current 0f 2.00A for three hours. (Molar mass of Hg = 200.6 gmol-1)
11. Chromium metal is electroplated using an acidic solution containing CrO 3 according to the equation
: CrO3(aq) + 6H+ + 6e-→Cr(s) + 3H2O calculate how many grams of Chromium will be electroplated by
24000 coulombs.How long will it take to electroplate 1.5g Chromium using 12.5 A current. (Molar
mass of Cr = 52 gmol-1)
12. Three electrolytic cells A,B,C containing solutions ZnSO4,AgNO3,and CuSO4 respectively are connected
in series .A steady current of 1.5 amperes was passed though them until 1.45g of silver deposited at
the cathode of cell B.How long did the current flow? What mass of copper and zinc were deposited?
(Molar mass of Zn = 65,Cu = 63.5, Ag = 108 gmol-1
13. A steady current of 2 amperes was passed through two electrolytic cells X & Y connected in series
 containing FeSO4 &ZnSO4 until 2.8 g of Fe deposited at the cathode of cell X.How long did the current
flow? What mass of zinc were deposited? (Molar mass of Zn = 65,Fe = 56 gmol-1 )
a. How many electrons flow through a metallic wire if a current of 0.5A is passed for 2 h .

TOPIC :BATTERIES AND CORROSION

1. Primary Cell : In the primary batteries, the reaction occurs only once and after use over a period of time
battery becomes dead and cannot be reused again. For Example Dry cell & Mercury Cell
2. Dry Cell : The cell consists of a zinc container that also acts as anode and the cathode is a carbon
(graphite) rod surrounded by powdered manganese dioxide and carbon . The space between the
electrodes is filled by a moist paste of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2). The
electrode reactions are complex, but they can be written approximately as follows :
Anode Zn(s) → Zn2++2e- Cathode MnO2 + NH4+ + e- → MnO(OH) + NH3
Overall reaction: Zn(s) +2 NH4+ + MnO2 (s)→ [Zn(NH3)4]2+ + Mn2O3 + H2O It is used commonly in our
transistors and clocks. Important Note: Ammonia produced in the reaction forms a complex with Zn2+
to give [Zn(NH3)4]2+. The cell has a potential of nearly 1.5 V
3. Mercury Cell : It consists zinc-mercury amalgam as anode and a paste of HgO and carbon as the
cathode. The electrolyte is a paste of KOH & ZnO.
Cathode: HgO + H 2O + 2e− → Hg(1) + 2OH − Anode: Zn(Hg) + 2OH − → ZnO(s) + H 2O + 2e−
Overall reaction Zn(Hg) +HgO(s)→ZnO +Hg(l) Zn Mercury cell suitable for low current devices
like hearing aids, watches, etc. The cell potential is approximately 1.35 V and remains constant during
its life as the overall reaction does not involve any ion in solution whose concentration can change
during its life time.
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. e.g. lead storage batteries, Nickel – cadmium cell.

4. Lead Storage Battery :It consists of a lead anode and a grid of lead packed with lead dioxide (PbO2 ) as
cathode. A 38% solution of sulphuric acid is used as an electrolyte
Anode Pb(s) + SO42- (aq) →PbSO4(s)+2e-
Cathode PbO2(S) + SO42- + 4H+ (aq) +2e- → PbSO4(s) + 2H2O(l)

Overall Reaction Pb(s)+ PbO2(S)+2 H2SO4(aq)→ 2PbSO4(s) + 2H2O(l)

On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is converted into
Pb and PbO2, respectively. 2PbSO4(s) + 2H2O(l) → Pb(s)+ PbO2(S)+2 H2SO4(aq)
The most important secondary cell is the lead storage battery commonly used in automobiles and invertors
5. Nickel cadmium cell is a secondary cell which has longer life than the lead storage cell but more
expensive to manufacture.The overall reaction during discharge is:
Cd(s)+2Ni(OH)3(s)→CdO(s)+2Ni(OH)2(s)+H2O(l)
6. Fuel Cell : Galvanic cells that aredesigned to convert the energy of combustion of fuels like hydrogen,
methane, methanol, etc. directly into electrical energy are called fuel cells.One of the most successful
fuel cells uses the reaction of hydrogen with oxygen to form water .The cell was used for providing
electrical power in the Apollo space programme. The water vapours produced during the reaction were
condensed and added to the drinking water supply for the astronauts. In the cell, hydrogen and oxygen
are bubbled through porous carbon electrodes into concentrated aqueous sodium hydroxide solution.
Catalysts like finely divided platinum or palladium metal are incorporated into the electrodes for
increasing the rate of electrode reactions.
Cathode : O2 (g) + 2H 2O(l) + 4e− → 4OH − (aq) Anode : 2H 2 + 4OH − → 4H 2O + 4e−

Overall Reaction 2H2 (g) + O2 (g) → 2H2O(l) Fuel cells produce electricity with an efficiency of about
 70 % compared to thermal plants whose efficiency is about 40%. Fuel cells are pollution free.

7. Corrosion : The slow process of eating away of metals when exposed to the atmosphere is called corrosion. It
is electro-chemical phenomenon in which metal is oxidized by loss of electrons to form metal oxide. The
rusting of iron, tarnishing of silver, development of green coating on copper and bronze are some of the
examples of corrosion. In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of oxides.
Corrosion of iron occurs in presence of water and air. The chemistry of corrosion is quite complex but it may
be considered essentially as an electrochemical phenomenon. At a particular spot of an object made of iron,
oxidation takes place and that spot behaves as anode and we can write the reaction
Mechanism of Corrosion :Oxidn :Fe→ Fe2+ + 2e- Redn: O2 (g) + 4H + (ag) + 4e− → 2H 2O(l)
Atmospheric Oxidation 2Fe2+(aq) + 2H2O(l)+1/2O2 → Fe2O3(s)+4H+(aq)
Rusting : Corrosion of iron is called rusting formula of rust Fe2O3. xH2O
Prevention of Corrosion : (1). By covering the surface with paint (2). Sacrificial Protection : . An
electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn, etc.) which
corrodes itself but saves the object (3) Using anti-rust solution by some chemicals (e.g. bisphenol)

Questions based on Batteries and Corrosion.

1. Define Corrosion. How it is prevented.
2. Rusting of iron is said to be an electrochemical phenomenon. Explain using reactions.
3. Classify Primary Cell or Secondary cell: Dry Cell ,Mercury Cell ,Lead Storage Battery Nickel
cadmium cell .
4. Write the name of the cell which is generally used in transistors. Write the reactions taking place at
the cathode and anode of this cell.
5. Set up Nernst equation for the standard dry cell.Using this equation show that the voltage of a dry
cell decreases with use.
6. Write the name of the cell which is generally used in hearing aids. Write the reactions taking place
at the cathode and anode of this cell
7. Why does the voltage of a mercury cell remain constant during its operation.
8. Write the name of the cell which is generally used in automobiles & inverters?
9. Write the reaction involved in the Lead Storage Battery. What happens when Lead Storage Battery
is recharged?
10. What is Nickel-Cadmium cell.State its one advantage & disadvantage over Lead Storage Battery.
11. Which cell was used in Apollo space programme.
12. What is Fuel Cell? Explain with diagram & reaction involved in the following cell.
13. Write two advantages of H2-O2 fuel cell over ordinary cell.
14. Suggest two materials other than hydrogen that can be used as fuels in fuel cells.
15. Define Corrosion. How it is prevented.
16. The Chemistry of corrosion of iron is essentially an electrochemical phenomenon .Explain the
reactions occurring during the corrosion of iron in the atmosphere.
 TOPIC: PRODUCTS OF ELECTROLYSIS
Products of electrolysis depend on the nature of material being electrolysed and the type of electrodes being
used. If the electrode is inert (e.g., Pt or Gold), it does not participate in the chemical reaction and acts only as
source or sink for electrons. On the other hand, if the electrode is reactive, it participates in the electrode
reaction. Thus, the products of electrolysis may be different for reactive and inert electrodes. The products of
electrolysis depend on the different oxidizing and reducing species present in the electrolytic cell and their
standard electrode potentials. Moreover, some of the electrochemical processes although feasible, are so slow
kinetically that at lower voltages these don’t seem to take place and extra potential (called overpotential) has
to be applied, which makes such process more difficult to occur.
Note: (i) The reaction at a Cathode with higher value of E oredis preferred (ii)The reaction at anode with lower
value of E ored is preferred
S.No Electrolysis of CATHODE ANODE
1 Aqueous solution of AgNO3 with Ag metal(Ag+ are discharged Ag+ions(Silver electrode
silver electrodes compared to H+as its Eored is being reactive dissolves
higher) to produce Ag+ions)
S.No Electrolysis of CATHODE ANODE
2 Aqueous solution of AgNO3 with Ag metal(Ag+ are discharged O2 gas(OH- ions
platinum electrodes compared to H+as its Eored is discharged compared to
higher) NO3-as its Eored is lower)
3 Aqueous solution of CuCl2 with Copper metal Cl2 gas
platinum electrodes
4 Molten NaCl Sodium metal Cl2 gas
5 Aqueous sodium chloride solution H2 gas Cl2 gas
6 Dilute Sulphuric acid with platinum H2 gas O2 gas
electrodes
7 Copper sulphate using inert Copper metal O2 gas
electrodes (Pt)
8 Aqueous sodium bromide H2 gas Br2 gas

QUESTIONS BASED ON PRODUCTS OF ELECTROLYSIS

1. Predict the products of electrolysis: (a) An aq. Solution of AgNO3 with silver electrodes. (b) An
aq. Solution of AgNO3 with platinum electrodes. (c). An aq. Solution of H2SO4 with platinum
electrodes. (d). An aq. Solution of CuCl2 with platinum electrodes. (e) Aqueous sodium
bromide (f) Copper sulphate using inert electrodes (Pt) (g) Molten NaCl (h) Aqueous sodium
chloride solution
2. Following reactions occur at cathode during electrolysis of Aqueous solution of AgCl solution:
(a)Ag+ (aq) + e-→Ag(s) E0=+0.80V (b) H+ (aq) + e-→H2(s) E0=0.00V on the basis of their
standard electrode potential values which reaction is feasible at the cathode and why?
3. During electrolysis of Aqueous solution of NaBr solution there are two possible reactions
(a)2H2O(I) -→O2 +4H+ + 4e- E0=+1.23V (b) 2 Br- (aq) -→Br2(s) + 2e E0=1.08 V on the basis of
their standard electrode potential values which reaction is feasible at the anode and why?
4. On the basis of E° values, O2 gas should be liberated at anode but it is Cl2 gas which is
liberated in the electrolysis of aqueous NaCl. Explain.
STANDARD POTENTIALS AT 298 K IN ELECTROCHEMICAL ORDER